ES2238854T3 - DETERGENT COMPOSITIONS FOR WASHING CLOTHING WITH A COMBINATION OF COPOLYMERS BASED ON CYCLIC AMINES AND HYDROPHOBICALLY MODIFIED CELLULOSE. - Google Patents

Abstract

A detergent composition characterized by: a) from 1% to 80% by weight of surfactants selected from the group consisting of nonionic, anionic, cationic, amphoteric, hybrid ion surfactants and mixtures thereof; and b) at least 0.01%, preferably at least 0.1% and most preferably at least 0.5%, and not more than 50%, preferably not more than 25.0% and most preferably not more than 5 , 0%, by weight, of a mixture of polymers, oligomers or copolymers based on cyclic amines and hydrophobically modified cellulosic polymers or oligomers, wherein the ratio between hydrophobically modified cellulose and the polymer, oligomer or copolymer based on cyclic amines is in the range of 1000: 1 to 1: 1000.

Description

Detergent compositions for washing clothes with a combination of copolymers based on cyclic amines and hydrophobically modified cellulose.

Technical field

The present invention relates to compositions, in liquid or granulated form, for use in washing applications of clothing, wherein the compositions comprise certain materials of polymers, oligomers or copolymers based on cyclic amines in combination with hydrophobically modified carboxymethylcellulose. This combination provides advantages in terms of appearance and integrity to fabrics and fabrics washed in wash solutions formed with these compositions.

Background of the invention

It is logically known that alternating cycles of use and washing of fabrics and textiles such as, p. eg garments of dress, inevitably affect the appearance and integrity of the fabrics and textiles thus used and washed. Tissues and Textiles simply wear out over time and use. Washing of fabrics and textiles is necessary to eliminate dirt and stains that accumulate in them during use normal. However, the washing operations themselves, after many cycles, can accentuate and contribute to the deterioration of the integrity and appearance of these fabrics and textiles.

The deterioration of the integrity and appearance of The tissues can manifest in several ways. Short fibers they move in the knitted and knitted structures of the fabrics / textiles due to the mechanical action of washing. These displaced fibers may form frayed, lint or "little balls" that are visible on the surface of the tissues and reduce the new look of the fabric. On the other hand, the continuous fabric and textile washes, especially with washing products of clothes that contain bleaches, can discolor tissues and textiles and give them a faded and worn look like result of loss of color intensity and, in many cases, as a result of changes in hue or color tone.

Given the above, there is clearly a need of identifying materials that can be added to products laundry detergents and are associated with fibers of the fabrics and textiles washed with these detergent products, in order to reduce or minimize the tendency to deteriorate the appearance of washed fabrics / textiles. These additive materials from detergent product must logically be able to provide advantages in terms of appearance and integrity of the tissues without this affect the ability of laundry detergent to Perform your tissue cleaning function. The present invention refers to the use of a mixture of certain materials of polymers, oligomers or copolymers based on cyclic amines and hydrophobically modified cellulose in washing applications of clothes that act in this desired way.

Summary of the invention

The present invention relates to a detergent composition comprising:

to)

of 1% at 80% by weight of surfactants selected from the group consisting in nonionic, anionic, cationic, amphoteric surfactants of hybrid ion and mixtures thereof; Y

b)

to the minus 0.01%, preferably at least 0.1% and most preferably at least 0.5%, and less than 50%, preferably less than 25.0% and with maximum preference less than 5.0%, by weight of a mixture of polymers, oligomers or copolymers based on cyclic amines and hydrophobically modified cellulosic polymers or oligomers, in where the relationship between hydrophobically modified cellulose and materials of polymers, oligomers or copolymers based on Cyclic amines are in the range of 1000: 1 to 1: 1000.

The materials of polymers, oligomers or copolymers based on cyclic amines that are suitable for use in laundry operations and provide the advantages desired appearance and integrity of the tissues can be characterized by the following general formula:

one

in where;

-

every T independently selected from the group consisting in H, C 1 -C 12 alkyl, alkyl replaced,

rented C_ {7} -C_ {12},

- (CH 2) h COOM, - (CH 2) h SO 3 M, CH 2 CH (OH) SO 3 M, - (CH 2) h OSO 3 M,

2

       \ vskip1.000000 \ baselineskip
    

3

-

in where W comprises at least one cyclic element selected from the group consisting of:

4

       \ vskip1.000000 \ baselineskip
    

5

in addition to at least one element cyclic, W may also comprise an aliphatic or aliphatic moiety replaced with the structure general;

6

-

each B is, independently of each other, alkylene C 1 -C 12, alkylene C 1 -C 12 substituted, alkenylene C 3 -C 12, dialkylarylene C 8 -C 12, dialkylarylenediyl C_ {8} -C_ {12} and - (R 5 O) n R 5 -;

-

each D is, independently of each other, alkylene C 2 -C 6;

-

every Q independently selected from the group consisting in hydroxy, C 1 -C 18 alkoxy, hydroxyalkoxy C 2 -C 18, amino, alkylamino C 1 -C 18, dialkylamino, groups trialkylamino, heterocyclic monoamine groups and groups diamino;

-

every R_ {1} is independently selected from the group that consists of H, C 1 -C 8 alkyl and C 1 -C 8 hydroxyalkyl;

-

every R2 is independently selected from the group that consists of C 1 -C 12 alkylene, alkenylene C_ {1} -C_ {12}, -CH 2 -CH (OR 1) - CH 2, C 8 -C 12 alkylene, dihydroxyalkylene C_ {4} -C_ {12}, poly (C2-C4) alkyleneoxy) alkylene, H 2 CH (OH) CH 2 OR 2 OCH 2 CH (OH) CH 2-  and C 3 -C 12 hydrocarbyl moieties;

with the condition that when R2 is a hydrocarbyl moiety C 3 -C 12, the hydrocarbyl moiety can comprise 2 to 4 branched remains of the structure general:

7

-

every R_ {3} is independently selected from the group that consists of H, O, R2, hydroxyalkyl C 1 -C 20, alkyl C 1 -C 20, substituted alkyl, aryl C 6 -C 11, substituted aryl, alkylaryl C 7 -C 11, aminoalkyl C_ {1} -C_ {20},

- (CH 2) h COOM, - (CH 2) h SO 3 M, CH 2 CH (OH) SO 3 M, - (CH 2) h OSO 3 M,

       \ vskip1.000000 \ baselineskip
    

8

       \ vskip1.000000 \ baselineskip
    

-

every R_ {4} is independently selected from the group that consists of H, C 1 -C 22 alkyl, C 1 -C 22 hydroxyalkyl, aryl and alkylaryl C 7 -C 22;

-

every R5 is independently selected from the group that consists of C 2 -C 8 alylene, alkyl C 2 -C 8, substituted alkyl; Y

A is an anion monovalent or divalent or polyvalent compatible;

M is a cation compatible;

b = number necessary to balance the load;

every x is, independently of each other, from 3 to 1,000;

every c is, independently of each other, 0 or 1;

every h is, independently of each other, from 1 to 8;

every q is independently of each other, from 0 to 6;

every n is, independently of each other, from 1 to 20;

every r is, independently of each other, from 0 to 20; Y

every t is, independently of each other, from 0 to 1.

The materials of polymers or oligomers cellulosics that are suitable for use in washing operations of clothing and provide the desired benefits of appearance and integrity of the tissues can be characterized by the following formula general:

       \ vskip1.000000 \ baselineskip
    

9

       \ newpage
    

where each R is selected from group consisting of R_ {2}, R_ {c} Y

       \ vskip1.000000 \ baselineskip
    

10

       \ vskip1.000000 \ baselineskip
    

in where:

-

every R2 is independently selected from the group that it consists of H and C 1 -C 4 alkyl;

-

every R_ {c} is

 \ hskip0.5cm 

--- (CH2) y ---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- OZ

where every Z independently selected from the group consisting in M, R 2, R c and R H;

-

every R_ {H} is independently selected from the group that consists of C 5 -C 20 alkyl, C 5 cycloalkyl - C 7, C 7 -C 20 alkylaryl, arylalkyl C 7 -C 20, substituted alkyl, hydroxyalkyl, alkoxy-2-hydroxyalkyl C_ {1} -C_ {20}, alkyloxy-2-hydroxyalkyl C_ {7} -C_ {20}, (R 4) 2 N-alkyl, (R 4) 2 N-2-hydroxyalkyl,  (R 4) 3 N-alkyl, (R 4) 3 N-2-hydroxyalkyl, aryloxy-2-hydroxyalkyl C_ {6} -C_ {12},

       \ vskip1.000000 \ baselineskip
    

eleven

       \ vskip1.000000 \ baselineskip
    

-

every R_ {4} is independently selected from the group that consists of H, C1-C20 alkyl, C 5 -C 7 {cycloalkyl, alkylaryl C 7 -C 20, arylalkyl C 7 -C 20, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl;

-

every R5 is independently selected from the group that consists of H, C1-C20 alkyl, C 5 -C 7 {cycloalkyl, alkylaryl C 7 -C 20, arylalkyl C 7 -C 20, substituted alkyl, hydroxyalkyl, (R 4) 2 N-alkyl and (R 4) 3 N-alkyl;

in where:

M is a cation suitable selected from the group consisting of Na, K, 1/2 Ca and 1/2 Mg;

each x is 0 to 5; Y

each and is from 1 to 5; Y

with the condition of what:

-

he degree of substitution for the group R_ {H} is between 0.0005 and 0.1, more preferably between 0.005 and 0.05 and most preferably between 0.01 and 0.05;

-

he degree of substitution for the group R_ {C} where Z is H or M is between 0.2 and 2.0, more preferably between 0.3 and 1.0 and with maximum preference between 0.4 and 0.7;

-

yes any R_ {H} carries a positive charge, it is balanced for a suitable anion; Y

-

two R 4 of the same nitrogen can together form a structure of ring selected from the group consisting of piperidine and morpholine

The materials of polymers, oligomers or copolymers based on cyclic amines defined above can be used, together with cellulosic polymers or oligomers hydrophobically modified, as a wash solution additive in granulated or liquid form. Alternatively, they can be mixed with granulated detergents, dissolve in detergent compositions liquid or added to fabric softener compositions.

The relationship between cellulosic materials hydrophobically modified and polymer materials, oligomers or copolymers based on cyclic amines are in the 1000: 1 to 1: 1000 range, preferably between 100: 1 and 50: 1, more preferably between 50: 1 and 1: 1 and even more preferably between 10: 1 and 1: 1.

Detergent compositions for laundry of the present invention comprise from 1% to 80% by weight of a detersive surfactant, from 0.01% to 80% by weight of an additive organic or inorganic detergent builder and from 0.01% to 5% by weight of the mixture of polymer materials, oligomers or copolymers based on cyclic amines and polymers or oligomers hydrophobically modified cellulosics for the treatment of tissues of the present invention. The detersive surfactant and the detergency builder additives can be any of the used in conventional detergent washing products clothes.

Aqueous solutions of the mixture of materials of polymers, oligomers or copolymers based on cyclic amines and hydrophobically modified cellulosic polymers or oligomers of The present invention comprises from 0.01% to 80% by weight of the mixture of polymer, oligomer or copolymer materials based on cyclic amines and cellulosic polymers or oligomers hydrophobically modified for tissue treatment dissolved in water and other ingredients such as stabilizers and pH regulators

In this aspect of the method, the present invention refers to the washing or treatment of fabrics and textiles in aqueous wash or treatment solutions formed from effective amounts of the detergent compositions described in the present invention or from the individual components of such compositions. The washing of fabrics and textiles in these washing solutions, followed by rinsing and drying, provides advantages of appearance to the fabrics and textiles thus treated. These advantages may include an improved overall appearance, a reduction of the balls / fluff, a protection against fading, a greater resistance to abrasion and / or an improvement in softness. It has been surprisingly observed that the mixture of materials from polymers, oligomers or copolymers based on cyclic amines and hydrophobically modified cellulosic polymers or oligomers according to this invention provides greater advantages of appearance and integrity to the treated tissues than those achieved with a corresponding amount of any of the components individual.

Detailed description of the invention

As mentioned, when washing fabrics or textiles in wash solutions comprising the mixture of materials of polymers, oligomers or copolymers based on cyclic amines and hydrophobically modified cellulosic polymers or oligomers of the present invention, the appearance and integrity of the tissues. The mixture of polymers, oligomers or copolymers based on cyclic amines and hydrophobically modified cellulosic polymers or oligomers can be added to the washing solutions by incorporating it into a detergent composition, a fabric softener or adding it separately to the washing solution. The mixture of polymers, oligomers or copolymers based on cyclic amines and hydrophobically modified cellulosic polymers or oligomers is described herein basically as liquid or granulated detergent additives, although the present invention should not be considered limited thereto. The mixture of polymers, oligomers or copolymers based on cyclic amines and hydrophobically modified cellulosic polymers or oligomers, the components of the detergent composition, the optional ingredients for these compositions and the method of use of these compositions are described in detail below. All percentages are expressed in weight unless specified
tricky

A) Materials of polymers, oligomers or copolymers based on cyclic amines

An essential component of the compositions of the The present invention comprises one or more polymers, oligomers or copolymers based on cyclic amines. It has been observed that these materials provide a number of advantages in terms of appearance of fabrics and textiles washed in aqueous wash solutions formed from detergent compositions containing a mixture of polymers, oligomers or copolymers based on amines cyclic and hydrophobically cellulosic polymers or oligomers modified for tissue treatment. These advantages as far as the appearance of the tissues may include, for example, an aspect General improved washed fabrics, reducing the ball and lint formation, fading protection, greater abrasion resistance, etc. Materials based on cyclic amines for the treatment of tissues used in compositions and methods of the present invention can provide these advantages of tissue appearance with a loss acceptably small or no cleaning capacity provided by laundry detergent compositions to which these materials are incorporated.

The polymeric, oligomeric component or amine-based cyclic copolymer of the compositions of the present invention may comprise combinations of these cyclic materials based on amines. So, for example, a mixture of piperadin and epihalohydrin condensates can be combined, by example, with a mixture of morpholine and epihalohydrin condensates to achieve the desired tissue treatment results. In addition, the molecular weight of amines based materials Cyclic for tissue treatment may vary in the mixture as illustrated in the following Examples.

As the person skilled in the art will evidently know, an oligomer is a molecule consisting only of some monomer units, while the polymers comprise a considerably higher number of monomer units. For the present invention, oligomers are defined as molecules having a weight average molecular weight less than 1,000 and polymers as molecules having a weight average molecular weight greater than 1,000. The copolymers are polymers or oligomers in which two or more different monomers have been polymerized simultaneously or sequentially. The copolymers of the present invention may include, for example, polymers or oligomers polymerized from a mixture of a primary cyclic monomer based on amines such as, for example, piperadine, and a secondary cyclic monomer based on amines such as, for example,
morpholine

The mixture of polymers, oligomers or copolymers based on cyclic amines and cellulosic polymers or oligomers hydrophobically modified detergent compositions of the The present invention will generally comprise about 0.01% at 5% by weight of the detergent composition. More preferably, the mixture of polymers, oligomers or copolymers based on amines cyclic and hydrophobically cellulosic polymers or oligomers modified will comprise from 0.1% to 4% by weight of the compositions detergents and most preferably from 0.75% to 3%. But nevertheless, as discussed above, when used as an additive of the wash solution, that is, when the polymer mixture, oligomers or copolymers based on cyclic amines and polymers or Hydrophobically modified cellulosic oligomers are not incorporated to detergent compositions, the concentration of the mixture of polymers, oligomers or copolymers based on cyclic amines and hydrophobically modified cellulosic polymers or oligomers it can comprise from 0.01% to 5.0% by weight of the additive material. He laundry additive will also comprise 1% to 80% by weight of water.

The materials of polymers, oligomers or cyclic amine-based copolymers that are suitable for use in laundry processes that provide the advantages desired in terms of appearance and integrity, can be characterized by means of the general formula expressed in the Summary of the invention.

The preferred compounds included in this General structure include the compounds:

-

in where each R1 is H; Y

-

for the minus a W is selected from the group consisting of:

       \ vskip1.000000 \ baselineskip
    

12

13

       \ vskip1.000000 \ baselineskip
    

Even more preferred compounds for their advantages of Aspect and integrity are as follows:

-

in where each R1 is H; Y

-

for the minus a W is selected from the group consisting of:

14

fifteen

       \ vskip1.000000 \ baselineskip
    

The most preferred compounds for their advantages of appearance and integrity of the tissues are:

-

in where each R1 is H; Y

-

to the minus a W is selected from the group consisting of

       \ vskip1.000000 \ baselineskip
    

16

       \ vskip1.000000 \ baselineskip
    

Preferred compounds for use as a group R 2 binding include, but is not limited to: polyepoxides, ethylene carbonate, propylene carbonate, urea, acids α, β-unsaturated carboxylic esters of α-carboxylic acids, β-unsaturated, carboxylic acid amides α, β-unsaturated, acid anhydrides α, β-unsaturated carboxylic acids, acids dicarboxylic or polycarboxylic esters of dicarboxylic acids or polycarboxylic, dicarboxylic acid amides or polycarboxylic, dicarboxylic acid anhydrides or polycarboxylic, glucidylhalogens, chloroform esters, esters chloroacetic acids, derivatives of chloroform esters, derivatives of chloroacetic esters, epihalohydrins, glycerol dichlorohydrins, bis- (halohydrins). Other preferred compounds are those polyether dihalogenates, phosgene, polyhalogens, glycidyl ethers functionalized and mixtures thereof. In addition, R2 also may comprise a reaction product obtained by the reaction of one or more polyether diamines, alkylenediamines, polyalkylene polyamines, alcohols, alkylene glycols and polyalkylene glycols with α-carboxylic acids, β-unsaturated carboxylic acid esters α, β-unsaturated, acid amides α, β-unsaturated carboxylic and α carboxylic acid anhydrides, β-unsaturated, with the proviso that reaction products contain at least two double bonds, two carboxyl groups, two amide groups or two ester groups.

Other materials of polymers, oligomers or cyclic copolymers based on amines also preferred for Use in the present invention include addition compounds of two or more compositions selected from the group consisting of piperazine, piperadine, epichlorohydrin, benzyl epichlorohydrin quaternary, quaternary methyl epichlorohydrin, morpholine and mixtures from the same.

These cyclic amine-based polymers can Be linear or branched. A specific type of branching can be performed using a polyfunctional crosslinking agent. A Example of these polymers is illustrated below.

       \ vskip1.000000 \ baselineskip
    

17

       \ vskip1.000000 \ baselineskip
    

B) Hydrophobically cellulosic polymers or oligomers modified

The essential component of the compositions of the The present invention comprises one or more polymers or oligomers cellulosic It has been observed that these materials provide a series of advantages regarding the appearance of fabrics and textiles washed in aqueous wash solutions formed from detergent compositions containing these cellulosic materials for tissue treatment. These advantages in terms of appearance of the tissues may include, for example, a better overall appearance of the washed tissues, the reduction of the formation of pellets and lint, fading protection, increased resistance to abrasion, etc. Cellulosic materials for treatment of tissues used in the compositions and methods herein invention can provide these advantages of appearance to the tissue with an acceptably small or no loss of capacity cleaner of laundry detergent compositions a those that incorporate these materials.

As the expert in the field will obviously know technique, an oligomer is a molecule that consists only of some monomer units, while the polymers comprise a considerably higher number of monomer units. In the In the present invention, oligomers are defined as molecules that they have a weight average molecular weight less than about 1,000 and polymers are molecules that have a molecular weight weight average greater than about 1,000. An appropriate type of polymers or cellulosic oligomers for tissue treatment useful in the present invention has an average molecular weight weight from 5,000 to 2,000,000, preferably from 50,000 to 1,000,000

The cellulosic component for the treatment of fabrics of the detergent compositions of the present invention generally will comprise from 0.1% to 5% by weight of the composition Detergent. More preferably, these cellulosic materials for tissue treatment will comprise 0.5% to 4% by weight of the detergent compositions and most preferably from 0.75% to 3%. However, as discussed above, when used as an additive of the wash solution, that is, when the Cellulosic component for tissue treatment is not incorporated to a detergent composition, the concentration of the component cellulosic may comprise from 0.1% to 80% by weight of the material additive.

A suitable group of polymers or oligomers Cellulosics for use in the present invention are characterized by the following formula:

18

where each R is selected from group consisting of R2, R2 Y

19

in where:

-

every R2 is independently selected from the group that it consists of H and C 1 -C 4 alkyl;

-

every R_ {C} is

 \ hskip0.5cm 

--- (CH2) y ---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- OZ

where every Z independently selected from the group consisting in M, R 2, R C and R H;

-

every R_ {H} is independently selected from the group that consists of C 5 -C 20 alkyl, cycloalkyl C 5 C 7, C 7 -C 20 alkylaryl, C 7 -C 20 arylalkyl, substituted alkyl, hydroxyalkyl, alkoxy-2-hydroxyalkyl C_ {1} -C_ {20}, alkylaryl-2-hydroxyalkyl C_ {7} -C_ {20}, (R 4) 2 N + -alkyl, (R 4) 2 N + -2-hydroxyalkyl, aryloxy-2-hydroxyalkyl C_ {6} -C_ {12},

twenty

       \ vskip1.000000 \ baselineskip
    

-

every R_ {4} is independently selected from the group that consists of H, C1-C20 alkyl, C 5 -C 7 {cycloalkyl, alkylaryl C 7 -C 20, arylalkyl C 7 -C 20, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidoinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl;

-

every R5 is independently selected from the group that consists of H, C1-C20 alkyl, C 5 -C 7 {cycloalkyl, alkylaryl C 7 -C 20, arylalkyl C 7 -C 20, substituted alkyl, hydroxyalkyl and (R 4) 2 N + -alkyl;

in where:

M is a cation suitable selected from the group consisting of Na, K, ½ Ca and ½ Mg;

each X is 0 to 5;

each and is from 1 to 5; Y

with the condition of that:

-

he degree of substitution for the group R_ {H} is between 0.0005 and 0.1, more preferably between 0.005 and 0.05 and most preferably between 0.01 and 0.05;

-

he degree of substitution for the group R_ {C} where Z is H or M is between 0.2 and 2.0, more preferably between 0.3 and 1.0 and with maximum preference between 0.4 and 0.7;

-

yes any R_ {H} carries a positive charge, it is balanced for a suitable anion; Y

-

two R 4 units of the same nitrogen can together form a ring structure selected from the group consisting of Piperidine and morpholine.

The "degree of substitution" for the group R_ {C}, which is sometimes abbreviated herein as "DS_ {RC}", means the number of moles of the components of the group R_ {C}, where Z is H or M, which are substituted by an anhydrous glucose unit, an anhydrous glucose unit being a six-member ring as shown in the repetitive unit of the previous general structure. The requirement that Z be H or M is necessary to ensure that there is a sufficient number of groups carboxymethyl so that the resulting polymer is soluble. Be It means that, in addition to the necessary number of components R_ {C} where Z is H or M, can exist, and with maximum preference there are, additional R_C components where Z is a group other than H or M.

The production of materials according to the present The invention is defined in more detail in the following examples.

C) Detersive surfactant

The detergent compositions herein invention comprise from 1% to 80% by weight of a surfactant detersive. Preferably these compositions comprise from 5% to 50% by weight of surfactant. The detersive surfactants used they can be anionic, nonionic, hybrid ion, ampholytic or cationic or may comprise compatible mixtures of these types. Detergent surfactants useful in the present invention are described in patents US-3,664,961, granted to Norris on May 23, 1972, US-3,919,678, granted to Laughlin et al. on December 30, 1975, US-4,222,905, granted to Cockrell on the 16th of September 1980 and US-4,239,659, granted to Murphy on December 16, 1980. Of all the surfactants, he they prefer anionic and nonionic surfactants.

Useful anionic surfactants can be of different types. For example, water soluble salts of acids fatty acids of greater molecular weight, that is, soaps, are anionic surfactants useful in the compositions herein invention. These include alkali metal soaps such as the sodium, potassium, ammonium and alkyl ammonium salts of acids higher molecular weight fatty acids containing approximately 8 to about 24 carbon atoms, and preferably from 12 to 18 carbon atoms

Other anionic surfactants that are not of the type soap and are suitable for use in the present invention include water soluble salts, preferably metal salts alkali and ammonium, or organic sulfuric reaction products which have in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a ester group of sulfonic acid or sulfuric acid (in the expression "alkyl" includes the alkyl portion of acyl groups). Especially valuable are chain alkylbenzene sulfonates linear in which the average number of carbon atoms in the group alkyl is 11 to 13, and that is abbreviated as C_ {11-13} LAS.

Preferred non-ionic surfactants are those of the formula R 1 (OC 2 H 4) n OH, in where R 1 is a C 10 -C 16 alkyl group or a C 8 -C 12 alkyl phenyl group, and n is from 3 to 80. Especially preferred are the products of condensation of C 12 -C 15 alcohols with 5 to 20 moles of ethylene oxide per mole of alcohol, e.g. eg the C 12 -C 13 alcohol condensed with 6.5 moles of ethylene oxide per mole of alcohol.

Other suitable surfactants, including fatty acid and amine polyhydroxyamide type surfactants, are described in PCT co-pending application WO98 / 14300, published March 25, 1999 under the heading Laundry Detergent Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith , filed on September 15, 1997 on behalf of Panadiker et al.

D) Detergent builder additive

The detergent compositions herein invention may also comprise from 0.1% to 80% by weight of a detergent booster additive. Preferably you are Liquid form compositions will comprise from 1% to 10% by weight of the additive component of detergency builder. Preferably these compositions in granular form will comprise from 1% to 50% in weight of the additive component of the detergency builder. The detergency builders are well known in the technique and may comprise, for example, phosphate salts and different organic detergency builders non-phosphoric inorganic.

Additives strengthening detergency Water-soluble non-phosphoric organic compounds useful herein invention include the different polyacetates, carboxylates, alkali metal polycarboxylates and polyhydroxy sulfonates, ammonium and substituted ammonium. Polycarboxylates suitable for use in The present invention is the polyacetal carboxylates described in US Patents 4,144,226, issued to Crutchfield and cabbage. on March 13, 1979, and US-4,246,495, granted to Crutchfield et al. on March 27, 1979. Additives polycarboxylate type detergency builders especially Preferred are the detergent builder compositions of type oxidisuccinate and carboxylate ether comprising a combination of tartrate monosuccinate and tartrate disuccinate described in US Patent 4,663,071, granted to Bush et al. May 5, 1987.

Examples of additives reinforcing the suitable inorganic, non-phosphoric detergents include silicates, aluminosilicates, borates and carbonates. Especially Preferred are carbonates, bicarbonates, sesquicarbonates, tetraborates decahydrate and sodium and potassium silicates that have a weight ratio between SiO2 and alkali metal oxide 0.5 to 4.0, preferably 1.0 to 2.4. Are also preferred aluminosilicates that include zeolites. These materials used as detergency builder additives are discussed in more detail in US-4,605,509, granted to Corkill et al. They are also discussed in the patent US-4,605,509 crystalline laminar silicates suitable for use in the detergent compositions of this invention.

E) Optional detergent ingredients

In addition to surfactants, additives builders and mixtures of polymers, oligomers or copolymers based on cyclic amines and polymers or oligomers hydrophobically modified cellulosics described above, the detergent compositions of the present invention also can include any number of optional ingredients additional. These include conventional components of detergent compositions such as enzymes and agents Enzyme stabilizers, formation enhancers soaps or suds suppressors, agents against tarnish and corrosion, bleaching agents, suspensions stains, dirt release agents, germicides, regulators pH, non-reinforcing alkalinity sources of detergency, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical brighteners, dyes and perfumes.

Preferred optional ingredients for your Incorporation into the detergent compositions herein invention comprise a bleaching agent, that is, an agent peroxygen bleach. These peroxygen bleaching agents They can be organic or inorganic in nature. The agents inorganic peroxygen bleach are frequently used along with a bleach activator.

Organic peroxygen bleaching agents useful include percarboxylic acid bleaching agents and You leave it. Among the appropriate examples of this kind of agents is magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, acid 4-nonylamino-4-oxoperoxybutyric and diperoxidedecanedioic acid. This type of agents bleaches are described in the patent US 4,483,781, granted to Hartman on November 20 of 1984; application EP-A-133,354, granted to Banks et al. and published on February 20, 1985; and the US 4,412,934, issued to Chung et al. on November 1 of 1983. Highly preferred bleaching agents include also the acid 6-nonylamino-6-oxoperoxicaproproic  (NAPAA) as described in the patent 4,634,551, issued January 6, 1987 to Burns et al.

Also, in the detergent compositions of the present invention peroxy bleaching agents can be used inorganic, generally in the form of particles. In fact it they prefer inorganic bleaching agents. Such compounds inorganic peroxygenates include alkali metal perborates and percarbonated materials. Can be used, for example, perborate sodium (for example, monohydrate or tetrahydrate). The agents suitable inorganic bleaches may also include carbonate sodium or potassium peroxyhydrate and bleach type equivalent "percarbonate", sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Too a persulfate bleach can be used (e.g., OXONE, marketed by DuPont). Often bleaching agents inorganic peroxygenates will be coated with silicate, borate, sulfate or water-soluble surfactants. Thus, for example, the Coated percarbonate particles are marketed by Different manufacturers such as FMS, Solvay Interox, Tokai Denka and Taste

Inorganic peroxygen bleaching agents p. eg, perborates, percarbonates, etc., are preferably combined with bleach activators, which entails production in situ in aqueous solution (i.e., during use of the compositions of the present invention for washing / bleaching of tissues) of the peroxyacid corresponding to the bleach activator. Different non-limiting examples of activators are described in US Patent 4,915,854, issued April 10, 1990 to Mao et al .; and US Patent 4,412,934, issued November 1, 1983 to Chung et al. Typical preferred activators are nonanoyloxybenzene sulfonate (NOBS) and tetracetylethylene diamine (TAED). Mixtures thereof can also be used. See also US Patent 4,634,551, mentioned above, for other typical bleach and activators useful in the present invention.

Other amidoderivative bleach activators Useful are the ones with the formulas:

\hskip0.5cm

o

\hskip0.5cm

R^{1}C(O)N(R^{5})R^{2}C(O)LR 1 N (R 5) C (O) R 2 C (O) L

 \ hskip0.5cm 

or

 \ hskip0.5cm 

R 1 C (O) N (R 5) R 2 C (O) L

where R 1 is a group alkyl containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to 6 carbon atoms, R 5 is H or alkyl, aryl or alkylaryl which It contains 1 to 10 carbon atoms, and L is any group adequate outgoing. An outgoing group is any group that is displaced from bleach activator as a result of nucleophilic attack of the perhydrolysis anion on the activator of the bleach. Phenolsulfonate is a leaving group favorite.

Preferred examples of activators of bleach of the above formulas include the (6-decanamido-caproyl) oxybenzenesulfonate, el (6-nonanamidocaproil) oxybenzene sulfonate, the (6 decanamido-caprol) oxybenzenesulfonate and mixtures thereof, as described in the patent US-4,634,551 previously referenced in the present memory

Other class of useful bleach activators comprises the benzoxacin type activators described by Hodge and cabbage. in US-4,966,723, issued on 30 October 1990, and incorporated herein as reference. See also US-4,545,784, granted to Sanderson on October 9, 1985 and incorporated into the present memory for reference, where acyl are described caprolactams, including benzoyl caprolactam, adsorbed on sodium perborate

If used, peroxygenated bleaching agent will generally comprise about 2% to 30% by weight of the detergent compositions of the present invention. Plus preferably, the peroxy bleaching agent will comprise 2% to 20% by weight of the compositions. Most preferably, the peroxygen bleaching agent will be present in an amount of 3% to 15% by weight of the composition of the present invention. Whether use, bleach activators can comprise from 2% to 10% by weight of the detergent compositions herein invention. Frequently the activators are used so that the molar ratio between the bleaching agent and the activator is of 1: 1 to 10: 1, more preferably 1.5: 1 to 5: 1.

Other suitable bleaching agents and bleach activators are described in PCT co-pending application WO98 / 14300, published March 25, 1999 under the title Laundry Detergent Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith , filed on September 15, 1997 on behalf of Panadiker et al.

Another optional ingredient very preferred in detergent compositions of the present invention is a component detersive enzyme. Enzymes can be included in these detergent compositions for different purposes such as, e.g. eg remove protein or triglyceride stains on substrates, prevent the transfer of fugitive dyes in washing tissues or tissue regeneration. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures of the same, of any suitable origin as. p. e.g., of vegetable, animal, bacterial, fungal or yeast.

Preferred selections are influenced by factors such as pH activity and / or stability, the optimum thermostability and stability against detergents assets, detergency builders and the like. To this bacterial or fungal enzymes, such as bacterial amylases and proteases and fungal cellulases.

Here the expression "enzyme detersive "means any enzyme that has an effect Beneficial cleaning, stain removal or other in a laundry detergent composition. Enzymes Preferred for laundry purposes include, but not limiting form, proteases, cellulases, lipases, amylases and peroxidases

Enzymes are normally incorporated into the detergent compositions in a concentration sufficient to provide an "effective amount for cleaning". The expression "effective amount for cleaning" refers to any quantity capable of producing an effect improving the cleaning, stain removal, dirt removal, bleaching, deodorization or freshness in substrates such as tissues. In the practice, for current commercial preparations quantities Typical are up to 5 mg by weight and more typically 0.01 mg at 3 mg of active enzyme per gram of the detergent composition. Saying otherwise, the compositions of the present invention typically comprise 0.001% to 5%, preferably of 0.01% to 1%, by weight of a commercial enzyme preparation. The protease enzymes are normally present in said commercial preparations at sufficient levels to provide 0.005 to 0.1 Anson units (AU, English, Anson unit) of activity per gram of composition. May be desirable higher active levels in detergent formulations very concentrated.

Cellulases useful in the present invention include those described in US Pat. Nos. 4,435,307, granted to Barbesgoard et al. on March 6, 1984, and GB-A-2,075,028; GB-A2.095.275 and DE-OS-2,247,832. The products CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 9117243, to Novo.

The compositions of the present invention that contain enzymes can also optionally comprise 0.001% at about 10%, preferably from 0.005% to 8% and with maximum preference of 0.01% to 6%, by weight of a stabilizer system of enzymes The enzyme stabilizer system can be any stabilizer system that is compatible with the detersive enzyme. These types of systems can be inherently provided by other active substances of the formulation or can be added by separate, p. e.g., by the formulator or in the form of prepared enzymes by the detergent manufacturer. These stabilizer systems they can, for example, comprise calcium ions, boric acid, propylene glycol, short chain carboxylic acids, acids boronic, and mixtures thereof, and are designed to solve different stabilization problems depending on the type and physical form of the detergent composition.

The compositions of the present invention may also include transfer inhibitors dyes such as polyvinyl pyrrolidine polymers, polymers of poly (N-oxide amine), copolymers of N-vinyl pyrrolidone and N-vinylimidazole, manganese phthalocyanide, peroxidases and mixtures thereof. These agents typically comprise from 0.01% to 10%, preferably from 0.01% to 5% and more preferably from 0.05% to 2%, by weight of the composition.

More specifically, the polymers of Preferred poly (N-oxide) for use herein invention contain units that have the following formula structural; R-AX -P; where P it is a polymerizable unit to which a group can join N-O or the N-O group can form part of the polymerizable unit or the N-O group It can be attached to both units; A is one of the following structures: -NC (O) -, -C (O) O-, -S-, -O-, and -N =; x is 0 or 1; and R are aliphatic, aliphatic ethoxylated groups, aromatic, heterocyclic or alicyclic, or any combination of the same, to which the group's nitrogen can be attached N-O, or the N-O group is part of These groups. Preferred poly (N-oxides) are those where R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives of same.

The N-O group can be represented by the following general structures:

       \ vskip1.000000 \ baselineskip
    

\melm{\delm{\para}{(R _{3} ) _{z} }}{N}{\uelm{\para}{O}}

--- (R_{2})_{y};

\hskip0.5cm

\biequal

\uelm{N}{\uelm{\para}{O}}

--- (R_{1})_{x}(R 1) x ---

 \ melm {\ delm {\ para} {(R 3) _ {z}}} {N} {\ uelm {\ para} {O}} 

--- (R 2) y;

 \ hskip0.5cm 

\ biequal

 \ uelm {N} {\ uelm {\ para} {O}} 

--- (R 1) x

       \ vskip1.000000 \ baselineskip
    

wherein R_ {1}, R2_, R_ {3} they are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y, z are 0 or 1; and the nitrogen of N-O group can be linked to be part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably pKa <7 and more preferably pKa < 6.

Any main chain can be used polymeric as long as the amine oxide polymer formed is water soluble and have transfer inhibitory properties of dyes Examples of suitable polymeric main chains they are polyvinyl, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. The polymers include random or block copolymers wherein a type of monomer is an amine N-oxide and the other type of monomer It is an N-oxide. The amine N-oxide polymers are shaped typical an amine: amine N-oxide ratio of 10: 1 a 1: 1,000,000. However, it is possible to modify the number of groups amine oxide present in the polyamine oxide polymer by appropriate copolymerization or by a degree appropriate N-oxidation. Polyamine oxides They can be obtained with almost any degree of polymerization. From Typically, the weight average molecular weight is in the range from 500 to 1,000,000; more preferably from 1,000 to 500,000 and with highest preference of 5,000 to 100,000.

The most preferred poly (N-oxide) useful in the detergent compositions of the present invention is the poly (4-vinylpyridine N-oxide) having a weight molecular weight average of approximately 50,000 and a proportion amine: 1: 4 amine N-oxide. This preferred class of material is called "PVNO".

Other transfer inhibitors suitable dyes are described in the patent US 5,466,802, issued November 14, 1995 to Panadiker et al.

F) Preparation of the detergent composition

Detergent compositions according to the present invention may have a liquid, pasty or granulated form. These compositions can be prepared by combining the components essential and optional, in the required concentrations, in any suitable order and by any conventional means. The previous description of uses for mixing polymers, oligomers or copolymers based on cyclic amines and polymers or oligomers hydrophobically modified cellulosics defined herein memory is intended to be illustrative, other uses being evident for the person skilled in the art whose inclusion in the field of a Present invention is provided.

Granulated compositions, for example, are generally prepared by combining granulated ingredients, e.g. eg surfactants, detergency builders, water, etc., to form an aqueous suspension, and by spray drying this resulting aqueous suspension until a low humidity level is reached residual (5-12%). The remaining dry ingredients, p. eg, granules of the essential blend of polymers, oligomers or copolymers based on cyclic amines and polymers or oligomers hydrophobically modified cellulosics, can be mixed in form of granulated powder with spray-dried granules in a rotating mixing drum. Liquid ingredients, p. eg solutions of the essential mixture of polymers based on amines cyclics, oligomers, enzymes, binders and perfumes, can sprayed on the resulting granules to form the finished detergent composition. The granulated compositions according to the present invention may also have "compact form", it is that is, they can have a relatively higher density than conventional granulated detergents, that is, from 550 to 950 g / l. In such case, the granulated detergent compositions according to the The present invention will contain a smaller amount of "diluent inorganic "than conventional granulated detergents; Typical diluents are sulfate salts and metal chlorides alkaline earth metals, typically sodium sulfate; the detergents "compact" typically comprise no more than 10% of diluent

Liquid detergent compositions may be prepared by mixing the essential and optional ingredients of the themselves in the order desired to provide compositions that contain the components in the required concentrations. The liquid compositions according to the present invention can also be in "compact form", in which case the compositions detergent liquids according to the present invention will contain a less water than conventional liquid detergents. The addition of the mixture of polymers, oligomers or copolymers based on cyclic amines and cellulosic polymers or oligomers hydrophobically modified to liquid detergent or others Aqueous compositions of this invention can be made by the simple addition to the liquid solutions of the desired mixture of polymers, oligomers or copolymers based on cyclic amines and hydrophobically modified cellulosic polymers or oligomers.

The methods and compositions described also can be applied to the production of particles for use as one of the detergent components in a detergent composition granulated

G) Tissue washing method

The present invention also provides a method for washing fabrics so that advantages of fabric appearance provided by the polymer blend, oligomers or copolymers based on cyclic amines and polymers or hydrophobically modified cellulosic oligomers of the present invention. One such method is to put these tissues in contact with an aqueous wash solution formed by an amount effective of the detergent compositions described above or formed by individual components of such compositions. The contact with tissue washing solutions occurs generally under agitation conditions, although the compositions of the present invention can also be used for solutions aqueous soaking without shaking for cleaning and treatment purposes tissues.

Stirring will preferably take place in a clothes washer to get a good cleaning. The washing will go preferably followed by drying the wet tissue in a dryer conventional. An effective amount of a detergent composition granulated or high density liquid in the aqueous wash solution of a clothes washer is preferably 500 to 7000 ppm, more preferably from 1000 to 3000 ppm.

H) Conditioning and fabric softening

The mixture of polymers, oligomers or copolymers based on cyclic amines and cellulosic polymers or oligomers hydrophobically modified above described as components of laundry detergent compositions of The present invention can also be used to treat and condition fabrics and textiles in the absence of the components of surfactant and detergent builder additive embodiments of the detergent composition of this invention. So, for example, during the rinse cycle of a wash operation conventional household can be added a composition for conditioning fabrics comprising only the polymer blend, oligomers or copolymers based on cyclic amines and the ones themselves hydrophobically modified cellulosic polymers or oligomers, or which comprises an aqueous solution of the polymer mixture, oligomers or copolymers based on cyclic amines and polymers or hydrophobically modified cellulosic oligomers, to obtain the advantages of appearance and integrity of the desired tissues previously described.

Other suitable fabric softeners are described in PCT co-pending application WO98 / 14300, published on March 25, 1999, entitled Laundry Detergent Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith filed September 15, 1997 on behalf of Panandiker et al.

The compositions of the present invention may comprise at least 1%, preferably 10% and more preferably from 20% to 80%, and more preferably at 60%, by weight of the composition of one or more active fabric softeners.

Examples

The following examples illustrate the compositions and methods of the present invention, but not necessarily mean a limitation or a definition of another type of scope of the invention.

Example 1 Synthesis of the imidazole and epichlorohydrin addition compound (proportion of imidazole: epichlorohydrin 1: 1)

Polycationic condensate is prepared by making react the imidazole and epichlorohydrin. In a bottom flask round, equipped with magnetic stirrer, a condenser and a thermometer, imidazole (0.68 mol) and 95 ml of water are introduced. The solution is heated to 50 ° C and then the drop is added dropwise epichlorohydrin (0.68 mol). Once all the epichlorohydrin, the temperature is raised to 80 ° C until consumed All the alkylating agent. The condensate produced has a weight molecular of 12,500.

Example 2 Synthesis of the imidazole and epichlorohydrin addition compound (proportion of imidazole: epichlorohydrin 1.4: 1)

In a round bottom flask, equipped with magnetic stirrer, a condenser and a thermometer, is introduced imidazole (0.68 mol) and 95 ml of water. The solution is heated to 50 ° C and then epichlorohydrin (0.50 mol) is added dropwise. A once all epichlorohydrin has been added, the temperature is raised to 80 ° C until all the alkylating agent has been consumed. Condensate produced had a molecular weight of 2000.

Example 3 Synthesis of the addition compound of piperazine, morpholine and epichlorohydrin (ratio 1.8 / 0.8 / 2.0)

In a round bottom flask equipped with stirrer, thermometer, drip funnel and reflux condenser se add 154.8 g (1.8 mol) of piperazine, 69.6 g (0.8 mol) of morpholine and 220 ml of water. Once a solution is obtained transparent at 40 ° C, the solution is heated to 55-65 ° C and, stirring vigorously, 185 g are added (2 moles) of epichlorohydrin at this rate but without the temperature exceeds 80ºC. Once all the epichlorohydrin, the reaction mixture is heated at 85 ° C until all alkylating agents have been consumed (proof of Preussmann negative after 4 hours). 108.8 g (0.68 are added moles) of 25% NaOH and 40 g of water and the reaction mixture is stir for another hour at 85 ° C. Then another 47 g are added of water and allow the mixture to cool to room temperature.

Example 4 Synthesis of piperacin / morpholine / epi addition compound, in a proportion of 1.8 / 0.8 / 2.0

In a round bottom flask equipped with stirrer, thermometer, drip funnel and reflux condenser se add 154.8 g (1.8 mol) of piperazine, 69.6 g (0.8 mol) of morpholine and 220 ml of water. Once a solution is obtained transparent at 40 ° C, the solution is heated to 55-65 ° C and, stirring vigorously, 185 g are added (2 moles) of epichlorohydrin at this rate so that the temperature does not exceed 80ºC. Once all epichlorohydrin has been added, the reaction mixture is heated to 85 ° C until they have been consumed all alkylating agents (Preussmann test negative after 4 hours). 108.8 g (0.68 mol) of NaOH are added 25% and 40 g of water and the reaction mixture is stirred for another hour at 85 ° C. Then another 47 g of water are added and allowed to cool the mixture at room temperature.

Example 5 Piperacin / morpholine / epi addition compound of Example 4, 100% oxidized

233.6 g (equivalent to 1,292 moles of oxidizable nitrogen atoms) of the material of Example 4 above with 22.1 g (0.276) of 50% NaOH and the mixture is heated to 55-65 ° C. At this temperature 102.4 g (1,421 are added moles) of H2O2 (47.2%) dropwise over a period of 3.5 hours.  Once the addition is complete, the reaction mixture is maintained at the same temperature for another 3 hours and then stirred at room temperature overnight. After Pt / C was added, it was destroyed the unreacted H2O2 and the solution was filtered.

The reaction product has the following features:

Content of Water 58% pH 5.6 Content of chloride 1,593 mmol / g

Example 6 Synthesis of the imidazole / piperazine / epi addition compound, in a ratio 1.0 / 3.0 / 4.0

68.8 g (1.0 mol) of limidazole are dissolved and 260.6 g (3.0 moles) of piperazine in 700.2 g of water and at a temperature of 50-60 ° C and then 370 g are added (4.0 moles) of epichlorohydrin drop by drop. Once the In addition, the reaction mixture is stirred for another 5 hours at 80 ° C

Example 7 Imidazole / piperazine / epi addition compound of Example 6, 100% oxidized

To 237 g of the product of Example 6 above (equivalent to 1.022 moles of oxidizable nitrogen atoms) is add 80.7 g (1.12 mol) of a 47.2% solution of H2O2 in water over a period of 5 hours at 40 ° C. Then the mix at 50-60 ° C until the theoretical amount of H2O2. Unreacted H2O2 is destroyed using Pt / C and then the solution is filtered.

The reaction product has the following features:

Content of Water: 58.6% pH: 2.86 Content of chloride 3,694 mmol / g Mn (GPC): 340 P.m (GPC): 940 Mn / Pm: 2.8 +/- 0.1

Example 8 Synthesis of hydrophobically modified CMC materials

The carboxylation of cellulose to produce CMC it is a procedure that is well known to the expert in technique. One method to prepare the modified CMC materials is add the material during the CMC preparation process or materials that must be replaced. An example of a procedure of this type is shown below. The same procedure can be used with the other replacement materials described in the present report replacing the hydrochloride with the materials of substitution or materials of interest, for example, cetylchloride. The amount of material to be added to the preparation process CMC to achieve the desired degree of substitution will be easily calculated by the person skilled in the art in light of the Following Examples.

Example 9 CMC Hexyl Ether Synthesis

This example illustrates the preparation of a hydrophobically modified carboxymethyl cellulose and is representative of the preparation of all ether derivatives of cellulose.

In a 500 ml glass reactor they are loaded cellulose (20 g), sodium hydroxide (10 g), water (30 g) and ethanol (150 g). The resulting alkaline cellulose is stirred for 45 minutes at 25 ° C Monochloroacetic acid (15 g) and hexylchloride are added (1 g) and the temperature rises gradually to 95 ° C to keep it at 95 ° C for 150 minutes. The reaction is cooled first at 70 ° C and then at 25 ° C. The neutralization is done by adding a sufficient amount of nitric acid / acetic acid to obtain a pH of the aqueous suspension between 8 and 9. The aqueous suspension is filter to obtain a CMC hexyl ether.

Example 10 Cellulosic polymers used in detergent compositions of proof

Modified Cellulosic Polymers Representative for use in detergent compositions liquid and granulated described below are shown in the Tables 10A and 10B. The general parameters of the polymers are common to all polymers while the chemical structure Specific material analyzed is presented in the Specific parameters of polymers.

TABLE 10 A General parameters of the polymers

       \ vskip1.000000 \ baselineskip
    

twenty-one

TABLE 10 B Table of specific parameters of the polymers

2. 3

CMC = carboxymethyl cellulose Manufactured by Metsa Specialty Chemicals ** Made by Akzo *** The DS_ {RH} value for these materials was in the range of 0.001 to 0.1

Example 11

Below are chemical structures idealized for certain polymers, oligomers or copolymers based in cyclic amines of this invention. The reactions do not occur Secondary expected during condensation.

TABLE 11

25

26

27

28

29

30

31

32

33

3. 4

       \ newpage
    

Example 12 Preparation of the granulated detergent composition of test

Different compositions were prepared granulated cleaning detergents containing a mixture of polymers, oligomers or copolymers based on amines cyclic and hydrophobically cellulosic polymers or oligomers modified. These granulated detergent compositions have all The following basic formula:

TABLE 12

35

       \ vskip1.000000 \ baselineskip
    

Example 13 Preparation of the liquid test detergent composition

Different compositions were prepared liquid detergents for intensive cleaning with a mixture of polymers, oligomers or copolymers based on cyclic amines and hydrophobically modified cellulosic polymers or oligomers. These liquid detergent compositions all have the following basic formula:

TABLE 13

       \ vskip1.000000 \ baselineskip
    

37

       \ vskip1.000000 \ baselineskip
    

Example 14 Preparation of the granulated detergent composition of test

Different compositions were prepared granulated detergents containing a mixture of polymers, oligomers or copolymers based on cyclic amines and polymers or hydrophobically modified cellulosic oligomers. These granulated detergent compositions all have the basic formula next:

TABLE 14

       \ vskip1.000000 \ baselineskip
    

39

       \ vskip1.000000 \ baselineskip
    

Example 15

A detergent agglomerate was prepared that can be used as a particulate component in a detergent composition according to the following formulas and intervals. The granule can be manufactured by agglomeration methods known to those skilled in the art, some of which are described in the present application.

41

1: The dispersant is Polyacrylate Na 4500, Polyethylene Glycol or a mixture of both of them.

Claims (10)

1. A detergent composition characterized by:

to)

of 1% at 80% by weight of surfactants selected from the group consisting in nonionic, anionic, cationic, amphoteric surfactants of hybrid ion and mixtures thereof; Y

b)

to the minus 0.01%, preferably at least 0.1% and most preferably at least 0.5%, and not more than 50%, preferably not more than 25.0% and most preferably not more than 5.0%, by weight, of a mixture of polymers, oligomers or copolymers based on cyclic amines and hydrophobically modified cellulosic polymers or oligomers, in where the relationship between hydrophobically modified cellulose and the polymer, oligomer or copolymer based on cyclic amines is in the range of 1000: 1 to 1: 1000.

2. The detergent composition of claim 1, in which the hydrophobically cellulosic polymers or oligomers  Modified have the general formula: 42 where each R is selected from group consisting of R_ {2}, R_ {c} Y 43 in where:

-

every R2 is independently selected from the group that it consists of H and C 1 -C 4 alkyl;

-

every R_ {c} is

 \ hskip0.5cm 

--- (CH2) y ---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- OZ

where every Z independently selected from the group consisting in M, R 2, R c and R H;

-

every R_ {H} is independently selected from the group that consists of C 5 -C 20 alkyl, cycloalkyl C_ {5} -C_ {7}, alkylaryl C 7 -C 20, arylalkyl C 7 -C 20, substituted alkyl, hydroxyalkyl, alkoxy-2-hydroxyalkyl C_ {1} -C_ {20}, alkyloxy-2-hydroxyalkyl C 7 -C 20, (R 4) 2 N + I rent, (R 4) 2 N + 2-hydroxyalkyl, aryloxy-2-hydroxyalkyl C_ {6} -C_ {12},

         \ vskip1.000000 \ baselineskip
      

44

-

every R_ {4} is independently selected from the group that consists of H, C1-C20 alkyl, C 5 -C 7 {cycloalkyl, alkylaryl C 7 -C 20, arylalkyl C 7 -C 20, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl;

-

every R5 is independently selected from the group that consists of H, C1-C20 alkyl, C 5 -C 7 {cycloalkyl, alkylaryl C 7 -C 20, arylalkyl C 7 -C 20, substituted alkyl, hydroxyalkyl and (R 4) 2 N + alkyl;

in where:

M is a cation suitable selected from the group consisting of Na, K, 1/2 Ca and 1/2 Mg;

each x is 0 to 5;

each and is from 1 to 5; Y

with the condition of that:

-

he degree of substitution of the group R_ {H} is between 0.0005 and 0.1, plus preferably between 0.005 and 0.05 and most preferably between 0.01 and 0.05;

-

he degree of substitution of the group R_ {C} where Z is H or M is between 0.2 and 2.0, more preferably between 0.3 and 1.0 and with maximum preference between 0.4 and 0.7;

-

yes any R_ {H} carries a positive charge, it is balanced for a suitable anion;

-

and two R 4 of the same nitrogen can together form a structure of ring selected from the group consisting of piperidine and morpholine

3. The detergent composition of any of the claims 1-2, wherein the polymers, oligomers or copolymers based on cyclic amines have the formula general:

         \ vskip1.000000 \ baselineskip
      

Four. Five

         \ vskip1.000000 \ baselineskip
      

in where;

-

every T independently selected from the group consisting in H, C 1 -C 12 alkyl, alkyl replaced,

rented C_ {7} -C_ {12},

- (CH 2) h COOM, - (CH 2) h SO 3 M, CH 2 CH (OH) SO 3 M, - (CH 2) h OSO 3 M,

         \ vskip1.000000 \ baselineskip
      

46

         \ vskip1.000000 \ baselineskip
      

47

         \ vskip1.000000 \ baselineskip
      

-

where W is characterized by having at least one cyclic element selected from the group consisting of:

48 49

besides so less a cyclic element, W may also comprise a remainder aliphatic or substituted aliphatic of general structure;

fifty

-

each B is, independently of each other, alkylene C 1 -C 12, alkylene C 1 -C 12 substituted, alkenylene C 3 -C 12, dialkylarylene C 8 -C 12, dialkylaryldiodiyl C_ {8} -C_ {12} and - (R 5 O) n R 5;

-

each D is, independently of each other, alkylene C 2 -C 6;

-

every Q independently selected from the group consisting in hydroxy, C 1 -C 18 alkoxy, hydroxyalkoxy C 2 -C 18, amino, alkylamino groups, dialkylamino, C 1 -C 18 trialkylamino, heterocyclic monoamine groups and diamino groups;

-

every R_ {1} is independently selected from the group that consists of H, C 1 -C 8 alkyl and C 1 -C 8 hydroxyalkyl;

-

every R2 is independently selected from the group that consists of C 1 -C 12 alkylene, alkenylene C_ {1} -C_ {12}, -CH 2 -CH (OR 1) - CH 2, C 8 -C 12 alkylene, dihydroxyalkylene C 4 -C 12, poly (alkyleneoxy C 2 -C 4) alkylene, H 2 CH (OH) CH 2 OR 2 OCH 2 CH (OH) CH 2 - and C 3 -C 12 hydrocarbyl moieties;

with the condition that if R2 is a hydrocarbyl moiety C 3 -C 12, the hydrocarbyl moiety can comprise 2 to 4 branched remains of structure general:

51

-

every R_ {3} is independently selected from the group that consists of H, O, R2, hydroxyalkyl C 1 -C 20, alkyl C 1 -C 20, substituted alkyl, aryl C 6 -C 11, substituted aryl, alkylaryl C 7 -C 11, aminoalkyl C_ {1} -C_ {20},

- (CH 2) h COOM, - (CH 2) h SO 3 M, CH 2 CH (OH) SO 3 M, - (CH 2) h OSO 3 M,

52

-

every R_ {4} is independently selected from the group that consists of H, C 1 -C 22 alkyl, C 1 -C 22 hydroxyalkyl, aryl and alkylaryl C 7 -C 22;

-

every R5 is independently selected from the group that consists of C2-C8 alkylene, alkyl C 2 -C 8, substituted alkylene and

A is an anion monovalent, divalent or polyvalent compatible;

M is a cation compatible;

b = number necessary to balance the load;

every x is, independently of each other, from 3 to 1000;

every c is, independently of each other, 0 or 1;

every h is, independently of each other, from 1 to 8;

every q is independently of each other, from 0 to 6;

every n is, independently of each other, from 1 to 20;

every r is, independently of each other, from 0 to 20; Y

every t is, independently of each other, from 0 to 1.

4. The detergent composition of the claim 3, where each R_ {1} is H and at least one W is selected from group consisting of: 53 54 5. The detergent composition according to any of claims 3-4, wherein each R1 is H and at least a W is selected from the group consisting of: 55 56 6. The detergent composition according to any of claims 3 to 5, wherein each R1 is H and at least a W is selected from the group consisting of: 57 7. The detergent composition according to any one of claims 1 to 6, wherein each R H is independently selected from the group consisting of C 5 -C 20 alkyl, C 5 cycloalkyl -C 7, C 7 -C 20 alkylaryl, C 7 -C 20 arylalkyl, substituted alkyl, hydroxyalkyl, C 1 -C 20 alkoxy-hydroxyalkyl, alkyloxy- 2-C 7 -C 20 hydroxyalkyl, (R 4) 2
N-alkyl, (R 4) 2 N-2-hydroxyalkyl, (R 4) 3 N-alkyl, (R 4) 3 N-2-hydroxyalkyl and C 6 -C 12 aryloxy-2-hydroxyalkyl. 8. A composition of laundry additive characterized by:

to)

of 1% at 80% by weight of water; Y

b)

from 0.01% to 5.0%, preferably 0.1% to 4.0%, by weight of a mixture of polymers, oligomers or copolymers based on cyclic amines and hydrophobically cellulosic polymers or oligomers modified.

9. The detergent composition according to any one of claims 1 to 7, wherein the composition is further characterized by an inorganic peroxygen bleach compound, which is preferably selected from the group consisting of alkali metal salts of perborate, percarbonate and mixtures thereof. themselves, and a bleach activator, which is preferably nonanoyloxybenzene sulfonate. 10. The detergent composition according to any one of claims 1 to 7, wherein the composition is further characterized by a cellulase enzyme.