CN1351644A - Laundry detergent composition containing certain cationically charged dye maintenance polymers - Google Patents

Abstract

The present invention relates to laundry detergent compositions that provide dye protection benefits to fabrics, comprising: a) from about 4% to about 70% by weight of a surfactant; b) from about 0.01% by weight of a dye maintenance polymer or oligomer, said polymer or copolymer comprising one or more linear polymerized monomers, cyclic polymerized monomers, and mixtures thereof; and c) the balance of carriers and adjunct ingredients.

Description

Laundry detergent composition containing certain cationically charged dye maintenance polymers

Field of the invention

The present invention relates to compositions in liquid or granular form for laundry applications comprising certain dye maintenance polymers with a net positive charge. Compositions of the present invention comprising dye maintenance polymers impart appearance and integrity benefits to fabrics and textiles laundered in laundry solutions formed from the compositions.

Background of the invention

It is well known that alternating cycles of use and laundering of fabrics and textiles such as worn clothes and garments will inevitably adversely affect the appearance and integrity of used and laundered fabrics and textiles. Fabrics and textiles simply wear out due to overtime use. Laundering of fabrics and textiles is necessary in order to remove dirt and stains that accumulate in and on them during daily use. However, the laundering operation itself, through multiple cycles, can aggravate and contribute to the deterioration of the integrity and appearance of such fabrics and textiles.

Deterioration of fabric integrity and appearance can manifest itself in several ways. The mechanical movement of laundry removes staple fibers from woven and knitted fabric/textile structures. These dislodged fibers can form piles, fuzz, or "balls" that are visible on the surface of the fabric, reducing the appearance of newness to the fabric. Furthermore, repeated laundering of fabrics and textiles, especially with laundry products containing bleach, can remove dyes from fabrics and textiles, reducing color intensity and, in many cases, changing the hue or shade of the color, The result is a faded, worn look.

The above description points to a clear need to identify substances that can be added to laundry products that bind themselves to the fibers of fabrics and textiles that are to be washed with such products, thereby reducing the amount of fabric/ The tendency to deteriorate the appearance of textiles may be minimized. Of course, any such detergent product additives should be able to benefit the appearance and integrity of the fabrics without unduly affecting the laundry product's ability to perform its intended function. The present invention relates to the use of dye maintenance polymers in laundry applications performed in this desirable manner.

A brief description of the invention

The present invention fulfills the above needs in that it has been surprisingly found that fabrics treated and subsequently retreated with the composition of the invention are resistant to common fading and loss of color. In addition, fabric dye loss is reduced after untreated fabrics are washed with the laundry detergent compositions of the present invention. The composition of the invention may take any form, in particular high-efficiency liquid (HDL), high-efficiency granule (HDG), stick, paste, thixotropic composition.

A first aspect of the present invention relates to laundry detergent compositions for providing dye protection benefits to fabrics, comprising:

a) from about 4% to about 70% by weight of surfactants selected from the group consisting of nonionic, anionic, cationic, amphoteric, zwitterionic surfactants and mixtures thereof, preferably at least one of said surfactants is anionic type surfactant;

b) from about 0.01%, preferably from about 0.1%, more preferably from about 0.5%, most preferably from about 0.8% to about 10%, preferably to about 8%, more preferably to about 6%, most preferably to about 5% weight of dye maintaining polymers or oligomers comprising one or more units having the formula:

其中各R¹独立为a)氢；b)C₁-C₄烷基；c)取代或未取代苯基；d)取代或未取代苄基；e)碳环；f)杂环；g)以及它们的混合物；各R²独立为a)氢；b)卤素；c)C₁-C₄烷基；d)C₁-C₄烷氧基；e)取代或未取代苯基；f)取代或未取代苄基；g)碳环；h)杂环；i)以及它们的混合物；各Z独立为a)氢；b)羟基；c)卤素；d)-(CH₂)_mR；1) A linear polymer unit having the formula:

wherein each R ¹ is independently a) hydrogen; b) C ₁ -C ₄ alkyl; c) substituted or unsubstituted phenyl; d) substituted or unsubstituted benzyl; e) carbocycle; f) heterocycle; g) and mixtures thereof; each R ² is independently a) hydrogen; b) halogen; c) C ₁ -C ₄ alkyl; d) C ₁ -C ₄ alkoxy; e) substituted or unsubstituted phenyl; f) Substituted or unsubstituted benzyl; g) carbocycle; h) heterocycle; i) and mixtures thereof; each Z is independently a) hydrogen; b) hydroxyl; c) halogen; d) -(CH ₂ ) _m R;

where R is:

i) hydrogen;

ii) Hydroxyl;

iii) halogen;

iv) nitrilo;

v) -OR ³ ;

vi) -O(CH ₂ ) _n N(R ³ ) ₂ ;

vii) -O(CH ₂ ) _n N ⁺ (R ³ ) ₃ X ⁻ ;

viii) -OCO(CH ₂ ) _n N(R ³ ) ₂ ;

ix) -OCO(CH ₂ ) _n N ⁺ (R ³ ) ₃ X ⁻ ;

x) -NHCO(CH ₂ ) _n N(R ³ ) ₂ ;

xi) -NHCO(CH ₂ ) _n N ⁺ (R ³ ) ₃ X ⁻ ;

xii) -(CH ₂ ) _n N(R ³ ) ₂ ;

xiii) -(CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- ;

xiv) carbon ring;

xv) heterocycle;

xvi) quaternary ammonium nitrogen heterocycle;

xvii) N-oxide nitrogen heterocycles;

xviii) quaternary ammonium aromatic N-heterocycles;

xix) N-oxide aromatic N-heterocycle;

xx) -NHCHO;

xxi) or mixtures thereof;

Each R ³ is independently hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₈ hydroxyalkyl and mixtures thereof; X is a water-soluble anion; subscript n is 0-6; e)-(CH ₂ ) _m COR'

where R' is:

i) -OR ³ ;

ii) -O(CH ₂ ) _n N(R ³ ) ₂ ;

iii) -O(CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- ;

iv) -NR ³ (CH ₂ ) _n N(R ³ ) ₂ ;

v) -NR ³ (CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- ;

vi) -(CH ₂ ) _n N(R ³ ) ₂ ;

vii) -(CH ₂ ) _n N ⁺ (R ³ ) ₃ X ⁻ ;

viii) or mixtures thereof;

Each R ³ is independently hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₈ hydroxyalkyl and mixtures thereof; X is a water-soluble anion; subscript n is 0-6; f) and mixtures thereof;

The subscript m is 0-6; II) a cyclic unit derived from a cyclically polymerized monomer having the formula:

wherein each R ⁴ is independently an alkene, and ^the alkene contains

In addition to forming a cyclic residue, it can also increase the polymerization reaction unit; R ⁵ is C ₁ -C ₁₂

Linear or branched alkyl, benzyl, substituted benzyl and mixtures thereof; X is

Water-soluble anions; and III) mixtures thereof;

provided that the polymer or copolymer has a net cationic charge; and wherein the

The dye maintenance polymer is not polyethyleneimine or its alkoxylated derivatives; and

c) Balanced amounts of carriers and other auxiliary ingredients.

In addition to the surfactants and the dye maintenance polymers of the present invention, the laundry detergent compositions herein comprise from about 0.01% to about 80% by weight of organic or inorganic soil removal builders and other conventional laundry detergent products. In its method aspects, the present invention relates to washing in the form of an effective amount of any of the detergent compositions, fabric softener compositions, or aqueous treatment agents described herein, or the individual components of these compositions. , rinsing or treatment of fabrics and textiles in aqueous solutions. After the fabrics and textiles are laundered in such wash, rinse and/or treatment solutions, they are dried to provide fabric appearance benefits to the treated fabrics and textiles. Such benefits may include improved overall appearance, reduced pilling/fuzzing, resistance to fading, improved abrasion resistance, and/or increased softness. It was surprisingly determined that the dye maintenance polymers of the present invention confer fabric appearance and integrity benefits greater than those achieved by the corresponding amounts of either component by itself.

These and other objects, features and benefits of the present invention will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight unless otherwise indicated. All temperatures are in degrees Celsius (° C.) unless otherwise indicated. All cited documents are hereby incorporated by reference in relevant part.

Detailed Description of the Invention

As noted above, when fabrics or textiles are laundered in solutions comprising the dye maintenance polymers of the present invention, fabric appearance and integrity are enhanced. Dye maintenance polymers can be added to laundry solutions by incorporating them into detergent compositions, fabric softeners, or by themselves. The dye maintenance polymers described herein are primarily used as liquid or granular detergent additives, but the invention is not limited thereto. The dye maintenance polymers, detergent composition components, optional ingredients for use in the compositions and methods of using the compositions are described in detail below. All percentages are by weight unless otherwise indicated.

Dye Maintenance Polymer

The compositions and systems of the present invention comprise from about 0.1%, preferably from about 1%, more preferably from about 2%, most preferably from about 3% to about 10%, preferably to about 7%, more preferably to about 5% by weight Polymers, copolymers or mixtures thereof, wherein the polymer or copolymer comprises at least one cationic charged unit, especially a quaternary ammonium moiety, or a unit capable of forming a cationic charge in situ, especially a primary amine moiety . In other words, the oligomer, polymer or copolymer resulting from the monomer units described below must have a net cationic charge. Charge can be distributed between any of the units described herein.

The dye maintenance polymers of the present invention can be used in any fabric laundering process and provide certain cosmetic benefits to fabrics laundered by such processes. These fabric appearance benefits may include, for example, improved overall appearance of the fabric after laundering, reduction in pilling and fuzzing, resistance to fading, improved abrasion resistance, and the like. Such fabric appearance benefits can be provided when the dye maintenance polymers used in the compositions and methods herein are incorporated into wash or rinse added products.

It will be apparent to those skilled in the art that oligomers are molecules consisting of only a small number of monomeric units, whereas polymers contain very many monomeric units. For purposes of this invention, oligomers are defined as molecules having an average molecular weight of less than about 1,000, and polymers are molecules having an average molecular weight of greater than about 1,000. Copolymers are polymers or oligomers formed by the simultaneous or sequential polymerization of two or more different monomers. The copolymer of the present invention may include, for example, polymers or oligomers produced by copolymerizing acrylamide with dimethyldiallylammonium chloride, vinylamine with vinyl alcohol, and the like.

Common cationic polymers and their preparation are known. A detailed description of cationic polymers can be found, for example, in the article by M. Fred Hoover, Journal of Macromolecular Science-Chemistry, October 1970, A4(6), pp. 1327-1417. The entire disclosure of Hoover's article is hereby incorporated by reference. The dye maintenance polymers of the present invention will be better understood by reading the Hoover article, the present disclosure and the examples herein.

I) Linear polymer unit

其中R¹、R²和Z如下文定义。优选线性聚合物单元由线性聚合单体形成。线性聚合单体在本文中被定义为在标准聚合条件下产生线性聚合物链或者可以线性地增长聚合反应的单体。本发明的线性聚合单体具有下式：

但是，本领域技术人员认为很多有用的线性单体单元是间接引进的，尤其是乙烯胺单元、乙烯醇单元，并不是通过线性聚合单体。例如，乙酸乙烯酯单体一被结合进主链，即发生水解形成乙烯醇单元。为了实现本发明的目的，线性聚合物单元可以被直接引进，即通过线性聚合单元，或者间接地，即如上文所引用的乙烯醇的情况一样通过前体引进。The polymers or copolymers of the present invention may comprise one or more linear polymer units having the formula:

wherein R ¹ , R ² and Z are as defined below. Preferably the linear polymer units are formed from linear polymerized monomers. A linear polymerizing monomer is defined herein as a monomer that, under standard polymerization conditions, produces a linear polymer chain or that can linearly extend the polymerization reaction. The linear polymerizable monomers of the present invention have the formula:

However, those skilled in the art believe that many useful linear monomer units are introduced indirectly, especially vinylamine units and vinyl alcohol units, rather than through linear polymerization of monomers. For example, once vinyl acetate monomers are incorporated into the backbone, hydrolysis occurs to form vinyl alcohol units. For the purposes of the present invention, the linear polymer units may be introduced directly, ie via linear polymerized units, or indirectly, ie via precursors as in the case of vinyl alcohol cited above.

Each R ¹ is independently hydrogen, C ₁ -C ₄ alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocycle, heterocycle, and mixtures thereof. Preferably R ¹ is hydrogen, C ₁ -C ₄ alkyl, phenyl and mixtures thereof, more preferably hydrogen and methyl.

Each R ² is independently hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocycle, heterocycle, and mixtures thereof. Preferred R ² are hydrogen, C ₁ -C ₄ alkyl and mixtures thereof.

Each Z is independently hydrogen; hydroxyl; halogen; -(CH ₂ ) _m R, wherein R is hydrogen, hydroxyl, halogen, nitrilo, -OR ³ , -O(CH ₂ ) _n N(R ³ ) ₂ , - O(CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- , -OCO(CH ₂ ) _n N(R ³ ) ₂ , -OCO(CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- , -NHCO( CH ₂ ) _n N(R ³ ) ₂ , -NHCO(CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- , -(CH ₂ ) _n N(R ³ ) ₂ , -(CH ₂ ) _n N ⁺ ( R ³ ) ₃ X ^- , non-aromatic nitrogen-heterocycles containing quaternary ammonium ions, non-aromatic nitrogen-heterocycles containing N-oxide moieties, aromatic nitrogen-containing heterocycles in which one or more or nitrogen atoms are quaternized Heterocycles, aromatic nitrogen-containing heterocycles in which at least one nitrogen is an N-oxide, -NHCHO (formamide), or mixtures thereof, wherein each R ³ is independently hydrogen, C ₁ -C ₈ alkyl, C ₂ - C ₈ hydroxyalkyl groups and their mixtures, X is a water-soluble anion, subscript n is 0-6; carbocycle, heterocycle or their mixture; -(CH ₂ ) _m COR', wherein R' is -OR ³ , -O(CH ₂ ) _n N(R ³ ) ₂ , -O(CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- , -NR ³ (CH ₂ ) _n N(R ³ ) ₂ , -NR ³ (CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- , -(CH ₂ ) _n N(R ³ ) ₂ , -(CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- or mixtures thereof, wherein R ^3. X and n are the same as defined above. A preferred Z is -O(CH ₂ ) _n N ⁺ (R ³ ) ₃ X ⁻ , wherein the subscript n is 2-4. Subscript m is 0-6, preferably 0-2, more preferably 0.

Non-limiting examples of linear polymerizable monomers containing heterocyclic Z units include 1-vinyl-2-pyrrolidone, 1-vinylimidazole, 2-vinyl-1,3-dioxolane, 4-vinyl- 1-cyclohexene-1,2-epoxide and 2-vinylpyridine.

The polymers and copolymers of the present invention comprise Z units which carry a cationic charge or which can generate units which form a cationic charge in situ. When the copolymers of the present invention contain more than one Z unit, eg ^Z1 , ^Z2 ... ^Zn units, at least about 1% of the monomers making up the copolymer contain cationic units. Preferred cationic units include -O(CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- and -(CH ₂ ) _n N ⁺ (R ³ ) ₃ X ^- . When the copolymer of the present invention is formed from two monomers, ^Z1 and ^Z2 , it is preferred that the ratio of ^Z1 to ^Z2 is from about 9:1 to about 1:9.

随后对共聚物进行处理，从而使一部分甲酰胺单元发生水解形成包含乙烯胺单元的共聚物，所述聚合物具有下式：其中Z可以是包含阳离子单元或包含非阳离子单元的部分，并且x′+x＂＝x。Non-limiting examples of Z units that allow cationic charges to be formed in situ are -NHCHO units, formamide. Formulators can prepare polymers or copolymers containing formamide units, a portion of which are subsequently hydrolyzed to form vinylamine equivalents. For example, a formulator can prepare a copolymer comprising formamide units having the following general formula:

The copolymer is then treated to hydrolyze a portion of the formamide units to form a copolymer comprising vinylamine units, the polymer having the formula: where Z may be a moiety comprising cationic units or comprising non-cationic units, and x'+x"=x.

它的一个非限制性例子为4-乙烯基(N-烷基)吡啶，其中R¹和R²各自为氢，R⁶为甲基。Another preferred class of linear polymerizable monomers includes cationically charged heteroaromatic Z units having the formula:

A non-limiting example thereof is 4-vinyl(N-alkyl)pyridine, wherein R ^{and R} are each hydrogen and ^R is methyl.

Another preferred class of heterocyclic-containing linear polymerizable monomers includes Z units comprising N-oxides, such as N-oxides of the formula: A non-limiting example thereof is 4-vinylpyridine N-oxide.

The N-alkylvinylpyridine monomers and N-oxide vinylpyridine monomers may suitably be combined with other non-aromatic monomers, especially vinylamines. However, preferred polymers of the present invention include copolymers derived from combinations of quaternized N-oxides and nitrogen-containing heteroaromatic monomers, non-limiting examples of which include N-methyl Copolymers of vinylpyridine and vinylpyridine, copolymers of N-methylvinylpyridine and vinylpyridine at a ratio of 4:6, poly(N-methylpyridine at a ratio of polymer to monomer of 4:1 Copolymers of vinylpyridine) and vinylpyridine N-oxides, copolymers of poly(N-methylvinylpyridine) and vinylpyridine N-oxides in a ratio of polymer to monomer of 4:6, and their mixture.

其中Z¹具有下式：

Z²具有下式：

其中X为氯，x的值为约10-约100,000，y的值为约10-约100,000，x与y之比为9∶1-1∶9。该类型的共聚物是可以得到的，例如来自BASF的Sedipur^CF104。Preferred linear copolymers of the present invention have the formula:

where ^Z1 has the following formula:

Z ² has the following formula:

Wherein X is chlorine, the value of x is from about 10 to about 100,000, the value of y is from about 10 to about 100,000, and the ratio of x to y is from 9:1 to 1:9. Copolymers of this type are available, for example, as Sedipur ^(R) CF104 from BASF.

As noted above, some preferred polymer residues can be formed by treating the resulting polymer. For example, vinylamine residues are preferably introduced via formamide monomers which are subsequently hydrolyzed to form free amino units. Vinyl alcohol units are also obtained by hydrolysis of residues formed from vinyl acetate monomers. Likewise, acrylic acid residues may be esterified after polymerization, for example after backbone formation by polymerization with acrylic acid or acrylic precursor monomers, to more conveniently form units of the formula:

II) Cyclic units derived from cyclically polymerized monomers

The polymers or copolymers of the present invention may comprise one or more cyclic polymer units derived from cyclic polymerized monomers. Cyclic polymerizable monomers are defined herein as monomers which, under standard polymerization conditions, produce a cyclic polymer residue and linearly propagate the polymerization reaction. Preferred cyclic polymerizable monomers of the present invention have the formula: Wherein each R ⁴ is independently an alkene, and it contains a unit that can not only form a cyclic residue with an adjacent R ⁴ unit, but also increase the polymerization reaction; R ⁵ is C ₁ -C ₁₂ linear or branched chain alkyl, benzyl , substituted benzyl groups and mixtures thereof; X is a water-soluble anion.

Non-limiting examples of ^R units include allyl and alkyl substituted allyl units. Preferably the resulting cyclic residue is a six-membered ring containing a quaternary nitrogen atom.

Preferably R ⁵ is C ₁ -C ₄ alkyl, most preferably methyl.

它导致具有下式单元的聚合物或共聚物：

其中优选下标z为约10-约50,000。An example of a cyclic polymerizable monomer is dimethyldiallylammonium having the formula:

It leads to polymers or copolymers having units of the formula:

Among them, subscript z is preferably from about 10 to about 50,000.

III) their mixture

The polymers or copolymers of the present invention must retain a net cationic charge, whether generated in situ or a formal positive charge carried by the polymer or copolymer itself. Preferably the polymer or copolymer has at least 10%, more preferably at least about 25%, more preferably at least about 35%, most preferably at least about 50% residues that contain cationic charges.

The polymers or copolymers of the present invention may comprise a mixture of linear and cyclic polymerized monomers, such as poly(dimethyldiallylammonium chloride/acrylamide) copolymers having the formula: wherein Z ¹ , Z ² , x, y and z are as defined above, and X is chloride ion.

A particularly preferred embodiment of the present invention is a composition comprising a polymer based on dimethyldiallylammonium chloride and a copolymer based on acrylamide with a comonomer selected from From N,N-dialkylaminoalkyl (meth)acrylate, N,N-dialkylaminoalkyl acrylate, N,N-dialkylaminoalkylacrylamide, N,N-dioxane Aminoalkyl (meth)acrylamides, their quaternized derivatives and mixtures thereof.

Non-limiting examples of preferred polymers of the invention include dye maintenance copolymers comprising:

i) a first monomer selected from N,N-dialkylaminoalkyl (meth)acrylates, N,N-dialkylaminoalkyl acrylates, N,N-dialkylaminoalkylpropylenes Amides, N,N-dialkylaminoalkyl(meth)acrylamides, their quaternized derivatives and mixtures thereof; and

ii) A second monomer selected from the group consisting of acrylic acid, methacrylic acid, C ₁ -C ₆ alkyl methacrylate, C ₁ -C ₆ alkyl acrylate, C ₁ -C ₈ hydroxyalkyl acrylate, methyl C ₁ -C ₈ hydroxyalkyl acrylates, acrylamides, C ₁ -C ₁₆ alkylacrylamides, C ₁ -C ₁₆ dialkylacrylamides, 2-acrylamide-2-methylpropanesulfonic acid or their bases Salt, methacrylamide, C ₁ -C ₁₆ alkyl methacrylamide, C ₁ -C ₁₆ dialkyl methacrylamide, vinyl formamide, vinyl acetamide, vinyl alcohol, C ₁ -C ₈ Vinyl alkyl ethers, vinyl pyridines, itaconic acid, vinyl acetate, vinyl propionate, vinyl butyrate, and mixtures thereof, wherein the copolymer comprises at least 25 mole percent of the first monomer.

Auxiliary ingredients

The compositions of the present invention may also optionally contain one or more accessory ingredients. Non-limiting examples of adjunct ingredients are selected from detergent surfactants, electrolytes, stabilizers, low molecular weight water soluble solvents, chelating agents, dispersing aids, soil release agents, non-ionic fabric softeners, concentration aids, fragrances , preservatives, colorants, optical brighteners, opacifiers, bactericides, fungicides, anti-corrosion agents, defoamers and their mixtures.

The following applications describe various detergent additives, methods of making these additives, and methods of using them, all of which are incorporated herein by reference. WO 99/07813 A1Randall et al., "Laundry detergent compositions containing amino acid-based Laundry detergent compositions based on polymers that provide appearance and integrity benefits to fabrics washed therewith"; WO 99/14299 A1 Panandiker et al., "Laundry detergents containing polymers based on anionically modified cyclic amines"; Detergent compositions"; WO 99/14300 A1 Panandiker et al., "Laundry detergent compositions containing cyclic amine-based polymers to provide appearance and integrity benefits to fabrics washed therewith"; WO 99/14301 A1 Panandiker et al., "Laundry detergent compositions and fabric conditioning compositions containing oxidized cyclic amine-based polymers" and US 99/23146 Panandiker et al., "Cyclic amine-based polymers Carboxymethylcellulose-incorporated Laundry Detergent Compositions".

Surfactant system

The laundry detergent compositions of the present invention comprise a surfactant system. The surfactant system of the present invention may comprise any type of detersive surfactant, non-limiting examples of which include one or more mid-chain branched alkyl sulfate surfactants, one or more mid-chain branched Branched alkyl alkoxy sulfate surfactants, one or more mid-chain branched aryl sulfonate surfactants, one or more non-mid-chain branched sulfonates, sulfates , cationic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof.

Surfactants are present in the compositions of the present invention in a total amount of from about 4%, preferably from about 10%, more preferably from about 15% to about 60%, preferably to about 30%, by weight of the composition.

Non-limiting examples of surfactants useful in the present invention include: a) C ₁₁ -C ₁₈ alkylbenzene sulfonates (LAS); b) C ₆ -C ₁₈ mid-chain branched aryl sulfonates (BLAS); c) C ₁₀ -C ₂₀ primary, α or ω-branched and random alkyl sulfates (AS); d) C ₁₄ -C ₂₀ mid-chain branched alkyl sulfates (BAS); e) C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfates, such as US3,234,258 authorized to Morris on February 8, 1966, US5,075,041 authorized to Lutz on December 24, 1991 , US _{Pat .} alkyl alkoxysulfate (AE _x S), wherein preferably x is 1-7; g) C ₁₄ -C ₂₀ mid-chain branched alkyl alkoxysulfate (BAE _x S); h) C ₁₀ - C ₁₈ alkyl alkoxy carboxylates, preferably comprising 1-5 ethoxy units; i) C ₁₂ -C ₁₈ alkyl ethoxylates, C ₆ -C ₁₂ alkylphenol alkoxylates, wherein Alkoxylate units are mixtures of ethyleneoxy and propyleneoxy units, C ₁₂ -C ₁₈ alcohols and C ₆ -C ₁₂ alkylphenol condensates containing ethylene oxide/propylene oxide block polymers, especially ^Pluronic® from BASF, which are disclosed in US 3,929,678 issued December 30, 1975 to Laughlin et al., which patent is incorporated herein by reference; j) C ₁₄ -C ₂₂ mid-chain branched alkyl alkoxy k) alkyl polysaccharides disclosed in US 4,565,647, issued January 26, 1986 to Llenado, which is incorporated herein by reference; ₁ ) polyhydroxy fatty acid amides having the formula: Wherein R ⁷ is C ₅ -C ₃₁ alkyl, R ⁸ is selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkane

group; Q is a polyhydroxyalkyl moiety having a linear alkyl chain or an alkoxylated derivative thereof

wherein the linear alkyl chain has at least 3 hydroxyl groups directly attached to the chain; preferably

The alkoxy group is ethoxy or propoxy, and mixtures thereof; preferred O-derived

Reducing sugar in the self-reductive amination reaction, more preferably Q is a glycityl moiety; more preferably

Q is selected from -CH ₂ (CHOH) _n CH ₂ OH, -CH (CH ₂ OH) (CHOH) _n-1 CH ₂ OH,

-CH ₂ (CHOH) ₂ (CHOR′)(CHOH)CH ₂ OH, and their alkoxylated derivatives

wherein n is an integer from 3 to 5 including 3 and 5, and R' is hydrogen or cyclic or aliphatic

family of monosaccharides, the polyhydroxy fatty acid amides licensed to Connor on February 6, 1996

U.S. 5,489,393 to Murch et al. and U.S.

5,45,982, which are incorporated herein by reference.

其中R为C₇-C₂₁线性烷基、C₇-C₂₁支化烷基、C₇-C₂₁线性链烯基、C₇-C₂₁支化链烯基以及它们的混合物。A non-limiting example of a nonionic surfactant suitable for use in the present invention has the formula:

Wherein R is C ₇ -C ₂₁ linear alkyl, C ₇ -C ₂₁ branched alkyl, C ₇ -C ₂₁ linear alkenyl, C ₇ -C ₂₁ branched alkenyl and mixtures thereof.

R ¹ is ethylene, R ² is C ₃ -C ₄ linear alkyl, C ₃ -C ₄ branched alkyl and mixtures thereof, preferably R ² is 1,2-propylene. Preferred nonionic surfactants comprising a mixture of R ^and R ^units comprise from about 4 to about 12 ethylene units in combination with from about 1 to about 4 1,2-propylene units. These units may be alternated or grouped together in any combination deemed appropriate by the formulator. Preferably the ratio of ^R1 units to ^R2 units is from about 4:1 to about 8:1. Preferably the ^R2 unit (ie 1,2-propylene) is attached to the nitrogen atom followed by a chain comprising 4-8 ethylene units for balance.

R ² is hydrogen, C ₁ -C ₄ linear alkyl, C ₃ -C ₄ branched alkyl and mixtures thereof, preferably hydrogen or methyl, more preferably hydrogen.

R ⁴ is hydrogen, C ₁ -C ₄ linear alkyl, C ₃ -C ₄ branched alkyl and mixtures thereof, preferably hydrogen. When the subscript m is equal to 2, the subscript n must be equal to 0, and there is no R ⁴ unit, but a -[(R ¹ O) _x (R ² O) _y R ³ ] unit instead.

Subscript m is 1 or 2, subscript n is 0 or 1, the condition is that when m is equal to 1, n is equal to 1; and when m is 2, n is 0; preferably m is equal to 1, n is equal to 1, thus forming A -[(R ¹ O) _x (R ² O) _y R ³ ] unit, and R ⁴ is present on nitrogen. The subscript x is from 0 to about 50, preferably from about 3 to about 25, more preferably from about 3 to about 10. The subscript y ranges from 0 to about 10, preferably 0, but when the subscript y is not equal to 0, y ranges from 1 to about 4. Preferably all alkenyloxy units are ethyleneoxy units. Those skilled in the art of ethoxylated polyoxyalkylene alkylamide surfactants will recognize that the values for the subscripts x and y are average values and that the true values may vary within a range of several values, depending on the value used. Method for alkoxylation of amides.

The mid-chain branched alkyl sulfate surfactants of the present invention have the formula:

Alkyl alkoxy sulfates have the formula:

其中R、R¹和R²各独立为氢、C₁-C₃烷基以及它们的混合物，条件是R、R¹和R²中至少有一个不为氢，优选R、R¹和R²为甲基；优选R、R¹和R²中的一个为甲基，并且其它单元为氢。中链支化的烷基硫酸盐和烷基烷氧基硫酸盐表面活性剂中碳原子的总数为14-20；下标w为0-13的整数；x为0-13的整数；y为0-13的整数；z是至少为1的整数；条件是w+x+y+z为8-14，表面活性剂中碳原子总数为14-20；R³为C₁-C₄线性或支化亚烷基，优选为亚乙基、1，2-亚丙基、1，3-亚丙基、1，2-亚丁基、1，4-亚丁基以及它们的混合物。但是，本发明的一个优选的实施方案包含1-3个其中R³为1，2-亚丙基、1，3-亚丙基或它们的混合物的单元，之后是用来平衡的包含亚乙基单元的R³单元。另一个优选的实施方案包含R³单元，该单元为无规亚乙基和1，2-亚丙基单元。下标m的平均值至少约为0.01。当下标m的值较低时，表面活性剂体系主要包含烷基硫酸盐，以及少量的烷基烷氧基硫酸盐表面活性剂。烷基链中可以存在一些叔碳原子，但是该实施方案并不理想。Alkyl alkoxylates have the formula:

wherein R, ^R1 and ^R2 are each independently hydrogen, _C1 - _C3 alkyl and mixtures thereof, provided that at least one of R, ^R1 and ^R2 is not hydrogen, preferably R, ^R1 and ^R2 is methyl; preferably one of R, ^R1 and ^R2 is methyl and the other unit is hydrogen. The total number of carbon atoms in the mid-chain branched alkyl sulfate and alkyl alkoxy sulfate surfactant is 14-20; subscript w is an integer of 0-13; x is an integer of 0-13; y is An integer of 0-13; z is an integer of at least 1; the condition is that w+x+y+z is 8-14, and the total number of carbon atoms in the surfactant is 14-20; R ³ is C ₁ -C ₄ linear or Branched alkylene, preferably ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene and mixtures thereof. However, a preferred embodiment of the invention comprises 1 to 3 units wherein ^R3 is 1,2-propylene, 1,3-propylene or mixtures thereof, followed by balancing ethylene The R ³ unit of the base unit. Another preferred embodiment comprises ^R3 units which are random ethylene and 1,2-propylene units. The subscript m has an average value of at least about 0.01. When the value of subscript m is low, the surfactant system mainly contains alkyl sulfate, and a small amount of alkyl alkoxy sulfate surfactant. Some tertiary carbon atoms may be present in the alkyl chain, but this embodiment is not ideal.

M represents a cation, preferably hydrogen, water-soluble cations and mixtures thereof. Non-limiting examples of water-soluble cations include sodium, potassium, lithium, ammonium, alkylammonium, and mixtures thereof.

detergent aid

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

Water-soluble, phosphorus-free organic builders useful herein include the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids, carboxylic acids, polycarboxylic acids and polyhydroxysulfonic acids. Suitable polycarboxylates for use in the present invention are polyacetal carboxylates, which are listed in U.S. Patents 4,144,226, Crutchfield et al., issued March 13, 1979, and in U.S. Patents 4,246,495, Crutchfield et al. Both of these patents are described in, and these two patents are incorporated herein by reference. Particularly preferred polycarboxylate builders are oxidized disuccinate and ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate, which compositions describe In US Patent 4,663,071, Bush et al., issued May 5, 1987, incorporated herein by reference.

Examples of suitable phosphorus-free inorganic builders include silicates, aluminosilicates, borates and carbonates. Particularly preferred are sodium and potassium carbonates, bicarbonates, sesquicarbonates, tetraborate decahydrates, and _SiO2 to alkali metal oxides in a weight ratio of from about 0.5 to about 4.0, preferably from about 1.0 to Silicate of about 2.4. Aluminosilicates including zeolites are also preferred. These materials and their use as builders are more fully discussed in US Patent 4,605,509 to Corkill et al., the disclosure of which is incorporated herein by reference. Crystalline layered silicates suitable for use in the detergent compositions of the present invention are also discussed in US Patent No. 4,605,509.

optional detergent ingredients

In addition to surfactants, the builder and dye maintenance polymers of the detergent compositions of the present invention may also comprise a number of other optional ingredients. These ingredients include conventional detergent composition ingredients such as enzymes and enzyme stabilizers, suds boosters or suppressors, antitarnish and corrosion inhibitors, bleaching agents, stain suspending agents, soil release agents, bactericides, pH adjusters , non-builder alkalinity, chelating agents, organic and inorganic fillers, solvents, solubilizers, optical brighteners, dyes and fragrances.

In certain applications where the pH of the wash solution is greater than about 10.0, a pH adjuster is necessary because at higher pH the fabric integrity benefit of the defined composition will begin to diminish. Therefore, if the pH of the wash solution is greater than about 10.0 after addition of the dye maintenance polymers of the present invention, the pH of the wash solution should be lowered to below about 10.0, preferably below about 9.5, most preferably below at about 7.5. Suitable pH regulators are known to those skilled in the art.

Preferred optional ingredients for incorporation into the detergent compositions of the present invention include bleaches, such as peroxygen bleaches. Such peroxygen bleaches may in fact be organic or inorganic. Inorganic peroxygen bleaches are often used in combination with bleach activators.

Useful organic peroxygen bleaches include percarboxylic acid bleaches and their salts. Suitable examples of such bleaching agents include magnesium monoperoxyphthalate hexahydrate, m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Magnesium salt. Disclosed in U.S. Patent 4,483,781 issued November 20, 1984 to Hartman, European Patent Application EP-A-133,354 issued February 20, 1985 to Banks et al., and U.S. Patent 4,412,934 issued November 1, 1983 to Chung et al. these bleaches. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) described in US Patent 4,634,551, issued January 6, 1987 to Bums et al.

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

Preferably, inorganic peroxygen bleaches such as perborates, percarbonates, etc. are combined with bleach activators which result in in situ generation of the corresponding bleaching agent in aqueous solution (i.e. during washing/bleaching of fabrics with the compositions of the present invention). Activator peroxyacid. Various non-limiting examples of activators are disclosed in US Patent 4,915,854, issued April 10, 1990 to Mao et al., and US Patent 4,412,934, issued November 1, 1983 to Chung et al. Representative and preferred are nonanoylbenzensulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators. Mixtures thereof can also be used. See also US Patent 4,634,551, cited above, for other typical bleaches and activators useful herein.

Other useful amido-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 a compound containing about 6 to about 12 carbon atoms R is an alkylene group ^{containing 1} to about 6 carbon atoms, R 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 displaced from the bleach activator due to the nucleophilic attack of the bleach activator by the perhydrolysis anion. A preferred leaving group is phenolsulfonate.

Preferred examples of bleach activators of the above formula include (6-octaamidocaproyl)oxybenzenesulfonate, (6-nonamidocaproyl)oxybenzenesulfonic acid described in U.S. Patent No. 4,634,551 cited above. salt, (6-decanoylaminocaproyl)oxybenzenesulfonate and mixtures thereof.

Another class of useful bleach activators includes the benzoxazin-type activators disclosed in US Patent 4,966,723, Hodge et al., issued October 30, 1990, which is incorporated herein by reference. See also US Patent 4,545,784, Sanderson, issued October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.

Peroxygen bleach, if employed, will generally comprise from about 2% to about 30% by weight of the detergent compositions herein. More preferably, the peroxygen bleach comprises from about 2% to about 20% by weight of the composition. Most preferably the peroxygen bleach comprises from about 3% to about 15% by weight of the composition. Bleach activators, if employed, can comprise from about 2% to about 10% by weight of the detergent compositions herein. Activators are often used so 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.

Other suitable bleaches and bleach activators are disclosed in one or more of the co-pending PCT applications listed in Table A, which are incorporated herein by reference.

Another highly preferred optional ingredient in the detergent compositions of the present invention is a detersive enzyme ingredient. Enzymes may be included in the detergent compositions of the present invention for a variety of purposes, including removal of protein-based, carbohydrate-based or triglyceride-based stains from substrates, preventing the transfer of refugee dye in fabric laundering , and the reply fabric. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof of any suitable origin such as vegetable, animal, bacterial, fungal and yeast origin. The preferred choice is influenced by factors such as pH activity and/or stability, optimum thermostability, and stability to high performance detergents, builders, and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases.

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

Enzymes are generally incorporated into detergent compositions at levels sufficient to provide a "detergent effective amount". The term "detergency effective amount" refers to any amount capable of producing a cleaning, stain removal, stain removal, whitening, deodorizing or lint improving effect on a substrate such as a fabric. In current practice in commercial preparations, active enzymes are typically present at levels up to about 5 mg, more typically 0.01 mg to 3 mg, per gram of detergent composition. In other words, the compositions of the invention generally comprise from 0.001% to 5% by weight, preferably from 0.01% to 1% by weight of a commercial enzyme preparation. Proteases are usually present in such commercial preparations in an amount sufficient to provide 0.005-0.1 Anson Unit (AU) activity per gram of composition. In highly concentrated detergent formulations, higher active levels are desirable.

Cellulases that can be used in the present invention include those disclosed in U.S. Patent 4,435,307, Barbesgoard et al., March 6, 1984, and GB-A-2.075.028, GB-A-2.095.275, DE-OS-2.247.832 those enzymes. CAREZYME® ^{and CELLUZYME®} (Novo) are especially useful. See also WO9117243 to Novo.

The enzyme-containing compositions of the present invention may also optionally comprise 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 detergent enzyme. Such a system may be provided internally by other formulation actives or added separately, for example by the formulator or the manufacturer of detergent-ready enzymes. Such stabilizing systems can comprise, for example, calcium ions, boron ions, propylene glycol, short chain carboxylic acids, boric acids, and mixtures thereof, and can be designed to address different stability issues depending on the type and physical form of the detergent composition.

Preparation of detergent compositions

The detergent compositions of the present invention may be in liquid, paste or granular form. The compositions may be prepared by combining the essential and optional ingredients in any suitable order and in the desired concentrations, or by any conventional method. The foregoing descriptions of the applications of the dye maintenance polymers defined herein are illustrative examples, other applications will be apparent to those skilled in the art and are within the scope of the invention.

For example, granular compositions are usually prepared by combining basic granular ingredients such as surfactants, builders, water, etc. into a slurry, and spray-drying the resulting slurry to contain a small amount of residual moisture (5- 12%). The remaining dry ingredients, such as granules of the necessary dye maintenance polymer, can be mixed in the form of a granulated powder with the spray-dried granules in a rotating mixing drum. Solutions of liquid ingredients such as necessary dye maintenance polymers, 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 "compressed form", that is to say they may have a density relatively higher than conventional granular detergents, ie 550-950 g/l. In such cases, the granular detergent compositions of the present invention will contain lower amounts of "inorganic filler salts" than conventional granular detergents; typical filler salts are alkaline earth metal sulphates and chlorides, having Sodium sulphate is typical; "compressed" detergents generally contain no more than 10% filler salts.

Liquid detergent compositions can be prepared by admixing the essential and optional ingredients of the liquid detergent composition together in any desired order to provide compositions containing the ingredients in the desired concentrations. The liquid compositions of the present invention may also be in "compressed form", in which case the liquid detergent compositions of the present invention will contain a lower amount of water than conventional liquid detergents. Dye maintenance polymers can be added to liquid detergent or other aqueous compositions of the present invention by simply mixing the desired dye maintenance polymer into the liquid solution.

fabric washing method

The present invention also provides a method of laundering fabrics in a manner which imparts to the fabric the appearance benefits provided by the dye maintenance polymers used in the present invention. The method comprises contacting the fabrics with an aqueous wash solution formed from an effective amount of the above-described detergent composition or from the individual ingredients of the composition. Contacting of the fabrics with the wash solution typically occurs under agitation, although the compositions of the present invention may also be used to form aqueous non-agitated soaking solutions for laundering and treating fabrics. As noted above, preferably the wash 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 good wash results, it is preferred to wash in a washing machine to provide agitation. The wet fabrics are preferably dried in a conventional laundry dryer after washing. Preferably, the effective amount of the high density liquid or granular detergent composition in the aqueous wash solution in the washing machine is from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm.

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.

Embodiment 1

Table I includes a number of examples of the present invention as well as some comparative examples of materials known in the laundry detergent art. The chemical structures shown in the examples below are idealized structures. Side reactions expected to occur during concentration are not shown.

Table I Examples# substance 1 Poly(N,N dimethylaminoethyl methacrylate) 2 Poly(N,N dimethylaminoethyl methacrylate), MW 9700 3 Poly(N,N dimethylaminoethyl methacrylate), MW 15,700 4 Poly(N,N dimethylaminoethyl methacrylate), MW 39,700 5 Poly(N,N dimethylaminoethyl methacrylate-co-dimethylacrylamide) ratio 1:1 MW 13670 6 Poly(N,N dimethylaminoethyl methacrylate-co-dimethylacrylamide) ratio 2:1 MW 14,400 7 Poly(N,N dimethylaminoethyl methacrylate-co-dimethylacrylamide) ratio 3:1 MW 16,300 8 Methyl quat of poly(N,N dimethylaminoethyl methacrylate) 9 Amine oxide of poly(N,N dimethylaminoethyl methacrylate) 10 Poly(N,N dimethylaminoethyl methacrylate-co-octylacrylamide) ratio 3:1, MW 6730 11 Poly(N,N dimethylaminoethyl methacrylate-co-acrylic acid) ratio 1:1, MW 14,950 12 Poly(N,N dimethylaminoethyl methacrylate-acrylamide) ratio 1:1 Poly(N,N dimethylaminoethyl methacrylate-propane sultone) ratio 1:1 13 Poly(dimethyldiallylammonium chloride) sold under the trade name Merquat 100 by Calgon Corporation, Pittsburg, PA 14 Poly(dimethyldiallylammonium chloride-co-acrylamide) sold under the trade name Merquat Plus (Calgon Corporation, Pittsburg, PA) 15 Poly(dimethyldiallylammonium chloride-co-acrylamide) sold under the trade name Merquat 550 (Calgon Corporation, Pittsburg, PA) 16 Poly(dimethyldiallylammonium chloride-co-acrylic acid) sold under the trade name Merquat 280 (Calgon Corporation, Pittsburg, PA) 17 Poly(N-methyl,N-octadecylaminoethyl methacrylate) quaternized with dimethyl sulfate (CTFA nomenclature polyquatemium 8) 18 Ionene polymer of N,N,N',N'tetramethylhexamethylenediamine and 1,6-dibromohexane in a ratio of 4:3 19 polyvinylamine 20 Poly(vinylamine-co-vinyl alcohol) ratio 1:1 twenty one Poly(vinylamine-co-acrylic acid) ratio 1:1 twenty two polyallylamine twenty three Poly(vinylamine-co-vinylformamide) ratio 1:1 twenty four Polyvinylamine ethoxylated with 0.5 mole ethylene oxide/NH 25 Polyvinylamine propoxylated with 0.5 mole propylene oxide/NH 26 Polyquaternium 2 sold under the tradename Mirapol A15 by Rhone Poulenc, Paris, France (CTFA nomenclature) 27 Polyquaternium 17 sold under the tradename Mirapol AD-1 (CTFA nomenclature) by Rhone Poulenc, Paris, Fratnce 28 Copolymer of N-methylvinylpyridine-co-vinylpyridine (ratio 4:1) 29 Copolymer of N-methylvinylpyridine-co-vinylpyridine (ratio 4:6) 30 Poly(N-methylvinylpyridine-co-vinylpyridine N oxide) ratio 4:1 31 Poly(N-methylvinylpyridine-co-vinylpyridine N-oxide) ratio 4:6

Example II

Preparation of Granular Detergent Test Compositions

Several high-efficiency granular detergent compositions were prepared which contained one or more dye maintenance polymers with the DMPs of the present invention. These granular detergent compositions all have the following basic formula:

Table II Composition Weight % C ₁₂ linear alkylbenzene sulfonate 9.31 C _14-15 alkyl ether (0.35 EO) sulfate 12.74 Zeolite builder 27.79 Sodium carbonate 27.31 PEG 4000 1.60 Dispersant 2.26 C _12-13 fatty alcohol ethoxylate (9 EO) 1.5 Sodium perborate 1.03 Soil release polymer 0.41 Enzyme 0.59 Dye Maintenance Polymer 3.0 Fragrances, brighteners, foam suppressors, other minor balancing ingredients, moisture, sulfates 100%

Example III

Preparation of Liquid Detergent Test Composition

Several high performance liquid detergent compositions were prepared which contained one or more dye maintenance polymers with the DMPs of the present invention. These liquid detergent compositions all have the following basic formula:

Table III Composition 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 Dye Maintenance Polymer 1.0 Dyes, fragrances, brighteners, preservatives, balance of foam suppressors, other minor ingredients, water 100%

Example IV

Preparation of Granular Detergent Test Compositions

Several granular detergent compositions were prepared which contained one or more dye maintenance polymers with a DMP according to the invention. These granular detergent compositions all have the following basic formula:

Table IV Example Comparative example Composition Weight % Weight % Sodium C ₁₂ linear alkylbenzene sulfonate 9.40 9.40 Sodium C _14-15 alkylsulfonate 11.26 11.26 Zeolite builder 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 Dye Maintenance Polymer 0.8 0 Other auxiliary ingredients Balance amount Balance amount 100% 100%

Claims (11)

1. detergent composition, it comprises: a) tensio-active agent of 4%-70% weight, b) dye maintenance polymers of 0.01%-5% weight or oligopolymer, described polymkeric substance or

Multipolymer comprises one or more and has unit of following formula:

I) have the linear polymer unit of following formula: Each R wherein ¹Independent is a) hydrogen; B) C ₁-C ₄Alkyl; C) replacement or unsubstituted phenyl; D) replacement or not substituted benzyl; E) carbocyclic ring; F) heterocycle; G) and their mixture; Each R ²Independent is a) hydrogen; B) halogen; C) C ₁-C ₄Alkyl; D) C ₁-C ₄Alkoxyl group; E) replacement or unsubstituted phenyl; F) replacement or not substituted benzyl; G) carbocyclic ring; H) heterocycle; I) and their mixture; Each Z independently is an a) hydrogen; B) hydroxyl; C) halogen; D)-(CH ₂) _mR;

Wherein R is:

I) hydrogen;

Ii) hydroxyl;

Iii) halogen;

Iv) nitrilo;

v)????-OR ³；

vi)???-O(CH ₂) _nN(R ³) ₂；

vii)??-O(CH ₂) _nN ⁺(R ³) ₃X ^-；

viii)?-OCO(CH ₂) _nN(R ³) ₂；

ix)???-OCO(CH ₂) _nN ⁺(R ³) ₃X ^-；

x)????-NHCO(CH ₂) _nN(R ³) ₂；

xi)???-NHCO(CH ₂) _nN ⁺(R ³) ₃X ^-；

Xii)??-(CH ₂) _nN(R ³) ₂；

xiii)?-(CH ₂) _nN ⁺(R ³) ₃X ^-；

Xiv) carbocyclic ring;

Xv) heterocycle;

Xvi) quaternary nitrogen heterocycle;

Xvii) N-oxide compound nitrogen heterocyclic;

Xviii) quaternary ammonium aromatics N-heterocycle;

Xix) N-oxide compound aromatics N-heterocycle;

xx)???-NHCHO；

Xxi) or their mixture;

Each R ³Independent is hydrogen, C ₁-C ₈Alkyl, C ₂-C ₈Mixing of hydroxyalkyl and theirs

Compound; X is a water soluble anion; Subscript n is 0-6; E)-(CH ₂) _mCOR '

Wherein R ' is:

i)???-OR ³；

ii)??-O(CH ₂) _nN(R ³) ₂；

iii)?-O(CH ₂) _nN ⁺(R ³) ₃X ^-；

iv)??-NR ³(CH ₂) _nN(R ³) ₂；

v)???-NR ³(CH ₂) _nN ⁺(R ³) ₃X ^-；

vi)??-(CH ₂) _nN(R ³) ₂；

vii)?-(CH ₂) _nN ⁺(R ³) ₃X ^-；

Viii) or their mixture;

Each R ³Independent is hydrogen, C ₁-C ₈Alkyl, C ₂-C ₈Hydroxyalkyl and they

Mixture; X is a water soluble anion; Subscript n is 0-6;

F) and their mixture;

Subscript m is 0-6; II) derived from the annular unit of ring-type polymerization single polymerization monomer with following formula:

Each R wherein ⁴Independent is alkene, this alkene contain except can with adjacent R ⁴

The unit forms outside the ring-type residue, can also increase the unit of polyreaction; R ⁵For

C ₁-C ₁₂Linearity or branched-alkyl, benzyl, substituted benzyl and their mixing

Thing; X is a water soluble anion; And III) their mixture; Condition is that described polymkeric substance or multipolymer have clean cationic charge; And wherein said dye maintenance polymers is not polymine or its oxyalkylated derivative, and c) carrier of equal amount and other ancillary component.

2. the detergent composition of claim 1, wherein said dye maintenance polymers is a multipolymer, it comprises:

I) first monomer, be selected from (methyl) vinylformic acid N, N-dialkyl aminoalkyl ester, vinylformic acid N, N-dialkyl aminoalkyl ester, N, N-dialkyl aminoalkyl acrylamide, N, N-dialkyl aminoalkyl (methyl) acrylamide, their quaternary ammonium derivative and the mixture of above-mentioned substance; With

Ii) second monomer is selected from vinylformic acid, methacrylic acid, methacrylic acid C ₁-C ₆Alkyl ester, vinylformic acid C ₁-C ₆Alkyl ester, vinylformic acid C ₁-C ₈Hydroxy alkyl ester, methacrylic acid C ₁-C ₈Hydroxy alkyl ester, acrylamide, C ₁-C ₁₆Alkyl acrylamide, C ₁-C ₁₆Dialkyl group acrylamide, 2-acrylamide-2-methyl propane sulfonic acid or its alkali salt, Methacrylamide, C ₁-C ₁₆Alkyl methyl acrylamide, C ₁-C ₁₆Dialkyl methyl acrylamide, vinyl formamide, vinyl acetamide, vinyl alcohol, C ₁-C ₈Vinyl alkyl ethers, vinyl pyridine, methylene-succinic acid, vinyl-acetic ester, propionate, vinyl butyrate and their mixture, described multipolymer comprise first monomer of at least 25 moles of %.

3. claim 1 or 2 composition, wherein said ancillary component is selected from ionogen, stablizer, low-molecular weight water-soluble solvent, sequestrant, dispersed auxiliary agent, stain remover, non-ionic type fabric softener, concentrated assistant, spices, sanitas, tinting material, white dyes, opalizer, sterilant, mycocide, anticorrosive agent, defoamer and their mixture.

4. detergent composition, it comprises:

A) tensio-active agent of 4%-70%;

B) dye maintenance polymers of 0.01%-10% weight or oligopolymer, described dye maintenance polymers are selected from homopolymer, multipolymer, terpolymer and their mixture with following formula:

Each R wherein ¹, R ²Be hydrogen or methyl; Z has following formula:

-(CH ₂) _mR

Wherein m equals 0 or 1; R is

-N (R ³) ₂Or-N ⁺(R ³) ₃X ^-

R ³Be selected from hydrogen, C ₁-C ₄Alkyl, C ₂-C ₄Hydroxyalkyl and their mixture; X

Be water soluble anion; With

C) carrier of equal amount and ancillary component.

5. each composition among the claim 1-4, it comprises the described dye maintenance polymers of 0.1%-8% weight.

6. each composition among the claim 1-5, wherein said dye maintenance polymers is the multipolymer that comprises linear polymerization monomer and ring-type polymerization single polymerization monomer, described ring-type polymerization single polymerization monomer has following formula:

R wherein ⁵Be C ₁-C ₄Alkyl and composition thereof; X is a water soluble anion.

7. each composition among the claim 1-5, wherein said dye maintenance polymers is selected from muriate, bromide or Methylsulfate and the monomeric homopolymer of copolymerization, multipolymer, terpolymer and their mixture of diallyl dimethyl ammonium, and described comonomer is selected from vinylformic acid, methacrylic acid, methacrylic acid C ₁-C ₆Alkyl ester, vinylformic acid C ₁-C ₆Alkyl ester, vinylformic acid C ₁-C ₈Hydroxy alkyl ester, methacrylic acid C ₁-C ₈Hydroxy alkyl ester, acrylamide, C ₁-C ₁₆Alkyl acrylamide, C ₁-C ₁₆Dialkyl group acrylamide, 2-acrylamide-2-methyl propane sulfonic acid or its alkali salt, Methacrylamide, C ₁-C ₁₆Alkyl methyl acrylamide, C ₁-C ₁₆Dialkyl methyl acrylamide, vinyl formamide, vinyl acetamide, vinyl alcohol, C ₁-C ₈Vinyl alkyl ethers, vinyl pyridine, methylene-succinic acid, vinyl-acetic ester, propionate, vinyl butyrate and their mixture.

8. each composition among the claim 1-5, wherein said dye maintenance polymers is the multipolymer that comprises linear polymerization monomer and ring-type polymerization single polymerization monomer, described ring-type polymerization single polymerization monomer has following formula:

R wherein ⁵Be C ₁-C ₄Alkyl and composition thereof; X is a water soluble anion.

9. each composition among the claim 1-5, it comprises multipolymer, and wherein Z has following formula:

-(CH ₂) _mCOR wherein each R independently is-O (CH ₂) _nN (R ³) ₂,-O (CH ₂) _nN ⁺(R ³) ₃X ^-,-(CH ₂) _nN (R ³) ₂,-(CH ₂) _nN ⁺(R ³) ₃X ^-And their mixture, m is 0, n is 2-4.

10. multipolymer, polymkeric substance and the monomer ratio that the composition of claim 1, wherein said dye maintenance polymers comprise multipolymer that ratio is 4: 1 N-ethylene methacrylic yl pyridines and vinyl pyridine, N-ethylene methacrylic yl pyridines that ratio is 4: 6 and vinyl pyridine be 4: 1 poly-(N-ethylene methacrylic yl pyridines) and vinyl pyridine N-oxide compound multipolymer, to contain polymkeric substance and monomer ratio be 4: 6 poly-(N-ethylene methacrylic yl pyridines) and the polymkeric substance of vinyl pyridine N-oxide compound and their mixture.

11. a method that reduces the dye for fabrics loss, it comprises the step that DYED FABRICS is contacted with cloth-washing detergent, and described washing composition comprises:

A) tensio-active agent of 4%-70% weight,

B) dye maintenance polymers of 0.01%-5% weight or oligopolymer, described polymkeric substance or multipolymer comprise one or more and have unit of following formula:

I) have the linear polymer unit of following formula:

Each R wherein ¹Independent is a) hydrogen; B) C ₁-C ₄Alkyl; C) replacement or unsubstituted phenyl; D) replacement or not substituted benzyl; E) carbocyclic ring; F) heterocycle; G) and their mixture; Each R ²Independent is a) hydrogen; B) halogen; C) C ₁-C ₄Alkyl; D) C ₁-C ₄Alkoxyl group; E) replacement or unsubstituted phenyl; F) replacement or not substituted benzyl; G) carbocyclic ring; H) heterocycle; I) and their mixture; Each Z independently is an a) hydrogen; B) hydroxyl; C) halogen; D)-(CH ₂) _mR;

Wherein R is:

I) hydrogen;

Ii) hydroxyl;

Iii) halogen;

Iv) nitrilo;

v)????-OR ³；

vi)???-O(CH ₂) _nN(R ³) ₂；

vii)??-O(CH ₂) _nN ⁺(R ³) ₃X ^-；

viii)?-OCO(CH ₂) _nN(R ³) ₂；

ix)???-OCO(CH ₂) _nN ⁺(R ³) ₃X ^-；

x)????-NHCO(CH ₂) _nN(R ³) ₂；

xi)???-NHCO(CH ₂) _nN ⁺(R ³) ₃X ^-；

xii)??-(CH ₂) _nN(R ³) ₂；

xiii)?-(CH ₂) _nN ⁺(R ³) ₃X ^-；

Xiv) carbocyclic ring;

Xv) heterocycle;

Xvi) quaternary nitrogen heterocycle;

Xvii) N-oxide compound nitrogen heterocyclic;

Xviii) quaternary ammonium aromatics N-heterocycle;

Xix) N-oxide compound aromatics N-heterocycle;

xx)???-NHCHO；

Xxi) or their mixture;

Each R ³Independent is hydrogen, C ₁-C ₈Alkyl, C ₂-C ₈Hydroxyalkyl and their mixture; X is a water soluble anion; Subscript n is 0-6; E)-(CH ₂) _mCOR '

Wherein R ' is:

i)???-OR ³；

ii)??-O(CH ₂) _nN(R ³) ₂；

iii)?-O(CH ₂) _nN ⁺(R ³) ₃X ^-；

iv)??-NR ³(CH ₂) _nN(R ³) ₂；

v)???-NR ³(CH ₂) _nN ⁺(R ³) ₃X ^-；

vi)??-(CH ₂) _nN(R ³) ₂；

vii)?-(CH ₂) _nN ⁺(R ³) ₃X ^-；

Viii) or their mixture;

Each R ³Independent is hydrogen, C ₁-C ₈Alkyl, C ₂-C ₈Hydroxyalkyl and their mixture; X is a water soluble anion; Subscript n is 0-6; F) and their mixture;

Subscript m is 0-6; II) derived from the annular unit of ring-type polymerization single polymerization monomer with following formula:

Each R wherein ⁴Independent is alkene, this alkene comprise except can with adjacent R ⁴Single

Unit forms outside the ring-type residue, can also increase the unit of polyreaction; ^R5 is C ₁-

C ₁₂Linearity or branched-alkyl, benzyl, substituted benzyl and their mixture;

X is a water soluble anion; And III) their mixture; Condition is that described polymkeric substance or multipolymer have clean cationic charge; And described dye maintenance polymers is not polymine or its oxyalkylated derivative, and c) carrier of equal amount and other ancillary component.