CZ2000246A3 - Cleansing preparation containing mixtures of tensides with interrupted crystallinity - Google Patents

Abstract

A cleaning composition comprising: a) about 0.1 wt. % to about 99.9 wt. % of said composition is an alkylaryl sulfonate a surfactant system comprising from about 10 wt. % to about 100 wt. % of said surfactant system two or more alkylarylsulfonate surfactants with interrupted crystallinity of the formula: (B-Ar-D) and (Mq) b (as defined herein above); and b) from about 0.00001 wt. % to about 99.9 wt. % of said of the detergent additive composition, of which at least one is selected from the group consisting of: i) purification enzymes; (ii) organic detergent builders; iii) oxygen bleaching agents; iv) bleach activators; in) transition metal bleach catalysts; (vi) transfer agents oxygen and precursors; (vii) polymeric soil release agents reagents; viii) water-soluble ethoxylated amines having properties that allow the removal of clay soils and prevents it from settling back; ix) polymeric dispersion reagents; (x) color transfer polymeric agents; xi) alkoxylated polycarboxylates; and xii) mixtures thereof.

Description

READER CONTAINING MIXTURES OF INTERRUPTED CRYSTALINITY

Technical field

The present invention relates to detergent compositions comprising an alkylarylsulfonate surfactant system comprising a mixture of interrupted crystallinity isomers, preferably branched, alkylarylsulfonate surfactants, and may also contain one or more non-crystallinity, interrupted, alkylarylsulfonate surfactants.

Detergents also contain detergent ingredients selected from cleaning enzymes, organic detergent builders, oxygen bleaching agents, bleach activators, bleach catalysts of transition metals, oxygen transfer agents and precursors, polymeric soil release agents, water-soluble ethoxylated amines having removal properties clayey dirt and prevents it from settling back, polymeric dispersing agents, polymeric dye transfer inhibiting agents, alkoxylated polycarboxylates and mixtures thereof. The detergent composition also typically includes additional detergent adjuvants. These detergents are particularly useful in detergent compositions to be used in laundry processes involving hard or low water wash conditions.

BACKGROUND OF THE INVENTION

Historically, highly branched alkylbenzene sulfonate surfactants have been used in detergents, such as those based on tetrapropylene (known as "ABS"). These were, however, found to be very poorly biodegradable. There was a long period of improvement in the production processes of alkylbenzene sulfonates making them as linear as practicable ("LAS"). The vast part of the extensive technique for the production of linear alkylbenzeneolfonate surfactants is focused on this task. All of the major commercial large-scale alkylbenzene sulfonates currently used are focused on linear alkylbenzene sulfonates. Linear alkylbenzene sulfonates are not, of course, without limitation; they would be more desirable if they were improved in terms of hard water and / or cold water properties. Thus, they can often fail and not show good cleaning results, for example when mixed with non-phosphate components and / or used where hard water is present. Due to the restriction of alkylbenzene sulfonates, they often needed a higher level of accompanying surfactants, components, and detergents. and other ingredients than would need a better alkylbenzenesulfonate.

It would therefore be highly desirable to simplify detergent compositions and to provide the consumer with both better performance and better value. In addition, given the huge amount of alkylbenzene sulfonate surfactants and detergent products used worldwide, even a slight improvement in the performance of basic alkylbenzene sulfonate detergents could have a major impact.

In order to understand the techniques for the production and use of sulfonated alkylaromatic detergents, we must realize that it has gone through many stages and involves (a) the initial production of highly branched, non-biodegradable LAS (ABS); (b) developing processing such as HF or AlCl 3 catalyzed method (note that each method gives a different mixture, eg HF / olefin gives lower 2-phenyl or classical AlCl 3 / chloroparaffin typically yields by-products which, although perhaps useful, are solubility, they are undesirable in terms of biodegradation); (c) the market has moved to LAS where a large portion of the alkyl is linear; (d) improvements including so-called "high 2-phenyl" or DETAL methods (in fact, not really "high" 2-phenyl due to solubility problems if the hydrophobic component is too linear); and (e) current progress in understanding biodegradation.

The technique of alkylbenzene sulphonate detergents is extremely abundant in references which speak for and against almost every aspect of these compositions. For example, some techniques speak of high 2-phenyl LAS as desirable, while other techniques speak exactly the opposite. In addition, there are many incorrect teachings and technical misconceptions about the mechanism of LAS operating under conditions of use, especially in the area of hardness tolerance. A huge number of such references reduce the technique as a whole and make it difficult to distinguish useful teachings from useless without a large number of repeated experiments. To better understand the state of the art, we should realize that not only was it unclear which path to take to solve the linear LAS problem, but there were also many misconceptions not only in terms of understanding biodegradability, but also in terms of basic mechanism of LAS action in the presence of hardness. According to literature and general practice, surfactants having alkali or alkaline earth salts that are relatively insoluble (their Na or Ca salts having a relatively high Krafft temperature) are less desirable than those having alkali or alkaline earth salts that are relatively more soluble (Na or Ca salts have lower Krafft temperature). According to the literature, LAS mixtures precipitate in the presence of free Ca or Mg hardness. It is also known that 2- or 3-phenyl or " terminal " isomers are known.

LASs have higher Krafft temperatures than, say, 5- or 6-phenyl "internal" isomers. Thus, one would assume that changing the LAS composition to increase the 2- and 3-phenyl isomer content would decrease the hardness tolerance and solubility, which would not be good. On the other hand, it is also known that under conditions in which isomers of both 2- and 3-phenyl and internal phenyl of the same chain length are soluble, the isomers of 2- and 3-phenyl are surfactants. Thus, one would assume that if we change the composition of the LAS to increase the content of 2- and 3-phenyl isomers, the cleaning effect may increase. However, the unresolved problems of solubility, hardness tolerance and low temperature effect remain.

U.S. Pat. No. 5,026,933; 4,990,718; U.S. 4,301,316; U.S. 4,301,317; US 4,855,527; 4,870,038; 2,477,382; EP 466,558, 1/15/92; EP 469,940, 2/5/92; FR 2 697 246, 4/29/94; SU 793 972 1/7/81; U.S. 2,564,072; U.S. Pat. No. 3,196,174; U.S. 3,238,249; US

355 484; U.S. 3,442,964; U.S. 3,492,364; 4,959,491; WO 88/07030, 9/25/90; US

962 256; U.S. 5,196,624; U.S. 5,196,625; EP 364,012B, 2/15/90; U.S. Pat. No. 3,312,745; US

341 614; U.S. 3,442,965; U.S. 3,674,885; U.S. 4,447,664; U.S. 4,533,651; U.S. 4,587,374;

4,996,386; U.S. Pat. No. 5,210,060, U.S. Pat. WO 95/17961, 7/6/95; WO 95/18084; US

510 306; U.S. 5,087,788; 4,301,316; 4,301,317; 4,855,527; 4,870,038; 5,026,933;

625 105 and 4 973 788 are useful as a basis for the invention. Recently, the production of alkylbenzene sulfonate surfactants has been reported. See vol. 56 in the series "Surfactant Science", Marcel Dekker, New York, 1996, including in particular Chapter 2 entitled "Alkylarylsulfonates: History, Manufacture, Analysis and Environmental Properties", pages 39 to 108, which contain 297 references. The documents referred to here are incorporated in their summary.

SUMMARY OF THE INVENTION

Surprisingly, it has now been found that if an alkylarylsulfonate surfactant system contains two or more isomers of interrupted crystallinity of alkylarylsulfonate surfactants, in addition it may also contain one or more of the unbroken crystallinity alkylarylsulfonate surfactants, a surprising increase in activity relative to the non-isomer-containing alkylarylsulfonate surfactant system with interrupted crystallinity.

The present invention has numerous advantages in addition to one or more of the aspects indicated above, for example, better cold water solubility, for example, in cold water wash;

better hardness tolerance; and great washing ability. Further, the invention is expected to be 4 4 9 4 4 9 9 4 9 9 4 9 9 4 9 9 4 9 4 »

444444 4 9 4 4 «· ·· will reduce the collection of old textile softener residues from washed fabrics and improve the removal of fatty or greasy dirt from the fabrics. Advantages are also expected in applications other than washing, for example in dishwashing. The development offers substantial expected improvements in facilitating the manufacture of relatively important 2-phenylsulfonate formulations, as well as in facilitating the manufacture and quality of the resulting detergent compositions; and attractive economic benefits.

The present invention is based on the unexpected discovery that there are certain alkylbenzenesulfonates that are both significantly more potent than the newer and more biodegradable than the previous ones in the middle way between old, highly branched, non-biodegradable alkylbenzene sulfonates and new linear types.

The novel alkylbenzene sulfonates are readily available by several of the many known alkylbenzene sulfonate production methods. The use of certain dealuminized color fixatives, for example, allows their easy manufacture.

In accordance with the present invention, a new detergent composition is prepared. This new detergent contains

a) from about 0.1 wt% to about 99.9 wt%; an alkylarylsulfonate surfactant system comprising from about 10 wt.% to about 100 wt. % of said surfactant system of two or more interrupted crystalline alkylarylsulfonate surfactants of general formula (B-Ar-D) and (Mq +) ^b wherein D is SO 3 -, M is a cation or a cationic mixture, q is a valency of said cation, and b are numbers chosen so said composition being electroneutral; Ar is selected from benzene, toluene and combinations thereof; and B comprises a total of at least one portion of a primary hydrocarbon containing from 5 to 20 carbon atoms, more preferably from 7 to 16, preferably 9 to 15, preferably 10 to 14 carbon atoms, and one or more crystallinity interrupted moieties, wherein said crystallinity interrupted moieties interrupted or branched from said hydrocarbon moiety; and wherein said alkylarylsulfonate surfactant system has interrupted crystallinity to such an extent that its critical sodium solubility temperature, as measured by the CST assay, is not greater than about 40 ° C, and wherein said alkylarylsulfonate surfactant system has at least one of the following characteristics:

percent biodegradation as measured by a modified SCAS assay that exceeds tetrapropylenebenzenesulfonate; and • 4 • 4

4 · 4 · 4 * 4 4 4 4

A weight ratio of non-quaternary and quaternary carbon atoms in B of at least 5: 1 (more preferably at least about 10: 1; more preferably at least about 100: 1); and b) from about 0.00001 wt. % to about 99.9 wt. % of said composition of an adjunct component of a cleaning composition, wherein at least one of them is selected from the group consisting of: i) cleaning enzymes, more preferably selected from proteinase, amylase, lipase, cellulase, peroxidase, and mixtures thereof; ii) organic detergent builders, more preferably selected from polycarboxylate compounds, etherhydroxypolycarboxylates, substituted ammonium salts of polyacetic acids, and mixtures thereof; iii) oxygen bleaching agents, more preferably selected from hydrogen peroxide, inorganic perhydrates, organic perhydrates and organic peroxyacids, including hydrophilic and hydrophobic mono- and peroxyacids, and mixtures thereof; iv) bleach activators, more preferably selected from TAED, NOBS and mixtures thereof; (v) oxygen transfer agents and precursors; vii) polymeric soil release agents; (viii) water-soluble ethoxylated amines having properties to remove clay soil and prevent it from settling back; ix) polymer dispersing agents; (x) polymeric dye transfer inhibiting agents; xi) alkoxylated polycarboxylates; and xii) mixtures thereof.

More preferably, the cleaning composition will comprise at least about 0.1 wt. %, preferably at least about 0.5 wt. %, although preferably at least 1 wt. a surfactant system. Also preferably, the cleaning composition will not contain more than about 80 wt. %, preferably no more than about 60 wt. %, although preferably not more than about 40 wt. a surfactant system.

More preferably, the surfactant system will comprise at least about 15 wt. %, preferably at least about 30 wt. %, although preferably at least about 40 wt. % of said surfactant system of two or more interrupted crystallinity of alkylarylsulfonate surfactants. Also, the surfactant system will preferably not contain more than about 100 wt. %, preferably no more than about 90 wt. %, although preferably not more than about 80 wt. % of said surfactant system of two or more interrupted crystallinity of alkylarylsulfonate surfactants.

It is therefore an aspect of the present invention to provide novel cleaning compositions. These and other aspects will be apparent from the following detailed description and the appended claims.

«· · ·

Unless otherwise indicated, all percentages, ratios and proportions herein are based on the weight of the ingredients used in the preparation of the finished compositions. Unless otherwise stated, all temperatures are in degrees Celsius (° C). All documents cited herein are incorporated herein by reference.

The present invention relates to novel detergent compositions. Component (a) comprises from about 0.1 wt. % to about 99.9 wt. an alkylarylsulfonate surfactant system comprising from about 10 wt. % to about 100 wt. % of said surfactant system of two or more interrupted crystallinity of alkylarylsulfonate surfactants of general formula (B-Ar-D) and (Mq +) ^b wherein D is SO 3 -. M is a cation or a cationic mixture. Preferably, M is an alkali metal, an alkaline earth metal, ammonium, substituted ammonium or mixtures thereof, preferably sodium, potassium, magnesium, calcium or mixtures thereof. The power of said cation, q, is preferably 1 to 2. The numbers are selected such that said composition is electroneutral, and b and are preferably 1 or 2 and 1, respectively.

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

B comprises a whole of at least one part of a primary hydrocarbon containing from 5 to 20 carbon atoms and one or two crystalline-disrupted portions, wherein said crystalline-disrupted portions are interrupted or branched from said hydrocarbon portion. More preferably, B comprises both odd and even chain lengths of the hydrocarbon moiety. That is, B more preferably should not be limited to all odd or even even chain lengths of the hydrocarbon moiety. The primary hydrocarbon moiety B has from 5 to 20, more preferably from 7 to 16, hydrocarbon atoms. It may have from one to three crystalline-disrupted portions. The interrupted crystallinity portions interrupt or branch off from said hydrocarbon portion. When the crystallinity moieties are branched, preferably C 1 -C 3 alkyls, preferably C 1 -C 2 alkyls, are more preferably methyl. Preferably, if the crystallinity-disrupted portions interrupt the hydrocarbon portion, ether, sulfone, silicone, and mixtures thereof are ether. Preferably, the alkylarylsulfonate surfactants contain two or more homologues. "Homologues" differ in the number of carbon atoms contained in B. "Isomers", which are described in more detail below, include in particular those compounds having different positions of attachment of the interrupted crystallinity moieties to B.

It is also preferable that the interrupted crystallinity of alkylarylsulfonate surfactants contain at least two "isomers" selected from "feefef" feefefefe feefefefe fefe · • fe fefe ·· fefe

(i) ortho-, meta- and para- isomers based on the positions of attachment of substituents to

Ar wherein Ar is substituted or unsubstituted benzene. This meant that B can be ortho-, meta-, and para- to D, B can be ortho-, meta-, and para- to the substituent on Ar other than D, D can be ortho-, meta-, and para- to the substituent on Ar other than B, or any other possible alternative;

ii) positional isomers based on the attachment positions of said crystalline-disrupted moieties to said primary hydrocarbon moiety B; and iii) stereoisomers based on chiral carbon atoms in B.

Preferably, the interrupted crystallinity alkylarylsulfonate surfactants comprise at least two type ii) isomers, more preferably at least four type ii) isomers.

At least about 60 wt. % of said surfactant system of said interrupted crystalline alkylarylsulfonate surfactants is more preferably in the form of isomers wherein Ar is attached to B at the first, second or third carbon atom in said primary hydrocarbon moiety, more preferably about 70 wt. % or more, preferably about 80 wt. % or more.

A possible component of the compositions of the present invention is from about 0 wt. % to about 85 wt. % of a surfactant system of one or more uninterrupted crystallinity of alkylarylsulfonate surfactants of general formula (L-Ar-D) and (Mq +) ^b wherein D, M, q, a, b, Ar are as defined above. L is a linear primary hydrocarbon moiety containing from 5 to 20 carbon atoms. More preferably, L is a linear hydrocarbon moiety having from 7 to 16 carbon atoms. The alkylarylsulfonate surfactant system has a crystallinity break such that its critical sodium solubility temperature, as measured by the CST assay as defined above, is no more than about 40 ° C, more preferably no more than about 20 ° C, most preferably no more than about 5 ° C. It is also preferred that its critical calcium solubility temperature, as measured by the CST assay, be below 80 ° C, more preferably no more than about 40 ° C, most preferably no more than about 20 ° C.

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

(a) the percentage of biodegradation, as measured by the modified SCAS test (described below), which exceeds tetrapropylenebenzenesulfonate; or

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

100: 1.

More preferably, the percentage of biodegradation under absolute conditions is more preferably at least about%, preferably at least 70%, more preferably at least 80%, and most preferably at least 90%, as measured by the modified SCAS assay.

The cleaning compositions of the present invention comprise component (b) which is from about 0.00001 wt. % to about 99.9 wt. % of said composition of a cleaning additive.

Crystallinity break

The term "broken crystalite" as defined herein means that the surfactant in question is one that contains a hydrophobic moiety selected to result in a surfactant that is less effective in crystalline lattice than said surfactant in which the hydrophobic moiety is pure a linear hydrocarbon chain of formula CH3 (CH2) n- having a length or range of chain lengths comparable to the surfactant described.

The intermittent crystallinity may, in general, be derived from any one of several surfactant modifications at the molecular level. Remarkably, it may be a linear hydrophobic substance, for example

i.e., CH 3 (CH 2) 11 -, which is itself "uninterrupted crystallinity", modified to form the interrupted crystallinity structure of the invention by inserting various moieties such as ether moieties, silicone or sulfones into the chain as in:

Me or o

• 4444 »· 4444» 4 <* 5

4 4 4 4 · 4 · 4 4 · 4 4 4 4 4 44 44 • 4 <4 444 4 4 4

4 '»444 4444

444445 4 «4 4 4 44

More preferably, there is a break in crystallinity when one or more of the branches of B is added to the structure, as in:

Note, with respect to surfactants herein having the general formula (B-Ar-D) and (Mq +) ^b and (L-Ar-D) and (Mq +) ^b , that B represents a hydrophobic substance with interrupted crystallinity, while L represents a hydrophobic a substance with uninterrupted crystallinity. Also, otherwise, the hydrophobic interrupted crystallinity B comprises a primary moiety consisting of (i) all components B other than the interrupted crystallinity moieties; and (ii) crystallinity interrupted moieties.

In a suitable embodiment, B has a (i) moiety having from 7 to 16 carbon atoms, and (ii) a crystallinity interrupted moiety selected from (a) branches (or "side chains") bonded to B, which may generally be different, but more preferably, they are selected from C 1 -C 3 alkyls, hydroxyls, and mixtures thereof, more preferably C 1 -C 3 alkyls, most preferably C 1 -C 2 alkyls, more preferably methyl; (b) moieties that disrupt structure B selected from ether, sulfone and silicone; and (c) mixtures thereof. Other interrupted crystallinity moieties, not suitable herein, include olefin.

Alkylarylsulfonate surfactant system

An essential component of the detergent compositions herein is an alkylarylsulfonate surfactant system. The alkylarylsulfonate surfactant system contains an intermittent crystallinity constituent.

Ftftftftft ftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftft

The present invention relates to detergent compositions comprising at least two or more of such interrupted crystallinity alkylarylsulfonate surfactants and which additionally may comprise one or more interrupted crystallinity alkylarylsulfonate surfactants. These two components are described as follows:

(1) Interrupted crystallinity alkylarylsulfonate surfactants:

The detergent compositions of the present invention comprise an alkylarylsulfonate surfactant system comprising at least two or more interrupted crystallinity alkylarylsulfonate surfactants having the general formula (B-Ar-D) and (Mq +) ^b wherein D, Β, M, q, a, b, Ar are defined above. Possible alkylarylsulfonate surfactants include:

SOj 'M • ftftftft ··· · *

I »ft 4 ft ft ft ft ft ft I

(g)>

(h), (i),

ŠOj'M ⁺

SO3-M ⁺ (j)>

(1), (k), φ ♦ φφ

(η)

(ο) ·

Arrangements (a) to (ο) are merely illustrative of some of the possible interrupted crystallinity of alkyarylsulfonate surfactants and are not intended to limit the scope of the invention.

It is also desirable that the crystallinity-interrupted alkyarylsulfonate surfactants contain at least two isomers selected from

i) ortho-, meta- and para- isomers based on substituent attachment positions on Ar, where Ar is substituted or unsubstituted benzene. This means that B may be ortho-, meta- and para- relative to D, B may be ortho -, meta- and • «· ♦ ·· • 99« 9

99 · 9 9 »9 9 4» 9 · 1 »9 9«> 9 9 4 · 9 9 para- relative to a substituent on Ar other than D, D may be ortho-, meta- and para- relative to a substituent on Ar other than B, or any other possible alternative;

(ii) positional isomers based on the positions of attachment of said interrupted crystallinity moieties to said primary hydrocarbon moiety B; and iii) stereoisomers based on the chiral carbon atoms in B

An example of two types of (ii) isomers are structures (a) and (c). The difference is that the methyl in (a) is attached at the 5-position, but in (c) the methyl is attached at the 7th position.

Examples of two types of (i) isomers are arrangements (I) and (n). The difference is that the sulfonate group in (I) is meta- relative to the hydrocarbon moiety, but in (n) the sulfonate group is ortho- relative to the hydrocarbon moiety.

Examples of two types of (iii) isomers are arrangements (c) and (d). The difference is that these isomers are stereoisomers. Chiral carbon is the seventh carbon atom in the hydrocarbon moiety (2) Uninterrupted crystallinity of alkylarylsulfonate surfactants

The inventive detergent compositions may further comprise an alkylarylsulfonate surfactant system which may comprise one or more uninterrupted crystallinity alkylarylsulfonate surfactants having the general formula (L-Ar-D) and (Mq +) ^b wherein D, M, L, q, a, b, Ar are as defined above. Possible alkylarylsulfonate surfactants with uninterrupted crystallinity include conventional linear alkylbenzene sulfonates, for example those that are commercially available, e.g., so-called high 2-phenyl linear alkylbenzene sulfonates, better known as DETAL or traditional LAS available from Huntsman or Vista. These linear alkylarylsulfonates may be added to the interrupted crystallinity alkylarylsulfonate surfactants to provide the alkylarylsulfonate surfactant system used in the detergent compositions of the invention. Or, uninterrupted crystallinity alkylarylsulfonate surfactants and interrupted crystallinity alkylarylsulfonate surfactants are produced in the same reaction, perhaps due to isomerization either before, during or after the reaction. The ratio of uninterrupted crystalline alkylarylsulfonates to interrupted crystalline alkylarylsulfonates depends on the catalyst used. Whatever the catalyst is used, the surfactant system must not have a critical sodium solubility temperature greater than about 40 ° C and either the percentage of biodegradation measured by the modified SCAS test is such that it exceeds tetrapropylenebenzenesulfonate, more preferably greater than 60%, more preferably greater than 80%. a ratio of non-quaternary and quaternary carbon atoms in B of at least about 5: 1.

• tttt ·· 11 · 11 · 11 11

11 1119 1

111 · ♦ · · · · · 9 1 1 1 9 1 1 9 11111

9 · 11 11 19

DETAILED DESCRIPTION OF THE INVENTION

Example 1: Interrupted crystallinity surfactant system prepared using a skeletally isomerized linear olefin

Step (a): At least partial limitation of olefin linearity (by skeletal isomerization of olefin pretreated to chain lengths suitable for a cleaning product)

A mixture of 1-decene, 1-undecene, 1-dodecene and 1-tridecene (available, for example, from Chevron) of a 1: 2: 2: 1 weight ratio is treated at 220 ° C with Pt-SAPO catalyst and any suitable LHSV, e.g. , 0. The catalyst is prepared in Example 1 of US 5,082,956. See WO 95/21225, e.g. Example 1 and its specification. The product is a skeletally isomerized lightly branched olefin having a range of chain lengths suitable for the production of alkylbenzene sulfonate surfactants used in consumer cleaners. More generally, the temperature in this step may be from about 200 ° C to about 400 ° C, more preferably from about 230 ° C to about 320 ° C. The pressure is typically from about 15 psig to about 2000 psig, more preferably from about 15 psig to about 1000 psig, more preferably from about 15 psig to about 600 psig. A suitable pressurized gas is hydrogen. A suitable velocity space (LHSV or WHSV) is from about 0.05 to about 20. Low pressure and low hourly velocity provide better selectivity, greater isomerization and less cracking. Distil to remove any volatiles boiling up to 40 ° C / 10 mmHg.

Step (b): Alkylating the Product of Step (a) Using an Aromatic Hydrocarbon. To the autoclave glass column is added 1 molar equivalent of a lightly branched olefin mixture produced according to step (a), 20 molar equivalents of benzene and 20 wt. % based on olefin blend of treated selective zeolite catalyst (Zeocat ™ FM-8 / 25H acid-base catalyst). The glass column is tightly sealed inside a swinging stainless steel autoclave. The autoclave is cleaned twice with 250 psig N2, and then loaded to 1000 psig N2. While stirring, the mixture is heated to 170-190 ° C for 14-16 hours, after which time it is cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst and is concentrated by distillation of unreacted starting materials and / or impurities (e.g., benzene, olefin, φφφφ t).

ových par látek par par par par par par par par par af af af af af par af par par af af par af af af af af af af af af af af af af af af af af af af af af af af af af af). The product can then be converted to a desirable interrupted crystallinity surfactant system, which may be sent, for example, to a remote manufacturing facility where further sulfonation steps can be completed and incorporated into consumer cleaners.

Step (c): Sulfonate the product of step (b)

The product of step (b) is sulfonated with chlorosulfuric acid equivalent using methylene chloride as solvent. The methylene chloride is distilled off.

Step (d): Neutralizing the product of step (c)

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

Example 2: Interrupted crystallinity surfactant system prepared by skeletally isomerized linear olefins

The procedure of Example 1 is repeated except that the sulfonation step, (c), uses sulfur trioxide (without methylene chloride solvent) as the sulfonating agent. Details of sulfonation using a suitable air / sulfur trioxide mixture are provided in US 3,427,342, Chemithon. In addition, in step (d) sodium hydroxide is used to neutralize instead of sodium methoxide.

Example 3: Interrupted crystallinity surfactant system prepared by skeletal isomerization of linear olefins

Step (a): At least partially reducing the olefin linearity

The lightly branched olefin mixture is prepared using a H-ferrite catalyst from a mixture of C11, C12 and C13 monoolefins at a weight ratio of 1: 3: 1 at 430 ° C. The method and catalyst of US 5,510,306 can be used in this step. Distil to remove any volatiles boiling to 40 ° C / 10 mmHg.

Step (b) Alkylation of the product of step (a) using an aromatic hydrocarbon

In a glass column of the autoclave, 1 weight equivalent of the lightly branched olefin mixture of step (a), 20 weight equivalents of benzene, and 20 weight percent of benzene are added. % based on olefin blend of treated selective zeolite catalyst 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 0 * 00 (Zeocat ™ FM-8 / 25H acid-base catalyst). The glass column is tightly sealed inside a swinging stainless steel autoclave. The autoclave is cleaned twice with 250 psig N2, and then loaded to 1000 psig N2. While stirring, the mixture is heated to 170-190 ° C for 14-15 hours overnight, then cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst. Benzene is distilled off and recycled, volatile impurities are also removed. A clear colorless or almost colorless liquid product is obtained.

Step (c): Sulfonate the product of step (b)

The product of step (b) is sulfonated with chlorosulfuric acid equivalent using methylene chloride as solvent. The methylene chloride is distilled off.

Step (d): Neutralizing the product of step (c)

The product of step (c) is neutralized with sodium methoxide in methanol and the methanol is evaporated to give a crystalline interrupted surfactant system, a mixture of sodium salts.

Example 4: Interrupted crystallinity surfactant system prepared by skeletal isomerization of paraffin

Step (s)

A mixture of n-undecane, n-dodecane, n-tridecane, 1: 3: 1 by weight is isomerized by a Pt-SAPO-11 conversion of better than 90% at a temperature of about 300 to 340 ° C, at 1000 psig under hydrogen gas. , having a mass hourly space velocity of between 2 and 3 and 30 moles of H2 / mol hydrocarbon. For more details on such isomerization, see Microporous Materials, Vol. 2., (1994), 439-449, by S.J. Miller. In other examples, the linear initial paraffin blend may be the same as that used in conventional LAB production. Distil to remove any volatiles boiling to 40 ° C / 10 mmHg.

Step (a)

The paraffin of step (a) can be dehydrogenated by conventional methods. See, eg, US 5,012,021, 4/30/91 or US 3,562,797, 2/9/71. A suitable dehydrogenation catalyst is any of the catalysts disclosed in US 3,274,287; 3,315,007; 3,315,008; 3,745,112;

430 517; and 3,562,797. For the purpose of the present invention, the dehydrogenation of US 3,562,797 is the catalyst. The catalyst is zeolite A. The dehydrogenation is conducted in the gas phase in the presence of oxygen (paraffin: molecular oxygen 1: 1 molar). The temperature is in the range of 450 ° C to 550 ° C. The ratio of grams of catalyst to moles of total feed per hour is 3.9.

ft ·

Step (b): Alkylation of the product of step (a) using an aromatic hydrocarbon

A 1 molar equivalent of the mixture of step (a), 5 molar equivalents of benzene and 20 wt. % based on olefin blend, treated selective zeolite catalyst (Zeocat ™ FM-8 / 25H acid-base catalyst). The glass column is tightly sealed inside a swinging stainless steel autoclave. The autoclave is cleaned twice with 250 psig N2, and then loaded to 1000 psig N2. While stirring, the mixture is heated to 170-190 ° C for 14-15 hours overnight, then cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst. Benzene and any unreacted paraffins are distilled off and recycled. A clear colorless or almost colorless liquid product is obtained.

Step (c): Sulfonate the product of step (b)

The product of step (b) is sulfonated without solvent with sulfur trioxide / air. See US 3,427,342. The molar ratio of sulfur trioxide to alkylbenzenes is from about 1.05: 1 to about 1.15: 1. The reaction stream is cooled and separated from the excess sulfur trioxide.

Step (d): Neutralizing the product of step (c)

The product of step (c) is neutralized with a slight excess of sodium hydroxide to produce a crystalline-interrupted surfactant system.

Example 5: Interrupted crystallinity surfactant system prepared using a specific tertiary alcohol mixture by Grignard reaction

A mixture of 5-methyl-5-undecanol, 6-methyl-6-dodecanol and 7-methyl-7-tridecanol is prepared by the following Grignard reaction. A mixture of 28 g of 2-hexanone, 28 g of 2-heptanone, 14 g of 2-heptanone and 100 g of diethyl ether is placed in an addition funnel. The ketone mixture is then added dropwise over 1.75 hours to a nitrogen-coated, stirred, three-neck round bottom flask equipped with a reflux condenser and containing 350 mL of 2M hexylmagnesium bromide in diethyl ether and an additional 100 mL of diethyl ether. The reaction mixture was stirred for an additional hour at 20 ° C until the addition was complete. The reaction mixture is then added with stirring to 600 g of a mixture of ice and water. To this mixture is added a solution of 228.6 g of 30% sulfuric acid. The two resulting liquid phases are added to a separatory funnel. The aqueous layer is drained and the remaining ether layer is washed twice with 600 ml of water. The ether layer is then evaporated in vacuo to give 115.45 g of the desired alcohol mixture. A 100 g sample of the slightly yellow alcohol mixture is placed in a glass column of the autoclave along with 300 ml of benzene and 20 g of the treated &quot; ftftft &quot; ftftft &quot; ftftftftft &quot;

4 4 4 ft of selective zeolite catalyst (Zeocat ™ FM-8 / 25H acid-base catalyst). The glass column is tightly sealed inside a swinging stainless steel autoclave. The autoclave is cleaned twice with 250 psig N2, and then loaded to 1000 psig N2. While stirring, the mixture is heated to 170 ° C for 14-15 hours, then cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst and concentrated by distilling off the benzene, which is dried and recycled. A clear colorless or almost colorless lightly branched elefin mixture is obtained.

mg of the lightly branched olefin blend obtained by dehydrating the Grignard alcohol blend as above is placed in an autoclave glass column together with 150 ml of benzene and 10 g of treated selective zeolite catalyst (Zeocat ™ FM-8 / 25H acid-base catalyst). The glass column is tightly sealed inside a swinging stainless steel autoclave. The autoclave is cleaned twice with 250 psig N2, and then loaded to 1000 psig N2. While stirring, the mixture is heated at 195 ° C for 14-15 hours overnight, then cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst and concentrated by distilling off the benzene, which is dried and recycled. A clear colorless or almost colorless liquid product is obtained. The product is distilled under vacuum (1-5 mmHg) and the fraction from 95 ° C to 135 ° C is collected.

The captured fraction, i.e., a clear colorless or almost colorless product, is then sulfonated with a molar equivalent of SO 3 and the resulting product is neutralized with sodium methoxide in methanol and the methanol evaporated to give a tenside system with interrupted crystallinity.

Critical solubility temperature test or CST test

The critical solubility temperature test is a measure of the critical solubility temperature of the surfactant system. The critical solubility temperature, simply put, is the temperature limit of the surfactant system at which solubility suddenly and dramatically increases. With current trends towards ever lower and lower wash temperatures, this temperature is becoming increasingly important. It has surprisingly been found that the critical solubility temperature of the alkylarylsulfonate surfactant system of the present invention can be reduced by the amount and type of interrupted crystallinity alkylarylsulfonate surfactants present in the alkylarylsulfonate surfactant system.

The critical solubility temperature is measured as follows:

4944 44 44 • 9 9 4 9 4 4 9 • 94 4 4 4 4 9 9 4 • 4 4 4 4 9 4 9 9 4 • 9 9 · 4 4 4 6 4

445 64 4 9 4 · 44

Used glassware is cleaned and thoroughly dried. All theolts are measured using a calibrated mercury thermometer. The weights of the samples used are based on the anhydrous form of the solid surfactant or surfactant mixture.

A) Critical Sodium Solubility Temperature - An amount of 99 g deionized water is weighed into a clean, dry beaker equipped with a magnetic stirrer. The beaker is then placed in an ice water bath until the deionized water has cooled to 0 ° C. Then a 1 g sample of the solid sodium surfactant or surfactant mixture whose critical solubility temperature of the sodium is to be measured is added. The resulting heterogeneous solution is stirred for one hour. If the theside sample dissolves within an hour and any heating and a pure homogeneous solution is formed, the critical solubility temperature of sodium is reported as <0 ° C. If the surfactant sample does not dissolve within an hour to form a pure homogeneous solution, the heterogeneous solution is slowly heated with stirring at a rate of 0.1 ° C per minute. The temperature at which the surfactant sample dissolves to form a pure homogeneous solution is reported as the critical solubility temperature of sodium.

B) Critical Calcium Solubility Temperature - An amount of 99 g deionized water is weighed into a clean, dry beaker equipped with a magnetic stirrer. The beaker is then placed in an ice water bath until the deionized water has cooled to 0 ° C. Then a 1 g sample of the solid calcium salt of a surfactant or a mixture of surfactants whose critical solubility temperature of calcium is to be measured is added. The resulting heterogeneous solution is stirred for one hour. If the theside sample dissolves within an hour and with any heating and a pure homogeneous solution is formed, the critical solubility temperature of the calcium is given as <0 ° C. If the surfactant sample does not dissolve within an hour to form a pure homogeneous solution, the heterogeneous solution is slowly heated with stirring at a rate of 0.1 ° C per minute. The temperature at which the surfactant sample dissolves to form a pure homogeneous solution is reported as the critical solubility temperature of calcium.

The sodium salts of the surfactant compositions herein are the most common form in which the surfactant compositions are used. Conversion to calcium salts by a simple double-exchange, e.g. in a dilute solution or with suitable organic solvents, is well known.

Modified SCAS test

This method is an adaptation of the Soap and Detergent Association method of semi-continuous activated sludge (SCAS) to assess primary biodegradation of alkylbenzene sulphonates.

• 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 44 · ··

This method involves exposing the chemical substance to a relatively high concentration of microorganisms for a long time (more preferably several months). The viability of the microorganisms is maintained during this time by the daily supply of settled sewage feed. This modified test is also a standard OECD basic biodegradation test or 302A. This test was approved by the OECD on May 12, 1981. Details regarding the "raw" SCAS test can be found in "A Procedure and Standards for Determination of Biodegradability of Alkyl Benzene Sulphonate and Linear Alkylate Sulphonate", Journal of American Oil Chemists ¹ Society, Vol. 42, p. 986 (1965).

The results obtained with the tested surfactant or surfactant system show that it has a high biodegradation potential and is therefore most suitable as a baseline biodegradation test.

The aeration devices used are identical to those described in the "raw SCAS test". Thus, the Plexiglas tube 83 mm (3 1/4 inch) I.D. (inner diameter), taper the lower end 30 ° from the vertical to 13 mm (1/2 inch) of the hemisphere at the bottom. 25.4 mm (1 inch) above the vertical and tapered wall contact, place a 25.4 mm (1 inch) bottom hole to insert the air supply hose. The total length of the aeration chamber should be at least 600 mm (24 inches). A separate drain port for sampling can be placed at 500 ml. The devices are left open to the atmosphere. The air is supplied to the aeration equipment by a small laboratory air compressor. The air is filtered with cotton wool or any suitable material to remove contamination, oil, etc. The air is delivered at a rate of 500 ml / minute (1 cubic foot / hour). Air is supplied by 8 mm O.D. (external diameter), 2 mm I.D. capillary tube. The end of the capillary tube is located 7 mm (1/4 inch) from the bottom of the aeration chamber.

Modified SCAS test - The aeration devices are cleaned and attached to a suitable support. This process is carried out at 25 ° + 3 ° C. Stocks of test surfactant or surfactant system are prepared: the normally required concentration is 400 mg / liter, since organic carbon normally gives a test surfactant or surfactant system concentration of 20 mg / liter carbon at the beginning of each biodegradation cycle if no biodegradation occurs.

A sample of the mixed activated sludge fluid from a plant treating mostly domestic waste water is provided. Each aeration unit is filled with 150 ml of mixed fluid and aeration is started. After 23 hours there is aeration

4 4444 and· • • 44 • 4 ·· • · • • 4 4 4 4 • • • • 44 4 • • • · • • ♦ ♦ 4 • 4 4 · 4 · • 4 • • * 4 • 4 4 · • 4 »4 4 4 4 4 4 4

stop and allow sludge to settle for 45 minutes. 100 ml of supernatant is removed.

Immediately before use, a sample of settled domestic sludge is provided and 100 ml is added to the sludge remaining in each aerator. Aeration is resumed. At this stage no test substances are added and the equipment is supplied daily with domestic waste water only until a clear liquid is obtained above the sediment sediment. This typically takes up to two weeks, until the dissolved organic carbon in the supernatant at the end of each aeration cycle should be less than 12 mg / liter.

At the end of this stage, the individual settled sludge is mixed and 50 ml of the resulting composite sludge is added to each device.

100 ml of settled sludge is added to the aeration devices, which will be control devices. Add 95 ml of settled sludge and 5 ml of the stock solution (400 mg / l) of the respective surfactant or surfactant system tested to the aeration devices that will be control devices. The aeration is resumed and continues for 23 hours. The sludge is then allowed to settle for 45 minutes and the supernatant is collected and analyzed for dissolved organic carbon content. The carbon content (D.O.C.) is analyzed using a SHIMADZU model TOC-5000 TOC analyzer. This filling and unloading procedure is repeated daily during the test. Before settling, it may be necessary to clean the walls of the device to prevent solids from accumulating above the liquid level. A separate scraper or brush is used for each device to prevent cross contamination.

Dissolved organic carbon in supernatant is ideally determined daily, although less frequent analysis is acceptable. The liquids are filtered through washed 0.45 micron membrane filters prior to analysis and centrifuged. The sample temperature must not exceed 40 ° C while in the centrifuge.

The results of the dissolved organic carbon in the liquids above the sediment of the tested aeration devices and control aeration devices are plotted as a function of time. As biodegradation is achieved, the level found in the aeration equipment tested approximates that found in the control aeration equipment. When the difference between the two levels is found to be constant for three consecutive measurements, three additional measurements are taken and the percentage of biodegradation of the test surfactant or surfactant system is calculated according to the following equation:

4 * ···% biodegradation =

100 k - (o, - drawbar).

_ ¹

4 * 44 *

···

4 · • 44

4 * 4

4 4 4

4 4 4

4 4 4

4 4 4 4

4 4 4

4 4 4 where

Ot = concentration of test surfactant or surfactant system as organic carbon added to the sediment sludge at the beginning of the aeration stage.

Oi = concentration of dissolved organic carbon found in the supernatant of the aeration equipment tested at the end of the aeration stage.

Oc = concentration of dissolved organic carbon found in the supernatant of the control aeration equipment.

The degree of biodegradation is thus the percentage of organic carbon removal.

This modified test provides the following data (as recorded on page 7 of the standard OECD Basic Biodegradation Test, or 302A) for tetrapropylenebenzenesulfonate ("TPBS"; see "Surfactant Science Series", vol. 56, Marcel Dekker, N.Y., 1996, page 43):

test surfactant; or Q. O, -Oc percent biodegradation surfactant system (mg / l) (mg / l) TPBS 17.3 8.4 51.4

Detergents

The detergent compositions of the present invention include a variety of consumer detergent products including powders, liquids, granules, gels, pastes, tablets, pouches, sticks, types supplied in two-piece containers, spray or foam detergents, and other homogeneous or multiphase forms of consumer cleaning products. They can be used or applied manually and / or can be used in a single or freely varying dose, or by automatic dosing means, or can be used in appliances such as washing machines or dishwashers or can be used in connection with institutional cleaning, including personal cleaning in public equipment, bottle washing, cleaning of surgical instruments or cleaning of electronic components. They can have a large pH range, for example from about 2 to about 12 or more, and can have a large alkalinity preservation range, which can include a very high alkalinity preservation as in such uses as waste release, where tens of grams of NaOH equivalent may be present. 100 g of preparation, can range from 1 to 10 g of NaOH equivalent and mild or low-alkaline liquid ranges ·· ·······

999

9

9 9

9 9

9 9

9 9 9

99

99

9 9 9

9 9 9

9 9 9 9 • 4 4 4 4 4 manual cleaners, down to the acid part as in hard surface acid cleaners. Both high-foaming and low-foaming detergent types are included.

Consumer cleaners are described in the "Surfactant Science Series" by Marcel Dekker, New York, Volumes 1 to 67 and above. Liquid formulations are described in particular in Volume 67, "Liquid Detegents", Ed. Kuo-Yann Lai, 1997, ISBN 0-8247 9391-9, incorporated herein by reference. More classical preparations, especially granular types, are described in "Detergent Manufacture including Zeolite Builders and Other Materials", Ed. M. Sitting, Noyes Data Corporation, 1979, incorporated herein by reference. See also Encyclopedia of Chemical Technology by Kirk Othmers.

Consumer cleaners include, but are not limited to:

Less Powerful Liquid Detergents (LDL): these compositions include LDL compositions having magnesium ions that improve surface activity (see, for example, WO 97/00930 A; GB 2 292 562 A; US 5 376 310; US 5 269 974; US 5 230 823 U.S. Pat. No. 4,923,635; U.S. Pat. No. 681,704; U.S. Pat. No. 4 316 824; U.S. Pat. No. 4 133 779) and / or organic diamines and / or various foam stabilizers and / or foam boosters such as amino oxides (see, for example, U.S. Pat. skin sparing modifiers or surfactants, emollient and / or enzymatic types including protease; and / or antimicrobial additives; a more comprehensive list of patents is in the Surfactant Science Series, Vol. 67, pages 240-248.

High Performance Liquid Detergents (HDL): these compositions include both so-called "structural" or multi-phase (see, for example, US 4 452717; US 4,526,709; US 4,530,780; US 4,618,446; US 4,793,943; US 4,659,497; U.S. Pat. No. 4,871,467; U.S. Pat. No. 4,891,147; U.S. Pat. No. 5,006,273; U.S. Pat. No. 5,021,195; U.S. Pat. No. 5,147,576; U.S. Pat. No. 5,160,655) and &quot; non-structural &quot; or isotropic liquid types and may be generally aqueous or anhydrous EP 738 778 A; WO 97/00937 A; WO 97/00936 A; EP 752 466 A; DE 19623623 A; WO 96/10073 A; WO 96/10072 A; US 4,647,393; US 4,648,983; US 4 655,954;

661 280; EP 225,654; U.S. 4,690,771; 4,744,916; 4,753,750; U.S. 4,950,424; US

004 556; U.S. 5,102,574; WO 94/23009; and may be with a bleaching agent (see, e.g.

U.S. Pat. No. 4,470,919; 5,250,212; EP 564,250; U.S. 5,264,143; 5,275,753; U.S. 5,288,746; WO 94/11483; EP 598,170; EP 598,973; EP 619,368; U.S. Pat. No. 5,431,848; US 5,445,756) and / or enzymes (see for example US 3,944,470; US 4,111,855; US 4,261,868; US 4,287,082; US 4,305,837; US 4,404,115; US 4,462,922; US 4,529 5225; US 4,537,706; US 4,537,707; US 4,670,179; US 4,842,758; US 4,900,475; US 4,908,150; US ··················· · 9 9 9 9 9 9 9 9 9 9 9 · 9 9 9

4β 99

082 585; 5,156,773; WO 92/19709; EP 583,534; EP 583,535; EP 583,536; WO 94/04542; 5,269,960; EP 633,311; U.S. Pat. No. 5,422,030; U.S. Pat. No. 5,431,842; US 5,442,100) or without bleaching agent and / or enzymes. Other patents relating to potent liquid detergents are reviewed or enumerated in the Surfactant Science Series, Vol. 67, pages 309 to 324.

High Performance Granular Detergents (HDG): These compositions include both so-called "compact" or agglomerated or otherwise non-spray dried, so-called "fluffy" or spray-dried types. Both the phosphate and non-phosphate types are included. These detergents may include the more common types based on anionic surfactants or may be the so-called "highly nonionic surfactant" types in which usually a nonionic surfactant is held in or on an absorbent such as zeolite or other porous inorganic salts. The manufacture of HDG is described, for example, in EP 753 571 A; WO

96/38531 A; 5,576,285; 5,573,697; WO 96/34082 A; US 5,569,645; EP 739,977 A; 5,565,422; EP 737,739 A; WO 96/27655 A; 5,554,587; WO 96/25482 A; WO 96/23048 A; WO 96/22352 A; EP 709,449 A; WO 96/09370 A; 5,496,487; US 5,489,392 and EP 694,608 A.

"Softergents" (STW): these compositions include various granular or liquid (see, for example, 753,569 A; US 4,140,641; US 4,639,321; US 4,751,008; EP 315 126; US 4,844,821; US 4,844,824; U.S. Pat. No. 4,873,001; U.S. Pat. No. 4,911,852; U.S. Pat. No. 5,017,296; EP 422,787) during the washing process, softening product types and generally may have organic (e.g., quaternary) or inorganic (e.g., clay) plasticizers.

Hard Surface Cleaners (HSC): These compositions include all-purpose cleaners such as cream cleaners and liquid all-purpose cleaners; general purpose spray cleaners including glass and tile cleaners; and bathroom cleansers including mold-removing, bleach-containing, antimicrobial, acidic, neutral and alkaline types. See, for example, EP 743 280 A; EP 743 279 A. Acidic cleaning agents include those of WO 96/34938 A.

Lump Soaps (BS&HW): these personal cleansing soaps as well as so-called laundry soaps (see, for example, WO 96/35772 A); including both synthetic detergents and soap-based and plasticizer types (see US 5,500,137 or WO 96/01889 A); such compositions may include those made by conventional soap making methods, for example, by the intensive method and / or the more traditional methods, for example, by casting, absorption of surfactants in a porous carrier, or the like. Other piece soaps (see, for example, BR 9502668; WO 96/04361 A; WO 96/04360 A; US

540 852) are also incorporated. Other hand wash detergents include, for example, those described in GB 2 292 155 A and WO 96/01306 A.

Shampoos and Conditioners (S&C): (see, for example, WO 96/37594 A; WO 96/17917 A; WO 96/17590 A; WO 96/17591 A). These compositions generally include both simple shampoos and so-called "two in one" or conditioner types.

Liquid soaps (LS): these compositions include both so-called "antibacterial" and traditional types, as well as those with or without skin conditioner, and include types suitable for use in spray dispensers and in other ways, for example, in solid dispensers used institutionally.

Fabric Softeners (FS): these compositions include both traditional liquid and liquid concentrated types (see, for example, EP 754 749 A; WO 96/21715 A; US 5,531,910; EP 705,900 A; US 5,500,138) as well as an added dehydrator or support substrate (see, for example, US 5,562,847; US 5,559,088; EP 704 522 A). Other fabric softeners include solids (see, for example, US 5,505,866).

Special Purpose Detergents (SPCs) including dry cleaning preparations for domestic use (see, for example, WO 96/30583 A; WO 96/30472 A; WO 96/30471 A; US 5,547,476; WO 96/37652 A); bleaching products for pretreating laundry (see EP 751 210 A); articles for pretreatment of substances (see for example EP 752 469 A); liquid detergent types for delicate substances, in particular high-foaming types, dishwashing rinse aid; liquid bleaches including both chlorine and oxygen type, and disinfectants, mouthwashes, dental cleaners (see, for example, WO 96/19563 A; WO 96/19562 A), car or carpet cleaners or shampoos (see, for example, EP 751 213 A; WO 96/15308 A), hair rinsing preparations, shower gels, bath foams and personal care cleaners (see, for example, WO 96/37595 A; WO 96/37592 A; WO 96/37591 A; WO 96 / WO 96/37588 A; GB 2,297,975 A; GB 2,297,762 A; GB 2,297,761 A; WO 96/17916 A; WO 96/12468 A) and metal cleaning preparations; as well as cleaning aids such as bleaching agents and "adhesive stains" or other types of pretreatment, including special foam cleaning agents (see, for example, EP 753 560 A; EP 753 559 A; EP 753 558 A; EP 753 557 A; EP 753 556 A) and sunscreen fading agents are also incorporated.

Persistent fragrance detergents (see, for example, US 5,500,154; WO 96/03369 A) are becoming increasingly popular.

• ·

4

Laundry or cleaning additives and methods:

The detergent compositions of the present invention comprise from about 0.00001 wt. % to about 99.9 wt. % at least one additional cleaning agent selected from the group consisting of: i) cleaning enzymes, more preferably selected from proteinases, amylases, lipases, cellulases, peroxidases, and mixtures thereof; ii) organic detergent builders, more preferably selected from polycarboxylate compounds, etherhydroxypolycarboxylates, substituted ammonium salts of polyacetic acids, and mixtures thereof; iii) an oxygen bleaching agent, more preferably selected from hydrogen peroxide, inorganic perhydrates, organic perhydrates and organic peroxyacids, including hydrophilic and hydrophobic mono- and peroxyacids, and mixtures thereof; iv) bleach activators, more preferably selected from TAED, NOBS, and mixtures thereof; v) bleach catalysts of transition metals, more preferably manganese-containing bleach catalysts; (vi) oxygen transfer agents and precursors; vii) polymeric soil release agents; (viii) water-soluble ethoxylated amines having properties that allow clay soil removal and prevent it from settling back; ix) polymer dispersing agents; (x) polymeric dye transfer inhibiting agents; xi) alkoxylated polycarboxylates; and xii) mixtures thereof.

In general, laundry or cleaning additives are any substances required to convert a composition containing only a minimum of a constituent into a laundry detergent and cleaning composition. In a suitable embodiment, laundry or cleaning additives are readily recognized by those skilled in the art as being quite typical of laundry and cleaning products, particularly laundry and cleaning products intended for direct use by the customer in the home environment.

The precise nature of these excipients and the degree of their combinations will depend on the physical form of the composition and the nature of the purification process for which it is to be used.

Additives, when used with a bleach, should preferably have good stability with it. Certain suitable detergent compositions herein should be boron free and / or phosphate free as required by law. The level of additives is from about 0.00001 wt. % to about 99.9 wt. %, typically from about 70 wt. % to about 95 wt. % of funds. The level of aggregate used may vary greatly depending on the intended use, for example from a few ppm in solution to the so-called "direct use" of the undiluted detergent on the surface to be cleaned.

Common additives include fillers, surfactants, enzymes, polymers, bleaches, bleach activators, catalysts and the like, except any of the substances defined above as ftftft ftftft ftftft ftft ftftft ftft ft ftft ftft ftft ftft ftft ftft ftft ftft part of the basic component of the inventive means. Other additives herein may include various active ingredients or special ingredients such as dispersing polymers (e.g., from BASF or Rohm & Haas), colored speckles, silver treating agents, matt and anti-corrosion additives, paints, fillers, disinfectants, alkaline sources , hydrotropes, antioxidants, enzyme stabilizing additives, proparfems, perfumes, solubilizers, carriers, processing aids, pigments and, for liquid formulations, solvents, as detailed below.

Detergents at this location, such as laundry detergents, laundry detergent additives, hard surface cleaners, synthetic or soap-based laundry soaps, fabric softeners and liquids for cleaning fabrics, solids and cleaning articles of all kinds will typically require several additives, although certain simple form products such as bleaching agents may only require, for example, an oxygen bleaching agent and a surfactant as described herein. A complete list of suitable laundry or cleaning additives and methods can be found in Application No. 60/053 319 for a US provisional patent filed July 21, 1997 and assigned to Procter & Gamble.

Detersive Surfactants - Conventional compositions suitably include a detersive surfactant. Detergent surfactants are extensively described in US 3,929,678, Dec. 30, 1975 to Laughlin, et al, and US 4,259,217, Mar. 31, 1981 to Murphy; in the series "Surfactant Science" by Marcel Dekker, Inc., New York and Basel; in "Handbook of Surfactants", M.R. Porter, Chapman and Hall, 2nd edition 1994; in "Surfactants in Consumer Products", Ed. J. Falbe, Springer-Verlag, 1987; and many patents related to detergents assigned to Procter & Gamble and other detergent and consumer product manufacturers.

Thus, the cleaning surfactant herein includes anionic, nonionic, zwitterionic or amphoteric surfactant types known for use as laundry detergent additives, but does not include wholly foam-free or completely insoluble surfactants (although these may be used as possible additives). Examples of the type of surfactants considered optional for these purposes are not relatively common in comparison to cleaning surfactants, but include, for example, conventional fabric softening agents such as dioctadecyldimethylammonium chloride.

More specifically, cleaning surfactants preferred herein, typically at levels of from about 1 wt. % to about 55 wt. %, suitably include: (1) conventional alkylbenzene sulfonates; (2) olefin sulphonates, including α-olefin sulphonates and sulphonates derived from fatty acids and fatty esters; (3) alkyl or alkenyl sulfosuccinates, including diester and semi-ester types, as well as sulfosuccinamates and other sulfonate / carboxylate types of surfactants such as sulfosuccinates derived from ethoxylated alcohols and alkanolamides; (4) paraffin or alkanesulfonate - and alkyl or alkenylcarboxysulfonate - types including the product of the addition of bisulfite to alpha olefins; (5) alkylnaphthalenesulfonates; (6) alkyl 2-hydroxyethanesulfonates and alkoxypropane sulfonates, as well as fatty esters of 2-hydroxyethanesulfonate, ethoxylated fatty esters

hydroxyethane sulfonate and other sulfonate esters such as 3-hydroxypropanesulfonate ester or AVANEL S types; (7) benzene, cumene, toluene, xylene and naphthalenesulfonates, particularly suitable for their hydrotropic properties; (8) alkyl ether sulfonates; (9) alkylamide sulfonates;

(10) α-sulfo-salts of fatty acids or esters and internal sulfoesters of fatty acids;

(11) alkyl glycerylsulfonates; (12) lignin sulfonates; (13) petrolsulfonates, sometimes known as heavy alkyl sulfonates; (14) diphenyloxide disulfonates; (15) linear or branched alkyl sulfates or alkenyl sulfates; (16) alkyl or alkylphenolalkoxylated sulfates and corresponding polyalkoxylates, sometimes known as alkyl ether sulfates, as well as alkenylalkoxy sulfates or alkenyl polyalkoxy sulfates; (17) alkylamide sulfates or alkenylamide sulfates, including sulfated alkanolamides and their alkoxylates and polyalkoxylates; (18) sulphated oils, sulphated alkylglycerides, sulphated alkyl polyglycosides or sulphated surfactants derived from sugars; (19) alkylalkoxycarboxylates and alkylpolyalkoxycarboxylates, including galacturonic acid salts; (20) alkyl ester carboxylates and alkenyl ester carboxylates; (21) alkyl or alkenyl carboxylates, especially conventional soaps and α, β-dicarboxylates, including alkyl and alkenyl succinates; (22) alkyl or alkenylamide alkoxy and polyalkoxycarboxylates; (23) alkyl and alkenylamidocarboxylate types of surfactants, including sarcosinates, taurides, glycinates, aminopropionates and iminopropionates; (24) amide soaps, sometimes called fatty acid cyanamides; (25) alkylpolyaminocarboxylates; (26) phosphorus-based surfactants, including alkyl or alkenyl phosphate esters, alkyl ether phosphates including their alkoxylated derivatives, phosphatidic acid salts, alkylphosphonic acid salts, alkyldi (polyoxyalkylenalkanol) phosphates, amphoteric phosphates such as lecithins; and phosphate / carboxylate, phosphate / sulphate and phosphate / sulphonate types; (27) Pluronic and Tetronic types of nonionic surfactants; (28) so-called EO / PO Block polymers, including diblock and triblock EPE and PEP types; (29) fatty acid polyglycol esters;

(30) closed and unclosed alkyl or alkylphenol ethoxylates, propoxylates and butoxylates including polyethylene glycol ethers of fatty alcohols; (31) fatty alcohols, especially where they are suitable as surfactant viscosity modifiers or present as unreacted; · · · · · · · · · · · · · · · · · · Components of other surfactants; · other constituents of other surfactants; (32) N-alkyl polyhydroxy fatty acid amides, especially alkyl-N alkyl glucamides; (33) nonionic surfactants derived from mono- or polysaccharides or sorbitan, especially alkylpolyglycosides, as well as sucrose fatty acid esters; (34) ethylene glycol, propylene glycol, glycerol and polyglyceryl esters and their alkoxylates, especially glycerol ethers and monoesters and diesters of fatty acid / glycerol; (35) aldobionamide surfactants; (36) alkyl succinimide nonionic surfactant types; (37) acetylene alcohol surfactants such as SURFYNOLS; (38) alkanolamide surfactants and their alkoxylated derivatives including fatty acid alkanolamides and fatty acid alkanolamide polyglycol ethers; (39) alkylpyrrolidones; (40) alkylamine oxides, including alkoxylated or polyalkoxylated amine oxides and amine oxides derived from sugars; (41) alkylphosphine oxides; (42) sulfoxide surfactants; (43) amphoteric sulfonates, especially sulfobetaines; (44) betaine amphoteric types, including types derived from aminocarboxylates; (45) amphoteric sulfates such as alkylamoniopolyethoxysulfates; (46) fatty and petroleum alkylamines amine salts; (47) alkylimidazolines; (48) alkylamidoamines and their alkoxylated and polyalkoxylated derivatives; and (49) conventional cationic surfactants, including water-soluble alkyltrimethylammonium salts. Also included are less common types of surfactants such as: (50) alkylamidoamine oxides, carboxylates and quaternary salts; (51) sugar-derived surfactants formed according to any of the more common non-sugar types mentioned above; (52) fluorotensides; (53) biotensides; (54) organosilicon surfactants; (55) geminal surfactants, other than the aforementioned diphenyloxide disulfonates, including those derived from glucose; (56) polymeric surfactants including amphopolycarboxyglycinates; and (57) spherical surfactants.

With respect to the conventional alkylbenzene sulfonates mentioned above, especially for the substantially linear types, including those formed by AlCl 3 or HF alkylation, chain lengths of about C 10 to about C 14 are suitable. Such linear alkylbenzene sulfonate surfactants may be present in conventional formulations either as a product of the prior art which has been admixed or as a product present in one or more of the crystalline disrupted basic surfactant precursors. The ratio of linear and interrupted crystalline alkylbenzene sulfonates of the present invention can vary from 100: 1 to 1: 100; more typically, when using alkylbenzene sulfonates of at least about 0.1 weight percent, preferably at least about 0.25 weight percent, is the crystallinity interrupted surfactant of the present invention.

In any of the above-mentioned cleaning surfactants, the length of the hydrophobic chain is typically within the total range of C8-C20, with chain lengths in the range of C8-C18 being • 00 0

00 00 0 0000 • 0 0 0 0 · 0 ·· ·

0 0 0 0 0 0000

000000 00 00 00 00 is often more suitable, especially when washing is to be carried out in cold water. The choice of chain lengths and degree of alkoxylation for common purposes are taught in common manuals. If the cleaning surfactant is a salt, any suitable cation including H (i.e., the acidic or partially acidic form of the potential surfactant), Na, K, Mg, ammonium or alkanolammonium, or a combination of cations may be present. Conventionally, detergent surfactant compositions having different charges are suitable, especially anionic / cationic, anionic / nonionic, anionic / nonionic / cationic, anionic / nonionic / amphoteric, nonionic / cationic and nonionic / amphoteric mixtures. In addition, any simple cleaning surfactant may be substituted, often with desirable cold water wash results, by mixtures of otherwise similar cleaning surfactants having varying chain lengths, degree of unsaturation or branching, degree of alkoxylation (especially ethoxylation), insertion of substituents such as ether of oxygen atoms in hydrophobes substances, or any combination thereof. Suitable among the above-mentioned cleaning surfactants are: acidic, sodium and ammonium C9-C20 linear alkylbenzenesulfonates, especially sodium linear secondary alkyl C10-C15 benzenesulfonates (1); olefin sulfonate salts, (2) that is, a substance formed by reacting olefins, especially C10-C20 α-olefins, with sulfur trioxide and subsequent neutralization and hydrolysis of the reaction product; sodium and ammonium C7-C12 dialkylsulfosuccinates, (3); alkanmonosulfonates, (4) such as those produced by reacting C8-C20 α-olefins with sodium metabisulfite and those produced by reacting paraffins with SO2 and Cl2 and then hydrolyzing to form an irregular sulfonate; α-sulfo salts or fatty acid esters, (10) sodium alkylglyceryl sulfonates, (11), in particular higher alcohol ethers made from tallow or coconut oil and synthetic alcohols made from petroleum; alkyl or alkenyl sulfates, (15), which may be primary or secondary, saturated or unsaturated, branched or unbranched. Such compounds, when branched, may be irregular or regular. If they are secondary, they are more preferably of the general formula

CH3 (CH2) x (CHOSO3-M +) CH3 or CH3 (CH2) y (CHOSO3-M +) CH2CH3, wherein xa (y + 1) are integers from at least 7, preferably at least 9, and M is a water-soluble cation, more preferably sodium . When unsaturated, sulphates such as oleoyl sulphate are suitable, although sodium and ammonium alkyl sulphates, particularly those made by sulphating C8-C18 alcohols, made for example from tallow or coconut oil, are also suitable; also suitable are alkyl or alkenyl ether sulfates, (16), especially ethoxy sulfates having about 0.5 moles or higher ethoxylation, preferably from 0.5 to 8; alkyl ether carboxylates, (19), in particular EO 1 to 5 ethoxycarboxylates; soaps or fatty acids (21), more preferably water types more více k k k k k k k k k k k k k k k k k k k · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · amino acid surfactant types, (23) such as sarcosinates, especially oleylsarcosinate; phosphoric acid esters, (26); alkyl or alkylphenol ethoxylates, propoxylates and butoxylates, (30), in particular ethoxylates "AE", including the so-called narrow peak alkyl ethoxylates and C6-C12 alkylphenolalkoxylates, as well as products of aliphatic primary or secondary linear or branched C8-C18 alcohols with ethylene oxide EO; N-polyhydroxy fatty acids, especially C12-C18 N-methylglucamides, (32), see WO 9206154, and N-alkoxypolyhydroxy fatty acids, such as C10-C18 N- (S-methoxypropyl) glucamide, although N-propyl to N-hexyl C12- C18 glucamides can be used for low soap formation; alkylpolyglycosides, (33); amine oxides, (40), more preferably alkyldimethylamine-N-oxides and dihydrates thereof; sulfobetaines or 'sultains', (43); betaines (44); and geminal surfactants.

A suitable level of anionic detersive surfactants is here in the range of about 1 wt. % to about 50 wt. % or more, more preferably from about 2 wt. % to about 30 wt. %, more preferably from about 5 wt. % to about 20 wt. % detergent composition.

A suitable level of nonionic detersive surfactants herein is from about 1% to about 40%, more preferably from about 2% to about 30%, more preferably from about 5% to about 20%.

Desirable weight ratios of anionic and nonionic surfactants in combination are from 1.0: 9.0 to 1.0: 0.25, preferably 1.0: 1.5 to 1.0: 0.4.

A suitable level of cationic detersive surfactants herein is from about 0.1% to about 20%, more preferably from about 1% to about 15%, although a much higher level, e.g., up to about 30% or more, may be particularly useful in non-ionic surfactants. : cationic (ie, restricted or anion-free) preparations.

When amphoteric or zwitterionic cleaning surfactants are present, it is generally preferred that levels in the range of about 0.1 wt. % to about 20 wt. % detergent composition. Often levels will be limited to about 5% or less, especially when the amphoteric agent is expensive.

Cleaning Enzymes - Enzymes are suitably incorporated into current detergent compositions for a variety of reasons, including removal of protein, carbohydrate or triglyceride stains from substrates, to prevent the transfer of faded dyes when washing fabrics, and to renovate fabrics. Recent discoveries regarding enzymes suitable for detergents herein include bleach / amylase / proteinase combinations (EP 755 799 A; EP 756 001 A; EP 756 000 A); chondriotinase (EP 747 469 A); proteinase variations (WO 96/28566 A; WO 96/28557 A; WO 96/28556 A; WO 96/25489 A); xylanase (EP 709 452 A); keratinase (EP 747 470 A); lipase (GB 2,297,979 A; WO 96/16153 A; WO 96/12004 A; EP 698659 * A; WO 96/16154 A); cellulase (GB 2,294,269 A; WO 96/27649 A; GB 2,203,147 A); termitase (WO 96/28558 A). More generally, suitable enzymes include proteinases, amylases, lipases, cellulases, peroxidases, xylanases, keratinases, chondriotinases, termitases, cutinases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Suitable choices are influenced by factors such as pH activity and / or optimal stability, thermostability and stability to the active detergents, ingredients and the like. Accordingly, bacterial and fungal enzymes such as bacterial amylase and proteinase and fungal cellulase are suitable. Suitable enzymes are also described in U.S. Patent Nos. 5,677,272, 5,679,630, 5,703,027, 5,703,034, 5,705,464,

707,950, 5,707,951, 5,710,115, 5,710,116, 5,710,118, 5,710,119 and 5721,202.

"Cleaning enzyme" as used herein means any enzyme that has a cleaning, stain-removing or otherwise beneficial effect in a detergent composition for washing, hard surface cleaning or personal care. Suitable purification enzymes are hydrolases such as proteinases, amylases and lipases. Suitable enzymes for washing purposes are, for example, proteinases, cellulases, lipases and peroxidases. Very suitable are amylases and / or proteinases, including both currently commercially available types and improved types, which, although increasingly interchangeable bleaching agents due to successful improvements, have the remaining degree of bleach deactivation capability.

Enzymes are normally incorporated into detergent or detergent adjuvants at a level sufficient to provide a "cleansing effective amount".

The term "cleaning effective amount" refers to any amount capable of delivering cleaning, stain removing, dirt removing, bleaching, deodorizing or freshness enhancing effects on substrates such as fabrics, dishes, and the like. In practice, current commercial preparations typically contain amounts of active enzyme per gram of detergent composition up to about 5 mg, more typically 0.01 mg to 3 mg. In other words, these compositions will typically contain from 0.001 wt% to 5 wt%. %, more preferably 0.01 wt. % to 1 wt. % of a commercial enzyme preparation. Proteinase enzymes are generally present at such levels in such commercial formulations to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain detergents, it may be desirable to increase the active enzyme content of a commercial preparation to minimize the total amount of active crystalline material and thereby improve soiling / thin coating or other end results. A higher active level may also be desirable in highly concentrated detergent compositions.

Interesting examples of proteinase are subtilisins that are obtained from individual B. subtilis strains of B. licheniformis. One suitable proteinase is obtained from a Bacillus strain, has a maximum activity at a pH in the range of 8-12, is developed and sold as ESPERASE® by Novo Industries A / S from Denmark, hereinafter Novo. The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 by Novo. Other suitable proteinases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, The Netherlands; as well as Proteinase A as described in EP 303 761 A, 28 April 1987 and EP 130 756 A, 9 January 1985. See also high pH proteinase from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzyme detergents containing proteinase, one or more other enzymes, and a reversible proteinase inhibitor are described in WO 9203529 A to Novo. Other suitable proteinases include those in WO 9510591 A to Procter & Gamble, if desired, a proteinase having reduced adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin type proteinase suitable for the detergents described herein is described in WO 9425583 to Novo.

In particular, a particularly suitable proteinase, called "Proteinase D", is a non-naturally occurring carbonylhydrase sequence that is made from a carbonylhydrase precursor by substituting another amino acid for a plurality of amino acid residues at the position of said carbonyl hydrolase equivalent to the +76 position, in combination with one or more amino acid residue positions equivalent to those 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 by numbering Bacillus amyloliquefaciens subtilisin as described in WO 95/10615 published April 20, 1995 by Genencor International.

Suitable proteinases are also described in PCT publications: WO 95/30010 published November 9, 1995 by The Procter &Gamble; WO 95/30011 published November 9, 1995 by The Procter &Gamble; WO 95/29979 published November 9, 1995 by The Procter & Gamble.

Suitable amylases herein include, for example, the α-amylases described in GB 1,296,839 to Novo; RAPIDASE (R), International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo is particularly suitable. Enzyme techniques for improved stability, e.g., oxidative stability, are known. See, for example, J. Biological Chem., Vol. 260, No. 11,

9 4494

4444

44

94

4 4 4

4 9 9

9 4 9 4

4 9 9

Certain suitable embodiments of the present compositions may use amylases having improved detergent stability, particularly improved oxidation stability, as measured against the TERMAMYL® reference point in commercial use in 1993. These suitable amylases share here. an amylase feature of "enhanced stability", characterized by at least measurable improvement at one or more of: oxidative stability, eg to hydrogen peroxide / tetraacetylethylenediamine in a buffer solution at pH 9 to 10; thermal stability, eg, at normal wash temperatures such as about 60 ° C; or alkaline stability, e.g., at a pH of from about 8 to about 11, measured against the amylase reference point as defined above. Stability can be measured using any of the technical tests described in the art. See, for example, the references described in WO 9402597. Amylases with enhanced stability can be obtained from Novo and Genencor International. One class of highly suitable amylases here has a common feature since it has been produced by site-directed mutagenesis from one or more Bacillus amylases, particularly Bacillus α-amylases, regardless of whether one, two or multiple amylase strains are immediate precursors. Amylases with increased oxidative stability are more suitable for use than the above reference amylase, especially in bleaching, preferably oxygen bleaching, as opposed to chlorine bleaching, in detergent compositions therein. Such suitable amylases include (a) amylase according to the above incorporated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made with alanine or threonine, preferably threonine, a residue of methionine located at position 197 of B. licheniformis alpha -amylases, known as TERMAMYL®, or at the homologous position of a variation similar to maternal amylases such as B. amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b) Amylases with enhanced stability as described by Genencor International in a paper entitled "Oxidatively Resistant alpha- Amylases" presented at C. 207 of the American Chemical Society National Meeting, March 13-17, 1994, by C. Mitchinson. It was pointed out that bleaches in automatic dishwashing detergents inactivate alpha-amylases, but that amylases with improved oxidation stability were produced by Genencor of B. licheniformis NCIB8061. Methionine (Met) was determined to be the most suitable residue for modification. Met was substituted, one after the other, at positions 8, 15, 197, 256, 304, 366 and 438 leading to certain mutants, particularly important are M197L and M197T, with the M197T variation being the most stable expressed variation. Stability was measured in CASCADE® and SUNLIGHT®; here particularly suitable mylases include amylase variations having further modifications in the nearest parent, as described in WO 9510603 A, and are available from • 4 4 4 · 4 4 · 4 4 · 4

4 4 4 4 4

4 4 4 4

4 4 4 Novo as DURAMYL®. Other particularly suitable amylases with increased oxidative stability include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other amylase with increased oxidative stability can be used, for example, that is made by site-directed mutagenesis from a known chimeric form, a hybrid, or a single mutant of the parent forms of amylases available. Other suitable enzyme modifications are available. See WO 9509909 A to Novo.

Other amylase enzymes include those described in WO 95/26397 and in the joint pending application of Novo Nordisk PCT / DK96 / 00056. Specific amylase enzymes for use in the detergent compositions of the present invention include α-amylases characterized by having a specific activity at least 25% higher than that of Termamyl® at temperatures ranging from 25 ° C to 55 ° C and at pH in the range of 8 to 10 as measured by the Phadebas® α-amylase activity assay. (Such an assay of Phadebas® α-amylase activity is described on pages 9-10, WO 95/26397.) Also included are α-amylases that are at least 80% homologous to the amino acid series shown in the SEQ ID lists in the references. These enzymes are incorporated into the laundry detergent compositions more preferably at a level of pure enzyme from 0.00018 wt. % to 0.060 wt. % of the total composition. Celluloses useful herein include both bacterial and spongy types having a suitable optimum pH between 5 and 9.5. U.S. Patent 4,435,307, Barbesgoard et al., Mar. 6, 1984, discloses suitable spongy cellulases from Humicola insolens or Humicola DSM1800 or cellulase 212 producing a fungus belonging to the Aeromonas class, and cellulase extracted from Dolabella Auricula Solander hepatopancreas. Suitable cellulases are also disclosed in GB-A-2 075 028; GB-A-2 095 275 and DE-OS-2 247 832. CAREZYME® and CELLUZYME® (Novo) are particularly suitable. See also WO 9117243 to Novo. Suitable lipase enzymes for detergent use include those produced by microorganisms of the Pseudomonas family, such as Pseudomonas stutzeri ATCC 19,154, as disclosed in GB 1,372,034. See also Lipases in Japanese Patent Application 53,

20487, published Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano" or "Amano P". Other suitable commercial lipases include Amano-CES, Chromobacter viscosum lipases, e.g.

Chromobacter viscosum lipolyticum NRRLB 3673 variation from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipase from U.S. Pat. Biochemical Corp., U.S.A. and Disoynth 4 4 4 4 4 ·

Co., The Netherlands, and lipases from Pseudomonas gladioli. LIPOLASE®, an enzyme made from

Humicola lanuginosa and commercially available from Novo, see also EP 341 947, is a suitable lipase for use herein. Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. See also WO 9205249 and RD

4444

44

4 4 4 4

4 4 4 • 44 44 4

4 44

94359044.

Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.

Peroxidase enzymes may be used in combination with sources of oxygen, such as percarbonate, perborate, hydrogen peroxide, etc. to "bleach in solution" or prevent the transfer of dyes or pigments removed from the substrates during washing to other substrates present in the wash solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed in WO 89099813 A, Oct. 19, 1989 to Novo and WO 8909813 A to Novo. A number of enzyme substances and methods for their incorporation into synthetic detergent compositions are also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. Pat.

No. 553,139, January 5, 1971 to McCarthy et al. Enzymes are further disclosed in U.S. Pat.

No. 101,457, Place et al, July 18, 1978, and U.S. Pat. No. 4,507,219, Hughes, Mar. 26, 1985. Enzymes suitable for liquid detergent compositions and their incorporation into such compositions are disclosed in U.S. Pat. No. 4,261,868, Hora et al, Apr. 14, 1981. Enzymes for use in detergents can be stabilized by various methods. Enzyme stabilization methods are disclosed and exemplified in U.S.3,600,319.17. August 1971,

Gedge et al, EP 199 405 and EP 200 586, Oct. 29, 1086, Venegas. Enzyme stabilization systems are also disclosed, for example, in U.S. Pat. A suitable Bacillus, a species of AC13 giving proteinases, xylanases and cellulases, is described in WO 9401532 A to Novo.

Fillers - Detergent builders are preferably included in the compositions herein, for example, to help control mineral, especially Ca and / or Mg, hardness of the wash water, or to assist in removing and / or suspending certain dirt from surfaces and sometimes providing alkalinity and / or buffering. action. In solid formulations, fillers sometimes serve as absorbents for surfactants. Some compositions may be formulated with fully water-soluble fillers, whether organic or inorganic, depending on the intended use.

9999 • 9 · 9 9 9

99 9 9 9 9 9 9 9 · 9 9 9 9 9 9 9 9 • 9 9 9 9 9 9 9 9 ··· ··· ··· Suitable silicate builders include water-soluble and water-containing solid types, including those having a chain, layered or three-dimensional structure, as well as amorphous solid silicates or other types, for example especially adapted for use in disordered liquid detergents. Alkali metal silicates, particularly those of liquid and solids having a SiO 2: Na 2 O ratio ranging from 1.6: 1 to 3.2: 1, including solid water-containing silicates with a ratio from PQ Corp. are suitable. under the trade name BRITESIL®, eg BRITESIL H2O; and layered silicates, such as those described in U.S. Pat. 4,664,839, May 12, 1987, Η. P.

Rieck. NaSKS-6, sometimes abbreviated as "SKS-6", is crystalline layered

5-Na2SiO5 aluminum-free morphological silicate marketed by Hoest and is particularly useful in granular laundry detergents. See preparative methods in German DE-A-3 417 649 and DE-A-3 742 043. Other layered silicates, such as those having the general formula NaMSixO2x + 1, yH2O, where M is sodium or hydrogen, x is a number from 1 , 9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, may also be used herein or alternately. Layered silicates from Hoest also include NaSKS-5, NaSKS-7 and NaSKS-11 as α, β, and γ layered silicates. Other silicates may also be suitable, such as magnesium silicate, which may serve as a brittle in granules, as a bleach stabilizer, and as a component of soap control systems.

Also suitable for use herein are crystalline ion exchange materials or hydrates thereof having a chain structure and composition represented by the following general formula in the form of anhydrides: xM2OySiO2.zMO, wherein M is Na and / or K, M 'is Ca and / or Mg; y / x is 0.5 to 2.0 and z / x is 0.005 to 1.0 as taught in U.S. Pat. 5,427,711

Sakaguchi et al., June 27, 1995.

Aluminosilicate builders such as zeolites are particularly useful in granular detergents, but may also be incorporated in liquids, pastes or gels. Suitable for this purpose are those having the empirical formula: [Mz (AlO2) z (SiO2) v] xH2O, where zav are integers of at least 6, the molar ratio of z to v ranges from 1.0 to 0.5, and x is an integer from 15 to 264. The aluminosilicates may be crystalline or amorphous, naturally occurring or synthetically prepared. The aluminosilicate production method is in U.S. Pat.

985 669, Krummel, et al, Oct. 12, 1976. Suitable synthetic crystalline aluminosilicate ion exchange materials are present as Zeolite A, Zeolite Ρ (B),

Zeolite X and, to any extent different from Zeolite P, the so-called Zeolite MAP. Naturally occurring types, including clinoptilolite, may be used. Zeolite A has the formula: Na12 [(AlO2) 12 (SiO2) 12] .xH2O, where x is from 20 to 30, especially 27. Dehydrated zeolites • ftftft * ft * • ft ·· · ft · ft · ftft · ft ftft ftft (x = 0 to 10) can also be used. Preferably, the aluminosilicate has an average particle size of from 0.1 to 10 microns.

Detergent builders in place or in admixture to the silicates or aluminosilicates described above may optionally be included in the compositions at that location, for example, to help control the mineral, especially Ca and / or Mg, hardness of the wash water, or to help remove dirt particles from surfaces. The fillers can act through a variety of mechanisms including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by providing a more favorable surface to precipitate hardness ions than the surfaces of the particles to be cleaned. The level of filler can vary greatly depending on the end use and physical form of the composition. Compound detergents typically comprise at least 1% builder. Liquid formulations typically contain from about 5% to about 50%, more typically 5 to 35%, of a filler. Granular formulations typically contain from about 10 wt. % to about 80 wt.%, more typically 15 wt. % to 50 wt. % detergent composition. Lower or higher filler levels are not excluded. Certain detergent ingredients or high surfactant compositions may, for example, be unfolded.

Suitable fillers here may be selected from the group of phosphates and polyphosphates, especially sodium salts; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; organic mono-, di-, tri- and tetracarboxylates, particularly water-soluble non-surfactant carboxylates in the form of an acid, sodium, potassium or alkanolammonium salt, as well as low molecular weight oligomeric or water-soluble polymeric carboxylates, including aliphatic and aromatic types; phytic acid. These may be supplemented with borates, eg for pH-buffering purposes, or sulfates, especially sodium sulfate, and any other builders or carriers that may be important for stable surfactant techniques and / or detergent-containing builders.

Mixer mixtures, sometimes called "filler systems", can be used and typically can contain two or more conventional fillers, optionally supplemented with chelants, pH buffers or fillers, although the latter are generally considered to be separate when describing the amount of substances herein. In terms of relative amounts of surfactants and builder in such detergents, suitable builder systems are typically formed at a surfactant to builder weight ratio of from about 60: 1 to about 1:80. Certain suitable laundry detergents have a ratio of 0.9: 1.0. to 4.0: 1.0, preferably from 0.95: 1.0 to 3.0: 1.0.

• ΦΦ φ

φ φ φ φ φ φ φ φ φ φ φ φ φ φ

P-containing detergent builders often suitable where permitted by law, for example, include alkali metal salts, ammonium and alkanolammonium salts of polyphosphates exemplified by, for example, tripolyphosphates, pyrophosphates, glassy polymeric metaphosphates; and phosphonates.

Suitable carbonate builders include alkali earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001, published November 15, 1973, although sodium bicarbonate sodium carbonate, sodium sesquicarbonate and other carbonate minerals such as tron or any suitable multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na 2 CO 3. CaCO 3 when anhydrides and even calcium carbonates including calcite, aragonite and vaterite, especially forms having a high surface area relative to compact calcite may be suitable, for example as seed crystals or for use in synthetic detergent bar soaps.

Suitable "organic detergent builders" as described herein for use with an alkylarylsulfonate surfactant system include polycarboxylate compounds, including water-soluble non-surfactant dicarboxylates and tricarboxylates. More typical filler polycarboxylates have a large number of polycarboxylate groups, preferably at least 3 carboxylates. The carboxylate builders may be in acid, partially neutral, neutral or over-neutralized form. They are in the form of salts, suitable are alkali metal salts such as sodium, potassium and lithium. Polycarboxylate builders include ether polycarboxylates such as oxydisuccinate, see Berg, U.S. Pat. No. 3,128,287, Apr. 7, 1964, and Lambert et al, Jan. 18, 1972, &quot; TMS / TDS &quot; 4,663,071, Bush et al, May 5, 1987; and other ether carboxylates including cyclic and alicyclic compounds such as those described in U.S. Pat. Patents 3,923,679; 3835 163; 4,158,635; 4,120,874 a

102 903.

Other suitable organic detergent builders are etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or methyl vinyl ether; 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid; carboxymethyloxysuccinic acid; various alkali metal salts, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid; as well as melitic acid, succinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

• 4 · 4 4

4 4 4 4444 44 44 44 44 44 44 44 44 44 44 44 44 44

Citrates such as citric acid and its soluble salts are important carboxylate builders, e.g., for high performance liquid detergents, due to accessibility from renewable sources and biodegradation. Citrates can also be used in granular compositions, particularly in combination with zeolites and / or layered silicates. Oxydisuccinates are also particularly useful in such compositions and combinations.

Where permitted, and especially in the formation of lump soaps used for hand washing operations, alkali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate may be used.

Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates, e.g. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and have stone-preventing properties.

Certain cleaning surfactants or their short-chain homologues also have the effect of fillers. For a non-meaningful rule explaining the purposes when they have a surfactant capability, these substances are summarized as detersive surfactants. Suitable types for acting as fillers are illustrated by: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds disclosed in U.S. Pat. No. 4,566,984, Bush, Jan. 28, 1986. Succinic acid builders include C5-C20 alkyl and alkenyl succinic acids and salts thereof. Succinate builders also include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (suitable), 2-pentadecenyl succinate, and the like. Lauryl succinates are described in European Patent Application 86200690.5 / 0,200,263, issued November 5, 1986.

Fatty acids, e.g., C12-C18 monocarboxylic acids, can also be incorporated into the compositions as surfactants / fillers alone or in admixture with the aforementioned fillers, especially citrate and / or succinate builders, to provide an additive action of the fillers. Other suitable polycarboxylates are disclosed in U.S. Pat. No. 4,144,226, Crutchfield et al., Mar. 13, 1979; No. 3,308,067, Diehl, Mar. 7, 1967. See also Diehl, U.S. Pat.

723 322.

Other types of inorganic fillers that can be used have the general formula (Mx) and Cay (CO3) z, where x and 1 are integers from 1 to 15, y is an integer from 1 to 10, z is an integer from 1 to 25 , Mi are cations of which at least one is water-soluble, and equation i i = 1 -15 (xi multiplied by the value of Mi) + 2y = 2z is satisfied such that the formula has a neutral or "balanced" charge. These fillers are referred to herein as "mineral fillers," examples of such fillers, their use and preparation can be found in U.S. Patent 5,707,959. Another suitable class of inorganic fillers are magnesium silicates, see WO97 / 0179.

* · · · · · ♦ ♦ * * * * * * * * * * * * * * * * * * * * * · • · · · ·· · ♦

Oxygen bleaching agents:

Suitable compositions of the present invention comprise as part or all of the laundry or cleaning adjuvants an "oxygen bleaching agent". The oxygen bleaching agents of the present invention may be any of the oxidizing agents known for the purpose of washing, cleaning hard surfaces, automatic dishwashing or dentures. Oxygen bleaches or mixtures thereof are suitable, although oxidative bleaches such as oxygen, an enzymatic hydrogen peroxide producing system, or hypohalites such as chlorine bleaches such as hypochlorite can also be used.

Conventional oxygen bleaches of the peroxygen type include hydrogen peroxide, inorganic perhydrates, organic perhydrates and organic peroxyacids, including hydrophilic and hydrophobic mono- or di-peroxyacids. These may be peroxycarboxylic acids, peroxyimidic acids, amidoperoxycarboxylic acids, or salts thereof including calcium, magnesium or mixed cation salts. Peracids of various kinds can be used in free form as precursors known as "bleach activators" or "bleach promoters", which when combined with a hydrogen peroxide source perhydrolyses to release the corresponding peracid.

Also suitable as oxygen bleaches herein are inorganic peroxides such as Na2O2, hyperoxides such as KO2, organic hydroperoxides such as cumenyl hydroperoxide and t-butyl hydroperoxide, and inorganic peroxoacids and salts thereof such as peroxosulfuric acid salts, especially potassium peroxodisulfuric acid and, preferably, peroxosulfuric acid including commercial form. Triols sold as OXONE from DuPont as well as any equivalent commercially available forms such as CUROX from Akzo or CAROAT from Degussa. Certain organic peroxides such as dibenzoyl peroxide may be suitable, particularly as auxiliary rather than basic oxygen bleaches.

Mixed oxygen bleach systems, such as mixtures of any oxygen bleach with known bleach activators, organic catalysts, enzymatic catalysts, and mixtures thereof are generally suitable; in addition, such compositions may further comprise brighteners, photo-bleaches, and color transfer inhibitors of the types well known in the art.

Suitable oxygen bleaches, as known, include peroxohydrates, sometimes known as peroxyhydrates or peroxohydrates. They are organic or, more commonly, inorganic salts

0 »9999

9999

99

9 9

9 9

9 9 9 • 0 00 0

99

9 9 9

9 9 9

0 0 0

0 0 0 ·· 00 capable of releasing hydrogen peroxide readily. Peroxohydrates are the most common examples of 'hydrogen peroxide sources' and include perborates, percarbonates, perphosphates and persilicates. Suitable peroxohydrates include sodium carbonate peroxyhydrate and equivalent commercial "percarbonate" bleaches, and any of the so-called sodium perborate hydrates, "tetrahydrate" and "monohydrate" are preferable; although sodium pyrophosphate peroxyhydrate may be used. Many such peroxohydrates are available in coated coated forms such as silicate and / or borate and / or waxy substances and / or surfactants, geometric arrangement of the particles as a compact sphere, which improves storage stability. Urea peroxyhydrate can also be used as organic perhydrate.

Percarbonate bleaches include, for example, dry particles having a particle size diameter in the range of about 500 microns to about 1000 microns, no more than about 10 wt. % of said particles should be less than about 200 microns and no more than about 10 wt. % of said particles should be greater than about 1250 microns. Percarbonates and perborates are widely available in the store, for example from FMC, Solvay and Tokai Denka.

Organic percarboxylic acids useful herein as oxygen bleach include magnesium monoperoxyphthalate hexahydrate available from Interox, m-chloroperbenzoic acid and salts thereof, 4-nonylamino-4-oxoperoxybutyric acid, and diperoxydodecanedioic acid and salts thereof. Such bleaches are disclosed in U.S. Pat. No. 4,483,781, U.S. Pat. prihl. 740,446, Burns et al, filed June 3, 1985, EP-A 133,354, published Feb. 20, 1985, and U.S. Pat. The organic percarboxylic acids useful herein include those containing one, two, or three peroxy groups, and may be aliphatic or aromatic. Highly suitable oxygen bleaches also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in U.S. Pat. 4,634,551.

Extensive and exhaustive list of suitable oxygen bleaches, including inorganic peroxyhydrates, organic peroxohydrates and organic peroxyacids, including hydrophilic and hydrophobic mono- or di-peroxyacids, peroxycarboxylic acids, peroxyimidic acids, amidoperoxycarboxylic acids or their salts including calcium, magnesium or magnesium salts can be found in US Patents 5,622,646 and 5,686,014.

Other suitable peracids and bleach activators herein are in the group of peracids and imidoperacids and imide bleach activators. These include phthaloylimidoperoxycaproic acid and related arylimido-substituted and acyloxynitrogen _{/ 10} <4 ···· fefe 4 ··· 4fe ··· · ······· · ··· · · Fefe · 4 · 4 · fefe derivatives. For a list of such compounds, preparations, and their incorporation into detergent compositions including both granules and liquids, see US 5,487,818 US 5,470,988;

U.S. Pat. 5,466,825; U.S. Pat. 5,419,846; U.S. Pat. 5,415,796; U.S. Pat. 5,391,324; U.S. Pat. 5,328,634; U.S. Pat.

310 934; U.S. Pat. 5,279,757; U.S. Pat. 5,246,620; U.S. Pat. 5,245,075 U.S. Pat. 5,294,362; U.S. Pat.

423 998; U.S. Pat. 5,208,340; U.S. Pat. No. 5,132,431 and U.S. Pat. 5,087,385.

Suitable diperoxy acids include, for example, 1,12-diperoxydodecanedioic acid (DPDA); 1,9-diperoxyazelaic acid; diperoxybrasilic acid; diperoxysebacic acid and diperoxyisophthalic acid; 2-decylperoxybutane-1,4-dioic acid and acid

4,4‘-sulfonylbisperoxybenzoic acid.

More generally, the terms &quot; hydrophilic &quot; and &quot; hydrophobic &quot; used herein in conjunction with any oxygen bleach, especially peracids, and bleach activators are based, in the first case, on whether the oxygen bleach effectively performs bleaching of unstable colors in solution. it prevents the fabrics from graying and fading and / or removes more hydrophilic stains such as tea, wine and grapefruit juice - in this case the term "hydrophilic". If the oxygen bleach or bleach activator has significant stain removal, whiteness-enhancing or cleansing effects on faded, greasy, carotenoid or other hydrophobic soils, this is the term "hydrophobic". The terms are also applicable when referring to peracids or bleach activators used in combination with a hydrogen peroxide source. Current comparative tests for the hydrophilic performance of oxygen bleaching systems are:

TAED or peracetic acid for comparative testing of hydrophilic bleaching. NOBS or NAPAA are corresponding comparative tests for hydrophobic bleaching. The terms "hydrophilic", "hydrophobic" and "hydrotropic" with reference to oxygen bleaches, including peracids, and extended here to bleach activators have also been used somewhat more narrowly in the literature. See in particular Encyclopedia of Chemical Technology by Kirk Othmer, Vol. 4, pages 284-285. This reference provides a chromatographic retention time and a set of critical features based on micelle concentration and is useful for identifying and / or characterizing suitable subclasses of hydrophobic, hydrophilic and hydrotropic oxygen bleaches and bleach activators that may be used in this invention. invention.

Bleach activators

Suitable bleach activators herein include amides, imides, esters, and anhydrides. Typically, at least one substituted or unsubstituted acyl moiety is covalently bonded to a leaving group in the structure R-C (O) -L. Depending on the application, bleach activators are combined with a source of hydrogen peroxide, such as perborates or percarbonates, according to one suitable application method. , in a single product. Typically, a single product results in the formation of a percarboxylic acid corresponding to a bleach activator in situ in an aqueous solution (i.e. during the washing process). The product itself may contain water, for example a powder, provided that the amount and mobility of the water is controlled so that storage stability is acceptable. The product may also be anhydrous solid or liquid. In another method, a bleach activator or oxygen bleach is incorporated into a pretreatment product such as a stain stick; dirty, pretreated substrates can then be subjected to further exposure, for example, to a hydrogen peroxide source. With respect to the aforementioned structure of the bleach activator RC (O) L, the atom in the leaving group is attached to the peracid forming R (C) O- most typically O or N. or uncharged, positively or negatively charged leaving groups. One or more peracid-forming moieties or leaving groups may be present. See, for example, U.S. Pat.

No. 595,967, U.S. Pat. 5,561,235; No. 5,560,862 or the bis (peroxycarbon) system of U.S. Pat.

Mixtures of suitable bleach activators may also be used. The bleach activators may be substituted with electron donating moieties or electron donating moieties either in the leaving group or in the peracid forming moiety or moieties, thereby altering their reactivity and making them more or less suitable for certain pH or wash conditions. For example, electron withdrawing groups such as NO 2 improve the efficiency of bleach activators intended for use in low pH washing conditions (eg, from about 7.5 to about 9.5).

Extensive and exhaustive data on suitable bleach activators and suitable leaving groups as well as on how to identify suitable activators can be found in US patents 5,686,014 and 5,622,646.

Cationic bleach activators include quaternary carbamate, quaternary carbonate, quaternary ester-quaternary amide-types providing the laundry with a variety of cationic peroxyimide, peroxycarbonic or peroxycarboxylic acids. A similar but non-cationic palette of bleach activators is available when quaternary derivatives are not desired. More specifically, cationic activators include quaternary ammonium substituted activators WO 96-06915, U.S. Pat. Nos. 4,751,015 and 4,397,757, EP-A-284292, EP-A-331 229 and EP-A-03520. Also suitable are cationic nitriles as described in EP-A-303 520 and European Patent Specifications 458 396 and 464 880. Other nitrile types have electron withdrawing substituents as described in U.S. Pat. 5,591,378.

Further data regarding bleach activators include GB 836 988; 864 798;

907 356; 1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522;

EP-A-0174132; EP-A-0120591; U.S. Pat. U.S. Pat. No. 1,246,339; 3,332,882; 4,128,494; 4,412,934 a

675,393 and the alkanoyl amino acid phenolsulfonate ester disclosed in U.S. Pat. Suitable bleach activators include any acetylated types of diamines, whether hydrophilic or hydrophobic in nature.

Of the aforementioned classes of bleach precursors, suitable classes include esters including acylphenolsulfonates, acylalkylphenolsulfonates or acyloxylbenzenesulfonates (OBS leaving group); acyl amides; and quaternary ammonium substituted peroxyacid precursors including cationic nitriles.

Suitable bleach activators include N, N, N‘N‘-tetraacetylethylenediamine (TAED) or any of its close relatives including triacetyl or other asymmetric derivatives. TAED and acetylated hydrocarbons such as pentaacetate glucose and tetraacetyl xylose are suitable hydrophilic bleach activators. Depending on the use, acetyltriethyl citrate, a liquid as well as phenylbenzoate also has some benefit.

Suitable hydrophobic bleach activators include sodium nonanoyloxybenzenesulfonate (NOBS or SNOBS), N - (- alkanoyl) aminoalkanoyloxybenzenesulfonates, such as 4- [N- (nonanoyl) aminohexanoyloxy] benzenesulfonate or (NACA-OBS) as described in U.S. Pat. No. 5,534,642 and in EPA 0 355 381 A1, substituted amide types described in detail below as activators related to NAPAA, and activators related to certain imidoperacid bleaches, for example as described in U.S. Pat. No. 5,061,807, issued Oct. 29, 1991, assigned to Hoechst Aktiengesellschaft of Frankfurt, Germany, and Japanese Public Patent Application (Kokai) No. 4-28799.

Another group of peracids and bleach activators herein are those derived from acyclic imidoperoxycarboxylic acids and their salts, see US patent 5,415,796, and cyclic imidoperoxycarboxylic acids and their salts, see US Patents 5,061,807,

132 431, 5 654 269, 5 246 620, 5 419 864 and 5 438 147.

Other suitable bleach activators include sodium 4-benzoyloxy-benzenesulfonate (SBOBS); sodium 1-methyl-2-benzoyloxy-benzene-4-sulfonate; sodium 4-methyl-3-benzoyloxybenzoate (SPCC); trimethyl-ammonium-toluyloxy-benzenesulfonate; or sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate (STHOBS).

Bleach activators can be used in amounts up to 20 wt. %, more preferably from 0.1 to 10 wt. %, of the formulation, although higher levels of 40% or more are acceptable ttttttt tttttt tttttt tttttttt tttttttt tttttt tttt tttt for example in highly concentrated bleaching auxiliary forms products or in forms intended for automatic dosing in apparatus.

Highly suitable bleach activators preferred herein are substituted amides, and an extensive and exhaustive description of these activators can be found in US Patents 5,686,014 and 5,622,646.

Other suitable activators described in U.S. Pat. No. 4,966,723, benzoxazine types such as the C6H4 ring to which the --C (O) 0C (R1) = N- moiety is attached at the 1,2-positions: A very suitable benzoxazine-type activator is:

Depending on the activator and the precise use, good bleaching results can be obtained from systems having a pH of from about 6 to about 13, more preferably from about 9.0 to about 10.5. Typically, for example, electron withdrawal activators are used for the pH range close to neutral or lower. Bases and buffering agents may be used to provide such pH.

Acyl lactam activators are very useful herein, particularly acyl caprolactams (see for example WO 94-28102 A) and acylvalerolactams (see U.S. 5,503,639). See also U.S. Pat.

No. 545,784, which describes caprolactams including benzoylcaprolactam adsorbed on sodium perborate. In certain suitable embodiments of the invention, NOBS, lactam activators, imide activators or amide functional activators, particularly hydrophobic derivatives, are suitably combined with hydrophilic activators such as TAED, typically in a hydrophobic activator: TAED weight ratio ranging from 1: 5 to 5: 1. suitable lactam activators are alpha-modified, see WO 96-22350 A1,25. The lactam activators, particularly the more hydrophobic types, are suitably used in combination with TAED, typically in a weight ratio of amide or caprolactam activators: TAED ranging from 1: 5 to 5: 1, more preferably about 1: 1. See also bleach activators having a cyclic amidine leaving group described in U.S. Pat. 5,552,556.

Unlimited examples of other activators useful herein are found in U.S. Pat.

• ·

915,854; Nos. 4,412,934 and 4,634,551. The hydrophobic activator (nonanoyloxybenzenesulfonate NOBS) and the hydrophilic tetraacetylethylenediamine (TAED) activator are typical and mixtures thereof may also be used.

Other activators useful herein include U.S. Pat. 5,545,349.

Bleach catalysts of transition metals:

If desired, bleaching compositions can be catalyzed using manganese mixtures. Such mixtures are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. U.S. Pat. No. 5,246,621, U.S. Pat. U.S. Pat. 5,244,594; Narcotize. 5,194,416; U.S. Pat. U.S. Pat. 5114 606; European Pat. prihl. Nos. 594 271A1, 549 272A1, 544 440A2, 544 490AI; and PCT applications PCT / IB98 / 00298 (Attorney Docket No. 6527X), PCT / IB98 / 00299 (Attorney Docket No. 6537), PCT / IB98 / 00300 (Attorney Docket No. 6525XL &), and PCT / IB98 / 00302 (Attorney Docket # 6524 #). Suitable examples of these catalysts include Mn11V2 (µO) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF6) 2, Mn1112 (µO) 1 (u-OAc) 2 (1,4,7 - trimethyl-triazacyclononane) 2 (CIO4) 2,

MnlV4 (µ-O) 6 (1,4,7-triazacyclononane) 4 (CIO4) 4,

Mn111-Mn114 (uO) 1 (u-OAc) 2- (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (CIO4) 3, Mn11V (1,4,7-trimethyl-1,4 , 7-triazacyclononane) - (OCH 3) 3 (PF 6), and mixtures thereof. Other metal-based bleach catalysts include those described in U.S. Pat. U.S. Patents 4,430,243, 5,114,611, 5,622,646 and 5,686,014. The use of manganese with various complex ligands to enhance bleaching is reported in the following U.S. Pat. patents:

728 455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161 a

227 084.

Cobalt bleach catalysts suitable herein are known and are described, for example, in M. L. You, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1 to 94. The most suitable cobalt catalysts useful herein are the cobalt salts of pentaaminacetate having the formula [Co (NH 3) 5 OAc], where "OAc" represents the acetic moiety and "Ty" is anion and particularly (cobalt -pentaaminacetate) chloride, [Co (NH 3) 5 EtOAc] Cl 2; as well as [Co (NH 3) 5 EtOAc] (OAc) 2; [Co (NH 3) 5 EtOAc] (PF 6) 2; [Co (NH 3) 5 EtOAc] (SO 4); [Co (NH 3) 5 EtOAc] (BF 4) 2; and [Co (NH 3) 5 EtOAc] (NO 3) 2 (here "PAC"). These cobalt catalysts can be readily prepared by known methods in which, for example, the article teaches you and the references cited therein, and U.S. Pat. No. 4,810,410, Diakun et al, issued March 7, 1989.

• · »·

As a bleach catalyst, the compositions herein may also include a class of macropolycyclic solid ligand transition metal complexes. The phrase 'macropolycyclic solid ligand' is sometimes abbreviated as 'MRL'. One suitable MRL is [MnByclamCl 2], where "Bcyclam" is (5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane). See PCT applications PCT / IB98 / 00298 (Attorney Docket # 6537), PCT / IB98 / 00300 (Attorney Docket # 6525XL &), and PCT / IB98 / 00302 (Attorney Docket # 6524 #). The amount used is a catalytically effective amount, suitably about 1 ppb or more, more preferably from about 0.05 ppm to about 500 ppm (where "ppb" refers to parts per billion and "ppm" refers to parts per million).

Practically, and not by way of limitation, the compositions and cleaning process herein may be adapted to provide at least one part per hundred million effective bleach catalyst species in an aqueous wash environment, and more preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm of the bleach catalyst species in the wash fluid. To obtain such levels in the washing fluid of the automatic laundry process, typical compositions herein will contain from about 0.0005 wt. % to about 0.2 wt. %, preferably from about 0.004 wt. % to about 0.08 wt. % of a bleaching catalyst, in particular manganese or cobalt catalysts.

Enzyme sources of hydrogen peroxide

Other than the bleach activators described above, there is another hydrogen peroxide producing system, a combination of a C1-C4 alkanol oxidase and a C1-C4 alkanol, especially a combination of methanol oxidase (MOX) and ethanol. Such combinations are described in WO 94/03003. Other bleach-related enzymes such as peroxidases, haloperoxidases, oxidases, superoxide dismutases, catalase and their "enhancers" or, more commonly, inhibitors, can be used as possible additives in conventional compositions.

Oxygen transfer agents and precursors

Also suitable are any of the known organic bleach catalysts, oxygen transfer agents, and precursors therefor. These include the compounds themselves and / or their precursors, for example any suitable ketone for the production of dioxiranes and / or any hetero atom containing dioxirane precursor analogs or dioxiranes such as sulfonimines R1 R2C = NSO2R3, see EP 446 982 A, published 1991 and sulfonyloxaziridines, see EP Suitable examples of such materials include hydrophilic or hydrophobic ketones, used in particular in conjunction with monoperoxysulfates for the production of dioxirans in situ,

and / or imines disclosed in U.S. Pat. 5,576,282 and in the references described therein. Suitable oxygen bleaches used in conjunction with such oxygen transfer agents or precursors include percarboxylic acids and salts, percarboxylic acids and salts, peroxymonosulfuric acid and salts, and mixtures thereof. See also U.S. Pat. 5,360,568; U.S. Pat. 5,360,569; U.S. Pat. No. 5,370,826 and U.S. Pat. 5,442,066.

Although oxygen bleach systems and / or precursors thereof may be eager to decompose during storage in the presence of moisture, air (oxygen and / or carbon dioxide) and trace metals (particularly corrosion or free of salts or colloidal transition metal oxides) and when exposed to light , stability can be improved by adding conventional shielding agents (chelants) and / or polymer dispersants and / or a small amount of antioxidant to the bleach system or product. See, for example, U.S. Pat. Often, antioxidants are added to detergent ingredients ranging from enzymes to surfactants. Their presence is not necessarily inconsistent with the use of an oxidizing bleach, for example, phase barriers may be used to stabilize the apparently incompatible combination of enzyme and antioxidant on the one hand, and oxygen bleach on the other. Although commonly known substances may be used as antioxidants, for example, see US Patents 5,686,014, 5,622,646, 5,502,218, 4853 + CA, 4539130 and 4483778. Suitable antioxidants are 3,5-di-1,1-dimethylethyl-4-hydroxytoluene, 2,5 -di-1,1-dimethylethylhydroquinone and D, L-alpha-tocopherol.

Polymic soil release agents - The compositions of the invention may optionally contain one or more soil release agents. Polymeric soil release agents are characterized by having both hydrophilic segments to hydrophilize the surface of hydrophobic fibers, such as polyester or nylon, and hydrophobic segments to settle on the hydrophobic fibers and remain attached thereto during the wash cycle and thereby serve to attach hydrophilic segments. This will allow stains that subsequently occur after treatment with soil release agents to be easier to clean in subsequent washing procedures.

When utilized, soil release agents will generally comprise from about 0.01 wt. % to about 10 wt. %, more preferably from about 0.1 wt. % to about 5 wt. %, preferably from about 0.2 wt. % to about 3 wt. % of the composition.

All of the following, incorporated herein by reference, describes soil release polymers suitable for us in the present invention. U.S. Pat. No. 5,691,298 to Gosselink et al., Issued Nov. 25, 2003;

1997; U.S. Pat. No. 5,599,782 to Pan et al., Issued Feb. 4, 1997; U.S. Pat. No. 5,415,807 to Gosselink et al., Issued May 16, 1995; U.S. Pat. No. 5,182,043 Morrall et al., Issued Jan. 26, 1993; U.S. Pat.

956,447 Gosselink et al., Issued Nov. 1, 1990; U.S. Pat. No. 4,976,879 to Maldonado et al. published December 11, 1990; U.S. Pat. No. 4,968,451 Schiebel et al., Issued Nov. 6, 1990; U.S. Pat. 4,925,577 Borcher, Cf. et al., issued May 15, 1990; U.S. Pat. 4,861,512 Gosselink, issued Aug. 29, 1989; U.S. Pat. 4,877,896 Maldonado et al., Issued Oct. 31, 1989; U.S. Pat. No. 4,702,857 Gosselink et al., Issued Oct. 27, 1987; U.S. Pat. No. 4,711,730 to Gosselink et al., Issued Dec. 8, 1987; U.S. Pat. No. 4,721,580 Gosselink, issued Jan. 26, 1988;

Nicot et al., Issued December 28, 1976; U.S. Pat. 3,959,230 Hayes, issued May 25, 1976; U.S. Pat. No. 3,893,929 to Basadur, issued July 8, 1975; and European Patent Application 0 219 048, published April 22, 1987 by Kud et al.

Other suitable soil release agents are described in U.S. Pat. 4,201,824 Voilland et al .; U.S. Pat. 4,240,918 Lagase et al .; U.S. Pat. 4,525,524 Tung et al .; U.S. Pat. 4,579,681 Ruppert et al .; U.S. Pat. 4,220,918; U.S. Pat. 4,787,989; EP 279,134 A, 1988 Rhone-Poulec Chemistry; EP 457,205 A BASF (1991); and DE 2,353,044 Unilever N.V., 1974; all references incorporated herein.

Clay Dirt Removal / Redeposition Agents - Also, the compositions of the present invention may optionally include water-soluble ethoxylated amines having properties that allow clay soil to be removed and prevent it from settling back. Granular detergent compositions typically containing these compounds typically contain from about 0.1 wt. % to about 10.0 wt. % water-soluble ethoxylated amines; liquid detergent compositions typically contain about 0.01% to about 5%.

A suitable soil removal and anti-fouling agent is ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are further described in U.S. Pat. No. 4,597,896, VanderMeer, issued July 1, 1986. Another group of suitable soil removal and re-deposition agents are the cationic compounds described in European Patent Application 111,965, Oh and Gosselink, issued June 27, 1984. Other soil removal and re-deposition agents blocking agents that may be used include ethoxylated amine polymers described in European Patent Application 111 984, Gosselink, issued June 27, 1984; zwitterionic polymers described in European Patent Application 112,592, Gosselink, issued July 4, 1984; and amine oxides described in U.S. Pat. No. 4,548,744, Connor, issued Mar. 22, 1993;

October 4, 1985. Other clay dirt-removing and re-settling agents known in the art can also be utilized in the compositions herein. See U.S. Pat. U.S. Patent 4,891,160, VanderMeer, issued January 2, 1990, and WO 95/32272, issued November 30, 1995. Another suitable type of antifouling agent includes carboxymethylcellulose (CMC) agents. Such materials are well known in the art.

Polymeric Dispersing Agents - Polymeric dispersing agents may advantageously be used at levels of from about 0.1 wt. % to about 7 wt. % in the compositions herein, particularly in the presence of zeolite and / or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. When polymeric dispersants are used in combination with other fillers (including low molecular weight polycarboxylates), it is believed that they increase overall performance by inhibiting crystal growth, releasing some dirt, peptizing, and counteracting deposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, cisaconitic acid, mesaconic acid, citraconic acid, and methylenemalonic acid. In polymers of polycarboxylates at this point, the presence of monomer segments that contain no carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc. is suitable, provided such segments do not comprise more than about 40 wt. %.

Particularly suitable polymeric polycarboxylates can be made from acrylic acid. Such acrylic acid-based polymers useful herein are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in acid form more preferably ranges from about 2000 to 10,000, preferably from about 4000 to 7000, and most preferably from about 4000 to 5000. Water-soluble salts of such acrylic acid polymers may include, for example, alkali metal, ammonium and substituted ammonium salts. . Suitable polymers of this type are known substances. The use of polycarboxylates of this type has been described, for example, in Diehl, U.S. Pat. No. 3,308,067, issued March 7, 1967.

«7 ♦ · · · · · · · · · · · · · · · © © © © © © © © © © © © © • · ···· ···· ······ ·

Acrylic / maleic acid-based copolymers can also be used as suitable components of a scattering / re-settling composition which inhibits properties. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in acid form more preferably ranges from about 2000 to 100,000, preferably from about 5000 to 75,000, most preferably from about 7,000 to 65,000. In such copolymers, the ratio of acrylate and maleate segments will generally range from about 30: 1 to about 1: 1, preferably from about 10: 1 to 2: 1.

Water-soluble salts of such acrylic / maleic acid copolymers may include, for example, alkali metal, ammonium and substituted ammonium salts.

Soluble acrylate / maleate copolymers of this type are known materials described in European Patent Application No. 66915, issued December 15, 1982, as well as in EP 193 360, published September 3, 1986, which also discloses such polymers containing hydroxypropyl acrylate. Still other suitable dispersants include maleic / acrylic / vinyl alcohol terpolymers. Such materials are also described in EP 193 360 including, for example, a 45/45/10 acrylic / maleic / vinyl alcohol terpolymer.

Another polymeric substance that may be included is polyethylene glycol (PEG). PEG can deliver the performance of the dispersing agent, as well as acting as a clay soil removal and anti-sediment agent. a typical molecular weight for these purposes ranges from about 500 to about 100,000, more preferably from about 1000 to about

%, Preferably from about 1500 to about 10,000.

Polyaspartate and polyglutamate scattering agents can also be used, particularly in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (average) of about 10,000.

Other types of polymers that may be more desirable for biodegradability, greater bleach stability or cleaning purposes include various terpolymers and hydrophobically treated copolymers, including those marketed by Rohm & Haas, BASF, Nippon Shokubai and others for all purification methods. water, textile cleaning or the use of detergents.

Brightener - Any optical brightener or other polishing or brightener known in the art may be present in detergent compositions at levels typically from about 0.01 wt. % to about 1.2 wt. % incorporated if they are designed for washing or treating fabrics.

• 4444 4 4 44 • · • • 4 4 4 4 4 4 • 444 4 4 4 • · • 4 • • 4 4 4 4 4 4 4 • 4 • • 4 4 4 4 4 4 4 4 4 · • 4 4 4 • 4

Certain examples of optical brighteners useful in the present compositions are those disclosed in U.S. Pat. No. 4,790,856, issued to Wixon on December 13, 1998. These brighteners include a number of PHORWHITE brighteners from Verona. Other brighteners described in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geiga; Arctic White CC and Arctic White CWD, 4,4‘-bis (styryl) bisphenyls and aminocoumarins. Certain examples of such brighteners include 4-methyl-7-diethylaminocoumarin; 1,2-bis (benzimidazol-2-yl) ethylene;

1,3-diphenyl-pyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphtho [1,2-d] oxazole and 2- (stilben-4-yl) -2H-naphtho [1,2-d] triazole. See also U.S. Pat. U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton.

Polymeric Color Transfer Suppressing Agents - The compositions of the present invention may also include one or more materials useful to suppress the transfer of colors from one fabric to another during the laundry process. Generally, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxydases, and mixtures thereof. When used, these agents typically comprise from about 0.01 wt. % to about 10 wt. % of the composition, more preferably from about 0.01 wt. % to about 5 wt. % and most preferably from about 0.05 wt. % to about 2 wt. %.

The amine-N-oxide polymers typically have an amine to amine-N-oxide ratio of from 10: 1 to 1: 1,000,000. The number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by a suitable degree of N-oxidation. Polyamine oxides can be obtained at almost any degree of polymerization. Typically, the average molecular weight ranges from 500 to 1,000,000; preferably from 1000 to 500,000; preferably from 5,000 to 100,000. This suitable class of substances may be called "PVNO". See U.S. Pat. No. 5,633,255 to Fredj.

The most preferred polyamine N-oxide useful in detergent compositions herein is poly (4-vinylpyridine N-oxide) having an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1: 4. suitable for use herein, copolymers of N-vinylpyrrolidone and polymers of N-vinylimidazole (called the class "PVPVI"). The PVPVI preferably has a molecular weight ranging from 5000 to 1,000,000, preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al.,

I * ftftft ftftftftft ftft ftft ftft ftft ftft ftft ftft ftft ftft

Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization", the disclosures of which are incorporated herein by reference.) PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of from 1: 1 to 0.2: 1, more preferably from 0.8: 1 to 0.3: 1, preferably from 0.6: 1 to 0.4: 1. These copolymers may be either linear or branched.

The compositions of the invention may also use polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5000 to about 400,000, more preferably from about 5000 to about 200,000, and most preferably from about 5000 to about 50,000. known; see, for example, EP-A-262 897 and EP-A-256 696, incorporated herein by reference. The PVP-containing compositions may also comprise polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, more preferably from about 1000 to about 10,000. Preferably, the ratio of PEG to PVP based on ppm is delivered in laundry solutions of about 2: 1 to about 50: 1 and more preferably from about 3: 1 to about 10: 1.

The detergent compositions herein may also optionally comprise from about 0.005 wt. % to 5 wt.% of certain types of hydrophilic optical brighteners which also provide a color transfer inhibiting effect. If used, the compositions herein will preferably comprise from about 0.01 wt. % to about 1 wt.% of such optical brighteners.

Hydrophilic optical brighteners useful herein include, for example, 4,4'-bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] disodium salt, 2'-stilbendisulfonic acid (Tinopal-UNPA-GX), 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] disodium salt -2,2'-stilbendisulfonic acid (Tinopal 5BM-GX) and 4,4'-bis [(4-anilino-6-morphilino-s-triazin-2-yl) amino] sodium] -2,2'- Stilbendisulfone (Tinopal AMS-GX), all from Ciba Geigy.

Certain types of optical brighteners selected for use in the present invention provide particularly the benefits of effectively suppressing color transfer when used in combination with the selected polymeric color transfer suppressing agents described above. The combination of such selected polymeric substances (eg, PVNO and / or PVPVI) with such selected optical brighteners (eg, Tinopal-UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides significantly better suppression of transmission in aqueous wash solutions than those provided by either of the two detergent ingredients, when used alone. The exhaustion coefficient is generally defined as the ratio of a) the brightener applied to the substance to b) tt ttttttt tt ttttt tttttt tttttttt ttttttttt tttttttttttttttttttttttttttttttt · Tttt tt tttt tt · tttt the final brightener concentration in the wash liquid. Brightening agents with relatively high exhaustion coefficients are most suitable for the suppression of color transmission in the context of the present invention.

Optionally, other conventional types of optical brighteners may be used in the present invention to provide conventional advantages with respect to the brightness of the fabrics, rather than the effect of suppressing color transfer. Such use is common and well known in detergent compositions.

Chelating Agents - The detergent compositions herein may also optionally contain one or more chelating agents, particularly chelating agents for random transition metals. Those commonly found in wash water include iron and / or manganese in a water-soluble, colloidal or particulate form and can be associated as oxides or hydroxides, or found in association with dirt such as humic substances. Suitable chelating agents are those that effectively control such transition metals, particularly including suppressing the deposition of such transition metals or compounds thereof on fabrics and / or suppressing undesirable redox reactions in the wash environment and / or fabrics or at the hard surface interface. Such chelating agents include those having both low molecular weight and polymer types, which typically have at least one, preferably two or more heteroatoms such as 0 or N, capable of coordinating with the transition metal. Conventional chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof, all as defined below.

Aminocarboxylates suitable as voluntary chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraamine hexaacetates, diethylenetriaminepentaacetates and ethanediglycines, and their alkali metals, their alkali metals, and their alkali metals.

Amino phosphonates are also suitable as chelating agents in the compositions of the invention when at least low levels of total phosphorus in detergent compositions are allowed, and include ethylenediaminetetrakis (methylene phosphonates) such as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Also polyfunctionally substituted aromatic chelating agents and mixtures thereof are suitable in the compositions herein. See U.S. Pat.

• 0 0 00 0 • · · 0 0 0 0 0

00 00 00 0000

000 000 000 000 0

0000 0000

No. 3,812,044, issued May 21, 1974 to Conor et al. Suitable compounds of this type in acid form are dihydroxydisulfobenzenes such as

1,2-dihydroxy-3,5-disulfobenzene.

A suitable biodegradable chelating agent herein is ethylene diamine disuccinate ("EDDS"), particularly the [S, S] isomer as disclosed in U.S. Pat. No. 4,704,233, Nov. 3, 1987 to Hartman and Perkins.

The compositions herein may also contain water-soluble salts (or acid form) of methylglycine diacetic acid (MGDA) as chelating agents or together with fillers, suitable, for example, with insoluble fillers such as zeolites, layered silicates and the like.

When used, chelating agents will generally comprise from about 0.001 wt. % to about 15 wt. % of such detergent compositions. Preferably, if used, the chelating agents will comprise from about 0.01 wt. % to about 3 wt. % of such funds.

Foam Suppressors - Compounds that reduce or suppress the formation of foam can also be incorporated into the compositions of the present invention if so desired by the intended use, in particular by washing or washing in laundry appliances. Other compositions, such as those designed for handwashing, may suitably be high-foaming or omit such components. Foam suppression can be particularly important in the so-called "high concentration cleaning process" as described in U.S. Pat. 4,489,455 and 4,489,574, and in the European type of washing machine with front loading.

A variety of substances well known in the art can be used as foam control agents. See, for example, Encyclopedia of Chemical Technology by Kirk Othmer, 3rd Edition, Volume 7, pages 430 to 447 (Wiley, 1979).

Compositions at this site will generally contain from 0% to 10% foam suppressants. When used as suds suppressors, the monocarboxylic fatty acids and their salts will typically be present in an amount of up to about 5 wt. %, more preferably from 0.5 wt. % to 3 wt. % of the detergent composition, although they can be used in larger amounts. More preferably, from about 0.01% to about 1% of a silicone foam suppressor is used, more preferably from about 0.25% to about 0.5%. These weight percentages include any silica that can be used in combination with a polyorganosiloxane, as well as any foam suppressing excipients that can be used. Monostearylphosphate foam suppressors are generally used in an amount of ost 7

D i «··························· In the range of about 0.1 wt. % to about 2 wt. % of the composition. Hydrocarbon foam suppressors are typically used in an amount ranging from about 0.01% to about 5.0%, although higher levels may be used. The alcohol foam suppressors are typically used from 0.2 wt. % to 3 wt. % of final funds.

Alkoxylated Polycarboxylates - Alkoxylated polycarboxylates, for example those prepared from polyacrylates, are useful herein to allow further grease removal.

Such substances are described in WO 91/08281 and PCT 90/01815 at pages 4 et seq., Incorporated herein by reference. Chemically, these include polyacrylates having one ethoxylated side chain for every 7 to 8 acrylate units. The side chains have the general formula - (CH 2 CH 2 O) m (CH 2) n CH 3 where m is 2 to 3 and n is 6 to 12. The side chains are ester-linked to the polyacrylate backbone to provide a "comb" polymer type of structure. The molecular weight may vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates may comprise from about 0.05 wt. % to about 10 wt. % of funds at this location.

Fabric Softening Agents - Various fabric softeners operating during washing, particularly U.S. Pat. U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softening clays known in the art, can be used voluntarily at levels of from about 0.5 wt. % to about 10% by weight of such compositions, in order to simultaneously soften the fabrics. Clay emollients may be used in combination with amine and cationic emollients, as described, for example, in U.S. Pat. No. 4,375,416, Crisp et al., Mar. 1, 1983; No. 4,291,071, Harris et al, issued September 22, 1981. In addition, known fabric softeners, including biodegradable, prewash, main wash, post wash, and drying modes, can be used in the washing and cleaning methods herein. .

Perfumes - Perfume and perfume ingredients useful in the present compositions and methods contain a large number of natural and synthetic chemical ingredients, for example, aldehydes, ketones, esters, and the like. Also included are various natural extracts and essences, which may contain complex mixtures of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, healing essences, sandalwood oil, pine oil, cedar and the like. The finished perfumes herein typically comprise from about 0.01 wt. % to about 2 wt. % of the detergent compositions, and the individual fragrance ingredients may comprise from about 0.0001% to about 90% of the finished composition. perfume composition.

Other Ingredients - A wide variety of other ingredients useful in detergent compositions may be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing agents, paints or pigments, solvents for liquid formulations, solid fillers for soap bars, etc. if large foaming is desired, suds boosters such as C10-C16 alconolamides can be incorporated into the composition, typically at levels of 1% to 10%. The C10-C14 monoethanolamide and diethanolamide show a typical class of such suds boosters. It is also preferred to use such suds boosters with the high sudsing additional surfactants, for example, the amino oxides, betaines and sultaines mentioned above. If desired, water-soluble calcium and / or magnesium salts such as MgCl 2, MgSO 4, CaCl 2, CaSO 4, and the like may be added in an amount, typically 0.1% to 2%, to provide additional foam and increase degreasing, especially for purpose of washing dishes in liquid. The various cleaning ingredients used in these compositions may optionally be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate and then coating said substrate with a hydrophobic coating, the cleaning component preferably being admixed with surfactants prior to absorption into the porous substrate. In use, the cleaning component is released from the substrate into an aqueous wash liquid to perform its intended function.

Liquid cleaning compositions may contain water and other solvents as carriers. Primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol are suitable. Monohydroxy alcohols are suitable for a dissolving surfactant, but polyols for example those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxyl groups (e.g., 1,3-propanediol, ethylene glycol, glycerin, and 1,2-propanediol), can also be used. The compositions may contain from 5% to 90%, typically 10% to 50%, of such carriers.

The detergent compositions herein will preferably be formed such that during use in aqueous cleaning processes the wash water will have a pH of between about 6.5 and about 11, more preferably between about 7.0 and 10.5, more preferably between about 7.0 and about 9, 5. More preferably, the liquid dishwashing compositions have a pH between about 6.8 and about 9.0. Detergent compositions typically have a pH of 9-11. Methods for controlling pH at recommended levels of use include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

CQ * Φ «« «· Φ ΦΦΦΦ ΦΦ ΦΦ

Φ Φ Φ ΦΦΦΦΦΦΦ φφφφ φφ φ ΦΦΦΦ

Φ ΦΦΦΦ φφφ φφφ

ΦΦΦΦ Φ ΦΦΦΦ ΦΦΦΦ

ΦΦ Φ ΦΦΦ ΦΦ Φ Φ φφ

Forms of means

The compositions may take many physical forms in accordance with the invention, including granules, gels, tablets, pieces and liquid forms. The compositions include so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in a laundry drum with a load of dirty laundry.

More preferably, the mean particle size of the components of the granular compositions of the invention should be such that no more than 5% of the particles have a diameter greater than 1.7 mm and no more than 5% of the particles have a diameter smaller than 0.15 mm.

The mean particle size as defined herein is calculated by sieving the formulation into a number of fractions (typically 5) on a series of Tyler screens. The weight fractions thus obtained are evaluated against the mesh size of the sieves. The mean particle size is considered to be the mesh size through which 50 wt. % of the sample.

Certain suitable granular detergent compositions of the present invention are high density types currently commercially available; typically have a bulk density of at least 600 g / liter, more preferably from 650 g / liter to 1200 g / liter

Agglomerated surfactant grains

One suitable method of supplying surfactants to consumer products is to produce agglomerated surfactant grains which may be in the form of flakes, prills, marumes, noodles, ribbons, but preferably in the form of granules. A suitable way of making the particles is to use agglomerating powders (eg aluminosilicate, carbonate) with highly active surfactant pastes and controlling the particle size of the resulting agglomerates to certain limits. Such a method involves mixing an effective amount of a high-active surfactant paste powder in one or more agglomerators, for example in a ladle agglomerator, in a Z-blade mixer, or preferably in an in-line mixer such as manufactured by Schugi (Netherlands) BV. Chroomstraat 8211 AS, Lelystad, The Netherlands and Gebruder Lódige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenestrasse 7 to 9, Postfach 2050,

Germany. It is preferable to use a high shear mixer, such as the Lódige CB (trade name).

Typically, a highly active surfactant paste containing from 50 wt. % to 95 wt. %, preferably from 70 wt. % to 85 wt. % surfactants. The paste may be pumped into the agglomerator at a temperature high enough to maintain the viscosity, e.g.

49 4

44 which can be pumped but low enough to prevent the anionic surfactants from being distributed. A typical paste temperature of 50 ° C to 80 ° C is typical.

Washing method

Laundry methods herein typically involve subjecting dirty laundry to an aqueous washing solution in a washing machine in which an effective amount of a laundry detergent composition of the invention is dissolved or prepared. By effective amount of detergent composition herein is meant from 40 g to 300 g of product dissolved or dispersed in a wash solution in a volume of from 5 to 65 liters, as are typical product doses and wash solution volumes commonly used in traditional washing machine methods.

Surfactants are used herein as known in detergent compositions, preferably in combination with other detergent surfactants, at levels that are effective to achieve at least a direct improvement in cleaning performance. In the context of fabric washing compositions, such &quot; levels of use &quot; can vary greatly not only depending on the type and thickness of dirt and stains, but also on the temperature of the wash water, the volume of wash water and the type of washing machine.

From a user's point of view, it is suitable that a dosing device is used in the washing method. The dispensing device is filled with a detergent product and is used to introduce the product directly into the drum of the washing machine before starting the washing cycle. Its volume should be such that it can contain sufficient detergent product as would normally be used in a washing method.

Once the washing machine is filled with laundry, the dispensing device containing the detergent product is placed in the drum. At the beginning of the washing cycle in the machine, the drum is filled with water and the drum rotates periodically. The design of the dispensing device should be such as to protect the dry detergent product, but then allow the product to be released during the wash cycle in response to the rotation of the drum during rotation and also as a result of its contact with the wash water.

Alternatively, the dispensing device may be a flexible container, such as a bag or pocket. The sachet may be of fibrous construction coated with a water impermeable protective material to retain the contents as described in European Patent Application No. 00188678. Alternatively, it may be a water-insoluble synthetic polymeric material provided with a sealed closure or closure designed to be damaged in an aqueous environment as described in European Patent Application Nos. 0011500, 0011501, 0011502 and 0011968. Suitable form with water • <9 99 9 ·· · ·

9 9 9 9 9

9 9 9 9 9 9

9 9 9 9 9

The frangible seal comprises a water-soluble adhesive disposed along and closing one side of the pocket of a water-impermeable polymer film, for example polyethylene or polypropylene.

Examples

In the following examples, the abbreviations for the various components used in the compositions have the following meanings.

MLAS

LAS

MBASx

MBAExSz

MBAEx

Endolasa C18-1,4-disulfate

MEA

DEA

PG

EtOH

NaOH

NaTS

CxyFA

CxyEz

Carbonate

Citrate

Crystalline disrupted sodium alkylbenzene sulfonate

Irregular sodium um-allylbenzenesulfonate branched primary alkyl (average total carbons = x) mid-chain sulphate sodium branched primary alkyl (average total carbons = z) ethoxylated (average EO = x) mid-chain branched primary alkyl ( average total number of carbons = x) ethoxylate (average EO = 8)

2-octadecylbutane-1,4-disulfate enzyme endoglunase activity of 3000 CEVU / g sold by

NOVO Industries A / S monoethanolamine diethanolamine propanediol ethanol sodium hydroxide solution sodium toluenesulfonate

Citric acid anhydrous citric acid C1x-C1y fatty acid

A C1x-1y branched primary alcohol condensed on average from a mole of ethylene oxide anhydrous sodium carbonate with a particle size between 200 pm and 900 pm tri-sodium citrate dihydrate activity of 86.4% with a particle distribution between 425 pm and 850 pm

999 ·

9

449 494

TFAA

APA

Fatty acid C12-C14

Fatty Acid (TPK)

Fatty Acid (RPS)

Borax

PAA

PEG

MES

SAS

NaPS

CxyAS

CxyEzS

CxyEz

QAS

STPP Zeolite A

NaSKS-6

Hydrogen carbonate

Silicate

Sulfate

PAE

PIE

PAEC • 9 9 9 *

9 4 9 9

49 99 99

C16-18 alkyl-N-methylglucamide

C8-C10 amidopropyldimethylamine

C12-C14 fatty acid mixture of topical palm kernel fatty acid rapeseed kernel fatty acid sodium tetraborate decahydrate polyacrylic acid (molecular weight = 4500) polyethylene glycol (molecular weight = 4600) alkyl methyl ester sulfonate secondary sodium paraffin sulphonate sodium-C1x-C1y alkylsulfate (or other salt, if any) sodium-C1x-C1y alkylsulfate condensed from a mole of ethylene oxide (or other salt, if any)

A C1x-1y branched primary alcohol condensed on average from a mole of ethylene oxide

R 2 .N + (CH 3) x ((C 2 H 4 O) y H) z with R 2 = C 8 -C 18 x + z = 3, x = 0 to 3, z = 0 to 3, y = 1 to 15.

Anhydrous sodium tripolyphosphate hydrated sodium aluminosilicate of formula

Na12 (AlO 2 SiO 2) 12.27H 2 O having a primary particle size in the range of 0.1 to 10 microns crystalline layered silicate of the formula 5-Na 2 Si 2 O 5 anhydrous sodium bicarbonate with a particle size distribution between 400 µm and 1200 µm amorphous sodium silicate (SiO 2: Na 2 O; ethoxylated tetraethylenepentamine anhydrous ethoxylated polyethylenimine quaternary ethoxylated methyldihexylenetriamine

* * χη · ············ drawbar ··· ······ « • · ·· · · · · • · · · · ······ • · ···· ···· ··· ··· ·· ·· ·· · « MA / AA maleic / acrylic acid copolymer 1: 4, average molecular weight about 70,000 CMC sodium carboxymethylcellulose Proteinasa proteolytic enzyme activity 4 KNPU / g sold by NOVO Industries A / S under the trade name Savinase Celulasa cellulite enzyme activity of 1000 CEVU / g sold by NOVO Industries A / S under the trade name Carezyme Amylasa amylolytic enzyme activity 60 KNU / g sold by NOVO Industries A / S under the trade name Termamyl 60T Lipasa a lipolytic enzyme activity of 100 kLU / g sold by NOVO Industries A / S under the trade name Lipolase PB1 sodium perborate monohydrate PB4 bleaching agent sodium perborate tetrahydrate Percarbonate sodium percarbonate of the nominal formula 2Na2CO3.3H2O2 NaDCC sodium dichloroisocyanurate NOBS nonanoyloxybenzenesulfonate sodium TAED tetraacethylethylenediamine DTPMP diethylenetriaminpenta (methylene phosphonate) sold by the company Photobleach Monsanto as Dequest 2060 bleach; sulfonated zinc phthalocyanine encapsulated in Brightener 1 Brightener 2 a soluble polymer of dextrins disodium-4,4‘-bis (sulfostyryl) biphenyl disodium-4,4‘-bis (4-anilino-6-morpholino-1,3,5-triazine-2- HEDP -yl) amino) stilben-2: 2‘-disulfonate 1,1-hydroxyethane diphosphonic acid CFP 1 esters provided with a sulfobenzoyl terminus and CFP 2 oxyethyleneoxy- and tetraftaloyl- in the main chain sulfonated ethoxylated terephthalate polymer CFP 3 methyl-ethoxylated terephthalate polymer Silicone anti-foam a polydimethylsiloxane foam regulator with a copolymer of siloxanoxyalkylene as a dispersant with a ratio of said foam regulator to said dispersion from 10: 1 to 100: 1

• · · · · ·

Isofol 16

CaCl2

MgCl 2

Diamin

DTPA

Dimethicon

NTA BPP EGME EG DME PVP K60 Minory trade name Condea for C16 (average) Guerbet alcohols calcium chloride magnesium chloride alkyldiamine, eg 1,3-propanediamine, Dytek EP, Dytek A, where Dytek is the trade name of Dupont, 2-hydroxypropanediamine diethylenetriaminepentaacetic acid mixture of a weight ratio of 40 (resin) / 60 (liquid) SE-76 dimethicone resin from General Electric Silicones Division and dimethicone liquids having a viscosity of 350 centistokes butoxypropoxypropanol ethylene glycol monohexyl ether dimethylpolyethylene. wt. 2000 vinyl pyrrolidone homopolymer, diameter, mol. wt. 160,000 low level substances such as paints, perfumes or dyes and / or fillers (eg talc, NaCL, sulphates)

Unless otherwise stated, the ingredients are anhydrous.

In the following examples, all levels are by weight of the composition. The following examples illustrate the invention but do not intend to limit or otherwise define its scope. All proportions, percentages, or ratios used herein are by weight unless otherwise specified.

Example 6

The following laundry detergent compositions A to D suitable for handwashing dirty laundry are made according to the invention:

AND (B) C D MLAS 18 22nd 18 22nd STPP 20 May 40 22nd 28 Carbonate 15 Dec 8 20 May 15 Dec

• · · · · · · · · · · · · · · · · · · ·

Silicate 15 Dec 10 15 Dec 10 Proteinasa 0 0.3 0.3 0.3 Celulasa 0.5 0.3 0 0 PB1 0 10 0 10 Sodium chloride 25 15 Dec 20 May 10 Brightener 0 to 0.3 0.2 0.2 0.2 Moisture and minors - rest—

Example 7

The following laundry detergent compositions E to H suitable for handwashing dirty laundry are made according to the invention:

E F G H MLAS 22nd 16 11 1 to 6 Any combination of: C45AS C45E1S C45E3S LAS MBAS16.5 MBAE2S15.5 0 0 to 5 5 to 15 10 to 20 QAS 0 to 5 0 to 1 0 to 5 0 to 3 Any combination of: C23E6.5 C45E7 0 to 2 0 to 4 0 to 2 0 to 2 STPP 5 to 45 5 to 45 5 to 45 5 to 45 PAA 0 to 2 0 to 2 0 to 2 0 to 2 CMC 0 to 0.5 0 to 0.5 0 to 0.5 0 to 0.5 Proteinasa 0.1 0 to 0.5 0 to 0.5 0 to 0.5 Celulasa 0 to 0.3 0 to 0.3 0 to 0.3 0 to 0.3 Amylasa 0 to 0.5 0 to 0.5 0 to 0.5 0.1

• • •

CFP 1, 2 or 3 0 to 0.5 0.4 0 to 0.5 0 to 0.5 Brightener 1 or 2 0 to 0.3 0 to 0.2 0 to 0.3 0 to 0.2 Photobleach Oaž 0,1 Oaž 0,1 0.05 0 to 0.1 Carbonate 15 Dec 10 20 May 15 Dec Silicate 7 15 Dec 10 8 Sulfate 5 5 5 5 Moisture and minors - rest -

Example 8

The following laundry detergent compositions I-L suitable for handwashing dirty laundry are made according to the invention:

AND J TO L MLAS 18 25 15 Dec 18 QAS 0.6 0 to 1 0.5 0.6 Any combination of: C23E6.5 C45E7 1,2 1.5 1,2 1.0 C25E3S 1.0 0 1.5 0 STPP 25 40 22nd 25 Bleach activator (NOBS or TAED) 1.9 1,2 0.7 0 to 0.8 PB1 2.3 2.4 1.5 0.7 to 1.7 DTPA or DTPMP 0.9 0.5 0.5 0.3 PAA 1.0 0.8 0.5 0 CMC 0.5 1.0 0.4 0 Proteinasa 0.3 0.5 0.7 0.5 Celulasa 0.1 0.1 0.05 0.08

• · ·· ·· ··

Amylasa 0.5 0 0.7 0 SRP 1,2 or 3 0.2 0.2 0.2 0 Polymemie dispersant 0 0.5 0.4 0 Brightener 1 or 2 0.3 0.2 0.2 0.2 Photobleach 0.005 0.005 0,002 0 Carbonate 13 15 Dec 5 10 Silicate 1 5 6 7 Moisture and minors - rest -

Example 9

The following laundry detergent compositions A to E are made according to the invention:

AND (B) C D E MLAS 22nd 16.5 11 1 to 5.5 10 to 25 Any combination of: C45 AS C45E1S LAS C16SAS C14-17NaPS C14-18MES 0 1 to 5.5 11 16.5 0 to 5 QAS 0 to 4 0 to 4 0 to 4 0 to 4 0 to 8 C23E6.5 or C45E7 1.5 1.5 1.5 1.5 0 to 4 Zeolite A 27.8 27.8 27.8 27.8 20 to 30 PAA 2.3 2.3 2.3 2.3 0 to 5 Carbonate 27.3 27.3 27.3 27.3 20 to 30 Silicate 0.6 0.6 0.6 0.6 0 to 2 PB1 1.0 1.0 1.0 1.0 0 to 3 Proteinasa 0 to 0.5 0 to 0.5 0 to 0.5 0 to 0.5 0 to 0.5 Celulasa 0 to 0.3 0 to 0.3 0 to 0.3 0 to 0.3 0 to 0.5

4 4 4 ·

• 4 • 44

Amylasa 0 to 0.5 0 to 0.5 0 to 0.5 0 to 0.5 Oaž 1 CFP 1 0.4 0.4 0.4 0.4 Oaž 1 Brightener 1 or 2 0.2 0.2 0.2 0.2 0 to 0.3 PEG 1.6 1.6 1.6 1.6 Oaž 2 Sulfate 5.5 5.5 5.5 5.5 0 to 6 Silicone anti-foam 0.42 0.42 0.42 0.42 0 to 0.5

Example 10

The following laundry detergent compositions F to K are made according to the invention:

F G H AND J TO MLAS 32 24 16 8 4 1 to 35 Any combination of: C45 AS C45E1S LAS C16SAS C14-17 NaPS C14-18MES MBAS 16,5 MBAE1,5S15,5 0 8 16 24 28 0 to 35 C23E6.5 or C45E7 3.6 3.6 3.6 3.6 3.6 0 to 6 QAS 0 to 1 0 to 1 0 to 1 0 to 1 0 to 1 0 to 8 Zeolite A 9.0 9.0 9.0 9.0 9.0 Oaž 20 PAA or MA / AA 7.0 7.0 7.0 7.0 7.0 0 to 10 Carbonate 18.4 18.4 18.4 18.4 18.4 5 to 25 Silicate 11.3 11.3 11.3 11.3 11.3 5 to 25 PB1 3.9 3.9 3.9 3.9 3.9 1 to 6 NOBS 4.1 4.1 4.1 4.1 4.1 0 to 6 Proteinasa 0.9 0.9 0.9 0.9 0.9 Oaž 1,3 Amylasa 0 to 0.5 0 to 0.5 0 to 0.5 0 to 0.5 0 to 0.5 0 to 0.5

Celulasa 0 to 0.3 0 to 0.3 0 to 0.3 0 to 0.3 0 to 0.3 0 to 0.3 SRP1 0.5 0.5 0.5 0.5 0.5 0 to 1 Brightener 1 or 2 0.3 0.3 0.3 0.3 0.3 0 to 0.5 PEG 0.2 0.2 0.2 0.2 0.2 0 to 0.5 Sulfate 5.1 5.1 5.1 5.1 5.1 0 to 10 TFAA 0 to 1 0 to 1 0 to 1 0 to 1 Oaž 1 0 to 3 Silicone anti-foam 0.2 0.2 0.2 0.2 0.2 0 to 0.5 Moisture and minors - the rest ™

Example 11

The following liquid laundry detergent compositions L to P are made according to the invention:

L M AND O P MLAS 1 to 7 7 to 12 12 to 17 17 to 22 1 to 35 Any combination of: C25 AExS * Na (x = 1,8 to 2,5) MBAE1,8S15,5 MBAS15,5 C25 AS (linear to high 2-alkyl C14-17 NaPS C12-16 SAS C18 1,4 disulfate LAS C12-16MES 15 to 21 10 to 15 5 to 10 0 to 5 Oaž 25 LMFAA 0 to 3.5 0 to 3.5 0 to 3.5 0 to 3.5 Oaž 8 C23E9 or C23E6.5 Oaž 2 Oaž 2 Oaž 2 Oaž 2 0 to 8 APA 0 to 0.5 0 to 0.5 0 to 0.5 0 to 0.5 0 to 2 Citric acid 5 5 5 5 Oaž 8 Fatty acid (TPK or 2 to 7.5 2 to 7.5 2 to 7.5 2 to 7.5 Oaž 14

C12 / 14) Fatty Acid (RPS) 0 to 3.1 Oaž 3,1 Oaž 3,1 Oaž 3,1 Oaž 3,1 EtOH 4 4 4 4 0 to 8 PG 6 6 6 6 Oaž 10 MEA 1 1 1 1 Oaž 3 NaOH 3 3 3 3 Oaž 7 Na TS 2.3 2.3 2.3 2.3 0 to 4 Forms 0.1 0.1 0.1 0.1 0 to 1 Borax 2.5 2.5 2.5 2.5 0 to 5 Proteinasa 0.9 0.9 0.9 0.9 Oaž 1,3 Lipasa 0.06 0.06 0.06 0.06 0 to 0.3 Amylasa 0.15 0.15 0.15 0.15 0 to 0.4 Celulasa 0.05 0.05 0.05 0.05 0 to 0.2 PAE 0 to 0.6 0 to 0.6 0 to 0.6 0 to 0.6 0 to 2.5 PIE 1,2 1,2 1,2 1,2 0 to 2.5 PAEC 0 to 0.4 0 to 0.4 0 to 0.4 0 to 0.4 Oaž 2 CFP 2 0.2 0.2 0.2 0.2 0 to 0.5 Brightener 1 or 2 0.15 0.15 0.15 0.15 0 to 0.5 Silicone anti-foam 0.12 0.12 0.12 0.12 0 to 0.3 Fuming quartz 0.0015 0.0015 0.0015 0.0015 0 to 0.003 Perfume 0.3 0.3 0.3 0.3 0 to 0.6 Color 0,0013 0,0013 0,0013 0,0013 0 to 0.003 Moisture / Minor residue residue residue residue residue Product pH (10% in D1 water) 7.5 to 8.5 7.5 to 8.5 7.5 to 8.5 7.5 to 8.5 6 to 9.5

Example 12

A non-limiting example of a bleaching composition comprising a non-aqueous liquid laundry detergent having the following composition is prepared:

• ··············································· ·

Component Q wt. % R range (wt. Liquid phase MLAS 15 Dec 1 to 35 LAS 12 0 to 35 C24E5 14 10 to 20 Hexylene glycol 27 Mar: 20 to 30 Perfume 0.4 0 to 1 Solids Proteinasa 0.4 0 to 1 Anhydrous Na3 citrate 4 3 to 6 PB1 3.5 2 to 7 NOBS 8 2 to 12 Carbonate 14 5 to 20 DTPA 1 Oaž 1,5 Brightener 1 or 2 0.4 0 to 0.6 Foam suppressor 0.1 0 to 0.3 Minory Residue residue

The resulting composition is a stable anhydrous, strong-acting liquid laundry detergent which, when used in normal fabric washing processes, provides excellent stain and dirt removal performance.

Example 13

The following examples further illustrate the invention at this point with respect to fluid

for manual dishwashing. WITH T Component wt. % range (wt%) MLAS 15 Dec 0.1 to 25 Amonium C23AS 5 0 to 35 C24E1S 5 0 to 35 Cocoamide MEA / DEA 2.5 Oaž 10 LMFAA 0.5 Oaž 10 Coconut amine oxide 2.6 1 to 5

• • · ··· · • · • · · · · · • · • · • · ·· • ♦ • ·· ♦ · • 4 » • 0 • AND • • · · • · · • · ♦ 4 • fl • · · · • · • ·

Betain ** 0.87 / 0.1 0.2 / 0 to 0.5 C9.11E9 5 2 to 10 NH3 xylensulfonate 4 1 to 6 EtOH 4 0 to 7 Amoniumcitrat 0.1 0 to 1 MgCl 2 3.3 0 to 4 CaCl2 2.5 0 to 4 Diamin 2 0 to 8 Amoniumsulfat 0.08 0 to 4 Hydrogen peroxide 200 ppm 10 to 300 ppm Perfume 0.18 0 to 0.5 Maxatase® proteinase 0.50 0 to 1.0 Water and minors residue residue

** cocoalkyl betaine

Example 14

The following examples further illustrate the invention at this point with reference to

shampoo preparations. Component AT IN w X Y Amonium C24E26 5 3 2 10 8 Amonium C24AS 5 5 4 5 8 MLAS 0.6 1 4 5 7 Cocamide MEA / DEA 0 0.68 0.68 0.8 0 PEG 14,000 mol. mass 0.1 0.35 0.5 0.1 0 Cocoamidopropylbetain 2.5 2.5 0 0 1.5 Ceylalkohol 0.42 0.42 0.42 0.5 0.5 Stearyl alcohol 0.18 0.18 0.18 0.2 0.18 Ethylenglykoldistearat 1.5 1.5 1.5 1.5 1.5 Dimethicon 1.75 1.75 1.75 1.75 2,0 Perfume 0.45 0.45 0.45 0.45 0.45 Water and minors residue residue residue residue he remained

Λ

Example 15 • φ φ φ φ · φ φ φ φ φ φ φ • φ • φ φ φ φ φ • • • • • φ φ φ φ • · · ·

Various soap compositions may be prepared having the following compositions.

EE FF (weight percent) MLAS 0 to 10 21.5 Coconut greasy Oaž 20 0 alkoholsulfat Sodium ash 14 15 Dec Sulfuric acid 2.5 2.5 STP 11.6 12 Calcium carbonate 39 25 Zeolite 1 0 Sodium sulfate 0 3 Magnesium sulphate 0 1.5 Silicate 0 3.3 Talc 0 10 Coconut greasy 1 1 alcohol PB1 2.25 5 Proteinasa 0 0.08 Coconut 1,2 2,0 monoethanolamide Fluorescent agents 0.2 0.2 Substituted 0.5 1.4 methylcellulose Perfume 0.35 0.35 DTPMP 0.9 0 Humidity; minory residue residue

Example 16

The following laundry detergent compositions GG to KK are made according to the invention:

GG HH II JJ KK MLAS 16.5 12.5 8.5 4 1 to 25

• • · · · ·· 9 99 9 94 49 • · • • • · • 9 9 9 • 999 • • 9 9 9 9 9 • 9 9 • 9 4 4 9 9 9 9 • • · 4 4 9 4 9 9 9

Any combination of: C45 AS C45E1S LAS C16 SAS 014-17 NaPS C14-18MES MBAS16,5 MBAE2S15.5 0 to 6 10 14 18.5 0 to 20 QAS 0 to 2 0 to 2 0 to 2 0 to 2 0 to 4 TFAA 1.6 1.6 1.6 1.6 0 to 4 C24E3, C23E6,5 or C45E7 5 5 5 5 0 to 6 Zeolite A 15 Dec 15 Dec 15 Dec 15 Dec 10 to 30 NaSKS-6 11 11 11 11 5 to 15 Citrate 3 3 3 3 0 to 8 MA / AA 4.8 4.8 4.8 4.8 Oaž 8 HEDP 0.5 0.5 0.5 0.5 Oaž 1 Carbonate 8.5 8.5 8.5 8.5 Oaž 15 Percarbonate or PB1 20.7 20.7 20.7 20.7 Oaž 25 TAED 4.8 4.8 4.8 4.8 0 to 8 Proteinasa 0.9 0.9 0.9 0.9 Oaž 1 Lipasa 0.15 0.15 0.15 0.15 0 to 0.3 Celulasa 0.26 0.26 0.26 0.26 0 to 0.5 Amylasa 0.36 0.36 0.36 0.36 0 to 0.5 CFP 1 0.2 0.2 0.2 0.2 0 to 0.5 Brightener 1 or 2 0.2 0.2 0.2 0.2 0 to 0.4 Sulfate 2.3 2.3 2.3 2.3 Oaž 25 Silicone anti-foam 0.4 0.4 0.4 0 to 1 moisture and minors - rest -

Example 17

The following high density detergent compositions LL to OO of the present invention are manufactured:

Ftft ftft ftft ft ftft ftft ftft ftft ftft ftft ftftftft ftftftft ftft ftft ftft ftft ftft

LL MM NN OO Agglomerate C45 AS 11.0 4.0 0 14.0 MLAS 3.0 10.0 17.0 3.0 Zeolite A 15.0 15.0 15.0 10.0 Carbonate 4.0 4.0 4.0 8.0 PAA or MA / AA 4.0 4.0 4.0 2,0 CMC 0.5 0.5 0.5 0.5 DTPMP 0.4 0.4 0.4 0.4 Injection C25E5 5.0 5.0 5.0 5.0 Perfume 0.5 0.5 0.5 0.5 Dry ingredients C45 AS 6.0 6.0 3.0 3.0 QAS Oaž 20 0 to 20 0 to 20 Oaž 20 HEDP 0.5 0.5 0.5 0.3 SKS-6 13.0 13.0 13.0 6.0 Citrate 3.0 3.0 3.0 1.0 TAED 5.0 5.0 5.0 7.0 Percarbonate 20.0 20.0 20.0 20.0 CFP 1 0.3 0.3 0.3 0.3 Proteinasa 1.4 1.4 1.4 1.4 Lipasa 0.4 0.4 0.4 0.4 Celulasa 0.6 0.6 0.6 0.6 Amylasa 0.6 0.6 0.6 0.6 Silicone anti-foam 5.0 5.0 5.0 5.0 Brightener 1 0.2 0.2 0.2 0.2 Brightener 2 0.2 0.2 0.2 - Rest (water / minors) 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN!

Example 18

The following examples are examples of hard surface cleaners.

4

4

4

4 444 4 4 4 4 4 • 44 4 4 4 4

4 «4444

4

4 ·

4

MLAS PP 3.0 QQ 4.0 RR 4.0 SS 0.25 TT 0.25 NaPS - 1.0 - - - Coconut fatty acid 0.5 - - - - Trimethylammonium C6AS - - - -, 3.1 C24E5 - - 2.5 - - Carbonate 2,0 2,0 1.0 - - Hydrogen carbonate 2,0 - - - - Citrate 8.0 1.0 - 0.5 - Sodium sulphite 0.2 - - - - Fatty acid (C12 / C14) - - 0.4 - - Natriumkumensulfonat 5.0 - 2.3 - - NTA - 2,0 - - - Hydrogen peroxide - - - - 3.0 Sulfuric acid - - - - 6.0 Ammonia 1.0 - - 0.15 - BPP 2,0 3.0 - - - Isopropanol - - - 3.0 - EGME - - - 0.75 - Butylcarbitol 9.5 2,0 - - - 2-Butyloctanol - - 0.3 - - PEG DME - - 0.5 - - PVP K60 - - 0.3 - - Perfume 2,0 0.5 - - 0.4 Water + minors, etc. residue residue residue residue residue

• ·· ♦ · Φ · 4 94 4 • · 4 9 * · • • 9 9 9 4 9 ♦ • • ·· • 4 · 9 4 4 • • • · • • 9 9 9 4 • • • • • 9 4 4 4 4 ··

PATENT CLAIMS

Claims (9)

PATENT CLAIMS A cleaning composition comprising: a) 0.1 wt. % to 99.9 wt. an alkylarylsulfonate surfactant system comprising from 10 wt. % to 100% by weight of said surfactant system of two or more interrupted crystalline alkylarylsulfonate surfactants of the formula: (B-Ar-D) a (Mq +) ^b wherein D is SO 3 ·, M is a cation or a cationic mixture, q is a valency of said cation, and b are numbers selected such that said preparation is electroneutral; Ar is selected from benzene, toluene and combinations thereof; and B comprises a total of at least one primary hydrocarbon moiety containing from 5 to 20 carbon atoms and one or more crystallinity interrupted moieties, wherein said crystallinity interrupted moieties interrupt or branch from said hydrocarbon moiety; and wherein said alkylarylsulfonate surfactant system has interrupted crystallinity to such an extent that its critical sodium solubility temperature, as measured by the CST assay, is not greater than 40 ° C; and wherein the below alkylarylsulfonate surfactant system has at least one of the following properties: percent biodegradation as measured by a modified SCAS assay that exceeds tetrapropylenebenzenesulfonate; and a weight ratio of non-quaternary and quaternary carbon atoms in B of at least 5: 1; and b) from 0.00001 wt. % to 99.9 wt. % of said detergent additive component, at least one of which is selected from the group consisting of: i) cleaning enzymes; (ii) organic detergent builders; (iii) oxygen bleaching agents; (iv) bleach activators; (v) bleaching transition metal catalysts; (vi) oxygen transfer agents and precursors; vii) polymeric soil release agents; (viii) water-soluble ethoxylated amines having properties to remove clay soil and prevent it from settling back; ix) polymer dispersing agents; (x) polymeric dye transfer inhibiting agents; xi) alkoxylated polycarboxylates; and xii) mixtures thereof. «··· • · · · ··· W jooo - 4½ 49 49 4 4 4 4 4 9 5 4 4 4 4 4 4 4 4 4 4 9 4 4 4 4 4 4 4 4 4 ·· 44 44 44 The detergent composition of claim 1 wherein Ar is benzene. A detergent composition according to any one of claims 1 to 2, wherein said interrupted crystalline alkylarylsulfonate surfactants comprise at least two isomers selected from: i) ortho-, meta-, and para-isomers based on substituent attachment positions to Ar, wherein Ar is substituted or unsubstituted benzene; ii) positional isomers based on the positions of attachment of substituents to B; and iii) stereoisomers based on the chiral carbon atoms in B Compositions according to any one of claims 1 to 3, characterized in that the alkylarylsulfonate surfactant system further comprises from 0 wt. % to 85 wt. % of said surfactant system of one or more uninterrupted crystallinity of alkylarylsulfonate surfactants of the general formula: (L-Ar-D) a (M ^{q +} ) b wherein D, M, q, a, b, Ar are as defined for interrupted crystallinity of alkylarylsulfonate surfactants; and L is a linear hydrocarbon moiety containing from 5 to 20 carbon atoms. The composition of any one of claims 1 to 4, wherein B comprises both odd and even carbon chain lengths. Compositions as claimed in any one of claims 1 to 5, characterized in that the primary moiety B is exactly one hydrocarbon moiety having from 7 to 16 carbon atoms and wherein said crystalline-interrupted moiety or moieties are selected from: i) branches attached to B selected from C 1 -C 3 alkyl, C 1 -C 3 alkyloxy, hydroxyl and mixtures thereof; ii) parts which disrupt structure B, selected from ether, sulfone, silicone; and iii) mixtures thereof Composition according to any one of claims 1 to 6, characterized in that at least 60 wt. % of said surfactant system of said interrupted crystallinity alkylarylsulfonate surfactants is in the form of isomers wherein Ar is attached to B at the second or third carbon atom in said linear hydrocarbon moiety. · · * * · · · * * * * * * * * * * * * * * * · · ♦ · · · · · · · · · · A detergent composition according to any one of claims 1 to 7, wherein said alkylarylsulfonate surfactant system has crystallinity interrupted to such an extent that its critical sodium solubility temperature measured by the CST test is not greater than Deň: 18 ° C. A detergent composition according to any one of claims 1 to 8 wherein said alkylarylsulfonate surfactant system has crystallinity interrupted to such an extent that its critical calcium solubility temperature measured by the CST test is not greater than 80 ° C. The cleaning composition of any one of claims 1 to 9, wherein said percentage of biodegradation measured by the modified SCAS test is at least 60%.