CN106459842A

CN106459842A - Cleaning compositions containing cationic polymers, and methods of making and using same

Info

Publication number: CN106459842A
Application number: CN201580016211.7A
Authority: CN
Inventors: 司刚; 秦鹏; 张祺; S·夏拉; S·伯克尔; 秦东言; 汤鸣; M·R·斯维克; R·K·帕纳戴克; C·曼德拉; A·佛罗瑞斯-菲格罗亚; 葛慧
Original assignee: Procter and Gamble Ltd
Current assignee: BASF SE
Priority date: 2014-03-26
Filing date: 2015-03-13
Publication date: 2017-02-22
Anticipated expiration: 2035-03-13
Also published as: EP3122854A1; WO2015144053A1; CN106795461A; CN106795461B; WO2015143997A1; WO2015144053A8; EP3122856A1; CN106459842B; EP3122854B1

Abstract

The present invention relates to cleaning composition, preferably a laundry detergent composition, comprising a cationic polymer capable of improving the overall sudsing profile of such cleaning composition.

Description

Comprise Cleasing compositions and its preparation and application of cationic polymer

Technical field

The present invention relates to Cleasing compositions, and specifically it is related to laundry detergent composition, preferably liquid laundry Composition of detergent, it comprises the cationic polymer of the effective dose for optimizing sudsing profile.The invention still further relates to preparation and Method using such Cleasing compositions.

Background technology

Sudsing profile is important for Cleasing compositions, specifically laundry detergent compositions, wherein in washing and rinse cycle It is the key reference of performance that the proper volume of middle formation of foam and speed, holding and dissolving are considered by consumers.With regard to clothes washing Although sudsing profile is important for machine washing process for agent, but it is even more important during typical hand washing, because Consumer can be seen that the change of bubble content in washing and rinse cycle.Generally, consumer, specifically hand washing consumer it is desirable to The laundry detergent compositions being dissolved in wash liquid produce the performance that a large amount of foams to represent enough during cycles of washing.Then described Foam proceeds in rinsing solution and requires additional time, water and labour to be thoroughly rinsed from laundering of textile fabrics.

However, reducing foam overall content is not feasible option, because consumer is seen seldom during cycles of washing Or there is no foam, it leads to consumer to believe that laundry detergent compositions are not active.Additionally, current market demand is laundry detergent compositions There is the Environmental Sustainability (for example, less water consumption) of improvement but the sense of clean-up performance or clean-up performance can not adversely be affected Know the outward appearance of foam (that is, on fabric or in rinsing solution).This strengthens certainly to the Sudo controlling compositions with improvement The preference of laundry detergent compositions, to accelerate rinse cycle during foam dissolving in case reduce from the fabric/rinsing solution cleaning Extra rinse circulation needed for scumming.Accordingly, it would be desirable to a kind of Cleasing compositions, it has sudsing profile, wherein in washing There is high-load foam volume during circulation, but the purpose for cost savings and environmental conservation, quick in drift solution Collapse to substantially reduce foam or there is zero foam.This is referred to as " once rinsing " theory.

A solution is addition defoamer during rinse cycle, but this option is for great majority hand washing consumer Speech high cost.In addition, prior art discloses have the laundry detergent composition of various foam controllers or defoamer with Attempt to solve this problem.For example, PCT Publication WO2011/107397 (Unilever) discloses laundry detergent composition, its Comprise the defoamer based on amino-siloxanes of sustained release, described defoamer absorbs on carrier or filler to follow in rinsing Act on thus reducing or eliminating foam in ring, preferably after rinse cycle twice.However, by such based on amino-silicon The foam control beneficial effect that the defoamer of oxygen alkane gives may still occur under sacrificing washing foam, i.e. because siloxanes Release time is difficult to control to, so washing foam volume can substantially reduce.The out of season release of silicone antifoam agent can be led Cause substantially reducing of washing foam volume, this comprises relatively low surface-active contents by giving consumer's composition of detergent, from And there is the impression of lower quality/value.European publication EP0685250A1 (Dow Corning) discloses and washes for medicated clothing Wash the Sudo controlling compositions in agent, the formation of new foam during its suppression washing post rinse circulation, but its seem not accelerate from The elimination of the foam having existed that cycles of washing proceeds to.

Accordingly, it would be desirable to Cleasing compositions, preferably laundry detergent composition, it can strengthen bubble during cycles of washing Foam forms (stability or sustainability two side that the quick formation of Bulky foam and the foam having produced are passed in time Face), during one or many rinse cycle, quick minimizing and elimination foam (preferably wash in a series of consumers and practise simultaneously In the range of used and washed fabrics/materials surface) so that once washing circulation can be enough to remove foam such that it is able to reality Existing " once rinsing " theory.

Additionally, it is known that conventional defoamer or defoamer, especially polymer defoamer or defoamer circulate in repeated washing Lead to the loss of whiteness in significant fabric afterwards, i.e. be exposed to the Lycoperdon polymorphum Vitt in the fabric of many cycles of washing or dead color.Cause This, limited the use of such polymer defoamer or defoamer in laundry detergent composition.Therefore, also have The loss of whiteness reducing in fabric after repeated washing will be the advantage of laundry detergent composition.

Content of the invention

The present invention relates to laundry detergent composition, it shows significantly foam minimizing during rinse cycle, makes simultaneously During cycles of washing, the minimizing of foam volume minimizes, and less fabric whiteness loss after also resulting in repeated washing. It has now been found that the challenge being proposed above for conventional garments detergent can meet by using cationic polymer, Described cationic polymer comprises (methyl) acrylamide (AAm) of specific monomer ratio, cationic monomer unit and optionally Nonionic monomer unit (it is not AAm) simultaneously has molecular weight within the specified range.The cationic polymer of the I present invention is Excellent sudsing profile is shown and does not have or there is less fabric whiteness loss.

In one aspect, the present invention relates to laundry detergent composition, it comprises the effective dose optimizing for sudsing profile Cationic polymer, such cationic polymer comprises：I () about 10mol% to about 70mol% is derived from (methyl) propylene First nonionic structure unit of amide (AAm)；(ii) the second cationic structural unit of about 5mol% to about 40mol%； (iii) about 5mol% to about 60mol% is different from the 3rd nonionic structure unit of described first nonionic structure unit；With (iv) optionally, at least one additional knot different from described first, second, and third construction unit of 0mol% to 20mol% Structure unit, simultaneously total mol% of (i)-(iv) add up as 100mol%, and the feature of described cationic polymer simultaneously exists In the molecular weight (Mw) in the range of 15,000 to 1,000,000 dalton, and it is substantially free of derived from any siloxanes Construction unit.

In addition to cationic polymer, the laundry detergent composition of the present invention also can comprise one or more anion Surfactant.The content of described anion surfactant is in the range of 1 weight % to 50 weight %, and preferably selects From：C₁₀-C₂₀Linear alkylbenzene sulfonate (LAS), there is the C of average degree of alkoxylation in the range of 0.1 to 5.0₁₀-C₂₀Straight or branched Alkyl alkoxy sulfate, C₁₀-C₂₀The alkyl sulfate of straight or branched, C₁₀-C₂₀The Arrcostab sulphuric acid of straight or branched Salt, C₁₀-C₂₀The alkylsulfonate of straight or branched, C₁₀-C₂₀The alkyl ester sulfonate of straight or branched, C₁₀-C₂₀Straight chain or The alkylphosphonic of chain, C₁₀-C₂₀The alkyl phosphonate of straight or branched, C₁₀-C₂₀The alkyl carboxylate of straight or branched and Combinations thereof.

Second cationic structural unit preferably derived from or made by selected from following monomer：Diallyl dimethyl ammonium Salt (DADMAS), N, N- dimethylaminoethylacryl hydrochlorate, N, N- dimethyl aminoethyl methacrylate (DMAM), [2- (methacrylamido) ethyl] leptodactyline, N, N- dimethylaminopropylacryl amide (DMAPA), N, N- diformazan Base propyl methacrylamide (DMAPMA), acrylamido propyl trimethyl ammonium salt (APTAS), Methacrylamide propyl group Leptodactyline (MAPTAS), quatemized vinylimidazol (QVi) and combinations thereof.It is highly preferred that cationic polymer The second cationic structural unit derived from or be made up of diallyldimethylammonium chloride (DADMAC).

3rd nonionic structure unit preferably derived from or made by selected from following monomer：Vinyl pyrrolidone (VP), vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ethers, vinylpyridine, ethylene Base imidazoles, caprolactam and combinations thereof.It is highly preferred that the 3rd nonionic structure list of cationic polymer Unit is derived from VP.

The cationic polymer of the present invention also can comprise the 4th anion structure unit, and its content is 0mol% to about 20mol%, but described 4th anion structure unit preferably derived from ethylene yl carboxylic acid and its anhydride.Notice that incorporation is described 4th anion structure unit does not change the overall cationic characteristic of polymer, i.e. taken by described 4th anion structure unit Total anionic charge of band is less than the overall cationic charge that carried by the second cationic structural unit so that the total electrical charge of polymer Still it is rendered as cation.

In one embodiment of the invention, described cationic polymer comprises：I () about 15mol% is to about The first nonionic structure unit of 60mol%；(ii) the second cationic structural unit of about 10mol% to about 40mol%；With (iii) the 3rd nonionic structure unit of about 20mol% to about 55mol%.Preferably but without necessary, the sun of the present invention from Sub- polymer is substantially made up of said structure unit.

The molecular weight of cationic polymer, i.e. weight average molecular weight, preferably in about 15,000 to about 1,000,000 dongle , more preferably about 20,000 to about 500,000 dalton and most preferably about 20,000 to about 250,000 dalton In the range of.

Cationic polymer can be (i.e. similar to do not comprise described cationic polymer enough to give foaming beneficial effect Laundry detergent composition is compared, the washing foam volume of increase or the rinsing foam volume of minimizing or above-mentioned both) any Amount is present in laundry detergent composition.Preferably, the content of cationic polymer in about 0.01 weight % to about 15 weights Amount %, preferably about 0.05 weight % to about 10 weight %, more preferably about 0.1 weight % are to about 5 weight % and most preferably In the range of ground about 0.2 weight % to about 1 weight %.

On the other hand, the present invention relates to laundry detergent composition as described above is preferred for washing fabrics with reality The sudsing profile now optimizing and the purposes of minimum loss of whiteness.The sudsing profile optimizing can be by following sign：(1) be more than 100%, Preferably more than 105% and be more preferably larger than 110% washing foam index (WSI)；(2) be less than 50%, preferably Less than 45% and be even more preferably less than 40% rinsing foam index (RSI), such as pass through sudsing profile test hereinafter described Determined by.

On the other hand, the present invention relates to liquid laundry detergent composition, described compositionss comprise：

(1) cationic polymer of about 0.2 weight % to about 1 weight %, it has about 20,000 to about 250,000 dongle The molecular weight pausing, described cationic polymer substantially consists of：(i) about 15mol% to about 60mol% derived from The first nonionic structure unit of (methyl) acrylamide (AAm)；(ii) about 10mol% to about 40mol% is derived from diene Second cationic structural unit of diallyidimethylammonium chloride (DADMAC)；(iii) about 20mol%'s to about 55mol% is derivative The 3rd nonionic structure unit from vinyl pyrrolidone (VP)；(iv) 0mol% to about 10mol% is derived from (first Base) acrylic acid (AA), maleic acid (MA) and its anhydride the 4th anion structure unit；And

(2) about 1 weight % to about 50 weight % is selected from one or more following anion surfactant：C₁₀-C₂₀ The alkyl alkoxy sulfate of straight or branched, it has the average degree of alkoxylation in the range of about 0.5 to about 3, and it Combination.

When reading detailed description below in conjunction with claims, these and other features of the invention are for ability Will become clear from for the technical staff in domain.

Specific embodiment

Definition

As used herein, " foam " refers to non-equilibrium dispersion in relatively small volume of liquid for the bubble.Term such as " bubble Foam ", " foam ", " soap bubble " can in the implication of the present invention used interchangeably.

As used herein, " sudsing profile " refer to wash and rinse cycle in the related composition of detergent of foam characteristics Characteristic.The sudsing profile of composition of detergent includes but is not limited to the speed that foam produces when being dissolved in laundry wash liquor The volume of foam and disappearance in degree, the volume of foam and retentivity and rinse cycle in cycles of washing.Preferably, foaming is special Levy including washing foam index and rinsing foam index, as the method for testing disclosed in Examples below specifically defines 's.It may also include additional foam relevant parameter, foam stability of measurement etc. during cycles of washing.

As used herein, term " Cleasing compositions " refers to for processing fabric, hard surface and fabric and family's shield The liquid or solid compositionss on any other surface in reason field, and include hard surface cleaning and/or process, including ground Plate and bathroom detergent (such as Closestool cleanser)；Hand washing dishwashing detergent or gently dirty dishwashing detergent, especially high alveolitoid Those；Machine washing dishwashing detergent；Personal care composition；Pet nursing compositionss；Car care composition；And home care Compositionss.In one embodiment, Cleasing compositions of the present invention are hard surface cleaning composition it is preferable that wherein said Hard surface cleaning composition impregnated nonwoven substrate.

As used herein, term " laundry detergent composition " is the subset of " Cleasing compositions ", and include liquid or Solid composite, and except as otherwise noted, the multipurpose for fabric including granule or powder type or " weight dirt type " are washed Wash agent, especially cleaning detergent and cleaning adjuvant such as bleach, rinse aid, additive or pretreatment type.At one In embodiment, described laundry detergent composition is solid laundry detergent composition, and is preferably free-flowing Granular laundry detergent composition (i.e. detergent granules product).

As used herein, term " cationic polymer " refers to the polymer with cation net charge.Such polymer Generally comprise one or more cationic monomer.In addition to cationic monomer, it also can comprise one or more anion list Body and/or non-ionic monomer, but be positive (that is, cation) by the total electrical charge that all monomeric units in polymer carry.

As used herein, " charge density " refers to the net charge density of polymer itself, and may differ from monomer feed Net charge density.Can be by each being repeated the molecular weight divided by described repetitives for the net charges of (structure) unit, meter Calculate the charge density of homopolymer.Positive charge can be located on main polymer chain and/or polymer lateral chain.For some polymer, Such as have amine structure unit those, charge density depend on carrier pH.For these polymer, charge density is based on Monomer charge under pH 7 calculates.Generally, electric charge, with respect to paradigmatic structure unit, is not necessarily female monomer to determine.

As used herein, term " cationic charge density " (CCD) refers to the amount of the net positive charge that every gram of polymer exists. Cationic charge density (being counted in units of milliequivalent electric charge/gram polymer) can be calculated according to below equation：

Wherein：E2 is the molar equivalent of the electric charge of the second cationic structural unit；E4 is for the 4th anion structure unit (such as Fruit have if) electric charge molar equivalent；C2 is the molar percentage of the second cationic structural unit；C4 is the 4th anion knot The molar percentage of structure unit (if any)；C1 and C3 be first and the 3rd nonionic structure unit molar percentage； W1, W2, W3 and W4 be respectively the first nonionic structure unit, the second cationic structural unit, the 3rd nonionic structure unit and The molecular weight of the 4th anion structure unit (if any).For example, AAm, 5mol% of 80mol% are just comprised respectively For the AAm/QVi/VP polymer of QVi and 15mol%VP, its cationic charge density (meq/g) is calculated as：CCD=1000 ×E₂×C₂/(C₁W₁+C₂W₂+C₃W₃), wherein E₂=1, C₁=80, C₂=5, C₃=15, W₁=71.08, W₂=220.25 and W₃ =111.14.Therefore, the cationic charge density of this copolymer is CCD-1000 × 1 × 5/ (80 × 71.08+5 × 220.25+ 15×111.14)-0.59.And for example, AAm, 5mol%DADMAC, 15mol%VP and 4mol% of 76mol% are just comprised respectively For the Am/DADMAC/VP/AA polymer of VP, its cationic charge density (meq/g) is calculated as：CCD=1000 × (E₂C₂– E₄C₄)/(C₁W₁+C₂W₂+C₃W₃+C₄W₄), wherein E₂=1, E₄=1, C₁=76, C₂=5, C₃=15, C₄=4, W₁=71.08, W₂ =161.67, W₃=111.14 and W₄=72.06.Therefore, the cationic charge density of this copolymer is

As used herein, term " molecular weight " refers to the weight average molecular weight of polymer chain in polymer composition.In addition, " weight average molecular weight "

(" Mw ") can be calculated using below equation：

Mw=(Σ i Ni Mi²)/(Σi Ni Mi)

Wherein Ni is the number of the molecule with molecular weight Mi.Weight average molecular weight must be described in Test Methods section Method measures.

As used herein, " mol% " refers to the Relative mole percentage ratio of specific monomer construction unit in polymer.Should manage , in the implication of the present invention, the Relative mole percentage ratio being present in all monomeric building blocks in cationic polymer should be total for solution Meter reaches 100mol%.

As used herein, term " derived from " refer to (can be had by any derivant of compound or such compound One or more substituent groups) monomeric building blocks in the polymer made.Preferably, such construction unit is directly by discussing Compound is made.For example, term " construction unit derived from (methyl) acrylamide " refer to can by (methyl) acrylamide or There are the monomeric building blocks in the polymer that its any derivants of one or more substituent groups is made.Preferably, such knot Structure unit can be directly made up of (methyl) acrylamide.Term " (methyl) acrylamide " refers to Methacrylamide or acryloyl Amine, and it is referred to herein simply as " AAm ".

As used herein, term " ammonium salt " or " ammonium salt " refer to selected from following various compounds：Ammonium chloride, ammonium fluoride, Ammonium bromide, ammonium iodide, ammonium hydrogen sulfate, alkylsurfuric acid ammonium, ammonium dihydrogen phosphate, alkyl phosphoric acid hydrogen ammonium, Acidic phosphates ammonium etc..Example As diallyl dimethyl ammonium salt as described herein includes but is not limited to：Diallyldimethylammonium chloride (DADMAC), two Allyl dimethyl base ammonium fluoride, diallydimethyl ammonium bromide, diallydimethyl ammonium iodide, diallyidimethyl Sour hydrogen ammonium, diallydimethyl alkylsurfuric acid ammonium, diallydimethyl ammonium dihydrogen phosphate, diallydimethyl alkyl phosphorus Sour hydrogen ammonium, diallydimethyl Acidic phosphates ammonium and combinations thereof.Preferably but without necessary, ammonium salt is chlorine Change ammonium.

As used herein, when in for claim, article such as " one " and " one " be understood to mean one or Multiple materials being claimed or describing by right.

As used herein, term "comprising", " inclusion ", " inclusion ", "comprising" and " containing " be nonrestrictive.Term " by ... form " or " substantially by ... form " refer to restricted, that is, exclude any component specially do not listed or one-tenth Point, except in the presence of they are as impurity.As used herein, term substantially free refers to that composition is completely absent or only Impurity as another kind of composition or the minimal amount of composition of unexpected by-product.

As used herein, term " solid " includes granule, powder, strip and tablet form.

As used herein, term " fluid " includes liquid, gel, paste and gas product form.

As used herein, term " liquid " refers at 25 DEG C and 20 seconds^-1Have about 1 to about 2000mPa*s under shear rate The liquid of viscosity fluid.In some embodiments, 25 DEG C and 20 seconds^-1Liquid viscosity under shear rate can be about 200 To about 1000mPa*s.In some embodiments, 25 DEG C and 20 seconds^-1Liquid viscosity under shear rate can be about 200 To about 500mPa*s.

Except as otherwise noted, all temperature are all represented with degree Celsius (DEG C) herein.Except as otherwise noted, herein all Measurement is all carried out under 20 DEG C and ambient pressure.

In all embodiments of the present invention, unless stated otherwise, all percentage ratios are all by described total combination The weight meter of thing.Unless stated otherwise, all ratios are weight ratio.Dimension value preset disclosed herein should not be understood For being strictly limited to cited exact value.On the contrary, except as otherwise noted, otherwise each such dimension be intended to indicate that described value with And around the functionally equivalent scope of this value.For example, the dimension being disclosed as " 40mm " is intended to indicate that " about 40mm ".

It should be appreciated that when being described in herein and being protected by the claims hereof it is necessary to be tested using the application Method of testing disclosed in method part come to determine applicant invention parameters value.

Cationic polymer

Cationic polymer used by the present invention is the terpolymer comprising at least three kinds of different types of construction units. Construction unit or monomer can random patterns or can be mixed in cationic polymer with block pattern.

In particularly preferred embodiment of the invention, such cationic polymer is only comprising as described above First, second and the 3rd construction unit terpolymer, it is substantially free of any other structural constituent.Alternatively, it can wrap Include the one or more additional structure units the (for example, the 4th in addition to first, second, and third construction unit mentioned above Anion structure unit).

First structure unit in the cationic polymer of the present invention is derived from (methyl) acrylamide (AAm).Preferably, Cationic polymer comprises about 10mol% to about 70mol% and more preferably about 15mol% spreads out to the AAm of about 60mol% Raw construction unit.

The second construction unit in the cationic polymer of the present invention is can be derived from any suitable water-soluble cationic The cationic structural unit of ethylenically unsaturated monomers, such as N, N- methacrylates, N, N- propylene Acid dialkyl aminoalkyl ester, N, N- dialkylaminoalkyl acrylamide, N, N- dialkyl aminoalkyl Methacrylamide, Methacrylamidoalkyl trialkyl ammonium salts, acrylamido alkyl trialkyl ammonium salts, vinyl amine, vinyl imidazole, season Ammonium vinyl imidazole and diallyldialkylammonihalide salt.

Preferably, the second cationic structural unit is derived from selected from following monomer：Diallyl dimethyl ammonium salt (DADMAS), N, N- dimethylaminoethylacryl hydrochlorate, N, N- dimethyl aminoethyl methacrylate (DMAM), [2- (methacrylamido) ethyl] leptodactyline, N, N- dimethylaminopropylacryl amide (DMAPA), N, N- dimethyl Propyl methacrylamide (DMAPMA), acrylamido propyl trimethyl ammonium salt (APTAS), Methacrylamide propyl group three Methyl ammonium salt (MAPTAS) and quatemized vinylimidazol (QVi).

It is highly preferred that the second cationic structural unit is derived from diallyl dimethyl ammonium salt (DADMAS), such as institute above State.

Alternatively, the second cationic structural unit can derived from [2- (methacrylamido) ethyl] leptodactyline, Such as [2- (methacrylamido) ethyl] trimethyl ammonium chloride, [2- (methacrylamido) ethyl] trimethyl fluorination Ammonium, [2- (methacrylamido) ethyl] trimethylammonium bromide, [2- (methacrylamido) ethyl] trimethyl ammonium iodide, [2- (methacrylamido) ethyl] trimethyl ammonium hydrogen sulfate, [2- (methacrylamido) ethyl] trimethyl alkylsurfuric acid Ammonium, [2- (methacrylamido) ethyl] trimethyl ammonium dihydrogen phosphate, [2- (methacrylamido) ethyl] trimethyl alkane Base ammonium hydrogen phosphate, [2- (methacrylamido) ethyl] trimethyl Acidic phosphates ammonium and combinations thereof.

In addition, the second cationic structural unit can be derived from APTAS, it is included for example：Acrylamidopropyl trimethyl Ammonium chloride (APTAC), acrylamidopropyl trimethyl ammonium fluoride, acrylamidopropyl trimethylammonium bromide, acrylamide Base oxypropyl trimethyl ammonium iodide, acrylamidopropyl trimethyl ammonium hydrogen sulfate, acrylamidopropyl trimethyl alkylsurfuric acid Ammonium, acrylamidopropyl trimethyl ammonium dihydrogen phosphate, acrylamidopropyl trimethyl alkyl phosphoric acid hydrogen ammonium, acrylamido Oxypropyl trimethyl Acidic phosphates ammonium and combinations thereof.

In addition, the second cationic structural unit can be derived from MAPTAS, it includes such as methacryloylaminopropyl three Ammonio methacrylate (MAPTAC), methacryloylaminopropyl trimethyl ammonium fluoride, methacryloylaminopropyl front three bromide Change ammonium, methacryloylaminopropyl trimethyl ammonium iodide, methacryloylaminopropyl trimethyl ammonium hydrogen sulfate, metering system Cocamidopropyl trimethyl alkylsurfuric acid ammonium, methacryloylaminopropyl trimethyl ammonium dihydrogen phosphate, methacrylamido Oxypropyl trimethyl alkyl phosphoric acid hydrogen ammonium, methacryloylaminopropyl trimethyl Acidic phosphates ammonium and their mixture.

It is highly preferred that the second cationic structural unit is derived from DADMAC, MAPTAC, APTAC or QVi.Most preferably, The second cationic structural unit as referred to herein is directly made up of DADMAC.With respect to comprising the poly- of other cationic monomers Compound, the more preferable stability that the cationic polymer comprising DADMAC is shown in after the long-term frame Tibetan time in finished product and more Low stench release.

Second cationic structural unit preferably with about 5mol% to about 40mol% and more preferably about 10mol% Amount to about 40mol% is present in cationic polymer.The second appropriate cationic structural in cationic polymer Unit contributes to the overall cationic charge density of balance cation polymer, this to realizing final Betengent product, especially For desired frothing capacity and phase stability in detergent product it is critical that.

3rd nonionic structure unit is preferably derived from the non-ionic monomer based on vinyl, such as vinylpyrrolidone (VP), vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ethers, vinylpyridine, ethylene Base imidazoles, caprolactam and combinations thereof.It is highly preferred that the 3rd nonionic structure list of cationic polymer Unit is derived from VP.The cationic polymer in the present invention with VP can be especially advantageous in terms of delivering high washing foam.Sun Ionomer can include about 5mol% to about 60mol% and more preferably about 20mol% to about 55mol% the 3rd non- Ionic structure unit.

The cationic polymer of the present invention also can comprise the 4th optional anion structure unit, its derived from ethylene base carboxylic Acid or its anhydride, such as (methyl) acrylic acid, acrylic anhydride, maleic acid, maleic anhydride and combinations thereof.Cation is gathered Compound can include about 0mol% to about 20mmol%, more preferably 0mol%, and to about 10mol% and most preferably 0mol% is extremely The 4th anion structure unit of about 5mol%.

In specific embodiments of the present invention, cationic polymer does not comprise the 4th anion structure unit the (that is, the 4th The content of anion structure unit be 0mol%) or additional structure units in any one.In other words, the cation of the present invention Polymer is substantially made up of first, second, and third construction unit as described above.For example, such cationic polymer can Think the terpolymer substantially by following material composition：I () about 10mol% is to about 70mol%, preferably about 15mol% To the first nonionic structure unit derived from AAm for the about 60mol%；(ii) about 5mol% to about 40mol%, preferably about The second cationic structural unit of 10mol% to about 40mol%, it is preferably derived from DADMAC；And (iii) about 5mol% To about 60mol%, the 3rd nonionic structure unit of preferably about 20mol% to about 55mol%, it is preferably derived from VP.

In another specific embodiments of the present invention, cationic polymer also comprise the 4th anion structure unit but It is substantially free of any additional construction unit.In other words, the cationic polymer of the present invention is substantially by as described above First, second, third and fourth construction unit composition.For example, such cationic polymer can be substantially by following material group Become：(i) about 10mol% to about 70mol%, preferably about 15mol% the first nonionic derived from AAm to about 60mol% Construction unit；(ii) the second cationic structural list of about 5mol% to about 40mol%, preferably about 10mol% to about 40mol% Unit, it is preferably derived from DADMAC；(iii) about 5mol% to about 60mol%, preferably about 20mol% is to about 55mol%'s 3rd nonionic structure unit, it is preferably derived from VP；And (iv) about 0.1mol% to about 20mol%, preferably about The 4th anion structure unit of 0.5mol% to about 10mol%, it is preferably derived from (methyl) acrylic acid or its anhydride.The There is, with suitable amount, the hydrophilic contributing to improving cationic polymer in four anion structure units, and therefore improvement comprises institute State the stability of the final Betengent product of cationic polymer.

The first, second, third of fixed cationic polymer as noted above and the optionally the 4th construction unit specific Molar percentage scope for optimize washing and rinse cycle during by the laundry detergent compositions group comprising such cationic polymer Compound produce sudsing profile for it is critical that.In addition, comprising the mutually steady of the finished product of the cationic polymer of the present invention The qualitative molar percentage range effects by corresponding construction unit in cationic polymer, described molar percentage scope also by It is carefully chosen to make the separated minimum of finished product.

The laundry detergent composition of the cationic polymer comprising the present invention is characterised by by foaming defined below Feature：(1) greater than about 100%, preferably more than about 105% and be more preferably more than about 110% washing foam index (WSI)；And (2) are less than about 50%, preferably less than about 45% and are more preferably less than about 40% rinsing foam index (RSI), as determined by by sudsing profile test hereinafter described.Specifically, the laundry detergent composition tool of the present invention Have by greater than about 100% WSI and less than about 50% RSI, preferably more than about 105% WSI and less than about 45% RSI and be more preferably more than about 110% WSI and less than about 40% RSI limit optimal sudsing profile.

The specified molecular weight scope of fixed cationic polymer as noted above also provides the sudsing profile of improvement.More important Ground, such molecular weight ranges are particularly effective in terms of reducing loss of whiteness, and described loss of whiteness is common in and is exposed to repeatedly In fabric after washing.Known cationic polymer contributes to fabric whiteness loss, and this is that such polymer more widely uses Limiting factor.However, it has been found by the inventor that passing through the molecular weight control of cationic polymer in specified model In enclosing, i.e. about 15,000 to about 1,000,000 dalton, preferably about 20,000 to about 500,000 dalton, more preferably About 20,000 to about 250,000 dalton, compared with conventional cationic polymers, is effectively reduced fabric whiteness loss.

In addition, finished product rheological characteristic also can be affected by the molecular weight of cationic polymer.Therefore, the cation of the present invention is gathered The molecular weight of compound is also carefully chosen into makes the adverse effect to finished product rheological characteristic minimize.

Cleasing compositions

The present invention provides Cleasing compositions, and it comprises cationic polymer as mentioned above.In one aspect, described clear Cleansing composition (can include for hard surface cleaners (such as dishwashing detergent) with for those in health and cosmetic field Shampoo and soap), it may also benefit from the product with the sudsing profile of improvement.At a preferred aspect of the present invention, clearly Cleansing composition is designed to laundry detergent compositions application, for example：Clothes washing, including automatic washing machine clothes washing or hand washing, Or cleaning adjuvant, such as bleach, rinse aid, additive or pretreatment type.

Described Cleasing compositions or laundry detergent composition can be in any form, i.e. form can be liquid, solid (such as powder, granule, agglomerate, paste, tablet, pouch, bar, gel), emulsion, delivered with double Compartment comtainers or pouch Type, spraying or foam shampoo, the cleaning piece (that is, the Cleasing compositions combining with non-woven material) pre-wetting, by The dry wipe (that is, the Cleasing compositions combining with non-woven material) that consumer is activated with water and other are homogeneous or many Consumer cleaning product's form of phase.

Laundry detergent composition is preferably liquid laundry detergent, and can produce for full formula laundry detergent compositions Product.Including the fluid composition being contained in encapsulating and/or unitized dose product, such as comprise two or more independently but join Close the compositionss of distribution portion.It is highly preferred that laundry detergent composition is the liquid laundry detergent being designed to hand-wash The foam effect of compositionss, wherein improvement or excellent sudsing profile are the most obvious to consumer.Liquid laundry detergent group Compound preferably comprises water as aqueous carrier, and it can comprise the mixed of single water or one or more organic solvent and water Compound is as one or more carrier.Suitable organic solvent is the rudimentary C of straight or branched₁-C₈Alcohol, glycol, glycerol or binary Alcohol；Rudimentary amine solvent such as C₁-C₄Alkanolamine, and their mixture.Exemplary organic solvent include 1,2- propylene glycol, Ethanol, glycerol, monoethanolamine and triethanolamine.The usual gross weight meter by described fluid composition of carrier is with about 0.1% to about 98%, the content in the range of preferably about 10% to about 95%, more preferably about 25% to about 75% is present in fluid composition In.In some embodiments, water is about 85 weight % of carrier to about 100 weight %.In other embodiments, water is not deposited And compositionss are anhydrous.Highly preferred compositionss provided by the present invention are clarification, isotropic liquid.

The liquid laundry detergent composition of the present invention has about 1 to about 2000 centipoise (1-2000mPa s), or about 200 Viscosity to about 800 centipoises (200-800mPa s).The measurement of viscosity can use Brookfield viscometer, No. 2 rotors, with The speed of 60RPM/s determines at 25 DEG C.

The cationic polymer amount of the present invention in laundry detergent compositions or Cleasing compositions is not particularly limited, as long as it is right There is provided optimal sudsing profile effectively, described optimal sudsing profile has significant foam volume during rinse cycle to be reduced Reduce with inapparent foam volume during cycles of washing, this specifically by greater than about 100%, preferably more than about 105% and And more preferably more than about 110% washing foam index (WSI) and less than about 50%, preferably less than about 45% and more The rinsing foam index (RSI) less than 40% preferably is quantitative, limits as tested by sudsing profile as herein described.

Preferably but without necessary, cationic polymer is with about 0.01 weight % to about 15 weight %, about 0.05 weight Amount % to about 10 weight %, the amount in the range of about 0.1 weight % to about 5 weight %, and 0.25 weight % to about 1 weight % exists There is provided in Cleasing compositions or laundry detergent composition.Additionally, it is preferred that but dispensable, cationic polymer is substantially not Containing carrier granular or coating.This is favourable, because which obviating and the extra step mixing that these materials are associated and one-tenth This.

In specific embodiments of the present invention, defoamer derived from siloxanes is combined with cationic polymer and is used for clearly Cleansing composition, or preferably in laundry detergent composition.Although dispensable for carrying out the present invention, such silica Defoamer derived from alkane can improve the sudsing profile of Cleasing compositions further.

Defoamer derived from siloxanes can be any suitable organosiloxane, including but not limited to：(a) nonfunctionalized Siloxanes such as polydimethylsiloxane (PDMS)；(b) siloxanes of functionalization such as has the silicon of one or more functional groups Oxygen alkane, described functional group is selected from group consisting of：Amino, acylamino-, alkoxyl, alkyl, phenyl, polyethers, acrylate, Silicone hydride, mercapto propyl group, carboxylate, sulfate radical, phosphate radical, quaternized nitrogen and combinations thereof.Typically real Apply in scheme it is adaptable to the organosiloxane of this paper has the viscosity model of at 20 DEG C about 10 to about 700,000CSt (centistoke) Enclose.In other embodiments, suitable organosiloxane has about 10 to about 100,000CSt viscosity.

Polydimethylsiloxane (PDMS) can be straight chain, side chain, ring-type, grafting or crosslinking or ring-type knot Structure.In some embodiments, composition of detergent comprises PDMS, and it has at 20 DEG C about 100 to about 700,000CSt's Viscosity.Exemplary functionalized siloxanes includes but is not limited to amino silicone, amide siloxanes, polyether silicon, alkyl silica Alkane, phenyl siloxane and season siloxanes.The preferred type of functionalized silicone comprises by making diamidogen and epoxide reaction And the cationic silicone producing.One embodiment of the present composition comprises organosiloxane emulsion, and it is included in breast It is dispersed in the organosiloxane in suitable carrier (usually water) in the presence of agent (usually anion surfactant).Another In one embodiment, organosiloxane is in the form of microemulsion, and it has in about 1nm to about 150nm, or about 10nm is to about Particle mean size in the range of 100nm, or about 20nm to about 50nm.

As mentioned above defoamer derived from siloxanes can by the gross weight meter of described compositionss about 0.01% to About 5%, preferably from about 0.1% to about 2% and the amount of more preferably about 0.2% to about 1% is present in Cleasing compositions.

The Cleasing compositions of the present invention or laundry detergent composition can comprise one or more surfactant, its content By described compositionss gross weight meter about 1% to about 80%, more preferably about 1% to about 50% and more preferably about 5% To in the range of about 30%.Detersive surfactant used can be anionic type, nonionic type, amphion type, Amphoteric type or cation type, or the compatible blend of these types can be included.

Anion surfactant is preferred.Available anion surfactant itself can have several different classes Type.For example, non-soap synthetic anion surface active agent is particularly well-suited to herein, and it includes water soluble salt, preferably organic reaction of Salmon-Saxl The alkali metal of product and ammonium salt, described product has the alkyl group comprising about 10 to about 20 carbon atoms in its molecular structure (term " alkyl " includes the moieties of carboxyl groups) and sulfonic acid or sulfate group group.This is combined into anionic surface and lives The example of property agent includes but is not limited to：A) there is alkyl sodium sulfate, alkylsurfuric acid potassium and the alkylsurfuric acid of straight or branched carbochain Ammonium, especially by sulphating higher fatty alcohol (C₁₀-C₂₀Carbon atom) obtain those, such as pass through to reduce Adeps Bovis seu Bubali or Cortex cocois radiciss Those of the glyceride generation of oil；B) there is alkyl alkoxy sodium sulfate, the alkyl alkoxy potassium sulfate of straight or branched carbochain With alkyl alkoxy ammonium sulfate, specifically wherein alkyl group comprises about 10 to about 20, and preferably about 12 to about 18 carbon are former Son, and wherein alkoxylate chain have average about 0.1 to about 5, preferably about 0.3 to about 4 and more preferably about 0.5 Those of ethoxylation degree in the range of about 3；C) sodium alkyl benzene sulfonate and alkyl benzene sulphonate potassium, wherein alkyl group comprise About the 10 of straight or branched carbochain configuration, preferably linear carbon chain configuration are to about 20 carbon atoms；D) sodium alkyl sulfonate, alkyl sulphur Sour potassium and alkyl sulfonic acid ammonium, wherein alkyl group comprise about 10 to about 20 carbon atoms in straight or branched configuration；E) alkyl Phosphoric acid or phosphonic acid sodium, alkyl phosphoric acid or phosphonic acids potassium and alkyl phosphoric acid or phosphonic acids ammonium, wherein alkyl group comprises in straight or branched About the 10 of configuration are to about 20 carbon atoms；F) sodium carboxylate, alkyl carboxylic acid potassium and alkyl ammonium carboxylate, wherein alkyl group comprises In straight or branched configuration about 10 are to about 20 carbon atoms, and combinations thereof；G) alkyl ester sulfonate sodium, alkyl ester sulfonate Potassium and alkyl ester sulfonate ammonium, for example, have formula R-CH (SO₃M)-CH₂COOR', or Arrcostab sodium sulfate, Arrcostab potassium sulfate and alkane Base ester ammonium sulfate, for example, have formula R-CH (OSO₃M)-CH₂COOR', wherein R represent C₁₀-C₂₀And preferably C₁₀-C₁₆Straight chain Or the alkyl group of side chain, R' represents C₁-C₆And preferably C₁-C₃Alkyl group, and M represents sodium, potassium or ammonium cation. Be especially preferred for use in the present invention practice be anionic surfactant system, its comprise C10-C20 linear alkylbenzene sulfonate (LAS), Have in the range of about 0.1 to about 5 that (preferably about 0.3 to about 4 and more preferably about 0.5 to about 3, and it is particularly conducive to improve The sudsing profile of composition of detergent) the alkyl alkoxy sulfate of C10-C20 straight or branched of average degree of alkoxylation, Or their mixture.

Be especially preferred for use in present invention practice is the anionic surfactant system comprising following material：C₁₀-C₂₀Directly Alkyl benzene sulphonate, has in the range of about 0.1 to about 5 that (preferably about 0.3 to about 4 and more preferably about 0.5 to about 3, it is particularly conducive to improve the sudsing profile of composition of detergent) average degree of ethoxylation C₁₀-C₂₀Straight or branched Alkyl alkoxy sulfate or their mixture.

It is highly preferred that the surfactant system of the present invention is rich in C₁₀-C₂₀The alkyl alkoxy sulfate of straight or branched (AES), i.e. one or more AES surfactant is with any other equal to or more than comprised by surfactant system Detersive surfactant (such as C₁₀-C₂₀Linear alkylbenzene sulfonate (LAS) or nonionic surfactant) amount exist.Even more preferably from Ground, the surfactant system of the present invention comprises the gross weight meter by described surfactant system, and 50% or more and Preferably 60% or more one or more AES surfactant, described AES surfactant preferably but not necessarily has Average degree of alkoxylation in the range of about 0.5 to about 3.Without being bound by theory it is believed that rich in alkyl alkoxy sulfate table Surfactant system can help to improve further the foaming beneficial effect of the cationic polymer of the present invention.

Anion surfactant can provide in the Cleasing compositions of the present invention, and its content presses described composition total weight It is calculated as about 1% to about 80%, more preferably about 1% to about 50% and more preferably about 5% to about 30%.

In an especially preferred embodiment, the Cleasing compositions of the present invention are liquid laundry detergent composition, It comprises about 1 weight % to one or more anion surfactant of about 50 weight %, described anion surfactant It is selected from：C₁₀-C₂₀Linear alkylbenzene sulfonate (LAS), there is the C of average degree of alkoxylation in the range of 0.1 to 5.0₁₀-C₂₀Straight chain or The alkyl alkoxy sulfate of chain, C₁₀-C₂₀The alkyl sulfate of straight or branched, C₁₀-C₂₀The Arrcostab sulphuric acid of straight or branched Salt, C₁₀-C₂₀The alkylsulfonate of straight or branched, C₁₀-C₂₀The alkyl ester sulfonate of straight or branched, C₁₀-C₂₀Straight chain or The alkylphosphonic of chain, C₁₀-C₂₀The alkyl phosphonate of straight or branched, C₁₀-C₂₀The alkyl carboxylate of straight or branched and Combinations thereof.It is highly preferred that described one or more anion surfactant is selected from C₁₀-C₂₀Linear alkylbenzene sulfonate (LAS), There is the C of the average degree of alkoxylation in the range of about 0.5 to about 3₁₀-C₂₀The alkyl alkoxy sulfate of straight or branched, have C₁₀-C₂₀The methyl ester sulfonates of straight or branched alkyl group and combinations thereof, and with liquid laundry detergent group The amount to about 30 weight % for about 5 weight % of compound exists.

The water soluble salt (i.e. " soap ") of higher fatty acids is also available anionic surface work in Cleasing compositions of the present invention Property agent.This includes alkali metal soap, such as comprises about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms is senior The sodium salt of fatty acid, potassium salt, ammonium salt and alkylammonium salt.Soap can be obtained by the Directly saponification of fat and oil, or by trip It is obtained from the neutralization of fatty acid.It is especially useful that the sodium salt of fatty acid mixt and the potassium derived from Oleum Cocois and Adeps Bovis seu Bubali Salt, i.e. Adeps Bovis seu Bubali sodium or Adeps Bovis seu Bubali potash soap and coconut palm sodium or coconut potassium soap.For example, Cleasing compositions can be liquid laundry detergent group Compound, it comprises about 0.1 weight % to about 5 weight %, preferably about 0.5 weight % to about 4 weight %, more preferably about 1 weight One or more fatty acid of amount % to about 3 weight % and/or their alkali metal salt.The acid of spendable Exemplary fatty or its Salt is selected from octanoic acid, capric acid, lauric acid, myristic acid, myristoleic acid, Palmic acid, palmitoleic acid, sapienic acid, Hard Fat Acid, Oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, alpha-linolenic acid, arachidic acid, arachidonic acid, eicosapentaenoic acid, Behenic acid, erucic acid and docosahexenoic acid and their salt.Additionally, it is preferred that the liquid laundry detergent combination of the present invention Thing comprises fatty acid or its salt of one or more saturation, such as octanoic acid, capric acid, lauric acid, myristic acid, Palmic acid, Hard Fat Acid, arachidonic acid, behenic acid and their salt.In satisfied fatty acid listed above, lauric acid, myristic acid, Petiolus Trachycarpi Acid and their salt are particularly preferred.

However, in some preferred embodiments of the present invention, Cleasing compositions comprise relatively low content of fatty acid Or salt, for example, no more than about 3 weight %, more preferably no more than about 2 weight % or about 1 weight % and most preferably described clear Cleansing composition is substantially free of fatty acid or its salt.

Nonionic surfactant can also reside in the surfactant volume of the present invention, and it includes formula R¹(OC₂H₄)_nThose of OH, wherein R¹For C₈-C₁₈Alkyl group or alkyl phenyl group, and n is about 1 to about 80.Particularly preferably C₈- C₁₈Alkyl alkoxylated alcohol, it has the average degree of alkoxylation of about 1 to about 20.Nonionic surfactant can be in cleaning combination In thing provide, its content in about 0.05 weight % to about 20 weight %, preferably about 0.1 weight % to about 10 weight % and Most preferably in the range of about 1 weight % to about 5 weight %.However, in some preferred embodiments of the present invention, cleaning group Compound comprises relatively low content of nonionic surfactant, for example, no more than about 3 weight %, more preferably no more than about 2 weights Measure % or about 1 weight % and most preferably described Cleasing compositions are substantially free of nonionic surfactant.

Can be used for this paper other surfactants include amphoteric surfactant, zwitterionic surfactant and sun from Sub- surfactant.Such surfactant in laundry detergent compositions using well known, and generally with about 0.2 weight Amount %, 0.5 weight % or 1 weight % exist to the content of about 10 weight %, 20 weight % or 30 weight %.

In the preferred of the present invention but in dispensable embodiment, Cleasing compositions liquid laundry detergent composition, It comprises one or more both sexes of about 0.5 weight % to about 20 weight % and/or zwitterionic surfactant.

Preferably amphoteric surfactant is selected from amine oxide surfactant, such as alkyl dimethyl amine oxide or alkyl acyl Amine dimethylamine oxide, more preferably alkyl dimethyl amine oxide and especially coco dimethyl amine oxide.Amine oxide Can have straight chain or mid-branched moieties.Typical linear amine oxide is characterised by formula R₁–N(R₂)(R₃)-O, its Middle R₁For C_8-18Alkyl, and wherein R₂And R₃Independently selected from C_1-3Alkyl and C_1-3Hydroxyalkyl, such as methyl, ethyl, propyl group, Isopropyl, 2- ethoxy, 2- hydroxypropyl and 3- hydroxypropyl." mid-branched " used herein refers to that described amine oxide has One moieties containing n1 carbon atom, has the alkyl branches containing n2 carbon atom on this moieties.Described Alkyl branches are located at the alpha-carbon atom of nitrogen-atoms on described moieties.The amine oxide of this type branch is in the art as interior Amine oxide is also known.The summation of n1 and n2 is about 10 to about 24, preferably about 12 to about 20 and more preferably about 10 to about 16 carbon atoms.The carbon number (n1) of one moieties should be approximately the carbon atom of one alkyl branches of identical Number (n2) is so that moieties and alkyl branches are symmetrical." symmetrical " used herein refers at least about In 50% weight, the medium branched amine oxide that can be used for this paper of more preferably at least about 75% to about 100% weight | n1 N2 | less than or equal to 5, preferably 4, more preferably 0 to 4 carbon atoms.And specifically, it is preferable to amphoteric surfactant be C₁₀- C₁₄Alkyl dimethyl amine oxide.

Preferably zwitterionic surfactant is beet alkali surface activator, and for example, alkyl betaine, alkylamide are sweet Dish alkali, imidazolinium betaine (amidazoliniumbetaines), sulfobetaines (also referred to as sulfobetaines) and phosphorus Acid esters glycine betaine.Especially preferred glycine betaine is cocamido propyl betaine.

In a preferred embodiment, the liquid laundry detergent composition of the present invention comprises：(1) about 0.25 weight The cationic polymer of amount % to about 1 weight %, it has the molecular weight of about 15,000 to about 50,000 dalton, and substantially On be made up of following construction unit：The first nonionic structure unit of 20mol% to 60mol%, described first nonionic structure Unit derived from (methyl) acrylamide (AAm), the second cationic structural unit of 10mol% to 40mol%, it is derived from two Allyl dimethyl ammonium chloride (DADMAC), the 3rd nonionic structure unit of 30mol% to 55mol%, its derived from ethylene Base ketopyrrolidine (VP), and the 4th anion structure unit of (iv) 0mol% to 10mol%, it is derived from (methyl) propylene Sour (AA) or its anhydride；And (2) about 1 weight % is to one or more anion surfactant of about 50 weight %, its choosing From C₁₀-C₂₀Linear alkylbenzene sulfonate (LAS), there is the C of average degree of alkoxylation in the range of about 0.5 to about 3₁₀-C₂₀Straight chain or The alkyl alkoxy sulfate of side chain, there is C₁₀-C₂₀The methyl ester sulfonates of the alkyl group of straight or branched and they Combination.Such liquid laundry detergent composition may also comprise about and disappears derived from the siloxanes of 0.2 weight % to about 1 weight % Infusion.

Additional laundry detergent compositions composition

When the liquid laundry detergent composition that the Cleasing compositions of this paper are as described above, it also can comprise outside Structural agent, its content press described compositionss gross weight meter can about 0.001% to about 1.0%, preferably about 0.05% to About 0.5%, in the range of more preferably about 0.1% to about 0.3%.Suitable external structure agent includes：I () non-polymeric contains hydroxyl The crystalline material of base, described material can form thread-like structure system in whole substrate when crystallizing on the spot in fluid matrix. The feature of such material typically may be in crystallised fat acid, fatty acid ester or the fatty wax of hydroxyl；And (ii) polymer knot Structure agent, such as polyacrylate and its derivant；Acrylate and the copolymer of methacrylate.The present invention is put into practice special Not preferably external structure agent is not castor oil hydrogenated, and it is also referred to as trihydroxy stearin, and with trade nameCommercially available Obtain.

The surplus of laundry detergent compositions generally comprises about 5 weight % to about 70 weight %, or about 10 weight % are to about 60 weights The auxiliary component of amount %.Suitable detergent ingredients include：Transition-metal catalyst；Imines bleach enhancers；Enzyme, such as starch Enzyme, carbohydrase, cellulase, laccase, Digestive Enzyme, bleaching enzymes such as oxidase and peroxidase, protease, pectate lyase and Mannase；Peroxygen source, such as percarbonate and/or perborate, preferably SODIUM PERCARBONATE, the preferably coated composition of peroxygen source is extremely Small part coat, preferably completely coat, described coating composition as carbonate, sulfate, silicate, borosilicate or they Mixture, including their salt-mixture；Bleach-activating such as tetra acetyl ethylene diamine, hydroxy benzene sulfonate bleach-activating such as nonanoyl Base hydroxy benzene sulfonate, caprolactam bleach activators, imide bleach activators such as N- pelargonyl group-N- methylacetamide, preformation Shape peracid such as N, N- phthalyl amido peroxy caproic acid, nonyl amide groups peroxide adipic acid or dibenzoyl peroxide；Suds body System, the such as foam inhibitor based on siloxanes；Brightening agent；Toner；Optical white；Fabric softener, such as clay, siloxanes and/or Quaternary ammonium compound；Flocculant, such as poly(ethylene oxide)；Dye transfer inhibitor, such as Polyvinylpyrrolidone, poly 4 vinyl pyridine N- oxide and/or the (co) polymer of vinyl pyrrolidone and vinyl imidazole；The complete component of fabric, such as by imidazoles and The oligomer that epichlorohydrin generates；Dirt dispersant and dirt antiredeposition auxiliary agent, such as alkoxylate polyamines and ethoxylation Epomine；Antiredeposition component, such as polyester and/or terephthalate polymer, Polyethylene Glycol (include by ethylene Alcohol and/or the Polyethylene Glycol of vinyl acetate side base replacement)；Spice, such as perfume microcapsule, the perfume delivery body of polymer auxiliary System's (including Schiff's base spice/polymer complex), the fragrance accord of starch encapsulated；Soap ring；Granule attractive in appearance, includes vitta Grain and/or pin grain；Dyestuff；Filler, such as sodium sulfate, but described compositionss are preferably substantially free from filler；Carbonate, including carbon Sour sodium and/or sodium bicarbonate；Silicate, such as sodium silicate, including 1.6R and 2.0R sodium silicate, or sodium metasilicate；Dicarboxylic acids and two The copolyesters of alcohol；Cellulosic polymer, such as methylcellulose, carboxymethyl cellulose, hydroxyl-oxethyl cellulose or other alkyl Or the cellulose of alkyl alkoxy cellulose and hydrophobically modified；Carboxylic acid and/or its salt, including citric acid and/or citric acid Sodium；And any combination of them.

Laundry detergent powder comprises low content or is even substantially free of builder, may also be especially preferred.Term " being substantially free of " refers to comprise the compositionss of the described composition that " unintentionally adding " measures.In preferred embodiments, originally The liquid laundry detergent composition of invention does not comprise builder.

The method preparing Cleasing compositions or laundry detergent composition

Cationic polymer as described above and various other composition are mixed Cleasing compositions or the medicated clothing of the present invention Can complete in any suitable manner in composition of detergent, and in general, can relate to any mixing or order of addition.

For example, can by the cationic polymer obtaining at manufacturer be introduced directly into final composition two or more its In the preform mixture of its component.This can be carried out in any time during preparing final composition, including in preparation work Skill last.That is, described cationic polymer can be added pre-prepared liquid laundry detergent to form the final of the present invention Compositionss.

In another example, cationic polymer can be premixed with emulsifying agent, dispersant or suspension and form emulsion, glue Then its other component with final composition (defoamer derived from such as siloxanes, is gone by breast, dispersion, suspension etc. Dirty surfactant etc.) mixing.These components can any in any order and in described final composition preparation process when Between add.

3rd example is related to mix described cationic polymer with one or more auxiliary agent of described final composition, and This pre-composition is added to remaining agent mixture.

Method using laundry detergent composition

The invention still further relates to the method for clean textile, the method comprising the steps of：I () provides medicated clothing as above Detergent；(ii) form clothes washing liquid by dilute with water laundry detergent compositions；(iii) wash in described clothes washing liquid and knit Thing；And (iv) rinses fabric in water, wherein after 2 times or less secondary rinsing, preferably after 1 time rinses, medicated clothing Cleaning mixture is substantially free of foam, or at least 75%, preferably at least 85%, more preferably 95%, and even more preferably The surface area of the clothes washing liquid on ground at least 99% does not contain foam.

The invention still further relates to the method saving water during clothes washing, the method comprising the steps of：I () provides such as Upper described laundry detergent compositions；(ii) described Cleasing compositions are diluted to form clothes washing liquid with washings in a reservoir； (iii) wash medicated clothing in clothes washing liquid；And (iv) rinsing clothes, wherein after 2 times or less rinsing, preferably exist After 1 rinsing, described clothes washing liquid is substantially free of foam.

The method of laundering of textile fabrics can be implemented in top-loaded formula or front loaded type automatic washing machine, or can be used for hand-washing clothing In thing washing application, this is particularly preferred in the present invention.

Method of testing

The characteristic to determine the present composition comprising cationic polymer for the various technology known in the art.However, must Must be using identified below so that as herein described and claimed invention can be understood completely.

Test 1：The measurement of weight average molecular weight (Mw)

The weight average molecular weight (Mw) of the polymeric material of the present invention is by having the volume of differential refractive index detector (RI) Exclusion chromatography (SEC) method is determining.A kind of suitable instrument is to useGPC/SEC software, version 1.2GPC-MDS system (Agilent, Santa Clara, USA).SEC separates using straight each other with linear series form (by Waters, Milford, USA manufacture three hydrophilic hydroxyl groups polymethyl methacrylate gel posts of joint Ultrahydrogel 2000-250-120) and by the GVWP film filter in 0.22 μm of aperture (MILLIPORE, Massachusetts, USA) the 0.1M sodium chloride that filters and 0.3% trifluoroacetic acid DI aqueous solution carrying out.RI detector needs To avoid baseline drift under the room temperature that about 5-10 DEG C of ambient temperature to be maintained above.It is set to 35 DEG C.The volume injected of SEC is 100μL.Flow is set to 0.8mL/min.For Polymer Standards molecular sieve (PSS, Mainz Germany) one group 10 narrow point Poly- (2- vinylpyridine) standard of cloth carries out calculating and the calibration of test polymer measurement, and wherein peak molecular weight is：Mp= 1110g/mol, Mp=3140g/mol, Mp=4810g/mol, Mp=11.5k g/mol, Mp=22k g/mol, Mp=42.8k G/mol, Mp=118k g/mol, Mp=256k g/mol, Mp=446k g/mol and Mp=1060k g/mol.

Each test sample is prepared by the following method：By the polymer solution of concentration be dissolved in above-mentioned 0.1M sodium chloride and In the DI aqueous solution of 0.3% trifluoroacetic acid, to produce the test sample of the polymer concentration with 1 to 2mg/mL.Make sample molten Liquid stands 12 hours to be completely dissolved, and and then be sufficiently stirred for and use 5mL syringe pass through 0.45 μm of aperture nylon membrane (by WHATMAN, UK manufacture) it is filled in auto injection bottle.Prepare the sample of Polymer Standards in an identical manner.For every kind of survey Examination polymer prepares two sample solutions.Each solution measures once.Will twice measurement result averagely to calculate test polymer Mw.

For each measurement, first the DI aqueous solution of 0.1M sodium chloride and 0.3% trifluoroacetic acid is expelled on post As background.Other samples measure before, by correcting sample (the 1mg/mL poly(ethylene oxide) of Mp=111.3k g/mol molten Liquid) analyze six times, so that the repeatability of checking system and accuracy.

Using the subsidiary software of instrument and select the menu option being applied to narrow standard calibration model to calculate test specimens The weight average molecular weight (Mw) of product polymer.Three rank multinomial curves are used for by calibration curve and from poly- (2- vinylpyridine) standard The data point matching of measurement.Data field for calculating weight average molecular weight is selected based on the signal intensity being detected by RI detector Select.Wherein RI signal is selected to be more than the data field of 3 times of corresponding baseline noise levels and include in Mw calculates.By all other number Abandon according to area and exclude from Mw calculates.For those areas outside correcting range that fall, curve extrapolation will be corrected for Mw Calculate.

Comprise the mean molecule quantity of the test sample of the polymeric blends of different molecular weight for measurement, the data that will select Area cuts into multiple equidistant fragments.The height of each fragment in selected areas or Y value represent the abundance of particular polymers (i) (Ni) the X value of each fragment represents the molecular weight (Mi) of particular polymers (i), and in selected areas.Then, based on institute above The formula stated, that is, Mw=(Σ i Ni Mi2)/(Σ i Ni Mi), to calculate the weight average molecular weight (Mw) of test sample.

Test 2：Monomer is quantified by HPLC

Every kind of monomer in cationic polymer carrys out quantitation according to arranged below by high pressure lipuid chromatography (HPLC) (HPLC)：

Measurement apparatus：	L-7000 series (Hitachi Ltd.)
		Detector：	UV detector, L-7400 (Hitachi Ltd.)
Pillar：	SHODEX RSpak DE-413 (product of Showa Denko K.K.)
		Temperature：	40℃
Eluent；	0.1% phosphoric acid aqueous solution
		Flow velocity：	1.0mL/min

Test 3：Performance Evaluation (sudsing profile test)

The sudsing profile of this paper composition of detergent passes through to measure using foam cylinder test device (SCT).Described SCT There are one group of 8 cylinder.Each cylinder generally long 60cm, a diameter of 9cm, and can be with the speed of 20-22 rpm (rpm) Rotate together.The method is used for determining the performance of laundry detergent compositions to obtain the ability producing foam and its foam stability and drift Wash the reading of foaming properties aspect.Following factor affects result, and therefore should suitable control：Detergent in (a) solution Concentration, (b) water hardness, the water temperature of (c) water, (d) rotating speed and revolution, the soil loading in (e) solution, and (f) pipe interior section Cleannes.

Performance is passed through by the cationic polymer comprising the present invention or without falling into the comparison cation in the scope of the invention The laundry detergent compositions of polymer, the foam height producing with respect to the comparison laundry detergent compositions not comprising any cationic polymer It is compared to determine.Deduct single wash liquid by recording total foam height (that is, foam adds the height of wash liquid) Highly to measure the foam height being produced by every kind of test compositionss.

1. weigh 1.5 grams of products and be dissolved in the 300ml water that the water hardness is about 16gpg, and continue at least 15min, to form the solution of the test product comprising about 5000ppm.Sample dissolution simultaneously.

2. sample aliquot is poured in pipe.Put into rubber stopper and pipe is locked in position.

3. rotate 10 turns.It is locked in stand up position.Wait 1min and from left to right quickly detect foam height (～10 seconds).Record the height of total foam height (that is, foam adds the height of wash liquid) and single wash liquid.This labelling Data after 10 turns.

4. rotate additional 20 turns.This marked the data after 30 turns.From left to right obtain record.

5. rotate more than 20 turn.This marked the data after 50 turns.From left to right obtain reading.Repeat this step and be more than one Secondary；Therefore, after the data of collection is 70 turns.

6. open pipe.The fabric of 1 bandy clay and 1/4 fabric with dirty edible oil (DCO) are added in each pipe.Put Enter rubber stopper.20 turns of rotation.This marked the data after 90 turns.Obtain reading.Repeat this step once；Therefore, the number of collection According to be 110 turns afterwards.

Add synthetic soil to be intended to imitate the wash conditions of real world, wherein more dirts are molten from the fabric of just washing In wash liquid.Therefore, this test and the initial sudsing profile determining compositionss and its sudsing profile in cycles of washing Related.

(note：The preparation of the fabric of bandy clay is carried out as follows：

Via stirring, the BJ- clay (clay that 15cm collects under China, Pekinese's earth's surface) of 20g is scattered in 80ml DI water in prepare slurry.

Such for 2g slurry brush is knitted in 10cm*10cm cotton by continuously stirred suspension in preparation process simultaneously The center of thing is to form circular dirt (d=5cm).

The bafta of bandy clay is kept being dried and being subsequently used for Performance Evaluation at room temperature.Fabric with DCO Preparation is carried out as follows：

The cured fish 2 hours that 100 grams of Oleum Arachidis hypogaeae semen are used at 150-180 DEG C fried 20 grams is to form dirty edible oil (DCO).

By the DCO brush of 0.6ml at the center of 10cm*10cm bafta to form circular dirt (d=5cm).

10cm*10cm bafta is cut into 4 equal sheet materials and is used for Performance Evaluation by one.)

7. pour out 37.5ml solution with gentle in pipe to pour in beaker, and 262.5ml is had desired hardness level Water add in beaker with prepare 300ml altogether 1/8 through dilute solution.Abandon surplus solution in pipe and with water washing from the beginning Pipe.300ml 1/8 dilute solution is poured in identical pipe.

8. rotate 20 turns.This marked the data after 130 turns.From left to right obtain reading.Repeat this step once；Cause This, after the data of collection is 150 turns.

9. pour out 150ml solution with gentle in pipe to pour in milliliter beaker, and 150ml is had desired hardness level Water add in beaker with prepare 300ml altogether 1/16 through dilute solution.Abandon surplus solution in pipe and with water washing from the beginning Pipe.300ml 1/16 dilute solution is poured in identical pipe.Repeat step 8.The data collected is the data after 190 turns.

10., in the test of typical sudsing profile, step 1-9 is repeated at least once more to guarantee test repeatability.

11. data analysiss：The subdivision of foam-type

Different types of average foam height mentioned above is by averagely to count the altitude information of each parallel sample Calculate.

Washing foam index (WSI) is by (90-110 turns) when observing foam stability during cycles of washing by compareing Average foam height (the WSH that sample produces_C) (that is, comprise the cationic polymer of the present invention or do not exist divided by by test sample Comparison cationic polymer in the scope of the invention) average foam height (WSH that produces_T), and it is then converted into percentage ratio To calculate, as follows：

WSI is indicated compared with the foam being produced with the control sample of any one not comprised in such cationic polymer, by The cationic polymer comprising washing foam can be had adverse effect (has specific monomer composition and as defined above point Son amount subject cationic polymer, or without falling into the comparison cationic polymer in the scope of the invention) test sample exist The foam volume producing during cycles of washing.Therefore, WSI percentage ratio is higher, and the foam producing during washing is more, and performance Better.

Rinsing foam index (RSI) pass through by control sample during 1/8 rinse cycle (i.e. 130-150 turns) produce put down All foam height (RSH_C) divided by the average foam height (RSH being produced by test sample_T), and it is then converted into percentage ratio Calculate, as follows：

On the other hand, RSI instruction with stayed by the control sample of any one not comprised in such cationic polymer Foam is compared, and (has specific monomer to form and as limited above by the cationic polymer comprising to be effectively reduced rinsing foam The subject cationic polymer of fixed molecular weight, or without falling into the comparison cationic polymer in the scope of the invention) test The foam volume that sample stays during rinse cycle.Therefore, RSI percentage ratio is lower, realize during rinsing foam reduce more, And performance is better.

As optimal sudsing profile defined in implication of the present invention includes the WSI more than 100% and the RSI less than 50%, The preferably more than 105% WSI and RSI less than 45% and be more preferably larger than 110% WSI (that is, during washing Promote bubble effect) and the RSI less than 40%.

Embodiment

I. cationic polymer embodiment

The following is the list of Exemplary cationic polymer within the scope of the present invention：

Table I

II illustrate to have the sudsing profile of cationic polymer of different AAm/DADMAC/VP molar percentages with mutually stable Property comparison test

Preparation eight (8) kind test liquid laundry detergent composition, including：(1) do not comprise the comparison of cationic polymer Compositionss, (2) 4 kinds of inventive composition, its each self-contained with reference composition identical composition but also comprise 0.5 weight % Inventive polymers in the scope of the invention；And (3) 3 kinds of comparative composition, its each self-contained and reference composition identical Composition, but also comprise the comparative polymers of 0.5 weight %, described comparative polymers have the AAm/ outside the scope of the invention DADMAC/VP molar percentage.The concrete composition that the following is reference composition is decomposed：

Table II

Form the test group comprising 5000ppm by every kind of compositionss are dissolved in the water that water hardness levels are 16gpg The clothes washing liquid of compound, to carry out sudsing profile survey mentioned above to each of these eight (8) kinds test compositionss Examination.Foam test is repeated twice and records average data.Compared to reference composition, based on measure to such composition Washing foam volume and rinsing foam volume calculate three (3) and plant each in comparative composition and four (4) the kind present compositions Washing foam index (WSI) and rinsing foam index (RSI).The following is measurement result：

Table III

* turn the foam stability of lower measurement in 90-110.

* turns the rinsing foam first of lower measurement in 130-150.

* * passes through, after prepared compositionss, compositionss to be placed in about 24 hours in the transparent glass tube of diameter about 2.5cm Visually determine the phase stability of this paper." stablizing " product is visually transparent in glass tubing, but " being separated " produces Product are visually opaque.

Three (3) kind comparative polymers included in comparative composition all are respectively provided with the AAm/ outside the scope of the invention DADMAC/VP molar percentage.Above-mentioned data illustrates the invention polymerization only with suitable AAm/DADMAC/VP molar percentage Both the offer of thing material is following：(i) optimal sudsing profile, i.e. there is the gratifying washing quantitative by the WSI more than 100% Foam volume and the rinsing foam volume being substantially reduced by the RSI quantitation less than 50%；And the phase stability of (ii) finished product.

III., the comparison test with the sudsing profile of the cationic polymer of different molecular weight is shown

Based on the reference composition that above identical described in embodiment II is not comprised with cationic polymer, prepare four (4) plant liquid laundry detergent composition, including：(1) 2 kind of inventive composition, its each self-contained with foregoing embodiments II in institute The reference composition identical composition stated but the present invention of the molecular weight having within the scope of the present invention that also comprises 0.5 weight % Polymer；And (2) 2 kinds of comparative composition, its each self-contained with foregoing embodiments II described in reference composition identical Composition, but also comprise the comparative polymers of the molecular weight having outside the scope of the invention of 0.5 weight %.

Form the test group comprising 5000ppm by every kind of compositionss are dissolved in the water that water hardness levels are 16gpg The clothes washing liquid of compound, to carry out sudsing profile survey mentioned above to each of these four (4) kinds test compositionss Examination.Foam test is repeated twice and records average data.Two (2) plant comparative composition and two (2) plants in inventive composition The washing foam (cm) of each and rinsing foam (cm) are summarized as follows：

Table IV

* turn the foam stability of lower measurement in 90-110.

* turns the rinsing foam first of lower measurement in 130-150.

Two (2) the kind comparative polymers comprising in comparative composition have the molecular weight outside the scope of the invention.Above-mentioned The invention polymer that data illustrates only to have suitable molecular weight provides optimal sudsing profile, that is, have quantitative gratifying Washing foam volume and sufficiently low rinsing foam volume.

IV. exemplary garment composition of detergent

(A). heavy duty detergent powder detergent

Prepare following heavy duty detergent powder detergent by mixing composition listed hereinafter via conventional method.Such Heavy duty liquid detergent is used for laundering of textile fabrics, is then done by extension and/or machine is dried described fabric drying.It is being dried Before and/or period, this kind fabric can be processed with fabric intensifier.Such fabric exhibits go out clean outward appearance and have soft Soft sensation.

Table V

(B). heavy duty liquid detergent

Prepare following heavy duty liquid detergent by mixing composition listed hereinafter via conventional method.Such Heavy duty liquid detergent is used for laundering of textile fabrics, is then done by extension and/or machine is dried described fabric drying.It is being dried Before and/or period, this kind fabric can be processed with fabric intensifier.Such fabric exhibits go out clean outward appearance and have soft Soft sensation.

Table VI

Table VII

Table VIII

Table ix

(C). fabric intensifier

Can be by ingredients listed being mixed together to fabric enhancing compositions are obtained in shown ratio：

Table X

(D). rinsing additive

Can be by ingredients listed being mixed together to rinsing additive compositionss are obtained in shown ratio：

Table X I

Composition	Weight %
		Structural material	0-1.0
Polymer 1-4 in the Table I of embodiment I	0.01-15
		Dyestuff	0-0.01
Perfumery oil	0-1.0
		Preservative	0-0.2
Deionized water	Surplus is to 100 weight %

Unless expressly excluded or limited, otherwise by every herein cited document, including any cross reference or phase Close patent or application, be all herein incorporated by reference in full.Quoting of any document is not with respect to any present invention to it Disclosed or claimed prior art herein accreditation, or be not to its individually or with any other The combination of list of references or multiple list of references proposes, advises or disclose the accreditation of such invention.If additionally, in this document Any implication of term or definition are mutually rushed with any implication being herein incorporated by reference in the literature same term or definition Prominent, the implication or definition that are given this term in this document are defined.

Although having illustrate and described the specific embodiment of the present invention, those skilled in the art are come Say it is readily apparent that multiple other changes and modification can be made in the case of without departing from spirit and scope of the present invention.Therefore, It is intended in claims, cover all such change belonging in the scope of the invention and change.

Claims

1. a kind of laundry detergent composition, comprises the cationic polymer of the effective dose for sudsing profile optimization, described sun Ionomer comprises：

The first nonionic structure unit derived from (methyl) acrylamide (AAm) of (i) 10mol% to 70mol%；

(ii) the second cationic structural unit of 5mol% to 40mol%；

(iii) the 3rd nonionic structure unit different from described first nonionic structure unit of 5mol% to 60mol%；

(iv) optionally, 0mol% to 20mol% different from described first, second, and third construction unit at least one is attached Plus construction unit,

Total mol% of wherein (i)-(iv) adds up as 100mol%, and wherein said cationic polymer is characterised by Molecular weight (Mw) in the range of 15,000 to 1,000,000 dalton, and it is substantially free of the derivative knot of any siloxanes Structure unit.

2. laundry detergent composition according to claim 1, also comprises one or more of 1 weight % to 50 weight % Anion surfactant, described one or more anion surfactant is selected from：C₁₀-C₂₀Linear alkylbenzene sulfonate (LAS), tool There is the C of the average degree of alkoxylation in the range of 0.1 to 5.0₁₀-C₂₀The alkyl alkoxy sulfate of straight or branched, C₁₀-C₂₀Directly The alkyl sulfate of chain or side chain, C₁₀-C₂₀The alkyl sulfate of straight or branched, C₁₀-C₂₀The alkyl sulfonic acid of straight or branched Salt, C₁₀-C₂₀The alkyl ester sulfonate of straight or branched, C₁₀-C₂₀The alkylphosphonic of straight or branched, C₁₀-C₂₀Straight chain or The alkyl phosphonate of chain, C₁₀-C₂₀The alkyl carboxylate of straight or branched and combinations thereof.

3. laundry detergent composition according to claim 1 and 2, the second sun in wherein said cationic polymer from Minor structure unit is derived from selected from following monomer：Diallyl dimethyl ammonium salt (DADMAS), N, N- dimethyl aminoethyl Acrylates, N, N- dimethyl aminoethyl methacrylate (DMAM), [2- (methacrylamido) ethyl] trimethyl Ammonium salt, N, N- dimethylaminopropylacryl amide (DMAPA), N, N- dimethylaminopropyl Methacrylamide (DMAPMA), acrylamido propyl trimethyl ammonium salt (APTAS), Methacrylamide oxypropyl trimethyl ammonium salt (MAPTAS), season Ammonium vinyl imidazole (QVi) and combinations thereof, wherein said second cationic structural unit is preferably derived from diene Propyl-dimethyl ammonium salt (DADMAS) and more preferably derived from diallyldimethylammonium chloride (DADMAC).

4. laundry detergent composition according to any one of claim 1 to 3, in wherein said cationic polymer 3rd nonionic structure unit is derived from selected from following monomer：Vinyl pyrrolidone (VP), vinyl acetate, vinyl alcohol, Vinyl formamide, vinyl acetamide, vinyl alkyl ethers, vinylpyridine, vinyl imidazole, caprolactam, And combinations thereof, and wherein said 3rd nonionic structure unit preferably derived from ethylene base ketopyrrolidine (VP).

5. laundry detergent composition according to any one of claim 1 to 4, wherein said at least one additional knot Structure unit comprises the 4th anion structure unit, described 4th anion structure unit preferably with 0mol% to 10mol% and And the amount in the range of more preferably 0mol% to 5mol% is present in described cationic polymer, and wherein said 4th the moon Ionic structure unit preferably derived from ethylene yl carboxylic acid and its anhydride, more preferably derived from selected from following monomer：(first Base) acrylic acid, (methyl) acrylic anhydride, maleic acid, maleic anhydride and combinations thereof.

6. laundry detergent composition according to claim 5, wherein said cationic polymer comprises, and preferably Substantially consist of：

The first nonionic structure unit of (i) 15mol% to 60mol%；

(ii) the second cationic structural unit of 10mol% to 40mol%；

(iii) the 3rd nonionic structure unit of 20mol% to 55mol%；And

(iv) the 4th anion structure unit of 0mol% to 10mol%.

7. laundry detergent composition according to any one of claim 1 to 6, wherein said cationic polymer point Son amount (Mw) in 15,000 to 1,000,000 dalton, preferably 20,000 to 500,000 dalton and more preferably 20, In the range of 000 to 250,000 dalton.

8. laundry detergent composition according to any one of claim 1 to 7, wherein said cationic polymer with 0.01 weight % to 15 weight %, preferably 0.05 weight % to 10 weight %, more preferably 0.1 weight % to 5 weight % and And the amount of most preferably 0.2 weight % to 1 weight % is present in described compositionss.

9. laundry detergent composition according to any one of claim 1 to 8 it is characterised in that：(1) be more than 100%, Preferably more than 105% and be more preferably larger than 110% washing foam index (WSI)；(2) be less than 50%, preferably Less than 45% and be even more preferably less than 40% rinsing foam index (RSI), such as tested by sudsing profile as herein described Determined by.

10. laundry detergent composition according to any one of claim 1 to 9, also comprises froth breaking derived from siloxanes Agent, its content presses the gross weight meter of described compositionss 0.01% to 5%, preferably 0.1% to 2% and more preferably In the range of 0.2% to 1%.

11. laundry detergent compositions according to any one of claim 1 to 10, also comprise 0.05 weight % to 5 weights One or more nonionic surfactant of amount %, described nonionic surfactant is selected from the average alcoxyl with 1 to 20 The C of base degree₈-C₁₈Alkyl alkoxylated alcohol, and combinations thereof.

12. laundry detergent compositions according to any one of claim 1 to 11 are used for hand-washing product to realize optimizing Sudsing profile purposes.

A kind of 13. liquid laundry detergent compositions, comprise：

The cationic polymer of (1) 0.2 weight % to 1 weight %, it has the molecular weight of 20,000 to 250,000 dalton (Mw), described cationic polymer substantially consists of：(i) 15mol% to 60mol% derived from (methyl) acryloyl First nonionic structure unit of amine (AAm)；(ii) 10mol% to 40mol% derived from diallyldimethylammonium chloride (DADMAC) the second cationic structural unit；(iii) derived from ethylene base ketopyrrolidine (VP) of 20mol% to 55mol% The 3rd nonionic structure unit；(iv) 0mol% to 10mol% derived from (methyl) acrylic acid (AA) or its anhydride 4th anion structure unit；And

(2) 1 weight % to 50 weight %, the anion surfactant of preferably 5 weight % to 30 weight %, it is selected from has The C of the average degree of alkoxylation in the range of 0.5 to 3₁₀-C₂₀The alkyl alkoxy sulfate of straight or branched.

14. liquid laundry detergent compositions according to claim 13, also comprise 0.2 weight % to the silicon of 1 weight % Defoamer derived from oxygen alkane.

15. liquid laundry detergent compositions according to claim 13 or 14 are used for washing fabrics to realize rising of optimization The purposes of bubble feature.