CN1361815A - Dishwashing detergent composition containing mixtures of crystallinity-disrupted surfactants - Google Patents

Abstract

A hand dishwashing composition comprising: a) from about 0.1% to about 99.9% by weight of said composition of an alkylaryl sulfonate surfactant system comprising from about 10% to about 100% by weight of said surfactant Two or more alkyl aryl sulfonate surfactants whose crystallinity is disrupted by the following formula: (B－Ar－D) _a (M ^q+ ) _b , where D is SO ₃ ^－ , and M is a cation or a mixture of cations, q is the valence of the cation, the number of a and b is selected so that the composition is electrically neutral; Ar is selected from benzene, toluene and combinations thereof; B includes at least one carbon containing 5-20 The sum of a primary hydrocarbyl moiety of an atom and one or more crystallization disrupting moieties, wherein the crystallinity disrupting moiety is interrupted or branched from the hydrocarbyl moiety; and wherein the crystallization of the alkylaryl sulfonate surfactant system and wherein the alkylaryl sulfonate surfactant system also has at least one of the following properties: and b) from about 0.00001% to about 99.9% by weight of said composition A conventional hand dishwashing aid; c) from about 0.01% to about 7% by weight of the composition of a divalent ion selected from the group consisting of magnesium, calcium and mixtures thereof.

Description

Dishwashing composition containing mixture of crystallinity disrupted surfactants

Field of Invention

The present invention relates to dishwashing compositions comprising an alkylarylsulfonate surfactant system comprising a mixture of isomers of a crystallinity disrupted, preferably branched, alkylarylsulfonate surfactant and optionally one or more undisrupted crystallinity alkylaryl sulfonate surfactants.

Background of the Invention

Typical commercial hand dishwashing compositions incorporate divalent ions (Mg, Ca) to ensure suitable grease properties in soft water. However, the presence of divalent ions in products containing anionic, nonionic or other surfactants (e.g. amine oxides, alkyl ethoxylates, LAS, alkanoyl glucamides, alkyl betaines) makes the product incompatible with water The speed of mixing is reduced (hence poor flash lather), the rinse is poor, and the low temperature stability is poor. Also, as the pH decreases, it is difficult to prepare stable dishwashing detergents containing Ca/Mg due to precipitation problems associated with Ca and Mg. Therefore, there is a need for a detergent composition suitable for hand dishwashing, which is stable at low temperatures, and which in addition can have the advantages of degreasing and cleaning hard foods in hard water and typically at a pH of 9 or lower, while conventional Ca/Mg The system will be unstable and will not have the benefits of degreasing and cleaning tough foods.

Background technique

US5,026,933; US4,990,718; US4,301,316; US4,301,317; US4,855,527; 697,246, 4/29/94; SU793,972, 1/7/81; US2,564,072; US3,196,174; US3,238,249; US3,355,484; US3,442,964; 9/25/90; US4,962,256; US5,196,624; US5,196,625; EP364,012B, 2/15/90; 533,651；US4,587,374；US4,996,386；US5,210,060；US5,510,306；WO95/17961，7/6/95；WO95/18084；US5,510,306；US5,087,788；4,301,316；4,301,317；4,855,527；4,870,038；5,026,933； 5,625,105 and 4,973,788. The production of alkylbenzene sulfonate surfactants has recently been observed. See "Surfactant Science" Series Vol. 56, Marcel Dekker, New York, 1996, especially including pages 39-108 entitled "Alkylarylsulfonates: History, Manufacture, Analysis, and Environmental Properties (Alkylarylsulfonates: History, Manufacturing, Analysis and Environmental Properties)", which includes 297 references. The entire contents of these references are incorporated herein.

Brief description of the invention

It has now been surprisingly found that when an alkylaryl sulfonate surfactant system comprises two or more isomers of crystallized disrupted alkylaryl sulfonate surfactants, optionally also containing one or A variety of alkylaryl sulfonate surfactants with undisrupted crystallinity than alkylaryl sulfonate surfactants without crystallinity-disrupted alkylaryl sulfonate surfactant isomers A surprising increase in performance.

The present invention has many advantages within one or more of the aspects described above, including but not limited to: excellent cold water solubility, such as when washing in cold water; excellent hardness tolerance; and excellent detergency. Furthermore, the present invention contemplates enhanced greasy stain removal. This development allows for a rather predictable increase in the ease of production of relatively high 2-phenylsulfonate compositions; also improves the ease and quality of preparation of the resulting articles; and confers attractive economic advantages.

The present invention is based on the unexpected discovery that there are certain alkylbenzene sulfonates in the intermediate range between the old highly branched non-biodegradable alkylbenzene sulfonates and the new linear types, which are more The latter performs better and is more biodegradable than the former.

These novel alkylbenzene sulfonates are readily obtained by several of the many known alkylbenzene sulfonate production methods. For example, the use of certain dealuminated mordenites facilitates their manufacture.

According to the present invention, a novel hand dishwashing composition is provided. The novel hand dishwashing composition comprises:

a) from about 0.1% to about 99.9% by weight of the composition of an alkylaryl sulfonate surfactant system comprising from about 10% to about 100% by weight of the surfactant system of two or A variety of crystallinity disrupted alkylaryl sulfonate surfactants of the formula:

(B-Ar-D)a(Mq+)b wherein D is SO ₃ ⁻ , M is a cation or a mixture of cations, q is the valency of the cation, and the numbers of a and b are selected so that the composition is electrically neutral Ar is selected from benzene, toluene and combinations thereof; B includes at least one carbon atom containing 5-20, preferably 7-16 carbon atoms, more preferably 9-15 carbon atoms, most preferably 10-14 carbon atoms the sum of a primary hydrocarbyl moiety and one or more crystallization-disrupting moieties, wherein the crystallization-disrupting moiety is interrupted or branched from the hydrocarbyl moiety; and wherein the crystallization-disruption of the alkylarylsulfonate surfactant system to the extent that its sodium critical solubility temperature, as determined by the CST test, is no greater than about 40° C., and wherein the alkylaryl sulfonate surfactant system also has at least one of the following properties:

Percent biodegradation over tetrapolypropylene benzene sulfonate as determined by the modified SCAS test; and

The weight ratio of non-quaternary carbon atoms to quaternary carbon atoms in B is at least about 5:1 (preferably at least about 10:1; more preferably at least about 100:1); and

b) from about 0.00001% to about 99.9% by weight of the composition of a conventional hand dishwashing aid;

c) From about 0.01% to about 7% by weight of the composition of a divalent ion selected from the group consisting of magnesium, calcium and mixtures thereof.

The compositions preferably contain at least about 0.1%, more preferably at least about 0.5%, even more preferably at least about 1%, by weight of the composition, of the surfactant system. Cleaning compositions also preferably contain no more than about 80%, more preferably no more than about 60%, even more preferably no more than about 40%, by weight of the composition, of a surfactant system.

The surfactant system preferably contains at least about 15%, more preferably at least about 30%, and even more preferably at least about 40%, by weight of the surfactant system, of two or more crystallinity disrupted alkylaryl sulfonates Surfactant. The surfactant system also preferably contains no more than about 100%, more preferably no more than about 90%, and even more preferably no more than about 80%, by weight of the surfactant system, of two or more crystalline disrupted of alkylaryl sulfonate surfactants.

Accordingly, one aspect of the present invention is to provide novel cleaning compositions. These and other aspects, features and advantages will become apparent from the following detailed description and appended claims.

All percentages, ratios and proportions herein are by weight of ingredients to prepare the final composition, unless otherwise specified. All temperatures are in degrees Celsius (° C.) unless otherwise indicated. All documents cited in relevant part herein are incorporated herein by reference.

                    Invention Details

The present invention relates to novel hand dishwashing compositions. Component (a) comprises from about 0.1% to about 99.9% by weight of said composition of an alkylaryl sulfonate surfactant system comprising from about 10% to about 100% by weight of both of said surfactant systems. or multiple crystallinity disrupted alkylaryl sulfonate surfactants of the following formula:

(B-Ar-D)a(Mq+)b wherein D is S0 ₃ ^- , and M is a cation or a mixture of cations. Preferably, M is an alkali metal, alkaline earth metal, ammonium, substituted ammonium or mixtures thereof, more preferably sodium, potassium, magnesium, calcium or mixtures thereof. The valence q of the cation is preferably 1 or 2. The numbers a and b such that the composition is electrically neutral are preferably 1 or 2 and 1, respectively.

Ar is preferably selected from benzene, toluene and combinations thereof, most preferably benzene.

B includes at least one primary hydrocarbyl moiety containing 5 to 20 carbon atoms and one or more segments or branches; preferably B includes both odd and even chain length hydrocarbyl moieties. That is, it is preferred that B is not limited to all odd or even chain length hydrocarbyl moieties. The primary hydrocarbyl portion of B has 5-20, preferably 7-16 carbon atoms. There may be 1-3 crystalline disrupted fractions. These crystallinity disrupted moieties are interrupted or branched from the hydrocarbyl moieties. When the crystallinity breaking moieties are branched, they are preferably C1-C3 alkyl, C1-C3 alkoxy, hydroxyl and mixtures thereof, more preferably C1-C3 alkyl, most preferably C1-C2 alkyl, even more preferably methyl. When the crystallization disrupting moiety interrupts the hydrocarbyl moiety, they are preferably ethers, sulfones, silicones and mixtures thereof, more preferably ethers. Preferred crystallinity disrupted alkylaryl sulfonate surfactants include two or more homologues. "Homologues" differ in the number of carbon atoms contained in B. "Isomers" as described in detail later herein specifically include those compounds in which the crystallinity-disrupting moieties have different attachment positions on B.

It is also preferred that the crystallinity disrupted alkylaryl sulfonate surfactant comprises at least two "isomers" selected from the group consisting of:

i) Ortho-, meta- and para-isomers based on the attachment position of the substituent to Ar, when Ar is a substituted or unsubstituted benzene. This means that B can be in the ortho, meta and para positions with D, B can be in ortho, meta and para positions with substituents on Ar other than D, and D can be with substituents on Ar other than B. Ortho, meta and para substituents, or any other possible choice;

ii) positional isomers based on the position of attachment of said crystallinity disrupting moiety at said primary hydrocarbyl moiety of B; and

iii) Stereoisomers based on the chiral carbon atom in B.

More preferably, the crystallinity disrupted alkylaryl sulphonate surfactant will comprise at least two isomers of type ii), most preferably at least four isomers of type ii).

Preferably at least about 60%, more preferably about 70% or more, or most preferably about 80% or more of the crystallinity disrupted alkylaryl sulfonate surfactant by weight of the surfactant system is an isomer form, wherein Ar is attached to the first, second or third carbon atom of said primary hydrocarbyl moiety of B.

An optional component of the compositions of the present invention is from about 0% to about 85% by weight of the surfactant system of one or more undisrupted crystallinity alkylaryl sulfonate surfactants of the formula:

     (L-Ar-D)a(Mq+)b where D, M, q, a, b, Ar are as defined above. L is a linear primary hydrocarbyl moiety containing 5-20 carbon atoms. Preferably L is a linear hydrocarbyl moiety of 7 to 16 carbon atoms.

The degree of crystallinity disruption of the alkylaryl sulfonate surfactant system is no greater than about 40°C, preferably no greater than about 20°C, and most preferably Not higher than about 5°C. It is also preferred that its calcium critical solubility temperature as determined by the CST test is less than about 80°C, preferably not greater than about 40°C, more preferably not greater than about 20°C.

The alkylaryl sulfonate surfactant system also has at least one of the following properties:

a) The percent biodegradation, as determined by the modified SCAS test (described below in this text), exceeds tetrapolypropylene benzene sulfonate; or

b) The weight ratio of non-quaternary carbon atoms to quaternary carbon atoms in B is at least about 5:1. Preferably, the weight ratio of non-quaternary carbon atoms to quaternary carbon atoms in B is at least about 10:1; more preferably at least about 20:1, and most preferably at least about 100:1.

More preferably, the absolute value of the percent biodegradation as determined by the modified SCAS test is preferably at least about 60%, more preferably at least 70%, even more preferably at least 80%, most preferably at least 90%.

The hand dishwashing compositions of the present invention also include b) from about 0.00001% to about 99.9% by weight of the composition of conventional hand dishwashing aids; and c) from about 0.01% to about 7% by weight of the composition of magnesium, calcium and Divalent ions of the mixture. These materials, and optionally other materials useful herein, are described in detail below.

As for the method of using the composition of the present invention, there is, for example, a method of contacting dirty tableware to be cleaned with either the pure composition or an aqueous solution of the composition. These methods may optionally include the step of diluting the composition with water. Furthermore, the composition may be applied neat or in aqueous solution directly to the dishes or surfaces to be cleaned, or directly to a cleaning implement such as a sponge or scouring cloth. These methods are part of the present invention. crystallinity destruction

The term "disrupted crystallinity" as defined herein means that the surfactant referred to is one that contains a hydrophobic moiety selected to form a surfactant that is about the same length or chain length range as the hydrophobic moiety. Compared to a reference surfactant of pure linear hydrocarbon chain of formula CH ₃ (CH ₂ ) _n — to which the surfactant is compared, the former surfactant is incorporated into the crystal lattice with a lower efficiency.

即CH₃(CH₂)₁₁-，其本身为“结晶性未破坏的”，按照本发明通过将不同部分如醚部分、硅酮或砜插入链中，如下所示，可以将其改性形成结晶性破坏的结构：

更优选，当将从B的一个或多个分支加入结构中时发生本文的结晶性破坏，如下所示：

就具有式(B-Ar-D)a(Mq+)b和(L-Ar-D)a(Mq+)b的本文表面活性剂而言，应说明的是，B代表代表结晶性破坏的疏水部分，而L代表结晶性未破坏的疏水部分。同样，在两种术语中，结晶性破坏的疏水部分B包括由以下组成的主要部分：(i)除结晶性破坏部分之外的B中所有部分；和(ii)结晶性破坏部分。In general, crystallinity disruption can flow from any of several modifications of surfactants at the molecular level. Especially linear hydrophobic moieties such as

That is CH ₃ (CH ₂ ) ₁₁ -, itself "unbroken in crystallinity", can be modified according to the invention by inserting different moieties such as ether moieties, silicones or sulfones into the chain, as shown below, to form Crystalline broken structure:

More preferably, the crystalline disruption herein occurs when one or more branches from B are added to the structure, as follows:

With respect to the surfactants herein having the formulas (B-Ar-D)a(Mq+)b and (L-Ar-D)a(Mq+)b, it should be noted that B represents a hydrophobic moiety representing crystallinity disruption , while L represents the hydrophobic moiety whose crystallinity is not destroyed. Also, in both terms, the crystallinity-disrupted hydrophobic portion B includes a major portion consisting of: (i) all of B except the crystallinity-disrupted portion; and (ii) the crystallization-disrupted portion.

In a preferred embodiment, B has (i) a moiety of 7-16 carbon atoms and (ii) a crystallinity disrupting moiety selected from (a) a branch (or "side chain") attached to B, In general it can vary, but is preferably selected from C ₁ -C ₃ alkyl, hydroxy and mixtures thereof, more preferably C ₁ -C ₃ alkyl, most preferably C ₁ -C ₂ alkyl, even more preferably methyl; (b) a moiety interrupting the structure of B selected from ethers, sulfones, silicones; and (c) mixtures thereof. Other crystallinity disrupting moieties not preferred herein include olefins. Alkylaryl Sulfonate Surfactant System

A major component of the hand dishwashing compositions of the present invention is an alkylaryl sulfonate surfactant system. The alkylaryl sulfonate surfactant system includes a major crystallinity disrupting component.

The present invention relates to compositions comprising at least two or more of these crystallinity disrupted alkylaryl sulfonate surfactants and optionally one or more crystallinity undisrupted alkylaryl sulfonate surfactants Cleansing composition. These two components are described as follows: (1) Alkylarylsulfonate Surfactant with Disrupted Crystallinity:

The hand dishwashing compositions of the present invention comprise an alkylaryl sulfonate surfactant system comprising at least two or more crystalline disrupted alkylaryl sulfonate surfactants having the formula:

(B-Ar-D)a(Mq+)b wherein D, B, M, q, a, b, Ar are as defined above herein. Possible crystallinity disrupted alkylaryl sulfonate surfactants include:

Structures (a)-(o) merely depict some possible crystallinity disrupted alkylaryl sulfonate surfactants and are not intended to limit the scope of the invention.

It is also preferred that the crystallinity disrupted alkylaryl sulfonate surfactant comprises at least two isomers selected from the group consisting of:

i) Ortho-, meta- and para-isomers based on the attachment position of the substituent to Ar, when Ar is a substituted or unsubstituted benzene. This means that B can be ortho, meta and para to D, B can be ortho, meta and para to substituents on Ar other than D, and D can be substituted with substituents on Ar other than B base ortho, meta and para, or any other possible choice;

ii) positional isomers based on the position of attachment of said crystallinity disrupting moiety at said primary hydrocarbyl moiety of B; and

iii) Stereoisomers based on the chiral carbon atom in B.

Two examples of isomers of type (ii) are structures (a) and (c). The difference is that the methyl group in (a) is attached at the 5th position, whereas in (c) the methyl group is attached at the 7th position.

Two examples of isomers of type (i) are structures (1) and (n). The difference is that in (1) the sulfonic acid group is meta to the hydrocarbyl moiety, but in (n) the sulfonate is ortho to the hydrocarbyl moiety.

Two examples of isomers of type (iii) are structures (c) and (d). The difference is that these isomers are stereoisomers. The chiral carbon is the 7th carbon atom of the hydrocarbyl moiety. (2) Alkylaryl sulfonate surfactants with unbroken crystallinity:

The hand dishwashing compositions of the present invention may also optionally include an alkylaryl sulfonate surfactant system which may contain one or more crystalline undisrupted alkylaryl sulfonate surfactants having the formula agent:

         (L-Ar-D)a(Mq+)b where D, M, L, q, a, b, Ar are defined the same as previously described herein. Possible crystallinity undisrupted alkylaryl sulfonate surfactants include standard linear alkylbenzene sulfonates, such as those commercially available, such as the so-called high 2-phenyl linear alkylbenzene sulfonates , known as DETAL or conventional LAS. Available from Huntsman or Vista. These linear alkylaryl sulfonates can be added to these crystallinity disrupted alkylaryl sulfonate surfactants to provide the alkylaryl sulfonate surfactants used in the cleaning compositions of the present invention system. Alternatively, an undisrupted crystallinity alkylarylsulfonate surfactant and a crystallinity disrupted alkylarylsulfonate surfactant are produced in the same reaction, possibly due to isomerization before, during or after the reaction agent. The ratio of crystallinity-destroyed alkylarylsulfonate to crystallinity-destroyed alkylarylsulfonate depends on the catalyst used. Regardless of the catalyst used, the surfactant system must have a sodium critical solubility temperature of not more than about 40° C. and or a percent biodegradation in excess of tetrapropylene benzenesulfonate, preferably greater than 60 percent, more preferably greater than 60 percent, as determined by the modified SCAS test. Preferably greater than 80%, or a weight ratio of non-quaternary carbon atoms to quaternary carbon atoms in B of at least about 5:1.

Example 1

      Prepared through skeletal isomerization of linear olefins

Crystallinity disrupted surfactant system step (a): at least partially reducing the linearity of olefins (by skeletal isomerization of preformed olefins to chain lengths suitable for cleaning product decontamination)

A mixture of 1-decene, 1-undecene, 1-dodecene and 1-tridecene (available for example from Chevron) in a weight ratio of 1:2:2:1 at 220°C and at any Suitable LHSV such as 1.0 is passed over a Pt-SAPO catalyst. The catalyst was prepared in the manner of the example of US 5,082,956. See WO95/21225, for example, Example 1 and description thereof. The product is a skeletally isomerized lightly branched olefin having a chain length suitable for the preparation of alkylbenzene sulfonate surfactants for consumer mix cleaning compositions. More typical temperatures for this step may range from about 200°C to about 400°C, preferably from about 230°C to about 320°C. The pressure is typically from about 15 psig to about 2000 psig, preferably from about 15 psig to about 1000 psig, more preferably from about 15 psig to about 600 psig. Hydrogen is a useful booster gas. The space velocity (LHSV or WHSV) is suitably from about 0.05 to about 20. Low pressure and low space velocity per hour will improve selectivity, more isomerization and less cracking. Boiling volatiles were distilled off at up to 40°C/10mmHg. Step (b): Alkylation of the product of step (a) with an aromatic hydrocarbon

In a glass autoclave sleeve, add the slightly branched olefin mixture produced in the step (a) of 1 molar equivalent, the benzene of 20 molar equivalents and the shape selective zeolite catalyst (acidic mordenite catalyst Zeocat ^™ FM-8/25H). The glass thimble was enclosed in a stainless steel shaker autoclave. The autoclave was purged twice with 250 psig _N2 , then 1000 psig _N2 was added. The mixture was heated to 170-190° C. with stirring for 14-15 hours, then it was cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst and concentrated by evaporating off unreacted starting materials and/or impurities (e.g. benzene, olefins, paraffins, trace materials, recovery of useful materials if desired) to obtain a clear, approximately colorless liquid product . This product is then formed into the desired crystallinity-disrupted surfactant system, which can alternatively be shipped to a remote processing facility where sulfonation and incorporation into consumer cleansing compositions can be accomplished. other steps. Step (c): Sulfonation of the product of step (b)

The product of step (b) was sulfonated with an equivalent of chlorosulfonic acid using dichloromethane as solvent. Dichloromethane was distilled off. Step (d): Neutralization of the product of step (c)

The product of step (c) is neutralized with sodium methoxide in methanol and the methanol is evaporated to obtain a crystallinity disrupted surfactant system.

Example 2

Prepared from skeletally isomerized linear olefins

Surfactant system with crystallization disruption

The procedure of Example 1 was repeated except that sulfur trioxide (without dichloromethane solvent) was used as the sulfonating agent in the sulfonation step (c). Details of sulfonation using a suitable air/sulfur trioxide mixture are given in US 3,427,342 to Chemithon. Also, step (d) uses sodium hydroxide instead of sodium methoxide for neutralization.

Example 3

      Prepared through skeletal isomerization of linear olefins

         Crystallization-disrupted surfactant system step (a): at least partially reducing the linearity of olefins

A mixture of C11, C12 and C13 monoolefins was passed over the H-ferrierite catalyst in a weight ratio of 1:3:1 at 430°C. The method and catalyst in US5,510,306 can be used for this step. Boiling volatiles were distilled off at up to 40°C/10mmHg. Step (b): Alkylation of the product of step (a) with an aromatic hydrocarbon

Add 1 molar equivalent of the slightly branched olefin mixture of step (a), 20 molar equivalents of benzene and 20 wt% of the shape-selective zeolite catalyst (acidic mordenite catalyst Zeocat ^™ based on the olefin mixture) in a glass autoclave jacket FM-8/25H). The glass thimble was enclosed in a stainless steel shaker autoclave. The autoclave was purged twice with 250 psig _N2 , then 1000 psig _N2 was added. The mixture was heated to 170-190° C. with stirring overnight for 14-15 hours, then it was cooled and removed from the autoclave. The reaction mixture was filtered to remove the catalyst. Benzene is recovered by distillation, and volatile impurities are also removed. A clear, colorless or nearly colorless liquid product is obtained. Step (c): Sulfonation of the product of step (b)

The product of step (b) was sulfonated with an equivalent of chlorosulfonic acid using dichloromethane as solvent. Dichloromethane was distilled off. Step (d): Neutralization of the product of step (c)

The product of step (c) is neutralized with sodium methoxide in methanol and the methanol is evaporated to obtain a crystallinity disrupted surfactant system.

Example 4

     Prepared through skeletal isomerization of paraffin wax

     Crystallization Destroyed Surfactant System Steps (ai)

n-Undecane, n-Dodecane, n-Decathene over Pt-SAPO-11 at a temperature of about 300-340°C, 1000 psig of hydrogen, an hourly gravimetric space velocity of 2-3, and 30 mol _H2 /mol hydrocarbon The mixture of trioxane 1:3:1wt is isomerized, and the conversion rate exceeds 90%. This isomerization is given in detail by SJ Miller in Microporous Materials, Vol. 2, (1994), 439-449. In another example, the linear feed wax mixture can be the same as that used in conventional LAB production. Boiling volatiles were distilled off at up to 40°C/10mmHg. step (a ii)

The paraffin of step (ai) is dehydrogenated using conventional methods. See eg US 5,012,021, 4/30/91 or US 3,562,797, 2/9/71. Suitable dehydrogenation catalysts are any of the catalysts disclosed in US Pat. For the purposes of this example, dehydrogenation was performed as in US 3,562,797. The catalyst is zeolite A. The dehydrogenation is carried out in the vapor phase in the presence of oxygen (paraffin:dioxygen 1:1 mol). The temperature is 450°C-550°C. The ratio of grams of catalyst per hour to moles of total charge was 3.9. Step (b): Alkylation of the product of step (a) with an aromatic hydrocarbon

Add 1 molar equivalent of the mixture of step (a), 5 molar equivalents of benzene and 20 wt% shape-selective zeolite catalyst (acidic mordenite catalyst Zeocat ^™ FM-8/25H) based on the olefin mixture into a glass autoclave jacket . The glass thimble is enclosed in a stainless steel shaker autoclave kettle. The autoclave was purged twice with 250 psig _N2 , then 1000 psig _N2 was added. The mixture was heated to 170-190° C. with stirring overnight for 14-15 hours, then it was cooled and removed from the autoclave. The reaction mixture was filtered to remove the catalyst. Benzene and any unreacted paraffin are recovered by distillation. A clear, colorless or nearly colorless liquid product is obtained. Step (c): Sulfonation of the product of step (b)

The product of step (b) is sulfonated using sulfur trioxide/air without solvent. See US 3,427,342. The molar ratio of sulfur trioxide to alkylbenzene is from about 1.05:1 to about 1.15:1. The reaction stream is cooled and separated from remaining sulfur trioxide. Step (d): Neutralization of the product of step (c)

The product of step (c) is neutralized with a slight excess of sodium hydroxide to obtain a crystallinity disrupted surfactant system.

Example 5

from the Grignard reaction

  A Surfactant System with Disrupted Crystallinity Prepared from a Specific Tertiary Alcohol

A mixture of 5-methyl-5-undecanol, 6-methyl-6-dodecanol and 7-methyl-7-tridecanol was prepared via the following Grignard reaction. A mixture of 28 g 2-hexanone, 28 g 2-heptanone, 14 g 2-octanone and 100 g diethyl ether was added to an addition funnel. The ketone mixture was then added dropwise over 1.75 hours to a nitrogen blanketed stirred three-neck round bottom flask equipped with a reflux condenser and containing 350 mL of 2.0 M hexylmagnesium bromide in diethyl ether and an additional 100 mL of diethyl ether. After the addition was complete, the reaction mixture was stirred for another 1 hour at 20°C. The reaction mixture was then added to 600 g of ice-water mixture with stirring. To this mixture was added 228.6 g of a 30% sulfuric acid solution. Add the resulting two liquid phases to a separatory funnel. The aqueous layer was drained and the remaining ether layer was washed twice with 600 mL of water. The ether layer was then evaporated under vacuum to obtain 115.45 g of the desired alcohol mixture. A 100 g sample of this pale yellow alcohol mixture was added to a glass autoclave jacket along with 300 mL of benzene and 20 g of a shape selective zeolite catalyst (acidic mordenite catalyst Zeocat ^™ FM-8/25H). The glass thimble was enclosed in a stainless steel shaker autoclave. The autoclave was purged twice with 250 psig _N2 , then 1000 psig _N2 was added. The mixture was heated to 170° C. with stirring overnight for 14-15 hours, then it was cooled and removed from the autoclave. The reaction mixture was filtered to remove the catalyst. It is concentrated by distilling off the benzene, which is dried and recovered. A clear, colorless or nearly colorless mixture of slightly branched olefins is obtained.

50 g of the lightly branched olefin mixture provided by dehydration of the above Grignard alcohol mixture was added to a glass autoclave jacket along with 150 mL of benzene and 10 g of a shape-selective zeolite catalyst (Acid Mordenite Catalyst Zeocat ^™ FM-8/25H) middle. The glass sleeve was enclosed in a stainless steel shaker autoclave. The autoclave was purged twice with 250 psig _N2 , then 1000 psig _N2 was added. The mixture was heated to 195° C. with stirring overnight for 14-15 hours, then it was cooled and removed from the autoclave. The reaction mixture was filtered to remove the catalyst. It is concentrated by distilling off the benzene, which is dried and recovered. A clear, colorless or nearly colorless mixture of slightly branched olefins is obtained. The product was distilled under vacuum (1-5 mm Hg), retaining the 95°C-135°C fraction.

The remaining fraction, a clear colorless or nearly colorless liquid product, is then sulfonated with 1 molar equivalent of sulfur trioxide, the resulting product is neutralized with sodium methoxide in methanol, and the methanol is evaporated to give a crystallinity-disrupted surface active agent system. Critical Solubility Temperature Test, or CST Test

The critical solubility temperature test is to determine the critical solubility temperature of a surfactant system. Briefly, the critical solubility temperature is the temperature of a surfactant system at which a sudden or dramatic increase in solubility is measured. This temperature is becoming more and more important as today's washing temperatures tend to be lower and lower. It has been surprisingly found that the critical solubility temperature of the alkylarylsulfonate surfactant systems of the present invention can be controlled by the presence of crystallinity disrupted alkylarylsulfonate salts in the alkylarylsulfonate surfactant systems. decrease with the amount and type of surfactant.

The critical solubility temperature is determined as follows:

All glassware used was washed and dried thoroughly. All temperatures were measured using a standardized mercury thermometer. The sample weights used are based on the solid surfactant or the anhydrous form of the surfactant.

A) Sodium Critical Solubility Temperature - Weigh 99 g of deionized water into a clean dry beaker equipped with a magnetic stirrer. The beaker was then placed in an ice water bath until the deionized water cooled to 0°C. A 1.0 g sample of the solid sodium salt of the surfactant or mixture of surfactants whose sodium critical solubility temperature is to be determined is then added. The resulting heterogeneous solution was stirred for 1 hour. If the surfactant sample dissolves within 1 hour without any heating to give a clear homogeneous solution, record its Sodium Critical Solubility Temperature as ≤ 0°C. If the surfactant sample does not dissolve into a clear homogeneous solution within 1 hour, the heterogeneous solution is slowly heated with stirring at a rate of 0.1°C/minute. The temperature at which the surfactant sample dissolves to give a clear homogeneous solution is recorded as its sodium critical solubility temperature.

B) Calcium Critical Solubility Temperature - Weigh 99 g of deionized water into a clean dry beaker equipped with a magnetic stirrer. The beaker was then placed in an ice water bath until the deionized water cooled to 0°C. A 1.0 g sample of the solid calcium salt of the surfactant or mixture of surfactants to be determined for the critical solubility temperature of calcium is then added. The resulting heterogeneous solution was stirred for 1 hour. If the surfactant sample dissolves within 1 hour without any heating to give a clear homogeneous solution, record its calcium critical solubility temperature as < 0°C. If the surfactant sample does not dissolve into a clear homogeneous solution within 1 hour, the heterogeneous solution is slowly heated with stirring at a rate of 0.1°C/minute. The temperature at which the surfactant sample dissolves to give a clear homogeneous solution is recorded as its calcium critical solubility temperature.

The surfactant mixture sodium salt herein is the most common form of surfactant used. Conversion to the calcium salt is known by simple displacement, for example in dilute solution or with the aid of a suitable organic solvent. Modified SCAS test

This method is suitable for the Soap and Detergent Association semi-continuous activated sludge (SCAS) step for evaluating the initial biodegradation of alkylbenzene sulfonates. The method involves exposing chemicals to relatively high concentrations of microorganisms for extended periods of time (possibly months). The microorganisms were kept alive during this period by adding a fixed daily feed of dirty feed. This modified test is also the standard OECD test or 302A for intrinsic biodegradability. The test was adopted by the OECD on April 12, 1981. Details of the "unmodified" SCAS can be found in "A procedure and Standards for the Determination of the Biodegradability of Alkyl Benzene Sulphonate and Linear Alkylate Sulphonate), Journal of the Ametican Oil Chemists' Society, Vol. 42, p. 986 (1965).

The results obtained with this test surfactant or surfactant system indicate that it has a high biodegradation potential and for this reason it is most useful as a measure of intrinsic biodegradability.

The ventilation apparatus used was the same as disclosed in the "unmodified" SCAS test. That is, a plexiglass tube 83mm (31/4 inch) ID (inside diameter) with the lower end of the steeple 30° from the vertical to the bottom 13mm (1/2 inch) hemisphere. 25.4mm (1 inch) above the junction of the vertical line with the tapered wall, at the bottom of the 25.4mm (1 inch) diameter opening for insertion of the air delivery tube. The overall length of the plenum shall be at least 600mm (24 inches). An optional discharge hole can be located at the 500ml level for easy sampling. Keep the device open to the atmosphere. Supply air to the ventilation unit from a small-scale laboratory air compressor. The air is filtered through glass wool or any other suitable medium to remove dirt, oil, etc. The air is also presaturated with water to reduce evaporation losses from the unit. Air is delivered at a rate of 500ml/min (1ft ³ /hour). Air is delivered through an 8mm OD (outer diameter), 2mm ID capillary. The capillary ends were located 7 mm (1/4 inch) from the bottom of the plenum.

Modified SCAS Test - Vents cleaned and secured in suitable brackets. This step is carried out at 25°C+3°C. Preparation of stock solutions for assay surfactants or surfactant systems: typically a concentration of 400 mg/l is required, whereas organic carbons typically have assay surfactants of 20 mg/l at the start of each biodegradation cycle where no biodegradation occurs Or surfactant system concentration.

Obtain mixed liquor samples from an activated sludge plant that primarily treats domestic sewage. Each ventilation unit was filled with 150ml of the mixture and started to ventilate. After 23 hours, the ventilation was stopped, and the rubbish was allowed to settle for 45 minutes. Draw 100ml supernatant. Obtain a sample of settled domestic sewage anytime before use and add 100 ml to the sewage retained in each aeration unit. Restart ventilation. During this period when no assay material was added, only domestic sewage was added to the apparatus daily until a clear supernatant was obtained by settling. This usually takes 2 weeks, by which time the dissolved organic carbon in the supernatant should be below 12 mg/l at the end of each aeration cycle.

At the end of this period the sludge from each settling was mixed and 50 ml of the resulting combined sludge was added to each unit.

100 ml of settled sewage was added to the aeration unit of the control unit. 95 ml of settled sewage and 5 ml of a suitable stock solution (400 mg/l) for the determination of surfactants or surfactant systems are added to the ventilation unit of the control unit. Ventilation was started again and continued for 23 hours. The sludge was then allowed to settle for 45 min and the supernatant was aspirated and analyzed for dissolved organic carbon content. The carbon content (D.O.C.) was analyzed using a SHIMADZU Model TOC-5000 TOC analyzer. This filling and withdrawal step was repeated daily throughout the assay. Before settling, it may be necessary to wash the walls of the apparatus to prevent solids from collecting on the liquid surface. Use a separate spatula or brush for each device to prevent cross-contamination.

Dissolved organic carbon in the supernatant is ideally determined daily, although less frequent analysis is permitted. Prior to analysis, supernatants were filtered through washed 0.45 micron membrane filters and centrifuged. The sample temperature must not exceed 40°C during its centrifugation.

The results of measuring the dissolved organic carbon of the supernatant in the aeration unit and the control aeration unit were plotted against time. When biodegradation was complete the levels found in the test vents were close to those found in the control vents. Once the difference between the two levels is found to be constant in 3 consecutive determinations, perform 3 further determinations and determine the percent biodegradation of the surfactant or surfactant system by calculating the following equation: in

O _T = concentration of surfactant or surfactant system measured as organic carbon added to settled effluent at start of aeration

O ₁ = concentration of dissolved organic carbon found in the supernatant of the ventilator when the ventilated structure is measured

_Oc = concentration of dissolved organic carbon found in the supernatant of the control ventilator

The level of biodegradation is therefore the percentage of organic carbon removed.

This modified test provides the following data (as used for intrinsic biodegradability Standard OECD test reported on page 7, or 302A): Determination of percent biodegradation of surfactant or O _T O ₁ -O _c Surfactant system (mg/l) (mg/l)

TPBS 17.3 8.4 51.4

Many variations of the present hand dishwashing compositions are useful. These changes include:

- hand dishwashing compositions containing industrially highly branched alkylbenzene sulfonate surfactants (such as TPBS or tetrapropylbenzene sulfonate) in an amount of at least about 0.1%, preferably not more than about 10%, More preferably no more than about 5%, even more preferably no more than about 1%;

- A hand dishwashing composition comprising a nonionic surfactant in an amount of from about 0.5% to about 25% by weight of the detergent composition, wherein the nonionic surfactant is in a capped or non-capped form Polyalkoxy alcohols: - Hydrophobic groups selected from the group consisting of straight chain C ₁₀ -C ₁₆ alkyl, medium chain C ₁ -C ₃ branched C ₁₀ -C ₁₆ alkyl, Guerbet branched C ₁₀ -C ₁₆ alkyl and mixtures thereof; and -hydrophilic groups selected from the group consisting of 1-15 ethoxylates, 1-15 propoxylates, 1-15 butoxylates, and mixtures thereof, as sealants capped or uncapped form. (When it is an unblocked form, there is also a terminal primary hydroxyl moiety, and when it is a capped form, there is also a terminal moiety of the formula -OR, wherein R is a C ₁ -C ₆ hydrocarbyl moiety, optionally including a primary hydrocarbyl group, preferably when present is a secondary alcohol);

A hand dishwashing composition comprising an alkyl sulfate surfactant; an amount of from about 0.5% to about 25% by weight of the detergent composition, wherein the alkyl sulfate surfactant has a selected from Hydrophobic groups: C ₁₀ -C ₁₈ alkyl, medium chain C ₁ -C ₃ branched C ₁₀ -C ₁₈ alkyl, Guerbet branched C ₁₀ -C ₁₈ alkyl and mixtures thereof, and selected from Na , K and cations of mixtures thereof;

A hand dishwashing composition containing an alkyl (polyalkoxy) sulfate surfactant in an amount of from about 0.5% to about 25% by weight of the detergent composition, wherein the alkyl (polyalkoxy ) sulfate surfactants having: - a hydrophobic group selected from the group consisting of straight chain C ₁₀ -C ₁₆ alkyl, medium chain C ₁ -C ₃ branched C ₁₀ -C ₁₆ alkyl, Guerbet branched C ₁₀ -C ₁₆ alkyl groups and mixtures thereof; and - a (polyalkoxy)sulfate hydrophilic group selected from the group consisting of 1-15 polyethoxysulfate, 1-15 polypropoxysulfate, 1 -15 polybutoxysulfate, 1-15 mixed poly(ethoxy/propoxy/butoxy)sulfate and mixtures thereof, in capped or uncapped form; and cations of the mixture;

Preferably when the hand dishwashing composition contains an alkyl (polyalkoxy) sulfate surfactant, the surfactant has a hydrophobic group selected from the group consisting of linear C ₁₀ -C ₁₆ alkyl, medium chain C ₁ -C ₃ branched C ₁₀ -C ₁₆ alkyl, Guerbet branched C ₁₀ -C ₁₆ alkyl and mixtures thereof; and a (polyalkoxy)sulfate hydrophilic group selected from: 1 -15 polyethoxysulfate, 1-15 polypropoxysulfate, 1-15 polybutoxysulfate, 1-15 mixed poly(ethoxy/propoxy/butoxy)sulfate and their a mixture, in capped or non-capped form; and a cation selected from Na, K, and mixtures thereof.

Preferably when the hand dishwashing composition contains a nonionic surfactant, the active agent is a polyalkoxy alcohol in blocked or non-blocked form, which has a hydrophobic group selected from the group consisting of linear C ₁₀ -C ₁₆ alkyl, medium chain C ₁ -C ₃ branched C ₁₀ -C ₁₆ alkyl, Guerbet branched C ₁₀ -C ₁₆ alkyl and mixtures thereof; and a hydrophilic group selected from the group consisting of: 1 - 15 ethoxylates, 1-15 propoxylates, 1-15 butoxylates and mixtures thereof, in blocked or unblocked form. When in uncapped form, there is also a terminal primary hydroxyl moiety, and when in capped form, there is also a terminal moiety of formula -OR, wherein R is a C ₁ -C ₆ hydrocarbyl moiety, optionally including a primary hydrocarbyl group, or preferably Secondary alcohols when present.

Preferably when the hand dishwashing composition contains an alkyl sulfate surfactant, the alkyl sulfate surfactant has a hydrophobic group selected from: C ₁₀ -C ₁₈ alkyl, medium chain C ₁ -C ₃ branched NaC ₁₀ -C ₁₈ alkyl, Guerbet branched C ₁₀ -C ₁₈ alkyl and mixtures thereof, and cations selected from Na, K and mixtures thereof.

The hand dishwashing compositions according to the invention can be applied or spread by hand and/or applied in unit or freely variable doses, or by automatic dosing devices, they can be used in aqueous or non-aqueous cleaning systems. Although alkaline detergent compositions having a pH of from about 8 to about 11 are preferred embodiments, they can have a wide range of pH, for example from about 2 to about 12 or higher, and they can have a wide range of alkalinity reserves. Both high suds and low suds types are included and can be used in all known aqueous and non-aqueous consumer product cleaning methods.

The hand dishwashing composition may be in any conventional form, ie liquid, powder, aggregates, paste, tablet, stick, gel, liquid gel, microemulsion, liquid crystals or granules. General hand dishwashing aids and methods:

The precise nature of these additional components and the amount added will depend upon the physical form of the composition and the nature of the cleaning operation to be used.

Amounts of conventional hand dish aids range from about 0.00001% to about 99.9% by weight of the composition. The amount of the overall composition used can vary widely depending on the intended use, for example ranging from a few ppm in solution to so-called direct application of the neat cleaning composition to the cleaning surface.

Preferred conventional hand dishwashing aids are selected from the group consisting of: builders, detergent enzymes, typically selected from the group consisting of anionic, cationic, amphoteric, zwitterionic, nonionic, and Surfactants for mixtures, polymers at least partially soluble or dispersible in water, abrasives, bactericides, tarnish inhibitors, dyes, solvents, hydrotropes, fragrances, thickeners, antioxidants, processing aids, Foam boosters, foam suppressors, buffers, antifungal agents, mildew control agents, insect repellants, anticorrosion aids, chelating agents and mixtures thereof. Most preferably conventional cleaning aids include one or more of the following:

Consumer product cleaning compositions are described in "Surfactant Science Series", Marcel Dekker, New York, vol. 1-67 and later. Liquid compositions are described inter alia in Volume 67, Liquid Detergents, edited by Kuo-Yann Lai, 1997, ISBN 0-8247-9391-9, which is incorporated herein by reference. More typical formulations, particularly in granular form, are described in "Detergent Manufacturing including Zeolite Builders and Other New Materials", edited by M. Sittig, Noyes Data Corporation, 1979, which is incorporated herein by reference. See also Kirk Othmer's Encyclopedia of Chemical Technology.

Detergents with long-lasting fragrances (see eg US 5,500,154; WO 96/02490) are becoming increasingly popular and are conceivable for use in combination with the present surfactant mixtures.

In general, conventional hand dishwashing aids are those that require the conversion of compositions containing only the minimum essential ingredients (here the essential crystallinity disrupted alkylaryl sulfonate surfactants) into compositions for hand dishwashing of any material. In preferred embodiments, those skilled in the art can readily recognize conventional hand dish aids as an absolute characteristic of cleaning products.

The precise nature of these additional components and the amount added will depend upon the physical form of the composition and the nature of the cleaning operation to be used.

Common hand dishwashing aids include builders, surfactants, enzymes and polymers, among others. Other additives herein may include foam boosters, foam suppressors (defoamers), etc., various active ingredients or specific materials such as dispersant polymers (for example from BASF or Rohm & Haas), color spots, silver protection, Rust and/or corrosion inhibitors, dyes, fillers, bactericides, alkalinity sources, hydrotropes, antioxidants, enzyme stabilizers, fragrance precursors, fragrances, solubilizers, carriers, processing aids, pigments, and for Solvents for liquid formulations are described in detail herein below.

Quite typically, the compositions herein will require several adjuncts, although some simply formulated products may require only one adjuvant. A comprehensive list of suitable laundry or cleaning aid materials and preservation can be found in U.S. Provisional Patent Application 60/053,318, filed July 21, 1997, and assigned to Procter & Gamble.

The crystallinity disrupted alkylaryl sulfonate surfactants of the present invention can be used in a wide variety of hand dishwashing preparations. This novel surfactant system can be used to fully or partially replace conventional LAS in existing hand dishwashing compositions. The crystallinity disrupted alkylaryl sulfonate surfactants of the present invention may be used as a supplement to existing surfactant systems or as a complete or partial replacement for LAS in such surfactant systems including, but not limited to :

WO98/12290；US5728668；WO98/05745；US5756441；US5714454；US5712241；US5707955；US4,133,779；WO97/47717；US5688754；US5665689；WO9738073；US5696073；WO97/38071；WO97/00930 A；GB2,292,562 A；US5, 376,310；US5,269,974；US5,230,823；US4,923,635；US4,681,704；US4,316,824；US4,133,779；US5700773；WO9735947；WO97/34976；US5629279；WO9715650；US5616548；US5610127；US5565421；WO96/31586；US5561106； US5552089；WO96/22347；US5503779；US 5480586；EP 573329；US5382386；EP487169；US5096622；EP431050；US5102573；US4772425；US4725337；EP228797；US4556509；US4454060；US4554098；US4430237；US4877546；US4064076；US4101456；US3944663；US4040989；US4102826； US5767051；US5780417；WO97/26315；US5290482；US3954679；US5700331；US5679877；US5565419；WO98/22569；US5736496；US5733560；US574169；US5733860；US5741770；US5719114；US5604195；EP848749；EP839177；US5646104；US5580848；EP781324US5415812；US5435936；US5082584； US5393468; Detersive Surfactants - The present compositions desirably include detersive surfactants for use as co-surfactants of the primary surfactant mixture. As the present invention is concerned with surfactants, in describing the preferred embodiments of the detergent compositions of the present invention, the surfactant materials are described and explained separately from the non-surfactant builders. Detersive surfactants are described extensively in US3929678, Laughlin et al., December 30, 1975 and US4259217, Murphy, March 31, 1981; "SurfactantScience" series, Marcel Dekker, Inc., New York and Basel; "Handbook of Surfactants", M.R.Porter, Chapman and Hall, 2nd Ed., 1994; "Surfactants in Consumer Products", Ed.J.Falbe, Springer-Verlag, 1987; Detergent-related patents and other detergent and consumer product manufacturers.

Detersive surfactants herein include anionic, nonionic, cationic, zwitterionic or amphoteric types of surfactants known to be useful as cleaning agents, but do not include completely non-foaming or completely insoluble surfactants (which can be used as any selected additives).

In more detail, detersive surfactants useful herein suitably include: (1) conventional alkylbenzene sulfonates, including hard (ABS, TPBS) or straight chain types and prepared by known methods such as various HF or solid HF , produced for example by DETAL ^® (UOP) method, or by using other Lewis acid catalysts such as AlCl ₃ , or by using acidic silica/alumina or by chlorinated hydrocarbons; (2) olefinic sulfonates, including α-olefinic Sulfonates and sulfonates obtained from fatty acids or fatty acid esters; (3) Alkyl or alkenyl sulfosuccinates including their diester and half-ester types and sulfosuccinamates and other sulfonates / Carboxylate surfactant types such as sulfosuccinates obtained from ethoxylated alcohols and alkanolamides; (4) paraffin or alkane sulfonate types and alkyl or alkenyl carboxysulfonate types including heavy Products of sulfites added to alpha olefins; (5) alkylnaphthalene sulfonates; (6) alkylisethionates and alkoxypropanesulfonates, and fatty isethionates, ethyl Oxylated isethionate fatty esters and other ester sulfonates such as esters of 3-hydroxypropanesulfonic acid or AVANEL S types; (7) Benzene, cumene, toluene, xylene and naphthalene sulfonates, for which Hydrotrope is particularly useful; (8) alkyl ether sulfonates; (9) alkamide sulfonates; (10) α-sulfo fatty acid salts or esters and internal sulfo fatty acid esters; (11) alkyl Glyceryl sulfonates; (12) Lignosulfonates; (13) Petroleum sulfonates, sometimes known as heavy alkylated sulfonates; (14) Diphenyl ether disulfonates; (15) Straight Chain or branched alkyl or alkenyl sulfates; (16) Alkyl or alkylphenol alkoxylate sulfates and corresponding polyalkoxylates, sometimes called alkyl ether sulfates, and alkenyl sulfates Alkoxysulfates or alkenyl polyalkoxysulfates; (17) Alkylamide sulfates or alkenylamide sulfates, including sulfated alkanolamides and their alkoxylates and polyalkoxylates; ( 18) Sulfated oils, sulfated alkyl glycerides, sulfated alkyl polyglycerides or sulfated sugar derived surfactants; (19) Alkyl alkoxy carboxylates and alkyl polyalkoxy carboxylates , including galacturonates; (20) alkyl and alkenyl ester carboxylates; (21) alkyl or alkenyl carboxylates, especially conventional soaps and α, ω-dicarboxylates , also includes alkyl and alkenyl succinates; (22) alkyl or alkenyl amido alkoxy and polyalkoxy carboxylates; (23) alkyl and alkenyl amido carboxylate surfactant types , including sarcosinates, taurates, glycinates, alanines, and iminopropionates; (24) amide soaps, sometimes called fatty acid cyanamides; (25) alkylpolyaminocarboxylates (26) Phosphorus-based surfactants, including alkyl or alkenyl phosphates, alkyl ether phosphates including their alkoxylated derivatives, phosphatidates, alkyl phosphonates, alkyl di(polyoxy alkylene alkanol) phosphates, amphoteric phosphates such as lecithin; and phosphate/carboxylate, phosphate/sulfate and phosphate/sulfonate types; (27) Pluronic- and Tetronic-type nonionic surfaces Active agents; (28) So-called EO/PO block polymers, including di-block and tri-block EPE and PEP types; (29) Fatty acid polyol esters; (30) Capped and non-capped alkyl or alkyl groups Phenol ethoxylates, propoxylates and butoxylates, including fatty alcohol polyglycol ethers; (31) Fatty alcohols, especially for use as viscosity-modifying surfactants or as unreacted surfactants of other surfactants (32) N-alkyl polyhydroxy fatty acid amides, especially alkyl N-alkyl glucamides; (33) nonionic surfactants obtained from mono- or polysaccharides or sorbitan, especially are alkyl polyglucosides, and sucrose fatty acid esters; (34) ethylene glycol-, propylene glycol-, glycerol- and polyglycerol-esters and their alkoxylates, especially glycerol ethers and fatty acids/mono- and di-glycerides (35) diuramide surfactants; (36) alkyl succinimide nonionic surfactants; (37) acetylenic alcohol surfactants, such as SURFYNOLS; (38) alkanolamide surfactants and Alkoxy derivatives thereof, including fatty acid alkanolamides and fatty acid alkanolamide polyol ethers; (39) alkylpyrrolidones; (40) alkylamine oxides, including alkoxylated or polyalkoxylated amine oxides and Amine oxides derived from sugars; (41) alkylphosphine oxides; (42) sulfoxide surfactants; (43) amphoteric sulfonates, especially sulfobetaines; (44) betaine-type amphoteric surfactants, Including aminocarboxylate-derived types; (45) amphoteric sulfates such as ammonium polyethoxylated ammonium sulfates; (46) fatty and petroleum derived alkylamines and amine salts; (47) alkylimidazolines; (48) Alkylamidoamines and their alkoxylate and polyalkoxylate derivatives; and (49) conventional cationic surfactants, including water-soluble alkyltrimethylammonium salts. Also, include less common surfactants such as: (50) alkylamido amine oxides, carboxylates, and quaternary salts; (51) sugar-derived surfaces mimicked after any of the more common non-glycoforms cited above Active agents; (52) Fluorosurfactants; (53) Biosurfactants; (54) Silicone or fluorocarbon surfactants; (55) Gemini surfactants other than diphenyl ether disulfonic acid cited above Salts, including those derived from glucose; (56) polymeric surfactants, including amphoteric polycarboxyglycinates; and (57) boleur surfactants; in short any surface known to be used for aqueous or non-aqueous cleaning active agent.

In any top detersive surfactant, the hydrophobic chain length is typically in the usual range of _C8 - _C20 , chain lengths _C8 - _C18 are often preferred, especially when laundering in cold water. The choice of chain length and degree of alkoxylation for conventional purposes is taught in standard texts. When the detersive surfactant is a salt, any compatible cation may be present, including H (i.e., the acid or partial acid form of a latent acidic surfactant may be used), Na, K, Mg, ammonium or alkanolammonium or cationic combination. Mixtures of detersive surfactants having different charges are generally preferred, especially anionic/cationic, cationic/nonionic, anionic/nonionic/cationic, anionic/nonionic/ampphoteric, nonionic/cationic and nonionic/amphoteric mixtures. Furthermore, any single detersive surfactant can be formulated with different chain lengths, degrees of unsaturation or branching, degrees of alkoxylation (especially ethoxylation), insertion of substituents such as ethers in hydrophobic groups Oxygen atoms, or mixtures of other similar detersive surfactants in any combination thereof, often achieve desirable results for cold water washes.

Preferred among the above detersive surfactants are: C ₉ -C ₂₀ linear alkylbenzene sulfonic acids, their sodium and ammonium salts, especially linear secondary alkyl C ₁₀ -C ₁₅ sodium benzene sulfonates, although in some places It is possible to use ABS, (1); olefinic sulfonates, (2), materials prepared by reacting olefins, especially C ₁₀ -C ₂₀ α-olefins, with sulfur trioxide followed by neutralization and hydrolysis of the reaction product; Sodium and ammonium C ₇ -C ₁₂ dialkyl sulfosuccinates, (3); alkane monosulfonates, (4), such as those obtained by reacting C ₈ -C ₂₀ α-olefins with sodium bisulfite and Those that react paraffin with _SO2 and _Cl2 and then neutralize with base to form random sulfonates; α-sulfo fatty acid salts or esters, (10); sodium alkylglycerol sulfonates, (11), especially Those ethers of higher alcohols obtained from tallow or coconut oil and of synthetic alcohols obtained from petroleum; alkyl or alkenyl sulfates, (15), which may be primary or secondary, saturated or unsaturated, branched or unbranched of. These compounds can be random or regular when branched. When secondary, they preferably have the formula CH ₃ (CH ₂ ) _x (CHOSO ₃ ⁻ M ⁺ )CH ₃ or CH ₃ (CH ₂ ) _y (CHOSO ₃ ⁻ M ⁺ )CH ₂ CH ₃ , where x and (y +1) is an integer of at least 7, preferably at least 9, M is a water-soluble cation, preferably sodium. When unsaturated, oleoyl sulfate sulfates are preferred, as are sodium and ammonium alkyl sulfates, especially those produced by sulfation of _C8 - _C18 alcohols, such as those produced from tallow or coconut oil Useful; also preferred are alkyl or alkenyl ether sulfates, (16), especially ethoxysulfates with 0.5 mol or more ethoxylation, preferably 0.5-8; alkyl ether carboxylates, (19), especially EO1-5 ethoxy carboxylate; Soap or fatty acid, (21), preferably more water-soluble type; Amino acid surfactant, (23), such as sarcosinate, especially is oleoyl sarcosinate; phosphate esters, (26); alkyl or alkyl partial ethoxylates, propoxylates and butoxylates, (30), especially the ethoxylates "AE", Includes so-called narrow peak alkyl ethoxylates and C ₆ -C ₁₂ alkyl partial alkoxylates and products of aliphatic primary or secondary linear or branched C ₈ -C ₁₈ alcohols with ethylene oxide, usually 2- 30 EO; N-alkyl polyhydroxy fatty acid amides, especially C ₁₂ -C ₁₈ N-methyl glucamides, (32), see WO9206154, and N-alkoxy polyhydroxy fatty acid amides, such as C ₁₀ -C ₁₈ N-(3-methoxypropyl) glucamides, while N-propyl to N-hexyl C ₁₂ -C ₁₈ glucamides can be used to reduce foaming; alkyl polyglycosides, (33); amine oxides , (40), preferably N-oxyalkyldimethylamines and their dihydrates; sulfobetaines or "sultaines", (43); betaines (44); and gemini surfactants.

Cationic surfactants suitable for use herein include those having long chain hydrocarbyl groups. Examples of these cationic cosurfactants include ammonium cosurfactants such as alkyldimethylammonium halides and those cosurfactants having the formula:

[R ² (OR ³ ) _y ][R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ⁺ X ^-wherein R ² is an alkyl or alkylbenzyl group having 8-18 carbon atoms in the alkyl chain , each R ³ is selected from -CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )-, -CH ₂ CH(CH ₂ OH)-, -CH ₂ CH ₂ CH ₂ -, and mixtures thereof; each R ⁴ is selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl ring structure formed by linking two R ⁴ groups, -CH ₂ CHOH-CHOHCOR ⁶ CHOHCH ₂ OH, wherein R ⁶ is any hexose or hexose polymer having a molecular weight below about 1000 ^and is H (when y is not 0), R is the same as R or is an alkyl chain, wherein R is ^the same as the carbon atom ^{in R} The sum of the numbers does not exceed about 18; each y is from 0 to about 10, and the sum of the y values is from 0 to about 15; and X is any compatible anion.

Examples of other suitable cationic surfactants are described in the following literature, which is incorporated herein by reference in its entirety: M.C. Publishing Co., McCutcheon's, Detergents & Emulsifiers, (North American edition 1997) Schwartz et al., Surface Active Agents, Their Chemistry and Technology, New York: Interscience Publishers, 1949; US3155591; US3929678; US3959461; US4387090 and US4228044.

其中R₁、R₂、R₃和R₄独立地选自1-约22个碳原子的脂族基团或者具有高达约22个碳原子的芳基、烷氧基、聚烯化氧、烷基酰氨基、羟基烷基、芳基或烷基芳基；并且X为成盐阴离子，例如选自卤素(例如Cl、Br)、乙酸根、柠檬酸根、乳酸根、甘醇酸根、磷酸根、硝酸根、硫酸根和烷基硫酸根的那些。除了碳和氢原子之外，该脂族基团可以含有醚键、以及例如氨基的其它基团。该长链脂族基团，例如约12个碳原子或更高的那些，可以为饱和或不饱和。优选当R₁、R₂、R₃和R₄独立地选自C₁-约C₂₂烷基时。特别优选含有两个长烷基链和两个短烷基链的阳离子材料或者含有1个长烷基链和3个短烷基链的那些。前面句子中所述化合物中的长烷基链具有约12-约22个碳原子，优选约16-约22个碳原子，并且前面句子中所述化合物中的短烷基链具有1-约3个碳原子，优选1-约2个碳原子。Examples of suitable cationic surfactants are those corresponding to the general formula:

wherein R ₁ , R ₂ , R ₃ and R ₄ are independently selected from aliphatic groups having 1 to about 22 carbon atoms or aryl groups having up to about 22 carbon atoms, alkoxy groups, polyalkylene oxides, alkanes and X is a salt-forming anion, for example selected from the group consisting of halogen (e.g. Cl, Br), acetate, citrate, lactate, glycolate, phosphate, Those of nitrates, sulfates and alkylsulfates. In addition to carbon and hydrogen atoms, the aliphatic group may contain ether linkages, and other groups such as amino groups. The long chain aliphatic groups, such as those of about 12 carbon atoms or greater, can be saturated or unsaturated. It is preferred when R ₁ , R ₂ , R ₃ and R ₄ are independently selected from C ₁ to about C ₂₂ alkyl groups. Cationic materials containing two long and two short alkyl chains or those containing one long and three short alkyl chains are particularly preferred. The long alkyl chains in the compounds in the preceding sentences have from about 12 to about 22 carbon atoms, preferably from about 16 to about 22 carbon atoms, and the short alkyl chains in the compounds in the preceding sentences have from 1 to about 3 carbon atoms, preferably 1 to about 2 carbon atoms.

Suitable amounts of cationic detersive surfactants herein are from about 0.1% to about 20%, preferably from about 1% to about 15%, although higher levels, for example up to about 30% or more, may be present in nonionic:cationic (i.e. Restricted or anion-free) preparations are particularly useful. One possible use of cationic surfactants is as a grease release agent. Cationic surfactants may be used alone or in combination with solvents and/or solubilizers. See US5552089.

Another class of useful surfactants are the so-called dianionic surfactants. These are surfactants in which at least 2 anionic groups are present on the surfactant molecule. Some suitable dianionic surfactants are also described in pending U.S. Serial Nos. 60/020503 (Case No. 6160P), 60/020772 (Case No. 6161P), 60/020928 (Case No. 6158P), filed June 28, 1996 , 60/020832 (Docket No. 6159P), and 60/020773 (Docket No. 6162P); and pending U.S. Serial Nos. 60/023539 (Docket No. 6192P), 60/023493 (Docket No. 6194P), filed August 8, 1996 , 60/023540 (Case No. 6193P) and 60/023527 (Case No. 6195P), the disclosures of which are incorporated herein by reference.

Additionally and preferably, the surfactant may be a mid-chain branched alkyl sulfate, a mid-chain branched alkyl alkoxylate or a mid-chain branched alkyl alkoxylate sulfate. These surfactants are also described in: 60/061,971, Attorney Docket No. 6881P, dated October 14, 1997, 60/061,975, Attorney Docket No. 6882P, dated October 14, 1997, Attorney 60/062,086 dated October 14, 1997, 60/061,916 dated October 14, 1997, 60/061,916 dated October 14, 1997, 6885P, dated October 14, 1997 Attorney's case number 60/062,407 at 6886P. Other suitable mid-chain branched surfactants can be found in the following U.S. Patent Application Serial Nos.: 60/032,035 (Case No. 6401P), 60/031,845 (Case No. 6402P), 60/031,916 (Case No. 6403P), 60/031, 031,917 (Case No. 6404P), 60/031,761 (Case No. 6405P), 60/031,762 (Case No. 6406P), and 60/031,844 (Case No. 6409P). Mixtures of these branched surfactants with conventional linear surfactants are also suitable for use in the present compositions.

其中R¹为C_n烷基，R²为H或C_m烷基，并且n+m为数11-14；Combinations of surfactants are also contemplated. Such a combination would be a modified alkylbenzene sulfonate surfactant of the present invention forming a negatively charged complex with an alkylene carbonate surfactant. See US5736496. Alternatively these alkylene carbonate surfactants may be combined with the modified alkylbenzene sulfonate surfactants of the present invention without forming negatively charged complexes. For example the compositions in US5733860. Either of these two combinations where the alkylene carbonate is suitable includes the formula:

Wherein R ¹ is C _n alkyl, R ² is H or C _m alkyl, and n+m is the number 11-14;

其中R为10-18个碳原子的脂族基，并且M为阳离子，选自钠、钾、铵和链烷醇胺。参见US5480586。Another possible combination with a modified alkylbenzenesulfonate surfactant is with a monoalkyl succinamate, more preferably with about 0.5 to about 6 wt% of a C ₁₀ -C ₁₈ monoalkyl succinamate , where the alkyl group can be ethoxylated with up to 8 moles of ethylene oxide, the monoalkyl succinamate has the structure:

wherein R is an aliphatic group of 10-18 carbon atoms, and M is a cation selected from sodium, potassium, ammonium and alkanolamines. See US5480586.

Suitable amounts of anionic detersive surfactants herein are from about 1% to about 50% or more, preferably from about 2% to about 30%, even more preferably from about 5% to about 20%, by weight of the detergent compositions.

Suitable amounts of nonionic detersive surfactants herein are from about 1% to about 40%, preferably from about 2% to about 30%, more preferably from about 5% to about 20%.

Desirable weight ratios of anionic surfactant to nonionic surfactant in the combination include 1.0:9.0 to 1.0:0.25, preferably 1.0:1.5 to 1.0:0.4.

Desirable weight ratios of anionic surfactant to cationic surfactant in the combination include 50:1 to 5:1, more preferably 35:1 to 15:1.

Suitable levels of cationic detersive surfactants herein are from about 0.1% to about 20%, preferably from about 1% to about 15%, but may be at higher levels, for example up to about 30% or more, especially in nonionic: May be useful in cationic (ie, limited or no anionic) preparations.

Amphoteric or zwitterionic detersive surfactants, when present, are often useful in amounts of from 0.1% to about 20% by weight of the detergent composition. Often levels are limited to about 5% or less, especially when the amphoteric surfactants are expensive. Surfactant

The compositions preferably contain at least about 0.01%, more preferably at least about 0.1%, even more preferably at least about 0.2%, even more preferably at least about 0.5%, by weight of the composition, of surfactant. The composition will also preferably contain no more than about 90%, more preferably no more than about 70%, even more preferably no more than about 60%, even more preferably no more than about 35%, by weight of the composition, of surfactant.

Anionic surfactants useful 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, alkanes alkyl alkoxy sulfates, alkyl sulfonates, alkyl alkoxy carboxylates, alkyl alkoxylated sulfates, sarcosinates, taurates, and mixtures thereof.

When present, anionic surfactants are typically present in effective amounts. More preferably the compositions may contain at least about 0.5%, more preferably at least about 5%, even more preferably at least about 10%, by weight of the composition, of anionic surfactant. The compositions also preferably contain no more than about 90%, more preferably no more than about 50%, even more preferably no more than about 30%, by weight of the composition, of anionic surfactant.

Alkyl sulfate surfactants are another important class of anionic surfactants useful herein. When the water-soluble salt or acid of formula ROSO ₃ M is used together with polyhydroxy fatty acid amides (see below), in addition to providing excellent overall cleaning power, it is also possible to obtain Good cleaning of grease/oil, solubility of alkyl sulfates, and improved formulation in liquid detergent formulations, R in the formula ROSO ₃ M is preferably a C ₁₀ -C ₂₄ hydrocarbyl group, preferably having a C ₁₀ -C ₂₀ Alkyl or hydroxyalkyl of the alkyl component, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, and M is H or a cation, such as an alkali metal cation (Group IA) (e.g. sodium, potassium, lithium), Substituted or unsubstituted ammonium cations such as methyl-, dimethyl- and trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium, as well as cations derived from e.g. ethanolamine, diethanolamine, triethanolamine Cations derived from alkanolamines, mixtures thereof, etc. Typically, C _12-16 alkyl chains are preferred for lower wash temperatures (eg below about 50°C) and C _16-18 alkyl chains are preferred for higher wash temperatures (eg above about 50°C).

Alkyl alkoxylated sulfate surfactants are another class of useful anionic surfactants. These surfactants are typically water soluble salts or acids of the formula RO(A) _m SO ₃ M where R is an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkane having a C ₁₀ -C ₂₄ alkyl component Group, preferably C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than 0, typically between about 0.5- about 6, more preferably about 0.5 to about 3, and M is H or a cation, such as may be a metal cation (eg, sodium, potassium, lithium, etc.), ammonium or substituted ammonium cations. Included herein are alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium, and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium, and cations derived from, for example, monoethanolamine, diethanolamine, and triethanolamine. cations derived from alkanolamines, and mixtures thereof. Exemplary surfactants are C ₁₂ -C ₁₈ alkyl polyethoxylated (1.0) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylated (2.25) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylated Ethoxylated (3.0) sulfates and C ₁₂ -C ₁₈ alkyl polyethoxylated (4.0) sulfates, where M is usually selected from sodium and potassium. The surfactants used herein can be made from natural or synthetic alcohol sources. Chain lengths represent average hydrocarbon distributions, including branched. The anionic surfactant component may contain alkyl sulfates and alkyl ether sulfates obtained from conventional sources of alcohols such as natural alcohols, synthetic alcohols such as under the trade names NEODOL ^™ , ALFOL ^™ , LIAL ^™ , Those marketed by LUTENSOL ^™ and the like. Alkyl ether sulfates are also known as alkyl polyethoxylated sulfates.

Examples of suitable anionic surfactants are given in "Surface Active Agents and Detergents" (Volumes I and II, Schwartz, Perry and Berch). Many of these surfactants are also generally disclosed in US Patent 3,929,678, issued December 30, 1975 to Laughlin et al at column 23, line 58 to column 29, line 23.

One class of anionic surfactants that may be utilized includes the alkyl ether sulfonates. They are desirable because they can be prepared from renewable, non-petroleum sources. The preparation of the alkyl ether sulfonate surfactants can be carried out according to known methods disclosed in the technical literature. For example, linear C8-C20 carboxylates can be sulfonated with gaseous _SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable materials include natural fatty materials obtained from tallow, palm and coconut oils and the like.

其中R³为C₈-C₂₀烃基，优选烷基，或其组合，R⁴为C₁-C₆烃基，优选烷基，或其组合，并且M为可溶性成盐阳离子。适宜的盐包括例如钠、钾和锂盐的金属盐，以及取代或未取代的铵盐，例如一甲基-、二甲基、三甲基和季铵盐，例如四甲基铵盐和二甲基哌啶鎓，以及由例如一乙醇胺、二乙醇胺、三乙醇胺的链烷醇胺获得的阳离子。优选R³为C₁₀-C₁₆烷基，R⁴为甲基、乙基或异丙基。特别优选R³为C₁₄-C₁₆烷基的甲基醚磺酸盐。Preferred alkyl ether sulfonate surfactants, especially for laundry use, include alkyl ester sulfonate surfactants of the formula:

Wherein R ³ is a C ₈ -C ₂₀ hydrocarbon group, preferably an alkyl group, or a combination thereof, R ⁴ is a C ₁ -C ₆ hydrocarbon group, preferably an alkyl group, or a combination thereof, and M is a soluble salt-forming cation. Suitable salts include metal salts such as sodium, potassium and lithium salts, and substituted or unsubstituted ammonium salts, such as monomethyl-, dimethyl, trimethyl and quaternary ammonium salts, such as tetramethylammonium and di Methylpiperidinium, and cations derived from alkanolamines such as monoethanolamine, diethanolamine, triethanolamine. Preferably R ³ is C ₁₀ -C ₁₆ alkyl, R ⁴ is methyl, ethyl or isopropyl. Particular preference is given to methyl ether sulfonate in which R ³ is C ₁₄ -C ₁₆ alkyl.

Other anionic surfactants useful for detersive purposes may also be included in the compositions of the present invention. These may include soap salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts), C ₉ -C ₂₀ linear alkylbenzene sulfonates, C ₈ -C ₂₂ primary or secondary chain Alkane sulfonates, C ₈ -C ₂₄ olefinic sulfonates, sulfonated polycarboxylic acids prepared by sulfonating the pyrolysis products of alkaline earth metal citrate salts as described in British Patent 1082179, alkyl glycerol sulfonates Salts, fatty oleyl glycerol sulfonates, fatty acyl glycerol sulfates, alkylphenol oxide ethylene ether sulfates, paraffin sulfonates, alkyl phosphates, isothiosulfates such as acyl Isothiosulfates, N-acyl taurates, fatty acid amides of methyl taurine, alkyl succinamates and sulfosuccinates, sulfosuccinate monoesters (especially are saturated and unsaturated C ₁₂ -C ₁₈ monoesters), sulfosuccinic acid diesters (especially saturated and unsaturated C ₆ -C ₁₄ diesters), N-acyl sarcosinates, alkyl Polysaccharide sulfates such as sulfates of alkyl polyglycosides (nonionic non-sulfated compounds described below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as formula RO(CH ₂ CH ₂ O) _k CH ₂ COO ^- M ⁺ , wherein R is a C ₈ -C ₂₂ alkyl group, k is an integer from 0 to 10, M is a soluble salt-forming cation, and isethionated and combined with Sodium hydroxide neutralized fatty acids. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Volumes I and II, Schwartz, Perry and Berch). A number of these surfactants are also generally 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.

Nonionic Detergent Surfactants - Suitable nonionic detergent surfactants are generally disclosed in US Pat. It is incorporated herein by reference. Exemplary, non-limiting classes of useful nonionic surfactants include: alkyl ethoxylates, alkanoyl glucamides, C ₁₂ -C ₁₈ alkyl ethoxylates ("AE"), including the so-called narrow Peak alkyl ethoxylates and C ₆ -C ₁₂ alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), and mixtures thereof.

When present, nonionic surfactants are typically present in an effective amount. More preferably the compositions may contain at least about 0.1%, more preferably at least about 0.5%, even more preferably at least about 0.5%, by weight of the composition, of nonionic surfactant. The compositions also preferably contain no more than about 20%, more preferably no more than about 15%, even more preferably no more than about 10%, by weight of the composition, of nonionic surfactant.

Polyoxyethylene, polyoxypropylene and polyoxybutylene condensates of alkylphenols. In general, polyoxyethylene condensates thereof are preferred. These compounds include the condensation products of alkylphenols with alkylene oxides in a linear or branched configuration and having an alkyl group of from about 6 to about 12 carbon atoms. In a preferred embodiment, ethylene oxide is present in an amount of about 5 to about 25 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal ⁽ R) CO-630 sold by the GAF Company; and Triton ⁽ R) X-45, X-114, X-100 and X-102 sold by the Rohm & Haas Company. These compounds are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

Condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are condensation products of alcohols having an alkyl group of from about 10 to about 20 carbon atoms with about 2 to about 18 moles of ethylene oxide. Examples of commercially available nonionic surfactants of this type include Tergitol ^® 15-S-9 (condensation product of C ₁₁ -C ₁₅ linear secondary alcohols with 9 moles of ethylene oxide), Tergitol ^® 24-L-6 NMW (condensation product of C ₁₂ -C ₁₄ primary alcohol with 6 moles of ethylene oxide, with narrow molecular weight distribution), both sold by Union Carbide; ^Neodol® 45-9 (C ₁₄ -C ₁₅ straight chain alcohol with 9 moles of oxyethylene Condensation product of ethylene), Neodol ^® 23-6.5 (condensation product of C ₁₂ -C ₁₃ straight chain alcohol and 6.5 moles of ethylene oxide), Neodol ^® 45-7 (condensation product of C ₁₄ -C ₁₅ straight chain alcohol and 7 moles of ethylene oxide Condensation product), Neodol ^® 45-4 (condensation product of C ₁₄ -C ₁₅ linear alcohol with 4 moles of ethylene oxide), sold by Shell Chemical Company, and Kyro ^® EOB (C ₁₃ -C ₁₅ alcohol with 9 moles of ethylene oxide condensation product) sold by the Procter & Gamble Company. Other commercially available nonionic surfactants include Dobanol 91-8 ^(R) from Shell Chemical Company and Genapol UD-080( ^R) from Hoechst. Such nonionic surfactants are commonly referred to as "alkyl ethoxylates".

Condensation products of hydrophobic bases formed by the condensation of ethylene oxide with propylene oxide and propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. The addition of a polyoxyethylene moiety to the hydrophobic moiety tends to increase the water solubility of the molecule as a whole, and when the polyoxyethylene content is up to about 50% by weight of the total condensation product, corresponding to condensation with up to about 40 moles of ethylene oxide, the product remains Maintains the liquid character of the product. Examples of such compounds include certain of the commercially available Pluronic ^(R) surfactants, sold by BASF.

Condensation products of ethylene oxide with the product obtained by the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide and generally has a molecular weight of from about 2500 to about 3000. The hydrophobic moiety is condensed with ethylene oxide such that the condensation product contains from about 40% to about 80% by weight polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of such nonionic surfactants include certain of the commercially available Tetronic ^(R) compounds, sold by BASF.

Examples of ethylene oxide-propylene oxide block copolymers suitable for use herein are described in detail in US 5,167,872, issued December 2, 1992 to Pancheri/Mao. This patent is incorporated herein by reference.

Preferred alkyl polyglycosides have the formula:

R ² O(C _n H _2n O) _t (glycosyl) _x wherein R ² is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl group contains about 10 - about 18, preferably about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is 0 to about 10, preferably 0; and x is about 1.3 to about 10, preferably about 1.3 to about 3, most Preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkyl polyethoxy alcohol is first formed and then reacted with glucose or a source of glucose to form the glycoside (attached at the 1-position). Further glycosyl units may then be attached between their 1-position and the 2-, 3-, 4- and/or 6-position of the preceding glycosyl unit, preferably predominantly in the 2-position.

Alkyl polyglycosides disclosed in US Pat. No. 4,565,647 issued to Llenado on January 21, 1986 have a hydrophobic group containing about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms, and a polysaccharide, such as polysaccharide Glucoside, a hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 sugar units. Any reducing sugar containing 5 or 6 carbon atoms can be used, eg glucose, galactose, and the galactosyl moiety can be replaced by a glucosyl moiety. (Optionally the hydrophobic group is attached in the 2-, 3-, 4-position, etc., thus opposing glucose or galactose to glucoside or galactoside.) Intersugar linkages may be at, for example, one position of other sugar units with Between the 2-, 3-, 4- and/or 6-positions on the preceding sugar unit.

Optionally, but less desirably, polyalkylene oxide chains can link the hydrophobic moiety and the polysaccharide moiety. A preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups that are either saturated or unsaturated, branched or unbranched, and contain from about 8 to about 18, preferably from about 10 to about 16 carbon atoms. Preferred alkyl groups are linear saturated alkyl groups. The alkyl group may contain up to about 3 hydroxyl groups and/or the polyalkylene oxide chain may contain up to about 10, preferably less than 5, alkylene oxide moieties. Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and Octadecyl, di-, tri-, tetra-, penta- and hexaglycosides, galactoside, lactoside, glucose, fructoside, fructose and/or galactose. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglycosides and tallowalkyl tetra-, penta-, and hexa-glucosides.

式(I)和

式(II)其中w等于1-4，最优选1。B选自氢或下式代表的基团：

其中R选自：具有6-22个碳原子，最优选11-15个碳原子的烷基和具有6-22个碳原子，最优选11-15个碳原子的烯基，其中最优选氢化牛油烷基链或可可烷基链，其中至少一个B基团由下式所示：

且R′选自：氢和甲基；x、y和z的值为0-60，更优选0-40，只要(x+y+z)等于2-100，优选4-24，最优选4-19，其中式(I)中一酯/二酯/三酯的重量比为45-90/5-40/1-20，更优选50-90/9-32/1-12，其中式(I)与式(II)的重量比值为3-0.02，优选3-0.1，最优选1.5-0.2，其中最优选形成化合物的混合物中式(II)比(I)多。Another class of nonionic surfactants comprises a mixture (hereinafter referred to as ethoxylated glycerol-type compounds) of fully esterified ethoxylated polyols, partially esterified ethoxylated polyols and non-esterified ethoxylated polyols. A mixture of esterified polyols, wherein the preferred polyol is glycerol, and the compound is:

Formula (I) and

Formula (II) wherein w is equal to 1-4, most preferably 1. B is selected from hydrogen or a group represented by the following formula:

wherein R is selected from the group consisting of: alkyl having 6-22 carbon atoms, most preferably 11-15 carbon atoms and alkenyl having 6-22 carbon atoms, most preferably 11-15 carbon atoms, most preferably hydrogenated An oleyl chain or a cocoalkyl chain wherein at least one B group is represented by the formula:

And R' is selected from: hydrogen and methyl; the values of x, y and z are 0-60, more preferably 0-40, as long as (x+y+z) is equal to 2-100, preferably 4-24, most preferably 4 -19, wherein the weight ratio of monoester/diester/triester in formula (I) is 45-90/5-40/1-20, more preferably 50-90/9-32/1-12, wherein formula ( The weight ratio of I) to formula (II) is 3-0.02, preferably 3-0.1, most preferably 1.5-0.2, wherein most preferably the compound is formed in a mixture with more formula (II) than (I).

Ethoxylated glycerol-type compounds useful in the present compositions are manufactured by the Kao Company and sold under the tradename Levenol, such as Levenol F-200 having an average EO of 6 and a molar ratio of cocoa fatty acids to glycerol of 0.55 or average EO Levenol V501/2 at 17 and a molar ratio of tallow fatty acid to glycerol of 1.0. Preferably the molar ratio of fatty acid to glycerol is below 1.7, more preferably below 1.5, and most preferably below 1.0. Ethoxylated glycerol type compounds have a molecular weight of 400-1600 and a pH (50 g/l water) of 5-7. Levenol compounds are hardly irritating to human skin and have an initial biodegradability higher than 90% as determined by Wickbold method Bias-7d. Two examples of such Levenol compounds are Levenol V-501/2 with 17 ethoxylated groups and a molecular weight of 1465 obtained from tallow fatty acid with a fatty acid to glycerol ratio of 1.0 and Levenol V-501/2 with 6 ethoxylated groups group and obtained from cocoa fatty acids with a fatty acid to glycerol ratio of 0.55. Both Levenol F-200 and Levenol V-501/2 consist of a mixture of formula (I) and formula (II). Levenol compounds have >100 mg/l algal growth inhibiting ecoxicity; >100 mg/l acute Daphnia toxicity and >100 mg/l fish acute toxicity. These Levenol compounds have a readily biodegradable capacity greater than 60% of the minimum required value as determined by OECD 301B for acceptable biodegradation. Polyesterified nonionic compounds also useful in the present compositions are Crovol PK-40 and Crovol PK-70 produced by Croda GMBH, The Netherlands. Crovol PK-40 is a polyoxyethylene(12) palm kernel glyceride with 12 EO groups. The preferred Crovol PK-70 is polyoxyethylene (45) palm kernel glyceride with 45 EO groups. More information on these nonionic surfactants can be found in US5719114,

其中：R¹为H、C₁-C₄烃基、2-羟基乙基、2-羟基丙基、或其混合物，优选C₁-C₄烷基，更优选C₁或C₂烷基，最优选C₁烷基(即甲基)；并且R²为C₅-C₃₁烃基，优选直链C₇-C₁₉烷基或链烯基，更优选直链C₉-C₁₇烷基或链烯基，最优选直链C₁₁-C₁₅烷基或链烯基，或其混合物；并且Z为具有至少3个直接与直链烃基链相连的羟基的直链烃基链的多羟基烃基、或烷氧基化衍生物(优选乙氧基化或丙氧基化)。Z优选在还原胺化反应中由还原糖获得；更优选Z为糖基(glycityl)。适宜的还原糖包括葡萄糖、果糖、麦芽糖、乳糖、半乳糖、甘露糖和木糖。作为原料，可以使用高蔗糖玉米糖浆、高果糖玉米糖浆和高麦芽糖玉米糖浆以及上面所列的各种糖。这些玉米糖浆可以获得用于Z的糖组分混合物。应理解为，决不打算排除其它适宜的原料。Z优选选自：-CH₂-(CHOH)_n-CH₂OH、-CH(CH₂OH)-(CHOH)_n-1-CH₂OH、-CH₂-(CHOH)₂(CHOR′)(CHOH)-CH₂OH、及其烷氧基化衍生物，其中n为3-5的整数，R′为H或环状或脂族单糖。最优选n为4的糖基，特别是-CH₂-(CHOH)₄-CH₂OH。Another class of suitable nonionic surfactants includes the polyhydroxy fatty acid amides. These materials are described in more detail in US Patent 5,332,528, Pan/Gosselink, issued July 26, 1994, which is incorporated herein by reference. These polyhydroxy fatty acid amides have the general formula:

Wherein: R ¹ is H, C ₁ -C ₄ hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably Preferably C ₁ alkyl (ie methyl); and R ² is C ₅ -C ₃₁ hydrocarbon group, preferably straight chain C ₇ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or chain alkenyl, most preferably straight chain C ₁₁ -C ₁₅ alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyl hydrocarbyl group having a straight chain hydrocarbyl chain having at least 3 hydroxyl groups directly attached to the straight chain hydrocarbyl chain, or Alkoxylated derivatives (preferably ethoxylated or propoxylated). Z is preferably obtained from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As raw materials, high sucrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be used as well as the various sugars listed above. These corn syrups can yield a mixture of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable starting materials. Z is preferably selected from: _-CH2- (CHOH) _n - _CH2OH , -CH( _CH2OH )-(CHOH) _{n-1 -CH2OH} , _-CH2- (CHOH) ₂ (CHOR')( CHOH)-CH ₂ OH, and its alkoxylated derivatives, wherein n is an integer of 3-5, R' is H or cyclic or aliphatic monosaccharide. Most preferred are glycityls where n is 4, especially _-CH2- (CHOH) _{4 -CH2OH} .

R' can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

R ² -CO-N< can be, for example, cocoamide, stearamide, oleamide, laurylamide, myristamide, capricamide, palmitamide, tallowamide, and the like.

Z can be 1-deoxyglucosyl, 2-deoxyfructosyl, 1-deoxymaltosyl, 1-deoxylactosyl, 1-deoxygalactosyl, 1-deoxymannosyl, 1-deoxymaltotriosyl, etc. .

Methods of preparing polyhydroxy fatty acid amides are known in the art. In general, they can be prepared by reacting an alkylamine with a reducing sugar in a reductive amination reaction to form the corresponding N-alkylpolyhydroxylamine, and then in a condensation/amination step the N-alkylpolyhydroxylamine Reaction with fatty aliphatic esters or triglycerides to form N-alkyl, N-polyhydroxy fatty acid amide products. Methods for preparing compositions containing polyhydroxy fatty acid amides are disclosed in, for example, GB809060 published February 18, 1959 by Thomas Hedley Ltd., US2965576 issued December 20, 1960 to E.R. Wilson, March 8, 1955 US2703798, issued to Anthony M. Schwartz, and US1985424, issued to Piggott on December 25, 1934, both of which are incorporated herein by reference.

Examples of these surfactants include C ₁₀ -C ₁₈ N-methyl, or N-hydroxypropyl, glucamides. The N-propyl to N-hexyl C ₁₂ -C ₁₆ glucamides can be used to reduce sudsing performance.

Preferred amides are _C8 - _C20 aminoamides, monoethanolamides, diethanolamides, and isopropanolamides.

其中R₁为具有约7-21，优选11-17个碳原子的饱和或不饱和、无羟基脂族烃基；R₂代表亚甲基或亚乙基；并且m为1、2或3，优选1。这些酰胺的特定例子为一乙醇胺椰子脂肪酸酰胺和二乙醇胺月桂酰脂肪酸酰胺。这些酰基部分可以由天然存在的甘油酯如椰子油棕榈油、大豆油和牛油获得，但是可以经合成获得，例如通过氧化石油或者通过Fischer-Tropsch法氢化一氧化碳。优选C_12-14脂肪酸的一乙醇酰胺和二乙醇酰胺。Another class of suitable surfactants are the alkanolamide surfactants, including the aminoamides, monoethanolamides, and diethanolamides of fatty acids having acyl moieties having from about 8 to about 18 carbon atoms. These materials are represented by the formula:

Wherein R ₁ is a saturated or unsaturated, hydroxyl-free aliphatic hydrocarbon group having about 7-21, preferably 11-17 carbon atoms; R ₂ represents methylene or ethylene; and m is 1, 2 or 3, preferably 1. Specific examples of these amides are monoethanolamine coco fatty acid amide and diethanolamine lauroyl fatty acid amide. These acyl moieties can be obtained from naturally occurring glycerides such as coconut palm oil, soybean oil and tallow, but can be obtained synthetically, for example by oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process. Monoethanolamides and diethanolamides of _C12-14 fatty acids are preferred.

Amphoteric Surfactants - Amphoteric surfactants can optionally be incorporated into the detergent compositions herein. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, where the aliphatic group can be straight or branched. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, eg, carboxy, sulfonate, sulfate. See US Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 19, lines 18-35 for examples of amphoteric surfactants. Preferred amphoteric surfactants include _C12 - _C18 betaines and sultaines ("sultaines"), _C10 - _C18 amine oxides, and mixtures thereof.

When present, amphoteric surfactants are typically present in an effective amount. More preferably the composition may contain at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about 0.5% by weight of the composition of amphoteric surfactant. The compositions also preferably contain no more than about 20%, more preferably no more than about 15%, even more preferably no more than about 10%, by weight of the composition, of amphoteric surfactant.

Amine oxides are amphoteric surfactants, including: water-soluble amine oxides containing an alkyl moiety of about 10 to about 18 carbon atoms and two alkyl and hydroxyalkane moieties having about 1 to about 3 carbon atoms a water-soluble phosphine oxide containing an alkyl moiety of about 10 to about 18 carbon atoms and two moieties selected from the group consisting of alkyl and hydroxyalkyl moieties of about 1 to about 3 carbon atoms; and water soluble A sulfoxide containing an alkyl moiety of about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl groups of about 1 to about 3 carbon atoms.

其中R³为含有约8-约22个碳原子的烷基、羟基烷基、或烷基苯基或其混合物；R⁴为含有约2-约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；并且每个R⁵为含有约1-约3个碳原子的烷基或羟基烷基、或者含有约1-约3个氧化乙烯基团的聚氧乙烯基团。R⁵基团可以彼此相连，例如通过氧原子或氮原子，形成一环状结构。Preferred amine oxide surfactants have the formula:

Wherein ^R is alkyl, hydroxyalkyl, or alkylphenyl or a mixture thereof containing about 8 to about 22 carbon atoms; ^R is an alkylene or hydroxyalkylene containing about 2 to about 3 carbon atoms or a mixture thereof; x is 0 to about 3; and each ^R is an alkyl or hydroxyalkyl group containing about 1 to about 3 carbon atoms, or a polyoxygen group containing about 1 to about 3 ethylene oxide groups Vinyl group. The ^R5 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 C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₈ -C ₁₂ alkoxyethyldihydroxyethylamine oxides, among others.

When present, amine oxide surfactants are typically present in an effective amount. More preferably the composition may contain at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about 0.5%, by weight of the composition, of an amine oxide surfactant. The compositions also preferably contain no more than about 20%, more preferably no more than about 15%, even more preferably no more than about 10%, by weight of the composition, of an amine oxide surfactant.

Examples of suitable amine oxide surfactants are given in "Surface Active Agents and Detergents" (Volumes I and II, Schwartz, Perry and Berch).

其中R为疏水基团，选自：含有约10-约22个碳原子，优选约12-约18个碳原子的烷基；烷基芳基和芳基烷基，它含有相似的碳原子数，其中苯环被当作与约2个碳原子等价，并且含有被氨基或醚键中断的相似结构；每个R¹为含有1-约3个碳原子的烷基；R²为含有1-约6个碳原子的亚烷基。Suitable betaine surfactants include those of the general formula:

wherein R is a hydrophobic group selected from: alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms; alkylaryl and arylalkyl groups containing a similar number of carbon atoms , wherein the benzene ring is considered equivalent to about 2 carbon atoms and contains a similar structure interrupted by amino or ether linkages; each R ¹ is an alkyl group containing 1 to about 3 carbon atoms; R ² is an alkyl group containing 1 - an alkylene group of about 6 carbon atoms.

Examples of preferred betaines are lauryl dimethyl betaine, cetyl dimethyl betaine, lauryl amidopropyl dimethyl betaine, tetradecyl dimethyl betaine, tetradecyl Amidopropyl Dimethyl Betaine and Lauryl Dimethyl Ammonium Betaine. Other suitable amidoalkyl betaines are disclosed in US 3,950,417, 4,137,191 and 4,375,421; and GB 2,103,236, all of which are incorporated herein by reference.

Zwitterionic Surfactants - Zwitterionic surfactants can also be incorporated into the detergent compositions herein. These surfactants can be broadly described as derivatives of secondary or tertiary amines, or derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See US Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 19, line 38 to column 22, line 48 for examples of zwitterionic surfactants. Amphoteric and zwitterionic surfactants are often used in combination with one or more anionic and/or nonionic surfactants. Detergent Enzymes - Enzymes are preferably included in the detergent compositions of the present invention for a variety of purposes including the removal of protein-based, carbohydrate-based or triglyceride-based stains from substrates. Enzymes recently found to be useful in the detergents of the present invention include chondroitinase (EP747,469A), protease variants (WO96/28566A, WO96/28557A, WO96/28556A, WO96/25489A), xylanase (EP709,452A), Keratinase (EP747,470A), lipase (GB2,297,979A, WO96/16153A, WO96/12004A, EP698,659A, WO96/16154A), cellulase (GB2,294,269A, WO96/27649A, GB2,303,147A ), thermase (WO96/28558A). More generally, suitable enzymes include: cellulase, hemicellulase, protease, glucoamylase, amylase, lipase, cutinase, pectinase, xylanase, keratinase, reductase, oxidase Enzyme, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, chondroitinase, thermase, pentosanase, mannanase (malanase), beta-glucan Enzymes, arabinosidases or mixtures thereof of any suitable origin such as vegetable, animal, bacterial, fungal and yeast origin. The preferred choice is influenced by factors such as pH-activity and/or stability optima, thermostability, and stability of active detergents, builders, and the like. Preference is given in this regard to bacterial or fungal enzymes, such as bacterial amylases and proteases, and fungal cellulases. Preferred combinations are detergent compositions containing mixtures of customary enzymes such as proteases, amylases, lipases, cutinases and/or cellulases. Suitable enzymes are also described in US Pat.

Compositions preferably contain at least about 0.0001%, more preferably at least about 0.0005%, even more preferably at least about 0.001% enzyme by weight of the composition. Cleaning compositions also preferably contain no more than about 5%, more preferably no more than about 2%, even more preferably no more than about 1%, by weight of the composition, of enzymes.

As used herein, "detergent enzyme" means any enzyme that has a cleaning, stain removal or other benefit in a cleaning composition. Preferred detergent enzymes are hydrolases such as proteases, amylases and lipases. Amylases and/or proteases are highly preferred, including both currently commercially available types and improved types.

Enzymes are generally incorporated into detergent or detergent builder compositions at levels sufficient to provide a "cleaning effective amount". The term "cleaning effective amount" refers to any amount capable of producing a cleaning, soil removal, stain removal, whitening, deodorizing or refreshing effect on substrates such as fabrics, dishware and the like. Typical amounts of active enzyme are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, per gram of detergent composition, in current commercial terms. In other words, the compositions herein typically contain from 0.001% to 5%, preferably from 0.01% to 1% by weight of a commercial enzyme preparation. Proteases are often present in these commercial preparations in amounts sufficient to provide 0.005-0.1 Anson Units (AU) of activity per gram of composition. For certain detergents, it may be desirable to increase the active enzyme content of the commercial article in order to minimize the total amount of non-catalytically active material, thereby improving spotting/filming or other end results. Higher active levels may also be desirable in highly concentrated detergent formulations. Proteolytic enzymes - Proteolytic enzymes may be of animal, vegetable or microbial (preferred) origin. Proteases useful in the detergent compositions herein include, but are not limited to, trypsin, subtilisin, chymotrypsin and elastase-like proteases. Preference is given here to the use of proteolytic enzymes of the subtilisin class. Particular preference is given to bacterial serine proteolytic enzymes obtained from Bacillus subtilis and/or Bacillus licheniformis.

Suitable proteolytic enzymes include the commercially available Novo Industri A/ ^SAlcalase® (preferred), ^Esperase® , ^Savinase® (Copenhagen, Denmark), Gist-brocades ^' Maxatase®, ^Maxacal® and Maxapem ^15® (Protein-designed ^Maxacal® ) (Delft, Netherlands) and the subtilisins BPN and BPN' (preferred). Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those manufactured by Genencor International, Inc. (San Francisco, California), which are described in EP251,446B, issued December 28, 1994 (particularly are pages 17, 24 and 98), also referred to herein as "Protease B". US Patent 5,030,378, Venegas, issued July 9, 1991, refers to a modified bacterial serine proteolytic enzyme (Genencor International), which is referred to herein as "Protease A" (identical to BPN'). See especially US 5,030,378, columns 2 and 3 for the full description, including the amino sequence of Protease A and variants thereof. Other proteases are sold under the tradenames: Primase, Durazym, Opticlean and Optimase. Preferred proteolytic enzymes are then selected from: ^A'lcalase® (Novo Industri A/S), BPN', Protease A and Protease B (Genencor) and mixtures thereof. Protease B is most preferred.

Proteases of particular interest for use herein are described in US 5,470,733.

Proteases as described in our co-pending application USSN 08/136,797 may also be included in the detergent compositions of the present invention.

Another preferred protease, termed "Protease D", is a carbonyl hydrolase variant whose amino acid sequence is not found in nature, and which is derived from a precursor carbonyl hydrolase by using A number of amino acid residues are obtained by substitution of different amino acids, preferably the substitution is also made in accordance with WO 95/10615 published on April 20, 1995 by Genencor International (A. Baeck et al., entitled "Containing Protease-Containing Cleaning Compositions (Protease-Containing Cleaning Compositions)" U.S. Application Serial No. 08/322,676) are equivalent to +99, +101, +103, +104, + 107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, One or more amino acid residue positions in +218, +222, +260, +265 and/or +274 are combined with a number of amino acid residue substitutions for different amino acids.

Useful proteases are also described in the following PCT published applications: WO95/30010, published November 9, 1995, by Procter & Gambe Company; WO95/30011, published November 9, 1995, by Procter & Gambe Company; November 1995 WO95/29979 published by Porcter & Gambe on the 9th.

Proteases may be added to the compositions of the present invention at levels of active enzyme ranging from 0.0001% to 2% by weight of the composition.

Compositions preferably contain at least about 0.0001%, more preferably at least about 0.0002%, more preferably at least about 0.0005%, even more preferably at least about 0.001%, by weight of the composition, of active protease. The compositions also preferably contain no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, even more preferably no more than about 0.05%, by weight of the composition, of active protease. Amylase - Amylase (alpha and/or beta) may be included for removal of carbohydrate based soils. Suitable amylases are ^Termamyl® (Novo Nordisk), ^Fungamyl® and ^BAN® (Novo Nordisk). These enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.

Compositions preferably contain at least about 0.0001%, more preferably at least about 0.0002%, more preferably at least about 0.005%, even more preferably at least about 0.001%, by weight of the composition, of active amylase. The compositions also preferably contain no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, even more preferably no more than about 0.05%, by weight of the composition, of active amylase.

Amylases also include those described in WO95/26397 and Novo Nordisk's co-pending application PCT/DK96/00056. Other specific amylases for use in the detergent compositions of the present invention include:

(a) an alpha-amylase having a specific activity at least 25% higher ^than Termamyl(R) as determined by the Phadebas ^(R) alpha-amylase activity assay at 25[deg.]C-55[deg.]C and a pH of 8-10. This ^Phadebas® alpha-amylase activity test is described on pages 9-10 of WO 95/26397.

(b) the α-amylase of (a) containing the amino sequence shown in the sequence listing (SEQ ID) of the above cited documents, or an α-amylase having at least 80% homology to the amino acid sequence shown in the sequence listing .

(c) The α-amylase of (a) obtained from the species Alcalophilus, containing the following amino sequence at the N-terminus: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln- Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp.

A polypeptide is said to be X% homologous to its parent amylase if comparison of the individual amino acid sequences by an algorithm (eg as described by Lipman and Pearson in Science 227, 1985, p. 1435) demonstrates an identity of X%.

(d) the α-amylase of (a-c), wherein this α-amylase can be obtained from alkaliphilic Bacillus species;

In the context of the present invention, the term "obtainable from" refers not only to the amylase produced by a Bacillus strain, but also to a host encoded by a DNA sequence isolated from this Bacillus strain and being transformed with said DNA sequence Amylases produced in living organisms.

(e) alpha-amylases showing positive immunological cross-reactivity with antibodies against alpha-amylases having amino acid sequences corresponding to these alpha-amylases in (a-d), respectively.

(f) Variants of the following parent alpha-amylases: (i) having one of the amino acid sequences respectively corresponding to those shown in (a-e) these alpha-amylases, or (ii) with one or more of said The amino acid sequence has at least 80% homology, and/or has immunological cross-reactivity with an antibody against an α-amylase having one of said amino acid sequences, and/or has an immunological cross-reactivity with an α-amylase encoding one of said amino acid sequences - DNA sequence coding for hybridization of probes identical to the DNA sequence of the amylase; wherein variants:

1. At least one amino acid residue of the parent alpha-amylase has been deleted; and/or

2. At least one amino acid residue of the parent alpha-amylase has been replaced by a different amino acid residue; and/or

3. At least one amino acid residue related to said parent alpha-amylase has been inserted;

The variant has alpha-amylase activity and exhibits at least one of the following properties associated with the parent alpha-amylase: increased thermostability, increased oxidative stability, decreased Ca ion dependence, neutral to relatively high Stability at pH and/or increased α-amylase hydrolytic activity, increased α-amylase hydrolytic activity at relatively high temperatures and increased or decreased isoelectric point (pI) such that the pi value of the (-amylase variant is comparable to The pH of the medium is better matched.

Said variants are described in patent application PCT/DK96/00056.

Other amylases suitable herein include, for example, the alpha-amylases described by Novo in GB1296839, RAPIDASE ^(R) from International Bio-Synthetics, Inc. and TERMAMYL ^(R) from Novo. Novo's FUNGAMYL ^(R) is particularly useful. Enzyme engineering to improve stability, eg oxidative stability, is known. See, eg, J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521. Certain preferred embodiments of the present invention may use amylases having increased stability in, for example, automatic dishwashing detergents, particularly starches with increased oxidative stability compared to the reference point determined by ^TERMAMYL® for industrial use in 1993 enzyme. These preferred amylases herein have the characteristics of "stability-improved" amylases, characterized by at least one or more of the following measurable increases: Oxidative stability, for example, in a pH 9-10 buffer against Oxidative stability of hydrogen peroxide/tetraacetylethylenediamine; thermal stability, e.g. at conventional washing temperatures such as about 60°C; or alkali stability, e.g. Measured by point amylase. Stability can be assayed using any technique disclosed in the art. See for example the parameters disclosed in WO9402597. Stability-enhanced amylases can be obtained from Novo or Genencor International. A class of highly preferred amylases herein has the common property of being obtained using site-directed mutagenesis from one or more Amylobacter, in particular (-Amylobacter, regardless of one, two or more amylase strains Whether it is a direct precursor or not. It is preferred to use amylases with increased oxidative stability together with the reference amylases identified above, especially for use herein in detergent compositions for bleaching, more preferably oxygen bleaching (as opposed to chlorine bleaching). These Preferred amylases include: (a) an amylase in WO9402597 (Novo, 3 February 1994) cited above, which is also described as using alanine or threonine, preferably threonine, in place of Mutants of the methionine residue at position 197 of the alpha-amylase of Bacillus licheniformis, known as TERMAMYL ^® , or of similar parental amylases such as Bacillus amyloliquefaciens, Bacillus subtilis, or Bacillus stearici Mutants with changes in homologous positions; (b) Amylases with increased stability, described by Genencor International in C. Mitchinson's presentation entitled " In the article "OxidativelyResistant alpha-Amylases (OxidativelyResistant alpha-Amylases)". It should be noted here that bleach in automatic dishwashing detergents inactivates alpha-amylases, but Genencor has been prepared from Bacillus licheniformis NCIB8061 Amylases with improved oxidative stability were obtained. Methionine (Met) was identified as the most likely residue to be modified. Met was substituted one at a time in positions 8, 15, 197, 256, 304, 366 and 438 to obtain Specific mutants, particularly important are M197L and M197T, and the M197T variant is the most stable expression variant. Measure the stability in ^CASCADE® and ^SUNLIGHT® ; (c) particularly preferred amylases herein are included in WO9510603A Amylase variants having additional modifications in the immediate parent described and are available from the assignee Novo as ^DURAMYL® . Other particularly preferred amylases with increased oxidative stability include those described by Genencor International in WO9418314 and Novo in WO9402597 Any other amylase with improved oxidative stability can be used, for example obtained by site-directed mutagenesis from known chimeric, hybrid or simply mutated parental forms of available amylases. Other preferred enzyme modifications can be utilized. See Novo WO9509909A.

Cellulases usable herein include both bacterial and fungal types, preferably with a pH optimum of 5-9.5. US Pat. No. 4,435,307 issued March 6, 1984 to Barbesgoard et al. ) or a suitable fungal cellulase from Humicola genus strain DSM1800 or a cellulase-producing fungus belonging to the genus Aeromonas, and a cellulase extracted from the hepatopancreas of the marine mollusc Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2075028; GB-A-2095275 and DE-OS-2247832. CAREZYME® ^{and CELLUZYME®} (Novo) are particularly useful. See also WO9117243 to Novo.

Compositions preferably contain at least about 0.0001%, more preferably at least about 0.0002%, more preferably at least about 0.0005%, even more preferably at least about 0.001%, by weight of the composition, of active cellulase and/or peroxidase. The compositions also preferably contain no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, even more preferably no more than about 0.05% by weight of the composition of active cellulase and/or peroxidase enzymes.

Cutinases [EC 3.1.1.50], which may be considered to be a specific class of lipases, ie lipases which do not require interfacial activation, are also suitable. The addition of cutinases to detergent compositions has been described eg in WO-A-88/09367 (Genencor). Lipase - Suitable lipases include those produced by microorganisms of the genus Pseudomonas, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. Suitable lipases include those produced by the microorganism Pseudomonas fluorescens IAM 1057 and which show positive immunological cross-reactivity with the lipase antibody. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan under the tradename Lipase P "Amano," hereinafter referred to as "Amano-P." Other suitable lipases are lipases such as M1 ^Lipase® and ^Lipomax® (Gist-Brocades). Other suitable commercial lipases include Amano-CES, a lipase obtained from Chromobacter viscosus, for example Chromobacter viscosus lipolytic variant (var. Lipolyticum) NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, from USA Chromobacterium viscosus lipase from US Biochemical Corp., USA and Disoynth, Netherlands, and lipase from Pseudomonas gladiolus. The LIPOLASE ^(R) enzyme obtained from Humicola villus and commercially available from Novo see also EP341,947 is a preferred lipase for use herein. Antioxidant enzyme stabilized lipase and amylase variants are described in WO9414951 to Novo. See also WO9205249 and RD94359044.

A highly preferred lipase is the D96L lipolytic enzyme variant of the native lipase obtained from Humicola tomentosa as described in US Application Serial No. 08/341,826. (see also patent application WO92/05249, replacement of the aspartic acid (D) residue at position 96 by leucine (L) in the native lipase obtained from Humicola villus. According to this nomenclature, The substitution of said aspartate with leucine at position 96 is shown as: D96L.) The Humicola villus strain DSM 4106 is preferably used.

Despite numerous applications for lipases, only lipases obtained from Humicola villus and produced with Aspergillus oryzae as a host have so far found widespread use as adjuncts for washing products. It is available from Novo Nordisk under the trade names Lipolase ^(R) and Lipolase Ultra( ^R) , as described above. To optimize the stain removal performance of Lipolase, Novo Nordisk has manufactured many variants. As described in WO92/05249, the D96L variant of the native Humicola tomentosa lipase was 4.4 times more efficient at removing lard stains than the wild-type lipase (compared to an amount of enzyme of 0.075-2.5 mg protein/l). 1994 Research Disclosure No. 35944, published by Novo Nordisk on March 10, 2009, discloses that the lipase variant (D96L) can be present in a corresponding amount of 0.001-100 mg (5-500000 LU/l) of the lipase variant per liter of wash solution Add to.

Compositions preferably contain at least about 0.0001%, more preferably at least about 0.0002%, more preferably at least about 0.0005%, even more preferably at least about 0.001%, by weight of the composition, of active lipase. The compositions also preferably contain no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, even more preferably no more than about 0.05%, by weight of the composition, of active lipase.

Various carbohydrases imparting antibacterial activity may also be contained in the present invention. These enzymes include endoglycosidases, type II endoglycosidases and glucosidases disclosed in US5041236, 5395541, 5238843 and 5356803, the disclosures of which are incorporated herein by reference. Of course, other enzymes with antimicrobial activity may also be used, including peroxidases, oxygenases, and various other enzymes.

A number of enzyme materials and their incorporation into synthetic detergent compositions are also described in WO9307263A and WO9307260A to Genencor International, WO8908694A to Novo and US 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are also disclosed in US 4,101,457, Place et al., issued July 18, 1978, and US 4,507,219, Hughes, issued March 26, 1985. Enzyme materials for use in liquid detergent products and their incorporation into these products are disclosed in US 4,261,868, Hora et al., issued April 14,1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in US Pat. Enzyme stabilization systems are also described eg in US 3,519,570. A useful protease, xylanase and cellulase-conferring Bacillus strain AC13 is described in WO9401532A to Novo.

When any enzyme is present in the composition, the composition of the invention may also contain an enzyme stabilization system. Enzyme Stabilizing System - Preferred compositions herein may additionally contain from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilization system can be any stabilization system compatible with the protease or other enzyme used in the compositions herein. These stabilizing systems may include calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, polyols, and mixtures thereof, such as US 4,261,868 issued April 4, 1981 to Hora et al., September 1983 4,404,115 awarded to Tai on March 13, 4,318,818 awarded to Letton et al., 4,243,543 awarded to Guildert et al. on January 6, 1981, 4,462,922 awarded to Boskamp on July 31, 1984, 4,532,064 awarded to Boskamp on July 30, 1985 and 1985 4,537,707 awarded to Severson Jr. on August 27, both of which are incorporated herein by reference.

Compositions preferably contain at least about 0.001%, more preferably at least about 0.005%, even at least about 0.01%, by weight of the composition, of an enzyme stabilizing system. The compositions also preferably contain no more than about 10%, more preferably no more than about 8%, more preferably no more than about 6%, by weight of the composition, of an enzyme stabilizing system.

One stabilizing approach is to use a water-soluble source of calcium and/or magnesium ions in the final composition that provides these ions to the enzymes. Calcium ions are generally more effective than magnesium ions, and calcium ions are preferred if only one type of ion is used. Typical detergent compositions, especially liquids, contain from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 mmol calcium ions/l final detergent composition, although depending on the multiple Nature, type and content can vary. Water-soluble calcium or magnesium ions are preferably used, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more conventionally calcium sulfate or corresponding to the exemplified calcium salts may be used of magnesium salts. Also increased amounts of calcium and/or magnesium are naturally available eg to facilitate the grease cutting action of certain types of surfactants. However, it is particularly preferred that the composition is free of added calcium ions, and even more preferred that the composition is free of calcium ions.

Another stabilization solution is the use of borates. See US 4,537,706 to Severson. Borate stabilizers, when used, may be present in amounts up to 10% or more of the composition, although more typically in amounts up to about 3% by weight boric acid or other borate mixtures such as borax or borates are suitable for use in liquids detergent. Substituted boronic acids such as phenylboronic acid, butyric acid, p-bromophenylboronic acid, etc. can be used instead of propionic acid, although the use of these substituted boron derivatives can reduce the total boron content of the detergent composition.

In addition, to prevent the chlorine bleach present in many water supplies from attacking or inactivating enzymes, 0% to about 10%, preferably from about 0.01% to about 6%, by weight, of chlorine bleach can be added to the compositions of the present invention scavenger for bleach or oxygen bleach. Although the chlorine content in the water may be small, typically from about 0.5 ppm to about 1.75 ppm, the chlorine available throughout the volume of water in contact with the enzyme during dishwashing is often large; thus enzyme stability may be problematic in use.

Suitable chlorine scavenger anions are salts containing ammonium cations. These may be selected from: reducing substances such as sulfites, bisulfites, thiosulfites, iodides, etc.; antioxidants such as carbonates, ascorbates, etc.; organic amines such as ethylenediaminetetraacetic acid (EDTA) or its alkali metal salts and monoethanolamine (MEA), and mixtures thereof. Other conventional scavenging anions such as sulfate, bisulfate, carbonate, bicarbonate, percarbonate, nitrate, chloride, borate, sodium perborate tetrahydrate, sodium perborate monohydrate can also be used , percarbonate, phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof. Builders - The compositions of the present invention optionally contain detergency builders. In solid products, builders are sometimes used as absorbents for surfactants. Alternatively, certain compositions can be formulated with either organic or inorganic fully water-soluble builders, depending on their intended use.

Suitable silicate builders include water-soluble and aqueous solid types and include those with chain, layered or three-dimensional structures as well as amorphous solid silicates or other types, such as are especially suitable for use in unstructured liquid detergents . Alkali metal silicates are preferred, especially those liquids and solids having a SiO ₂ :Na ₂ O ratio of 1.6-1 to 3.2-1, including the solid aqueous 2-ratio silicates sold under the trade name ^BRITESIL® by the company PQ, e.g. BRITESIL _H2O ; and layered silicates such as those described in US4664839, issued May 12, 1987 to HPRieck. NaSKS-6, sometimes abbreviated "SKS-6", is a _crystalline layered aluminum-free ( _-Na2SiO5 morphological silicate sold by Hoechst and is particularly preferred in granular compositions. See DE-A-3417649 and the preparation method in DE-A-3742043. Other phyllosilicates, such as those having the general formula _{NaMSixO2z +1.yH2O ,} where M is Na or H, can also or alternatively be used herein , x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0. The phyllosilicates from Hoechst also include NaSKS-5, NaSKS-7 in the form of α, β and γ phyllosilicates and NaSKS-11. Other silicates can also be used, such as magnesium silicate, which can act as a crispening agent in the granules and as a component of the foam control system.

Synthetic crystalline ion exchange materials or hydrates thereof having a chain structure and anhydrous form of a composition represented by the general formula: xM ₂ O.ySiO ₂ .zM'O, where M is Na and/or K are also suitable for use herein , M' is Ca and/or Mg; y/x is 0.5-2.0 and z/x is 0.005-1.0 as taught in US 5,427,711 issued June 27, 1995 to Sakaguchi et al.

Aluminosilicate builders, such as zeolites, are especially useful in granular detergents, but can also be added to liquids, pastes or gels. Suitable for this purpose are those having the following empirical formula: [M _z (AlO ₂ ) _z (SiO ₂ ) _v ].xH ₂ O, where z and v are integers of at least 6, M is an alkali metal, preferably Na and/or Or K, the molar ratio of z to v is 1.0 to about 0.5, and x is an integer of 15-264. Aluminosilicates can be crystalline or amorphous and can be naturally occurring or obtained synthetically. A method for the production of aluminosilicates is described in US 3,985,669, issued October 12, 1976 to Krummel et al. Preferred synthetic crystalline aluminosilicate ion exchange materials are available as zeolite A, zeolite P (B), zeolite X and, somewhat differently from zeolite P, called zeolite MAP. Natural types can be used, including clinoptilolite. Zeolite A has the following formula: Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ].xH ₂ O, where x is 20-30, especially 27. Dehydrated zeolites (x=0-10) can also be used. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns (diameter).

Detergent builders, instead of or in addition to the silicates and aluminosilicates described herein above, may optionally be included in the compositions herein, for example to help control minerals, particularly Ca and/or Mg, washing The hardness of the water may help remove particulate dirt from the surface. Builders can operate through various mechanisms, including forming soluble or insoluble complexes with hardness ions by ion exchange and by providing a surface on which hardness ions are more readily deposited than the surface of the item being cleaned. The level of builder can vary widely depending on the end use and physical form of the composition. Built detergents typically contain at least about 1% builder. Liquid formulations typically contain from about 5% to about 50%, more typically 5% to 35%, of builder. Granular formulations typically comprise from about 10% to about 80%, more typically 15% to 50%, by weight of the detergent composition, of builder. Neither low or high levels of builders are excluded. For example, certain articles may be unformulated, ie, the composition is free of builders, such as in certain hand dishwashing compositions.

Suitable builders herein may be selected from: phosphates and polyphosphates, especially sodium salts; carbonates, bicarbonates, sesquicarbonates and carbonate inorganics other than sodium carbonate and sodium sesquicarbonate ; Organic mono-, di-, tri- and tetra-carboxylates, especially water-soluble non-surfactant carboxylates in the form of acid, sodium, potassium or alkanolammonium salts, and oligomeric or water-soluble low molecular weight polymeric carboxylates, including aliphatic and aromatic types; and phytic acid. These may be supplemented with borates, e.g. for pH-buffering purposes, or with sulfates, especially sodium sulfate, and any other possible addition to stable surfactant and/or builder-containing detergent compositions. The design of the filler or carrier is important.

Builder mixtures may be used, sometimes called "builder systems", typically containing two or more conventional builders, optionally supplemented with chelating agents, pH-buffering agents or fillers, although when describing the amount of These latter substances are usually considered separately. Preferred builder systems are typically formulated at a surfactant to builder weight ratio of from about 60:1 to about 1:80, based on the relative amounts of surfactant to builder present in the detergents. The ratios stated in certain preferred laundry detergents are from 0.90:1.0 to 4.0:1.0, more preferably from 0.95:1.0 to 3.0:1.0.

Phosphorus-containing detergent builders that are often preferred where permitted by law include, but are not limited to, polyphosphoric acids such as tripolyphosphoric acid, pyrophosphoric acid, alkali metal, ammonium, and alkanolammonium salts of glassy polymeric metaphosphoric acid; and phosphonic acid Salt.

Suitable carbonate builders include alkaline earth and alkali metal carbonates, as disclosed in German Patent Application 2,321,001 published November 15, 1973, although for example sodium bicarbonate, sodium carbonate, sesqui _Sodium carbonate, and other carbonate inorganics such as trona or any convenient compound salts of sodium and calcium carbonate such as those having _the composition _{2Na2CO3.CaCO3} when anhydrous, and even calcite, aragonite, and spheres The calcium carbonate class of aragonite, especially the high surface area form relative to dense calcite.

Suitable "organic detergency builders" for use in cleaning compositions as described herein include polycarboxylate compounds, including dicarboxylates and tricarboxylates of water-soluble nonsurfactants. More typical builder polycarboxylates will have a plurality of carboxylate groups, preferably at least 3 carboxylates. Carboxylate builders can be formulated in acid, partial neutral, neutral or overbased forms. When used in salt form, alkali metals such as sodium, potassium and lithium, or alkanolammonium salts are preferred. Polycarboxylate builders include ether polycarboxylates such as oxydisuccinates, see US3128287, Berg, Apr. 7, 1964 and US3635830, Lamberti et al., Jan. 18, 1972; May, 1987 "TMS/TDS" builders of US 4,663,071 issued to Bush et al.; and other ether carboxylates including cyclic and alicyclic compounds, such as those described in US 3,923,679, 3,835,163, 4,158,635, 4,120,874 and 4,102,903.

Other suitable organic detergency builders are ether hydroxy polycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethoxysuccinic acid, different alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and benzene hexacarboxylic acid, succinic acid, polymaleic acid, benzene 1 , 3,5-tricarboxylic acid, carboxymethoxysuccinic acid and its soluble salts.

Citrate builders, such as citric acid and its soluble salts, are important carboxylate builders for example in light duty liquid detergents due to the availability of renewable sources and biodegradability. Citrates can also be used in granular detergents, especially in combination with zeolites and/or layered silicates. Oxydisuccinates are also particularly useful in such compositions and combinations.

Where permitted, especially in rod form, alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate may be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates such as those in US Pat. , and can have ideal anti-fouling properties.

Certain detersive surfactants or their short chain homologues also have a builder effect. For purposes of formulaic calculations, these materials are summarized as detersive surfactants when they possess surface active capacity. A preferred type of builder functionality is described by the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds disclosed in US Patent 4,566,984, Bush, issued January 28,1986. Succinic acid builders include _C5 - _C20 alkyl and alkenyl succinic acids and salts thereof. Succinate builders also include: lauryl succinate, myristyl succinate, cetyl succinate, 2-dodecenyl succinate (preferred), 2-decyl succinate Pentacenyl succinate, etc. Lauryl succinates are described in European Patent Application 86200690.5/0200263, published November 5, 1986. Fatty acids, such as C ₁₂ -C ₁₈ monocarboxylic acids, may also be added to the composition alone or together with the aforementioned builders, especially citrate and/or succinate builders, thereby providing additional builder activity . Other suitable polycarboxylates are disclosed in US 4,144,226, Crutchfield et al., March 13,1979 and US 3,308,067, Diehl, March 7,1967. See also US3723322 to Diehl.

Other types of inorganic builder materials that can be used have the formula (M _x ) _i Ca _y (CO ₃ ) _z where x and i are integers from 1 to 15, y is an integer from 1 to 10, and z is from 2 to 25 Integers of M _i are cations, at least one of which is water-soluble, and satisfy the equation Σ _{i = 1-15} ( _xi × M _i ) + 2y = 2z, so that the article has a neutral or "balanced" charge. These builders are referred to herein as "mineral builders" and examples of such builders, their use and methods of preparation can be found in US 5,707,959. Another class of suitable inorganic builders are the magnesium silicates, see WO 97/0179.

Suitable polycarboxylate builders for use herein include maleic acid, citric acid, preferably in the form of water soluble salts, succinic acid derivatives of the formula R-CH(COOH) _CH2 (COOH) wherein R is C _10-20 alkyl or alkenyl, preferably C _12-16 , or where R can be substituted with hydroxyl, thiosulfinyl, or sulfo substituents. Mixtures of such suitable polycarboxylate builders are also contemplated, including mixtures of maleic and citric acids. Specific examples include dodecylsuccinate, myristylsuccinate, hexadecylsuccinate, 2-dodecenylsuccinate, 2-tetradecenylsuccinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.

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

Particularly for the liquid practice herein, suitable fatty acid builders for use herein are saturated or unsaturated C _10-18 fatty acids, and the corresponding soaps. Preferred saturated species have 12-16 carbon atoms in the alkyl chain. A preferred unsaturated fatty acid is oleic acid. Other preferred builder systems for liquid compositions are based on dodecenylsuccinic acid and citric acid.

Compositions preferably contain at least about 0.2%, more preferably at least about 0.5%, more preferably at least about 3%, even more preferably at least about 5%, by weight of the composition, of builder. Cleaning compositions also preferably contain no more than about 50%, more preferably no more than about 40%, more preferably no more than about 30%, even more preferably no more than about 25%, by weight of the composition, of builder. Magnesium ions - The presence of magnesium (divalent) ions improves the oily stain cleaning performance of various compositions, ie, compositions containing alkyl ethoxy sulfates and/or polyhydroxy fatty acid amides. This is especially true when these compositions are used in soft water which contains very few divalent ions. It is believed, although not wishing to be bound by theory, that the magnesium ions increase the encapsulation of the surfactant at the oil/water interface, thereby reducing interfacial tension and improving grease cleaning. Compositions of the present invention containing magnesium ions have good oil removal properties, prove to be mild to the skin and have good storage stability.

The compositions preferably contain at least about 0.01%, more preferably at least about 0.015%, more preferably at least about 0.02%, even at least about 0.025%, by weight of the composition, of magnesium ions. Cleaning compositions also preferably contain no more than about 5%, more preferably no more than about 2.5%, more preferably no more than about 1%, even more preferably no more than about 0.05%, by weight of the composition, of magnesium ions. In any case, the magnesium ions are always present in an amount equimolar or lower than the diamine present in the composition.

Preferably magnesium ions are added to the compositions of the invention as hydroxides, chlorides, acetates, formates, oxides or nitrates.

Due to the incompatibility of divalent ions, especially magnesium ions, with hydroxide ions, it can be difficult to formulate these divalent ion-containing compositions in alkaline pH matrices. When both divalent ions and basic pH are combined with the surfactant mixture of the present invention, a better grease cleaning effect is obtained than that obtained by only basic pH or divalent ions alone. However, these compositions have poor stability during storage due to the formation of hydroxide precipitates. Therefore, it may also be desirable to add chelating agents as discussed later herein. Diamines - Preferably, the diamines used in the present invention are substantially free of impurities. That is, "essentially free" means that the diamine is more than 95% pure, ie preferably 97%, more preferably 99%, even 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, to avoid degradation of the diamines and formation of ammonia, it is believed that these diamines should be free of oxidation reactants. In addition, the amine oxide or surfactant, if present, should be free of hydrogen peroxide. The preferred content of hydrogen peroxide in the amine oxide or surfactant paste of amine oxide is 0-40 ppm, more preferably 0-15 ppm. Amine impurities in amine oxides and betaines, if present, should be minimized to the levels mentioned above with respect to hydrogen peroxide.

When the composition contains enzymes, it is important to prepare the composition free of hydrogen peroxide. Hydrogen peroxide can react with enzymes and destroy any performance benefits of enzymes added to the composition. Even small amounts of hydrogen peroxide can cause problems for enzyme-containing preparations. However, diamines can react with any peroxide present and act as enzyme stabilizers, preventing hydrogen peroxide from reacting with the enzyme. The only drawback to stabilization of enzymes by diamines is that the nitrogen compounds produced are believed to be malodorous, which can be present in diamine-containing compositions. The function of the diamine as an enzyme stabilizer also prevents imparting to the composition the advantages that the composition originally possessed, namely grease cleaning, foaming, solubility and low temperature stability. Therefore, it is preferably obtained by using components that contain little hydrogen peroxide and/or using non-diamine antioxidants (even though diamines can act as enzyme stabilizers, due to the possibility of producing malodorous compounds) and reducing the ability to carry out its original role. The amount of diamine minimizes the amount of hydrogen peroxide present as an impurity in the compositions of the present invention.

It is also preferred that the compositions of the present invention are free of "madodors". That is, the smell of the headspace does not give the user a negative olfactory response. This can be achieved in a number of ways including masking any unpleasant odors with perfumes, using stabilizers such as antioxidants, chelating agents, etc., and/or using diamines which are substantially free of impurities. It is believed, without wishing to be bound by theory, that impurities present in the diamine are the major source of malodour in the compositions of the present invention. These impurities can form during the preparation and storage of diamines. They may also be formed during preparation and storage of the compositions of the invention. The use of stabilizers such as antioxidants and chelating agents inhibits and/or prevents the formation of these impurities in the composition from manufacture through final use by the user and thereafter. Therefore, it is most preferred to remove, suppress and/or prevent the formation of these malodors by adding perfumes, stabilizers and/or using diamines which are substantially free of impurities.

A preferred class of organic diamines are those with pK1 and pK2 ranging from about 8.0 to about 11.5, preferably from about 8.4 to about 11, even more preferably from about 8.6 to about 10.75. Considering the performance and supply, the preferred materials are 1,3-bis(methylamine)-cyclohexane, 1,3-propylenediamine (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 materials are primary/primary diamines with an alkylene spacing of C4-C8. In general, it is believed that primary diamines are preferred over secondary and tertiary diamines.

Definitions of pK1 and pK2 - As used herein, "pKa1" and "pKa2" are quantities of the type known to those skilled in the art as "pKa", pKa is used herein in the same manner as is known to those skilled in the chemical arts. Values cited herein can be obtained from, for example, Smith and Martel, "Critical Stability Constants: Volume 2, Amines" Plenum Press, NY and London, 1975. Additional information on pKa can be obtained from relevant company literature, for example information provided by Dupont (supplier of diamines).

As defined operationally herein, the pKa of a diamine is specified in all aqueous solutions at 25°C and has 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 sometimes vary, depending on the assay method and conditions. In order to eliminate ambiguity, the relevant conditions and/or parameters used in the pKa of the present invention are as defined herein or in "Critical Stability Constants: Volume 2, Amines". A typical method of determination is potentiometric titration of the acid with sodium hydroxide and by a suitable method as described and referenced in "The Chemist's Ready Reference Handbook" by Shugar and Dean, McGraw Hill, New York, 1990 Determination of pKa.

Substitutions and structural modifications that lower pK1 and pK2 below about 8.0 have been determined to be undesirable and cause loss of performance. This can include substitutions resulting in ethoxylated diamines, hydroxyethyl substituted diamines, diamines with oxygen in the beta (and down to gamma) position of the spacer nitrogen (eg Jeffamine EDR 148). Furthermore, substances based on ethylenediamine are unsuitable.

其中R_2-5独立地选自H、甲基、-CH₃CH₂和氧化乙烯；C_x和C_v独立地选自亚甲基或支链烷基，其中x+y为约3-约6；并且A任选存在并选自经选择将二胺pKa调整至所需范围的给电子或吸电子部分。如果A存在，那么x和y必需都为1或更大。Some of the diamines used herein can be defined by the following structures:

Wherein R _2-5 are independently selected from H, methyl, -CH ₃ CH ₂ and ethylene oxide; C _x and C _v are independently selected from methylene or branched chain alkyl, wherein x+y is about 3 to about 6; and A is optionally present and selected from electron donating or electron withdrawing moieties selected to adjust the pKa of the diamine to the desired range. If A is present, then both x and y must be 1 or greater.

其中每个R⁶独立地选自H、C₁-C₄直链或支链烷基、具有下式的亚烷氧基：Alternatively, the diamines may be those organic diamines having a molecular weight lower than or equal to 400 g/mol. Preferably these diamines have the formula:

wherein each R ^is independently selected from H, C ₁ -C ₄ linear or branched chain alkyl, alkyleneoxy having the formula:

-(R ⁷ O) _m R ⁸ wherein R ⁷ is C ₂ -C ₄ linear or branched alkylene and mixtures thereof; R ⁸ is H, C ₁ -C ₄ alkyl and mixtures thereof; m is 1- about 10; X is a unit selected from:

i) C ₃ -C ₁₀ straight chain alkylene, C ₃ -C ₁₀ branched chain alkylene, C ₃ -C ₁₀ cycloalkylene, C ₃ -C ₁₀ branched cycloalkylene, having the following formula Alkyleneoxyalkylene:

-(R ⁷ O) _m R ⁷ -wherein R ⁷ and m are the same as defined above herein;

ii) C ₃ -C ₁₀ straight chain, C ₃ -C ₁₀ branched straight chain, C ₃ -C ₁₀ cyclic, C ₃ -C ₁₀ branched cycloalkylene, C ₆ -C ₁₀ arylene, wherein The unit comprises one or more electron-donating or electron-withdrawing moieties such that the pKa of the diamine is greater than about 8; and

iii) a mixture of (i) and (ii),

As long as the diamine has a pKa of at least about 8.

Examples of preferred diamines include the following: dimethylaminopropylamine, 1,6-hexanediamine, 1,3-propylenediamine, 2-methyl-1,5-pentanediamine, 1,3-pentanediamine Amine (available under the tradename Dytek EP), 1,3-diaminobutane, 1,2-bis(2-aminoethoxy)ethane (available under the tradename Jeffamine EDR 148), isophoronediamine , 1,3-bis(aminomethyl)-cyclohexane, and mixtures thereof. Polymeric Foam Stabilizer - The compositions of the present invention may optionally contain a polymeric foam stabilizer. These polymeric suds stabilizers provide increased suds volume and suds duration without compromising the grease cutting ability of liquid detergent compositions. These polymeric foam stabilizers are preferably selected from:

其中每个R各自为H、C₁-C₈烷基、及其混合物，R¹为H、C₁-C₆烷基、及其混合物，n为2-约6；和i) Homopolymers of (N,N-dialkylamino)alkyl acrylates having the formula

wherein each R is independently H, C ₁ -C ₈ alkyl, and mixtures thereof, R ¹ is H, C ₁ -C ₆ alkyl, and mixtures thereof, and n is 2 to about 6; and

其中R¹为H、C₁-C₆烷基、及其混合物，条件是(ii)与(i)的比为约2∶1-约1∶2；通过常规凝胶渗透色谱法测定的该聚合泡沫稳定剂的分子量为约1,000-约2,000,000，优选约5,000-约1,000,000，更优选约10,000-约750,000，更优选约20,000-约500,000，甚至更优选约35,000-约200,000。该聚合泡沫稳定剂可以任选以盐形式存在，或者为无机盐或者为有机盐，例如(N，N-二甲氨基)烷基丙烯酸酯的柠檬酸盐、硫酸盐或硝酸盐。ii) a copolymer of (i) and

wherein R ¹ is H, C ₁ -C ₆ alkyl, and mixtures thereof, provided that the ratio of (ii) to (i) is from about 2:1 to about 1:2; The molecular weight of the polymeric suds stabilizers is from about 1,000 to about 2,000,000, preferably from about 5,000 to about 1,000,000, 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 polymeric foam stabilizer may optionally be present in salt form, either inorganic or organic, such as citrate, sulfate or nitrate of (N,N-dimethylamino)alkylacrylate.

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

The compositions preferably contain at least about 0.01%, more preferably at least about 0.05%, even more preferably at least about 0.1%, by weight of the composition, of polymeric suds booster. Cleaning compositions also preferably contain no more than about 15%, more preferably no more than about 10%, even more preferably no more than about 5%, by weight of the composition, of polymeric suds booster.

Other useful polymeric foam stabilizers, including protenacious foam stabilizers and zwitterionic foam stabilizers, can be found in PCT/US98/24853 filed November 20, 1998 (Case No. 6938), PCT filed November 20, 1998 /US98/24707 (Docket No. 6939), PCT/US98/24699 (Docket No. 6943), filed November 20, 1998, and PCT/US98/24852 (Docket No. 6944), filed November 20, 1998.

其中R₁为H或CH₃，R₂和R₃独立地为C_1-4烷基，R₄为C_1-4烷基、C_2-3羟烷基或苯甲基，R₂、R₃和R₄总共含有低于9个碳原子，Z为一水溶性成盐阴离子，M可以为--CO--X--，那么X为--O--或--NR₅--，R₅为H或C_1-4烷基，并且x为1-6，或者M可以为亚苯基，那么x为1，并且含有疏水基团的单体具有下式：

其中R₁为H或CH₃，X为--O--或--NR₇--，Y为--C₂H₄O--或--C₃H₇O--，y为0-60，当X为--O--时，R₆为C_8-24烃基，并且当X为--NR7--时，R₆为C_1-24烃基并且R₇为H或C_1-24烃基，R₆和R₇中至少一个为C_8-24烃基。关于这些阳离子共聚物稳定剂的详细说明参见US4454060。增稠剂-本文的餐具洗涤剂组合物还可以含有约0.2％-5％的增稠剂。更优选这种增稠剂占本文组合物的约0.5％-2.5％。增稠剂典型地选自纤维素衍生物类。适宜的增稠剂包括羟乙基纤维素、羟甲基纤维素、羧甲基纤维素、Quatrisoft LM200等。优选的增稠剂为羟丙基甲基纤维素。Another class of suitable foam stabilizers are cationic copolymer stabilizers which contain by weight greater than about 50% units derived from acrylamide, methacrylamide or mixtures thereof, 0.5-2% pendant quaternary nitrogen and 0.1 - 10% of side chain C _8-24 hydrophobic groups, preferably the copolymer contains about 55-95% by weight of units obtained from acrylamide, methacrylamide or mixtures thereof, 4-30% has units derived from at least A hydrophilic functional unit of molecular configuration obtained from a monomer containing an ethylenically unsaturated quaternary ammonium group, and 1-15% by at least one containing an ethylenically unsaturated _C8-24 hydrophobic group and no quaternary Units obtained from monomers of nitrogen. More preferably monomers containing quaternary ammonium groups have the formula:

Wherein R ₁ is H or CH ₃ , R ₂ and R ₃ are independently C _1-4 alkyl, R ₄ is C _1-4 alkyl, C _2-3 hydroxyalkyl or benzyl, R ₂ , R ₃ and R ₄ contain less than 9 carbon atoms in total, Z is a water-soluble salt-forming anion, M can be --CO--X--, then X is --O-- or --NR ₅ --, _R is H or C _1-4 alkyl, and x is 1-6, or M can be phenylene, then x is 1, and the monomer containing the hydrophobic group has the following formula:

Where R ₁ is H or CH ₃ , X is --O-- or --NR ₇ -- , Y is --C ₂ H ₄ O-- or --C ₃ H ₇ O--, y is 0- 60. When X is --O--, R ₆ is C _8-24 hydrocarbon group, and when X is --NR7--, R ₆ is C _1-24 hydrocarbon group and R ₇ is H or C _1-24 Hydrocarbyl, at least one of R ₆ and R ₇ is a C _8-24 hydrocarbon group. See US4454060 for a detailed description of these cationic copolymer stabilizers. Thickeners - The dishwashing detergent compositions herein may also contain from about 0.2% to about 5% of thickeners. More preferably such thickeners comprise from about 0.5% to 2.5% of the compositions herein. Thickeners are typically selected from the class of cellulose derivatives. Suitable thickeners include hydroxyethylcellulose, hydroxymethylcellulose, carboxymethylcellulose, Quatrisoft LM200, and the like. A preferred thickener is hydroxypropylmethylcellulose.

The composition may preferably contain at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about 5%, by weight of the composition, of a thickener. The compositions also preferably contain no more than about 5%, more preferably no more than about 3%, and even more preferably no more than about 2.5% by weight of the composition of thickener.

The hydroxypropyl methylcellulose polymer has a number average molecular weight of about 50,000 to 125,000 and a viscosity of a 2 wt% aqueous solution (ADTMD2363) at 25°C of about 50,000 to about 100,000 cps. A particularly preferred hydroxypropyl cellulose polymer is Methocel(R ⁾ J75MS-N, which has a viscosity of about 75,000 cps at 25°C for a 2.0 wt% aqueous solution. Particularly preferred hydroxypropyl cellulose polymers are surface treated so that the hydroxypropyl cellulose polymers are readily dispersible in aqueous solutions having a pH of at least about 8.5 at 25°C.

When formulated into the dishwashing detergent compositions of the present invention, the hydroxypropylmethylcellulose polymer should impart to the detergent compositions a Brookfield viscosity of about 500-3500 cps at 25°C. More preferably, the hydroxypropylmethylcellulose will impart a viscosity of about 1000-3000 cps at 25°C. For the purposes of the present invention, viscosity was measured using a Brookfield LVTDV-11 viscometer apparatus with RV #2 spindle at 12 rpm.

Clay thickeners are also suitable for use as thickeners. One suitable clay thickener is Laponite. The Laponite clay, when used, is present in the present compositions at a concentration of from about 0.25% to about 2.0 wt%, more preferably from about 0.5 to about 1.75 wt%, which is the Laponite RDS optionally having at least about 5.0 wt% tetrapotassium pyrophosphate Synthetic colored clay for peptizers. <2% of the Laponite RDS produced by Laponite Inorganics UK has a particle size greater than 250 microns, a bulk density of about 1000 Kg/m ³ , and a surface area of about 330 m ³ /g. Laponite RD has no peptizer and <2% of it has a particle size greater than 250 microns, a surface area of about 370 m ² /g, and a bulk density of about 1000 Kg/m ³ .

When the composition contains abrasives, the dishwashing detergent composition may also contain a colloid-forming swellable clay which acts both as a thickening agent for the product and as a suspending agent for the abrasive. These expandable clays are those classified geologically as smectites and attapulgites. Suitable smectite clays are montmorillonite clays which are initially hydrated aluminosilicates and hectorites which are initially hydrated magnesium silicates. It should be understood that the proportion of water hydrated in smectite clay varies with the manner in which the clay is processed. However, since the expandable properties of hydrous smectite clays are determined by the silicate lattice structure, the amount of water present is not critical. Furthermore, the charge deficit in montmorillonite is compensated by cations such as sodium, calcium, potassium, etc., so that they are sorbed in three layers (two tetrahedral and one octahedral) of clay mineral interlayers. Smectite clays for use in liquid compositions are available under trade names such as Thixogel No. 1 and Gelwhite GP from Georgia Kaolin Company (both smectites) and Veegum Pro and Veegum F from RTVanderbilt (both smectites). Yes) obtained. A preferred clay is a high viscosity colloidal montmorillonite clay sold by the Georgia Kaolin company. The clay contains about 6%-10% by weight of water and is a mixture of the _following oxides: 59% _SiO2 , 21% _Al2O3 , 1% _Fe2O3 , 2.4% _CaO , 3.8% MgO, 4.1% _Na2 O and 0.4% _K2O . 100 wt% of the clay passed through a 200 mesh screen. Disperses readily in water, but requires maximum swelling in water prior to use. This swelling of the clay is important to eliminate liquid stratification. During this expansion, the clay/water mixture builds up considerable viscosity. It is also thixotropic and therefore exhibits a yield point, 350 dynes/ ^cm has been identified as the preferred yield point for clay/water mixtures of Gelwhite GP because of other physical properties of the final composition at this point such as castability, Dispersibility, suspending power and liquid layering are acceptable. (The term "delamination" refers to the amount (in millimeters) of clear liquid visible on the surface of the final article after aging at 49°C for 1 and 10 weeks.) Clay/water with a yield point of 350 dynes/ ^cm Mixtures are acceptable regardless of Gelwhite GP concentration. Yield point is usually determined using HAAKE rvl2, MVIP, E=0.3, R=100 O=113min, 18min duration, grooved rotor and cup. Another expandable clay material suitable for use in liquid compositions is geologically classified as attapulgite, a magnesium-rich clay. A typical attapulgite analysis has 55.02% SiO ₂ , 10.24% Al ₂ O ₃ , 3.53% Fe ₂ O ₃ , 10.49% MgO, 0.47% K ₂ O; 9.73% H ₂ O removal at 150°C and more 10.13% _H2O was removed at high temperature. These clays had a small particle size and 100% of the clay passed through a 200 mesh screen. Attagel clays are commercially available from Engelhard Minerals & Chemicals Corporation under trade designations such as Attagel 40, Attagel 50 and Attagel 150. Of course, mixtures of smectite clays and attapulgite clays are also suitable to impart a combination of properties not available with either of the above classes of clays. To achieve the desired swelling of the material, the clay suspension in water is subjected to high shear mixing for a sufficient time until the clay is substantially fully hydrated before it is added to the organic portion of the article. For example, the desired swelling can be achieved by high shearing an 8% aqueous clay dispersion for 25 minutes. When the clay is substantially fully hydrated, the viscosity of the aqueous suspension increases dramatically, so the swelling method allows the use of low concentrations of clay. For example, clay concentrations as low as 1%-1.55% and as high as a maximum of 3%, preferably 1.2%-2 wt%, are effective in stabilizing the abrasive compositions of the present invention without adversely affecting their dispersibility in water. As noted above, the clay/water mixture used in the composition preferably has a yield point of about 350 dyne/ ^cm , although aqueous clay dispersions with yield points as low as 300 dyne/cm ^and as high as 450 dyne/ ^cm can be used. Satisfactory abrasive compositions were prepared. The foregoing water-insoluble, low-density abrasives are suspended in the dishwashing detergent liquid composition at a concentration ranging from 3% to 15%, preferably from 5% to 15% by weight, if desired, a small amount, such as 1% to 25% by weight % (based on the total weight of abrasives in the composition) of crystalline abrasives such as silicon dioxide or calcium carbonate having a Mohs hardness of 2-7 to partially replace low density abrasives, as long as the resulting dishwashing detergent composition is substantially stable . Abrasives - The present cleaning compositions may optionally contain from about 0 to about 20 wt%, more preferably from about 0.5 to about 10 wt%, of abrasives. The abrasive is preferably selected from the group consisting of amorphous hydrated silica, calcite being limestone calcium carbonate, and polyethylene powder particles and mixtures thereof. Amorphous silica (oral grade) suitable for increasing the frictional ability of the composition was supplied by Zeoffin. Zeoffin silica has an average particle size of 8 up to 10 mm. Its apparent density is 0.32-0.37g/ml. Another silica is Tixosil 103 manufactured by Rhone-Poulenc. Amorphous hydrated silica of different particle sizes (9, 15 and 300 mm) from Crosfield at the same apparent density can also be used. A polyethylene powder suitable for use in the present invention has a particle size of from about 200 to about 500 microns and a density of from about 0.91 to about 0.99 g/l, more preferably from about 0.94 to about 0.96. Another preferred abrasive is calcite used in concentrations of about 0% to 20 wt%, more preferably 1 wt% to 10 wt%, and produced by JM Huber Corporation of Illinois. Calcite is calcite composed primarily of calcium carbonate and 1%-5% magnesium carbonate, has an average particle size of 5 microns, an oil absorption (rub off) of about 10 and a hardness of about 3.0 Mohs. Solvents - Various water-miscible liquids such as lower alkanols, glycols, other polyols, ethers, amines, etc. can be used. Particular preference is given to C ₁ -C ₄ alkanols. These solvents may be present in the compositions herein from about 1% to 8%.

When present, the composition preferably contains at least about 0.01%, more preferably at least about 0.5%, even more preferably at least about 1% solvent by weight of the composition. The composition also preferably contains 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 they can be used without any 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 of its distinguishing features is that solvents tend to exist as discrete wholes rather than as generalized mixtures of compounds. Examples of suitable solvents for the present invention include methanol, ethanol, propanol, isopropanol, 2-methylpyrrolidone, benzyl alcohol and morpholine n-oxide. Methanol and isopropanol are preferred among these solvents.

Suitable solvents for use herein include ethers and diethers of 4-14 carbon atoms, preferably 6-12 carbon atoms, more preferably 8-10 carbon atoms. Other suitable solvents are diols or alkoxylated diols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, straight chain C1-C5 alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halogenated hydrocarbons, C6-C16 glycol ethers and mixtures thereof.

Suitable diols for use herein are of the formula HO-CR1R2-OH, wherein R1 and R2 are independently H or a C2-C10 saturated or unsaturated aliphatic hydrocarbon chain and/or ring. Suitable diols for use herein are dodecanediol and/or propylene glycol. Also suitable are polypropylene glycols, such as those having a molecular weight of about 100-1000. One suitable polypropylene glycol has a molecular weight of about 2700.

Suitable alkoxylated diols for use herein are of the formula R-(A)n-R1-OH, wherein R is H, OH, 1-20 carbon atoms, preferably 2-15 carbon atoms and more preferably 2 - straight chain saturated or unsaturated alkyl of 10 carbon atoms, wherein R1 is H or 1-20 carbon atoms, preferably 2-15 carbon atoms and more preferably 2-10 carbon atoms straight chain saturated or unsaturated Alkyl, and A is alkoxy, 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 alkoxylated aromatic alcohols for use herein are those of the formula R(A) _n -OH wherein R is 1-20 carbon atoms, preferably 2-15 carbon atoms and more preferably 2-10 carbon atoms Alkyl-substituted or non-alkyl-substituted aryl, wherein A is alkoxy, preferably butoxy, propoxy and/or ethoxy, and n is an integer of 1-5, preferably 1-2. Suitable alkoxylated aromatic alcohols are benzoyloxyethanol and/or benzoyloxypropanol.

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

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

Suitable alkoxylated straight chain C1-C5 alcohols for use herein are those of the formula R(A) _n -OH, wherein R is a straight chain saturated or unsaturated alcohol of 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms Alkyl, wherein A is alkoxy, preferably butoxy, propoxy and/or ethoxy, and n is an integer of 1-5, preferably 1-2. Suitable alkoxylated aliphatic straight-chain C1-C5 alcohols are butoxypropoxypropanol (n-BPP), butoxyethanol, butoxypropanol, ethoxyethanol or mixtures thereof. Butoxypropoxypropanol is commercially available from Dow chemical under the trade designation n-BPP(R ⁾ .

Suitable straight chain C1-C5 alcohols for use herein are those of the formula R-OH, wherein R is a straight chain saturated or unsaturated alkyl group of 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms. Suitable linear C1-C5 alcohols are methanol, ethanol, propanol or mixtures thereof.

Other suitable solvents include, but are not limited to, butyl diglycol ether (BDGE), butyl triglycol ether, ter amilic alcohol, 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 2 - Compounds of the (2-alkoxyethoxy)ethanol class, where the alkoxy group is derived from ethyl, propyl or butyl; the preferred water-soluble carbitol is 2-(2-butoxyethoxy ) ethanol, which is 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 glycols 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® ^and mixtures thereof.

These solvents may also be selected from compounds including ether derivatives of mono-, di- and tri-ethylene glycol, propylene glycol ethers, butylene glycol ethers and mixtures thereof. The molecular weight of these solvents is preferably below 350, more preferably 100-300, even more preferably 115-250. Examples of preferable solvents include, for example, monoethylene glycol n-hexyl ether, monopropylene glycol n-butyl ether, and tripropylene glycol methyl ether. Glycol ethers and propylene glycol ethers are commercially available from Dow Chemical Company under the trade name "Dowanol" and from Arco Chemical Company under the trade name "Arcosolv". Other preferred solvents including monoethylene glycol n-hexyl ether and diethylene glycol n-hexyl ether are available from Union Carbide. Solubilizer - The present compositions may optionally contain from about 0% to about 12%, more preferably from about 1% to about 10% by weight of at least one solubilizing agent which may be a hydrotrope such as sodium xylene sulfonate or cumene sulfonate Sodium acid; C _2-3 mono- or dihydroxy alkanols such as ethanol, isopropanol and propylene glycol and mixtures thereof. In order to control low-temperature turbidity and clarification performance, it contains a solubilizer. Urea may optionally be used as a supplemental solubilizer in the present composition at a concentration of 0 to about 10 wt%, more preferably about 0.5 wt% to about 8 wt%. Other suitable solubilizers are glycerol; water-soluble polyethylene glycols with a molecular weight of _300-600 , polypropylene glycol of the formula HO( _CH3CHCH2O ) _nH , wherein n is a number of 2-18; polyethylene glycol and polypropylene glycol (Synalox) and C ₁ -C ₆ alkyl ethers and esters of ethylene glycol and propylene glycol of the formula R(X) _n OH and R ₁ (X) _n OH, where R is C ₁ -C ₆ Alkyl, R ₁ is C ₂ -C ₄ acyl, X is (OCH ₂ CH ₂ ) or (OCH ₂ (CH ₃ ) CH), n is the number 1-4, representative members of polypropylene glycol include dipropylene glycol and molecular weight is 200-1000 polypropylene glycol, such as polypropylene glycol 400. Other satisfactory glycol ethers are ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monobutyl ether, mono, di, tri Propylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, mono, di, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, propylene glycol tert-butyl ether, ethylene glycol monomethyl ether Diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monopentyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol Monopentyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monopentyl ether, triethylene glycol monohexyl ether, mono, di, tripropylene glycol monoethyl ether , one, two, tripropylene glycol monopropyl ether, one, two, tripropylene glycol monopentyl ether, one, two, tripropylene glycol monohexyl ether, one, two, tributylene glycol monomethyl ether, one, two, tributylene glycol Monoethyl ether, one, two, tributylene glycol monopropyl ether, one, two, tributylene glycol monobutyl ether, one, two, tributylene glycol monopentyl ether and one, two, tributylene glycol monohexyl ether, Ethylene glycol monoacetate and dipropylene glycol propionate. Polymeric Soil Release Agents - The compositions of the present invention may optionally contain one or more soil release agents. Polymeric soil release agents are characterized by both hydrophilic segments, such as polyesters and nylons, which render the surface of hydrophobic fibers hydrophilic, and the ability to deposit on hydrophobic fibers and adhere to them throughout the laundry cycle and thus act as a hydrophilic segment. The hydrophobic segment of the anchor of the water segment. This enables existing stains to be treated with soil release agents, making them easier to clean in subsequent wash steps.

Soil release agents, if used, generally comprise from about 0.01% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.2% to about 3%, by weight of the compositions.

The following references describe soil release polymers suitable for use in the present invention and are incorporated herein by reference. US5,691,298 issued Nov. 25, 1997 to Gosselink et al.; US5,599,782 issued Feb. 4, 1997 to Pan et al.; US5,415,807 issued May 16, 1995 to Gosselink et al.; Jan. 26, 1993 US5,182,043 issued to Morrall et al on September 11, 1990; US4,956,447 issued September 11, 1990 to Gosselink et al; US4,968,451 issued May 15, 1990 to Borcher, Sr. et al; US4,861,512 issued August 29, 1989 to Gosselink; US4,877,896 issued October 31, 1989 to Maldonado et al ; US4,702,857 issued October 27, 1987 to Gosselink et al; US4,711,730 issued December 8, 1987 to Gosselink et al; US4,721,580 issued January 26, 1988 to Gosselink; December 28, 1976 US 4,000,093 to Nicol et al; US 3,959,230 to Hayes on May 25, 1976; US 3,893,929 to Basadur on July 8, 1975; and EP0219048A published April 22, 1987 to Kud et al.

Other suitable soil release agents are described in US 4,201,824 to Voilland et al; US 4,240,918 to Lagasse et al; US 4,525,524 to Tung et al; US 4,579,681 to Ruppert et al; US 4,220,918; EP279,134A, Poulencchemie, 1988; EP457,205A, BASF (1991); and DE2,335,044, Unilever NV (1974); all of which are incorporated herein by reference. Polymeric Grease Release Agents - The compositions of the present invention may also optionally contain polymeric grease release agents. Suitable polymeric grease release agents include those of the formula: Wherein x is H and an alkali metal cation, n is the number 2-16, R1 is selected from: methyl or H, _R2 is C ₁ -C ₁₂ straight chain or branched chain alkyl, R ₃ is C ₂ -C ₁₆ straight chain or branched chain alkyl, y is a value such that the molecular weight is from about 5,000 to about 15,000. See US5573702. Clay Soil Removal/Anti-Redeposition Agents - The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; liquid detergent compositions typically contain from about 0.01% to about 5%.

A preferred soil release and antiredeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are also described in US Patent 4,597,898, issued July 1,1986 to VanderMeer. Another preferred class of clay soil removal-antiredeposition agents are the cationic compounds disclosed in EP 111,965, Oh and Gosselink, published June 27,1984. Other clay soil removal-anti-redeposition agents that may be used are the ethoxylated amine polymers disclosed in EP 111,984, Gosselink, June 27, 1984; EP 112, Gosselink, July 4, 1984, 592; and the amine oxides disclosed in US 4,548,744, issued October 22, 1985 to Connor. Other clay soil removal and/or anti-redeposition agents known in the art may also be used in the compositions herein. See US 4,891,160, issued January 2, 1990 to VanderMeer and WO 95/32272, published November 30, 1995. Another class of preferred anti-redeposition agents includes carboxymethylcellulose (CMC) materials. These materials are well known in the art. Polymeric Dispersants - Polymeric dispersants can advantageously be used in the compositions herein at levels of from about 0.1% to about 7% by weight, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. While not intending to be bound by theory, it is believed that when used in combination with other builders, including low molecular weight polycarboxylates, polymeric dispersants make the overall Detergent builder performance is improved.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, and methylene malonic acid. The polymeric polycarboxylates herein or monomeric segments suitably contain non-carboxylate groups such as vinylmethyl ether, styrene, ethylene, etc., provided such segments do not exceed about 40% by weight.

Particularly suitable polymeric polycarboxylates are obtainable from acrylic acid. The acrylic acid-based polymers used herein are water-soluble salts of polymerized acrylic acid. The average molecular weight of these polymers in the acid form is preferably about 2,000-10,000, more preferably about 4,000-7,000, most preferably about 4,000-5,000. Water-soluble salts of these acrylic acid polymers may include, for example, the alkali metal, ammonium and substituted ammonium salts thereof. Such soluble polymers are known materials. The use of such polyacrylates in detergent compositions is disclosed, for example, in US Patent 3,308,067, Diehl, issued March 7,1967.

Acrylic/maleic acid-based copolymers can also be used as a preferred component of the dispersing/anti-redeposition agent. These materials include the water soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of these copolymers in the acid form is preferably from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate moieties in these copolymers is generally from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water soluble salts of these acrylic acid/maleic acid copolymers may include, for example, the alkali metal, ammonium and substituted ammonium salts thereof. Such soluble acrylate/maleate copolymers are known materials and are described in EP66915, published November 15, 1982, and in EP193,360, published September 3, 1986, which also describes These copolymers of hydroxypropyl acrylate. Other useful dispersants include maleic/acrylic acid/vinyl alcohol terpolymers. These materials are also disclosed in EP 193,360, for example comprising a 45/45/10 terpolymer of acrylic acid/maleic acid/vinyl alcohol.

Another polymeric material that can be included is polyethylene glycol (PEG). PEG can have dispersant properties and can act as a clay soil removal-anti-redeposition agent. Typical molecular weights for these purposes are from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyaspartate and polyglutamate dispersants can also be used, especially in combination with zeolite builders. Dispersants such as polyaspartate preferably have a molecular weight (average) of about 10,000.

Other polymer types that may be desirable for biodegradability, increased bleach stability, or cleaning purposes include various terpolymers and hydrophobically modified copolymers, including those developed by Rohm & Haas, BASF Corp., Nippon Shokubai Those sold and others used in all manner of water treatment, textile treatment or detergent applications. Chelating Agents - The compositions herein may also optionally contain one or more chelating agents, particularly for exotic transition metals. Those commonly found in wash water include iron and/or manganese in water-soluble colloidal or particulate form, and can be found with oxides or hydroxides, or with soils such as humus. Preferred chelating agents are those effective in controlling these transition metals, in particular including controlling the deposition of these transition metals or their compounds on fabrics and/or controlling unwanted redox reactions in the wash medium and/or at fabric or hard surface interfaces. Those ones. These chelating agents include those of the low molecular weight and polymeric type, typically having at least one, preferably two or a single donor heteroatom such as O or N, which are capable of coordinating the transition metal. Common chelating agents can be selected from: amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof.

Amino carboxylates optionally used as chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, Ethylenetetraminehexaacetate, diethylenetriaminepentaacetate and ethanol diglycine, their alkali metal, ammonium and substituted ammonium salts and mixtures thereof.

Amino phosphonates are also suitable as chelating agents in the compositions of the invention when at least small amounts of total phosphorus are permitted in detergent compositions and include ethylenediaminetetrakis (methylene phosphonates), such as DEQUEST. Preferably, these amino phosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms.

Multifunctionally substituted aromatic chelating agents are also useful in the compositions herein. See US 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

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

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

If utilized, chelating agents will generally comprise from about 0.001% to about 15% by weight of the detergent compositions. More preferably, if used, chelating agents comprise from about 0.01% to about 3.0% by weight of these compositions. Suds Suppressors - Compounds that reduce or inhibit suds formation can be added to the compositions of the present invention when desired according to the intended use, particularly in laundry applications. Other compositions, such as those designed for hand washing, may desirably be high sudsing and may dispense with these components. Suppression of suds may be of particular importance in the so-called "high density wash method" described in US 4,489,455 and 4,489,574 and in front loading Euro washing machines.

Various materials can be used as suds suppressors and are well known in the art. See, eg, Kirk Othmer Encyclopedia of Chemical Technology, 3rd Edition, Vol. 7, pp. 430-447 (Wiley, 1979).

The compositions herein generally contain from 0% to about 10% suds suppressor. When used as suds suppressors, monocarboxylic fatty acids and salts thereof are typically present at levels up to about 5%, preferably from 0.5% to 3%, by weight of the detergent compositions. However, higher levels can be used. Preferably from about 0.01% to about 1%, more preferably from about 0.25% to about 0.5%, of silicone suds suppressor is used. These weight percents include any silica that may be used in combination with the polyorganosiloxane, as well as any suds suppressor adjunct material that may be utilized. Monostearyl phosphate suds suppressors are generally used at levels of from 0.1% to about 2% by weight of the composition. Hydrocarbon suds suppressors are typically used in amounts of from about 0.01% to about 5.0%, although higher levels can be used. Alcohol suds suppressors are typically used in amounts of 0.2% to 3% by weight of the final composition. Alkoxylated Polycarboxylates - Alkoxylated polycarboxylates such as those prepared from polyacrylates may be used herein to provide additional grease removal performance. These materials are described on pages 4 et seq. of WO91/08281 and PCT90/01815, which are incorporated herein by reference. Chemically these include polyacrylates having one ethoxy side chain per 7-8 acrylate units. These side chains are of the formula -(CH ₂ CH ₂ O) _m (CH ₂ ) _n CH ₃ , where m is 2-3 and n is 6-12. These side chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. Its molecular weight can vary, but is typically from about 2000 to about 50,000. These alkoxylated polycarboxylates can comprise from about 0.05% to about 10% by weight of the total compositions herein. Fragrances - Perfumes and fragrance ingredients useful in the compositions and methods of the present invention include a variety of natural and synthetic chemical ingredients including, but not limited to, aldehydes, ketones, esters, and the like. Also included are various natural extracts and fragrances which may contain complex mixtures of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, Cedar et al. The final flavor can contain very complex mixtures of these ingredients. Final perfumes typically comprise from about 0.01% to about 2% by weight of the detergent compositions herein, and individual perfume ingredients may comprise from about 0.0001% to about 90% of the final perfume compositions.

Non-limiting examples of fragrance ingredients used herein include: 7-acetyl-1,2,3,4,5,6,7,8-octaH-1,1,6,7-tetramethylnaphthalene; Methyl ionone; Gamma methyl ionone; Methyl cedronone; Methyl dihydrojasmonate; 1-yl ketone; 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene; 4-acetyl-6-tert-butyl-1,1-dimethylindane ; p-hydroxyphenylbutanone; benzophenone; methyl β-naphthyl ketone; 6-acetyl-1,1,2,3,3,5-hexamethylindane; 5-acetyl-3 -Isopropyl-1,1,2,6-tetramethylindane; 1-dodecanal, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1- Carboxaldehyde; 7-hydroxy-3,7-dimethyloctanal; 10-undecene-1-al; isohexenylcyclohexylcarbaldehyde; formyltricyclodecane; hydroxycitronellal and Condensation products of methyl anthranilate, condensation products of hydroxycitronellal and indole, condensation products of phenylacetaldehyde and indole; 2-methyl-3-(p-tert-butylphenyl)-propionaldehyde; Ethyl vanillin; piperonal; hexyl cinnamaldehyde; amyl cinnamaldehyde; 2-methyl-2-(p-isopropylphenyl)-propionaldehyde; coumarin; gamma-decalactone; cyclopentyldecane Amide; 16-Hydroxy-9-hexadecenolactone; 1,3,4,6,7,8-hexaH-4,6,6,7,8,8-hexamethyl-cyclopentyl -γ-2-benzopyran; β-naphthol methyl ether; hogsane; dodecaH-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; cedrol, 5- (2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclo penten-1-yl) 2-butan-1-ol; caryophyllenol; tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; cedrol acetate and p (tert-butyl)cyclohexyl acetate.

Particularly preferred perfume materials are those which provide the greatest odor improvement in the final product composition comprising cellulase. These fragrances include, but are not limited to: Hexylcinnamaldehyde; 2-Methyl-3-(p-tert-butylphenyl)-propionaldehyde; 7-Acetyl-1,2,3,4,5,6,7,8 - octah-1,1,6,7-tetramethylnaphthalene; benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene; Butyl)cyclohexyl acetate; methyl dihydrojasmonate; β-naphthol methyl ether; methyl β-naphthyl ketone; 2-methyl-2-(p-isopropylphenyl)-propane Aldehyde; 1,3,4,6,7,8-hexaH-4,6,6,7,8,8-hexamethyl-cyclopentyl-γ-2-benzopyran; dodecaH- 3a, 6, 6, 9a-tetramethylnaphtho[2,1b]furan; anisaldehyde; coumarin; cedrol; vanillin; cyclopentyldecenylamide; Decenyl Propionate.

Other fragrance materials include essential oils, resinoids, and resins from various sources including, but not limited to, Peru balsam, frankincense, styrax, styrax resin, nutmeg, cinnamon oil, benzoin resin, coriander and lavender. Other fragrance chemicals include phenylethyl alcohol, terpineol, coriander alcohol, linalyl acetate, citronellol, nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, Benzyl acetate and eugenol. Carriers such as diethylphthalate may be used in the final fragrance composition.

Especially in microemulsions, the composition may use essential oils or water-insoluble organic compounds such as water-insoluble hydrocarbons with 6-18 carbon atoms such as paraffin or isoparaffins such as isoparH, Isodecane, alpha-pinene, beta-pinene, decanol and terpineol. Suitable essential oils are selected from: Natural Anethole 20/21, Anise Oil China Star, Anise Oil Ball Brand, Balsam (Peru), Basil Oil (India), Black Pepper Oil, Black Pepper Oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol (China), Camphor Oil, White Camphor Powder Synthesis Technology, Ylang Ylang Oil (Java), Cardamom Oil, Cinnamon Oil (China), Fir Oil (China) BP, Cinnamon Bark Oil, Cinnamon Leaf Oil , citronella oil, clove bud oil, clove leaf, coriander (Russia), coumarin 69°C (China), cyclamen aldehyde, benzophenone, ethyl vanillin, eucalyptol, eucalyptus oil, Eucalyptus citriodora , Fennel Oil, Geranium Oil, Ginger Oil, Ginger Oleoresin (India), White Grapefruit, Guaiac Oil, Gua Balsam, Piperonal, Isobornyl Acetate, Isolongene, Juniper Berry Oil, L-Methyl Acetate, Lavender Oil, Lemon Oil, Lemongrass Oil, Lime Lime Oil Distilled, Litsea Cube Oil, Longifolene, Menthol Crystals, Methylcedaryl Ketone, Methylwilt Leaf Phenol, Methyl Salicylate, Musk Sunflower, Muscone, Musk Xylene, Nutmeg Oil, Orange Oil, Patchouli Oil, Peppermint Oil, Phenylethyl Alcohol, Pimento Berry Oil, Pimento Leaf Oil, Rosalin, Sandalwood Oil, Sandenol, Clary Sage Oil, Clary Sage, Sassafras Oil, Spearmint Oil, Lavender, Marigold, Tea Tree Oil, Vanillin, Vetyver Oil (Java), Oil of Wintergreen. Composition pH - The dishwashing detergent compositions of the present invention will be subjected to the acidic stress of food soils when used, ie diluted and spread onto soiled dishes. If a composition with a pH greater than 7 is more effective, a buffering agent capable of providing a generally more basic pH in the composition and diluent may optionally be included in the composition and diluent, i.e. about 0.1% by weight of the composition- 0.4% aqueous solution. The pKa of the buffer should be about 0.5-1.0 pH units below the desired pH of the composition (as determined above). Preferably the pKa of the buffer should be from about 7 to about 10. Under these conditions, a buffer is most effective in controlling its pH when its minimal amount is used.

Preferably the pH (measured as a 10% aqueous solution) of the compositions of the present invention is from about 2.0 to about 12.5, more preferably from about to about 12.5.

The buffering agent may itself be an active detergent, or it may be a low molecular weight, organic or inorganic material used in the present composition to maintain only 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. 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-propanediol, disodium glutamate, N-methyldiethanolamide, 1,3-diamino-propanol, N,N'-tetramethyl Base-1,3-diamino-2-propanol, N,N-bis(2-hydroxyethyl)glycine (N-diglycine) and N-tris(hydroxymethyl)methylglycine (N-triglycine ). Mixtures of any of the above are also acceptable. Useful inorganic buffers/sources of alkalinity include alkali metal carbonates and alkali metal phosphates, eg sodium carbonate, sodium polyphosphate. For other buffers see McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition, 1997, McCutcheon Division, MC Publishing Company Kirk and WO95/07971, both of which are incorporated herein by reference.

Compositions preferably contain at least about 0.1%, more preferably at least about 1%, even more preferably at least about 2%, by weight of the composition, of buffering agent. The composition also preferably contains no more than about 15%, more preferably no more than about 10%, even more preferably no more than about 8%, by weight of the composition, of buffering agent. Hydrotropes - The aqueous liquid carrier may contain one or more materials that are hydrotropes. Hydrotropes suitable for use in the compositions herein include C ₁ -C ₃ alkylaryl sulfonates, C ₆ -C ₁₂ alkanols, C ₁ -C ₆ carboxy sulfates and sulfonates, urea, C ₁ - C ₆ hydrocarbyl carboxylates, C ₁ -C ₄ carboxylates, C ₂ -C ₄ organic diacids and mixtures of these hydrotropes. The liquid detergent compositions of the present invention preferably contain from about 0.5% to 8% by weight of the liquid detergent composition of a hydrotrope selected from the group consisting of xylene sulfonates and toluene sulfonates of alkali metals and calcium.

Suitable C ₁ -C ₃ alkylaryl sulfonates include sodium, potassium, calcium and ammonium xylene sulfonates; sodium, potassium, calcium and ammonium toluene sulfonates; sodium, potassium, calcium and ammonium cumene sulfonates; and substituted or unsubstituted sodium, potassium, calcium and ammonium naphthalenesulfonates and mixtures thereof.

Suitable C ₁ -C ₈ carboxy sulfates or sulfonates are any water-soluble salts or organic compounds containing 1 to 8 carbon atoms (excluding substituents), substituted with sulfate or sulfonate and having at least one carboxyl group. The substituted organic compounds may be cyclic, acyl or aromatic, ie benzene derivatives. Preferred alkyl compounds have 1-4 carbon atoms substituted with sulfate or sulfonate and have 1-2 carboxyl groups. Examples of such hydrotropes include sulfosuccinates, sulfophthalates, sulfoacetates, m-sulfobenzoates and diester sulfosuccinates, preferably those disclosed in US3915903 sodium or potassium salt.

Suitable _C1 - _C4 hydrocarbyl carboxylates and _C1 - _C4 carboxylates for use herein include acetates and propionates and citrates. Suitable _C2 - _C4 diacids for use herein include succinic acid, glutaric acid and adipic acid.

Other compounds that impart a hydrotropic effect and are suitable for use herein as hydrotropes include _C6 - _C12 alkanols and urea.

Preferred hydrotropes for use herein are sodium, potassium, calcium, and ammonium cumene sulfonate; sodium, potassium, calcium, and ammonium xylene sulfonate; sodium, potassium, calcium, and ammonium toluene sulfonate; and mixtures thereof. Sodium cumene sulfonate and calcium xylene sulfonate and mixtures thereof are most preferred. These preferred hydrotropes can be present in the composition at about 0.5% to 8% by weight.

Compositions preferably contain at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about 0.5%, by weight of the composition, of a hydrotrope. The composition also preferably contains no more than about 15%, more preferably no more than about 10%, even more preferably no more than about 8%, by weight of the composition, of a hydrotrope. Other Components - The present detergent compositions may also preferably contain one or more detergency builders selected from the group consisting of soil release polymers, polymeric dispersants, polysaccharides, abrasives, bactericides, tarnish inhibitors, color stabilizers , dyes, electrolytes (such as NaCl, etc.), antifungal or mildew inhibitors, insect repellents, acaricides, hydrotropes, processing aids, foam boosters, brighteners, anti-rust additives, stabilizers and Antioxidants. Various other ingredients useful in detergent compositions may be included in the compositions herein, including other active ingredients, carriers, antioxidants, processing aids, dyes or pigments, solvents for liquid products, solids for bar compositions filler etc. If high sudsing is desired, suds boosters such as _C10 - _C16 alkanolamides can be added to the present compositions at levels typically from 1% to 10%. C ₁₀ -C ₁₄ monoethanols and diethanolamides are typical types of these suds boosters. It is also beneficial to use these suds boosters with the high suds builder surfactants mentioned above such as amine oxides, betaines and sultaines.

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

Various detersive ingredients used in the present compositions may also optionally be stabilized by absorbing the ingredients onto a porous hydrophobic substrate and then coating the substrate with a hydrophobic coating. The detersive ingredients are preferably mixed with a surfactant which is then absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous wash liquor where it performs its intended detersive function.

To describe the technique in detail, porous hydrophobic silica (trade name SIPERN TD10, DeGussa) was mixed with a proteolytic enzyme solution containing 3%-5% ethoxylated alcohol (EO7) nonionic surfactant. Typically, the enzyme/surfactant solution is 2.5 times the weight of silica. The obtained powder is dispersed in silicone oil (various silicone oils with a viscosity ranging from 500 to 12500 can be used) under stirring. The resulting silicone oil dispersion is emulsified or otherwise incorporated into the final detergent base. In this way, for example, the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable Surfactant components can be "protected". composition form

The compositions of the present invention may be in any conventional form of hand dishwashing compositions, such as pastes, liquids, granules, powders, gels, liquid gels, microemulsion crystals or combinations thereof. Highly preferred embodiments are in liquid or gel form. Liquid compositions may or may not contain water. When the composition is an aqueous liquid, the composition preferably also contains an aqueous liquid carrier for dissolving, dispersing or suspending the other essential and optional constituents.

When the composition is an aqueous liquid, the composition preferably contains at least about 5%, more preferably at least about 10%, even more preferably at least about 30%, by weight of the composition, of the aqueous liquid carrier. The compositions also preferably contain no more than about 95%, more preferably no more than about 60%, even more preferably no more than about 50%, by weight of the composition, of an aqueous liquid carrier.

A major component of the aqueous liquid carrier is, of course, water. However, the aqueous liquid carrier may contain other materials that are liquid or soluble in the liquid carrier at room temperature and may also serve some other function than that of a simple filler. These materials can include, for example, hydrotropes and solvents. Low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol are suitable. For solubilizing surfactants, monohydric alcohols are preferred, but polyhydric alcohols, such as those containing 2 to about 6 carbon atoms and 2 to about 6 hydroxyl groups (e.g., 1,3-propanediol, ethylene glycol, , glycerol and 1,2-propanediol).

An example of the steps for the preparation of the detergent composition granules herein is as follows: - Add modified alkylbenzene sulphonate, citric acid, sodium silicate, sodium sulphate perfume, diamine and water to a blender, heat and mix. The resulting slurry was spray dried into granular form.

An example of the steps for preparing the liquid detergent compositions herein is as follows: - Add citrate to free water and dissolve. To this solution is added amine oxide, betaine, ethanol, hydrotrope and nonionic surfactant. If free water is not available, add citrate to the above mixture and stir until dissolved. At this point acid is added to neutralize the preparation. Preferably the acid is selected from organic acids such as maleic acid and citric acid, however, inorganic acids may also be used. In a preferred embodiment, these acids are added to the formulation prior to the addition of the diamine. Finally join AExS.

        Anhydrous Liquid Detergent

Liquid detergent compositions containing anhydrous carrier media can be prepared as disclosed in: US 4,753,570, 4,767,558, 4,772,413, 4,889,652, 4,892,673, GB-A-2,158,838, GB-A-2,195,125, GB-A2,195,649 , US4,988,462, US5,266,233, EP-A-225,654 (6/16/87), EP-A-510,762 (10/28/92), EP-A-540,089 (5/5/93), EP-A- A-540,090 (5/5/93), US 4,615,820, EP-A-565,017 (10/13/93), EP-A-030,096 (6/10/81); which are incorporated herein by reference. These compositions may contain various particulate detersive ingredients stably suspended therein. These anhydrous compositions thus contain a liquid phase, optionally but preferably a solid phase, all of which are described in detail hereinafter and in the cited literature.

These compositions of the present invention are useful in forming aqueous wash liquors for hand dishwashing. Generally, an effective amount of these compositions is added to water to form an aqueous cleaning or soaking solution. The aqueous solution so formed is then brought into contact with tableware, tableware and cooking utensils.

An effective amount of the detergent compositions herein added to water to form an aqueous cleaning solution can include an amount sufficient to form an aqueous solution of about 500-20,000 ppm composition. More preferably, about 800-5,000 ppm of the detergent compositions herein are provided in the aqueous cleaning liquor.

Embodiments of the present invention are described below, but are not meant to limit or otherwise limit the scope thereof. All parts, percentages and ratios used herein are by weight unless otherwise indicated.

In the following examples, all amounts are quoted in % by weight of the composition. Examples of detergent compositions

In these examples, the following abbreviation is used for crystallinity disrupted alkylbenzenesulfonic acid, sodium salt form or potassium salt form prepared according to any of the preceding method examples: MLAS

The following abbreviations are used for cleaning product adjuvant materials: Cxy Amine oxide: Alkyldimethylamine N-oxide RN(O)Me ₂ with chain length Cxy,

      where the average total carbons of the non-methyl alkyl moiety R is 10+x to

10+yCxyAPG: A polyalkyl group of formula R ₂ O(C _n H _2n O) _t (glycosyl) _x with chain length Cxy

Glycoside, wherein R ₂ is C _10-18 alkyl; n is 2 or 3, and t is 0-about 10,

Preferably 0; and x is from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose

Glucose. Amylase: Amylolytic enzyme with an activity of 60KNU/g, manufactured by NOVO Industries

A/S sells it under the trade name Termamyl 60T. Alternatively, amylase

From: ^Fungamyl® , ^Duramyl® , ^BAN® , and WO95/26397

and Novo Nordisk's pending application PCT/DK96/00056

Alpha amylase APA described above: C ₈ -C ₁₀ amidopropyl dimethylamine Cxy betaine: alkyl dimethyl with an average total carbon number of the alkyl moiety of 10+x to 10+y

Calcium Betaine Calcium Salt Calcium Chloride, Calcium Sulfate, Calcium Hydroxide and their mixtures Carbonates: Sodium Carbonate Anhydrous, 200 microns - 900 Microns Citrate: Trisodium Citrate Dihydrate, 86.4%, 425 Microns - 850 Micron Citric Acid: Citric Acid Anhydrous CMC: Sodium Carboxymethylcellulose CxyAS: Alkyl Sulfate, Sodium Salt or Other Salts Specified, Average of Alkyl Moieties

                                                                                                            

chain), with an average total carbon number of the alkyl moiety from 10+x to 10+y, having

Ethylene oxide CxyEzS of average z moles: Alkyl ethoxylated sulfates, sodium salts (or other salts as specified),

The average total carbon number of the alkyl moiety is from 10+x to 10+y, with an average

Z moles of ethylene oxide DEA Diethanolamine diamine Alkyl diamines such as 1,3-propanediamine, Dytek EP, Dytek

A (Dupont) or selected from: dimethylaminopropylamine, 1,6-hexanedi

Amine, 1,3-propanediamine, 2-methyl-1,5-pentanediane, 1,3-pentanediamine

Amine, 1-methyl-diaminopropane, 1,3-cyclohexanediamine, 1,2-cyclo

Hexamethylenediamine, 1,3-bis(aminomethyl)-cyclohexane DTPA: Diethylenetriaminepentaacetic acid DTPMP: Diethylenetriaminepenta(methylene phosphonate), Monsanto (Dequest

                                                                                                  

Potassium, magnesium, calcium, ammonium or water-soluble substituted ammonium salts LAS: Linear alkylbenzene sulfonate (eg C11.8, sodium or potassium salt) Lipase: Lipase, 100 kLU/g, NOVO, ^Lipolase® . or

Lipase selected from: Amano-P, M1 Lipase ^® , Lipomax ^® ,

   Derived from Humicola tomentosa as described in US Application Serial No. 08/341,826

The obtained D96L-lipohydrolase variant of natural lipase; and velvet

Humicola lucifera strain DSM 4106LMFAA: C _12-14 alkyl N-methylglucamide MA/AA: 1:4 copolymer of maleic acid/acrylic acid, sodium salt, average molecular weight

                                                                                   

EO=y)MBAxEyS: mid-chain branched or modified primary alkyl ethoxylated sulfates, sodium salt

  (average total carbon number = x; average EO = y)

According to the present invention (see Example 9) MBAyS: mid-chain branched primary alkyl sulfate, sodium salt (average total carbon number = y) MEA: -ethanolamine CxyMES: alkyl methyl ester sulfonate, sodium salt, alkane Average total carbon number of the base part

Magnesium salts from 10+x to 10+y: Magnesium chloride, magnesium sulfate, magnesium hydroxide and mixtures thereof NaOH: Sodium hydroxide CxyNaPS: Paraffin sulfonates with an average total carbon number of the alkyl moiety from 10+x to

10+y sodium salt NaTS sodium toluenesulfonate PAA: polyacrylic acid (molecular weight = 4500) PAE: ethoxylated tetraethylenepentamine PEG: polyethylene glycol (molecular weight = 4600) PG: propylene glycol protease: proteolytic enzyme, 4KNPU/g, NOVO, ^Savinase® . or eggs

White enzyme is selected from: Maxatase ^® , Maxacal ^® , Maxapem 15 ^® ,

    Subtilisin BPN and BPN', Protease B, Protease A, Protease

Lease D, Primase ^® , Durazym ^® , Opticlean ^® and

Optimase® ^{and Alcalase®} . CxySAS Secondary alkyl sulfate, the average total carbon number of the alkyl moiety is 10+x to

10+y sodium salt silicate Amorphous sodium silicate (SiO ₂ : Na ₂ O = 2.0) solvent hexanediol, ethanol or propylene glycol STPP sodium tripolyphosphate, anhydrous foam-increasing polymer acrylic acid (N,N- Dimethylamino) alkyl esters; methacrylate (N,N-

    dimethylamino)ethyl ester homopolymer; dimethylaminoethyl methacrylate

Ester/dimethylacrylamide copolymer; poly(DMAM) homopolymer; poly

    (DMAM-co-AA) (2:1) copolymer; containing Lys, Ala, Glu,

Polypeptide sulfate of Tyr (5:6:2:1) with a molecular weight of about 52,000 Daltons Sodium sulfate, anhydrous TFA C _16-18 alkyl N-methylglucamide

What are often referred to as "minor" general ingredients can include fragrances, dyes, pH trims, etc.

The invention is illustrated by the following examples, which are not meant to limit or otherwise define its scope. All parts, percentages and ratios used are expressed as percent by weight unless otherwise indicated.

Example 6 Element wt%A wt%B wt%C Wt%D MLAS 5 10 20 30 Intermediate branched C _12-13 alkyl ethoxylate (9 moles EO) 1 1 1 1 C _12-13 Alkyl Ethoxy(1-3) Sodium Sulfate 25 20 10 0 C _12-14 Glucamide 4 4 4 4 Coconut Amine Oxide 4 4 4 4 EO/PO block copolymer Tetronic ^® 704 0.5 0.5 0.5 0.5 ethanol 6 6 6 6 Hydrotrope 5 5 5 5 Magnesium ⁺⁺ salt 3.0 3.0 3.0 3.0 water, thickener and minor ingredients to 100% to 100% to 100% to 100% pH@10% (prepared) 7.5 7.5 7.5 7.5

Example 7 A B C pH10% 9 10 10 MLAS 30 28 25 Amine oxide (C12-14) 5 3 7 betaine 3 0 1 Polyhydroxy fatty acid amides (C14) 0 1.5 0 AE Nonionic Surfactant 2 0 4 diamine 1 5 7 magnesium salt 0.25 0.2 0.5 Citrate (cit2K3) 0.25 0 0 Total (fragrance, dye, water, alcohol, etc.) (to 100%) D. E. f pH10% 9.3 8.5 11 MLAS 10 15 10 paraffin sulfonate 10 0 0 linear alkylbenzene sulfonate 5 15 12 betaine 3 1 0 Polyhydroxy fatty acid amides (C12) 3 0 1 AE Nonionic Surfactant 0 0 20 DTPA 0 0.2 0 Citrate (cit2K3) 0.7 0 0 diamine 1 5 7 magnesium salt 1 0 0 calcium salt 0 0.5 0.2 protease 0.01 0 0.05 Amylase 0 0.05 0.05 Hydrotrope 2 1.5 3 Total (fragrance, dye, water, alcohol, etc.) (to 100%)

Example 8 A B C D. E. f pH10% 8.5 9 9.0 9.0 8.5 8.0 MLAS 10 5 5 15 10 5 Intermediate Branched Alcohol Ethoxy(0.6) Sulfate 0 0 0 10 0 0 Intermediate Branched Alcohol Ethoxy(1) Sulfate 0 25 0 0 0 25 Intermediate Branched Alcohol Ethoxy(1.4) Sulfate 20 0 27 0 20 0 Intermediate Branched Alcohol Ethoxylate (2.2) Sulfate 0 0 0 10 0 0 Amine oxide 5 5 5 3 5 5 Betaine 3 3 0 0 3 3 AE Nonionic Surfactant 2 2 2 2 2 2 diamine 1 2 0 0 0 0 magnesium salt 0.25 0.25 0.01 0.3 0.25 0.2 Hydrotrope 0 0.4 0 0 0 0 Total (fragrance, dye, water, alcohol, etc.) (to 100%) G h I J K L pH10% 9.3 8.5 11 10 9 9.2 Intermediate Branched Alcohol Ethoxy(0.6) Sulfate 10 15 10 25 2 10 paraffin sulfonate 10 0 0 0 0 0 LAS 0 0 0 0 7 10 MLAS 5 15 12 2 7 10 Betaine 3 1 0 2 2 0 Amine oxide 0 0 0 2 5 7 Polyhydroxy fatty acid amides (C12) 3 0 1 2 0 0 AE Nonionic Surfactant 0 0 20 1 0 2 Hydrotrope 0 0 0 0 0 5 diamine 1 5 7 2 2 5 magnesium salt 1 0 0.2 0.3 0 0 calcium salt 0 0.5 0 0 0.1 0.1 protease 0.1 0 0 0.05 0.06 0.1 Amylase 0 0.07 0 0.1 0 0.05 Lipase 0 0 0.025 0 0.05 0.05 DTPA 0 0.3 0 0 0.1 0.1 Citrate (Cit2K3) 0.65 0 0 0.3 0 0 Total (fragrance, dye, water, alcohol, etc.) (to 100%)

Example 9 A B C D. E. pH10% 8.5 9 10 10 10 LAS 0 0 0 15 0 MLAS 30 30 27 15 33 Amine oxide 5 5 5 3 6 betaine 3 3 0 0 0 AE Nonionic Surfactant 2 2 2 2 4 diamine 1 2 4 4 5 potassium citrate 0.25 0.5 0 3.5 2 maleic acid 0.5 1 3 0 2 magnesium salt 0.25 0.25 0.01 0.02 0.2 Hydrotrope 0 0.4 0 0 0 Total (fragrance, dye, water, alcohol, etc.) (to 100%)

Example 10 C ₁₂ E _1.5 SMLAS Nonionic Surfactant Magnesium Salt Hydrotrope MEA/DEA Antibacterial Agent Solvent Water and Secondary Components 10% pH A B C D. E. - 11.20.1580.40.1 - Moderate to 100% 6.67 9.6613.71-0.19-1.070.14-QS to 100% 7.3 9.320.4-0.17-2.3-2.6 qs to 100% 7.3 22.413.40.142.311.44.5 QS to 100% 7.47 2.012.80.20.4----Appropriate amount to 100% 5.23

Example 11 C ₁₂ E _1.5 SC ₁₂ E _2.9 SC ₁₂ E _3.7 SMLAS Nonionic Surfactant Amine Oxide Citrate APG Betaine Magnesium Salt NaCl Soap Hydrotrope MEA/DEA Antimicrobial Sodium Carbonate Silicate Sodium Sulfate Solvent Water and Minor Composition form of ingredients (perfume, etc.) A B C D. E. 4--7--0.1-1-0.1--4.0-QS to 100% liquid ---250.211.02.026.0 - qs up to 100% paste 2.2-17.82.30.011.41.6 qs to 100% gel 6.7--0.60.80.10.06 qs to 100% liquid 14.36.07.10.816.60.34.33.70.35.2 qs to 100% liquid

Example 12 pH of C ₁₂ E _2.9 SC ₁₂ E _1.5 SMLASC ₁₂ E _2.9 MEA Hydrotrope APG Polymerization Thickener Betaine NaCl Solvent Magnesium Salt Spice Water and Minor Components 10% Solution A B C D. 4.04.02.020.61.41.1--5.41.1-0.110.2 Appropriate amount to 100% 4.9 2.02.04.020.61.41.1--5.41.1-0.110.2 Appropriate amount to 100% 4.9 -9.026.72.03.01.50.50.20.3 QS to 100% 7.5 22.01.351.52.5114.50.750.25 QS to 100% 7.5

Example 13

A B C D EAE0.6S 6 10 13 15 20 20 oxide 6.5 6.5 7.5 7.5C10E8 3 3 4.5 4.5MLAS 20 16 13 11 6 dihamine 0.5 1.25 1 0.2 0.4 1.0 0.1 0.2 Foam polymer 0 0.2 0.5 0.2 0.5 Water -soluble long agent 1.5 1.5 1 1 1 Ethanol 8 8 8 8 8 8 8 8 8 8 8 0.5 0 0.2ph 9 9 9 8 10 10

F g H IAE0.6S 6 10 13 20 20 oxide 6.50 6.50 7.20mlas 20 16 13 11 adding foam polymer 0.20 0.20 0.22 water soluble long agent 1.50 3.50 2.0 polyal (mW2700) 1 1C10E8 3.00 3.00 3.00 3.30 two two two two two. Miner 0.50 0 0.55 magnesium salt 0.22 0.3 0.5 0.25 sodium chloride 0.5-0.5-water and secondary component balance The balance of the balance of the amount of waste (CPS@70F) 150 330 650 330PH@10 % 8.0 9.0 9.0

J KAE0.6S 14.8 20mlas 14 8 8.20 7.20 7.20 Citric acid 3.00 ---- Malacinic acid ---- 2.50 Magnesium salt 0.22 0.1 Sodium chloride 0.5-Polyte 0.22 0.22 sodium carne sulfate 3.30 3.30 ethanol 6.50 6.50C10E8 --------- C11E9 3.33 3.33 dihamine 0.55 0.55 spice 0.31 0.31 Water remaining volume viscosity (CPS@70F) 330 330PH@10 % 9.0 9.0

Example 14

A A B B C C D D E

14.2 14.3 6.5 13.1 10MLAS---21.3 14AE1S-16.8 20.5AE0.8S 9.6 -AS 11.4AE3S-10 7APG 4.0 3.8 3.8 amide MEA 2.9 2MEA/DEA-1.5 beet-4.0C10E8 0.3 0.35 0.2 0.3 0.3 0.3 Magnesium Salt and Minor Components qs to qs to qs to qs to qs to

100% 100% 100% 100% 100%

Claims (29)

1. manual dishwashing composition comprises:

A) the alkylaryl sulfonate surfactants system of described composition weight meter 0.1%-99.9%, this system comprise two or more crystallinity-disrupted following formula alkylaryl sulfonate surfactants of described surfactant system weight meter 10%-100%:

(B-Ar-D) _a(M ^Q+) _bWherein D is SO ₃ ^-, M is positively charged ion or cation mixt, and q is described cationic valency, and the number of a and b is through selecting, so that described composition is an electric neutrality; Ar is selected from benzene, toluene and combination thereof; B comprises that at least one contains the summation of uncle hydrocarbyl portion and one or more crystallinity-disrupted parts of 5-20 carbon atom, and wherein said crystallinity-disrupted part is interrupted or branch from described hydrocarbyl portion; And the crystallinity-disrupted degree of wherein said alkylaryl sulfonate surfactants system is not higher than 40 ℃ for its sodium critical solubility temperature by the CST test determination, and wherein said alkylaryl sulfonate surfactants system also has at least one following performance:

Biological degradation percentage ratio by improved SCAS test determination surpasses tetrapropyl benzene sulfonate; With

The weight ratio of non-quaternary carbon atom and quaternary carbon atom is at least 5: 1 among the B; With

B) the conventional manual dishwashing auxiliary agent of described composition weight meter 0.00001%-99.9%;

C) divalent ion that is selected from magnesium, calcium and composition thereof of composition weight meter 0.01%-7%.

2. manual dishwashing composition as claimed in claim 1 also contains the detersive enzyme of described composition weight meter 0.0001%-10%, and wherein said detersive enzyme is selected from proteolytic enzyme, cellulase, lipase, amylase, peroxidase and composition thereof.

3. as each manual dishwashing composition of claim 1-2, wherein Ar is a benzene.

4. as each manual dishwashing composition of claim 1-3, wherein said crystallinity-disrupted alkylaryl sulfonate surfactants comprises and is selected from least two kinds of following isomer:

I) based on substituting group at the ortho position of the attachment position of Ar-, a position-and contraposition-isomer, when Ar for replacing or during unsubstituted benzene;

Ii) based on the positional isomers of substituting group at the attachment position of B; With

Iii) based on the steric isomer of chiral carbon atom among the B.

5. as each manual dishwashing composition of claim 1-4, wherein the alkylaryl sulfonate surfactants system also comprises the unbroken following formula alkylaryl sulfonate surfactants of one or more crystallinity of the described surfactant system weight of 0%-85%:

(L-Ar-D) _a(M ^Q+) _bWherein the definition of D, M, q, a, b, Ar and described crystallinity-disrupted alkylaryl sulfonate surfactants is identical; And L is the straight-chain alkyl part that contains 5-20 carbon atom.

6. as each manual dishwashing composition of claim 1-5, wherein said crystallinity-disrupted alkylaryl sulfonate surfactants comprises two or more homologues, and two or more isomer of at least a homologue.

7. as each manual dishwashing composition of claim 1-6, wherein B not only comprises the odd number carbon chain length but also comprise the even carbon chain length.

8. as each manual dishwashing composition of claim 1-7, wherein uncle's hydrocarbyl portion of B accurately is one to have the straight-chain alkyl part of 7-16 carbon atom, and wherein said crystallinity-disrupted part is selected from:

I) side chain that links to each other with B is selected from: C1-C3 alkyl, C1-C3 alkoxyl group, hydroxyl and composition thereof;

Ii) interrupt the part of B structure, be selected from: ether, sulfone, silicone; With

Iii) and composition thereof.

9. as each manual dishwashing composition of claim 1-8, at least 60% described crystallinity-disrupted alkylaryl sulfonate surfactants of wherein said surfactant system weight is an isomeric forms, and wherein Ar is attached on second of the described straight-chain alkyl part of B or the 3rd carbon atom.

10. as each manual dishwashing composition of claim 1-9, wherein said cleaning combination is liquid, paste, liquid gel, gel, microemulsion, liquid crystals, particle, aggregate or powder.

11. as each manual dishwashing composition of claim 1-10, wherein said cleaning combination auxiliary agent also comprises and is selected from following tensio-active agent: alkylene carbonate, an alkyl Succinamate class, alkyl polysaccharide class, ethoxylated glycerol compounds and composition thereof.

12. as each manual dishwashing composition of claim 1-11, the crystallinity-disrupted degree of wherein said alkylaryl sulfonate surfactants system is not higher than 20 ℃ for its sodium critical solubility temperature by the CST test determination.

13. as each manual dishwashing composition of claim 1-12, the crystallinity-disrupted degree of wherein said alkylaryl sulfonate surfactants system is not higher than 80 ℃ for its calcium critical solubility temperature by the CST test determination.

14. as each manual dishwashing composition of claim 1-13, wherein the described biological degradation percentage ratio by improved SCAS test determination is at least 60%.

15. as each manual dishwashing composition of claim 1-14, wherein said conventional manual dishwashing auxiliary agent is selected from: the tensio-active agent except that (a), washing assistant, detersive enzyme, at least be partially soluble in water or be scattered in the polymkeric substance of water, abrasive, sterilant, tarnish inhibitor, dyestuff, solvent, hydrotropic agent, spices, thickening material, antioxidant, processing aid, suds booster, suds suppressor, suds-stabilizing agent, diamines, carrier, enzyme stabilizers, antioxidant, polysaccharide, buffer reagent, anti-mycotic agent, mould control agent, insect repellent, the protection against corrosion auxiliary agent, sequestrant and composition thereof.

16. as each manual dishwashing composition of claim 1-15, also contain nonionogenic tenside, its amount is that the 0.5%-25% of described detergent composition weight, wherein said nonionogenic tenside are the poly-alkoxyl alcohol with following end-blocking or non-end-blocking form:

-be selected from following hydrophobic grouping: straight chain C ₁₀-C ₁₆Alkyl, medium chain C ₁-C ₃Branching C ₁₀-C ₁₆Alkyl, Guerbet branching C ₁₀-C ₁₆Alkyl and composition thereof; With

-being selected from following hydrophilic radical: 1-15 ethoxylate, 1-15 propoxylated glycerine, 1-15 butoxy thing and composition thereof are end-blocking or non-end-blocking form.

17. as each manual dishwashing composition of claim 1-16, also contain alkyl sulfate surfactant, its amount is the 0.5%-25% of described detergent composition weight, and wherein said alkyl sulfate surfactant has one to be selected from following hydrophobic grouping: straight chain C ₁₀-C ₁₈Alkyl, medium chain C ₁-C ₃Branching C ₁₀-C ₁₈Alkyl, Guerbet branching C ₁₀-C ₁₈Alkyl and composition thereof and be selected from the positively charged ion of Na, K and composition thereof.

18. as each manual dishwashing composition of claim 1-17, also contain alkyl (poly-alkoxyl group) sulfate surfactant, its amount is the 0.5%-25% of described detergent composition weight, and wherein said alkyl (poly-alkoxyl group) sulfate surfactant has:

-be selected from following hydrophobic grouping: straight chain C ₁₀-C ₁₆Alkyl, medium chain C ₁-C ₃Branching C ₁₀-C ₁₆Alkyl, Guerbet branching C ₁₀-C ₁₆Alkyl and composition thereof; With

-being selected from following (poly-alkoxyl group) sulfate radical hydrophilic radical: 1-15 polyethoxye sulfate radical, the poly-propoxy-sulfate radical of 1-15, the poly-butoxy sulfate radical of 1-15,1-15 mix poly-(oxyethyl group/propoxy-/butoxy) sulfate radical and composition thereof, are end-blocking or non-end-blocking form; With

-be selected from the positively charged ion of Na, K and composition thereof.

19. as each manual dishwashing composition of claim 1-18, also contain tensio-active agent, wherein said tensio-active agent is selected from: anion surfactant, nonionogenic tenside, amphoterics, zwitterionics and composition thereof.

20. as each manual dishwashing composition of claim 1-19, also contain organic diamine, wherein said diamines is selected from following formula:

R wherein _2-5Be independently selected from H, methyl, ethyl and ethylene oxide; C _xAnd C _vBe independently selected from methylene radical or branched-chain alkyl, wherein x+v is 3-6; And A is optional to be existed and is selected from through selecting to give electronics or electrophilic part with what diamines pKa was adjusted to required scope.If A exists, x and y must be 2 or bigger so.

21. as each manual dishwashing composition of claim 1-20, also contain organic diamine, wherein said diamines has following formula: Each R wherein ⁶Be independently selected from H, C ₁-C ₄The straight or branched alkyl, have the alkylene oxide group of following formula:

-(R ⁷O) _mR ⁸R wherein ⁷Be C ₂-C ₄Straight or branched alkylidene group and composition thereof; R ⁸Be H, C ₁-C ₄Alkyl and composition thereof; M is 1-10; X is selected from following unit:

I) C ₃-C ₁₀Straight-chain alkyl-sub-, C ₃-C ₁₀Branched alkylidene, C ₃-C ₁₀Ring alkylidene group, C ₃-C ₁₀Prop up the chain link alkylidene group, have the alkyleneoxyalkylene group of following formula:

-(R ⁷O) _mR ⁷-R wherein ⁷As defined above identical with m and this paper;

Ii) C ₃-C ₁₀Straight chain, C ₃-C ₁₀Branching straight chain, C ₃-C ₁₀Ring-type, C ₃-C ₁₀Branching ring alkylidene group, C ₆-C ₁₀Arylidene, wherein said unit comprise one or more pKa that make described diamines greater than 8 give electronic section or electrophilic part; With

Iii) (i) and mixture (ii),

As long as the pKa of described diamines is at least 8.

22. as each manual dishwashing composition of claim 20-21, wherein said diamines is selected from: dimethyl aminopropyl amine, 1,6-hexanediamine, 1,3-propylene diamine, 2-methyl isophthalic acid, 5-pentamethylene diamine, 1,3-pentamethylene diamine, 1,3-diaminobutane, 1,2-two (2-amino ethoxy) ethane, isophorone diamine, 1,3-two (methylamine)-hexanaphthene and composition thereof.

23. as each manual dishwashing composition of claim 1-22; also contain anion surfactant, wherein said anion surfactant is selected from: alkyl-sulphate, alkyl alkoxy sulfate, linear alkylbenzene sulfonate, α ethylenic sulfonate, paraffin sulfonate, methyl ester sulfonate, alkylsulfonate, alkyl alkoxylated suifate, sarcosinate, taurate, alkyl alkoxy carboxylate salt and composition thereof.

24. as each manual dishwashing composition of claim 1-23, also contain nonionogenic tenside, wherein said nonionogenic tenside is selected from: alkylethoxylate, polyhydroxy fatty acid amide, alkyl poly glucoside, alkylethoxylate and composition thereof.

25. as each manual dishwashing composition of claim 1-24, also contain amphoterics, wherein said amphoterics is selected from: trimethyl-glycine, sultaine, amine oxide and composition thereof.

26. as each manual dishwashing composition of claim 1-25, also contain the polymeric suds-stabilizing agent, it is selected from:

I) have the homopolymer of (N, N-dialkyl amido) alkyl acrylate of following formula:

Respectively do for oneself H, C of each R wherein ₁-C ₈Alkyl, and composition thereof, R ¹Be H, C ₁-C ₆Alkyl, and composition thereof, n is 2-6; With

The ii) multipolymer of (i) and following formula

R wherein ¹Be H, C ₁-C ₆Alkyl, and composition thereof, condition is to be 2 with the ratio of (i) (ii): 1-1: 2; And the molecular weight of wherein said foam of polymers stablizer is 1,000-2,000,000 dalton.

27. the method for a wash dining set, described method comprise that each the aqueous solution of composition of dirty tableware and claim 1-26 that needs are cleaned contacts.

28., also comprise the step of water with described composition dilution as the method for claim 27.

29., also comprise described composition is coated directly onto step on sponge or the towel as the method for claim 27.