CN1352679A - Laundry detergent compositions with fabric enhancing component - Google Patents

Abstract

Detergent compositions and fabric conditioning compositions which include from about 0.01 % to about 5.0 %, by weight of a fabric enhancing component selected from the group consisting of cyclic amine based polymers, oligomers or copolymers, hydrophobically modified cellulosic based polymers or oligomers, and mixtures thereof. A container for such compositions comprising fabric enhancing compositions is also provided.

Description

Laundry detergent composition with fabric enhancing component

  Technical field

The present invention relates to compositions in liquid or granular form for laundry applications containing certain fabric enhancing components which may be, for example, cyclic amine based polymers, oligomers or copolymer materials, hydrophobically modified Carboxymethylcellulose and its mixtures. Additionally, a container suitable for such compositions is provided.

Background of the invention

It is well known that alternating cycles of applying and laundering fabrics or textiles, such as abrading clothing and apparel, will inevitably have an unavoidable detrimental effect on the appearance and integrity of the fabrics and textiles so applied and laundered. Overtime wear of fabrics and textiles is nothing but wear and tear. Laundering fabrics and textiles must remove the dust and dirt that accumulates in and on them from daily use. However, the laundering operation itself, over many cycles, can enhance and promote the deterioration of the integrity and appearance of such fabrics and textiles.

Deterioration of fabric integrity and appearance can manifest itself in several ways. Due to the mechanical action of washing, staple fibers are released from the woven or knitted fabric/textile structure. These detached fibers can form lint, filaments or globules which are visible on the surface of the fabric and detract from the novel appearance of the fabric. In addition, repeated laundering of fabrics and textiles, especially with laundry products containing bleach, can remove dyes from fabrics and textiles, and due to weakening of color strength and, in many cases, changes in shade or color shade, Creates a faded, worn look.

As previously stated, there is clearly a further need to find materials that can be added to laundry detergent products, which themselves bind to the fibers of fabrics and textiles washed with such detergent products, thereby reducing or deteriorating the appearance of washed fabrics/textiles. tendency to be minimized. Of course, any such detergent product additives should be able to benefit the appearance and integrity of the fabrics without unduly interfering with the laundry detergent's ability to perform its fabric cleaning action.

Furthermore, there is a need for a container suitable for this product. The container should not only hold the composition, it should also communicate the benefits of this new product to the consumer.

Summary of Invention

The present invention is directed to a detergent composition comprising

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

b) from about 0.01% to about 5.0%, preferably from about 0.1% to about 4.0%, by weight, of a fabric reinforcing component selected from cyclic amine-based polymers, oligomers or copolymers, hydrophobically modified cellulose-based polymers Or oligomers, and mixtures thereof.

The detergent composition is housed in an inner box of a container comprising an outer surface with a composition instruction on the outer surface consisting of phrases selected from the group consisting of: Helps garments appear sound, before they fall off Helps stop fraying, maintains the appearance of garments, helps prevent garments from wearing out, enhances washing for better looking garments, strengthens threads to make garments look better, helps prevent garments from looking old, helps prevent washing in the washing machine which can make garments look better Old wear and tear, Helps keep clothes from aging, Helps clothes come out of the washing machine as good as they went in, Helps preserve the fabric integrity of clothes, Strengthens inner-out threads in better clothes, Extends clothes Lifespan, like a vitamin for clothes, acts like an anti-aging product for clothes, like "calcium" for clothes, like a supplement for clothes, clothes look better after 10 washes than if you wash them with other detergents Even better, the reinforcing threads make the garment sound, helping to keep the garment from showing signs of wear before its lifespan, like stopping the life of your clothes and keeping them looking good.

其中：每个T独立选自H，C₁-C₁₂烷基，取代的烷基，C₇-C₁₂烷芳基，-(CH₂)_hCOOM，-(CH₂)_hSO₃M，CH₂CH(OH)SO₃M，-(CH₂)_hOSO₃M，-其中W包含至少一个选自如下基团的环状构造：

除了至少一个环状构造外，W可以还含有一个脂族或取代脂族部分，该部分的通式结构为：

-每个B独立地为C₁-C₁₂亚烷基，C₁-C₁₂取代的亚烷基，C₃-C₁₂亚Cyclic amine based polymer, oligomer or copolymer materials suitable for application in laundry operations and providing desirable fabric appearance and integrity benefits are represented by the following general formula:

wherein: each T is independently selected from H, C ₁ -C ₁₂ alkyl, substituted alkyl, C ₇ -C ₁₂ alkaryl, -(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 comprises at least one cyclic configuration selected from the group consisting of:

In addition to at least one cyclic configuration, W may also contain an aliphatic or substituted aliphatic moiety, the general structure of which is:

- Each B is independently C ₁ -C ₁₂ alkylene, C ₁ -C ₁₂ substituted alkylene, C ₃ -C ₁₂ alkylene

alkenyl, C ₈ -C ₁₂ dialkylarylene, C ₈ -C ₁₂ dialkylarylene diyl, and

-(R ₅ O) _n R ₅ -; -each D is independently C ₂ -C ₆ alkylene; -each Q is independently selected from hydroxyl, C ₁ -C ₁₈ alkoxy, C ₂ -C ₁₈ hydroxyalkoxy, ammonia

group, C ₁ -C ₁₈ alkylamino, dialkylamino, trialkylamino, heterocyclic 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 alkarylene, C ₄ -C ₁₂ dihydroxyalkylene, poly

-每个R₃独立地选自H，O，R₂，C₁-C₂₀羟基烷基，C₁-C₂₀烷基，取(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 moieties; provided that when R ₂ is In the case of a _C3 - _C12 hydrocarbyl moiety, the hydrocarbyl moiety contains from about 2 to about 4 branched moieties of the general structure:

- each R ₃ is independently selected from H, O, R ₂ , C ₁ -C ₂₀ hydroxyalkyl, C ₁ -C ₂₀ alkyl, wherein

Substituted alkyl, C ₆ -C ₁₁ aryl, substituted aryl, C ₇ -C ₁₁ alkaryl, C ₁ -C ₂₀

Aminoalkyl, -( _CH2 ) _hCOOM , -( _{CH2 ) hSO3M} , _CH2CH (OH) _SO3M , - _{( CH2} ) _hOSO3M , - each R ₄ is independently selected from H, C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ hydroxyalkyl, aryl and

C ₇ -C ₂₂ alkaryl; - 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 polyvalent anion;

M is a compatible anion;

b = the number necessary to balance the charge;

each x is independently from 3 to about 1000;

each C is independently 0 or 1;

each h is independently from about 1 to about 8;

each q is independently 0 to about 6;

each n is independently from 1 to about 20;

each r is independently 0 to about 20; and

Each t is independently 0-1.

其中每个R选自R₂，R_c，和

其中：-每个R₂独立地选自H和C₁-C₄烷基；-每个R_c是

Cellulose-based polymeric or oligomeric materials suitable for use in laundry operations and providing desired fabric appearance and integrity benefits are represented by the general formula:

wherein each R is selected from R ₂ , R _c , and

wherein: - 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 alkaryl,

C ₇ -C ₂₀ aralkyl, substituted alkyl, hydroxyalkyl, C ₁ -C ₂₀ alkoxy-2-hydroxy

Alkyl, 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

Alkoxy-2-hydroxyalkyl, - each R ₄ is independently selected from H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkaryl

radical, C ₇ -C ₂₀ aralkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl,

piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl; -each R is _{independently} selected from H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkane base, C ₇ -C ₂₀ alkaryl

radical, C ₇ -C ₂₀ aralkyl, substituted alkyl, hydroxyalkyl, (R ₄ ) ₂ N-alkyl, and (R ₄ ) ₃

N-Alkyl; where:

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

each x is from 0 to about 5;

Each g is from about 1 to about 5; and with the proviso that: the degree of substitution of the -R _H group is about 0.001-0.1, preferably about 0.005-0.05 and most preferably 0.01-0.05; the degree of substitution of the -R group is H or In the case of M is about 0.2 to 2.0, preferably about 0.3 to 1.0, and most preferably about 0.4-0.7; - if any R _H has a positive charge, it will be balanced by a suitable anion; and - the same The two _R groups on the nitrogen atom can together form 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 wash solution additives either in granular or liquid form. Additionally, they can be incorporated into granular detergents, dissolved in liquid detergent compositions or added to fabric softening compositions.

The laundry detergent compositions of the present invention contain from about 1% to 80% by weight of detersive surfactants, from about 0.01% to 80% by weight of organic or inorganic detergency builders and from about 0.01% to 5% by weight of the fabric reinforcing components of the present invention point. The detersive surfactants and detergency builders can be any of those useful in conventional laundry detergent products.

The aqueous solution of the fabric reinforcing component of the object of the present invention contains 0.01%-80% by weight of cyclic amine-based polymers, oligomers or copolymers, hydrophobically modified cellulose-based polymers or copolymers and mixtures thereof dissolved in water 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 an aqueous wash solution or treatment solution formed from an effective amount of a detergent composition as described herein, or from such alone formed by some of the components of the composition. Washing fabrics and textiles in such wash solutions, followed by rinsing and drying, imparts fabric appearance benefits to the fabrics and textiles so treated. Such benefits may include improved overall appearance, reduced pilling/fuzz, resistance to fading, improved abrasion resistance, and/or enhanced softness.

A detailed description of the invention

As noted, when fabrics or textiles are laundered in a wash solution containing the fabric enhancing component of the present invention, the appearance and integrity of the fabric is enhanced. The fabric strengthening components, i.e. cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulose based polymers or oligomers can be added to the wash solution by mixing them into detergent compositions, fabric softeners or By adding separately to the wash solution.

The cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulose based polymers or oligomers are described herein primarily as liquid or granular detergent additives, but the invention is not meant to be so limited. The detergent container of the present invention also includes any suitable type of detergent composition container. Non-limiting examples of such containers include boxes, bags, and bottles, which can be fabricated from paper, plastic, cardboard, laminate, and the like. Those skilled in the art will know what materials of construction and material types are suitable for the detergent compositions of the present invention.

Cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulose based polymers or oligomers, components of detergent compositions, optional components for these compositions and methods of using these compositions Details below. All percentages are by weight unless otherwise indicated.

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

The compositions of the present invention may contain one or more cyclic amine based polymers, oligomers or copolymers, these materials have been found to be useful for fabrics and textiles washed in aqueous wash liquors consisting of detergent compositions containing these materials Brings many cosmetic benefits. Such fabric appearance benefits may include, for example, improved overall laundered fabric appearance, reduced pill and fuzz generation, resistance to fading, improved abrasion resistance, and the like. The cyclic amine-based fabric treatment materials used in the compositions and methods herein can provide such fabric appearance benefits with acceptably minimal loss or loss of cleaning performance provided by laundry detergent compositions into which such materials are incorporated. no loss.

The cyclic amine-based polymer, oligomer or copolymer component of the compositions of the present invention may comprise mixtures of such cyclic amine-based materials. For example, a mixture of piperidine and epihalohydrin condensates can be mixed with a mixture of morpholine and epihalohydrin condensates to obtain the desired fabric treatment results. In addition, the molecular weight of the cyclic amine-based fabric treatment material was variable in the mixture, as shown in the examples below.

It will be apparent to those skilled in the art that oligomers are molecules made up of only a few monomeric units, whereas polymers contain a considerable number of monomeric units. For 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. 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 polymerized from mixtures of primary cyclic amine-based monomers, such as piperidine, and secondary cyclic amine-based monomers, such as morpholine.

The fabric reinforcing component of the detergent composition comprising cyclic amine-based polymers, oligomers or copolymers, hydrophobically modified cellulose-based polymers or oligomers and mixtures thereof generally constitutes about 0.01% by weight of the detergent composition % - about 5%. More preferably, the fabric enhancing component will comprise from about 0.1% to about 4%, most preferably from about 0.75% to about 3%, by weight of the detergent compositions. However, as discussed above, when used as a wash solution additive, i.e. when the fabric enhancing material is not added to the detergent composition, the fabric enhancing component may be present in a concentration of from about 0.1% to about 1% by weight of the additive material. 80%.

更优选的提供织物外观和完整的好处的化合物是这样一些：-其中每个R₁是H；和-至少一个W是选自如下的基团：和最优选的提供织物外观和完整好处的化合物是这样一些：-其中R₁是H；和-至少一个W是选自如下的基团： Cyclic amine based polymer, oligomer or copolymer materials suitable for use in laundry operations and providing desired fabric appearance and integrity benefits can be represented by the general formulas given in the Summary of the Invention. Preferred compounds belonging to this general formula include compounds: - wherein _each R is H; and - at least one W is a group selected from:

More preferred compounds that provide fabric appearance and integrity benefits are those: - wherein each _R is H; and - at least one W is a group selected from: And the most preferred compounds that provide fabric appearance and integrity benefits are those: -wherein _R is H; and -at least one W is a group selected from:

Preferred compounds for use 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, amides of α,β-unsaturated carboxylic acids, anhydrides of α,β-unsaturated carboxylic acids, dicarboxylic or polycarboxylic acids, esters of di- or polycarboxylic acids, amides of di- or polycarboxylic acids, di- or polycarboxylic acids Acid anhydride, allyl halide, chloroformate, chloroacetate, derivatives of chloroformate, derivatives of chloroacetate, epihalohydrin, glycerol dichlorohydrin, bis-(halohydrin ), polyether dihalide-compounds, phosgene, polyhalides, functionalized glycidyl esters and mixtures thereof. In addition, _R can also comprise polyether diamines, alkylene diamines, polyalkylene polyamines, alcohols, alkylene glycols and polyalkylene glycols with α, β-unsaturated carboxylic acids, Reaction products formed by the reaction of esters of α,β-unsaturated carboxylic acids, amides of α,β-unsaturated carboxylic acids and anhydrides of α,β-unsaturated carboxylic acids, provided that these reaction products contain at least two double bonds, Two carboxyl groups, two amide groups or two ester groups.

Additional preferred cyclic amine-based polymer, oligomer or copolymer materials for use in the present invention include those selected from the group consisting of piperazine, piperidine, epichlorohydrin, epichlorohydrin benzyl quaternary ammonium compounds, epichlorohydrin methyl quaternary ammonium Compounds, adducts of two or more compositions of morpholines and mixtures thereof.

These cyclic amine-based polymers can be linear or branched. A particular type of branching can be introduced with multifunctional crosslinking agents. An example of one such polymer is listed below.

B) Hydrophobically modified cellulose-based polymers or oligomers

The compositions of the present invention may contain one or several cellulose-based polymers or oligomers. Such materials have been found to impart a number of cosmetic benefits to fabrics and textiles washed in aqueous wash solutions formed from detergent compositions containing such cellulose-based fabric treatment materials. These fabric appearance benefits can include, for example, improved overall appearance of laundered fabrics, reduced pill and fuzz formation, resistance to fading, improved abrasion resistance, and the like. The cellulose-based fabric treatment materials used in the compositions and methods herein can provide such fabric appearance benefits with only acceptably minimal cleaning performance provided by laundry detergent compositions incorporating such materials. Loss or no loss.

It will be apparent to those skilled in the art that oligomers are molecules made up of only a few monomeric units, whereas polymers contain very many monomeric units. For purposes of this invention, an oligomer is defined as having an average molecular weight of less than about 1,000, and a polymer is a molecule having an average molecular weight of greater than about 1,000. A type of cellulose-based polymer or oligomer suitable for use herein 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.

The cellulose-based fabric treatment components of the detergent compositions herein will generally comprise from about 0.1% to about 5% by weight of the detergent compositions. More preferably, such cellulose-based fabric treatment materials will constitute from about 0.5% to about 4%, most preferably from about 0.75% to about 3%, by weight of the detergent compositions. However, as discussed above, when used as a wash solution 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 constitute from 0.1% to 80% by weight of the additive material. %.

其中每个R选自R₂，R_c，和

其中：-每个R₂独立地选自H和C₁-C₄烷基；-每个R₂是 A suitable group of cellulosic based polymeric or oligomeric materials for use herein is represented by the formula:

wherein each R is selected from R ₂ , R _c , and

wherein: - each R ₂ is independently selected from H and C ₁ -C ₄ alkyl; - each R ₂ 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 alkaryl,

C ₇ -C ₂₀ aralkyl, substituted alkyl, hydroxyalkyl, C ₁ -C ₂₀ alkoxy-hydroxy

Alkyl, 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-hydroxyalkyl, C ₆ -C ₁₂ aromatic

Oxy-2-hydroxyalkyl, - each R ₄ is independently selected from H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkaryl

radical, C ₇ -C ₂₀ aralkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl,

piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl; -each R is _{independently} selected from H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkane base, C ₇ -C ₂₀ alkaryl

radical, C ₇ -C ₂₀ aralkyl, substituted alkyl, hydroxyalkyl, (R ₄ ) ₂ N-alkyl, and (R ₄ ) ₃

N-Alkyl; where:

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

Each x is from 0 to about 5;

Each y is from about 1 to about 5; and with the proviso that: -R _H groups have a degree of substitution of about 0.001-0.1, preferably 0.005-0.05, and most preferably 0.01-

0.05; The degree of substitution of -Rc group, wherein Z is H or M, is about 0.2-2.0, preferably about 0.3-1.0,

and most preferably about 0.4-0.7; - if any R _H carries a positive charge, it is balanced by a suitable anion; and - two _R groups on the same nitrogen atom can together form a group selected from the group consisting of piperin rings of pyridine and morpholine

structure.

The "degree of substitution" of the _RH group, sometimes abbreviated herein as "DS _RH ", means the number of moles of _RH group components substituted per anhydroglucose unit, wherein the anhydroglucose unit is a six-membered ring, As shown in the repeating unit of the general structure above.

The "degree of substitution" of the R _C group, sometimes abbreviated herein as "DS _RC ", means the number of moles of R _C group components (where Z is H or M) substituted per anhydroglucose unit, where anhydrous The glucose unit is a six-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 should be understood that in addition to the desired number of _Rc components where Z is H or M, there may be, and preferably are, additional Rc _'s wherein Z is a group other than H or M.

The fabrication of materials of the invention is further specified in the Examples below.

C) Detergent surfactant

The detergent compositions of the present invention contain from about 1% to about 80% by weight of detersive surfactant. Preferably such compositions contain from about 5% to about 50% by weight surfactant. The detersive surfactants employed may be of the anionic, nonionic, zwitterionic, amphoteric or cationic type or may contain compatible mixtures of these types. Detersive surfactants useful herein are described in U.S. 3 664 961, Norris, issued May 23, 1972, U.S. 3 919 678, Laughlin et al., issued December 30, 1975, U.S. 4 222 905, Cockrell, 9, 1980 Issued December 16, and recited in U.S. 4 239 659, Murphy, issued December 16, 1980. All such patents are incorporated herein by reference. Among these surfactants, anionic and nonionic surfactants 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 compositions of the present invention. It includes 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 and preferably from about 12 to about 18 carbon atoms.

Other non-soap anionic surfactants suitable for use herein include the alkali metal salts of organosulfur reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfate group and ammonium salts (the term "alkyl" includes the alkyl portion of an acyl group). Particularly useful are linear straight chain alkylbenzene sulfonates wherein the average number of carbon atoms in the alkyl group is about 11-13, abbreviated _C11-13 LAS.

Preferred nonionic surfactants are those of the 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 3- about 80. Particularly preferred are condensation products of _C12 - _C15 alcohols with about 5 to about 20 moles of ethylene oxide per mole of alcohol, for example, condensation of _C12 - _C13 alcohols with about 6.5 moles of ethylene oxide per mole of alcohol .

Additional suitable surfactants, including polyhydroxy fatty acid amides and amine-based surfactants, are disclosed in Laundry Detergent Compositions with Cylic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therwith, filed September 15, 1997. Laundry Detergent Compositions of Amino-Based Polymers Providing Appearance and Integrity Benefits to Fabrics Washed Therewith), co-pending PCT application in the name of Panandiker et al. [P&G Case No. 6834]. The entire publication referred to by Panandiker et al. is incorporated herein by reference.

D) Detergent Builder

The detergent compositions herein can also contain from about 0.1% to about 0.8% by weight of a detergent builder. Preferably such compositions in liquid form will contain from about 1% to about 10% by weight of the builder component. Preferably such compositions in granular form will contain from about 1% to about 50% by weight of the builder component. Detergents are well known in the art and can contain, 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 salts of polyacetic acids, carboxylic acids, polycarboxylic acids and polyhydroxysulfonic acids. Polycarboxylates suitable for use in the present invention are polyacetal carboxylates which are described in U.S. 4,144,226, issued March 13, 1979 to Cratchfield et al., and U.S. Patent 4,246,495 issued March 27, 1779 to Crutchfiede et al., two All are included in this article for reference. Particularly preferred polycarboxylate builders are oxydisuccinate and ethercarboxylate builder compositions containing a mixture of tartrate monosuccinate and tartrate disuccinate as described in U.S. 4,663,071, Bush et al. ., as described in issued May 5, 1987, the disclosure of 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, bicarbonates, sesquicarbonates, tetraborate decahydrate, and have a _SiO2 to alkali metal weight ratio of about 0.5 to about 40, preferably about 1.0 to about 2.4 of silicates. Also preferred are aluminosilicates comprising zeolites. These materials and their use as detergent builders are more fully discussed in Corkill et al., US No. 4,605,509, the disclosure of which is incorporated herein by reference. Crystalline layered silicates are also described in US No. 4,605,509 and are suitable for use in the detergent compositions of the present invention.

E) Optional detergent components

In addition to the surfactants, builders and fabric enhancing components previously described, the detergent compositions of the present invention may comprise a number of other optional ingredients. They include conventional detergent composition components such as enzymes and enzyme stabilizers, suds boosters, anti-tarnish and preservatives, bleaching agents, soil suspending agents, soil stripping agents, bactericides, pH regulators, non-builders Alkalinity sources, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optional brighteners, dyes and fragrances. A preferred additive is carboxymethylcellulose, most preferably at a concentration of from about 0.01 to about 5% by weight of the detergent.

A pH adjuster may be necessary in certain applications (where the pH of the wash solution is greater than 10.0) since the fabric integrity benefit of the defined composition starts to diminish at higher pH. Therefore, if the pH of the wash solution is greater than about 10.0 after the addition of the fabric enhancing component of the present invention, a pH adjusting agent should be used to lower the pH of the wash solution to below about 10.0, preferably a pH below about 9.5 and most preferably Below about 7.5. Suitable pH adjusting agents will be known to those skilled in the art.

Preferred optional ingredients for incorporation into the detergent compositions herein include bleaching agents such as peroxygen bleaching agents. Such peroxygen bleaches can be organic or inorganic in nature. Inorganic peroxygen bleaches are often used in combination with bleach activators.

Useful organic peroxygen bleaches include percarboxylic acid bleaches and salts thereof. Suitable examples of such bleaching agents include magnesium monoperoxyphthalate hexahydrate, magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecane di acid. Such bleaching agents are described in U.S. Patent 4,483,781, Hartman, Issued November 20, 1983; European Patent Application EP-A-133,354, Banks et al., Published February 20, 1985; and U.S. Patent 4,412,934, Chung et al., 19 Issued Nov. 1 in public. Highly preferred bleaching agents also include 6-nonylamino-6-oxopercaproic acid (NAPAA), as described in U.S. Patent 4,634,551, Issued January 6, 1987 to Bums et al.

Inorganic peroxygen bleaches, generally in particulate form, can also be used in the detergent compositions herein. Inorganic bleaches are actually preferred. Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials. For example, sodium perborate (eg, mono- or tetrahydrate) may be used. Suitable inorganic bleaching agents may also include sodium or potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxygen, urea peroxygen, and sodium peroxide. Persulfate bleaches (eg, OXONE, commercially available from Du Pont) may also be used. Often, inorganic peroxygen bleaches will be 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.

Inorganic peroxygen bleaches, such as perborates, percarbonates, etc. are preferably mixed with bleach activators, which result in in situ in aqueous solution (i.e. when fabric washing/bleaching is performed using the compositions of the present invention) and bleaching The corresponding peracid of the active agent. Non-limiting examples of various active agents are disclosed in U.S. Patent 4,915,854, Issued April 10, 1990 to Mao et al.; and U.S. Patent 4,412,934 Issued November 1, 1983 to Chung et al. Nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) active agents are typical and preferred. Mixtures thereof are also applicable. See also previously referenced U.S. 4,634,551 for other typical bleaches and activators useful herein.

Other useful amide-derived bleach activators are those of 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 a An alkyl group, ^R2 is an alkylene group containing 1 to about 6 carbon atoms, ^R5 is H or an alkyl, aryl, or alkaryl group containing about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is removed from a bleach activator as a result of nucleophilic attack by a hyperhydrolyzing anion. A preferred leaving group is phenolsulfonate.

Preferred examples of bleach activators in the above formula include (6-octylamidecaproyl)oxybenzenesulfonate, (6-nonanamidecaproyl)oxybenzenesulfonate, (6-decanoylamidecaproyl)oxybenzenesulfonate acid salts and mixtures thereof, as described in previously referenced U.S. 4,634,551.

Another class of useful bleach activators comprising benzoxazine-type activators is disclosed by Hodgt et al. in U.S. 4,966,723 Issued October 30, 1990, which is incorporated herein by reference. See also U.S. 4,545,784, Issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses the absorption of acyl caprolactams, including benzoyl caprolactam, 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 about 20% by weight of the composition. Most preferably, peroxygen bleach will be present at a level of from about 3% to about 15% by weight of the compositions herein. If used, bleach activators can comprise from about 2% to about 10% by weight of the compositions herein. Typically, the activators are used such that the molar ratio of bleach to activator ranges from about 1:1 to 10:1, more preferably from about 1.5:1 to 5:1.

Further suitable bleaches and bleach activators are described in the co-pending PCT application entitled Laundry Detergtnt Compositions with Cylic Amice Based Polymer to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith Laundry Detergent Compositions Providing Appearance and Integrity Benefits to Fabrics of ®, filed September 15, 1997, in the name of Panandiker et al. [P&G Case No. 6834]. The entire disclosure of the Panandiker et al. reference is incorporated by reference.

Another highly preferred optional ingredient in the detergent compositions of the present invention is a detersive enzyme component. Enzymes for a variety of purposes may be included in the detergent compositions of the present invention, including enzymes for removing protein-based, carbohydrate-based, or triglyceride-based soils from substrates, enzymes for preventing migration of fugitive dyes in fabric laundering and Enzymes that restore fabric. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. Preferred candidates are influenced by factors such as pH activity and/or stability, optimum thermostability, 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 that has a cleaning, soil removal or other benefit in a laundry detergent composition. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases.

Enzymes incorporated into detergent compositions are usually present in an amount sufficient to provide a "cleaning-effective amount". Any amount of odor or freshness improving effect. Typical amounts are not more than 5 mg by weight, more typically 0.01 mg to 3 mg of active enzyme, per gram of detergent composition, in current commercial terms. Stated another way, the compositions of the present invention will typically contain from 0.001% to 5%, preferably from 0.01% to 1% by weight of a commercial enzyme preparation. Proteases are typically present in such commercial formulations in amounts sufficient to provide 0.005-0.1 Anson Units (AU) of activity per gram of composition. Higher active levels are desirable in high strength detergent formulations.

Cellulases useful herein include those disclosed in US No. 4,435,307, Barbesgoard et al., March 6, 1984, 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 to Novo.

The enzyme-containing compositions of the present invention may 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 stabilization system can be any stabilization system compatible with the washing enzyme. Such a system may be provided intrinsically by other formulation actives, or added separately, for example by the formulator or by the manufacture of off-the-shelf detergent enzymes. Such stabilizing systems may contain, for example, calcium ions, boric acid, malonic acid, short chain carboxylic acids, boric acids and mixtures thereof, and are designed to address different stabilization problems, depending on the type and physical form of the detergent composition.

F) Detergent composition preparation

The detergent compositions of the present invention may be in liquid, paste or granular form. Such compositions may be prepared by admixing the essential and optional ingredients in the necessary concentrations, in a suitable order and by any conventional means. The foregoing description of the use of fabric reinforcement components is exemplary, and other applications will be apparent to those skilled in the art and are intended to be within the scope of the present invention.

Granular compositions, for example, are typically prepared by mixing the basic granular components, such as surfactants, builders, water, etc., as a slurry, and then spray drying the resulting slurry to a low residual water content (5-12% ) and made. The remaining dry components, such as the base fabric reinforcement component, can be mixed in granular powder form with the spray-dried granules in a tumble mixer. Solutions of liquid ingredients such as basic fabric strengthening ingredients, enzymes, binders and perfumes can be sprayed onto the resulting granules to form the final detergent composition. The granular compositions of the invention may also be in "compact form", ie they may have a higher density than conventional granular detergents, ie 550-950 g/L. In this case, the granular detergent composition of the present invention will contain a lower amount of "inorganic filler salt" than conventional granular detergents; typical filler salts are alkaline earth metal sulfates and chlorides, typically is sodium sulfate; "tight" detergents usually contain no more than 10% filler salts.

Liquid detergent compositions can be prepared by admixing the essential and optional components thereof in any desired order to provide compositions containing the requisite concentrations of each component. The liquid compositions of the present invention may also be in "compact form", in which case the liquid detergent compositions of the present invention will have a lower water content than conventional liquid detergents. Adding fabric enhancing components to liquid detergent or other aqueous compositions of the present invention can be accomplished by simply mixing the desired fabric enhancing component into the liquid solution.

G) Fabric washing method

The present invention also in a sense provides a method of laundering fabrics which provides fabric appearance benefits due to the use of fabric enhancing components. This method contacts the fabrics with an aqueous wash solution formed from an effective amount of the detergent composition or from the individual components of such a composition. Contacting of the fabrics with the wash solution will generally take place under agitation, although the compositions of the present invention may also be used to form non-agitated soaking solutions for fabric cleaning and treatment. As discussed above, it is preferred that the cleaning solution has a pH of less than about 10.0, preferably has a pH of about 9.5, and most preferably has a pH of about 7.5.

For adequate cleaning, agitation is preferably provided in the washing machine. Preferably washing is followed by drying of the wet fabrics in a conventional garment dryer. Effective amounts of dense liquid or granular detergent compositions are preferably from about 500 to about 700 ppm, more preferably from about 1000 to about 3000 ppm, in aqueous machine wash solutions.

H) Fabric conditioning and softening

The fabric strengthening components previously described as components of the laundry detergent compositions of the present invention may also be used to treat and Conditioning fabrics and textiles. Thus, for example, fabric conditioning compositions containing only the fabric enhancing component, or an aqueous solution of the fabric enhancing component, can be added during conventional home laundering operations in order to deliver the desired fabric appearance and integrity benefits previously described.

Additional suitable fabric softeners are disclosed in co-pending PCT application titled Laundry Detergent Compositions with Cylic Amire Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith, filed September 15, 1997, to Panandiker et al. The name of [P&GCase No.6834]. The entire disclosure referred to by Panandiker et al. is incorporated by reference.

The compositions of the present invention comprise 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 softening active ingredients.

Example

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

Instance 1

Synthesis of Adducts of Imidazole and Epichlorohydrin (Imidazole:Epichlorohydrin Ratio 1:1)

Preparation of polycation condensate by reaction of imidazole and epichlorohydrin. Into a round bottom flask equipped with a magnetic stirrer, condenser and thermometer was added imidazole (0.68 mol) and 95 ml of water. The solution was heated to 50°C, followed by the dropwise addition of epichlorohydrin (0.68 mol). After all the epichlorohydrin had been added, the temperature was raised to 80°C until all the alkylating agent was consumed. The resulting condensate has a molecular weight of about 12,500.

Instance 2

Synthesis of Adducts of Imidazole and Epichlorohydrin (Imidazole:Epichlorohydrin Ratio 1.4:1)

Into a round bottom flask equipped with a magnetic stirrer, condenser and thermometer was added imidazole (0.68 mol) and 95 ml of water. The solution was heated to 50°C, followed by the dropwise addition of epichlorohydrin (0.50 mol). After all the epichlorohydrin had been added, the temperature was raised to 80°C until all the alkylating agent was consumed. The resulting condensate has a molecular weight of about 2000.

Instance 3

Synthesis of adducts of piperazine, morpholine and epichlorohydrin (ratio 1.8/0.8/2.0)

154.8 g (1.8 mol) of piperazine and 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 and 185 g (2 mol) of epichlorohydrin were added under vigorous stirring at such a rate that the temperature did not exceed 80°C. After all the epichlorohydrin had been added, the reaction mixture was heated to 85° C. until all the alkylating agent was consumed (negative Preussmann result 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 for a further 1 hour at 85°C. 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/epichlorohydrin (ratio 1.8/0.8/2.0) adduct

154.8 g (1.8 mol) of piperazine and 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 and 185 g (2 mol) of epichlorohydrin were added under vigorous stirring at such a rate that the temperature did not exceed 80°C. After all the epichlorohydrin had been added, the reaction mixture was heated to 85° C. until all the alkylating agent was consumed (negative Preussmann result 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 for a further 1 hour at 85°C. A further 47 g of water were then added and the mixture was allowed to cool to room temperature.

Instance 5

Adduct of piperazine/morpholine/epichlorohydrin from example 4, 100% oxidation

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) of 50% NaOH and heated to 55-65°C. At this temperature, 102.4 g (1,421 mol) of H ₂ O ₂ (47.2%) were added dropwise over a period of 3.5 hours. After the dropwise addition was complete, the reaction mixture was kept at the same temperature for another 3 hours and then stirred overnight at room temperature. Pt/C was added, unreacted _H2O2 disappeared, and _the solution was filtered.

The characteristics of the reaction product are as follows:

Water content 58%

pH 5.6

Chloride content 1.593mmol/g

Example 6

Synthesis of Adducts of Imidazole/Pyrazine/Epichlorohydrin (Ratio 1.0/3.0/4.0)

68.8 g (1.0 mol) of imidazole and 260.6 g (3.0 mol) of pyrazine were dissolved in 700.2 g of water and 370 g (4.0 mol) of epichlorohydrin were added dropwise at a temperature of 50-60°C. After the addition was complete, the reaction mixture was stirred at 80°C for an additional 5 hours.

Example 7

Imidazole/piperazine/epichlorohydrin adduct from example 6, 100% oxidation

To 237 g of the product from Example 6 above (equivalent to 1,022 mol of oxidizable nitrogen atoms) was added 80.7 g (1.12 mol) of a 47.2% _H2O2 solution in water at ₄₀ °C over a period of 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 product are as follows:

Water content: 58.6%

pH: 2.86

Chloride content: 3.694mmol/g

Mn (number average molecular weight) (GPC): 340

Mw (weight average molecular weight) (GPC): 940

Mn/Mw: 2.8+/-0.1

Instance 8

Synthesis of Hydrophobic Modified CMC (Carboxymethyl Cellulose) Material

Carboxylation of cellulose to produce CMC is a method well known to those skilled in the art. A method of manufacturing the modified CMC of the present invention is to add one or several materials to be substituted during the CMC manufacturing process. An example of such a method is given below. This same approach can be used to substitute other substituted materials described herein by substituting one or several materials of interest, eg, cetyl chloride, for hexyl chloride. The amount of material that should be added to the CMC fabrication process to achieve the desired degree of substitution will be easily calculated by those skilled in the art according to the following examples.

Example 9

Synthesis of CMC Hexyl Ether

This example illustrates the preparation of hydrophobically modified carboxymethylcellulose and is representative of all cellulose ether derivatives of the 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 alkali cellulose was stirred at 25°C for 45 minutes. Monochloroacetic acid (15 g) and hexyl chloride (1 g) were then added, at which point the temperature was raised to 95°C and held at 95°C for 150 minutes. The reaction was cooled to 70°C, then to 25°C. Neutralization is accomplished by adding sufficient nitric/acetic acid to bring the pH of the slurry to 8-9. The slurry was filtered to obtain CMC hexyl ether.

Instance 10

Cellulosic polymers used in test detergent compositions

Representative modified cellulosic polymers described below for use in liquid and granular detergent compositions are characterized in Tables 10A and 10B. General polymer parameters are common to all polymers, while specific chemical structures of test materials are listed under specific polymer parameters.

Form 10A

Common Polymer Parameters Molecular parameters illustrate polymer backbone carboxymethyl cellulose Carboxylation degree DS _RC =0.3-2.0; preferably DS _RC =0.5-0.70 Distribution of carboxymethyl groups Carboxymethyl groups are evenly and randomly distributed along the backbone molecular weight Mw: 5000-2000000, preferably the middle value (about 250000g/mol) Modified type Ether modification (except carboxymethylation). mixed cellulose ethers modification level DS _RH = about 0.001 to about 0.1

Form 10B

Specific Polymer Parameters ID (item description) polymer Modification type ^*** chemical type ^* A Hexyl CMC Hexyl ether Chlorohexane is added to the CMC production process ^* B Decyl CMC Decyl ether Chlorodecane is added to the CMC production process ^** C C ₁₂ -C ₁₃ alkoxy-2 hydroxypropyl CMC C ₁₂ -C ₁₃ alkoxy-2 hydroxypropyl ether C ₁₂ -C ₁₃ alkyl glycidyl ether added to CMC production process ^* D Hexadecyl CMC cetyl ether Chlorohexadecane is added to the CMC production process ^* E Chloride salt of CMC 3-trimethylamino-2-hydroxypropyl ether Chloride salt of 3-trimethylamino-2-hydroxypropyl ether 2,3-Epoxypropyltrimethylammonium chloride is added to the CMC production process ^* F CMC [-(C(O)-CH(C ₁₆ H ₃₃ )-C(O)CH ₂ (C ₁₆ H ₃₃ )] ester or CMC 1,3-dioxo-2-hexadecyl octadecyl ester Cetyl ketene dimer added to CMC production process CMC = carboxymethyl cellulose ^* manufactured by Metsa Specialty Chemicals ^** manufactured by Akzo ^*** The DS _RH of these materials is in the range of about 0.001 to about 0.1

Instance 11

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

Table 11

Instance 12

Granular detergent test composition preparation

Certain heavy duty granular detergent compositions containing fabric enhancing components are prepared. These granular detergent compositions all have following basic formula:

Table 12 components weight% C ₁₂ linear alkylbenzene sulfonate 9.31 C _14-15 alkyl ether (0.35EO) sulfate 12.74 Zeolite Builder 27.79 Sodium carbonate 27.31 PEG4000 1.60 Dispersant 2.26 C _12-13 ethoxylated alcohol (9EO) 1.5 sodium perborate 1.03 dirt removal polymer 0.41 enzyme 0.59 Cyclic amine based polymer or oligomer 3.0 Hydrophobically modified cellulose-based polymers or oligomers 1.0 Fragrance, brightener, foam suppressor, other minor components, moisture, sulfates Balance 100%

Instance 13

Liquid detergent test composition preparation

A heavy duty liquid detergent composition is prepared comprising the fabric enhancing component of the present invention. These liquid detergent compositions all have following basic formula:

Table 13 components 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 MEAs 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 polymers or oligomers 0.1 Dyes, fragrances, brighteners, preservatives, foam suppressors, other minor components, water Balance 100%

Instance 14

Granular detergent test composition preparation

Certain granular detergent compositions containing fabric enhancing components are prepared. This type of granular detergent composition all has following basic formula:

Table 14 example control components weight% weight% C ₁₂ linear alkylbenzene sulfonate 9.40 9.40 C _14-15 alkyl sulfonate 11.26 11.26 Zeolite Builder 27.79 27.79 Sodium carbonate 27.31 27.31 PEG4000 1.60 1.60 Dispersant, sodium polyacrylate 2.26 2.26 C _12-13 Alkyl Ethoxylates (E9) 1.5 1.5 sodium perborate 1.03 1.03 Cyclic amine based polymer or oligomer 0.8 0 Hydrophobically modified cellulose-based polymers or oligomers 0.3 0 other additive components Balance Balance 100% 100%

Claims (11)

1. detergent composition that feature is following:

A) 1%-80% weight is selected from nonionic, negatively charged ion, positively charged ion, both sexes and both sexes

The tensio-active agent of ionic surface active agent and its mixture; With

B) 0.01%-5.0%, preferred 0.1%-4.0% weight be selected from cyclic amine based polymer,

The cellulose-based polymer of oligopolymer or multipolymer, hydrophobically modified or oligopolymer, and its

The fabric enhancing component of mixture; Wherein this detergent composition is to be contained in the inner box of a container; the further feature of this container is that an outside surface is arranged; this outside surface comprises the specification sheets of a characterize combinations; its term is selected from: help clothes to seem sound; before coming off, it prevents wearing and tearing; the outward appearance that keeps clothes; help prevent clothes to damage; reinforcement is to it seems the cleaning of better clothes; strengthening filament makes clothes seem better; help prevent clothes to show old; help prevent and in washing machine, can make clothes show old wearing and tearing and tear; help clothes to avoid aging; the clothes that help is come out from washing machine is the same good when entering in the washing machine with it; help the fabric integrity of protection clothes; strengthen better clothes the inside to the filament that turns up; prolong the clothes life-span; seem the VITAMIN of clothes, effect similarly is the anti-aging product of clothes, similarly is " calcium " of clothes; similarly be replenishing of clothes; clothes after 10 washings look will you wash their better off with other washing composition such as fruit, strengthen filament and make clothes sound, help prevent clothes apparent old before its usage period; similarly be the duration of service that has stopped your clothes, make them keep good.

2. the detergent composition of claim 1, wherein the general formula of the cellulose-based polymer of hydrophobically modified or oligopolymer is: Wherein each R is selected from R ₂, R _cAnd

Wherein :-each R ₂Be independently selected from H and C ₁-C ₄Alkyl;-each R _cBe

Wherein each Z is independently selected from M, R ₂, R _c, and R _H-each R _HBe to be independently selected from C ₅-C ₂₀Alkyl, C ₅-C ₇Cycloalkyl, C ₇-C ₂₀Alkaryl,

C ₇-C ₂₀Aralkyl, the alkyl of replacement, hydroxyalkyl, C ₁-C ₂₀Alkoxyl group-2-hydroxyl

The base alkyl, C ₇-C ₂₀Alkyl-aryloxy-2-hydroxyalkyl, (R ₄) ₂The N-alkyl, (R ₄) ₂

The N-2-hydroxyalkyl, (R ₄) ₃The N-alkyl, (R ₄) ₃The N-2-hydroxyalkyl, C ₆-C ₁₂

Aryloxy-2-hydroxyalkyl,

-each R ₄Be to be independently selected from H, C ₁-C ₂₀Alkyl, C ₅-C ₇Cycloalkyl, C ₇-C ₂₀Alkane

Aryl, C ₇-C ₂₀Aralkyl, aminoalkyl group, alkylamino alkyl, dialkyl amido alkane

Base, piperidino-(1-position only) alkyl, morpholino alkyl, cycloalkyl amino alkyl and hydroxyalkyl;-each R ₅Be independently selected from H, C ₁-C ₂₀Alkyl, C ₅-C ₇Cycloalkyl, C ₇-C ₂₀The alkane virtue

Base, C ₇-C ₂₀Aralkyl, the alkyl of replacement, hydroxyalkyl, (R ₄) ₂The N-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 0-5;

Each y is 1-5; With condition be :-R _HThe substitution value of base is 0.001-0.1, preferably 0.005-0.05 and most preferably 0.01-0.05;-wherein the substitution value of Rc base is to be 0.2-2.0 under the situation of H or M at Z, preferred 0.3-

1.0 0.4-0.7 most preferably; If-any R _HHave a positive charge, then it is by a suitable negatively charged ion institute balance; With two R on the same nitrogen ₄Base can form a ring texture that is selected from piperidines and morpholine together.

3. claim 1 or 2 detergent composition, cyclic amine based polymer wherein, the general formula of oligopolymer or multipolymer is: Wherein:

Each T is independently selected from H, C ₁-C ₁₂Alkyl, the alkyl of replacement, C ₇-C ₁₂The alkane virtue

Base,

-(CH ₂) _hCOOM ,-(CH ₂) _hSO ₃M, CH ₂CH (OH) SO ₃M ,-(CH ₂) _hOSO ₃M, -wherein the feature of W is that at least one atoll texture is selected from: Except above-mentioned at least one atoll texture, W also can contain the aliphatic part of aliphatic series or replacement, and the formula of this part is: -each B is C independently ₁-C ₁₂Alkylidene group, C ₁-C ₁₂The alkylidene group that replaces, C ₃-C ₁₂Inferior

Alkenyl, C ₈-C ₁₂The dialkyl group arylidene, C ₈-C ₁₂Dialkyl group arylidene two bases and

-(R ₅O) _nR ₅-;-each D is C independently ₂-C ₆Alkylidene group;-each Q is independently selected from hydroxyl, C ₁-C ₁₈Alkoxyl group, C ₂-C ₁₈The hydroxy alkoxy base, ammonia

Base, C ₁-C ₁₈Alkylamino, dialkyl amido, trialkyl amino, heterocycle one amino and

Diamino;-each R ₁Be independently selected from H, C ₁-C ₈Alkyl and C ₁-C ₈Hydroxyalkyl;-each R ₂Be independently selected from C ₁-C ₁₂Alkylidene group, C ₁-C ₁₂Alkylene group ,-CH ₂-CH (OR ₁)-CH ₂

, C ₈-C ₁₂Alkyl arylene, C ₄-C ₁₂Alkyl sub-dihydroxy, poly-

(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,

This hydrocarbyl portion can contain 2 chain portion to about 4 following formulas of having an appointment:

-each R ₃Be independently selected from H, O, R ₂, C ₁-C ₂₀Hydroxyalkyl, C ₁-C ₂₀Alkyl is got

The alkyl in generation, C ₆-C ₁₁Aryl, the aryl of replacement, C ₇-C ₁₁Alkaryl, C ₁-C ₂₀

Aminoalkyl group ,-(CH ₂) _hCOOM ,-(CH ₂) _hSO ₃M, CH ₂CH (OH) SO ₃M ,-(CH ₂) _hOSO ₃M,

-each R ₄Be independently selected from H, C ₁-C ₂₂Alkyl, C ₁-C ₂₂Hydroxyalkyl, aryl and

C ₇-C ₂₂Alkaryl;-each R ₅Be independently selected from C ₂-C ₈Alkylidene group, C ₂-C ₈The alkylidene group that alkyl replaces; With

A is consistency monovalence or divalence or multivalent anions;

M is a compatible cationic;

B=is the necessary number of balancing charge;

Each x is 3 to 1000 independently;

Each c is 0 or 1 independently;

Each h is 1-8 independently;

Each q is 0-6 independently;

Each n is 1-20 independently;

Each r is 0-20 independently; With

Each t is 0-1 independently.

4. arbitrary detergent composition of claim 1-3, cyclic amine based polymer wherein, oligopolymer or multipolymer are to be selected from piperazine, piperidines, Epicholorohydrin, Epicholorohydrin benzyl quaternary ammonium compounds, Epicholorohydrin methyl quaternary ammonium compounds, the adducts of morpholine and composition thereof.

5. arbitrary detergent composition of claim 1-4, wherein each R ₁Be that H and at least one W are selected from:

6. arbitrary detergent composition of claim 1-5, wherein each R ₁Be that H and at least one W are selected from:

7. arbitrary detergent composition of claim 1-6, wherein each R ₁Be that H and at least one W are selected from:

8. arbitrary detergent composition of claim 1-7, wherein each R _HBe independently selected from C ₅-C ₂₀Alkyl, C ₅-C ₇Cycloalkyl, C ₇-C ₂₀Alkaryl, C ₇-C ₂₀Aralkyl, 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.

9. arbitrary detergent composition of claim 1-8, wherein each R _HBe independently selected from:

10. arbitrary detergent composition of claim 1-9, wherein the molecular-weight average of cellulose-based polymer or oligopolymer is 5,000-2,000,000.

11. a laundry additive composition is characterized by and contains:

A) water of 1%-80% weight; With

B) 0.01%-5.0% weight, preferred 0.1%-4.0% weight be selected from the polymerization of cyclammonium base

Thing, oligopolymer or multipolymer, the cellulose-based polymer of hydrophobically modified, oligopolymer,

Fabric enhancing component with its mixture; Wherein this laundry additive composition is to be contained in the inner box of a container; this container further be characterized as an outside surface; this outside surface comprises a specification sheets that characterizes said composition; its term is selected from: help clothes to seem sound; before coming off, it prevents wearing and tearing; the outward appearance that keeps clothes; help prevent clothes to damage; reinforcement is to it seems the cleaning of better clothes; strengthening filament makes clothes seem better; help prevent clothes to show old; help prevent and in washing machine, can make clothes show old wearing and tearing and tear; help clothes to avoid aging; the clothes that help is come out from washing machine is the same good when entering in the washing machine with it; help the fabric integrity of protection clothes; strengthen better clothes the inside to the filament that turns up; prolong the clothes life-span; seem the VITAMIN of clothes, effect similarly is the anti-aging product of clothes, similarly is " calcium " of clothes; similarly be replenishing of clothes; clothes after 10 washings look will you wash their better off with other washing composition such as fruit, strengthen filament and make clothes sound, help prevent clothes apparent old before its usage period; similarly be the duration of service that has stopped your clothes, make them keep good.