CN1163576C - Laundry detergent composition containing a mixture of cyclic amine-based polymer and hydrophobically modified carboxymethylcellulose - Google Patents

Abstract

Detergent compositions and fabric conditioning compositions which include from about 0.01 % to about 5.0 %, by weight of a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers.

Description

Laundry detergent composition containing mixture of cyclic amine-based polymer and hydrophobically modified carboxymethyl cellulose

                      

The present invention relates to compositions for laundry use in liquid or granular form, wherein the composition comprises certain cyclic amine based polymeric, oligomeric or copolymeric materials in admixture with hydrophobically modified carboxymethylcellulose. The mixture imparts appearance and smoothness benefits to fabrics and textiles laundered in washes formed from such compositions.

Background of the Invention

Of course, it is well known that alternating cycles of using and washing fabrics and textiles, such as worn clothes and apparel, will inevitably adversely affect the appearance and smoothness of such used and laundered fabrics and textiles. Fabrics and textiles simply wear out with time and use. Laundering of fabrics and textiles must remove the dirt and stains that deposit on and in them during daily use. However, the laundering operation itself, over many cycles, can degrade the flatness and appearance of these fabrics and textiles.

Deterioration of fabric flatness and appearance can manifest itself in several ways. Short fibers are detached from woven and knitted fabric/textile structures by the mechanical action of laundering. These shed fibers can form visible lint, fuzz, or "balls" on the surface of the fabric and affect the new appearance of the fabric. Also, repeated laundering of fabrics and textiles, especially with laundry products containing bleach, removes dyes from fabrics and textiles, and as a result of reducing color intensity and, in many cases, of changing the hue and shade of color , creating a faded, worn look.

As previously stated, there is clearly a developing need to recognize that, to be added to laundry detergent products, they can associate themselves with the fibers of fabrics and textiles washed with such products, thereby making the A material that reduces or minimizes the tendency to deteriorate the appearance of laundered fabrics/textiles. Of course, the additives to any detergent product should be those which contribute to the appearance and smoothness of fabrics without unduly interfering with the laundry detergent's ability to perform its fabric cleaning function. The present invention relates to the use of certain cyclic amine based polymer, oligomer and copolymer materials in combination with hydrophobically modified carboxymethylcellulose (CMC) in laundry applications accomplished in the claimed manner.

Summary of the invention

The present invention relates to detergent composition, it consists of:

a) from about 1% to about 80% (by weight) of a surfactant selected from the group consisting of nonionic, anionic, cationic, amphoteric, zwitterionic surfactants and mixtures thereof; and

b) at least about 0.01%, preferably at least about 0.1%, most preferably at least about 0.5% and less than about 50%, preferably less than about 25.0%, most preferably less than about 5.0% (by weight) of cyclic amine-based polymer , a mixture of oligomers or copolymers and hydrophobically modified cellulose-based polymers or oligomers.

The present invention also relates to laundry additive compositions, consisting of:

a) from 1% to 80% by weight of water; and

b) from 0.01% to 5.0%, preferably from 0.1% to 4.0% by weight, of cyclic amine-based polymers, oligomers or copolymers and hydrophobically modified cellulose-based polymers or oligomers mixture.

Cyclic amine-based polymer, oligomer or copolymer materials suitable for use in laundry operations and providing desirable fabric appearance and smoothing benefits are characterized by the general formula:

in

Each T is independently selected from the following groups: H, C ₁ -C ₁₂ alkyl, substituted alkyl, C ₇ -C ₁₂ alkylaryl,

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

Wherein W includes at least one cyclic component selected from the following groups:

In addition to at least one cyclic component, W may also contain an aliphatic or substituted aliphatic moiety of the general formula:

Each B is C ₁ -C ₁₂ alkylene, C ₁ -C ₁₂ substituted alkylene, C ₃ -C ₁₂ alkenylene, C ₈ -C ₁₂ dialkylarylene, C ₈ -C ₁₂ dialkylarylene diradicals, and -(R ₅ O) _n R ₅ -;

each D is C ₂ -C ₆ alkylene;

Each Q is independently selected from hydroxyl, C ₁ -C ₁₈ alkoxy, C ₂ -C ₁₈ hydroxyalkoxy, amino, C ₁ -C ₁₈ alkylamino, dialkylamino, trialkylamino, heterocycle monoamino and diamino;

Each R ₁ is independently selected from H, C ₁ -C ₈ alkyl and C ₁ -C ₈ hydroxyalkyl;

Each R ₂ is independently selected from C ₁ -C ₁₂ alkylene, C ₁ -C ₁₂ alkenylene, -CH ₂ -CH(OR ₁ )-CH ₂ -, C ₈ -C ₁₂ alkylarylene, C ₄ -C ₁₂ dihydroxyalkylene, poly(C ₂ -C ₄ alkyleneoxy)alkylene, H ₂ CH(OH)CH ₂ OR ₂ OCH ₂ CH(OH)CH ₂ -, and C ₃ -C ₁₂ hydrocarbyl moiety;

Provided that when _R is a _C3 - _C12 hydrocarbyl moiety, the hydrocarbyl moiety may contain from about 2 to about 4 branched chain moieties of the general formula:

Each R ₃ is independently selected from H, O, R ₂ , C ₁ -C ₂₀ hydroxyalkyl, C ₁ -C ₂₀ alkyl, substituted alkyl, C ₆ -C ₁₁ aryl, substituted aryl, C ₇ -C ₁₁ alkylaryl, C ₁ -C ₂₀ aminoalkyl, -(CH ₂ ) _h COOM, -(CH ₂ ) _h SO ₃ M, CH ₂ CH(OH)SO ₃ M, -(CH ₂ ) _h OSO ₃ M,

Each R is _{independently} selected from H, C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ hydroxyalkyl, aryl and C ₇ -C ₂₂ alkylaryl;

Each R ₅ is independently selected from C ₂ -C ₈ alkylene, C ₂ -C ₈ alkyl substituted alkylene; and

A is a compatible monovalent or divalent or multivalent anion;

M is a compatible cation;

b = the number necessary to balance the charge;

each x is from 3 to about 1000 respectively;

Each c is 0 or 1 respectively;

each h is from about 1 to about 8 respectively;

each q is from 0 to about 6 respectively;

each n is from 1 to about 20 respectively;

each r is from 0 to about 20 respectively; and

Each t is from 0 to 1 respectively.

Cellulose-based polymeric or oligomeric materials suitable for use in laundry operations and capable of providing desirable fabric appearance and flattening benefits are characterized by the general formula:

where each R is selected from R ₂ , R _C and

in:

Each R ₂ is independently selected from H and C ₁ -C ₄ alkyl;

Each R _C is

wherein each Z is independently selected from M, R ₂ , R _C and R _H ;

Each R _H is independently selected from C ₅ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, substituted alkyl, hydroxyl Alkyl, C ₁ -C ₂₀ alkoxy-2-hydroxyalkyl, C ₇ -C ₂₀ alkylaryloxy-2-hydroxyalkyl, (R ₄ ) ₂ N-alkyl, (R ₄ ) ₂ N-2-hydroxyalkyl, (R ₄ ) ₃ N-alkyl, (R ₄ ) ₃ N-2-hydroxyalkyl, C ₆ -C ₁₂ aryloxy-2-hydroxyalkyl,

和

and

Each R is _{independently} selected from H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, aminoalkyl, Alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl;

Each R ₅ is independently selected from H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, substituted alkyl , hydroxyalkyl, (R ₄ ) ₂ N-alkyl and (R ₄ ) ₃ N-alkyl;

in:

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

each x is from 0 to approximately 5;

each y is from about 1 to about 5; and

requirement is:

- the degree of substitution for the R _H group is between about 0.0005 and 0.1, more preferably between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05;

- the degree of substitution for the _RC group wherein Z is H or M is between about 0.2 and 2.0, more preferably between about 0.3 and 1.0, and most preferably between about 0.4 and 0.7;

- if any R _H carries a positive charge, it is balanced by an appropriate anion; and

- 2 R ₄ on the same nitrogen can form together a ring structure selected from piperidine and morpholine.

The cyclic amine based polymer, oligomer or copolymer materials defined above may be used together with hydrophobically modified cellulose based polymers or oligomers as a lotion additive in granular or liquid form. Alternatively, they can be admixed to granular detergents, dissolved in liquid detergent compositions, or added to fabric softening compositions.

The ratio of hydrophobically modified cellulose polymer to cyclic amine-based polymer, oligomer or copolymer material is from 1000:1 to 1:1000, preferably from 100:1 to 50:1, more preferably from 50:1 to 1 :1, even more preferably in the range of 10:1 to 1:1.

Laundry detergent compositions contain from about 1% to 80% by weight of a detersive surfactant, from about 0.01% to 80% by weight of an organic or inorganic detergency builder based on the fabric treatment material of the present invention agent and from about 0.01% to 5% (by weight) of a mixture of cyclic amine-based polymers, oligomers or copolymers and hydrophobically modified cellulose-based polymers or oligomers. The detersive surfactant and detergency builder materials can be any of those used in conventional laundry detergent products.

Aqueous solutions of mixtures of cyclic amine-based polymers, oligomers or copolymers and hydrophobically modified cellulose-based polymers or oligomers of the present invention contain from about 0.01% to 80% (by weight) of cyclic amines dissolved in water. Blends of fabric treatment materials of amine based polymers, oligomers or copolymers with hydrophobically modified cellulose based polymers or oligomers, and other ingredients such as stabilizers and pH adjusters.

In its method aspects, the present invention relates to washing or treating fabrics and textiles in a wash or treatment liquor formed from an effective amount of said detergent composition, or the individual components of such a composition. Washing fabrics and textiles in such a lotion, followed by rinsing and drying, can impart fabric appearance benefits to the treated fabrics and textiles. Such benefits may include improved overall appearance, reduced pilling/fuzz, resistance to fading, improved abrasion resistance, and/or increased softness. Surprisingly, it has been determined that mixtures of cyclic amine-based polymers, oligomers or copolymers with hydrophobically modified cellulose-based polymers or oligomers according to the invention give fabric appearance and flattening benefits that are greater than those achieved by a corresponding amount of The benefit achieved by one of the two components is greater by itself.

Detailed description of the present invention

As pointed out, when fabrics or textiles are washed in a lotion containing a mixture of cyclic amine-based polymers, oligomers or copolymers of the present invention and hydrophobically modified cellulose-based polymers or oligomers, fabrics can be improved. appearance and smoothness. Mixtures of cyclic amine based polymers, oligomers or polymers thereof and hydrophobically modified cellulose based polymers or oligomers may be added to lotions by incorporating them into detergent compositions, fabric softeners, or by incorporating They are added separately to the wash. Mixtures of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulose based polymers or oligomers were initially described as liquid or granular detergent additives, but the invention is not intended to be so limited.

The following describes in detail the mixture of cyclic amine-based polymers, oligomers or copolymers and hydrophobically modified cellulose-based polymers or oligomers, components of detergent compositions, optional components of such compositions and the use of such composition method. All percentages are by weight unless otherwise indicated.

A) Cyclic amine-based polymer, oligomer or copolymer materials

Essential components of the compositions of the present invention include one or more cyclic amine based polymers, oligomers or copolymers. It has been found that this material can be imparted to an aqueous wash formed from a detergent composition comprising a mixture of a cyclic amine-based polymer, oligomer or copolymer and a hydrophobically modified cellulose-based polymer or oligomer fabric treatment material. Medium laundered fabrics and textiles have many appearance benefits. Such fabric appearance benefits can include, for example, improving the overall appearance of laundered fabrics, reducing pill and fuzz formation, preventing color fading, improving abrasion resistance, and the like. The cyclic amine-based fabric treatment materials and methods used in the compositions of the present invention can provide such fabric appearance benefits with acceptably little or no loss in cleaning performance provided by laundry detergent compositions incorporating such materials. no loss.

The cyclic amine-based polymers, oligomers or copolymers of the compositions of the present invention may contain mixtures of such cyclic amine-based materials, for example, a mixture of piperidine and epihalohydrin condensates may be condensed with morpholine and epihalohydrin mixtures of ingredients to achieve the desired fabric treatment results. Also, as illustrated in the examples below, the molecular weight of the cyclic amine-based fabric treatment material in the mixture can vary.

It will be apparent to those skilled in the art that oligomers are molecules containing only a few monomer units, whereas polymers contain a considerable number of monomer units. For the purposes of this invention, oligomers are defined as molecules having an average molecular weight of less than about 1000, while polymers are molecules having an average molecular weight of greater than about 1000. Copolymers are polymers or oligomers in which two or more different monomers are polymerized simultaneously or sequentially. Copolymers of the present invention may include, for example, polymers or oligomers derived from the polymerization of primary cyclic amine-based monomers, such as piperidine, and secondary cyclic amine-based monomers, such as morpholine.

The mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulose based polymers or oligomers of the detergent composition will generally comprise from about 0.01% to about 5% by weight of the detergent composition. More preferably, the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulose based polymers or oligomers will be present in an amount from about 0.1% to about 4% by weight of the detergent composition, most preferably From about 0.75% to about 3%, however, as discussed above, when used as a lotion additive, i.e. when a cyclic amine based polymer, oligomer or copolymer is combined with a hydrophobically modified cellulose based polymer or oligomer When the mixture of substances is not mixed into the detergent composition, the concentration of the mixture of cyclic amine-based polymers, oligomers or copolymers and hydrophobically modified cellulose-based polymers or oligomers can be from about 0.1% to About 80%.

Cyclic amine based polymeric, oligomeric or copolymeric materials suitable for use in laundry operations which provide desirable fabric appearance and smoothing benefits are characterized by the general formula given in the Summary of the Invention.

Preferred compounds included within this general structure include compounds:

- wherein each R ₁ is H; and

- at least one W is selected from the following groups:

More preferred compounds for fabric appearance and smoothing benefits are these:

- wherein each R ₁ is H; and

- at least one W is selected from the following groups:

The most preferred compounds for fabric appearance and smoothing benefits are these:

- wherein each R ₁ is H; and

- at least one W is selected from the following groups:

and

Preferred compounds that can be used as linking group _R include, but are not limited to, polyepoxides, ethylene carbonate, propylene carbonate, urea, α,β-unsaturated carboxylic acids, α,β-unsaturated carboxylic acids Esters, α,β-unsaturated carboxylic acid amides, α,β-unsaturated carboxylic acid anhydrides, di- or polycarboxylic acids, di- or polycarboxylates, di- or polycarboxylic acid amides, di- or polycarboxylic anhydrides, glycidol Halides, chloroformates, chloroacetates, chloroformate derivatives, chloroacetate derivatives, epihalohydrins, α-dichloroglycerols, bis(halohydrins), polyether dihalides , phosgene, polyhalides, functionalized glycidyl ethers and mixtures thereof. Moreover, R2 can also include polyether diamine, alkylene diamine, polyalkylene polyamine, alcohol, alkylene glycol, polyalkylene glycol and α, β-non- Reaction products formed by the reaction of saturated carboxylic acids, esters of α,β-unsaturated carboxylic acids, amides of α,β-unsaturated carboxylic acids and anhydrides of α,β-unsaturated carboxylic acids, provided that the reaction product contains at least 2 double bonds , 2 carboxyl groups, 2 amide groups or 2 ester groups.

Other preferred cyclic amine based polymer, oligomer or copolymer materials for use herein include those selected from the group consisting of piperazine, piperidine, epichlorohydrin, epichlorohydrin benzyl quat, epichlorohydrin methyl quat , morpholine and mixtures thereof.

These cyclic amine-based polymers can be linear or branched. A unique type of branching can be introduced using a multifunctional crosslinker. An example of such a polymer is exemplified below:

B) Hydrophobically modified cellulose-based polymers or oligomers

Essential components of the compositions of the present invention include one or more cellulose-based polymers or oligomers. Such materials have been found to impart a number of appearance benefits to fabrics and textiles washed in aqueous washes formed from detergent compositions containing such cellulose-based fabric treatment materials. Such fabric appearance benefits can include, for example, improving the overall appearance of laundered fabrics, reducing pill and fuzz formation, preventing color fading, improving abrasion resistance, and the like. The cellulose-based fabric treatment materials and methods used in the compositions of the present invention can provide such fabric appearance benefits with acceptably little loss in the cleaning performance provided by laundry detergent compositions incorporating such materials or no loss.

It will be apparent to those skilled in the art that oligomers are molecules consisting of only a few monomer units, whereas polymers contain a considerable number of monomer units. For the purposes of this invention, oligomers are defined as molecules having an average molecular weight of less than about 1000 and polymers are molecules having an average molecular weight of greater than about 1000. One suitable type of cellulosic based polymeric or oligomeric fabric treatment material for use in the present invention has an average molecular weight of from about 5,000 to about 2,000,000, preferably from about 50,000 to about 1,000,000.

Typical levels of the cellulose-based fabric treatment component of the detergent compositions of the present invention are from about 0.1% to about 5% by weight of the detergent compositions. More preferably, such cellulose-based fabric treatment materials comprise from about 0.5% to about 4% by weight of the detergent compositions. Most preferably from about 0.75% to about 3%. However, as discussed above, when used as a lotion additive, i.e., when the cellulose-based fabric treatment component is not incorporated into the detergent composition, the concentration of the cellulose-based component may range from about 0.1% to About 80%.

A suitable group of cellulose-based polymer or oligomer materials for use herein is characterized by the formula:

where each R is selected from R ₂ , R _C and

in:

- each R ₂ is independently selected from H and C ₁ -C ₄ alkyl;

—Each R _C is

wherein each Z is independently selected from M, R ₂ , R _C and R _H ;

- each R _H is independently selected from C ₅ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, substituted alkyl, Hydroxyalkyl, C ₁ -C ₂₀ alkoxy-2-hydroxyalkyl, C ₇ -C ₂₀ alkylaryloxy-2-hydroxyalkyl, (R ₄ ) ₂ N-alkyl, (R ₄ ) ₂ N-2-hydroxyalkyl, (R ₄ ) ₃ N-alkyl, (R ₄ ) ₃ N-2-hydroxyalkyl, C ₆ -C ₁₂ aryloxy-2-hydroxyalkyl,

and

- Each R is _{independently} selected from H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, aminoalkyl , alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl;

- Each R _is independently selected from H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, substituted alkyl radical, hydroxyalkyl, (R ₄ ) ₂ N-alkyl, and (R ₄ ) ₃ N-alkyl;

in:

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

each x is from 0 to approximately 5;

each y is from about 1 to about 5; and

requirement is:

- the degree of substitution for the group R _H is between about 0.0005 and 0.1, more preferably between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05;

- the degree of substitution of the group R _C where Z is H or M is between about 0.2 and 2.0, more preferably between about 0.3 and 1.0, and most preferably between about 0.4 and 0.7;

- if any R _H carries a positive charge, it is balanced by an appropriate anion; and

- 2 R ₄ on the same nitrogen can together form a ring structure selected from the group consisting of piperidine and morpholine.

The "degree of substitution" of the group _RH in the present invention is sometimes abbreviated as "DS _RH ", which means the number of moles of components of the group _RH substituted per anhydroglucose unit, where the anhydroglucose unit is one 6-membered ring, as shown in the repeating unit of the general structure above.

The "degree of substitution" for the group R _C in the present invention is sometimes abbreviated as "DS _RC ", which means that each anhydroglucose unit is substituted, where Z is the mole of the H or M group R _C component number, wherein the anhydroglucose unit is a 6-membered ring, as shown in the repeating unit of the general structure above. The requirement that Z is H or M is necessary to ensure a sufficient number of carboxymethyl groups so that the resulting polymer is soluble. It is understood that in addition to the desired number of R _C components where Z is H or M, other R _C components where Z is a group other than H or M are most preferred.

The production of materials according to the invention is further specified in the following examples.

C) Detergent surfactant

The detergent compositions of the present invention contain from about 1% to 80% by weight of detersive surfactant. Preferably such compositions contain from about 5% to 50% by weight of surfactant. The detersive surfactants used may be anionic, nonionic, zwitterionic, amphoteric or cationic, or may contain compatible mixtures of these types. Detersive surfactants useful herein are described in U.S.P. 3,664,961, Norris, 1972, issued 5.23, U.S.P. 3,919,678, Laughlin et al., 1975, issued 12.30, U.S.P. 4,222,905, Cockrell, 1980, issued 9.16, and U.S.P. 4,239,659, Murphy, 1980, published 12.16. All of these patents are incorporated herein by reference. Of all surfactants, anionic and nonionic are preferred.

Useful anionic surfactants can themselves be of several different types. For example, water soluble salts of higher fatty acids, ie "soaps" are useful anionic surfactants in the present compositions. These include alkali metal soaps such as the sodium, potassium, ammonium and alkanolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 12 to 18 carbon atoms.

Other non-soap anionic surfactants suitable herein include water-soluble salts of reaction products of organosulfurs, preferably alkali metal and ammonium salts, having an alkane containing about 10 to about 20 carbon atoms in their molecular structure. group and sulfuric acid or sulfate ester group. (Where the term "alkyl" is included is the alkyl portion of an acyl group). Of particular value are linear straight chain alkylbenzene sulfonates wherein the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated _C11-13 LAS.

Preferred nonionic surfactants are surfactants of formula R ₁ (OC ₂ H ₄ ) _n OH, wherein R ₁ is C ₁₀ -C ₁₆ alkyl or C ₈ -C ₁₂ alkylphenyl, and n is from 3 to about 80, particularly preferred are condensation products of C ₁₂ -C ₁₅ alcohols with about 5 to about 20 moles of ethylene oxide per mole of alcohol, for example C ₁₂ -C ₁₃ alcohols with about 6.5 moles of ethylene oxide condensed.

Other suitable surfactants, including polyhydroxy fatty acid amides and amine-based surfactants, are described in co-pending PCT application WO 98/14300, published on March 25, 1999, entitled "Gives fabrics washable thereby Laundry Detergent Compositions Containing Cyclic Amino-Based Polymers Providing Appearance and Smoothing Benefits", filed 9; 15, 1997, in the name of Panandiker et al. The text of Panandiker et al. is incorporated herein by reference in its entirety.

D) Detergent synergist

The detergent compositions can also contain from about 0.1% to 80% by weight of detergent builders. Preferably such compositions in liquid form will contain from about 1% to 10% by weight of the builder ingredient. Preferably such compositions in granular form will contain from about 1% to 50% by weight of the builder ingredient. Detergent builders are well known in the art and can include, for example, phosphates and various organic and inorganic non-phosphorus builders.

Water-soluble nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetic, carboxylic, polycarboxylic and polyhydroxysulfonic acid salts. Suitable polycarboxylates for use herein are polyacetal carboxylates, described in U.S.P. 4,144,226 (Crutchfield et al., issued 3.13, 1979) and U.S.P. 4,246,495 (Crutchfield et al., 1979, issued 3.27), both of which All papers are incorporated herein by reference. A particularly preferred polycarboxylate builder is an oxydisuccinate and ether carboxylate builder composition containing a mixture of tartrate monosuccinate and tartrate disuccinate, described in U.S.P. 4,663,071 ( Bush et al., 1987, issued 5.5), which is incorporated herein by reference.

Examples of suitable non-phosphorus inorganic builders include silicates, aluminosilicates, borates and carbonates. Particularly preferred are sodium and potassium carbonates, sodium and potassium bicarbonates, sodium and potassium sesquicarbonates, sodium and potassium tetraborate decahydrate, and sodium and potassium silicates, which have a weight ratio of _SiO2 to alkali metal oxides From about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Also preferred are aluminosilicates, including zeolites. These materials and their use as detergent builders are more fully described in Corkill et al., US Patent 4,605,509, which is incorporated herein by reference. Crystalline layered silicates suitable for use in the detergent compositions of the present invention are also described in USP 4,605,509.

E) Optional detergent components

In addition to surfactants, builders and mixtures of cyclic amine-based polymers, oligomers or copolymers and hydrophobically modified cellulose-based polymers or oligomers as previously described, the detergent combination of the present invention The composition may also include any number of other optional ingredients. They include conventional detergent composition components such as enzymes, enzyme stabilizers, suds boosters or suds suppressors, antitarnish and anticorrosion agents, bleaching agents, soil suspending agents, soil release agents, bactericides, pH adjustment agents, alkalinity sources for non-builders, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical brighteners, dyes and pigments.

An optional ingredient which is preferably added to detergent compositions is a bleaching agent, such as a peroxygen bleach. Such peroxygen bleaches can be organic or inorganic in nature. Inorganic peroxygen bleaches are often used with bleach activators.

Useful organic peroxygen bleaches include peroxycarboxylic acid bleaches and salts thereof. Suitable examples of such agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxyperoxybutyric acid and diperoxydodecanedioic acid. These bleaching agents are disclosed in the following documents: U.S.P.4,483,781, Hartman, 1984, issued on November 20; European patent application EP-A-133,354, Banks et al., published on February 20, 1985; hair and. Highly preferred bleaching agents also include 6-nonylamino-6-oxyperoxycaproic acid (NAPAA), as described in U.S.P. 4,634,551 (Burns et al., Issued 1.6, 1987).

Inorganic peroxygen bleaches are also generally available in granular form in detergent compositions. Inorganic bleaches are in fact preferred. Such inorganic peroxygen compounds include alkali metal perborates and alkali metal percarbonates. For example, sodium perborate (eg, mono- or tetrahydrate) may be used. Suitable inorganic bleaches may also include sodium and potassium carbonate peroxyhydrates and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide . Persulfate bleaches (eg, OXONE, commercially available from DuPont) can also be used. Inorganic peroxygen bleaches are often coated with silicates, borates, sulfates or water-soluble surfactants. For example, coated percarbonate granules are available from various commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa Corporation.

Inorganic peroxygen bleaches, such as perborates, percarbonates, etc., are preferably combined with a bleach activator, which results in a solution in aqueous solution (that is, in the case of using the compositions of the present invention for fabric washing/bleaching). process) generates in situ the corresponding peroxyacid to the bleach activator. Various non-limiting examples of activators are described in U.S.P. 4,915,854, Mao et al., issued April 10, 1990; U.S.P. 4,412,934, Chung et al., issued November 1, 1983. Nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical and preferred. Mixtures of these can also be used. See also U.S. Patent 4,634,551, referenced above, for other typical bleaches and activators.

Other useful amide-derived bleach activators are those having the formula:

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

wherein R ¹ is an alkyl group containing about 6 to about 12 carbon atoms, R ² is an alkylene group containing 1 to about 6 carbon atoms, R ⁵ is hydrogen or alkyl, aryl or containing about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from a bleach activator as a result of nucleophilic attack by a strongly hydrolyzing anion on the bleach activator. A preferred leaving group is phenolsulfonate.

Preferred examples of bleach activators of the above formula include (6-octanoylhexanoyl)oxybenzenesulfonate, (6-nonanoylhexanoyl)oxybenzenesulfonate, (6-decanoylhexanoyl) Oxybenzenesulfonates and mixtures thereof are described in U.S. Patent 4,634,551, referenced above.

嗪型活化剂，在1990，10，30发布的U.S.P.4,966,723中，由Hodge等人公开，在此已列入本文作参考。也见U.S.P.4,548,784，Sanderson，1985，10，8发布，已列入本文参考。它公开了被吸附进入过硼酸钠的酰基己内酰胺，包括苯甲酰基己内酰胺。Another class of useful bleach activators includes benzos

Hazine-type activators are disclosed by Hodge et al. in US Patent 4,966,723, issued October 30, 1990, which is incorporated herein by reference. See also USP 4,548,784, issued Oct. 8, 1985 by Sanderson, incorporated herein by reference. It discloses acyl caprolactams, including benzoyl caprolactams, adsorbed into sodium perborate.

If used, peroxygen bleach will generally comprise from about 2% to 30% by weight of the detergent compositions herein. More preferably, peroxygen bleach will comprise from about 2% to 20% by weight of the composition. Most preferably, peroxygen bleach will be present in an amount of from about 3% to 15% by weight of the compositions herein. If utilized, bleach activators can comprise from about 2% to 10% by weight of the detergent compositions herein. Typically, the activators are used in a molar ratio of bleach to activator in the range of from about 1:1 to 10:1, more preferably from about 15:1 to 5:1.

Other suitable bleaching agents and bleach activators are disclosed in co-pending PCT application WO 98/14300 published on March 25, 1999, entitled "Cyclic amine-containing compounds that provide appearance and smoothness benefits to fabrics washed therewith". Polymeric Laundry Detergent Compositions", filed by Panandiker et al., September 15, 1997. The Panandiker et al. reference is hereby incorporated by reference in its entirety.

Another highly preferred optional ingredient in detergent compositions is a detergent enzyme component. Enzymes may be included in the present detergent compositions for a variety of purposes including removal of protein-based, sugar-based, or triglyceride-based soils from substrates, to prevent the transfer of leached dyes in fabric laundering and to restore fabrics. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Optimum selection is influenced by factors such as pH activity and/or stability, optimum thermal stability, and stability to active detergents, builders, and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

"Detergent enzyme", as used herein, means any enzyme which has a cleaning, stain removal or other beneficial effect in a laundry detergent composition. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases.

Enzymes are typically incorporated into detergent compositions at levels sufficient to provide a "cleaning effective amount". The term "cleaning effective amount" means any amount capable of producing a cleansing, stain-removing, soil-removing, whitening, deodorizing or refreshing effect on a substrate such as fabrics. Typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg of active enzyme, per gram of detergent composition, as is practical in current commercial formulations. Additionally stated, the compositions of the present invention will typically contain from 0.001% to 5%, preferably 0.01% to 1% by weight of commercially available enzyme preparations. Proteases are typically present in such commercial formulations at levels sufficient to provide 0.005 to 0.1 Anson Units (AU) of activity per gram of composition, with higher activity levels being desired in highly concentrated detergent formulations.

Cellulase enzymes useful herein include those described in USP 4,435,307, Barbesgoard et al., 1984, 3, 6 and GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. ^CAREZYME® and ^CELLUZYME® (Novo) are particularly useful. See also WO 9117243, Novo.

The enzyme-containing compositions herein also optionally contain from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6% (by weight) of an enzyme stabilizing system, The enzyme stabilizing system can be any stabilizing system compatible with detergent enzymes. Such systems may be provided intrinsically by the formulator or detergent enzyme manufacturer through other formulation activators, or added separately. Such stabilizing systems may contain, for example, calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acid, and mixtures thereof, which 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 dye transfer inhibiting agents such as polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxide enzymes, and mixtures thereof. These agents typically comprise from about 0.01% to about 10%, preferably from about 0.01% to about 5%, most preferably from about 0.05 to 2%, by weight of the composition.

More specifically, the polyamine N-oxide polymers preferably used herein contain units having the formula: RA _X -P; where P is a polymerizable unit to which NO groups may be attached or NO groups may be Moieties or NO groups forming polymerizable units can be linked to two units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N =; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any mixture thereof, the nitrogen of the NO group can be combined with The linking or NO groups are part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

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

wherein R ₁ , R ₂ , R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or mixtures thereof; x, v and z are 0 or 1; and the nitrogen of the NO group may be attached Or form part of any of the aforementioned groups. The amine oxide units of the polyamine N-oxides have a pKa<10, preferably pKa<7, more preferably pKa<6.

As long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties, any polymer backbone can be used. Examples of suitable polymer backbones are polyethylenes, polyolefins, polyesters, Polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers in which one monomer type is amine N-oxide and the other type is N-oxide. Typical amine N-oxide polymers have a ratio of amine to amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied with appropriate copolymerization or with an appropriate degree of N-oxidation, and the polyamine oxides can be obtained in virtually any degree of polymerization. Typical average molecular weights are in the range of 500-1,000,000; more preferably 1,000-500,000; most preferably 5,000-100,000.

The most preferred polyamine N-oxide for use in the detergent compositions of the present invention is poly(4-vinylpyridine-N-oxide) having an average molecular weight of about 50,000 and a ratio of amine to amine N-oxide of about 1:4. A preferred material of this type may be denoted "PVNO".

More suitable dye transfer formulations can be found in U.S. Patent 5,466,802, issued by Panandiker et al., 1995, Nov. 14, incorporated herein by reference.

F) Preparation of detergent composition

The detergent compositions according to the invention may be in liquid, paste or granular form. Such compositions may be prepared by admixing the essential and optional ingredients in any suitable order and in the required concentrations by any conventional method. The previously described use of mixtures of cyclic amine-based polymers, oligomers or copolymers with hydrophobically modified cellulose-based polymers or oligomers as defined herein is intended as an example for those skilled in the art. Other uses are apparent and may be within the scope of the invention.

Granular compositions, for example, are typically prepared by mixing essential granular ingredients such as surfactants, builders, water, etc. into a slurry, and spray drying the resulting slurry to a low residual moisture level (5-12%) . The remaining dry ingredients, such as granules of the basic mixture of cyclic amine-based polymers, oligomers or copolymers and hydrophobically modified cellulose-based polymers or oligomers, can be mixed with The spray-dried granules were mixed. Liquid ingredients, such as solutions of basic mixtures of cyclic amine-based polymers, oligomers or copolymers with hydrophobically modified cellulose-based polymers or oligomers, enzymes, binders and fragrances, can be sprayed onto the resulting granules Form the final detergent composition. The granular compositions according to the invention can also be in "compacted form", that is to say they can have a relatively higher density than conventional granular detergents, ie from 550 to 950 g/l. In this case, the granular detergent compositions according to the invention will contain lower amounts of "inorganic filler salts" than conventional granular detergents; typical filler salts are alkaline earth metal sulphates and chlorides, typically sulfuric acid Sodium; "compact" detergents generally contain no more than 10% filler salts.

Liquid detergent compositions can be prepared by mixing the essential and optional ingredients thereof in any desired order to provide compositions containing the components in the desired concentrations. The liquid compositions according to the invention may also be in "compacted form", in which case the liquid detergent compositions according to the invention will contain less water than conventional liquid detergents. The addition of the mixture of cyclic amine-based polymers, oligomers or copolymers and hydrophobically modified cellulose-based polymers or oligomers to the liquid detergent or other aqueous compositions of the present invention can be achieved by adding the required cyclic A mixture of amine-based polymers, oligomers or copolymers and hydrophobically modified cellulose-based polymers or oligomers is simply mixed into a liquid solution to accomplish this.

The methods and compositions described above can also be applied to the production of granules for use as one of the components of detergent granules in granular detergent compositions.

G) Washing method of fabric

The present invention also provides a method of laundering fabrics in which the fabric appearance provided by the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulose based polymers or oligomers used herein can be imparted benefit. This method employs contacting the fabrics with an aqueous wash solution formed from an effective amount of the above-described detergent compositions or from the individual components of such compositions. Contacting of the fabrics with the lotion generally occurs under agitated conditions, although the compositions of the present invention may also be used to form non-agitated soaking solutions for fabric cleaning and treatment.

For good cleaning, it is preferred to provide agitation in the washing machine. Washing is preferably followed by drying of the wet fabrics in a conventional laundry dryer. An effective amount of high density liquid or granular detergent compositions is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm, in aqueous washing machine wash liquors.

H) Fabric conditioning and softening

The mixture of the cyclic amine-based polymers, oligomers or copolymers and hydrophobically modified cellulose-based polymers or oligomers described above as a component of the laundry detergent composition of the present invention can also be used in the detergent of the present invention Composition embodiments are used to treat and condition fabrics and textiles in the absence of surfactant and builder ingredients. Thus, for example, during the rinse cycle of a conventional domestic laundry operation, in order to impart the aforementioned desired fabric appearance and smoothness benefits, a fiber containing only cyclic amine-based polymers, oligomers or copolymers and hydrophobically modified fibers may be added. Fabric conditioning compositions of mixtures of vegan-based polymers or oligomers per se, or fabrics containing aqueous solutions of mixtures of cyclic amine-based polymers, oligomers or copolymers with hydrophobically modified cellulose-based polymers or oligomers Conditioning composition.

Other suitable fabric softeners are described in co-pending PCT application WO98/14300 published on March 25, 1999, entitled "Laundry Detergents Containing Cyclic Amine-Based Polymers Providing Appearance and Smoothness Benefits to Laundered Fabrics" Composition", applied by Panandiker et al. 1997.9.15. The text of Panandiker et al. is incorporated by reference above in its entirety.

The compositions of the present invention contain at least about 1%, preferably from about 10%, more preferably from about 20% to about 80%, more preferably to about 60% by weight of one or more fabric softener activators combination.

Example

The following examples illustrate the compositions and methods of the invention and are not meant to limit or otherwise define the scope of the invention.

Example 1

Synthesis of adducts of imidazole and 3-chloro-1,2-epoxypropane (commonly known as epichlorohydrin) (ratio of imidazole: 3-nitrogen-1,2-epoxypropane 1:1)

Preparation of polycation condensates by reaction of imidazole with 3-chloro-1,2-propylene oxide. Imidazole (0.68 mol) and 95 ml of water were added to a round bottom flask equipped with a magnetic stirrer, condenser and thermometer. The solution was heated to 50°C, followed by the dropwise addition of 3-chloro-1,2-propylene oxide (0.68 mol). After the addition of 3-chloro-1,2-propylene oxide was complete, the temperature was raised to 80°C until all the alkylating agent was consumed. The condensation product has a molecular weight of about 12500.

Example 2

Synthesis of adducts of imidazole and 3-chloro-1,2-propylene oxide (ratio of imidazole:3-chloro-1,2-propylene oxide 1.4:1)

Imidazole (0.68 mol) and 95 ml of water were added to a round bottom flask equipped with a magnetic stirrer, condenser and thermometer. After heating the solution to 50°C, 3-chloro-1,2-propylene oxide (0.50 mol) was then added dropwise. After all the 3-chloro-1,2-propylene oxide had been added, the temperature was raised to 80°C until all the alkylating agent was consumed. The condensation product has a molecular weight of about 2000.

Example 3

Synthesis of piperazine, morpholine and 3-chloro-1,2-propylene oxide adducts (ratio 1.8/0.8/2.0)

154.8 g (1.8 mol) of piperazine, 69.6 g (0.8 mol) of morpholine and 220 ml of water were added to a round bottom flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser. After obtaining a clear solution at 40°C, the solution was heated to 55-65°C. Under vigorous stirring, 185g (2mol) of 3-chloro-1,2-epoxy was added at such a rate that the temperature did not exceed 80°C propane. After all the 3-chloro-1,2-propylene oxide had been added, the reaction mixture was heated to 80°C until all the alkylating agent was consumed (negative Preussmann test after 4 hours). 108.8 g (0.68 mol) of 25% NaOH and 40 g of water were added and the reaction mixture was stirred at 85° C. for a further 1 hour. A further 47 g of water were then added and the mixture was allowed to cool to room temperature.

Example 4

Synthesis of piperazine/morpholine/3-chloro-1,2-propylene oxide adduct (ratio 1.8/0.8/2.0)

154.8 g (1.8 mol) of piperazine, 69.6 g (0.8 mol) of morpholine and 220 ml of water were added to a round bottom flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser. After obtaining a clear solution at 40°C, heat the solution to 55-65°C, and add 185g (2mol) of 3-chloro-1,2-epoxy at such a rate that the temperature does not exceed 80°C under vigorous stirring propane. After all the 3-chloro-1,2-propylene oxide had been added, the reaction mixture was heated to 80° C. until all the alkylating agent was consumed (negative Preussmann test after 4 hours). 108.8 g (0.68 mol) of 25% NaOH and 40 g of water were added and the reaction mixture was stirred at 85° C. for a further 1 hour. A further 47 g of water were then added and the mixture was allowed to cool to room temperature.

Example 5

100% oxidized piperazine/morpholine/3-chloro-1,2-propylene oxide adduct from example 4

233.6 g (equivalent to 1,292 moles of oxidizable nitrogen atoms) of material from Example 4 above were mixed with 22.1 g (0.276 moles) of 50% NaOH and heated to 55-65°C. At this temperature, 102.4 g (1,421 mol) H ₂ O ₂ (47.2%) were added dropwise within 3.5 hours. After the addition was complete, the reaction mixture was maintained at the same temperature for an additional 3 hours, then stirred at room temperature overnight. Pt/C _was added to destroy unreacted _H2O2 , and the solution was filtered.

The characteristics of the reaction products are as follows:

Water content 58%

pH 5.6

Chloride content 1.593mmol/g

Example 6

Synthesis of imidazole/piperazine/3-chloro-1,2-propylene oxide adduct, ratio 1.0/3.0/4.0

68.8g (1.0mol) of imidazole and 260.6g (3.0mol) of piperazine were dissolved in 700.2g of water, and 370g (4.0mol) of 3-chloro-1,2-propylene oxide was added dropwise at 50-60°C. After the addition was complete, the reaction mixture was stirred for an additional 5 hours at 80°C.

Example 7

100% oxidized imidazole/piperazine/3-chloro-1,2-propylene oxide adduct from Example 6

80.7 g (1.12 _mol ) of a 47.2% _H2O2 solution in water were added to 237 g of the product from Example 6 above (corresponding to 1,022 mol of oxidizable nitrogen atoms) at 40° C. within 5 hours. Thereafter, the mixture was heated to 50-60 °C until the theoretical amount _{of H2O2} was consumed. _{Unreacted H2O2} was destroyed with Pt/C, and the solution was filtered.

The characteristics of the reaction products are as follows:

Water content: 58.6%

pH: 2.86

Chloride content: 3.694mmol/g

Mn(GPC): 340

Mw(GPC): 940

Mn/Mw; 2.8+/-0.1

Example 8

Synthesis of Hydrophobic Modified CMC Materials

Carboxylation of cellulose to produce CMC is a method well known to those skilled in the art. One method of producing the modified CMC materials of the present invention is to incorporate the material, or several materials, that are substituted during the CMC manufacturing process. An example of this approach is as follows. This same method can be used with the other substituted materials described here by substituting the substituted material of interest, or several materials, such as hexadecyl chloride for hexyl chloride. The amount of material that should be added to the CMC fabrication process to achieve the desired degree of substitution is readily determined by one skilled in the art as follows

Examples are calculated.

Example 9

Synthesis of CMC Hexyl Ether

This example illustrates the preparation of hydrophobically modified carboxymethylcellulose and is representative of the preparation of all cellulose ether derivatives of the present invention.

Cellulose (20 g), sodium hydroxide (10 g), water (30 g) and ethanol (150 g) were charged into a 500 ml glass reactor. The resulting alkaline cellulose was stirred at 25°C for 45 minutes. Monochloroacetic acid (15 g) and hexyl chloride (1 g) were then added during which time the temperature was raised to 95°C and held at 95°C for 150 minutes. The reaction was cooled to 70°C and then to 25°C. Neutralization is accomplished by adding sufficient nitric/acetic acid to bring the slurry to a pH between 8-9. The slurry was filtered to obtain hexyl ether of CMC.

Example 10

Cellulosic polymers used in test detergent compositions

The characteristics of representative modified cellulosic polymers for use in the liquid and granular detergent compositions described below are listed in Tables 10A and 10B. The general polymer parameters are common to all polymers, while the specific chemical structure of the material tested is listed under the specific polymer parameters.

Table 10A

Common Polymer Parameters

Molecular parameters Description Polymer Backbone Carboxymethyl Cellulose Degree of Carboxvmethvlation DS _RC =0.3-2.0; preferred DS _RC =0.5-0.70 Distribution of carboxymethyl groups Even and random distribution of carboxymethyl groups along the backbone Molecular Weight Mw: 5,000-2,000000. Preferred: Intermediate (about 250,000g/mol) Type of modification Ether modification (except carboxymethylation). mixed cellulose ethers Modification level DS _RH = about 0.001 to about 0.1

Form 10B

Specialty Polymer Parameters

ID Polymer Modification Type ^*** Chemical Type ^* A Hexyl CMC Hexyl ether Chlorohexane added to CMC manufacturing process ^* B Decyl CMC Decyl ether Chlorodecane added to CMC manufacturing process ^** C C ₁₂ -C ₁₃ Alkoxy C ₁₂ -C ₁₃ Alkoxy C 12 -C ₁₃ Alkyl Glyceryl Ether added to CMC to produce _-2 -hydroxypropyl CMC -2-hydroxypropyl ether ^* D Hexadecyl CMC Cetyl ether Chlorohexadecane added to the CMC manufacturing process ^* E CMC's 3-trimethylammonium-2-3-trimethylammonium-2-hydroxyl is added to the 2,3-ring of the chloride salt range of CMC to make perhydroxypropyl ether chloride salt of propyl ether Oxypropyltrimethylammonium chloride ^* [-(C(O)-CH(C ₁₆ H ₃₃ ) of F CMC is added to CMC to produce C(O)CH ₂ (C ₁₆ H ₃₃ )] ester or 1 of hexadecylethylene CMC, 3-Dioxy-2-hexadecanone dimer alkyl octadecyl ester

CMC = carboxymethyl cellulose

^* Manufactured by Metsa Specialty Chemicals,

^** Prepared by Akzo

^*** The DS _RH for these materials is in the range of about 0.001 to about 0.1.

Example 11

The following are ideal chemical structures of some of the cyclic amine-based polymers, oligomers or copolymers of the present invention. Side reactions expected to occur during condensation are not shown.

Table 11

Example 12

Preparation of Granular Detergent Test Compositions

Several heavy duty granular detergent compositions have been prepared comprising mixtures of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulose based polymers or oligomers. These granular detergent compositions all have the following basic formula:

Table 12

Component Weight % C ₁₂ linear alkylbenzene sulfonate 9.31 C _14-15 alkyl ether (0.35 EO) sulfate 12.74 Zeolite Booster 27.79 Sodium carbonate 27.31 PEG 4000 1.60 Dispersant 2.26 C _12-13 fatty alcohol ethoxylate (9EO) 1.5 Sodium perborate 1.03 Soil Release Polymer 0.41 Enzyme 0.59 Cyclic amine-based polymer or oligomer 3.0 Hydrophobically modified cellulose-based polymer or oligomer 1.0 Fragrance, Brightener, Foam Inhibitor, Other Minor Ingredients, Balancing Moisture, Sulfates 100%

Example 13

Preparation of Liquid Detergent Test Compositions

Several heavy duty liquid detergent compositions have been prepared containing mixtures of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulose based polymers or oligomers. These liquid detergent compositions all have the following basic formulations:

Table 13

Component Weight % C _12-15 alkyl ether (2.5) sulfate 38 C ₁₂ Glucamide 6.86 Citric acid 4.75 C _12-14 fatty acids 2.00 Enzyme 1.02 MEA 1.0 Propylene Glycol 0.36 Borax 6.58 Dispersant 1.48 Sodium toluenesulfonate 6.25 Cyclic amine-based polymer or oligomer 1.0 Hydrophobically modified cellulose-based polymer or oligomer 0.1 Dyes, fragrances, brighteners, preservatives, foam suppressors, its balance it minor ingredients, water 100%

Example 14

Preparation of Granular Detergent Test Compositions

Several granular detergent compositions have been prepared containing mixtures of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulose based polymers or oligomers. These granular detergent compositions all have the following basic formula:

Table 14

Example comparison Component weight % weight % Sodium C ₁₂ linear alkylbenzene sulfonate 9.40 9.40 Sodium C _14-15 alkylsulfonate 11.26 11.26 Zeolite Booster 27.79 27.79 Sodium Carbonate 27.31 27.31 PEG 4000 1.60 1.60 Dispersant, sodium polyacrylate 2.26 2.26 C _12-13 Alkyl Ethoxylate (E9) 1.5 1.5 Sodium perborate 1.03 1.03 Cyclic amine-based polymer or oligomer 0.8 0 Hydrophobically modified cellulose-based polymer or oligomer 0.3 0 Other Additional Ingredients Balance Balance 100% 100%

Example 15

Detergent agglomerates useful as granular components in detergent compositions were prepared according to the following formulations and ranges. The particles can be produced by agglomeration methods known to those skilled in the art, some of which are described in this application.

Example 15A Example 15B Component wt% wt% Cyclic amine-based polymer or oligomer 2-7 8-10 Hydrophobically modified cellulose-based polymer or oligomer 20-70 80-90 Zeolite Booster 0-70 0 Dispersant/Binder ¹ 2-6 0 water and other balance                                                                                                                

1: The dispersant is Na Polyacrylate 4500 (Sodium Polyacrylate 4500), Polyethylene Glycol (Polyethylene Glycol) or a mixture of the two.

Claims (17)

1. detergent composition is characterized by and contains:

A) by weight, 1% to 80% be selected from nonionic, negatively charged ion, positively charged ion, both sexes, zwitterionics and composition thereof; With

B) by weight, at least 0.01% and no more than 50% cyclic amine based polymer, the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer, the hydrophobically modified cellulose polymer compound is to cyclic amine based polymer, the ratio of oligopolymer or copolymer material is in 1000: 1 to 1: 1000 scope, and described hydrophobically modified cellulose-based polymer or oligopolymer are following general formulas:

Wherein each R is selected from R ₂, R _CAnd

Wherein:

-each R ₂Be selected from H respectively, and C ₁-C ₄Alkyl;

-each R _CBe

Wherein each Z is selected from M, R respectively ₂, R _CAnd R _H

-each R _HBe selected from C respectively ₅-C ₂₀Alkyl, C ₅-C ₇Cycloalkyl, C ₇-C ₂₀Alkylaryl, C ₇-C ₂₀Arylalkyl, the alkyl of replacement, hydroxyalkyl, C ₁-C ₂₀Alkoxyl group-2-hydroxyalkyl, C ₇-C ₂₀Alkyl-aryloxy-2-hydroxyalkyl, (R ₄) ₂The N-alkyl, (R ₄) ₂The N-2-hydroxyalkyl, (R ₄) ₃The N-alkyl, (R ₄) ₃The N-2-hydroxyalkyl, C ₆-C ₁₂Aryloxy-2-hydroxyalkyl,

With

-each R ₄Be selected from H respectively, C ₁-C ₂₀Alkyl, C ₅-C ₇Cycloalkyl, C ₇-C ₂₀Alkylaryl, C ₇-C ₂₀Arylalkyl, aminoalkyl group, alkylamino alkyl, dialkyl aminoalkyl, piperidino-(1-position only) alkyl, morpholinyl alkyl, cycloalkyl amino alkyl and hydroxyalkyl;

-each R ₅Be selected from H respectively, C ₁-C ₂₀Alkyl, C ₅-C ₇Cycloalkyl, C ₇-C ₂₀Alkylaryl, C ₇-C ₂₀Arylalkyl, the alkyl of replacement, hydroxyalkyl, (R ₄) ₂N-alkyl and (R ₄) ₃The N-alkyl;

Wherein:

M is selected from Na, K, the suitable positively charged ion of 1/2Ca and 1/2Mg;

Each x is from 0 to 5;

Each y is from 1 to 5; With

Condition is:

-for radicals R _HSubstitution value be between 0.0005 and 0.1;

-be the radicals R of H or M for Z wherein _CSubstitution value be between 0.2 and 2.0;

If-any R _HHave a positive charge, it will be by a suitable anion balance so; With

-two R on identical nitrogen ₄Can form the ring texture that is selected from the group of forming by piperidines and morpholine together.

2. the detergent composition of claim 1 is wherein for radicals R _HSubstitution value be between 0.005 and 0.05 and/or for Z wherein to be the radicals R of H or M _CSubstitution value be between 0.3 and 1.0.

3. the detergent composition of claim 2 is wherein for radicals R _HSubstitution value be between 0.01 and 0.05; And/or be the radicals R of H or M for Z wherein _CSubstitution value be between 0.4 and 0.7.

4. the detergent composition of claim 1, wherein said cyclic amine based polymer, the content of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer by weight, is at least 0.1% and/or no more than 25.0%

5. the detergent composition of claim 4, wherein said cyclic amine based polymer, the content of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer by weight, is at least 0.5% and/or no more than 5.0%.

The detergent composition of claim 1-5 each, cyclic amine based polymer wherein, oligopolymer or multipolymer are following general formulas:

Wherein:

Each T is selected from H, C respectively ₁-C ₁₂Alkyl, the alkyl of replacement, C ₇-C ₁₂Alkylaryl ,-(CH ₂) _hCOOM ,-(CH ₂) _hSO ₃M, CH ₂CH (OH) SO ₃M ,-(CH ₂) _hOSO ₃M,

With-R ₂Q;

-wherein W is to be feature with at least one ring texture that is selected from following group:

Except at least one ring texture, W also can contain aliphatic or a replace aliphatic portion, and its formula is:

-each B is selected from C respectively ₁-C ₁₂Alkylidene group, C ₁-C ₁₂The alkylidene group that replaces, C ₃-C ₁₂Alkenylene, C ₈-C ₁₂The dialkyl group arylidene, C ₈-C ₁₂Dialkyl group arylidene two bases and-(R ₅O) _nR ₅-;

-each D is respectively C ₂-C ₆Alkylidene group;

-each Q is selected from hydroxyl, C respectively ₁-C ₁₈Alkoxyl group, C ₂-C ₁₈The hydroxy alkoxy base, amino, C ₁-C ₁₈Alkylamino, dialkyl amido: trialkyl amino, heterocyclic mono amino and diamino;

-each R ₁Be selected from H respectively, C ₁-C ₈Alkyl and C ₁-C ₈Hydroxyalkyl;

-each R ₂Be selected from C respectively ₁-C ₁₂Alkylidene group, C ₁-C ₁₂Alkenylene ,-CH ₂-CH (OR ₁)-CH ₂-, C ₈-C ₁₂Alkyl arylene, C ₄-C ₁₂Alkyl sub-dihydroxy, many (C ₂-C ₄Alkylene oxide group) alkylidene group, H ₂CH (OH) CH ₂OR ₂OCH ₂CH (OH) CH ₂-, and C ₃-C ₁₂Hydrocarbyl portion;

Condition is to work as R ₂Be C ₃-C ₁₂During hydrocarbyl portion, hydrocarbyl portion can contain from about 2 chain portions to about 4 formulas:

-each R ₃Be selected from H respectively, O, R ₂, C ₁-C ₂₀Hydroxyalkyl, C ₁-C ₂₀Alkyl, the alkyl of replacement, C ₆-C ₁₁Aryl, the aryl of replacement, C ₇-C ₁₁Alkylaryl, C ₁-C ₂₀Aminoalkyl group ,-(CH ₂) _hCOOM ,-(CH ₂) _hSO ₃M, CH ₂CH (OH) SO ₃M ,-(CH ₂) _hOSO ₃M,

-each R ₄Be selected from H respectively, C ₁-C ₂₂Alkyl, C ₁-C ₂₂Hydroxyalkyl, aryl and C ₇-C ₂₂Alkylaryl;

-each R ₅Be selected from C respectively ₂-C ₈Alkylidene group, C ₂-C ₈The alkylidene group that alkyl replaces; With

A is compatible monovalence or two valencys or multivalent anions;

M is compatible positively charged ion;

The necessary number of b=balancing charge;

Each x is respectively from 3 to 1000;

Each c is respectively 0 or 1;

Each h is respectively from 1 to 8;

Each q is respectively from 0 to 6;

Each n is respectively from 1 to 20;

Each r is respectively from 0 to 20; With

Each t is respectively from 0 to 1.

The detergent composition of claim 1-5 each, each R wherein ₁Be that H and at least one W are selected from following group:

The detergent composition of claim 1-5 each, each R wherein ₁Be that H and at least one W are selected from following group:

The detergent composition of claim 1-5 each, each R wherein ₁Be that H and at least one W are selected from following group:

With

The detergent composition of claim 1-5 each, each R wherein _HBe selected from C respectively ₅-C ₂₀Alkyl, C ₅-C ₇Cycloalkyl, C ₇-C ₂₀Alkylaryl, C ₇-C ₂₀Arylalkyl, the alkyl of replacement, hydroxyalkyl, C ₁-C ₂₀Alkoxyl group-2-hydroxyalkyl, C ₇-C ₂₀Alkyl-aryloxy-2-hydroxyalkyl, (R ₄) ₂The N-alkyl, (R ₄) ₂The N-2-hydroxyalkyl, (R ₄) ₃The N-alkyl, (R ₄) ₃N-2-hydroxyalkyl, and C ₆-C ₁₂Aryloxy-2-hydroxyalkyl.

11. composition is added in laundry, it is characterized by:

A) by weight, 1% to 80% water; With

B) by weight, 0.01% to 5.0% cyclic amine based polymer, the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer, the hydrophobically modified cellulose polymer compound is to cyclic amine based polymer, the ratio of oligopolymer or copolymer material is in 1000: 1 to 1: 1000 scope, and described hydrophobically modified cellulose-based polymer or oligopolymer are following general formulas:

Wherein each R is selected from R ₂, R _CAnd

Wherein:

-each R ₂Be selected from H respectively, and C ₁-C ₄Alkyl;

-each R _CBe

Wherein each Z is selected from M, R respectively ₂, R _CAnd R _H

-each R _HBe selected from C respectively ₅-C ₂₀Alkyl, C ₅-C ₇Cycloalkyl, C ₇-C ₂₀Alkylaryl, C ₇-C ₂₀Arylalkyl, the alkyl of replacement, hydroxyalkyl, C ₁-C ₂₀Alkoxyl group-2-hydroxyalkyl, C ₇-C ₂₀Alkyl-aryloxy-2-hydroxyalkyl, (R ₄) ₂The N-alkyl, (R ₄) ₂The N-2-hydroxyalkyl, (R ₄) ₃The N-alkyl, (R ₄) ₃The N-2-hydroxyalkyl, C ₆-C ₁₂Aryloxy-2-hydroxyalkyl,

With

-each R ₄Be selected from H respectively, C ₁-C ₂₀Alkyl, C ₅-C ₇Cycloalkyl, C ₇-C ₂₀Alkylaryl, C ₇-C ₂₀Arylalkyl, aminoalkyl group, alkylamino alkyl, dialkyl aminoalkyl, piperidino-(1-position only) alkyl, morpholinyl alkyl, cycloalkyl amino alkyl and hydroxyalkyl;

-each R ₅Be selected from H respectively, C ₁-C ₂₀Alkyl, C ₅-C ₇Cycloalkyl, C ₇-C ₂₀Alkylaryl, C ₇-C ₂₀Arylalkyl, the alkyl of replacement, hydroxyalkyl, (R ₄) ₂N-alkyl and (R ₄) ₃The N-alkyl;

Wherein:

M is selected from Na, K, the suitable positively charged ion of 1/2Ca and 1/2Mg;

Each x is from 0 to 5;

Each y is from 1 to 5; With

Condition is:

-for radicals R _HSubstitution value be between 0.0005 and 0.1;

-be the radicals R of H or M for Z wherein _CSubstitution value be between 0.2 and 2.0;

If-any R _HHave a positive charge, it will be by a suitable anion balance so; With

-two R on identical nitrogen ₄Can form the ring texture that is selected from the group of forming by piperidines and morpholine together.

12. composition is added in the laundry of claim 11, wherein said cyclic amine based polymer, and the content of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer is 0.1% to 4.0% by weight.

13. composition is added in the laundry of claim 11, wherein for radicals R _HSubstitution value be between 0.005 and 0.05 and/or for Z wherein to be the radicals R of H or M _cSubstitution value be between 0.3 and 1.0.

14. composition is added in the laundry of claim 13, wherein for radicals R _HSubstitution value be between 0.01 and 0.05; And/or be the radicals R of H or M for Z wherein _CSubstitution value be between 0.4 and 0.7.

15. each composition of claim 1-5 and 11-14, wherein, the further feature of composition is inorganic peroxy bleaching compounds and bleach-activating agent.

16. the composition of claim 15, wherein said inorganic peroxy bleaching compounds is selected from an alkali metal salt of peroxyboric acid and percarbonic acid and composition thereof, and/or described bleach-activating agent is a nonanoly acyloxy benzene sulfonate.

17. each composition of claim 1-5 and 11-14, wherein, the further feature of composition is a cellulase.