CZ20001222A3 - Aqueous, liquid detergent preparation intended for light working conditions - Google Patents

Abstract

Aqueous liquid detergent for lightweight use working conditions, is useful for washing soiled dishes in very low temperature cold water. This means it contains surfactants, production promoters foams / stabilizers, polymeric surfactant, enzymes, organic low molecular weight diamine and aqueous liquid carrier. Detergent compositions exhibit excellent phase performance low temperature stability and can be very well mixed with water at low temperatures and / or mix with very hard water

Description

Technical field

The present invention relates to liquid or gel dishwashing detergent compositions suitable for manual dishwashing. The liquid detergent compositions comprise a surfactant system which comprises mid-chain branched surfactants. The compositions may additionally contain, from time to time, other surfactants, suds enhancers, viscosity control agents, and other ingredients that combine to provide dishwashing detergent products that are more beneficial to the consumer in terms of both food stains and foaming characteristics.

BACKGROUND OF THE INVENTION

Liquid (LDL) or gel detergent compositions intended for light duty conditions that are useful for manual dishwashing are well known in the art. These products are generally formulated to work in different ways and to provide different aesthetic properties and characteristics. Liquid or gel dishwashing products must be formulated primarily with such types and amounts of surfactants and other cleaning agents to provide acceptable dissolution and removal of food stains, particularly greasy stains, from the dishwashing composition or aqueous solutions formed therefrom. from these funds, cleaned.

Heavily soiled dishes can cause special problems during manual washing. Dishes such as plates, bowls, pots, pans, porcelain and the like can be very dirty in the sense that relatively large amounts of food and residue stains can be detected on the dishes when the soiled dishes are washed by hand. The dishes may also be very dirty in the sense that food stain residues are adhered or adhered to the surfaces of the dishwasher. This may be due to the type of food stain present or it may depend on the nature of the surfaces of the dishes. Tightly adhering residues of food stains may also be the result of the type of cooking operations to which soiled dishes have been subjected. A suitable combination of surfactants must be used to clean such dishes.

• ·

Further, to be suitable for dishwashing, LDL or gel cleaning compositions must also have other desirable properties that enhance the aesthetics or impression related to the efficacy of manual dishwashing that the consumer obtains. Useful liquid or gel formulations intended for hand washing should therefore also contain substances which enhance the foaming characteristics of the solutions of these products. The foaming behavior includes both the formation of a suitable amount of foam in the water initially and the formation of foam during washing.

Liquids or gels intended for manual dishwashing should also contain substances that increase the phase stability of the product at low temperatures. Low phase stability can lead to unacceptable rheological and aesthetic properties and poor performance. These low temperatures may occur in warehouses of goods, in a consumer's garage, in a consumer's car, during street sales, on a kitchen window sill, etc. Liquids and gels intended for manual dishwashing should also contain substances that increase dissolution in water or the rate of mixing of the product with water. Liquids and gels intended for manual dishwashing should contain substances that increase the resistance of the system to hardness, in particular to avoid precipitation of calcium salts of anionic surfactants. It is known that the precipitation of calcium salts of anionic surfactants causes suppression of foam formation and skin irritation.

On the basis of the above, it is clear that liquids and gels intended for manual dishwashing need to be formulated so as to provide an acceptable and desirable balance between cleaning performance and product aesthetics. It is therefore an object of the present invention to provide liquid or gel dishwashing compositions intended for light working conditions which are particularly effective in removing food stains from dirty dishes when used in the context of manual dishwashing.

Further, it has been found that mid-chain branched surfactants provide significantly higher hardness resistance, significantly higher end product stability at low temperatures, and significantly higher product-water mixing rates.

It is a further object of the invention to provide compositions whose rheological characteristics are desirable for use in both direct application to dishes and aqueous solutions.

It is a further object of the present invention to provide such compositions so as to provide suitable and desirable foaming behavior.

It has been found that certain selected surfactant systems can be prepared which include the mid-chain branched surfactants as defined below, as well as foam enhancers, viscosity control agents, and other agents. Systems • ··· ··· · · · · · _a ··· ····· · · · · · ···· ·· ·· ·· · · · · • · · ···· Ready to provide dishwashing detergents that meet the previous objectives. The individual components of these selected additive combinations are described below.

SUMMARY OF THE INVENTION

The present invention relates to aqueous liquid or gel formulations intended for light working conditions which, when used to clean heavily soiled dishes, desirably remove stains in particular and have desirable foaming characteristics. These compositions contain up to 70 wt. % of a surfactant system comprising a mixture of branched surfactants comprising mid-chain branched compounds and linear surfactants.

The surfactant system comprises at least about 10 wt. %, more preferably at least about 20 wt. %, even more preferably at least about 30 wt. %, most preferably at least about 50 wt. % of the branched surfactant mixture, wherein the branched surfactant mixture comprises mid-chain branched surfactants and linear surfactants. Said linear compounds contain less than 25 wt. %, more preferably less than about 15 wt. %, even more preferably less than about 10 wt. % and most preferably less than about 5 wt. % of the mixture of branched surfactants and the compound branched in the middle of the chain have the general formula:

A ^b -B (1) wherein A ^b is a hydrophobic alkyl group having a total carbon number of C 9 to C 18, more preferably from about C 10 to about C 15, branched in the middle of the chain having: (1) the longest linear carbon chain attached to the -B group in from 8 to 17 carbon atoms; (2) one or more C 1 to C 3 alkyl groups branching from this longest linear carbon chain; (3) at least one of the branching alkyl groups attached directly to the carbon of the longest linear carbon chain at a position ranging from position 3 of the carbon, calculated from carbon # 1, which is attached to the group -B, to position ω-2; which is terminal carbon minus 2 carbons; and (4) the surfactant-containing composition has an average total number of carbon atoms in group A ^b in the above general formula (1) in the range of more than 12 to about 14.5.

B is a hydrophilic group selected from the group consisting of OSO3M, (EO / PO) _m OSC> 3M, (EO / PO) _m OH and mixtures thereof. EOZPOs are alkoxy groups selected from the group consisting of ethoxy, propoxy groups and mixtures thereof and m is at least about 0.01 to about 30. The average total number of carbon atoms in the A ^b group in the mixture of branched surfactants defined above, it should range from more than about 12 to about 14.5, more preferably from more than about to about 14, and most preferably from more than about 12 to about 13.5.

The surfactant system of the liquid detergent compositions of the present invention may occasionally also contain other surfactants such as anionic and nonionic. When an anionic surfactant component is present, it essentially comprises alkyl ether sulfates containing from about 9 to 18 carbon atoms in the alkyl group. These alkyl ether sulfates also contain from 1 to 12 moles of ethylene oxide per molecule. If a nonionic surfactant component is present, it essentially comprises C8-C18 polyhydroxy fatty acid amides. In the non-ionic surfactant components, these polyhydroxy fatty acid amides may be combined with about 0.2% to about 2% of a composition comprising a non-ionic surfactant adjuvant. The surfactant is selected from C 5 to C 18 alcohol ethoxylates having from about 1 to 30 moles of ethylene oxide, surfactants based on ethylene oxide-propylene oxide block copolymers and combinations of these nonionic surfactants.

The compositions of the present invention may also occasionally comprise a foam forming / stabilizing agent selected from betaine surfactants, fatty acid alkanolamides, amine oxide semipolar nonionic surfactants, and C8 to C22 alkyl polyglycosides. Combinations of these foam-enhancing agents / stabilizers may also be employed.

The compositions of the present invention may also occasionally contain buffering agents selected from organic diamines and alkanolamines. Combinations of these diamines and alkanolamines may also be used.

The foregoing main ingredients, as well as a number of other adjunct ingredients, may be combined appropriately to form a liquid or gel dishwashing detergent composition for light working conditions of the present invention.

The liquid or gel light dishwashing detergent compositions of the present invention comprise a surfactant system comprising certain mid-chain branched alkyl surfactants, certain non-ionic surfactants, and an aqueous liquid carrier. A variety of occasional ingredients may also be added to improve the effect and theological and / or aesthetic characteristics of the compositions herein.

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The main and occasional components of the present liquid or gel dishwashing detergents intended for light working conditions are described in more detail along with the preparation and use of the composition below. When describing the compositions of the present invention, it should be noted that the term "light dishwashing detergent composition" as used herein refers to those compositions which are used for manual (i.e., manual) dishwashing. These compositions generally form a lot of soaps or very foaming. When describing the compositions of the present invention, it should also be noted that, unless otherwise specified, all concentrations and ratios are by weight.

Mixture of branched surfactants

The surfactant system contained in the present liquid detergent compositions comprises at least about 10 wt. %, more preferably at least about 20 wt. %, even more preferably at least about 30 wt.%, most preferably at least about 50 wt. % of the branched surfactant mixture, wherein the branched surfactant mixture comprises mid-chain branched surfactants and the linear surfactants, said linear compounds, contain less than 25 wt. %, more preferably less than about 15 wt. %, even more preferably less than about 10 wt. % and most preferably less than about 5 wt. % of the branched surfactant mixture. Said compounds branched in the middle of the chain have the general formula:

A ^b -B (1) where:

A ^b is a hydrophobic alkyl group having a total number of carbons of C 9 to C 18, more preferably from about C 10 to about C 15, branched in the middle of the chain having: (1) the longest linear carbon chain attached to the -B group of 8 to 17 carbon atoms; (2) one or more C 1 to C 3 alkyl groups branching from this longest linear carbon chain; (3) at least one of the branching alkyl groups attached directly to the carbon of the longest linear carbon chain at a position ranging from position 3 of the carbon, calculated from carbon # 1, which is attached to the group -B, to position ω-2; which is terminal carbon minus 2 carbons; and (4) the surfactant-containing composition has an average total number of carbon atoms in group A ^b in the above general formula (1) in the range of more than 12 to about 14.5. fefe fefe fefe fefe fefe fefe fefe fefe fefe

B is a hydrophilic group selected from the group consisting of OSO ₃ M, (EO / PO) _m OSO ₃ M, (EO / PO) _m OH and mixtures thereof, EO / PO are alkoxy groups selected from the group consisting of ethoxy the propoxy groups and mixtures thereof and m is at least about 0.01 to about 30. The average total number of carbon atoms in the A ^b group in the branched surfactant mixture as defined above should be in the range of more than about 12 to about 14.5, more preferably from greater than about 12 to about 14, and most preferably from greater than about 12 to about 13.5. As used herein, the term "total" number of carbon atoms means the total number of carbon atoms in the longest chain, ie. in the backbone of the molecule, plus the number of carbon atoms in all short chains; in branching chains.

A ^{b the} mid-chain branched surfactant group of the present invention is more preferably a branched alkyl group having the general formula:

RR ¹ R ²

I I I

CH ₃ CH ₂ (CH ₂ ) _w CH (CH ₂ ) _x CH (CH ₂ ) _y CH (CH ₂ ) _z CH ₂ where the total number of carbon atoms in the branched alkyl group including R, R ¹ and R ² branching R 10, R ¹ and R ² are each independently selected from hydrogen and C 1 to C ₃ alkyl, more preferably methyl, provided that R, R ¹ and R ² are not all hydrogen. Further, when z is 0, at least R or R ¹ is not hydrogen. Furthermore, w is an integer from 0 to 10; x is an integer from 0 to 10; y is an integer from 0 to 10; z is an integer from 0 to 10 and w + x + y + z is from 3 to 10.

In another more preferred embodiment of the present invention, A ^{b is} a mid-chain branched surfactant group, a branched alkyl group having a general formula selected from the group consisting of:

CH ₃

I (3)

CH ₃ (CH ₂ ) _and CH (CH ₂ ) _b CH ₂ CH ₃ ch ₃

I I (3)

CH ₃ (CH ₂ ) d CH (CH ₂ ) _B CHCH ₂ or mixtures thereof.

• · ·

0000 0 0

00 00 00 0 0 0 0 0

9990 0 00 10

090 00 0

9 0 0 9 98 9

0 · 0 0 99 90 99 99

In formulas, a, b, d and e are integers, a + b is from 6 to 13, d + e is from 4 to 11. Furthermore, if a + b = 6, then a is an integer from 2 to 5 and b is an integer from 1 to 4 if a + b-7, then a is an integer from 2 to 6 and b is an integer from 1 to 5 if a + b = 8, then a is an integer from 2 to 7 and ab is an integer from 1 to 6 if a + b = 9, then a is an integer from 2 to 8 and b is an integer from 1 to 7 if a + b = 10, then a is an integer from 2 to 9 and b is an integer from 1 to 8 if a + b = 11, then a is an integer from 2 to 10 and b is an integer from 1 to 9 if a + b = 12, then a is an integer from 2 to 11 and b is an integer from 1 to 10 if a + b = 13, then a is an integer from 2 to 12 and b is an integer from 1 to 11 if d + e = 4, then d is an integer from 2 to 3 and e is an integer from 1 to 2 if d + e = 5, then d is an integer from 2 to 4 and e is an integer from 1 to 3 if d + e = 6, then d is an integer from 2 to 5 and e is an integer from 1 to 4 if d + e = 7, then d is an integer from 2 to 6 and e is an integer from 1 to 5 if d + e = 8, then d is an integer from 2 to 7 and e is an integer from 1 to 6 if d + e = 9 , then d is an integer from 2 to 8 and e is an integer from 1 to 7 if d + e = 10, then d is an integer from 2 to 9 and e is an integer from 1 to 8 if d + e = 11, then d is an integer from 2 to 10 and e is an integer from 1 to 9.

Mid-chain branched primary alkyl sulfate surfactants

Compositions of the present invention comprising a mid-chain branched surfactant may comprise one or more mid-chain branched primary alkyl sulfate surfactants having the general formula

RR ¹ R ²

III (5)

CH ₃ CH ₂ (CH ₂ ) _w CH (CH ₂ ) _x CH (CH ₂ ) _in CH (CH ₂ ) _z ch ₂ oso ₃ m

More specifically, the branched surfactant mixtures of the present invention comprise molecules having a backbone of the primary alkyl sulfate (i.e., the longest linear carbon chain that includes the sulfated carbon atom) as the backbone. These alkyl chains contain from about 9 to about 18 carbon atoms. The molecules further comprise primary branched alkyl groups or groups having at least about 1 but not more than 3 carbon atoms. Furthermore, the surfactant mixture has an average total number of branched carbon atoms

4 44 4 «4» ·· • 4 · 4 4 4 4 4 4 4

Δ 4 4 4 4 4 44 * 4 44 · δ 4 4444 44 44 4 * 4 44 ·

4,444,444; 44,444,444,444 primary alkyl groups less than about 14.5, more preferably in the range of about 12 to about 14.5. Thus, the compositions of the present invention comprise at least one primary branched alkyl sulphate surfactant having a longest linear carbon chain of not less than 8 carbon atoms or longer than 17 carbon atoms and an average total number of carbon atoms in the branched primary alkyl chains of more than 12 to about 14.5, more preferably more than about 12 to about 14, and most preferably more than about 12 to about 13.5.

For example, a primary alkyl sulfate surfactant with a total number of C 14 carbons in which 11 carbon atoms form the backbone must have 1, 2 or 3 branching units (i.e., R, R ¹ and / or R ² ), the total number of carbon atoms in the molecule is 14. In this case, the requirement 14 of total carbons can also be fulfilled, for example, via one propyl branching unit or three methyl branching units.

R ¹ , R ¹ and R ² are each independently selected from hydrogen and C 1 -C ₃ alkyl (more preferably hydrogen or C 1 -C ₂ alkyl, even more preferably hydrogen or methyl and most preferably methyl) provided that R, R ¹ and R 2 ² are not all hydrogen. Further, if z is 0, then at least R or R ¹ is not hydrogen.

Although for the purposes of the surfactant-containing compositions of the present invention, the above formula (5) does not include those molecules in which R, R ¹ and R ² units are all hydrogen (i.e., linear unbranched primary alkyl sulfates), it should be understood that the compositions of the present invention may further comprise a certain amount of linear unbranched primary alkyl sulfate. The linear unbranched primary alkyl sulphate surfactant may be present either as a result of a process used to produce a mixture of surfactants having one or more of the branched primary alkyl sulphates needed, or to form a detergent composition in the final product some amount of linear unbranched primary alkyl sulfate.

Similarly, it should further be appreciated that the mid-chain branched unsulfated alcohols may contain some of the compositions of the present invention. These materials may be present either due to incomplete sulfation of the alcohol used to prepare the alkyl sulfate surfactant or the alcohols together with the mid-chain branched alkyl sulfate surfactant of the present invention may be separately added to the detergent compositions of the present invention.

Toto toto · · toto toto to to * * toto toto * * * * to e to to to e to to e e e to e *

Depending on the method of synthesis, M is hydrogen or a salt forming a cation. Examples of cation forming salts are lithium, sodium, potassium, calcium, magnesium and quaternary alkylamines having the general formula:

R ³

R ⁶ -N ⁺ -R ⁴ (7)

R ⁵ wherein R ³ , R ⁴ , R ⁵ and R ⁶ are independently hydrogen, C 1 to C 22 alkylene, C 4 to C 22 branched alkylene, C 1 to alkanol, C 1 to C ₂₂ alkenylene, C 4 to C 22 branched alkenylene and mixtures thereof. More preferred cations are ammonium (R ³ , R ⁴ , R ⁵ and R ⁶ is hydrogen), sodium, potassium, mono-, di- and trialkanolammonium cations and mixtures thereof. The monoalkanolammonium compounds of the present invention have R ³ equal to C 1 -C 6 alkanol, R ⁴ , R ⁵ and R ⁶ equal to hydrogen; the dialkanolammonium compounds of the present invention have R ³ and R ⁴ equal to C 1 -C 6 alkanol, R ⁵ and R ⁶ equal to hydrogen; The trialkanolammonium compounds of the present invention have R ³ , R ⁴ and R ⁵ equal to C 1 -C 6 alkanol and R ⁶ equal to hydrogen. More preferred alkanolammonium salts of the present invention are the mono-, di- and tri-quaternary ammonium compounds having the general formulas:

H ₃ N ⁺ CH ₂ CH ₂ OH, H ₂ N ⁺ (CH ₂ CH ₂ OH) ₂ , H N / CH ₂ CH ₂ OkOa (7)

M is preferably sodium, potassium and the _C2 alkanol ammonium salts listed above; Most preferably, M is sodium.

Further, with respect to the above general formula (5), w is an integer from 0 to 10; x is an integer from 0 to 10; y is an integer from 0 to 10; z is an integer from 0 to 10 and w + x + y + z is an integer from 2 to 11.

The surfactant compositions of the present invention more preferably have at least about 10 wt. %, even more preferably at least about 20 wt. %, even more preferably at least about 30 wt. % and most preferably at least about 50 wt. % of a mixture of one or more branched primary alkyl sulfates having the general formula

R ¹ R ²

CH ₃ CH ₂ (CH 2) _x CH (CH 2) _y CH (CH ₂ ) _z CH ₂ OSO ₃ M (8) where the total number of carbon atoms including the branching ranges from 10 to 16 and where the average total number of carbon atoms in the branched primary alkyl groups having the above general formula (8) ranges from more than 12 to about 14. R ¹ and R ² are independently hydrogen or C 1 -C ₃ alkyl. M is a water-soluble cation, x is from 0 to 10; y is from 0 to 10; z is from 0 to 10 and x + y + z is from 4 to 10. Furthermore, R and R are not both hydrogen. Even more preferred are compositions having at least 5% of a composition comprising one or more of the mid-chain branched primary alkyl sulfates wherein x + y is 6 and z is at least 1.

More preferably, the surfactant compositions comprise at least 5% of a mid-chain branched primary alkyl sulphate having R ¹ and R ² independently of hydrogen or methyl, provided that R ¹ and R ² are not both hydrogen. It is further assumed that x + y is equal to 5, 6 or 7 and z is at least 1. More preferred surfactant mixtures comprise at least 20% of the mid-chain branched primary alkyl sulfates having R ¹ and R ² independently hydrogen or methyl, provided that: that R ¹ and R ² are not both hydrogen, x + y is 5, 6 or 7 and z is at least 1.

The mid-chain branched primary alkyl sulphate surfactants which are more preferred for use in the detergent compositions herein are selected from the group of compounds having the general formula:

CH ₃

I (9)

CH ₃ (CH ₂ ) _and CH (CH ₂ ) b CH ₂ OSO ₃ M

CH ₃ CH ₃

I I (9)

CH ₃ (CH ₂ ) _d CH (CH ₂ ) e CHCH ₂ OSO ₃ M or mixtures thereof.

In formulas, a, b, d and e are integers, a + b is from 6 to 13, d + e is from 4 to 11. Furthermore, if a + b = 6, then a is an integer from 2 to 5 and b is an integer from 1 to 4 if a + b = 7, then a is an integer from 2 to 6 and b is an integer from 1 to 5 if a + b = 8, then a is an integer from 2 to 7 and ab is an integer from 1 to 6 if a + b = 9, then a is an integer from 2 to 8 and b is an integer from 1 to 7 if a + b = 10, then a is an integer from 2 to 9 and b is an integer from 1 to 8 if a + b = 11, then a is an integer from 2 to 10 and b is an integer from 1 to 9 if a + b = 12, then a is an integer from 2 to 11 and b is an integer from 1 to 10 if a + b = 13, then a is an integer from 2 to 12 and b is an integer from 1 to 11

if d + e = 4, then d is an integer from 2 to 3 and e is an integer from 1 to 2 if d + e = 5, then d is an integer from 2 to 4 and e is an integer from 1 to 3 if d + e = 6, then d is an integer from 2 to 5 and e is an integer from 1 to 4 if ά + & ~ Ί, then d is an integer from 2 to 6 and e is an integer from 1 to 5 if d + e = 8, then d is an integer from 2 to 7 and e is an integer from 1 to 6 if d + e = 9, then d is an integer from 2 to 8 and e is an integer from 1 to 7 if d + e = 10 , then d is an integer from 2 to 9 and e is an integer from 1 to 8 if d + e = l 1, then d is an integer from 2 to 10 and e is an integer from 1 to 9

The average total number of carbon atoms in the branched primary alkyl groups having the aforementioned general formulas (9, 10) ranges from more than 12 to about 14.5.

Particularly preferred are those mid-chain branched surfactants which contain a mixture of compounds having formulas (9) and (10) and wherein the molar ratio of compounds of formula (9) to compounds of formula (10) is greater than 4. : 1, more preferably greater than 9: 1 and most preferably greater than 20: 1.

Further, a surfactant-containing composition of the present invention may comprise a mixture of linear and branched surfactants, wherein the branched primary alkyl sulfates have the general formula:

RR ¹ R ² and II (11)

CH ₃ CH ₂ (CH ₂ ) _w CH (CH ₂ ) _x CH (CH ₂ ) _y CH (CH ₂ ) _z CH ₂ OSO ₃ M where the total number of carbon atoms in the molecule including the branching is from 10 to 17 and the average total The carbon atoms in the branched primary alkyl groups having the above general formula (11) are in the range of more than 12 to about 14.5. R, R and R are independently selected from hydrogen and C 1 to C 3 alkyl, provided that R, R ¹ and R ² are not all hydrogen. M is a water-soluble cation, w is an integer from 0 to 10; x is an integer from 0 to 10; y is an integer from 0 to 10; z is an integer from 0 to 10 and w + x + y + z is from 3 to 10. Provided that when R is C 1 to C 3 alkyl, then the ratio of surfactants having z equal to 0 to surfactants having at least 1 or greater is at least about 1: 1, more preferably at least about 1: 5, even more preferably at least about 1:10, and most preferably at least about 1:20. Also more preferred are surfactant-containing compositions wherein R ² is C 1 to C 3 alkyl, containing less than about 20%, more preferably less than 10%, even more preferably less than 5%, most preferably less than 1% of branched primary alkyl sulfates having the above general formula (11) in which z is 0.

• ·

More preferred primary alkyl sulfates branched with one methyl group are selected from the group consisting of: 3-methyldodecanolsulfate, 4-methyldodecanolsulfate, 5-methyldodecanolsulfate, 6-methyldodecanolsulfate, 7-methyldodecanolsulfate, 8-methyldodecanolsulfate,

9-methyltrodecanol sulphate, 10-methyltrodecanol sulphate, 3-methyltridecanol sulphate, 4-methyltridecanol sulphate, 5-methyltridecanol sulphate, 6-methyltridecanol sulphate, 7-methyltridecanol sulphate, 8-methyltridecanol sulphate, methyltridecane sulphate, 9-methyltridecane sulphate.

The following branched primary alkyl sulfates containing 13 carbon atoms and having one branching unit are exemplary of the more preferred branched surfactants useful for the compositions of the present invention:

5-methyldodecyl sulfate having the general formula:

(12)

6-methyldodecyl sulfate having the general formula:

(13)

7-methyldodecyl sulfate having the general formula:

(15) (15)

9-methyldodecyl sulfate having the general formula:

ch ₃

10-methyldodecyl sulfate having the general formula:

CH.

OSO ₃ M

(17) wherein M is more preferably sodium.

More preferred primary alkyl sulfates branched with two methyl groups are selected from the group consisting of: 2,3-dimethylundecanolsulfate, 2,4-dimethylundecanolsulfate, 2,5-dimethylundecanolsulfate, 2,6-dimethylundecanolsulfate, 2,7-dimethylundecanolsulfate; , 8-dimethyldodecanol sulfate, 2,9-dimethylundecanol sulfate, 2,3-dimethyldodecanol sulfate, 2,4-dimethyldodecanol sulfate, 2,5-dimethyldodecanol sulfate, 2,6-dimethyldodecanol sulfate, 2,7-dimethyldodecanol sulfate, 2,7, 8-dimethyldodecanol sulfate, 2,9-dimethyldodecanol sulfate, 2,10-dimethyldodecanol sulfate and mixtures thereof.

The following branched primary alkyl sulfates containing 14 carbon atoms and having two branching units exemplify the more preferred branched surfactants of the present invention:

(18) 9

9 9 9 9 9

9 9 9999 9 99 · ···· 99 99 999 9 9 9

9 9 9 9 9

99 99 · 99 99

2,6-Dimethyldodecyl sulphate having the general formula:

(19)

2,7-Dimethyldodecylsulfate having the general formula:

2,8-dimethyidodecyl sulphate having the general formula:

Italy (21)

2,9-Dimethyldodecylsulfate having the general formula:

Italy (22)

2,10-Dimethyldodecylsulfate having the general formula:

(23) wherein M is more preferably sodium.

Fefe fe

Mid-chain branched primary alkylalkoxy sulphate surfactants

The mid-chain branched surfactants of the present invention may comprise one or more (more preferably a mixture of two or more) mid-chain branched primary alkyl alkoxylated sulfates having the general formula:

RR ¹ R ²

I I I (23)

CH ₃ CH ₂ (CH ₂ ) _w CH (CH ₂ ) _x CH (CH ₂ ) _y CH (CH ₂ ) ₂ CH ₂ (EO / PO), _n OSO ₃ M

The surfactant compositions of the present invention comprise molecules having a backbone of the primary alkoxylated sulfate backbone (i.e., the longest linear carbon chain that includes the alkoxy-sulfated carbon atom) as the backbone. These alkyl chains contain from about 9 to about 18 carbon atoms. The molecules further comprise a branched primary alkyl group or groups having at least about 1 but not more than 3 carbon atoms. The surfactant composition further has an average total number of carbon atoms in the branched primary alkyl groups of less than about 14.5, more preferably in the range of about 12 to about 14.5. Thus, the compositions of the present invention comprise at least one branched primary alkyl sulphate surfactant compound having a longest linear carbon chain of not less than 9 carbon atoms or no more than 17 carbon atoms and an average total number of carbon atoms for branched primary alkyl chains in the range of more than about 12 to about 14.5, more preferably from more than 12 to about 14, and most preferably from more than about 12 to about 13.5.

For example, a primary alkyl sulfate surfactant with a total number of Ch carbons, where 11 carbon atoms form the backbone of the chain, must have 1, 2 or 3 branching units (i.e., R, R ¹ and / or R ² ), the total number of carbon atoms in the molecule is 14. In this example, the requirement of a total of 14 carbon atoms can be met by, for example, one propyl branching unit or 3 methyl branching units.

R, R ¹ and R ² are each independently selected from hydrogen and C 1 -C ₃ alkyl (more preferably hydrogen or C 1 -C ₂ alkyl, even more preferably hydrogen or methyl and most preferably methyl) provided that R, R and R are not all hydrogen. Further, if z is 0, then at least R or R is not hydrogen.

Although for the purposes of the present invention, the surfactant components of the general formula above do not include such molecules where the R, R ¹ and R ² units are all hydrogen (i.e., linear unbranched primary alkoxylated sulfates), it should be understood The compositions of the present invention may further comprise an amount of a linear, unbranched primary alkoxylated sulfate. The linear unbranched primary alkoxylated sulphate surfactant may further be present either as a result of a process used to produce a mixture of surfactants with the necessary mid-chain branched primary alkoxylated sulphates of the present invention or for formulating detergent compositions. a certain amount of linear unbranched primary alkoxylated sulfate may be incorporated into the final product.

It should also be appreciated that some of the mid-chain branched alkyl sulfate may be present in the compositions. This is mostly the result of the sulfation of the nonalkoxylated alcohol which remains after incomplete alkoxylation of the mid-chain branched alcohol used to prepare the alkoxylated sulfate useful herein. However, it should also be understood that the compositions of the present invention also take into account the separate addition of these mid-chain branched alkyl sulfates.

Similarly, it should further be appreciated that the mid-chain branched unsulfated alcohol (including polyoxyalkylene alcohols) may contain some amount of the compositions of the present invention comprising alkoxylated sulfate. These may be present either as a result of incomplete sulfation of the alcohol (alkoxylated or nonalkoxylated) used to prepare the alkoxylated sulfate surfactant, or together with the mid-chain branched alkoxylated sulfate surfactant of the present invention separately added to the detergent compositions of the present invention.

M is the same as previously described.

Further, with respect to the above general formula (24), w is an integer from 0 to 10; x is an integer from 0 to 10; y is an integer from 0 to 10; z is an integer from 0 to 10 and w + x + y + z is an integer from 2 to 11.

EO / PO are alkoxy groups selected more preferably from ethoxy, propoxy and mixed ethoxy / propoxy groups wherein m is at least about 0.01, more preferably in the range of about 0.1 to about 30, even more preferably from about 0.5 to about The group (EO / PO) _m may be either an arrangement with an average degree of alkoxylation (e.g. ethoxylation and / or propoxylation) corresponding to m, or it may be a simple specific chain with alkoxylation (e.g. ethoxylation) and / or propoxylation), which is equal to the number of units corresponding to m.

9 9 9 9 9 9 9 9 9 9 9 9 9

9 9 9

99

Preferred surfactant mixtures of the present invention have at least about 10 wt. %, even more preferably at least about 20 wt. %, even more preferably at least about 30 wt.

% and most preferably at least about 50 wt. % of a mixture of one or more primary alkyl alkoxylated sulphates, branched mid-chain, of the general formula

R ¹ R ² i I

CH ₃ CH ₂ (CH ₂ ) _x CH (CH ₂ ) _y CH (CH ₂ ) _z CH ₂ (EO / PO) _m OSO ₃ M where the total number of carbon atoms including the branching is from 10 to 16a the branched primary alkyl groups having the above formula (25) are in the range of more than 12 to about 14. R ¹ and R ² are each independently hydrogen or C 1 to C ₃ alkyl; M is a water-soluble cation; x is from 0 to 10; y is from 0 to 10; z is from 0 to 10 and x + y + z is from 4 to 10. Further, R ¹ and R ² are not both hydrogen and EOZPO are alkoxy groups selected from ethoxy, propoxy and mixed ethoxy / propoxy groups. In the formula, m is at least about 0.01, more preferably in the range of about 0.1 to about 30, even more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5. Even more preferred are compositions having at least % of a composition comprising one or more primary alkylalkoxylated mid-chain branched sulfates wherein x + y is up to 6 and z is at least 1.

The surfactant compositions preferably comprise at least 5% of a mid-chain branched primary alkyl sulfate having R ¹ and R ² independently of hydrogen or methyl, provided that R ¹ and R ² are not both hydrogen. Further, x + y is up to 5, 6 or 7 and z is at least 1. More preferred surfactant mixtures comprise at least 20% of a mid-chain branched primary alkyl sulfate having R ¹ and R ² independently hydrogen or methyl, provided that: R ¹ and R ² are not both hydrogen, x + y is 5, 6 or 7 and z is at least 1.

More preferred mixtures of the primary chain branched alkylalkoxylated sulfates and linear alkylalkoxylated sulfate surfactants comprise at least about 5 wt. % of one or more mid-chain branched alkyl alkoxylated sulphates having the general formula:

ch ₃

I (26)

CH ₃ (CH ₂ ) _and CH (CH ₂ ) b CH ₂ (EOZPO) _{m and} OSO ₃ M

CH ₃ ch ₃ ί I (27)

CH ₃ (CH ₂ ) _d CH (CH ₂ ) _e CHCH ₂ (EOZPO) _m OSO ₃ M

4 4

4444 4 4 44 44 44

4 4 4 4 4

443 4 44 4

444 44 4 • 4 4 4 4 4 4 ·· · 4 44 44 or mixtures thereof. In formulas, a, b, d and e are integers, a + b is from 6 to 13, d + e is from 4 to 11. Furthermore, if a + b = 6, then a is an integer from 2 to 5 and b is an integer from 1 to 4 if a + b = 7, then a is an integer from 2 to 6 and b is an integer from 1 to 5 if a + b = 8, then a is an integer from 2 to 7 and ab is an integer from 1 to 6 if a + b = 9, then a is an integer from 2 to 8 and b is an integer from 1 to 7 if a + b-10, then a is an integer from 2 to 9 and b is an integer from 1 to 8 if a + b = 11, then a is an integer from 2 to 10 and b is an integer from 1 to 9 if a + b = 12, then a is an integer from 2 to 11 and b is an integer from 1 to 10 if a + b = 13, then a is an integer from 2 to 12 and b is an integer from 1 to 11 if d + e = 4, then d is an integer from 2 to 3 and is an integer from 1 to 2 if d + e = 5, then d is an integer from 2 to 4 and is an integer from 1 to 3 if d + e = 6, then d is an integer from 2 to 5 and is an integer from 1 to 4 if d + e = 7, then d is an integer from 2 to 6 and is an integer from 1 to 5 if d + e = 8, then d is an integer from 2 to 7 and is an integer from 1 to 6 if d + e = 9 , then d is an integer from 2 to 8 and is an integer from 1 to 7 if d + e = 10, then d is an integer from 2 to 9 and is an integer from 1 to 8 if d + e = 11, then d is an integer from 2 to 10 and is an integer from 1 to 9.

The average total number of carbon atoms in the branched primary alkyl groups having the aforementioned general formulas (26, 27) ranges from more than about 12 to about 12.

14.5 and EO / PO are alkoxy groups selected from ethoxy, propoxy and mixed ethoxy / propoxy groups wherein m is at least about 0.01, more preferably in the range of about 0.1 to about 30, even more preferably from about 0, 5 to about 10, and most preferably from about 1 to about 5.

Particularly preferred are those mid-chain branched surfactants which contain a mixture of compounds having formulas (26) and (27) and a molar ratio of compounds of formula (26) to compounds of formula (27) is greater than 4: 1 , more preferably greater than 9: 1 and most preferably greater than 20: 1.

Further, the surfactant-containing composition of the present invention may comprise a mixture of linear and branched surfactants, wherein the primary alkyl alkoxy sulfates have the general formula:

RR ¹ R ²

CH ₃ CH ₂ (CH ₂ ) _w CH (CH ₂ ) _x CH (CH ₂ ) _y CH (CH ₂ ) _z CH ₂ (EO / PO) _m OSO ₃ M (28)

9 · ··· 9 9 9 0 0 0 0

1 000 00000 * 000

IV 0 * 000 · 00 000 00 · • * 9 9 9 9 0000 ** · 9 ··· 90 0 · 0 · where the total number of carbon atoms in the molecule including the branching is from 10 to 17 and the average total number of carbon atoms in the branched primary alkyl groups having the above general formula (28) ranges from more than about 12 to about 14.5. R ¹ , R ¹ and R ² are each independently selected from hydrogen and C 1 -C 3 alkyl, provided that R, R ¹ and R ² are not all hydrogen. M is a water-soluble cation; w is an integer from 0 to 10; x is an integer from 0 to 10; y is an integer from 0 to 10; z is an integer from 0 to 10 and w + x + y + z is from 3 to 10. EO / PO are alkoxy groups, more preferably selected from ethoxy, propoxy and mixed ethoxy / propoxy groups, and wherein m is at least about 0.01 more preferably from about 0.1 to about 30, even more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5. If R ² is C 1 to C 3 alkyl, then the ratio of surfactants having from 2 equal to 0 to surfactants having from 1 or greater is at least about 1: 1, more preferably at least about 1: 5, even more preferably at least about 1:10 and most preferably at least about 1:20. Also preferred are surfactant-containing compositions wherein R ² is C 1 -C 3 alkyl, containing less than about 20%, more preferably less than about 10%, even more preferably less than about 5%, most preferably less than about 1% a primary branched alkylalkoxylated sulfate having the above general formula (28) wherein z is 0.

More preferred primary alkyl ethoxylated sulfates branched with one methyl group are selected from the group consisting of: 3-methyldodecanol ethoxylated sulfate, 4-methyldodecanol ethoxylated sulfate, 5-methyldodecanol ethoxylated sulfate, 6-methyldodecanol ethoxylated sulfate, 7-methyldodecanate,

9 methyldodekanolethoxylovaný sulfate, 10 methyldodekanolethoxylovaný sulfate, 3-methyItridekanolethoxylovaný sulfate, 4-methyltridekanolethoxylovaný sulfate, 5-methyltridekanolethoxylovaný sulfate, 6-methyltridekanolethoxylovaný sulfate, 7-methyltridekanolethoxylovaný sulfate, 8-methyltridekanolethoxylovaný sulfate, 9-methyltridekanolethoxylovaný sulfate, 10 methyltridekanolethoxylovaný sulfate, 11-Methyltridecanolethoxylated sulfate and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of from about 0.1 to about 10.

More preferred primary alkyl ethoxylated sulfates branched with two methyl groups are selected from the group consisting of: 2,3-dimethylundecanol ethoxylated sulfate, 2,4-dimethylundecanol ethoxylated sulfate, 2,5-dimethylundecanol ethoxylated sulfate, 2,6-dimethylundecanol ethoxylated sulfate, 2,7- dimethylundecanol ethoxylated sulfate, 2,8-dimethylundecanol ethoxylated sulfate, 2,6-dimethyldodecanol ethoxylated sulfate, 2,6-dimethyldodecanol ethoxylated sulfate, 2,6-dimethyldodecanol ethoxylated sulfate, 2,6-dimethyldodecanol ethoxylated sulfate, 2,6-dimethyldodecanol ethoxylated sulfate, 2,6-dimethyldodecanol ethoxylated sulfate, 2,6-dimethyldodecanol ethoxylated sulfate, sulfate, 2,8-dimethyldodecanol ethoxylated sulfate, 2,9-dimethyldodecanol ethoxylated sulfate, •

0 · 00 00 000 000 0000 ~ 0000 _n 000 00000

2U 0000000 00 000 000

0 0000 0000 000 0 00 0 · 00 * 0

2,10-Dimethyldodecanol ethoxylated sulfate and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of from about 0.1 to about 10.

Mid-chain branched primary alkyl polyoxyalkylene surfactants

Compositions of the present invention comprising a branched surfactant may comprise one or more primary alkylpolyoxyalkylene surfactants based on a branched mid-chain branch having the general formula

RR ¹ R ²

I I i (28)

CH ₃ CH ₂ (CH ₂ ) _w CH (CH ₂ ) _x CH (CH ₂ ) _y CH (CH ₂ ) _z CH ₂ (EO / PO) _m OH

The surfactant compositions of the present invention comprise molecules having a backbone of the primary polyoxyalkylene linear chain (i.e., the lowest linear carbon chain that includes the alkoxylated carbon atom) as the backbone. These alkyl chains contain from 9 to 18 carbon atoms. The molecules further comprise a branched primary alkyl group or groups having at least about 1 but not more than 3 carbon atoms. The surfactant mixture has an average total number of carbon atoms in the branched primary alkyl groups ranging from more than about 12 to about 14.5. Accordingly, the compositions of the present invention comprise at least one polyoxyalkylene compound having the shortest linear carbon chain of not less than 9 carbon atoms or longer than 17 carbon atoms and an average total number of carbon atoms in the branched primary alkyl chains in the range of more than 12 to about 14.5 more preferably from greater than about 12 to about 14, and most preferably from greater than about 12 to about 13.5.

For example, a primary polyoxyalkylene surfactant with a total number of Ch carbons, of which 11 carbon atoms form the backbone of the chain, must have 1, 2 or 3 branching units (i.e., R, R ¹ and R ² ), the total number of carbon atoms in In this example, the requirement of a total of 14 carbon atoms can also be met by, for example, one propyl branching unit or 3 methyl branching units.

R, R ¹ and R ² are independently selected from hydrogen and C 1 -C ₃ alkyl (more preferably hydrogen or C 1 -C ₂ alkyl, even more preferably hydrogen or methyl and most preferably methyl) provided that R, R ¹ and R ² not all hydrogen. Further, if z is 0, then at least R or R ¹ is not hydrogen.

Although for the purposes of the surfactant-containing compositions of the present invention, the above general formula (29) does not include those molecules in which the units are: 0 0000 9 9 0 0

0,000 0 0 0 0 «0,000,000 · 0 t

0 0 0 0 0 0

000 0 00 · 0 · ···

R, R ¹ and R ² all hydrogen (i.e., linear unbranched primary polyoxyalkylenes), it should be understood that the compositions of the present invention may still contain some amount of linear, unbranched primary polyoxyalkylene. Furthermore, the linear unbranched primary polyoxyalkylene surfactant may be present either as a result of a process used to produce a mixture of surfactants having the necessary primary polyoxyalkylenes of the present invention branched in the mid-chain or may be formulated for detergent compositions some linear unbranched primary polyoxylkylene is added to the final product.

Similarly, it should further be appreciated that non-alkoxylated mid-chain branched alcohols may contain some amount of polyoxyalkylene-containing compositions of the present invention. These may be present either as a result of incomplete alkoxylation of the alcohol used to prepare the polyoxyalkylene surfactant or may be added to the detergent compositions of the present invention together with the mid-chain branched polyoxyalkylene surfactant of the present invention. .

Referring further to the above general formula (29), w is an integer from 0 to 10; x is an integer from 0 to 10; y is an integer from 0 to 10; z is an integer from 0 to 10 and w + x + y + z is an integer from 2 to 11.

EO / PO are alkoxy groups, more preferably selected from ethoxy, propoxy and mixed ethoxy / propoxy groups, even more preferably ethoxy groups wherein m is at least about 1, more preferably in the range of about 3 to about 30, even more preferably from about 5 to about 20 and most preferably from about 5 to about 15. The group (EO / PO) _m may be either an arrangement with an average degree of alkoxylation (e.g. ethoxylation and / or propoxylation) corresponding to m, or it may be a single specific chain with alkoxylation (e.g. ethoxylation and (or propoxylation), which is equal to the number of units corresponding to m.

More preferred surfactant mixtures of the present invention comprise at least about 10 wt. %, even more preferably at least about 20 wt. %, even more preferably at least about 30 wt. % and most preferably at least 50 wt. % of a mixture of one or more mid-chain branched primary alkyl polyoxyalkylenes having the general formula

R ¹ R ² (30)

CH ₃ CH ₂ (CH ₂ ) _x CH (CH ₂ ) _y CH (CH ₂ ) _from CH ₂ (EO / PO) _m OH fe · · • fefefe fefe fefe fefe • fefe fefefefe · · fefefe · · · · Wherein the total number of carbon atoms including the branching ranges from 10 to 16 and the average total number of carbon atoms in the branched primary alkyl groups is in the range of more than 12 to about 14. R ¹ and R ² are each independently hydrogen or C 1 -C 3 alkyl; x is from 0 to 10; y is from 0 to 10; z is from 0 to 10 and x + y + z is from 4 to 10. The assumption is that R ¹ and R ² are not both hydrogen. EO / PO are alkoxy groups selected from ethoxy, propoxy and mixed ethoxy / propoxy groups, more preferably ethoxy groups wherein m is at least about 1, more preferably in the range of about 3 to about 30, even more preferably from about 5 to about 20, and most preferably from about 5 to about 15. Even more preferred are compositions having at least 5% of a composition comprising one or more primary mid-chain branched polyoxyalkylenes, wherein z is at least 1.

The surfactant compositions comprise at least 5%, more preferably at least about 20%, of a mid-chain branched primary alkylpolyoxyalkylene having R ¹ and R ² independently having hydrogen or methyl. The assumption is that R ¹ and R ² are not both hydrogen; x + y is 5, 6 or 7 and z is at least 1.

Preferred detergent compositions of the present invention, such as those used in laundry, contain from about 0.001% to about 99% of a mixture of primary alkyl polyoxyalkylene surfactants branched in the mid-chain. Said composition comprises at least about 5 wt. % of one or more mid-chain branched alkyl polyoxyalkylenes of the general formula:

CH3 i (32)

_{CH3 (CH2)} CH (CH2) ₂ BCH (EO / PO) _n OH

CH ₃ CH ₃

I I (32)

CH ₃ (CH 2) d CH (CH ₂ ) _e CHCH ₂ (EO / PO) _m OH and mixtures thereof.

In formulas, a, b, d and e are integers, a + b is from 6 to 13, d + e is from 4 to 11. Furthermore, if a + b = 6, then a is an integer from 2 to 5 and b is an integer from 1 to 4 if a + b = 7, then a is an integer from 2 to 6 and b is an integer from 1 to 5 if a + b = 8, then a is an integer from 2 to 7 and ab is an integer from 1 to 6 if a + b = 9, then a is an integer from 2 to 8 and b is an integer from 1 to 7 if a + b = 10, then a is an integer from 2 to 9 and b is an integer from 1 to 8 if a + b = 11, then a is an integer from 2 to 10 and b is an integer from 1 to 9 if a + b = 12, then a is an integer from 2 to 11 and b is an integer from 1 to 10 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · To · to · If a + b = 13, then a is an integer from 2 to 12 and b is an integer from 1 to 11 if d + e = 4, then d is an integer from 2 to 3 ae is an integer from 1 to 2 if d + e = 5, then d is an integer from 2 to 4 and e is an integer from 1 to 3 if d + e = 6, then d is an integer from 2 to 5 and e is an integer a number from 1 to 4 if d + e = 7, then d is an integer from 2 to 6 and e is an integer from 1 to 5 if d + e = 8, then d is an integer from 2 to 7 and e is an integer from 1 to 6 if d + e = 9, then d is an integer from 2 to 8 and e is an integer from 1 to 7 if d + e = 10, then d is an integer from 2 to 9 and e is an integer from 1 to 8 if d + e = 11, then d is an integer from 2 to 10 and e is an integer from 1 to 9.

Further, the average total number of carbon atoms in the branched primary alkyl groups having the above formulas (31, 32) ranges from more than about 12 to about 14.5. EO / PO are alkoxy groups selected from ethoxy, propoxy and mixed ethoxy / propoxy groups. In the formula, m is at least about 1, more preferably in the range of about 3 to about 30, even more preferably from about 5 to about 20, and most preferably from about 5 to about 15.

Further, a surfactant-containing composition of the present invention may comprise a mixture of branched primary alkyl polyoxyalkylenes having the general formula:

RR ¹ R ²

I I I (34)

CH ₃ CH ₂ (CH ₂ ) _w CH (CH ₂ ) _x CH (CH ₂ ) _y CH (CH ₂ ) _z CH ₂ (EO / PO) _m OH where the total number of carbon atoms in the molecule including the branching is from 10 to 17 and the average total number of carbon atoms in the branched primary alkyl groups having the above general formula (33) ranges from more than about 12 to about 14.5. R, R ¹ and R ² are each independently selected from hydrogen and C 1 to C 3 alkyl, provided that R, R and R are not all hydrogen, w is an integer from 0 to 10; x is an integer from 0 to 10; y is an integer from 0 to 10; z is an integer from 0 to 10 and w + x + y + z is from 3 to 10. EO / PO are alkoxy groups, more preferably selected from ethoxy, propoxy and mixed ethoxy / propoxy groups, wherein m is at least about 1, more preferably from about 3 to about 30, even more preferably from about 5 to about 20, and most preferably from about 5 to about 15. It is assumed that when R ² is C 1 to C 3 alkyl, the ratio of surfactants having a moiety 2 or greater to surfactants having z equal to 1 is at least about 1: 1, more preferably at least about 1.5: 1, even more preferably at least about 3: 1, and most preferably at least about 4: 1. Also preferred are surfactant-containing compositions wherein R ² is C 1 to C ₃ alkyl, containing less than about 50%, more preferably less than about 40%, even more preferably less than about 10%

9 0 0

0 0 0 0

0 0 0

%, Most preferably less than about 20% of primary branched alkyl polyoxyalkylenes having the above general formula (33), in where z equals 0.

More preferred primary alkyl ethoxylates branched with one methyl group are selected from the group consisting of: 3-methyldodecanol ethoxylate, 4-methyldodecanol ethoxylate, 5-methyldodecanol ethoxylate, 6-methyldodecanol ethoxylate, 7-methyldodecanol ethoxylate, 8-methyldodecanol ethoxylate, 8-methyldodecanol ethoxylate, 3-methyltridecanol ethoxylate, 4-methyltridecanol ethoxylate, 5-methyltridecanol ethoxylate, 6-methyltridecanol ethoxylate, 7-methyltridecanol ethoxylate, 8-methyltridecanol ethoxylate, 9-methyltridecanol ethoxylate, 10-methyltridecanol ethoxylate, about 5-methyltridecanol ethoxylate; to about 15.

More preferred primary alkyl ethoxylates branched with two methyl groups are selected from the group consisting of: 2,3-dimethylundecanol ethoxylate, 2,4-dimethylundecanol ethoxylate, 2,5-dimethylundecanol ethoxylate, 2,6-dimethylundecanol ethoxylate, 2,7-dimethylundecanol ethoxylate, 2,8-dimethylundecanol ethoxylate, 2,8 dimethylundecanol ethoxylate, 2,9-dimethylundecanol ethoxylate, 2,3-dimethyldodecanol ethoxylate, 2,4-dimethyldodecanol ethoxylate, 2,5-dimethyldodecanol ethoxylate, 2,6-dimethyldodecanol ethoxylate, 2,7-dimethyldodecanol ethoxylate, 2,7-dimethyldodecanol ethoxylate, 2,8-dimethyldodecanol ethoxylate, 2,8-dimethyldodecanol ethoxylate dimethyldodecanol ethoxylate, 2,10-dimethyldodecanol ethoxylate, and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of from about 1 to about 15.

Preparation of mid-chain branched surfactants

The following reaction scheme outlines a general approach to the preparation of a mid-chain branched primary alcohol that is useful for alkoxylation and / or sulfation and by which the mid-chain branched primary alkyl surfactants of the present invention are prepared.

RX

OAc

Mg Cl (CH ₂ ) _{3 -} LiH ₃ rhri? ^H Ac ₂ o - —L- RMgX --- it_C_ (CH2) 3 Cl-R- (CH2) 3Cl

ČH3

CH 3 - HOAc

R-CH- (CH ₂ ) 5 OH CH ₃ / ° \

CH 2 -CH 2

RMsCl

Mg

R-CB- (CH ₂₎ 4 0H <5H3

HCHO

H ₂ cat r_ch- (ch2) 3 α

CH3 • · «0 9 0 0 • 0000 0 00 *

00 000 0 · · 0909 0999

00 00 00 90 0 0000

The alkyl halide is converted to a Grignard reagent which further reacts with the haloketone. After conventional acid hydrolysis, acetylation and thermal elimination of acetic acid, an intermediate olefin (not shown in the scheme) is formed which is immediately hydrogenated with any suitable hydrogenation catalyst such as Pd / C.

This route is preferred over others because branching, in this scheme 5-methyl branching, is incorporated at the beginning of the reaction sequence.

The alkyl halide formulation formed in the first hydrogenation step results in an alcohol, as shown in the scheme. This can be alkoxylated using standard techniques and / or sulfated using a conventional sulfating agent such as chlorosulfuric acid, SO ₃ / air or oleum to give the resulting branched primary alkyl surfactant. There is some flexibility to extend the branching by one additional carbon further, which can be achieved by simple formulation. This extension can be accomplished, for example, by reaction with ethylene oxide, as found, for example, in "Grignard Reactions of Nonmetallic Substances", MS Kharasch and O. Reinmuth, Prentice-Hall, NY, 1954; J. Org. Chem., J. Cason and WR Winans, Sv. 15 (1950), pp. 139-147; J. Org. Chem., J. Cason et al., Vol. 13 (1948), pp. 239-248; J Org. Chem., J. Cason et al., Vol. 14 (1949), pp. 147-154 and J. Org. Chem., J. Cason et al., Vol.

(1950), pp. 135-138. All publications are incorporated herein by reference.

Other variations of haloketones or Grignard reagents may be used in various modifications of the above process. Halogenation with PBr ₃ alcohol from formulation or ethoxylation can be used to achieve repeated chain extension.

More preferably, the mid-chain branched primary alkyl alkoxylated sulfates (as well as the polyoxyalkylenes and alkyl sulfates, by selecting only the alkoxylates or sulfates of the alcohol intermediate produced) that are the subject of the present invention can also be readily prepared by the following process.

Br (Ph) 3P + Brs

CHgCN

Reflux (Ph) 3 R @ +

2N «H

DMSO *

THF (Ph) 3P <

(Ph) 3 Po

DMSO

THF

ri alkoxylation / sulphation (EO / PO) mOSO 3 Na ⁺ • · ········· 99 99

9 9 9 9 9

9999 9 »· 9 • 9 9 9 9 9 9 9 9

9 9 9 9 9

999 99 99 99 99

Conventional bromoalcohol is reacted with triphenylphosphine, followed by treatment with sodium hydride, suitably in dimethylsulfoxide / tetrahydrofuran, to form a Wittig addition compound. It further reacts with alpha-methylketone to form an internally unsaturated alcoholate branched with methyl. Hydrogenation is followed by alkoxylation and / or sulfation to give the desired primary alkyl surfactant, branched in the mid-chain. Although the Wittig procedure does not allow the hydrocarbon chain to be extended as permitted by the Grignard reagent procedure, the Wittig procedure generally provides higher yields, see, e.g., Agricultural and Biological Chemistry, M. Horiike et al., Vol. 42 (1978), pp. 1963-1965, which is incorporated herein by reference.

Any alternative synthetic procedures which are in accordance with the present invention may be used to prepare the branched primary alkyl surfactants. The mid-chain branched primary alkyl surfactants can be further synthesized or formulated in the presence of conventional homologues, e.g., in the presence of any of those agents that can be produced in an industrial process to produce 2-alkyl branching as a result of hydroformylation.

In certain more preferred embodiments of the surfactant compositions of the present invention, particularly those derived from commercial processes involving fossil fuel sources, said surfactant compositions comprise at least 1 mid-chain branched primary alkyl surfactant, more preferably at least 2, even more preferably Particularly suitable for the preparation of certain surfactant mixtures of the present invention are "oxo" reactions in which the branched olefin is subjected to catalytic isomerization and hydroformylation prior to alkoxylation and / or sulfation. More preferred processes resulting in these mixtures process fossil fuels as the basic raw material. More preferred processes utilize oxo reactions on olefins (alpha or internal) with limited branching. Suitable olefins can be prepared by dimerization of linear alpha or internal olefins, controlled oligomerization of low molecular weight linear olefins, rearrangement of the detergent range olefin skeleton, dehydrogenation / rearrangement of the detergent range paraffin skeleton, or Fischer-Tropsch reaction. These responses will generally be aimed at:

1) obtaining a large proportion of olefins in the desired detergent range (although taking into account the addition of a carbon atom in the subsequent oxo reaction),

2) obtaining a limited number of branches, more preferably in the middle of the chain,

3) obtaining a branching of the C 1 to C ₃ chain, more preferably ethyl, most preferably methyl • 00

0 0 0

0 i 0 * 0 0 0 0 • 0 0 0

00 ·· · · ««

0 * • · 9 «9,999

0 0 0

0 0 0 0 0 0

4) reducing or eliminating geminal dialkyl branching, i. Avoid the formation of quaternary carbon atoms.

Suitable olefins may be subjected to an oxo reaction to form primary alcohols either directly or indirectly via the corresponding aldehydes. When an internal olefin is used, an oxo reaction catalyst that is capable of first isomerizing the internal olefins to alpha-olefins is commonly used. Although separately catalyzed (i.e. not oxo) isomerization of internal olefins to alpha-olefins can be accomplished, this is occasional. On the other hand, if the olefin formation step itself leads directly to the formation of an alpha-olefin (e.g., detergent-range olefins obtained by the Fischer-Tropsch reaction at high pressure), the use of non-isomerizing oxo reaction catalysts is not only possible, but advantageous.

The above-described process, which is carried out by stridecene, provides more preferred 5-methyltridecyl alcohol and thus surfactants in higher yields than the less preferred 2,4-dimethyldodecyl materials. This mixture is desirable in such scales and linkages of the present invention wherein each product contains a total of 14 carbon atoms with linear alkyl chains having at least 12 carbon atoms.

The following examples provide methods of synthesizing various compounds that are useful in the compositions of the present invention.

The following 2 analytical methods of characterizing branching in the surfactant-containing compositions of the present invention are useful.

1) Separation and identification of constituents in fatty acid-derived alcohols (prior to alkoxylation or after hydrolysis of alcohol-sulfate for analytical purposes). The position and length of branching found in fatty acid precursor alcohols are determined by GC / MS techniques [see D. J. Harvey, Biomed, Environ. Mass Spectrom (1989). 18 (9), 719-23; Harvey, D. J., Tiffany, J. M., Chromatogr. (1984), 301 (1), 173-87; K. A. Karlsson, Β. E. Samuelsson, G.O. Steen, Chem. Phys. Lipids (1973), 11 (1), 17-38].

2) Identification of separated components of fatty acid alcohol alkoxysulfates by MS / MS. The branching position and length can also be determined by Ion Spray-MS / MS or FABMS / MS techniques for pre-isolated fatty acid alcohol sulphate components.

The average total carbon atoms of the branched primary alkyl surfactants can be calculated from the hydroxyl value of the fatty acid precursor alcohol mixture or the hydroxyl value of the alcohols recovered after hydrolysis of the alcohol sulfate mixture using conventional procedures as outlined in "Bailey's Industrial" Oil and Fat Products', Vol. 2, Fourth Edition, edited by Daniel Swern, pp. 440-441.

• 44 »4 * 44 44

4 4 4 4 4 4 4 4 4444 4 4 4 4 * 4 444 4 4 4

444 44 44 44 44

Aqueous liquid carrier

The lightweight detergent dishwashing detergent compositions further comprise from about 30% to 95% of an aqueous liquid carrier in which other necessary and occasional ingredients of the compositions are dissolved, dispersed, or suspended. Even more preferably, the aqueous liquid carrier will comprise from about 50% to 65% of the compositions herein.

Of course, one indispensable component of the aqueous liquid carrier is water. However, the aqueous liquid carrier may contain other substances which are liquid or are dissolved in the liquid carrier at room temperature and which may perform some other functions in addition to those of the fill itself. Such materials may include, for example, hydrotropes and solvents. In particular, due to the mid-chain branched properties of the surfactants of the present invention, the water hardness in the aqueous liquid carrier may be at least about 15 gpg or higher ("gpg" is a water hardness measure well known to those skilled in the art and means "grains per gallon "or" gallon grains ").

(a) Hydrotropes

The aqueous liquid carrier may contain one or more hydrotropes. Hydrotropes suitable for use in the compositions of the present invention include C 1 -C ₃ alkylarylsulfonates, C 8 -C ₁₂ alkanols, sulfates and sulfonates of C 1 -C ₆ carboxylic acids, urea, C 1 -C 8 hydrocarbylates, C 1 -C 4 carboxylates, C ₂ -C 4 carboxylates C4 organic diacids and mixtures of these hydrotropes. More preferably, the liquid detergent composition of the present invention comprises from about 0.5 wt. % to 8 wt. % of a hydrotrope selected from alkali metal sulfonates, calcium xylene sulfonate and toluenesulfonates.

Suitable Ci to C ₃ alkyl aryl sulfonates include sodium, potassium, calcium and ammonium xylene sulfonates; sodium, potassium, calcium and ammonium toluenesulfonates, sodium, potassium, calcium and ammonium cumene sulfonates and sodium, potassium, calcium and ammonium substituted or unsubstituted naphthalenesulfonates and mixtures thereof.

Suitable C 1 -C 8 carboxylic acid sulfates or sulfonates are any water-soluble salts or organic compounds containing 1 to 8 carbon atoms (without substituent groups) that are substituted with a sulfate or sulfonate and have at least one carboxyl group. Substituted organic compounds may be cyclic, acyclic or aromatic. benzene derivatives. More preferred alkyl compounds have from 1 to 4 carbon atoms.

Substituted with sulphate or sulphonate and have 1 to 2 carboxyl groups. Examples of this type of hydrotrope include sulfosuccinate salts, sulfophthalates, sulfoacetates, m-sulfobenzoic acid salts, and sulfosuccinate diesters, more preferably sodium and potassium salts, as disclosed in US Patent 3915903.

C 1 to C 4 hydrocarbylates and C 1 to C 4 carboxylates suitable for use in the present invention include acetates, propionates and citrates. C ₂ to C 4 diacids suitable for use in the present invention include succinic acid, gutaric acid and adipic acid.

Other compounds which impart hydrotropic effects and which are useful in the present invention as hydrotropes include C 6 to C 12 alkanols and urea.

Hydrotropes that are more preferred for use in the present invention are sodium, potassium, calcium and ammonium cumene sulfonates; sodium, potassium, calcium and ammonium xylene sulfonates and sodium, potassium, calcium and ammonium toluenesulfonates and mixtures thereof. Most preferably, sodium cumene sulphonate and calcium xylene sulphonate and mixtures thereof. These more preferred hydrotropic materials may be present in the composition in an amount of from about 0.5 wt. % to 8 wt. %.

b) Solvents

A variety of water-miscible liquids such as lower alkanols, diols, other polyols, ethers, amines, and the like can be used as part of the aqueous liquid carrier. Particularly preferred are C 1 to C 4 alkanols. These solvents may be present in the compositions of the present invention in an amount of from about 1% to 8%.

Special additives

More preferred particular ingredients of the dishwashing compositions herein include anionic and nonionic surfactants, surfactant aids, calcium and / or magnesium ions, enzymes such as protease, and enzyme stabilizing system. These and other special ingredients are described below.

Anionic surfactant

In addition to the branched surfactant mixture disclosed above, the compositions of the present invention may contain from about 5% to 40% of the anionic surfactant component. Even more preferably, the anionic component of the surfactant comprises from about 15% to 35% of the compositions herein.

More preferably, the anionic surfactant comprises alkyl sulfates and alkyl ether sulfates derived from conventional sources of alcohols such as natural alcohols, synthetic alcohols such as alcohols sold under the trade names NEODOL ™, ALFOL ™, LIAL ™, LUTENSOL ™, and the like. Alkyl ether sulfates are also known as alkylpolyethoxysulfates. The following ethoxylated alkyl sulfates are those that conform to the general formula:

R 1 -O- (C ₂ H 4 O) _n SO ₃ M (34) wherein R is a C 5 to C 18 alkyl group, n is from about 0.01 to 6 and M is a salt-forming cation. More preferably, R 1 is C 1 to 16 alkyl, n is from about 0.01 to 4, and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium ion. Most preferably, R 1 is C ₁₂ to C ₁₁ n is from about 0.01 to 3 and M is sodium. Alkyl ether sulfates will generally be used in the form of mixtures containing different lengths of R 'chains having different degrees of ethoxylation. Normally, these compositions will also unconditionally contain certain non-ethoxylated alkyl sulfate materials, e.g., surfactants of the above formula (34) for ethoxylated alkyl sulfate where n = 0.

Other surfactants useful in the preparation of detersive compositions may also be incorporated into the compositions. Such surfactants include soap salts (including, e.g., sodium, potassium, ammonium and substituted ammonium salts such as mono-, di-, and triethanolamine salts), linear C? to C ₁₈ alkylbenzene sulfonates, C 8 to C ₂₂ primary or secondary alkane sulfonates, C 8 to C ₂₂ olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonating the pyrolyzed alkaline earth citrate product as described in, eg, GB Patent No. 1082179, C 8 to C ₂₂ alkyl glycerosulfonates, acyl glycerol fatty acid esters, glycerol oleate, a secondary Cu to C16 soaps, alkylfenolethyíenoxidéthersulfáty, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated _Ci2 to Cis monoesters), sulfosuccinate diesters (especially saturated and unsaturated C 6 -C 14 diesters), N-acyl sarcosinates, alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (non-ionic unsulfated compounds will be described below), branched primary alkyl sulfates those C _2-16 alkylpolyalkoxycarboxylates, such as those having the general formula

RO (CH ₂ CH ₂ O) _to CH ₂ COO74 ⁺ (35) · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Where R is C 8 to C 22 alkyl, k is an integer from 0 to 10 and M is a soluble salt-forming cation and further fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Also suitable are resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, resin acids and hydrogenated resin acids which are either present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents", Vol. I and Π (Schwartz, Perry and Berch). Many of these surfactants are also generally disclosed in U.S. Patent No. 3929678, issued December 30, 1975 to Laughlin et al., At Section 23, line 58 to section 29, line 23.

One type of anionic surfactant that can be used includes alkyl ester sulfonates. These substances are desirable because they can be prepared from renewable non-petroleum sources. The preparation of the alkyl ester sulfonate-based surfactant can be carried out according to known procedures which are disclosed in the technical literature. E.g. linear esters of C8 to C20 carboxylic acids can be sulfonated with SO3 gas by the method described in The Journal of the American Oil Chemists Society, 52 (1975), pp. 323-329. Suitable starting materials may be natural fatty substances. Suitable salts include metal salts such as sodium, potassium and lithium salts and substituted or unsubstituted ammonium salts such as methyl-, dimethyl-, trimethyl-, and quaternary ammonium cations such as tetramethylammonium. and dimethylpiperidinium ion and alkanolamine-derived cations such as monoethanolamine, diethanolamine and triethanolamine. Particular preference is given to methyl esters of sulfonates in which the alkyl group is C12 to C18.

Secondary surfactants

The secondary detersive surfactants may be selected from the group consisting of nonionic, cationic, ampholytic, zwitterionic surfactants and mixtures thereof. Based on the choice of the type and amount of detersive surfactant, the detergent compositions of the present invention, together with the other adjuvants listed herein, may be formulated so as to be used in laundry washing or other cleaning applications, including, in particular, dishwashing. Thus, the particular surfactants employed may vary widely depending upon the concept of the particular end use. Suitable secondary surfactants are described below.

Nonionic surfactants

In addition to the mixture of branched surfactants disclosed above, the compositions of the present invention may also contain from about 3% to 10% of a certain type of nonionic surfactant component. Even more preferably, the nonionic surfactant will comprise from about 4% to 6% of the compositions herein. Suitable non-ionic detergent surfactants are generally disclosed in U.S. Pat. No. 3,929,668, Laughlin et al., Issued December 30, 1975, at section 13, line 14 to section 16, line 6, which is incorporated herein by reference. E.g. non-limiting classes of useful nonionic surfactants include: alkyl dialkylaminoxides, alkyl ethoxylates, alkanoyl glucoamides, alkyl betaines, and mixtures thereof.

One indispensable type of nonionic surfactant present in the compositions of the present invention is the amides of C 8 to C 18, more preferably C 10 to C 16 polyhydroxy fatty acids. These substances are described in more detail in Pan / Gosselink; U.S. Patent 5,332,528, issued July 26, 1994, which is incorporated herein by reference. These polyhydroxy fatty acid amides have the structure according to the general formula.

OR ¹

AND

^R2 - C - N Z (36) wherein R ¹ is H, Cl-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or mixtures thereof; R ² is a Cg to Cis hydrocarbyl, and Z is polyhydroxylhydrokarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Examples of such surfactants are C10 to C18 N-methyl or N-hydroxypropyl glucamides. N-propyl to N-hexyl C12 to Cu glucamides can be used to reduce foaming. More preferably, the polyhydroxy fatty acid amides will comprise from about 1% to 5% of the compositions herein.

In the nonionic surfactant of the compositions herein, the aforementioned polyhydroxy fatty acid amides may be combined with certain other types of nonionic surfactant aids. These other types include ethoxylated alcohols, ethylene oxide-propylene oxide copolymer surfactants, and combinations of these auxiliary nonionic surfactants.

Other nonionic surfactants that may be used include: polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols. Generally, it is more convenient to use the ######################################### Polyethylene oxide condensates. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a linear or branched configuration with alkylene oxide. In a more preferred embodiment, the ethylene oxide is present in an amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkylphenyl. Commercially available nonionic surfactants of this type are Igepal® CO-630, distributed by GAF Corporation and Triton® X-45, X-114, X-100 and X-102, distributed by the Rohm & Haas Company. These compounds are commonly referred to as alkylphenolalkoxylates (e.g., alkylphenol ethoxylates).

Ethoxylated alcohol surfactants which are useful as nonionic surfactants comply with the general formula.

R ¹ -O- (C ₂ H ₄ O) _n H (37) wherein R ¹ is a C _{8 to} C ₁₈ alkyl group and r ranges from about 5 to 15. R ¹ is more preferably an alkyl group which may be primary or secondary and which contains from about 9 to 15 carbon atoms, more preferably from about 9 to 12 carbon atoms. Ethoxylated fatty acid alcohols will more preferably contain from about 2 to 12 ethylene oxide groups per molecule, even more preferably from about 8 to 12 ethylene oxide groups per molecule. The non-ionic ethoxylated fatty acid alcohol adjunct surfactant will typically have a hydrophilic-lipophilic balance (HLB) such that its values will range from about 6 to 15, more preferably from about 10 to 15.

Examples of fatty acid alcohol ethoxylates useful as nonionic surfactant aids herein include those prepared from C12-15 alcohols and containing about 7 moles of ethylene oxide. These are commercially marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful Neodols include Neodol 1-5, which is an ethoxylated fatty acid alcohol having an average number of carbon atoms in the alkyl chain of 11 and about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C ₂ to C alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C9-Cn primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type are also sold by Shell Chemical Company under the trade name Dobanol. Dobanol 91-5 is an ethoxylated C9-Cn fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 257 is an ethoxylated _Ci2 to C15 fatty alcohol with an average of 7 moles of ethylene oxide to 1 mol of fatty acid alcohol.

• · · · · · · · · · ·

Other examples of suitable nonionic ethoxylated alcohol surfactants include Tergitol 15-S-7 and Tergitol 15-S-9, both of the secondary alcohol ethoxylates, which are commercially distributed by Union Carbide Corporation. Initially, the mixed ethoxylation product of a linear Cn to C15 secondary alkanol was reacted with 7 moles of ethylene oxide and later it was a similar product but with 9 moles of ethylene oxide.

Other types of nonionic alcohol ethoxylate surfactants useful in the compositions of the present invention are higher molecular weight nonionic agents such as Neodol 45-11, which is similar to the condensation products of ethylene oxide and higher fatty acid alcohols, the higher fatty acid alcohol having The number of ethylene oxide groups per mole is about 11. These products are also commercially distributed by Shell Chemical Company.

Non-ionic ethoxylated alcohol surfactants will generally comprise about 0.2% to 0.4% of the compositions herein. Even more preferably, these ethoxylated alcohols will comprise from about 0.5% to 1.5% of the compositions.

Another type of nonionic surfactant auxiliary which is useful in combination with a nonionic surfactant comprises ethylene oxide-propylene oxide block copolymers, thereby having the same function as the polymeric surfactant. These block copolymers contain one or more hydrophobic groups which contain mostly ethylene oxide groups and one or more hydrophobic groups which contain mostly propylene oxide groups. These groups are attached to the remainder of the compound containing one or more hydroxyl groups or amino groups. The molecular weight of these polymeric surfactants ranges from about 400 to 60,000.

More preferred are those ethylene oxide propylene oxide polymer surfactants in which propylene oxide is condensed with an amine, especially a diamine, to provide a base which then condenses with ethylene oxide. Substances of this type are sold under the trade name Tetronic®. Similar structures in which ethylenediamine is replaced by a polyol such as propylene glycol are sold under the trade name "Pluronic®". More preferred ethylene oxide-propylene oxide (EO-PO) polymer surfactants have an HLB in the range of about 4 to 30, more preferably about 10 to 20.

The ethylene oxide-propylene oxide block copolymers used in the present invention are described in more detail in Pancheri / Mao; U.S. Patent 5,167,872, issued December 2, 1992, which patent is incorporated herein by reference.

··························· 4 4 4

The ethylene oxide-propylene oxide block copolymers will normally be present in an amount of from about 0.1% to 2%. Even more preferably, these polymeric surfactant-containing materials will comprise from about 0.2% to 0.8% of the compositions herein.

The alkylpolysaccharides disclosed in US Patent 4565647 (Llenado), issued January 21, 1986, have a hydrophobic group containing from about 6 to about 30 carbon atoms, more preferably from about 10 to about 16 carbon atoms, and a polysaccharide such as a polyglycoside, a hydrophilic group containing from about 1.3 to about 10, more preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 carbohydrate units. Any reducing carbohydrate containing 5 or 6 carbon atoms can be used e.g. glucose, galactose and galactosyl groups can replace glucosyl groups. The hydrophobic moiety is optionally attached at the 2-, 3-, 4-, etc. position, thereby producing glucose or galactose over the glucoside or galactoside. Inter-saccharide linkages may exist between, for example, one position of additional saccharide units and the 2-, 3-, 4- and / or 6- position preceding the saccharide unit.

Occasionally, but less desirable, there may be a polyalkylene oxide chain linking the hydrophobic group and the polysaccharide. More preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include saturated or unsaturated, branched or unbranched alkyl groups containing from about 8 to about 18, more preferably from about 10 to about 16 carbon atoms. More preferably, the alkyl group is a linear chain of saturated alkyl. The alkyl group may contain up to about 3 hydroxy groups and / or the polyalkylene oxide chain may contain up to about 1, more preferably less than 5 alkylene oxide groups. Suitable alkylpolysaccharides are octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta- and hexaglucosides, galactosides, lactosides, glucose, fructosides, fructosides, fructosides, fructosides, or galactose. Suitable mixtures include coconut alkyl, di-, tri-, tetra- and pentaglucosides and tallylalkyltetra-, penta- and hexaglucosides.

More preferred alkyl polyglycosides have the general formula

R ² O (C _"H2n OXglykosyl) _x (38) wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which alkyl groups contain from about 10 to about 18, more preferably from about 12 up to about 14 carbon atoms; n is 2 or 3, more preferably 2, t is from 0 to about 10, more preferably 0 and x is from about 1.3 to about 10, more preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2, 7. More preferably, the glycosyl is derived from glucose. To prepare these compounds, an alcohol or alkylpolyethoxy alcohol is first formed, which is then reacted with glucose or a source of glucose to form a glucoside (attachment at the 1- position). The other glycosyl units can then be attached between> 00 00 00 00 00 00 00 00 000 00 00 0

0 000 0 0 0 0 00 00 00 00 their 1-position and the 2-, 3-, 4- and / or 6-position of the preceding glycosyl units, more preferably predominantly the 2-position.

Foam builders / stabilizers

The compositions of the present invention may further comprise from about 2% to 8%, more preferably from about 3% to 6%, of foam enhancers or stabilizing components such as betaine surfactants, fatty acid alkanolamides, amine oxide semipolar nonionic surfactants and C 2-6 surfactants. to C22 alkyl polyglycosides. Combinations of these foam builders / stabilizers may also be used.

Betaine surfactants which can be used as foam-enhancing agents have the general formula:

(-) (-)

RN ^(R) 2-R ² COO (39) wherein R is a hydrophobic group selected from alkyl groups containing from about 10 to about 22 carbon atoms, more preferably from about 12 to about 18 carbon atoms, from alkylaryl and arylalkyl groups containing a similar number of carbon atoms, the benzene nucleus being considered equivalent to about 2 carbon atoms and similar structures interrupted by amino or ether bonds; each R ¹ is an alkyl group containing from 1 to about 3 carbon atoms and R ² is an alkylene group containing 1 to about 6 carbon atoms.

Examples of more preferred betaines are dodecyldimethyl betaine, cetyldimethyl betaine, dodecylamidopropyldimethyl betaine, tetradecyldimethyl betaine, tetradecylamidopropyldimethyl betaine and dodecyldimethylammonium hexanoate. Other suitable amidoalkyl betaines are disclosed in US Patent Nos. 3,950,417, 4,137,191 and 4,375421 and GB Patent No. 2,103,336. All of these patents are incorporated herein by reference.

Alkanolamide-based surfactants which are useful as suds enhancers include ammonium monoethanol and fatty acid diethanolamides having an acyl group containing from about 8 to about 18 carbon atoms. These substances are represented by the general formula:

Ri - C0-N (H) .I _m (R ₂ OH) _{3. m} (40) • 0 00 00 00 00 • 00 0 0 0 0 0 00

000 0 0000 0 00 0

0000 00 00 000 000 0

0000 0000

Wherein R 1 is a saturated or unsaturated aliphatic hydrocarbon group without hydroxy groups having from about 7 to 21, more preferably from about 11 to 17 carbon atoms; R 2 represents a methylene or ethylene group and m is 1, 2 or 3, more preferably 1. A specific example of these amides is coconut oil fatty acid monoethanolamine and dodecyl fatty acid amide diethanolamine. These acyl groups may be derived from naturally occurring glycerides such as coconut oil, palm oil, soybean oil and talc, but may be derived synthetically such as by oil oxidation or hydrogenation of Fischer-Tropsch carbon monoxide. More preferred are C12 to 14 fatty acid monoethanolamides and diethanolamides.

Semi-polar nonionic amine oxide surfactants useful as suds / stabilizers include compounds and mixtures of compounds having the general formula:

R ₂

R - ^ fLOjn - N ---------- O (41)

R 3 wherein R 1 is alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl or 3-alkoxy-2-hydroxypropyl radical wherein the alkyl and alkoxy contain from about 8 to about 18 carbon atoms, R 2 and R 3 are each methyl, ethyl, propyl, isopropyl , 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl and is from 0 to about 10. In particular, amine oxides having the general formula:

R ₂

R 1 -N ---------- o (42) r ₃ wherein R 1 is C 12 to alkyl and R 2 and R 3 are methyl or ethyl. The aforementioned amides which do not contain hydroxy groups and amine oxides are described in detail in U.S. Patent 4,316,824, which is incorporated by reference.

Other surfactants which are suitable for use as foam builders / stabilizers in the compositions of the present invention are nonionic alkyl polyglycosides. These materials have the general formula:

R ₂ O (C _n H 2 _n O) _y (Z) _x (43) wherein Z is derived from glucose, R is a hydrophobic group selected from alkyl, alkylphenyl, hydroxyalkylphenyl and mixtures thereof, wherein said alkyl groups contain from 8 to 22 more preferably from 12 to 14 carbon atoms; n is 2 or 3, more preferably 2, y is from 0 to 10, more preferably 0; x is from 1.5 to 8, more preferably from 1.5 to 4, most preferably from 1.6 to 2.7. US Patents 4393203 and 4732704, which are incorporated herein by reference, disclose these alkylpolyglycoside-based surfactants.

Thickener

The dishwashing detergent compositions herein may also contain from about 0.2% to 5% of a thickening agent. Even more preferably, these thickeners will comprise from about 0.5% to 2.5% of the compositions of the present invention. Thickening agents are generally selected from the cellulose derivatives class. Suitable thickeners include hydroxyethylcellulose, hydroxyethylmethylcellulose, carboxymethylcellulose, Quatrisoft LM200 and the like. A more preferred thickening agent is hydroxypropyl methylcellulose.

The hydroxypropyl methylcellulose polymer has an average molecular weight of about 50,000 to 125,000 and a viscosity of 2 wt. % aqueous solution at 25 ° C (ADTMD2363) of about 50,000 to about 10,000 cps. A particularly preferred hydroxypropylcellulose polymer is Methocel (R) J75MS-N, which has a viscosity of 2 wt. % aqueous solution at 25 ° C about 75000 cps. Particularly preferred hydroxypropyl cellulose polymers are surface-treated polymers such that the hydroxypropyl cellulose polymer is readily dispersible at 25 ° C into an aqueous solution having a pH of at least about 8.5.

When hydroxypropyl methylcellulose polymers are formulated in the dishwashing detergent compositions of the present invention, the polymer should confer a Brookfield viscosity at 25 ° C of from about 500 to 3500 cps. Even more preferably, hydroxypropyl methylcellulose will confer a viscosity at 25 ° C of from about 1000 to 3000 cps. For the purposes of the present invention, the viscosity is measured using a Brookfield viscometer LVTDV11 using RV # 2 at 12 rpm.

Calcium and / or magnesium ions

The presence of calcium and / or magnesium (divalent) ions increases in various formulations, i. compositions containing alkyl ethoxy sulfates and / or polyhydroxy fatty acid amides; This is particularly true when the compositions are used in softened water that contains few divalent ions. Calcium and / or magnesium ions are believed to increase the aggregation of surfactants at the oil / water interface, thereby reducing interfacial tension and improving grease cleaning.

Compositions of the present invention that contain magnesium and / or calcium ions exhibit good grease removal, softness to the skin, and exhibit good storage stability. These ions may be present in the compositions herein in an effective amount of from about 0.1 wt. % to wt. 4%, more preferably from about 0.3 wt. % to 3.5 wt. %, even more preferably from about 0.5 wt. % to 1 wt. %.

More preferably, the magnesium or calcium ions are added to the compositions of the present invention in the form of hydroxide, chloride, acetate, formate, oxide or nitrate. Calcium ions can also be added as hydrotrope salts.

The amount of calcium or magnesium ions present in the compositions of the present invention will depend on the total amount of surfactant present. When calcium ions are present in the compositions of the present invention, the molar ratio of calcium ions to total anionic surfactant should be from about 0.25: 1 to about 2: 1.

Due to the incompatibility of divalent ions, in particular magnesium, with hydroxide ions, it may be difficult to formulate compositions containing these divalent ions into alkaline pH matrices. When both divalent ions and alkaline pH are combined in the surfactant mixtures of the present invention, better grease cleaning is achieved than either the alkaline pH alone or the divalent ions alone. However, the stability of these compositions is low during storage due to the formation of hydroxide precipitates. Therefore, the presence of chelating agents, which will be discussed later, may also be necessary.

Protease and / or other enzymes

The detergent compositions of the present invention may further comprise one or more enzymes that are beneficial in the purification process. Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malate, arabinosidases and mixtures thereof. A more preferred combination is a detergent composition which comprises a mixture of corresponding applicable enzymes such as proteases, amylases, lipases, cutinases and / or cellulases.

• ·· «0 00 00 • 000 000 • • 0 0 000 0 0 0 0

0 0 0 0 0 00 000 00 0 • 0000 0000 • ·· 0 · 00 00

The compositions of the present invention may also occasionally contain from about 0.0001 wt. % to about 5 wt. %, even more preferably from about 0.003 wt. % to about 4 wt. %, most preferably from about 0.005 wt. % to about 3 wt. % of active protease, i. proteolytic enzyme. Protease activity can be expressed in Anson units (AU) per kilogram of detergent composition. Activities of from 0.01 to about 150, more preferably from about 0.05 to about 80, most preferably from about 0.1 to about 40 AU per kilogram have been determined to be acceptable for the compositions of the present invention.

The source of useful proteolytic enzymes may be animals, plants or more preferably microorganisms. Even more preferred is a serine proteolytic enzyme of bacterial origin. Purified or unpurified forms of this enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included herein by definition as structurally similar enzyme variants. Proteases used herein in detergent compositions include, but are not limited to, trypsin, subtilisin, chymotrypsin, and elastase type proteases. Preferred for use in the present invention are proteolytic enzymes of the subtilisin type. More particularly, the bacterial serine proteolytic enzyme obtained from Bacillus subtilis and / or Bacillus lichenforniis is more preferred.

Suitable proteolytic enzymes include the commercially available Alcalase® (more preferred) from Novo Industrie A / S, Esperase®, Savinase® (Copenhagen, Denmark), Maxatase®, Maxacal® and Maxapem 15® (Maxacal® modified by protein engineering) from Gist-brocades (Delft, The Netherlands) and subtilisin BPN and BPN (more preferred). More preferred proteolytic enzymes are also modified bacterial broad proteases such as proteases produced by Genencor International, Inc. (San Francisco, California), which are described in EU patent EP-B-251446, issued December 28, 1994 and published January 7, 1998 (specifically pages 17, 24, and 98), also referred to herein as "Protease B". ". U.S. Pat. No. 5,030,378 (Venegas), issued July 9, 1991, relates to a modified bacterial serine proteolytic enzyme (Genencor International), referred to herein as "Protease A" (same as BPN '). A complete description, including the amino acid sequence of Protease A and variants thereof, can be found in particular in sections 2 and 3 of US patent 5030378. More preferred proteolytic enzymes are then selected from the group consisting of Alcalase® (Novo Industri A / S), BPN ', Protease A, Protease B (Genencor) and mixtures thereof. Protease B is most preferred.

Of particular interest for use in the present invention are the proteases disclosed in US Patent No. 5,470,733. Proteases described in U.S. Pending Application No. 08/136797 may also be incorporated into the detergent compositions of the present invention.

9 9 9 4

9 9 9

4 4 • 4 ····

99

9 9

9 9 · 9

9 9

44

Another more preferred protease, referred to as "Protease D", is a carbonyl hydrolase variant having an amino acid sequence that is not naturally occurring and which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a number of amino acid residues at position corresponding to +76 in said carbonyl hydrolase. also in combination with positions of one or more amino acid residues that are equivalent to positions selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, + 126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or + 274 according to the numbering of subtilisin from Bacilhis amyloliquefaciens as described in WO 95/10615, published April 20, 1995 (Genencor International).

Useful proteases are also described in PCT publications: WO 95/30010, published November 9, 1995 (The Procter & Gamble Company), WO 95/30011, published November 9, 1995 (The Procter & Gamble Company), WO 95/29979, published November 9, 1995 (The Procter & Gamble Company).

Other enzymes such as lipase and / or amylase may occasionally be added to the compositions of the present invention to further improve the cleansing performance.

Cellulases - The cellulases that can be used in the present invention include both bacterial and fungal cellulases. Suitable cellulases are disclosed in U.S. Patent 4,435,307 to Barbesgoard et al., Which discloses fungal cellulase produced by Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028, GB-A-2.095.275 and DE-OS-2.247.832.

Examples of cellulases are cellulases produced by Humicola insolens (Humicola grisea var. Thermoidea), in particular Humicola strain DSM 1800. Other suitable cellulases are cellulases derived from Humicola insolens and having a molecular weight of about 50 kDa, an isoelectric point of 5.5 and containing 415 amino acids. Particularly suitable are cellulases which are beneficial in terms of effect on color. Examples of such cellulases are described in EP application no. 91202879.2, filed Nov. 6, 1991 (Novo).

Peroxidase enzymes are used in combination with oxygen sources such as percarbonate, perborate, persulfate, hydrogen peroxide, etc. These enzymes are used to "whiten the solution" ie. to prevent the transfer of dyes or dyes removed from the substrates during the wash to other substrates in the wash solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro and bromoperoxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT Application WO 89/099813 and EP Application No. 91202882.6, filed November 6, 1991.

Said cellulases and / or peroxidases are normally present in the detergent compositions in an amount of from 0.0001 wt. % to 2 wt. % active enzyme.

00

0 0 0

0 0 0

0000 0 0 0 0

0

0 0 * 0 0 0 0 * 0 0

Lipase

Suitable lipase enzymes include those produced by Pseudomonas microorganisms such as Pseudomonas stutzeri, AICL 19.154, which is disclosed in British Patent 1372034. Suitable lipases are those that exhibit a positive immunological cross reaction with a lipase antibody produced by Pseudomonas fluorescens IAM 1057. 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, for example, M1 Lipase® and Lipomax® (Gist-Brocades). Other suitable commercial lipases include Amano-CES, Chromobacter viscosum lipases such as Chromobacter viscosum var. Lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Pat. Biochemical Corp., USA and Disoynth Co., The Netherlands and lipases from Pseudomonas gladioli. LIPOLASE® derived from Humicola lanuginosa and commercially available from NOVO, see also EP 341947, is preferred for use in the present invention. Lipase and amylase variants that are stabilized against peroxidases are described in WO 9414951 A (Novo) or in WO 9205249 and RD 94359044.

Very preferred are lipases D96L, which is a lipolytic enzyme variant of native lipase derived from Humicola lanuginosa, which is described in US periodical no. 08/341826. This is also disclosed in patent application WO 92/05249, in which the aspartic acid residue (D) at position 96 is changed to leucine (L) in the native Humicola lanuginosa lipase. According to this nomenclature, said substitution of aspartic acid for leucine at position 96 is shown as: D96L. More preferably, Humicola lanuginosa strain DSM4106 is used.

Despite a large number of lipase publications, only lipases originating from Humicola lanuginosa and produced in Aspergillus oryzae as hosts as detergent additives find wide application. They are available from Novo Nordisk under the trade names Lipolase® and Lipolase Ultra® mentioned above. To optimize the effect of Lipolas on stain removal, Novo Nordisk has prepared a number of variants. As described in WO 92/05249, the D96L variant of native Humicola lanuginosa lipase improves the grease stain removal effect of a factor of 4.4 compared to conventional lipase (enzymes are compared in amounts of 0.075 to 2.5 mg protein / L). Research Report No. 35944, published March 10, 1994 (Novo Nordisk), discloses that the lipase variant (D96L) can be added in amounts corresponding to 0.001 to 100 mg (5 to 500000 LU / L) of variant per 1 liter of wash solution.

• »0 # 00 0» 00 ··· 000 0000

000 0 · 0 <· 0000

T 0 000000 00 0 00 0 «0 • 0000 0000 • 0 0 00 00 00 00

Also suitable are cutinases (EC 3.1.1.50), which can be considered a special kind of lipase, namely lipases that do not require interphase activation. The addition of cutinases to detergent compositions has been described, for example, in WO-A-88/09367 (Genencor).

Lipases and / or cutinases are normally present in the detergent composition in an amount of from 0.0001 wt. % to 2 wt. % active enzyme.

Amylase

Amylases (and and / or β) may be incorporated to remove carbohydrate-based stains. Suitable amylases are Termamyl® (Novo Nordisk), Fungamyl® and BAN® (Novo Nordisk). The enzymes may be derived from any suitable sources such as plant, animal, bacteria, fungi and yeast. Amylases are normally present in detergent compositions in an amount of from 0.0001 wt. % to 2 wt. % active enzyme.

Amylases also include those described in WO 95/26397 and PCT / DK96 / 00056 filed by Novo Nordisk. Thus, other specific amylases used in the detergent compositions of the present invention include:

(a) α-amylase, characterized by having a specific activity at least 25% higher than that of Termamyl® at a temperature in the range of 25 ° C to 55 ° C and at a pH in the range of 8 to 10, wherein the α-amylase activity was measured using a Phadebas® aamylase activity assay kit. The determination of α-amylase activity by Phedebas® is described on pages 9-10, WO 95/26397.

(b) the α-amylase of (a) comprising the amino acid sequence shown in SEQ ID NO in the references cited above, or α-amylase having at least 80% homology to the amino acid sequence shown in SEQ ID NO.

(c) α-amylase according to (a), comprising at the N-terminus the following amino acid sequence: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp- Tyr-Leu-Pro-Asn-Asp.

A polypeptide exhibits X% homology to parental amylase when a comparison of the corresponding amino acid sequences, which is performed using an algorithm such as described by Lipman and Pearson in Science 227, 1985, p. 1435, shows X% identity.

(d) the α-amylase according to (a-c), wherein the α-amylase is obtainable from the alkalophilic Bacillus species and in particular from any strain of NCIB 12289, NCIB12512, NCIB 12513 and DSM 935.

In the context of the present invention, the term "recoverable from" is intended not only to find amylase produced by the Bacillus strain, but also to amylase, encoded by the DNA sequence, this to this to this to this. Isolated from this Bacillus strain and produced in a host organism that is transformed by this DNA sequence .

(e) α-amylase, showing positive immunological cross-reactivity with anti-α-amylase antibodies having an amino acid sequence corresponding to the corresponding aamylases sequences of (a-d).

(f) Variants of the following parent α-amylases which (i) have one of the amino acid sequences corresponding to the α-amylases in (ae) or (ii) exhibit at least 80% homology with one or more of said amino acid sequences and / or exhibit immunological cross-reactivity with an anti-α-amylase antibody having one of said amino acid sequences and / or encoded by a DNA sequence that hybridizes to the same probe as the α-amylase-encoding DNA sequence having one of said amino acid sequences. The variants were:

1. removing at least one amino acid residue of said parent α-amylase and / or

2. at least one amino acid residue of said parent α-amylase has been replaced by another amino acid residue and / or

3. inserting at least one amino acid residue similar to said parent α-amylase; a variant having α-amylase activity and exhibiting at least one of the following properties associated with parental α-amylase: increased thermostability, increased oxidation stability, decreased Ca ion dependence, increased stability and / or α-amylolytic activity at neutral to relatively high pH, increased α-amyolytic activity at relatively high temperatures, and increasing or decreasing the isoelectric point (pI) to achieve a better match of pI for the aamylase variant with the pH of the medium.

Variants are described in patent application PCT / DK96 / 00056.

Other α-amylases suitable for use in the present invention include, for example, α-amylases described in GB 1296839 (Novo); RAPIDASE® (International Bio-Synthetics, Inc.) and TERMAMYL® (Novo). FUNGAMYL® from Novo is particularly useful. Enzyme modifications are known to increase enzyme stability, e.g., oxidative stability. This can be found eg in J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521. Certain more preferred embodiments of the present compositions may use amylases that have increased stability in detergents such as automatic dishwashing detergents, in particular increased oxidation stability, as measured. against the reference value for TERMAMYL in commercial use in 1993. These more preferred amylases are involved here in the characteristics for which they are referred to as &quot; enhanced stability &quot;

by at least measurable increase of one or more of the following parameters: oxidative stability eg to a buffered hydrogen peroxide / tetraacetylethylenediamine solution at pH 9 to 10, temperature stability eg at normal wash temperatures such as about 60 ° C or alkaline stability eg at pH from about 8 to about 11. These parameters are measured against the above-identified reference α-amylase. Stability can be measured by any technical assay known in the art, see, for example, the references in WO 9402597. Amylases with increased stability can be obtained from Novo or Genencor International. For one class of particularly preferred amylases, it is essential that they are derived by site-directed mutagenesis from one or more Bacillus amylases, in particular Bacillus α-amylases, regardless of whether the immediate precursors are one, two or more α-amylase strains. Amylases having enhanced oxidation stability are superior to the above-identified reference amylases in terms of use, particularly in bleaching, more preferably oxygen bleaching, as distinct from chlorine-based bleaching detergent compositions. These more preferred amylases include (a) the amylase of WO 9402597 (Novo) hereinbefore, February 3, 1994, which is further elucidated by a mutant substituting a methionine residue located in B. licheniformis α-amylase known such as TERMAMYL®, at position 197, or at the homologous position, variants of a similar parental amylase such as from B. amyloliquefaciens, B. subtilis or B. stearothermophilus, alanine or threonine, more preferably threonine; (b) Amylases with enhanced stability, as described in Genencor International's article, "Oxidatively Resistant alpha-Amylases," presented by C. Mitchinson at the 207th American Chemical Society International Meeting, 13-17 March 1994. There was reported that the bleaching agents of the detergents used in automatic dishwashing inactivate the aamylases, but that Genencor prepared amylases with enhanced oxidative stability from B. licheniformis NCIB8061. Methionine (Met) has been identified as the easiest to modify. Met was substituted simultaneously at positions 8, 15, 197, 256, 304, 366 and 438 resulting in specific mutants, with M197L and M197T being particularly important and the M197T variant being the most stably expressed variant. Stability has been measured in CASCADE® and SUNLICHT® (c) more particularly preferred amylases herein include amylase variants that contain additional modifications to the immediate parent as described in WO 9510603 A and are available from Novo as DURAMYL®. Other particularly preferred amylases with enhanced oxidation stability are described in WO 9418314 (Genencor International) and WO 9402597 (Novo). Any other amylases with increased oxidation stability can be used, eg, modified by site-directed mutagenesis from known chimeric, hybrid or simply mutated parental forms of available enzymes. Other more preferred enzyme modifications are also possible. eg WO 9509909 A (Novo).

Enzyme stabilization system

More preferred compositions of the present invention may also further comprise from about 0.001 wt% to about 10 wt%. %, more preferably from about 0.005 wt. % to about 8 wt. %, most preferably from about 0.01 wt. % to about 6 wt. % enzyme stabilizing system. The enzyme stabilization system may be any stabilization system that is compatible with the protease or other enzymes used in the compositions of the present invention. Such stabilization systems may include calcium ions, boric acid, propylene glycol, short carboxylic acids, polyhydroxyl compounds, and mixtures thereof, described in U.S. Patents 4261868 (Hora et al), issued April 14, 1981, 4404115 (Tai), issued September 13, 1983. 4318818 (Letton et al.), 4243543 (Guildert et al.), Issued January 6, 1981; 4462922 (Boskamp), issued July 31, 1984; 4532064 (Boskamp), issued July 30, 1985; and 4537707 (Severson Jr.). issued August 27, 1985. All of these patents are incorporated herein by reference.

One approach to stabilization is the use of water-soluble sources of calcium and / or magnesium ions that provide these ions to the enzymes as part of the finished compositions. Calcium ions are generally more effective than magnesium ions and are more preferred when only one type of ion is to be used. Typical detergent compositions, particularly liquids, will contain from about 1 to about 30, more preferably from about 2 to about 20, even more preferably from about 8 to about 12 millimoles of calcium ions per liter of final detergent composition, however, depending on factors including multiplicity, type and amount of enzymes involved, some variation is possible. More preferably, water-soluble calcium or magnesium salts, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide, and calcium acetate, more generally calcium sulfate or magnesium salts corresponding to said calcium salts may be used. Furthermore, increased levels of calcium and / or magnesium may of course be used, for example, to support the grease disruption process by certain types of surfactants.

Another approach to stabilization involves the use of borates, see, e.g., Severson, US 4537706. If borate stabilizers are used, they may be present in amounts up to 10 wt. % or more, although up to about 3 wt.% are more typical for liquid detergents. % boric acid or other boric compounds such as borax or orthoborate. Substituted boric acids such as phenylboronic acid may be used in place of boric acid.

0 · 0 0 0 0 · ·· 0 ······ 0 0 0 · · · · 0

0000 00 · 0

00 00 0 · 00 butaneboronic acid, p-bromophenylboronic acid and the like. By using these substituted derivatives, it is also possible to reduce total boron levels in detergent compositions.

Further, chlorine or oxygen based bleaching agents can be added to the compositions in amounts ranging from 0 wt. % to about 10 wt. %, more preferably from about 0.01 wt. % to about 6 wt. %. These substances prevent chlorine-based bleaches present in a number of water sources from attacking and inactivating enzymes, particularly in alkaline conditions. Although the amount of chlorine in the water may be low, usually in the range of about 0.5 ppm to about 1.75 ppm, the amount of chlorine in the total volume of water that comes into contact with the enzyme during dishwashing is usually large and hence stability may be enzyme problem during use.

Suitable chlorine scavenger anions include salts containing ammonium cations. These may be selected from the group consisting of reducing agents such as sulfite, bisulfite, thiosulfite, thiosulfate, iodide etc., antioxidants such as carbonate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or its alkali metal salts and monoethanolamine (MEA) and mixtures thereof. Other conventional scavenger anions such as sulfate, hydrogen sulfate, carbonate, bicarbonate, percarbonate, nitrate, chloride, borate, sodium perborate tetrahydrate, sodium perborate monohydrate, percarbonate, phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, lactate, malate, tartrate, salicylate and the like, and mixtures thereof.

Various special ingredients

Other special additives which are generally used in amounts of less than 5% include opaque agents, antioxidants, bactericides, paints, perfumes and the like. Detergent builders may also be present in the compositions in amounts of from 0% to about 50%, more preferably from about 2% to about 30%, most preferably from about 5% to about 15%. Liquid or gel detergent dishwashing compositions intended for light working conditions are typically free of detergent builders. However, some formulations containing magnesium or calcium ions may require the presence of a small amount, more preferably from 0 to about 10%, even more preferably from about 0.5% to about 3% of a chelating agent selected from the group consisting of bicin / bis (2ethanol) (blycine), citrate-N- (2-hydroxyethyl) iminodiacetic acid (HIDA), N- (2,3-dihydroxypropyl) diethanolamine, 1,2-diamino-2-propanol N, N'-tetramethyl-1,3-diamino- 2-propanol, N, N-bis (2-hydroxyethyl) glycine (aka bicin), and more preferably N-tris is also preferably fefe. fefe fefe · ·· · • fefefefe ···· • fe fefe fefe fefe · (hydroxymethyl) methylglycine (aka tricine). Any mixtures of the above materials are also acceptable.

PH composition

The dishwashing compositions of the present invention will generally provide a pH of a 10% aqueous solution of from about 4 to 11. More preferably, the compositions of the present invention will be alkaline, with a pH of 10% aqueous solution of from about 7 to 10.5.

Dishwashing compositions of the present invention will be subjected to a load of acidity that will be created by soiling the food items during application (i.e., diluted and applied to soiled dishes). In order to be more effective at a pH of greater than 7, the composition should contain a buffering agent capable of providing a generally more alkaline pH of the composition and of the dilute solution, i.e., the pH of the composition. about 0.1 wt. % to 0.4 wt. % aqueous solution of the composition. The pKa of this buffering agent should be about 0.5 to 1.0 pH unit lower than the desired pH of the composition (as determined by the procedure described below). More preferably, the pKa of the buffering agent should be from about 7 to about 9.5. Under these conditions, the buffering agent most effectively regulates the pH, although a minimal amount is used.

The buffering agent may itself be an active detergent or may be a low molecular weight organic or inorganic substance which is used in the composition only to maintain the alkaline pH. Buffering agents that are more preferred for the compositions of the present invention are nitrogen-containing substances. Examples are amino acids or amines of lower alcohols such as mono-, di- and triethanolamine. Useful inorganic buffers / alkalinity sources include alkali metal carbonates such as sodium carbonate.

When a buffering agent is used, it is present in the compositions of the present invention in an amount of from about 0.1 wt. % to 15 wt. %, more preferably from about 1 wt. % to 10 wt. % and most preferably from about 2 wt. % to 8 wt. %.

A particularly preferred buffering agent comprises a class of substances known as organic diamines. More preferred are those organic diamines whose pK1 and pK2 are in the range of about 8.0 to about 11.5, more preferably in the range of about 8.4 to about 11, even more preferably from about 8.6 to about 10.75. Substances that are more preferred for efficacy and administration are 1,3-propanediamine (pK1 = 10.5; pK2 = 8.8), 1,6-hexanediamine (pK1 = 11; pK2 = 10), 1,3- pentanediamine (Dytek EP) (pK1 = 10.5; pK2 = 8.9), 2-methyl-1,5-pentanediamine (Dytek A) (pK1 = 11.2; pK2 = 10.0). Other more preferred materials include primary / primary diamines with alkylene arms having a length from C4 to Cs. It is generally believed that primary diamines are preferable to secondary and tertiary diamines.

• Φ

0

Definition of pK1 and pK2

As used herein, "pK1" and "pK2" are quantities generally known to those skilled in the art as "pKa". pKa is used herein in the same sense as is well known to those skilled in the art of chemistry. Values referred to herein may be found in literature such as "Critical Stability Constants: Volume 2, Amines" by Smith and Martel, Plenum Press, NY and London, 1975. Further information on pKa can be obtained from the appropriate company literature such as information from Dupont, a supplier of diamines.

In the working definition, the pKa of the diamines is specified for an aqueous solution at 25 ° C and for an ionic strength between 0.1 and 0.5 M. pKa is an equilibrium constant that can vary with temperature and ionic strength. Therefore, the values reported in the literature may sometimes vary depending on the measurement method used and conditions. To avoid ambiguity, the respective conditions and / or references used for the pKa of the present invention are defined herein or in "Critical Stability Constants: Volume 2, Amines". One typical measurement method is potentiometric titration of acid with sodium hydroxide and determination of pKa using suitable methods as described and referred to in the "The Chemist Ready Ready Handbook" by Shugar and Dean, McGraw Hill, NY, 1990.

It has been determined that substituents and structural modifications that lower pK1 and pK2 below about 8.0 are undesirable and cause efficacy losses. This may include substitutions leading to ethoxylated diamines, hydroxyethyl substituted diamines, diamines with oxygen in the β-position (and less gamma) relative to the wax nitrogen (eg, Jfamine EDR 148). Furthermore, ethylenediamine-based substances are not suitable.

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

RK / C _{x x} Cy / R 3> Ά <

R 2 R 4 (44) wherein R 1 to 4 are independently selected from hydrogen, methyl, -CH 3 CH 2 and ethylene oxides; C _x and C _y are independently selected from methylene groups or branched alkyl groups wherein x + y is from about 3 to about 6 and A is optionally present and is selected from electron donor or acceptor moieties which have been designed for adjusting the pKa of the diamines to the desired range. If A is present, then xiy must be 1 or higher.

Examples of more preferred diamines are as follows:

00

0 0 0

0 0 0 0 0

0

Dimethylaminopropylamine

1,6-hexanediamine

(45)

H ₂ N nh ₂ (46)

1,3-propanediamine

Η Ν ₂ ^{/ 'χΖΧ ΝΗ} ₂ (47)

2-methyl-1,5-pentanediamine

H ₂ N

(48)

1,3-pentanediamine, available under the tradename DytekEP nh ₂ (49)

-methyl-diaminopropane

(50)

JeffaminEDR 148

H ₂ N

nh ₂

fefe fefe fefe fefe fe fefe fefe fefe fefe fefe fefe fefe (51) and mixtures thereof.

Only when organic diamines as an approximately equimolar substitute to Ca / Mg are tested in a region close to neutral pH (7-8) do they provide the same grease cleaning effect as Ca / Mg. This cannot be achieved with Ca / Mg or with organic diamines below pH 8 or with salts of organic diamines below pH 8.

The diamines used in the present invention are more preferably pure or free of impurities. By the term "pure" is meant that the purity of the diamines is more than 97%, ie. they do not contain impurities more preferably 98%, even more preferably 99% and even more preferably 99.5%. Examples of impurities that may be present in commercially available diamines are 2-methyl-1,3-diamino-butane and alkyl hydropyrimidine. It is further believed that diamines should not contain oxidizing reactants to avoid diamine degradation and ammonia formation. Further, if amine oxides and / or other surfactants are present, the amine oxide or surfactant should not contain hydrogen peroxide. The amount of hydrogen peroxide in the amine oxide or amine oxide paste is more preferably 0 to 40 ppm, even more preferably 0 to 15 ppm. If amine impurities are present in amine oxide and betaine, they should be minimized to the levels indicated above for hydrogen peroxide. The compositions herein may further comprise antioxidants to prevent the formation of ammonia during aging as a result of trapping oxygen from the air and subsequently oxidizing the diamines.

Preparation of the composition

The dishwashing liquid or gel detergent compositions of the present invention can be prepared by combining the necessary and optional ingredients with any suitable mixing to form a homogeneous product. More preferred methods of preparing detergent compositions of the type disclosed herein and methods of preparing the various components of these compositions are described in detail in Ofos-Asante: US 5474710, issued December 12, 1995. To a large extent due to the chemical properties of surfactants 0 · 0 0

0 · 0 0000 0 00 0

00 ·· 00 00 0 0 0 0 · 0 ς 0000000000

The mid-chain branched objects of the present invention are liquid detergent compositions herein defined at temperatures above about 10 ° C in one phase and can be diluted during use with water having a hardness of at least about 40 gpg, wherein: there is no or only a small decrease in efficacy.

Method of washing dishes

Soiled dishes may come into contact with an effective amount of the detergent composition of the present invention, which is typically from about 0.5 ml to about 20 ml (per 25 pieces of dishwashed), more preferably from about 3 ml to about 10 ml. The actual amount of liquid detergent composition employed will depend on the consumer and will generally depend on factors such as the particular formulation of the composition, including the concentration of the active ingredient in the composition, the number of soiled dishes to be washed, the degree of soiling, etc. many factors such as market choice for the device (ie US, Europe, Japan, etc.). The following examples are examples of typical methods in which the detergent compositions of the present invention can be used for dishwashing. These examples are illustrative only and are not intended to be limiting in any way.

In an application typical of the US, from about 3 ml to about 15 ml, more preferably from about 5 ml, is combined in a sink having a bulk capacity ranging from about 5000 ml to about 20000 ml, more typically from about 10000 ml to about 15000 ml. to about 10 ml of a liquid detergent composition with from about 1000 ml to about 10000 ml, more typically from about 3000 ml to about 5000 ml of water. The concentration of the surfactant mixture in the detergent composition is from about 21 wt. % to about 44 wt.

%, more preferably from about 25 wt. % to about 40 wt. %. The soiled dishes are immersed in a container containing detergent and water, where the dishes are cleaned by contacting the soiled surface of the dishes with a cloth, sponge or the like. The rag, sponge or the like may be immersed in the detergent / water mixture prior to contact with the surface of the dishes. The length of time they are in contact with the surface of the dishes varies from about 1 to about 10 seconds, although the actual time will depend on each individual application and the consumer. The contact of the cloth, sponge or the like with the surface of the dish is more preferably accompanied by a simultaneous scrubbing of the surface of the dish.

In an application typical of the European market, from about ml to about 15 ml, more preferably from about 3 ml, to about 15 ml, more typically from about 10000 ml to about 15000 ml, is combined in a sink having a bulk capacity ranging from about 5000 ml to about 20000 ml. ml to about 10 ml of a liquid detergent composition having from 4 to 44 ml

444 4 4 4 4445

4 · 4444 4 · · 4

444 · ·· · 44 · · · · ·

4 4444 4444

444 4 ·· 44 44 44 at least 1000 ml to about 10000 ml, more typically from about 3000 ml to about 5000 ml of water. The concentration of the surfactant mixture in the detergent composition is from about 20 wt. % to about 50 wt. %, more preferably from about 30 wt. % to about 40 wt. %. The soiled dish is immersed in a sink containing detergent and water, where it is cleaned by bringing the soiled surface of the dish into contact with a cloth, sponge or the like. The rag, sponge or the like can be immersed in the detergent / water mixture prior to contact with the surface of the dishes. The length of time they are in contact with the cookware surface generally ranges from about 1 to about 10 seconds, although the actual time will depend on each individual application and consumer. The contact of the rag, sponge or the like with the surface of the dish is more preferably accompanied by a simultaneous scrubbing of the surface of the dish.

During an application typical of Latin America, from about 1 ml to about 50 ml, more preferably from about 1 ml to about 50 ml, more preferably about 1 ml to about 50 ml, more preferably about 1 ml to about 50 ml, is combined in a bowl. from about 2 ml to about 10 ml of the detergent composition with from about 50 ml to about 2000 ml, more typically from about 100 ml to about 1000 ml of water. The concentration of the surfactant mixture in the detergent composition is from about 5 wt. % to about 40 wt. %, more preferably from about 10 wt. % to about 30 wt. %. Soiled dishes are cleaned by contacting the soiled surface with a cloth, sponge, or similar object. The rag, sponge, or the like may be immersed in the detergent composition and water prior to contact with the surface of the dishes. The length of time they are in contact with the surface of the dishes varies from about 1 to about 10 seconds, although the actual time will vary for each application and consumer. The contact of the cloth, sponge or the like with the surface of the dish is more preferably accompanied by a simultaneous scrubbing of the surface of the dish.

Another method of dishwashing that is used worldwide includes direct application of the detergent composition herein, either undiluted or diluted in a storage bottle, to a soiled surface to be washed. Washing can be accomplished with an article for absorbing a liquid dishwashing detergent such as a sponge or dishcloth, which is placed directly into a separate amount of undiluted or somehow diluted liquid dishwashing composition for a time that is typically in the range of The absorbent article and hence the undiluted or somehow diluted liquid dishwashing composition may be contacted with the surface of the individual soiled items to remove soil from food. The absorbent article is generally contacted with each surface of the individual cookware for about 1 to about 10 seconds, although the actual application time will depend on factors such as the degree of soiling of the cookware. Absorbing Contact • to • to • to • to • to • to • to · to · to · to · to · to · to · to · to · to · to · to · to This article with the surface of the dishes is preferably accompanied by simultaneous scrubbing. Before the dishes are in contact with the detergent and before scrubbing, the method may further comprise immersing the soiled dishes in water that does not contain any liquid dishwashing detergent. After scrubbing, the dishes can be rinsed under running water.

The following examples illustrate the present invention and facilitate its understanding, but are not intended to be limiting or otherwise defining the scope of the invention. Unless otherwise specified, all parts, percentages and ratios used herein are by weight.

DETAILED DESCRIPTION OF THE INVENTION

Example I Preparation of 7-methyltridecylethoxylated (E2) sulfate

Synthesis of (6-hydroxyhexyl) triphenylphosphonium bromide

A 5 L 3-neck round bottom flask equipped with nitrogen inlet, condenser, thermometer, mechanical stirrer and nitrogen outlet was charged with 6-bromo-1-hexanol (500 g, 2.76 moles), triphenylphosphine ( 768 g, 2.9 mol) and acetonitrile (1800 mL). The reaction mixture is then heated under reflux for 72 hours. The reaction mixture is then cooled to room temperature and transferred to a 5 L beaker. The product is recrystallized from anhydrous ethyl ether (1.5 L) at 10 ° C. Vacuum filtration, followed by washing with ethyl ether and drying in a vacuum oven at 50 ° C for 2 hours, afforded 1140 g of the desired product as white crystals.

Synthesis of 7-methyltridecen-1-ol

70.2 g of 60% sodium hydride (1.76 moles) in mineral oil is placed in a 5L dry, three-necked round-bottomed flask equipped with mechanical stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet. . The mineral oil is removed by washing with hexane. Anhydrous dimethylsulfoxide (500 mL) is then added to the flask and the mixture is heated to 70 ° C until hydrogen evolves. Thereafter, the reaction mixture is cooled to room temperature, followed by the addition of 1 L of anhydrous tetrahydrofuran. dropping funnel slowly added • 0 00 00 90 00

000,000 0 · 0 ·

000 0 0000 0 00 0

9000 00 09 090 00 0

9 0900 0009

990 9 99 99 90 99 to the reaction mixture, the temperature of which is maintained at 25 to 30 ° C. The mixture is 30 min. After stirring at room temperature, 2-octanone (140.8 g, 1.1 mol) was added slowly via an addition funnel. The reaction is slightly exothermic and needs to be cooled to 25-30 ° C. The mixture is stirred for 18 hours and then poured into a 5 L beaker containing 1 L of purified water to be stirred. The oil phase (top) can be separated in a separating funnel and the aqueous phase is removed. The aqueous phase is washed with hexane (500 mL) and the organic phase is separated and mixed with the oil phase from the previous water wash. The organic mixture is then extracted 3 times with water (500 mL each extraction), followed by vacuum distillation to give a clear, oily product (110 g) at 140 ° C and 1 mm Hg.

Hydrogenation of 7-methyltridecen-1-ol

A 3 L rotary autoclave is charged with 7-methyltridecen-1-ol (108 g, 0.508 mol), methanol (300 mL) and platinum on carbon (10 wt%, 35 g). The mixture is hydrogenated at 180 ° C under a hydrogen pressure of 8.3 MPa for 13 hours, then cooled and vacuum filtered through Celite 545, wherein the Celite 545 is washed, more preferably with methylene chloride. If necessary, filtration can be repeated to remove traces of platinum catalyst and magnesium sulfate can be used to dry the product. To obtain a clear oil (104 g), the product solution is concentrated on a rotary evaporator.

Alkoxylation of 7-methyltridecanol

The alcohol from the previous step is supplied to a 1 L three-necked round-bottomed flask equipped with nitrogen inlet, mechanical stirrer, y-tube with thermometer and gas outlet. In order to remove trace amounts of moisture, the alcohol is bubbled with nitrogen for about 30 minutes, at a temperature of 80 to 100 ° C. With continued nitrogen purge, sodium metal is added as a catalyst and allowed to melt at 120-140 ° C with stirring. In 140 min. ethylene oxide gas is added with vigorous stirring and the reaction temperature is maintained at 120-140 ° C. After the correct amount (equal to 2 equivalents of ethylene oxide) is added, the apparatus is 20 to 30 minutes. purge nitrogen to cool the sample. The desired product 7-methyltridecyl ethoxylate (with an average of 2 ethoxylates per molecule) is then obtained.

• 00 00 00 • 0 0 0 0 0 0 • 0000 0 00 0

00 000 00 0

0 0 0 0 ···· 00 00 · 0 · 0 • 0 0000

Sulfation of 7-methyltridecyl ethoxylate (E2)

To a dry, three-necked, round-bottomed flask of 11, equipped with nitrogen inlet, dropping funnel, thermometer, mechanical agitation and nitrogen outlet, chloroform and 7-methyltridecyl ethoxylate (E2) from the previous step are given. While stirring, chlorosulfuric acid is added to the mixture and the temperature is maintained at 25-30 ° C with an ice bath. Once the HCl release is complete, sodium methoxide (25% solution in methanol) is slowly added, maintaining the temperature at 25-30 ° C. The methoxide is added until a pH of 10.5 is maintained at a concentration in water of 5%. Hot ethanol (55 ° C) is added to the mixture and the mixture is immediately vacuum filtered. The filtrate is concentrated to a slurry on a rotary evaporator, then cooled and poured into ethyl ether. The mixture is cooled to 5 ° C and vacuum filtered. The sodium salt of the desired product 7-methyltridecylethoxy (on average 2 ethoxylates per molecule) of sulfate is then obtained.

EXAMPLES Preparation of C12,13 and C14,15 mid-chain branched sodium alcohol sulfate, alcohol ethoxylate and sodium alcohol ethoxy (E1) sulfate from experimental samples of alcohol clathrates from Sasol Chemical Industries Prop. Ltd. ("Sasol").

Experimental test samples of mid-chain branched alcohols are derived through the formation of clathrates of C12,13 and C14,15 alcohols from Sasol (Sasol alcohols) with urea. Alcohol sulfates, alcohol ethoxylates and alcohol ethoxy sulfates were prepared from experimental alcohols. The formation of urea clathrates was used to separate mid-chain branched alcohols from higher amounts (35-45% by weight) of conventional linear alcohols present in alcohol samples from Sasol. The molar ratios of urea to alcohol of 10: 1 to 20: 1 were used in the separation. The formation of urea clathrates is described in Advanced Organic Chemistry, J. March, 4th edition, Wiley and Sons, 1992, pp. 87-88, and in Takemoto; Sonoda, at Atwood; Davis; MacNicol entitled Inclusion Compounds, Vol. 2, pp. 47 to 67. Original alcohol samples of Sasol were prepared by hydroformylation of alphaolefins prepared by the Fischer-Tropsch reaction described in WO 97/01521 and according to the Sasol R&D technical collection, dated October 1, 1996 and named SASOL DETERGENT ALCOHOLS. Clathrate formation reduced the linear alcohol content from 35 to 45 wt. %, depending on the sample, to less than about 5 wt. %, to give 02.13 and 04.15 alcohols such that they contained about 95% branched alcohols. About 70% of the branched alcohols were branched mid-chain alcohols and the remaining 30% were branched alcohols at the 2-carbon position, calculated from oxygen in the alcohol. For experimental

9

9 9 9 9 9

9 9 9 9 9 9 9

9 9 9 9 9

9 9 9 9 9

99 99 99 99

Both the C 2-13 and C 14,15 mid-chain branched alcohols were synthesized sodium forms of alkyl sulfates and alkyl ethoxy (1) sulfates. Further, alcohol ethoxylates with ethoxylation ranging from 5 to 9 moles were prepared.

Clathrate formation Sasol 02.13 alcohol with urea

In a dry, three-neck, 12 L, round-bottomed flask equipped with a mechanical stirrer is added Sasol 02.13 alcohol (399.8 g, 2.05 mol), urea (2398.8 g, 39.98 mol) and methanol ( 7 1). The reactants were stirred at room temperature for 20 hours. During this time, the urea forms a complex with the linear components of the Sasol alcohol but not with the branched components. After about 20 hours, the suspension was filtered through a medium frit. Evaporation of methanol under vacuum, washing of urea with hexane and vacuum evaporation of hexane gave 189 g of a mostly colorless liquid. GC analysis showed that the alcohol obtained was 5.4% linear and 94.6% branched. 67.4% of the branched alcohols are branched in the middle of the chain and 32.6% are branched at the 2-carbon position, calculated from the oxygen in the alcohol.

Sulfation of Sasol Cl2.13 alcohol clathrate

In a dry 500 ml three-necked round-bottomed flask equipped with a gas inlet, dropping funnel, mechanical stirrer, y-tube with thermometer and gas outlet, clathrate Sasol 02.13 alcohol (76.8 g, 0.4 mol) ) and diethyl ether (75 mL). While stirring, chlorosulfuric acid (48.9 g, 0.42 mol) is slowly added to the mixture and the reaction temperature is maintained at 5 to 15 ° C using an ice water bath. Upon completion of the addition of chlorosulfuric acid, HCl is slowly removed by introducing nitrogen and pressure (250 to 375 mm Hg). The reaction is also heated to 30-40 ° C in a hot water bath. After about 45 min. the pressure is increased to 625-750 mm Hg and maintained for a further 45 min. The acidic reaction mixture is slowly poured into a beaker with a vigorously stirred 25% solution of sodium methoxide (97.2 g, 0.45 mol) and methanol (300 mL), which is cooled in an ice water bath. After the pH of the solution is> 12, the solution is an additional 30 min. stir and then pour into a clean bowl. Most of the solvent was evaporated in a fume hood overnight. The next day the sample is transferred to a glass container and placed in a vacuum oven. The sample is dried all day and night at 40 to 60 ° C and at a pressure of 625 to 750 mm Hg. After transferring 120 g of a yellow gooey solid into a vial, the sample was found to be about 94% active by cat SO3 analysis. The pH of the sample is about 11.9.

• ♦ · fe * fefe ·· • fefefe fefefe • fe fe «fefefe · fefe fe • fefefe fefe fefe fefe · fe fefefe fefefe ·· fefe fefe fefe fefe

Ethoxylation of Sasol Cl2.13 alcohol clathrate on E1

In a 500 ml three-necked, dry, round-bottomed flask equipped with a gas inlet, a mechanical stirrer, a Y-tube with a thermometer and a gas outlet, is added cassate Sasol 02.13 alcohol (134.4 g, 0.7 mol). To remove traces of moisture, the alcohol is 30 min. nitrogen was bubbled through at 60-80 ° C. With continued nitrogen feed, sodium metal (0.8 g, 0.04 mol) is added as a catalyst and left under stirring at 120 to 140 ° C to melt. Stirring vigorously with stirring for 60 min. ethylene oxide gas (30.8 g, 0.7 mol) was added while maintaining the reaction temperature at 120-140 ° C. After the correct amount of ethylene oxide is added, it is for 20 to 30 minutes. Nitrogen is pumped through the apparatus until the sample is cooled. The yellow-brown liquid product (164.0 g, 0.69 mol) is transferred into a vial under nitrogen.

Sulphation of clathrate ethoxylate Sasol Cl2,13 alcohol (E1)

In a dry, 2-neck, 2-L round-bottomed flask equipped with a gas inlet, dropping funnel, mechanical stirrer, y-tube with thermometer and gas outlet, Sasol 02.13 alcohol (E1) ethoxylate (160.5 g, 0.68 mol) and diethyl ether (150 ml). While stirring, chlorosulfuric acid (82.7 g, 0.71 mol) is slowly added to the mixture and the reaction temperature is maintained at 5 to 15 ° C using an ice water bath. Upon completion of the addition of chlorosulfuric acid, HCl is slowly removed by introducing nitrogen and pressure (250 to 375 mm Hg). The reaction is also heated to 30-40 ° C in a hot water bath. After about 45 min. the pressure is increased to 625-750 mm Hg and maintained for a further 45 min. The acidic reaction mixture is slowly poured into a beaker with a vigorously stirred 25% solution of sodium methoxide (164.2 g, 0.76 mol) and methanol (500 mL), which is cooled in an ice water bath. After the pH of the solution is> 12, the solution is an additional 30 min. stir and then pour into a clean bowl. Most of the solvent was evaporated in a fume hood overnight. The next day the sample is transferred to a glass container and placed in a vacuum oven. The sample is dried all day and night at 40 to 60 ° C and at a pressure of 625 to 750 mm Hg. After transferring 239 g of a yellow gooey solid into a vial, the sample was found to be about 87% active by cat SO3 analysis. The pH sample is about 12.6.

Clathrate formation Sasol C 4.15 alcohol with urea

A 12 liter dry three-necked round-bottomed flask equipped with a mechanical stirrer is charged with Sasol Cl4.15 alcohol (414.0 g, 1.90 mol), urea (2220.0 g, 37.0 mol) and »· 0 «00» 0 00 0 · 0 0 0 0 0 0 · · 0 0 0 0 0 0 0

CQ 0 0000 00 00 000

J? 0000000000 • 00 0 »0 00 00» · methanol (3.5 L). The reactants were stirred at room temperature for 48 hours. During this time, the urea forms a complex with the linear components of the Sasol alcohol but not with the branched components. After about 48 hours, the suspension was filtered through a medium frit. Evaporation of methanol in vacuo, washing of urea with hexane and vacuum evaporation of hexane yielded 220 g of a mostly colorless liquid. GC analysis showed that the alcohol obtained was 2.9% linear and 97.1% branched. 70.4% of the branched alcohols are branched in the middle of the chain and 29.6% are branched at the 2-carbon position, calculated from the oxygen in the alcohol,

Sulfation of clathrate Sasol C14,15 alcohol

In a 250 ml dry three-necked round-bottomed flask equipped with a gas inlet, dropping funnel, mechanical stirrer, y-tube with thermometer and gas outlet, cassate Sasol 04.15 alcohol (43.6 g, 0.2 mol) and diethyl ether (50 mL). While stirring, chlorosulfuric acid (24.5 g, 0.21 mol) is slowly added to the mixture and the reaction temperature is maintained at 5 to 15 ° C using an ice water bath. Upon completion of the addition of chlorosulfuric acid, HCl is slowly removed with the supplied nitrogen and pressure (250 to 375 mm Hg). The reaction is also heated to 30-40 ° C in a hot water bath. After about 45 min. the pressure is increased to 625-750 mm Hg and maintained for a further 45 min. The acidic reaction mixture is slowly poured into a beaker with a vigorously stirred solution of 25% sodium methoxide (49.7 g, 0.23 mol) and methanol (200 mL), which is cooled in an ice bath. After the pH of the solution is> 12, the solution is an additional 30 min. stir and then pour into a clean bowl. Most of the solvent was evaporated in a fume hood overnight. The next day the sample is transferred to a glass container and placed in a vacuum oven. The sample is dried all day and night at 40 to 60 ° C and at a pressure of 625 to 750 mm Hg. After transferring 70 g of a tan powder to the vial, the sample was found to be about 79% active by cat SO3 analysis. The pH sample is about 13.1.

Ethoxylation of clathrate Sasol C14,15 alcohol on E1

A 500 mL dry three-necked round-bottomed flask equipped with a gas inlet, a mechanical stirrer, a y-tube with a thermometer and a gas outlet is charged with Sasol C 14.15 alcohol clathrate (76.3 g, 0.35 mol). The alcohol is 30 minutes to remove trace amounts of moisture. nitrogen was bubbled through at 60-80 ° C. With continued nitrogen addition, sodium metal (0.4 g, 0.02 mol) is added as a catalyst and left under stirring at 120 to 140 ° C to melt. Stirring vigorously is 35 min. gaseous ethylene oxide (15.4 g, 0.35 mol) was added and the reaction temperature was maintained at 120-140 ° C. After the correct amount of ethylene oxide is added, it is for 20 to 30 minutes. Nitrogen is pumped through the apparatus until the sample is cooled. The yellow-brown liquid product (90 g, 0.34 mol) is transferred into a vial under nitrogen.

Sulphation of clathrate ethoxylate Sasol 04,15 alcohol (E1)

In a 500 ml dry three-necked round-bottomed flask equipped with a gas inlet, dropping funnel, mechanical stirrer, y-tube with thermometer and gas outlet, Sasol 04.15 alcohol (E1) alcohol ethoxylate (86.5 g, 0.33 mol) and diethyl ether (100 ml). While stirring, chlorosulfuric acid (40.8 g, 0.35 mol) is slowly added to the mixture and the reaction temperature is maintained at 5 to 15 ° C using an ice water bath. Upon completion of the addition of chlorosulfuric acid, HCl is slowly removed by introducing nitrogen and pressure (250 to 375 mm Hg). The reaction is also heated to 30-40 ° C in a hot water bath. After about 45 min. the pressure is increased to 625-750 mm Hg and maintained for a further 45 min. The acidic reaction mixture is slowly poured into a beaker with vigorously stirred 25% sodium methoxide solution (82.1 g, 0.38 mol) and methanol (300 mL), which is cooled in an ice bath. After the pH of the solution is> 12, the solution is an additional 30 min. stir and then pour into a clean bowl. Most of the solvent was evaporated in a fume hood overnight. The next day the sample is transferred to a glass container and placed in a vacuum oven. The sample is dried all day and night at 40 to 60 ° C and at a pressure of 625 to 750 mm Hg. After transferring 125 g of a tan powder to a vial, the sample was found to be about 85% active by cat SO3 analysis. The pH sample is about 11.9.

Example III Preparation of sodium 7-methylenedecyl sulfate

Synthesis of 7-methylenedecen-1-ol

70.2 g of 60% sodium hydride (1.76 moles) in mineral oil is placed in a 5L dry, three-necked round-bottomed flask equipped with mechanical stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet. . The mineral oil is removed by washing with hexane. Anhydrous dimethylsulfoxide (500 mL) is then added to the flask and the mixture is heated to 70 ° C until hydrogen evolves. Thereafter, the reaction mixture is cooled to room temperature, followed by the addition of 1 L of anhydrous tetrahydrofuran. (6-hydroxyhexyl) triphenylphosphonium bromide (443.4 g, 1 mol, prepared as described above) is suspended in hot anhydrous dimethylsulfoxide (50 ° C, 500 mL), and the suspension is slowly added to the reaction mixture via an addition funnel. the temperature of which is maintained at 25-30 ° C. The mixture is 30 min. After stirring at room temperature, 2-hexanone (110 g, 1.1 mol) was added slowly via an addition funnel. The reaction is slightly exothermic and needs to be cooled to 25-30 ° C. The mixture is stirred for 18 hours and then poured into a 5 L beaker containing 1 L of purified water to be stirred. The oil phase (top) can be separated in a separating funnel and the aqueous phase is removed. The aqueous phase is washed with hexane (500 mL) and the organic phase is separated and mixed with the oil phase from the previous water wash. The organic mixture is then extracted 3 times with water (500 ml each extraction), followed by vacuum distillation to obtain a clear, oily product at 140 ° C and a pressure of 1 mm Hg.

Hydrogenation of 7-methylenedecen-1-ol

A 3 L rotary autoclave is charged with 7-methylenedecen-1-ol (93.5 g, 0.508 mol), methanol (300 mL) and platinum on carbon (10 wt%, 35 g). The mixture is hydrogenated at 180 ° C and at a hydrogen pressure of 8.3 MPa for 13 hours, then cooled and vacuum filtered through Celite 545, wherein the Celite 545 is washed, more preferably with methylene chloride. If necessary, filtration can be repeated to remove traces of platinum catalyst and magnesium sulfate can be used to dry the product. To obtain a pure oil, the product solution is concentrated on a rotary evaporator.

Sulfation of 7-methylenedecanol

To a dry, three-necked, round-bottom flask of 11, equipped with nitrogen inlet, addition funnel, thermometer, mechanical stirring and nitrogen outlet, was added chloroform (300 mL) and 7-methylenedecanol (93 g, 0.5 mol). While stirring, chlorosulfuric acid (60 g, 0.509 mol) is added to the mixture and the temperature is maintained at 25-30 ° C with an ice bath. As soon as the HCl evolution ceased (1 hour), sodium methoxide (25% in methanol) was slowly added and the temperature was maintained at 25-30 ° C. The methoxide is added until it is maintained at 10.5 at a pH of 5% in water. Hot ethanol (55 ° C, 21) is added to the mixture. The mixture is immediately vacuum filtered. The filtrate is concentrated to a slurry on a rotary evaporator, then cooled and poured into ethyl ether. The mixture is cooled to 5 ° C, during which crystallization takes place and vacuum filtered. The crystals are dried in a vacuum oven at 50 ° C for 3 hours and then a white solid is obtained.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Example IV Preparation of sodium 7-methyldodecyl sulfate

Synthesis of 7-methyldodecen-1-ol

70.2 g of 60% sodium hydride (1.76 moles) in mineral oil is placed in a 5L dry, three-necked round-bottomed flask equipped with mechanical stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet. . The mineral oil is removed by washing with hexane. Anhydrous dimethylsulfoxide (500 mL) is then added to the flask and the mixture is heated to 70 ° C until hydrogen evolves. Thereafter, the reaction mixture is cooled to room temperature, followed by the addition of 1 L of anhydrous tetrahydrofuran. (6-hydroxyhexyl) triphenylphosphonium bromide (443.4 g, 1 mol, prepared as described above) is suspended in hot anhydrous dimethylsulfoxide (50 ° C, 500 mL), and the suspension is slowly added to the reaction mixture via an addition funnel. the temperature is maintained at 25-30 ° C. The mixture is 30 min. After stirring at room temperature, 2-heptanone (125.4 g, 1.1 mol) was added slowly via an addition funnel. The reaction is slightly exothermic and needs to be cooled to 25-30 ° C. The mixture is stirred for 18 hours and then poured into a 5 L beaker containing 1 L of purified water to be stirred. The oil phase (top) can be separated in a separating funnel and the aqueous phase is removed. The aqueous phase is washed with hexane (500 mL) and the organic phase is separated and mixed with the oil phase from the previous water wash. The organic mixture is then extracted 3 times with water (500 ml each extraction), followed by vacuum distillation to obtain a clear, oily product at 140 ° C and a pressure of 1 mm Hg.

Hydrogenation of 7-methyldodecen-1-ol

A 3 L rotary autoclave is charged with 7-methyldodecen-1-ol (100.6 g, 0.508 mol), methanol (300 mL) and platinum on carbon (10 wt%, 35 g). The mixture is hydrogenated at 180 ° C under a hydrogen pressure of 8.3 MPa for 13 hours, then cooled and vacuum filtered through Celite 545, washing the Celite 545, preferably with methylene chloride. If necessary, filtration can be repeated to remove traces of platinum catalyst and magnesium sulfate can be used to dry the product. To obtain a pure oil, the product solution is concentrated on a rotary evaporator.

Fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe ···

Sulfation of 7-methyldodecanol

To a dry, three-necked, round-bottom flask of 11, equipped with nitrogen inlet, dropping funnel, thermometer, mechanical stirring and nitrogen outlet, was added chloroform (300 mL) and 7-methyldodecanol (100 g, 0.5 mol). While stirring, chlorosulfuric acid (60 g, 0.509 mol) is added to the mixture and the temperature is maintained at 25-30 ° C with an ice bath. As soon as the HCl evolution ceased (1 hour), sodium methoxide (25% in methanol) was slowly added and the temperature was maintained at 25-30 ° C. Methoxide is added until the pH is maintained at 10.5 at a concentration of 5% in water. Hot ethanol (55 ° C, 2 L) was added to the mixture. The mixture is immediately vacuum filtered. The filtrate is concentrated on a rotary evaporator, then cooled and poured into 2 L of ethyl ether. The mixture is cooled to 5 ° C during which crystallization occurs and vacuum filtered. The crystals are dried in a vacuum oven at 50 ° C for 3 hours and then a white solid is obtained (119 g, 92% active, detected by cat SO3 titration).

Example V Synthesis of sodium 7-methyltridecyl sulfate

Sulfation of 7-methyltridecanol

In a dry, three-necked, round-bottom flask of 11, equipped with nitrogen inlet, addition funnel, thermometer, mechanical stirring and nitrogen outlet, chloroform (300 mL) and 7-methyltridecanol (107 g, 0.5 mol) are added, prepared as an intermediate in Example I. While stirring, chlorosulfuric acid (61.3 g, 0.52 mol) was slowly added to the mixture and the temperature was maintained at 25-30 ° C with an ice bath. As soon as the HCl evolution ceased (1 hour), sodium methoxide (25% in methanol) was slowly added and the temperature was maintained at 25-30 ° C. Methoxide is added until the pH is maintained at 10.5 at a concentration of 5% in water. Methanol (1 L) and 300 mL of 1-butanol are added to the mixture. The precipitate of inorganic salts is filtered off under vacuum and methanol is removed from the filtrate on a rotary evaporator. After cooling to room temperature, 1 L of ethyl ether is added and the mixture is allowed to stand for 1 hour. The precipitate is collected by vacuum filtration. The product is dried in a vacuum oven at 50 ° C for 3 hours and then a white solid is obtained (76 g, 90% active, detected by cat SO 3 titration).

• · · · · · · · · r · r · r · j

D- + · ···· · · · ··· ··············

Example VI Synthesis of sodium 7-methyldodecyl ethoxylate (E5)

Alkoxylation of 7-methyldodecanol

A 1 L three-necked round-bottomed flask equipped with nitrogen inlet, mechanical stirrer, y-tube with thermometer and gas outlet is provided with hy-methyldodecanol synthesized as described in Example IV. To remove trace amounts of moisture, the alcohol is bubbled with nitrogen for about 30 minutes. at a temperature of 80 to 100 ° C. With continued nitrogen purge, sodium metal is added as a catalyst and allowed to melt at 120-140 ° C with stirring. In 140 min. ethylene oxide gas is added with vigorous stirring and the reaction temperature is maintained at 120-140 ° C. After the correct amount (equal to 5 equivalents of ethylene oxide) is added, the apparatus is 20-30 min. purge nitrogen to cool the sample. The desired product 7-methyldodecyl ethoxylate (on average 5 ethoxylates per molecule) is then obtained.

Example VII Preparation 03 of mid-chain branched sodium alcohol sulfate, alcohol ethoxylate and sodium alcohol ethoxy (E1) sulfate from experimental alcohol samples from Shell Research.

Experimental test samples of 03 alcohols from Shell Research are used for the production of alcohol sulfates, alcohol ethoxylates and alcohol ethoxy sulfates. These experimental alcohols are ethoxylated and / or sulfated according to the following procedures. In this case, the experimental alcohols are made from O 2 alpha-olefins. In order to obtain branched olefin chains, the 02 alpha-olefin skeletons are rearranged. Skeletal rearrangement produces a limited number of branches, more preferably mid-chain branching. Rearrangements yield C 1 to C ₃ branches, more preferably ethyl, most preferably methyl branches. The mixture of branched olefins is subjected to catalytic hydroformylation to obtain the desired mixture of branched alcohols.

Sulfation of experimental 03 alcohol from Shell

A 100 ml dry three-necked round-bottomed flask equipped with gas inlet, dropping funnel, mechanical stirrer, y-tube with thermometer and gas outlet is provided with Shell experimental alcohol 03 (14.0 g, 0.07 mol) ) and diethyl ether (20 mL).

·· ·· ·· · · · · 0 0

9 · · 9 9

09 /

While stirring, chlorosulfuric acid (8.6 g, 0.07 mol) is slowly added to the mixture and the reaction temperature is maintained at 5 to 15 ° C using an ice water bath. Upon completion of the addition of chlorosulfuric acid, HCl is slowly removed by introducing nitrogen and pressure (250 to 375 mm Hg). The reaction is also heated to 30-40 ° C in a hot water bath. After about 45 min. the pressure is increased to 625-750 mm Hg and maintained for a further 45 min. The acidic reaction mixture is slowly poured into a beaker with vigorously stirred 25% sodium methoxide solution (16.8 g, 0.8 mol) and methanol (50 mL), which is cooled in an ice bath. After the pH of the solution is> 12, the solution is an additional 30 min. stir and then pour into a clean bowl. Most of the solvent was evaporated in a fume hood overnight. The next day the sample is transferred to a glass container and placed in a vacuum oven. The sample is dried all day and night at 40 to 60 ° C and at a pressure of 625 to 750 mm Hg. After transferring 21 g of an oily ivory solid into a vial, the sample was found to be about 86% active by cat SO3 analysis. The pH sample is about 11.5.

Ethoxylation of Experimental 03 Alcohol from Shell to El

A 250 ml dry three-necked round-bottomed flask equipped with a gas inlet, a mechanical stirrer, a Y-tube with a thermometer and a gas outlet is charged with experimental O 3 alcohol from Shell (50.0 g, 0.25 mol). To remove traces of moisture, the alcohol is 30 min. nitrogen was bubbled through at 60-80 ° C. With continued nitrogen addition, sodium metal (0.3 g, 0.01 mol) is added as a catalyst and left under stirring at 120 to 140 ° C to melt. Stirring vigorously with stirring for 35 min. ethylene oxide gas (11.0 g, 0.25 mol) was added and the reaction temperature was maintained at 120-140 ° C. After the correct amount of ethylene oxide is added, it is for 20 to 30 minutes. Nitrogen is passed through the apparatus until the sample is cooled. The yellow liquid product (59.4 g, 0.24 mol) is transferred to a vial under nitrogen.

Sulfation of experimental 03 alcohol ethoxylate from Shell (El)

A 250 ml dry three-necked round-bottomed flask equipped with gas inlet, dropping funnel, mechanical stirrer, y-tube with thermometer and gas outlet is charged with experimental 03 ethoxylate from Shell (El) (48.8 g, 0 , 20 mol) and diethyl ether (50 ml). While stirring, chlorosulfuric acid (24.5 g, 0.21 mol) is slowly added to the mixture and the reaction temperature is maintained at 5 to 15 ° C using an ice water bath. Upon completion of the addition of chlorosulfuric acid, HCI is slowly removed by the introduction of nitrogen and the pressure (250 to 375 mm Hg) is applied. The reaction is also heated to 30-40 ° C in a hot water bath. After about 45 min. the pressure is increased to 625-750 mm Hg and maintained for a further 45 min. The acidic reaction mixture is slowly poured into a beaker with vigorously stirred 25% sodium methoxide (48.8 g, 0.23 mol) and methanol (100 mL), which is cooled in an ice bath. After the pH of the solution is> 12, the solution is an additional 30 min. stir and then pour into a clean bowl. Most of the solvent was evaporated in a fume hood overnight. The next day the sample is transferred to a glass container and placed in a vacuum oven. The sample is dried all day and night at 40 to 60 ° C and at a pressure of 625 to 750 mm Hg. After transferring 64.3 g of a gooey ivory solid to the vial, the sample was found to be about 92% active by cat SO3 analysis. The pH sample is about 10.8.

Example VIII

Liquid dishwashing detergent compositions for light working conditions are prepared comprising the surfactants of the present invention branched in the mid-chain:

Table VIII

Ingredient wt. % AND wt. % (B) wt. % C wt% D C12 to 15 alkylethoxy (0,6) sodium sulphate, branched in the middle of the chain 5 10 20 May 30 C12 to η alkyl ethoxylate (9 moles EO), branched in the middle of the chain 1 1 1 1 Sodium C 12 to C 13 alkyl ethoxy (1-3) sulfate 25 20 May 10 0 C12-20glucoamide 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 Calcium xylene sulfonate 5 5 5 5 Magnesium ⁺⁺ (added as chloride) 3.0 3.0 3.0 3.0 Water, thickeners and other minor constituents up to 100% up to 100% up to 100% up to 100% pH of 10% solution (as prepared) 7.5 7.5 7.5 7.5

• 0

The following liquid detergent compositions were prepared:

· «·

0 0 ·

0 0 0 *

0 0 0

0 00

Example IX

Table IX

AND (B) C pH of a 10% solution 9 10 10 Alcohol ethoxy (0,6) sulphate, branched in the middle of the chain 0 28 25 Alcohol ethoxy (1) sulphate, branched in the middle of the chain 30 0 0 Amine oxide (Cn & m) 5 3 7 Betaine 3 0 1 Polyhydroxy grease amide acids (Cm) 0 1.5 0 AE non-ionic 2 0 4 Diamin 1 5 7 Mg ⁺⁺ (as MgCl ₂ ) 0.25 0 0 Citrate (cit2K3) 0.25 0 0 Overall (perfumes, colors, water, ethanol, etc. up to 100%

D E F pH of a 10% solution 9.3 8.5 11 Alcohol ethoxy (0,6) sulphate, branched in the middle of the chain 10 15 Dec 10 Paraffin sulphonate 10 0 0 Linear alkylbenzenesulfonate 5 15 Dec 12

• • • fefe · fefe • fefe • fefe • fefe • fefe fe • fefe

Betaine 1 0 Polyhydroxy grease amide acids (C12) 3 0 1 AE non-ionic 0 0 20 May DTPA 0 0.2 0 Citrate (as Cit2K3) 0.7 0 0 Diamin 1 5 7 Mg ⁺⁺ (asMgCh) 1 0 0 Ca ⁺⁺ (as Ca (XS) ₂ ) 0 0.5 0 Protease 0.01 0 0.05 Amylase 0 0.05 0.05 Hydrotrop 2 1.5 3 Overall (perfumes, colors, water, ethanol, etc. up to 100%

The diamine is selected from: dimethylaminopropylamine; 1,6-hexanediamine; 1,3 propanediamine; 2-methyl-1,5-pentanediamine; 1,3-pentanediamine; 1-methyldiaminopropane.

The amylase is selected from: Termamyl®; Fungamyl®; Duramyl®; BAN® and aamylases described in WO95 / 26397 and the related PCT / DK96 / 00056 filed by Novo Nordisk.

The lipase is selected from: Amano-P; Ml Lipase®; Lipomax®; Lipolase®; D96 The lipolytic enzyme variant of native lipase derived from Humicola lanuginosa, which is described in US periodical No. 08/341826 and from Humicola lanuginosa strain DSM4106.

The protease is selected from: Savinase®; Maxatase®; Maxacal®; Maxapen 15®; subtilisin BPN and BPN '; Protease B; Protease A; Primase®; Durazym®; Opticlean® and Optimase® and Alcalase®.

The hydrotropes are selected from the group: sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluenesulfonic acid, naphthalenesulfonic acid, cumene sulfonic acid, and xylene sulfonic acid.

DTPA is diethylenetriamine pentaacetate chelate.

00

0 · · · ·

0008 0 · 0 ·

00 90 90 ♦ 0 0

00 · 0 · 0 0 00 ·· 0 * 00

0

0 0 0

Example X

Table X

AND (B) C D pH of a 10% solution 8.5 9 9.0 9.0 Alcohol ethoxy (0,6) sulphate, branched in the middle chain 0 0 0 15 Dec Alcohol ethoxy (1) sulphate, branched in the middle chain 0 30 0 0 Alcohol ethoxy (1,4) sulphate, branched in the middle chain 30 0 27 Mar: 0 Alcohol ethoxy (2,2) sulfate branched in the middle chain 0 0 0 15 Dec Amine oxide 5 5 5 3 Betaine 3 3 0 0 AE non-ionic 2 2 2 2 Diamin 1 2 4 2 Mg ⁺⁺ (as MgCl ₂ ) 0.25 0.25 0 0 Ca ^{+ T} (as Ca (XS) ₂ ) 0 0.4 0 0 Overall (perfumes, colors, water, ethanol, etc. up to 100%

E F G H AND J pH of a 10% solution 9.3 8.5 11 10 9 9.2 Alcohol ethoxy (0,6) sulphate, branched in the middle chain 10 15 Dec 10 27 Mar: 27 Mar: 20 May

4 ♦ 4 ·

4444

4 * 4 4

4 ·

4 4

4 4

4

4 4 4

4,444 4

4 4 4 4

4 4 4 4 4

Paraffin sulphonate 10 0 0 0 0 0 Linear alkylbenzenesulfonate 5 15 Dec 12 0 0 0 Betaine 3 1 0 2 2 0 Amine oxide 0 0 0 2 5 7 Polyhydroxy fatty acid amide (C _J2 ) 3 0 1 2 0 0 AE non-ionic 0 0 20 May 1 0 2 Hydrotrop 0 0 0 0 0 5 Diamin 1 5 7 2 2 5 Mg ⁺⁺ (as MgCl ₂ ) 1 0 0 0.3 0 0 Ca ⁺⁺ (as Ca (XS) ₂ ) 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 o, i Citrate (Cit2K3) 0.65 0 0 0.3 0 0 Overall (perfumes, colors, water, ethanol, etc. up to 100%

The diamine is selected from: dimethylaminopropylamine; 1,6-hexanediamine; 1,3 propanediamine; 2-methyl-1,5-pentanediamine; 1,3-pentanediamine; 1-methyldiaminopropane.

The amylase is selected from: Termamyl®; Fungamyl®; Duramyl®; BAN® and aamylases, described in WO95 / 26397 and the related PCT / DK96 / 00056 filed by Novo Nordisk.

The lipase is selected from: Amano-P; Ml Lipase®; Lipomax®; Lipolase®; The D96L-lipolytic enzyme variant of native lipase derived from Humicola lanuginosa, which is described in US periodical no. 08/341826 and from Humicola lanuginosa strain DSM4106.

The protease is selected from: Savinase®; Maxatase®; Maxacal®; Maxapem 15®; subtilisin BPN and BPN '; Protease B; Protease A; Protease D; Primase®; Durazym®; Opticlean® and Optimase® and Alcalase®.

The hydrotropes are selected from the group: sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluenesulfonic acid, naphthalenesulfonic acid, cumenesulfonic acid, xylenesulfonic acid.

• ·

DTPA is diethylenetriamine pentaacetate chelate.

Example XI

Table XI

AND (B) C D E pH of a 10% solution 8.5 9 10 10 10 Alcohol ethoxy (0,6) sulphate, branched in the middle of the chain 0 0 0 15 Dec 0 Alcohol ethoxy (1) sulphate, branched in the middle of the chain 0 30 0 0 33 Alcohol ethoxy (1,4) sulphate, branched in the middle of the chain 30 0 27 Mar: 0 0 Alcohol ethoxy (2,2) sulphate, branched in the middle of the chain 0 0 0 15 Dec 0 Amine oxide 5 5 5 3 6 Betaine 3 O J 0 0 0 AE non-ionic 2 2 2 2 4 Diamin 1 2 4 4 5 K citrate 0.25 0.5 0 3.5 2 Maleic acid 0.5 1 3 0 2 Mg ⁺⁺ (as MgCl ₂ ) 0.25 0.25 0 0 0 Ca ⁺⁺ (as Ca (XS) ₂ ) 0 0.4 0 0 0 Overall (perfumes, colors, water, ethanol etc. up to 100%

The diamine is selected from: dimethylaminopropylamine; 1,6-hexanediamine; 1,3-propanediamine; 2-methyl-1-1,5-pentanediamine; 1,3-pentanediamine; 1-methyldiaminopropane.

The amylase is selected from: Termamyl®; Fungamyl®; Duramyl®; BAN ® and α-amylases described in WO95 / 26397 and the related pending application PCT / DK96 / 00056 filed by Novo Nordisk.

0 ¹ ** aa · 00 0 0 0 · · ··· 0 00 00 00 00

The lipase is selected from: Amano-P; Ml Lipase®; Lipomax®; Lipolase®; D96 The lipolytic enzyme variant of native lipase derived from Humicola lanuginosa, which is described in US periodical no. 08/341826 and from Humicola lanuginosa strain DSM4106.

The protease is selected from: Savinase®; Maxatase®; Maxacal®; Maxapem 15®; subtilisin BPN and BPN '; Protease B; Protease A; Protease D; Primase®; Durazym®; Optíclean® and Optimase® and Alcalase®.

The hydrotropes are selected from the group: sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluenesulfonic acid, naphthalenesulfonic acid, cumene sulfonic acid, and xylene sulfonic acid.

DTPA is diethylenetriamine pentaacetate chelate.

Claims (11)

00 0 «dimethylaminopropylamine 'N' 'NH, 00 00 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0» 00 00 0 «00 0 0000 • 00 · 0 0 00' 0 0 0 0« PATENT REQUIREMENTS 1-Methyl-diaminopropane (50) Jeffamine EDR148 (51) and mixtures thereof. 1,3-pentanediamine (49) 1,3-propanediamine H ₂ N 'NH, (47) 1,6-hexanediamine (46) An aqueous liquid detergent composition intended for light working conditions, characterized in that it is characterized by: 2-Methyl-1,5-pentanediamine (48) Liquid detergent composition according to claim 1, characterized in that it is further characterized by 1 wt. % to 10 wt. % of a nonionic surfactant which is a surfactant selected from the group consisting of amides of C8 to C18 polyhydroxy fatty acids, C8 to C18 alcohol ethoxylates, and combinations thereof. TKc ^ oco • v * 0 · »·· 0 0 0 * 0 0 0 • 000 000 0 0 0 9. 0 0 00 0 09 0 · ·· · 0 0 0 0 · 0 Liquid detergent composition according to claim 1, characterized in that it is further characterized by 1 wt. % to 10 wt. % of suds / stabilizers selected from the group consisting of betaine surfactants, fatty acid alkanolamides, C 8 to C 22 alkyl polyglycosides, and combinations thereof. The liquid detergent composition of claim 1, further characterized by 0.2 wt. % to 0.8 wt. % of a polymeric surfactant characterized by ethylene oxide and propylene oxide condensed with ethylenediamine to form a block copolymer having a molecular weight of from 4000 to 6000 and an HLB value of from 10 to 20. 5. A liquid detergent composition according to claim 1, further characterized by a detersive amount of enzymes. 5 wt. % to 70 wt. % of a surfactant system comprising at least 10 wt. % of the mixture of branched surfactants, wherein the mixture of branched surfactants is characterized by mid-chain branched surfactants and linear surfactants. Said linear compounds are characterized by less than 25 wt. % of the mixture of branched surfactants and said compound, branched in the middle of the chain, have the general formula: A ^b -B (1) where: A ^b is a hydrophobic alkyl group having a total number of carbons of C 1 to C 18, branched in the middle of the chain, having: (1) the longest linear carbon chain attached to the -B group in the range of 8 to 17 carbon atoms; (2) one or more C 1 to C 3 alkyl groups branching from this longest linear carbon chain; (3) at least one of the branched alkyl groups attached directly to the carbon of the longest linear carbon chain at a position ranging from position 3 of the carbon, calculated from carbon # 1, which is attached to the group -B, to position ω-2; which is terminal carbon minus 2 carbons; and (4) the surfactant-containing composition has an average total number of carbon atoms in group A ^b in the above general formula (1) in the range of more than 12 to 14.5; and B is a hydrophilic group selected from the group consisting of OSO3M, (EO / PO) _m OSO3M, (EO / PO) _m OH and mixtures thereof, wherein EO / PO are alkoxy groups selected from the group consisting of ethoxy, propoxy groups and mixtures thereof and m are at least 0.01 to 30. 6. The liquid detergent composition of claim 1, further characterized by an effective amount of a low molecular weight organic diamine having both pK1 and pK2 in the range of 8.0 to 11.5 and wherein the pH of the detergent composition measured for 10% aqueous. solution, ranging from 8.0 to 12. 7. The hand dishwashing detergent composition of claim 6 wherein said diamine is selected from the group consisting of: R1 R2 .Cx N Ά Cy / R3 R4 (44) wherein R1 to R4 are independently selected from the group consisting of hydrogen, methyl, ethyl and ethylene oxides; C _x and C _y are independently selected from methylene groups or branched alkyl groups, x + y is from 3 to 6, A is present occasionally and, if present, is selected from electron donor or acceptor groups. The assumption is that if A is present, then both x and y are greater than or equal to 2. 8. The hand dishwashing detergent composition of claim 7, wherein said diamine is selected from the group consisting of: (45) • 0 »» 0 9. A liquid detergent composition according to claim 1 wherein the A ^b group of the mid-chain branched surfactant is a branched alkyl group having the general formula: RR ¹ R ² CH ₃ CH ₂ (CH ₂ ) _w CH (CH ₂ ) _x CH (CH ₂ ) _y CH (CH ₂ ) _z CH ₂ (2) where the total number of carbon atoms in the branched alkyl group including R, R ¹ and R ² branching, ranging from 10 to 17. R, R ¹ and R ² are independently selected from hydrogen and C 1 -C ₃ alkyl; w is an integer from 0 to 10; x is an integer from 0 to 10; y is an integer from 0 to 10; z is an integer from 0 to 10 and w + x + y + z is from 3 to 10, provided that R, R ¹ and R ² are not all hydrogen, and if z is 0, then at least R or R ^{1 has no} hydrogen. 10. The liquid detergent composition of claim 1, wherein the A ^b group of the mid-chain branched surfactant is a branched alkyl group having a general formula selected from the group consisting of: CH ₃ I (3) CH ₃ (CH ₂ ) _and CH (CH ₂ ) _b CH ₂ CH ₃ ch ₃ I I (3) CH ₃ (CH ₂ ) _d CH (CH ₂ ) e CHCH ₂ and mixtures thereof. In formulas, a, b, d and e are integers, a + b is from 6 to 13, d + e is from 4 to 11. If a + b-6 then a is an integer from 2 to 5 and b is an integer from 1 to 4 if a + b = 7, then a is an integer from 2 to 6 and ab is an integer from 1 to 5 if a + b = 8, then a is an integer from 2 to 7 and b is an integer from 1 to 6 if a + b = 9, then a is an integer from 2 to 8 and b is an integer from 1 to 7 if a + b = 10, then a is an integer from 2 to 9 and b is an integer from 1 to 8 if a + b = 11, then a is an integer from 2 to 10 and b is an integer from 1 to 9 if a + b = 12, then a is an integer from 2 to 11 and b is an integer from 1 to 10 if a + b = 13, then a is an integer from 2 to 12 and b is an integer from 1 to 11 if d + e = 4, then d is an integer from 2 to 3 and e is an integer from 1 to 2 ΊΊ Tylovo, »k k k lov lov lov lov _{((((((((((((((((} · · "If d + e = 5, then d is an integer from 2 to 4 and e is an integer from 1 to 3 if d + e = 6, then d is an integer from 2 to 5 and e is an integer from 1 to 4 if d + e ^ 7, then d is an integer from 2 to 6 and e is an integer from 1 to 5 if d + e = 8, then d is an integer from 2 to 7 and e is an integer from 1 to 6 if d + e = 9, then d is an integer from 2 to 8 and e is an integer from 1 to 7 if d + e = 10, then d is an integer from 2 to 9 and e is an integer from 1 to 8 if d + e- 11, then d is an integer from 2 to 10 and e is an integer from 1 to 9.