CN104053727B

CN104053727B - Thiophene azo carboxylate's dyestuff and comprise its fabric care composition

Info

Publication number: CN104053727B
Application number: CN201280027250.3A
Authority: CN
Inventors: E.托雷斯; J.D.布鲁恩克; S.K.戴; G.S.米拉克尔
Original assignee: Milliken and Co
Current assignee: Milliken and Co
Priority date: 2011-06-03
Filing date: 2012-05-25
Publication date: 2016-11-30
Anticipated expiration: 2032-05-25

Abstract

The application relates to the thiophene azo carboxylate's dyestuff as Toner (hueing agent), the clothes care composition comprising this type of dyestuff that can be used as Toner, this type of dyestuff and the preparation method of fabric care composition, and their using method.Above-mentioned dyestuff is containing formal electrically charged part and generally includes at least two component: at least one chromophore component and at least one polymers compositions.Suitably chromophore component generally sends blueness, redness, pansy or purple when being exposed to ultraviolet, or its absorbable light thus reflect these identical colors.This type of dyestuff has advantage on chromatic effect on providing, and such as, makes the effect of fabric brightening, will not accumulate in time and handled fabric causes bad blue-stain (blue discoloration) simultaneously.This type of dyestuff generally in fabric care composition use bleach be stable.

Description

Thiophene azo carboxylate's dyestuff and comprise its fabric care composition

Cross-Reference to Related Applications

This application claims entitled " the Thiophene Azo Carboxylate Dyes submitted to on June 3rd, 2011 And Laundry Care Compositions Containing the Same " U.S. Provisional Patent Application No. 61/492, The priority of 935, this provisional application is incorporated herein entirety with it by quoting.

Technical field

The application relates to the thiophene azo carboxylate's dyestuff as Toner (hueing agent), comprises this type of dyestuff Clothes care composition, this type of dyestuff and the preparation method of fabric care composition, and their using method.Above-mentioned dyestuff Containing formal electrically charged part and generally include at least two component: at least one chromophore component and at least one polymer group Point.Suitably chromophore component generally sends blueness, redness, pansy or purple when being exposed to ultraviolet, or it can Absorbing light thus reflect these identical colors.These dyestuffs have advantage on chromatic effect on providing, and such as, make fabric brightening Effect, simultaneously will not accumulate in time and handled fabric is caused bad blue-stain (blue discoloration). This type of dyestuff generally in fabric care composition use bleach be stable.

Background technology

Along with textile substrate is aging, their color is because being exposed to the fiber of light, air, earth and composition substrate Natural degradation and tend to fade or turn yellow.Therefore, the purpose of Toner be generally placed upon by these textile substrate in vision On brighten and offset fading and turning yellow of substrate.Generally, Toner may be present in laundry detergent compositions, fabric softener or rinsing and helps In agent, and thus it is applied in textile substrate in laundry processes.It is important, however, that Toner is treated for making Textile substrate brightens without textile substrate causes less desirable dyeing.Particularly, at the bottom of cellulose base be exposed to light, Tend to show yellow after air and/or contamination.This flavescence is often difficult to be reversed by regular laundry program.Therefore, need Want to eliminate the Toner of the improvement of the jaundice shown by aged fiber element substrate.By utilizing the Toner of this improvement, The life-span of textile substrate such as clothing product, table linen etc. can be extended.Regrettably, existing thiophene azo dye is not so good as institute Physically stable as expecting.Therefore, it needs special solvent/process, and this can limit dye product and fabric care composition system The motility of agent.It addition, thiophene azo carboxylate's dyestuff of the most disclosed English medicated clothing compositions can make in the product Level under required colouring benefit will not be provided, the most expensive and/or its can accumulate less desirable level, thus multiple Processing week after date makes handled position excessively colour.

Thiophene azo carboxylate's dyestuff disclosed herein and containing its fabric care composition relative in this field Previously make great efforts provide the advantage that, because unlike previous thiophene azo Toner, thiophene azo carboxylate's dyestuff of the present invention Comprising the most charged carboxylate moiety (higher than its pKa), this makes this type of dyestuff provide deposition, removal and the color strengthened Angle, and do not have polyurea fibre such asPretreatment stain negative-appearing image (negatives) of upper dyeing and/or excessive cost. Although not bound by theory, applicant believes that this type of negative-appearing image can be avoided by, reason is the thiophene azo carboxylate dye of the disclosure Material interacts with the metal ion in such as washings in the way of more favourable.Above-mentioned benefit carries in various fabrics type Supply.In short, applicants have appreciated that the source of existing colouring defect and provide the solution to this problem in this article. Colouring compound disclosed herein also visually neutralizes, applicable, the absorbing at wavelengths that substrate (including textile substrate) turns yellow Light.These compounds are ideal as the Toner of substrate (including textile substrate), and can be added into used by consumer Fabric care composition in.

Summary of the invention

The application relates to the thiophene azo carboxylate's dyestuff as Toner (hueing agent), comprises this type of and can be used as The clothes care composition of the dyestuff of Toner, this type of dyestuff and the preparation method of fabric care composition, and they make Use method.Above-mentioned dyestuff is containing formal electrically charged part and generally include at least two component: at least one chromophore component and At least one polymers compositions.Suitably chromophore component generally sends blueness, redness, pansy when being exposed to ultraviolet Or purple, or its absorbable light thus reflect these identical colors.This type of dyestuff has advantage on chromatic effect on providing, Such as, make the effect of fabric brightening, will not accumulate in time and handled fabric is caused bad blue-stain (blue simultaneously Discoloration).This type of dyestuff generally in fabric care composition use bleach be stable.

Detailed Description Of The Invention

As used herein, term " alkoxyl " is intended to include C₁-C₈Alkoxyl and have such as epoxy butane, oxidation contracting The alkoxyl derivatives of the polyhydric alcohol of the repetitive of water glycerol, oxirane or expoxy propane.

As used herein, term " alkyl " and " alkyl-blocked " are intended to include C₁-C₁₈Alkyl group, and at one Aspect, C₁-C₆Alkyl group.

As used herein, term " aryl " is intended to include C₃-C₁₂Aromatic yl group.

As used herein, term " aryl alkyl " is intended to include C₁-C₁₈Alkyl group, and in one aspect, C₁-C₆ Alkyl group.

As used herein, term " formal charged part (formally charged moiety) " refers to PH scope be 7-11 aqueous solution in there is at least one formal positive charge or the part of at least one form negative charge.

Term " oxirane ", " expoxy propane " and " epoxy butane " can respectively with its typical name " EO ", " PO " and " BO " shows herein.

Unless otherwise indicated, term used herein " fabric care composition " includes granule, powder, liquid, gel, soft Cream, unit dose bar shaped and/or the detergent of sheet form and/or fabric treatment composition.

Unless otherwise indicated, term " fabric " treatment compositions used herein " include that fabric softening compositions, fabric are strong Change compositions, the pure and fresh compositions of fabric and combinations thereof.Such compositions can be but need not to be rinse added compositions.

As used herein, term " at the bottom of cellulose base " is intended to include any cellulose comprising at least most of weight Substrate.Cellulose is found in wood, cotton, Caulis et Folium Lini, Corchorus olitorius L. and Fructus Cannabis.Can be powder, fiber, paper pulp and by powder at the bottom of cellulose base The object form that end, fiber and paper pulp are formed.Cellulose fibre includes but not limited to cotton, viscose rayon (regenerated cellulose), vinegar Acid esters (cellulose acetate), triacetate (Triafol T) and mixture thereof.The goods formed by cellulose fibre include The textile article of such as fabric.The goods formed by paper pulp include paper.

When using in the claims, used herein include " should/described ", the article of "// a kind of " should be by It is understood to mean that the one or more of things that is required or that describe.

As used herein, term " includes ", " comprising " and " containing " is expressed as nonrestrictive.

As used herein, term " maximum extinction coefficient " is intended to describe maximum wavelength in 400 nanometers to 750 nanometer range Under molar extinction coefficient.

Due to its manufacture process, thiophene azo carboxylate's dyestuff disclosed herein can be single containing repeating at its polymer moieties Unit's distribution.Therefore, in one aspect, the molecular weight of thiophene azo carboxylate's dyestuff disclosed herein can be reported as by its point The mean molecule quantity that son amount distribution is measured.

Method of testing disclosed in the Test Methods section of the application should be used for determining each ginseng of the invention of applicant The value of number.

Unless otherwise stated, the level of all components or compositions is the active part about this component or compositions, And being free from impurity (such as, residual solvent or by-product), the latter may be present in the business of such component or compositions In can originating.

Unless otherwise indicated, all percents and ratio calculate based on weight.Unless otherwise indicated, all percents and ratio Rate calculates based on total composition.

It should be understood that each greatest measure be given in description in the whole text limits includes that each relatively low numerical value limits, as This relatively low numerical value is limited in as clearly being write out herein.The each minimum value be given in description in the whole text limits Limit, as this higher numerical value is limited in and is clearly write out herein including each higher numerical value.Medicated clothing is logical The each numerical range be given in piece description includes each narrower numerical range falling in this type of broader numerical, as As this narrower numerical range is clearly write out in this article.

It is both incorporated herein by reference at all documents cited in relevant portion；Any document is quoted and should not explain For recognizing that it constitutes prior art relative to the present invention.

Comprise the fabric care composition of suitable Toner

In one aspect, the fabric care composition comprising Toner and one or more laundry care compositions is disclosed. Suitably Toner includes all Toners set forth below.

In one aspect, disclosing a kind of compositions, it comprises the thiophene azo carboxylate's dyestuff containing carboxylic moiety, front Carrying is that described thiophene azo carboxylate's dyestuff does not have following structure,

At an aspect of above-mentioned composition, described thiophene azo carboxylate's dyestuff is at the wavelength of about 400nm to about 750nm In the range of there are in methanol solution the maximum extinction coefficient of greater than about 1000 liters/mol/cm.

At an aspect of above-mentioned composition, described thiophene azo carboxylate's dyestuff is at the wavelength of about 540nm to about 630nm In the range of have about 20,000 to about 100,000l/mol/cm maximum extinction coefficient.

At an aspect of above-mentioned composition, described thiophene azo carboxylate's dyestuff is at the wavelength of about 560nm to about 610nm In the range of have about 20,000 to about 65,000l/mol/cm maximum extinction coefficient.

At an aspect of above-mentioned composition, described thiophene azo carboxylate's dyestuff has greater than about 232 dalton, about 233 dalton to about 5000 dalton, about 365 dalton to about 2500 dalton or the most about 4235 dalton are to about 1000 Daltonian molecular weight.

At an aspect of above-mentioned composition, described thiophene azo carboxylate's dyestuff is represented by leading to formula (I):

Wherein

a.)R₁、R₂And R₃Being each independently selected from hydrogen, electrophilic part and supplied for electronic part, condition is R₁、R₂And R₃In at least One is electrophilic part；With

B.) wherein X is that molecular weight is about 104 dalton to about 4871 dalton, about 236 dalton to about 2371 dongle , about 294 dalton are to about 871 daltonian organic moiety.

At an aspect of above-mentioned composition, for described thiophene azo carboxylate's dyestuff with Formulas I, each R₁、R₂And R₃ It is independently selected from hydrogen, (C₁-C₄)-alkyl, (C₃-C₁₀)-aryl, carboxylate radical, cyano group, sulfonate radical, phosphonate radical, sulfate radical, acetate, Nitro, (C₁-C₄)-Arrcostab, halogen or amino part.

At an aspect of above-mentioned composition, for described thiophene azo carboxylate's dyestuff with Formulas I, X be have under State the part of formula (II):

Wherein:

I.) R₄Selected from the following part with formula (III):

Wherein:

Each R₈It is independently selected from hydrogen, the substituted C of optional hydroxyl₁-C₈Alkyl or acetyl group；

M is the integer of 0-10；

Y is-OC (O) GCO₂M, wherein M is H or charge balance cation；G is derived from substituted or non-substituted succinic acid The organic group of acid anhydride, maleic anhydride, glutaric anhydride, adipic anhydride or phthalic anhydride, described anhydride has formula IV,

Described anhydride has less than about 353 dalton, about 98 dalton to 352 dalton or the most about 100 dalton To about 325 daltonian molecular weight；

Ii.) R₄Selected from the following part with formula (V):

Wherein

R₁₁And R₁₂It is each independently selected from hydrogen, C₁-C₈Alkyl, aryl, acetyl group or hydroxylic moiety；M and n is independent, and For the integer of 0-10,

Described anhydride has less than about 353 dalton, about 98 dalton to 352 dalton or the most about 100 dalton To about 325 daltonian molecular weight；Or

Iii.) R₄Selected from the following part with formula (VII):

Wherein

R₁₃Selected from C₆-C₁₀Aryl moiety, C₇-C₁₂Arylalkyl moieties, C₁-C₁₈Moieties or oxyalkylene segment；

Each R₁₄It is independently selected from hydrogen, C₁-C₄Alkyl；M is the integer of 0-10；

Y is-OC (O) GCO₂M, wherein M is H or charge balance cation；G is derived from substituted or non-substituted succinic acid The organic group of acid anhydride, maleic anhydride, glutaric anhydride, adipic anhydride or phthalic anhydride, described anhydride has Formula VIII,

R₅It is the most independently selected R₄Part, or R₅Selected from C₁-C₁₂Moieties, C₂-C₁₂Ether moiety, C₆- C₁₀Aryl moiety or C₇-C₁₂Arylalkyl moieties, its Exponential a is the integer of 0-4, each R₆It is independently selected from C₁-C₆Alkyl, C₁-C₄ Alkoxyl, nitro, hydroxyl, halogen or-NHC (O) R₂₂, wherein R₂₂Selected from H ,-NH₂、C₁-C₆Alkyl, phenyl ,-(CH₂)_sOR₂₃, its Exponential s is 1 or 2, and R₂₃Selected from Me, phenyl and-CO₂CH₂CN；-NHSO₂R₂₄, wherein R₂₄It is C₁-C₄Alkyl or phenyl；Described Alkyl, alkoxyl and acetamido moiety optionally replace with carboxylate moiety；

Or X is the part with above-mentioned Formula II:

The most each R₄And R₅Can be independently selected from:

a)[(CH₂CR'HO)_x(CH₂CR"HO)_yR₁₅]；

b)C₁-C₁₂Alkyl, C₆-C₁₀Aryl or C₇-C₁₂Aryl alkyl；

c)[CH₂CH(OR₁₆)CH₂OR₁₇]；

D) styrene oxide, Glycidyl methyl ether, isobutyl glycidyl ether, isopropyl glycidyl ether, the tert-butyl group The amino addition compound product of glycidyl ether, 2-hexyl glycidyl ether and glycidylhexadecyl ether, afterwards and 1- 10 alkylene oxide unit additions, the such alkylene oxide unit of at least one of which is not the R of-H₁₅Replace；Wherein R' selected from H, CH₃、CH₂O(CH₂CH₂O)_zR₁₅And mixture；R is " selected from H, CH₂O(CH₂CH₂O)_zR₁₅And mixture；x+y≤20；y≥1； Z=0-10, each R₁₅Being independently selected from-H and Y, wherein Y is-OC (O) GCO₂M, wherein M is H or charge balance cation；G is derived from The organic group of substituted or non-substituted succinic anhydrides, maleic anhydride, glutaric anhydride, adipic anhydride or phthalic anhydride, institute State anhydride and there is Formula IX,

R₁₆Selected from H, (CH₂CH₂O)_zR₁₅Wherein z=0-10, and mixture；R₁₇Selected from C₁-C₁₆Alkyl, C₆-C₁₀Virtue Base and mixture thereof；Exponent m is the integer of 0-4, and each R₆As defined above；Further condition is that described molecule is containing at least one The R of non-H₁₅Group.

Wherein:

I.) R₄Selected from the following part with formula (III):

Wherein:

R₈It is hydrogen, C₁-C₄Moieties or C₆-C₁₀Aryl moiety；

Or, R₄Selected from the following part with formula (V):

Wherein

R₁₁And R₁₂It is each independently selected from hydrogen, C₁-C₄Alkyl or C₆-C₁₀Aryl moiety；M and n is independent, and is 0-5's Integer,

Or, R₄Selected from the following part with formula (VII):

Wherein

R₁₃Selected from C₆-C₁₀Aryl moiety, benzyl moiety or C₁-C₁₈Moieties；

Each R₁₄It is independently selected from hydrogen or-CH₃；M is the integer of 0-10；

ii.)R₅It is the most independently selected R₄Part, or R₅It is selected from C₁-C₆Moieties or benzyl moiety R₅；

Iii.) its Exponential a is the integer of 0-2, each R₆It is independently selected from methyl, methoxyl group or acetamido moiety.

At an aspect of above-mentioned composition, for described thiophene azo carboxylate's dyestuff with Formulas I, each R₁、R₂And R₃ It is independently selected from hydrogen, (C₁-C₄)-alkyl, (C₆-C₁₀)-aryl, carboxylate radical, cyano group, sulfonate radical, acetate, nitro, (C₁-C₄)-alkane Base ester, halogen or amino part, in one aspect, each R₁、R₂And R₃It is independently selected from hydrogen, (C₁-C₄)-alkyl, carboxylate radical, cyano group, Sulfonate radical, nitro, (C₁-C₄)-Arrcostab or halogen moiety

At an aspect of above-mentioned composition, described thiophene azo carboxylate's dyestuff has a formula (X):

A-N=N-X

Formula X

Wherein part A is selected from table 1A numbering of part 1-118, and wherein X is selected from table 4X numbering of part 1-24, and wherein G is derived from The organic group of substituted or non-substituted succinic anhydrides, maleic anhydride, glutaric anhydride, adipic anhydride or phthalic anhydride, institute State anhydride and there is Formula X I,

Described anhydride has less than about 353 dalton, about 98 dalton to 352 dalton or the most about 100 dalton To about 325 daltonian molecular weight.

At an aspect of above-mentioned composition, described thiophene azo carboxylate's dyestuff has a formula (XII):

A-N=N-X

Formula X II

Wherein part A selected from table 1A numbering of part 9 11,15,23,34 35,37-39,41,43,47,50 51,57 58, 77,83,89,95,106 and 110-118；Wherein X section is selected from table 4X numbering of part 18,13,14 and 18 21, and wherein G is From the organic group of substituted or non-substituted succinic anhydrides, maleic anhydride, glutaric anhydride, adipic anhydride or phthalic anhydride, Described anhydride has Formula X III,

Described anhydride has less than about 353 dalton, about 98 dalton to 352 dalton or the most about 100 dalton To about 325 daltonian molecular weight.In one aspect, the described G part of described thiophene azo carboxylate's dyestuff is selected from table 5G portion Lacing number 1 48.

At an aspect of above-mentioned composition, described thiophene azo carboxylate's dyestuff has a following formula:

Wherein said part A is selected from table 1A numbering of part 1 118；a=0-2；As a=1 or 2, R₆Selected from table 2R₆Substituent group Name & Location numbering 1 40；And R₄And R₅Group is selected from table 3R₄And R₅Group numbering 1 83.

Wherein said part A selected from table 1A numbering of part 9 11,15,23,34-35,37-39,41,43,47,50-51, 57-58,77,83,89,95,106 and 110-118；a=0-2；As a=1 or 2, R₆Selected from table 2R₆Substituent group Name & Location is compiled Numbers 1,3,5,7,12,13,14,31,36 and 40；And R₄And R₅Group is selected from table 3R₄And R₅Group numbering 3-8,14,15,18- 23,29,30,33-38,44,45,48-53,59,60,63-66,71-76,82 and 83.

At an aspect of above-mentioned composition, described thiophene azo carboxylate's dyestuff has selected from table 6 preparation numbering 1-48 Structural formula, in one aspect, described thiophene azo carboxylate's dyestuff has the knot selected from table 6 preparation numbering 1 36,43 and 44 Structure formula.

Part A is selected from the part shown in table 1.

Table 1:A part

R₆It is selected from the substituent group shown in table 2:

Table 2:R₆Substituent group-Name & Location

R₄And R₅It is selected from the group shown in table 3:

Table 3:R₄And R₅Group

" * " represents the junction point of other parts.

" M " represents the charge-balancing counterion of H or suitable.

X section can be selected from the part shown in table 4:

Table 4:X part

" * " represents the junction point with azo moiety.

G part in X section in table 4 above is selected from part 1-48 shown in table 5:

Table 5:G part

The anhydride being suitable for producing the Y portion in the present invention includes but not limited to following: 3-(2E)-2-laurylene-1- Base dihydro-2,5-furasndione；(3aR, 7aS)-rel-3a, 4,7,7a-tetrahydrochysene-4,7-epoxyisobenzofuran-1,3-diketone； 3-hexyl dihydro-3-methyl-2,5-furasndione；3-hexyl dihydro-2,5-furasndione；(3aR, 8aS)-rel-hexahydro-1H- Suberyl [c] furan-1,3 (3aH)-diketone；(3aR, 6aS)-rel-tetrahydrochysene-1H-cyclopenta [c] furan-1,3 (3aH)-two Ketone；5-(1,1-dimethyl ethyl)-1,3-isobenzofurandione；Dihydro-3-(phenyl methyl)-2,5-furasndione；3-last of the ten Heavenly stems Base dihydro-2,5-furasndione；Dihydro-3,3-dimethyl-2,5-furasndione；(3aR, 4S, 7R, 7aS)-rel-hexahydro-4, 7-methylene isobenzofuran-1,3-diketone；3-ethyl dihydro-2,5-furasndione；(3aR,7aS)-rel-3a,4,7,7a- Tetrahydrochysene-5,6-dimethyl-1,3-isobenzofurandione；3-(2-hexene-1-base) dihydro-2,5-furasndione；Dihydro-3- (2-propylene-1-base)-2,5-furasndione；Hexahydro-4,7-methylene isobenzofuran-1,3-diketone；5,6-dimethyl-1,3- Isobenzofurandione；Tetrahydrochysene-1H-cyclopenta [c] furan-1,3 (3aH)-diketone；5-nitro-1,3-isobenzofurandione； Hexahydro-4,7-epoxyisobenzofuran-1,3-diketone；3a, 4,7,7a-tetrahydrochysene-4,7-epoxyisobenzofuran-1,3-diketone； 5,6-dimethoxy-1,3-isobenzofurandione；Dihydro-3-octyl group-2,5-furasndione；Dihydro-3-methyl-2,5-furan Diketone；1,3-dihydro-1,3-dioxo-5-isobenzofuran carboxylate methyl ester；3-dodecyl dihydro-2,5-furasndione；Dihydro- 3-phenyl-2,5-furasndione；3a, 4,7,7a-tetrahydrochysene-4,7-methylene isobenzofuran-1,3-diketone；4-nitro-1,3- Isobenzofurandione；1,3-dihydro-1,3-dioxo-5-isobenzofuran carboxylic acid；(3aR,4S,7R,7aS)-rel-3a,4, 7,7a-tetrahydrochysene-4,7-methylene isobenzofuran-1,3-diketone；4,5,6,7-tetra-chloro-1,3-isobenzofurandione；Dihydro- 2,5-furasndione；1,3-isobenzofurandione；3a, 4,7,7a-tetrahydrochysene-1,3-isobenzofurandione；Hexahydro-1,3-is different Benzofuran diketone；(3aR, 4S, 7R, 7aS)-rel-hexahydro-3a, 7a-dimethyl-4,7-epoxyisobenzofuran-1,3-two Ketone；4-hexyl dihydro-2H-pyrans-2,6 (3H)-diketone；Dihydro-4-(2-methyl-propyl)-2H-pyrans-2,6 (3H)-diketone； 4-[[(1,1-dimethyl ethyl) dimetylsilyl] epoxide] dihydro-2H-pyrans-2,6 (3H)-diketone；4,4-dimethyl- 1H-2-.alpha.-5:6-benzopyran-1,3 (4H)-diketone；4-ethyl dihydro-4-methyl-2H-pyrans-2,6 (3H)-diketone；8-oxaspiro [4.5] decane-7,9-diketone；Dihydro-4,4-dimethyl-2H-pyrans-2,6 (3H)-diketone；Dihydro-3-phenyl-2H-pyrans- 2,6 (3H)-diketone；Dihydro-3,3-dimethyl-2H-pyrans-2,6 (3H)-diketone；1H-2-.alpha.-5:6-benzopyran-1,3 (4H)-diketone； Dihydro-2H-pyrans-2,6 (3H)-diketone；1H, 3H-naphtho-[1,8-cd] pyrans-1,3-diketone；3-oxabicyclo [3.2.1] is pungent Alkane-2,4-diketone；Dibenzo [c, e] oxepin-5,7-diketone；4,5-dihydro-2-benzo oxepin-1,3- Diketone；With 2,7-Oxepane diketone.This type of suitable anhydride be available from following one or more: 3B Scientific Corporation,Libertyville,IL,60048;Accel Pharmtech,LLC,East Brunswick,NJ, 08816;A Chemtek,Worcester,MA,01606;AK Scientific,Inc.,Union City,CA,94587; AKos Consulting and Solutions Deutschland GmbH,Steinen,D-79585,Germany;Alfa Aesar,Ward Hill,MA,01835;Allichem LLC,Baltimore,MD,21224;American Custom Chemicals Corp.,San Diego,CA,92196-2527;Aurora Fine Chemicals LLC,San Diego, CA,92126;Beta Pharma Scientific,Inc.,Branford,CT,06405;City Chemical LLC,West Haven,CT,06516;Ryan Scientific,Inc.,Mt.Pleasant,SC,29465;Sigma-Aldrich, St.Louis,MO,63178;TCI America,Portland,OR,97203;Waterstone Technology,Carmel, IN,46032;and Youchemicals Limited,Minhang,Shanghai,201100,People's Republic of China。

Should be taken into account following also within the scope of the invention: described thiophene azo carboxylate's dyestuff can comprise the A selected from table 1 Any one of part；R selected from table 2₆Any one of substituent group；R selected from table 3₄And R₅Any one of group；X selected from table 4 Any one of part；And selected from table 5 G part any one.

In still another aspect of the invention, suitable thiophene azo carboxylate's dyestuff includes but not limited to the structure shown in table 6:

Table 6: thiophene azo carboxylate's dyestuff

As it was previously stated, the Toner described in this specification can introduce in fabric care composition, described laundry care group Compound includes but not limited to laundry detergent compositions and Fabrid care composition.Fabric care composition including laundry detergent compositions is permissible It is solid or liquid form, including gel form and/or unit dosage form, including multicompartmented unit dosage form.This type of group Compound can comprise one or more described Toners and laundry care composition.

On the one hand, described fabric care composition can comprise helping less than 15% based on fabric care composition gross weight Even agent, auxiliary agent less than 10% auxiliary agent less than 5%.

On the one hand, described fabric care composition can comprise based on fabric care composition gross weight total less than 20% Water；Amount to the water less than 15%；Amount to the water less than 10%；Or amount to the water less than 5%.

On the one hand, described fabric care composition can comprise based on fabric care composition gross weight about 10% to about 70% Molecular weight more than 70 daltonian miscible organic solvents.

On the one hand, described fabric care composition can comprise perfume microcapsule based on fabric care composition gross weight and Optional formaldehyde scavenger, this microcapsule includes core and encapsulates the shell of described core, and described perfume microcapsule has 0.01 micron extremely D [4, the 3] average grain of about 200 microns, this formaldehyde scavenger is supplied by adding microcapsule (is contained in and is added into medicated clothing and protects In perfume microcapsule serosity in reason compositions) and/or be fed directly in fabric care composition.On the one hand, described spice The shell of microcapsule can be prepared by any material, including selected from following material: polyethylene kind, polyamide-based, polystyrene type, poly- Isoprenoid, polycarbonate-based, polyesters, polyacrylate, polyureas, polyurethanes, TPO, polysaccharide, epoxy Resin, polyvinyl and mixture thereof.On the one hand, useful shell material includes the most impermeable material to core material Material, and by the material in the environment of application perfume microcapsules, to allow the spice delivered to obtain.Suitably impermeability Shell material includes selected from following material: one or more amine and the product of one or more aldehyde, such as, with formaldehyde or penta The urea of dialdehyde crosslinking, with the tripolycyanamide of formaldehyde crosslinking；Optionally and the gelatin-polyphosphate aggregate of glutaraldehyde cross-linking；Gelatin- Radix Acaciae senegalis aggregate；The silicone fluid of crosslinking；The polyamines reacted with polyisocyanate, and mixture.On the one hand, shell Material includes the tripolycyanamide with formaldehyde crosslinking and/or polyacrylate.Suitably perfume microcapsule is available from Appleton Papers of Appleton Wisconsin,USA。

On the one hand, suitable formaldehyde scavenger includes selected from following material: sodium sulfite, urea, ethylene-urea, half Guang Propylhomoserin, cysteamine, lysine, glycine, serine, carnosine, histidine, glutathion, 3,4-diaminobenzoic acid, allantois Element, glycouril, ortho-aminobenzoic acid, methyl 2-aminobenzoate, PABA methyl ester, ethyl acetoacetate, acetyl Acetamide, Malondiamide, ascorbic acid, 1,3-bis-hydroxy acetone dimer, biuret, oxamid, benzoguanamine, Jiao Glutamic acid, pyrogaelol, gallicin, progallin A, propylgallate, triethanolamine, succinamide, thiophene benzene miaow Azoles, benzotriazole, triazole, indoline, sulfanilic acid, oxamides, sorbitol, glucose, cellulose, poly-(vinyl alcohol), part Poly-(vinyl formamide), poly-(vinyl amine), poly-(aziridine) of hydrolysis, poly-(oxidation enamine), vinyl alcohol-vinyl Amine copolymer thing, poly-(4-aminostyryl), poly-(l-lysine), chitosan, hexanediol, ethylenediamine-N, N'-biacetyl acetyl Amine, N-(2-ethylhexyl) aceto-acetamide, 2-benzyloxyacetyl acetamide, N-(3-phenyl propyl) aceto-acetamide, Herba Convallariae Aldehyde, helional, melonal, ligustral, 5,5-dimethyl-hydroresorcinol, 2,4-dimethyl-3-cyclohexene formaldehyde, 2,2-dimethyl-1,3-dioxane-4,6-diketone, 2 pentanone, dibutylamine, trien, ammonium hydroxide, benzylamine, hydroxyl Base citronellol, Ketohexamethylene, 2-butanone, pentanedione, anhydrous acetic acid or its mixture.These formaldehyde scavengers are available from Sigma/ Aldrich/Fluka of St.Louis, MO.U.S.A. or PolySciences, Inc.of Warrington, PA U.S.A.

This type of formaldehyde scavenger can be with the slurry combination containing described perfume microcapsule, and its amount is about based on serosity gross weight Even 2wt.% is to about 18wt.%, about 3.5wt.% to about 14wt.% about 5wt.% to about 13wt.%.

On the one hand, this type of formaldehyde scavenger can be combined with the product containing perfume microcapsule, with described product group mutually The amount of described scavenger closed is based on about 0.005% to about 0.8% that product gross weight is product formulation, or about 0.03% to about 0.5%, or about 0.065% to about 0.25%.

On the other hand, this type of formaldehyde scavenger can be with the slurry combination containing described perfume microcapsule, and its amount is based on serosity Even gross weight is about 2wt.% to about 14wt.%, about 3.5wt.% to about 14wt.% about 5wt.% to about 14wt.%, and described serosity can Being added in product substrate, same or different scavenger may be added in this product substrate, and its amount is total based on product It is heavily about the 0.005% to about 0.5% of product formulation, or about 0.01% to about 0.25%, or about 0.05% to about 0.15%.One Aspect, one or more above-mentioned formaldehyde scavengers can contain the liquid fabric enhancing product of perfume microcapsule and combine, its amount base Total amount is described product formulation about 0.005% to about the 0.8% of product, or about 0.03% to about 0.4% is strengthened in liquid fabric, Or about 0.06% to about 0.25%.

On the one hand, this type of formaldehyde removing can be combined with the liquid laundry detergent containing perfume microcapsule, described scavenger Selected from sodium sulfite, urea, ethylene-urea, cysteine, cysteamine, lysine, glycine, serine, carnosine, histidine, paddy The sweet peptide of Guang, 3,4-diaminobenzoic acid, allantoin, glycouril, ortho-aminobenzoic acid, methyl 2-aminobenzoate, 4-amino Essence of Niobe, ethyl acetoacetate, aceto-acetamide, Malondiamide, ascorbic acid, 1,3-bis-hydroxy acetone dimer, Biuret, oxamid, benzoguanamine, pyroglutamic acid, pyrogaelol, gallicin, progallin A, gallic acid Propyl ester, triethanolamine, succinamide, thiabendazole, benzotriazole, triazole, indoline, sulfanilic acid, oxamides, sorbitol, Glucose, cellulose, poly-(vinyl alcohol), poly-(vinyl formamide), poly-(vinyl amine) of partial hydrolysis, poly-(ethylene Asia Amine), poly-(oxidation enamine), vinyl alcohol-vinyl amine copolymer, poly-(4-aminostyryl), poly-(l-lysine), shell gather Sugar, hexanediol, ethylenediamine-N, N'-biacetyl acetamide, N-(2-ethylhexyl) aceto-acetamide, 2-benzyloxyacetyl acetyl Amine, N-(3-phenyl propyl) aceto-acetamide, lilestralis, helional, melonal, ligustral, 5,5-dimethyl-1,3-ring Acetyl butyryl, 2,4-dimethyl-3-cyclohexene formaldehyde, 2,2-dimethyl-1,3-dioxane-4,6-diketone, 2 pentanone, dibutyl Amine, trien, ammonium hydroxide, benzylamine, hydroxycitronellol, Ketohexamethylene, 2-butanone, pentanedione, anhydrous acetic acid or its mix Compound, it is with following amounts and described liquid laundry detergent product mix, based on liquid laundry detergent product gross weight, is about Even 0.003wt.% is to about 0.20wt.%, about 0.03wt.% to about 0.20wt.% about 0.06wt.% to about 0.14wt.%.

Described Toner can use multiple applying technology to add in substrate.Such as, for cellulose textile base Applying at the end, Toner can be included as the component of laundry detergent compositions.Therefore, executing in cellulose textile substrate Add and actually occur in consumer when added in washing machine by laundry detergent compositions.Toner can be with the pact of composition weight 0.000001% to about 10%, about 0.00001% to about the 10% of composition weight, about the 0.0001% of composition weight arrive about 5% and even composition weight about 0.0001% to about 1% amount be present in laundry detergent composition.

Laundry detergent composition typically comprises the surfactant presenting in an amount at least sufficient to provide preferable sanitary characteristics.At one Aspect, laundry detergent composition can include the table of about 0.5% to about 99% based on total laundry detergent composition weight Face activating agent, the surfactant of about 1% to about 95%, the surfactant of about 5% to about 90%, about 5% to about 70% Surfactant, or the surfactant of the most about 5% to about 40%.Surfactant can include anion, nonionic, sun Ion, amphion and/or amphoteric surfactant.In one aspect, composition of detergent include anion surfactant, Nonionic surfactant or its mixture.

Fabrid care composition adds the most in the rinse cycle, and described in typical case's washing process, rinse cycle is After employing detergent solution and it replaced with rinsing solution.Fabrid care composition disclosed herein may be included in The fabric-softening active matter added during rinsing and the suitable Toner as disclosed in this specification.Fabrid care composition can wrap Include the fabric-softening active matter of about 1% to about 90% or about 5% to about 50% based on total Fabrid care composition weight. Toner can the amount of about 0.05ppb to about 50ppm or about 0.5ppm to about 30ppm be present in Fabrid care composition.

Suitably laundry care composition

Although being not necessarily required to the purpose of the present invention, the non-limiting list of hereinafter illustrated laundry care composition is fitted Share and can expect to be introduced in fabric care composition and in certain aspects of the invention, such as, help or improve wanting The performance of the process of cleaned substrate, or combination is changed when using the situation of spice, coloring agent, dyestuff or the like The aesthetics of thing.It should be understood that such composition is outside the component listed previously for any specific aspect.When by dyestuff When amount accounts for, the amount of these adjuvant can be about 90% to the 99.99999995% of fabric care composition weight.

The exact nature of these other components and addition level thereof will depend upon which that the physical form of compositions is wanted quilt with it For the character of operation.Suitably laundry care composition include but not limited to fabric-softening active matter, polymer such as sun from Sub-polymer, surfactant, washing assisant, chelating agen, dye transfer inhibitor, dispersant, enzyme and enzyme stabilizers, catalytic materials Matter, bleach-activating, polymeric dispersant, cohesive soil removal/anti redeposition agent, brightening agent, foam inhibitor, dyestuff, spice (include Quadrant spice) and other spice transmission systems (including the zeolite loading spice), accords and Schiff of starch encapsulated Alkali Pro-perfumes (pro-perfume), structure toughener, fabric softener, carrier, hydrotropic agent, process auxiliary agent and/or face Material.In addition to disclosure below, these other auxiliary agents and use level suitable example can in United States Patent (USP) 5,576, 282,6,306,812B1 and 6, find in 326,348B1, above-mentioned document is incorporated by reference into.

As it has been described above, laundry care composition is dispensable for the fabric care composition of applicant.Therefore, Shen Some aspect of the compositions asked someone is without one or more following adjunct materials: fabric-softening active matter, bleach-activating, table Face activating agent, washing assisant, chelating agen, dye transfer inhibitor, dispersant, enzyme and enzyme stabilizers, catalytic metal coordination compound, Polymeric dispersant, clay and earth removal/anti redeposition agent, brightening agent, foam inhibitor, dyestuff, other spice and spice transmission are System, structure toughener, fabric softener, carrier, hydrotropic agent, process auxiliary agent and/or pigment.But, when one or more In the presence of adjuvant, these one or more adjuvant can as detailed below as exist:

Surfactant

Suitable anion surfactant available herein include being generally used in detergent product any often Rule anionic surfactant types.These include alkyl benzene sulphonate and salt thereof and alkoxylate or non-alkoxylated alkyl sulfur Hydrochlorate material.

Exemplary anion surfactant is C₁₀-C₁₆Alkyl benzene sulphonate or C₁₁-C₁₄The alkali metal of alkyl benzene sulphonate Salt.In one aspect, alkyl group is linear, and this linear alkyl benzene sulfonate is referred to as " LAS ".Alkyl benzene sulphonate Salt, particularly LAS, be well known in the present art.This surfactant and preparation thereof are in such as United States Patent (USP) 2,220,099 Described in 2,477,383.Especially useful is linear straight chain benzene sulfonic acid sodium salt and potassium, wherein the average carbon in alkyl group Atomic number is about 11 to 14.C₁₁-C₁₄(such as, C₁₂) LAS sodium is the object lesson of this surfactant.

Another kind of exemplary anionic surfactants type includes ethoxylated alkyl sulfates surfactant.This Material is also referred to as alkyl ether sulfate or alkyl polyethoxylate sulfates, and it corresponds to those of the formula material: R '--O-- (C₂H₄O)_n--SO₃M, wherein R ' is C₈-C₂₀Alkyl, n is about 1 to 20, and M is salt-forming cation.In one aspect, R ' is C₁₀- C₁₈Alkyl, n is about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium or alkanol ammonium.In one aspect, R ' is C₁₂-C₁₆Alkyl, n is About 1 to 6, and M is sodium.

Alkyl ether sulfate is generally to include that the form of mixtures of variable R ' chain length and variable degree of ethoxylation uses.Logical Normal this mixture also will inevitably comprise some unethoxylated alkyl sulfate materials, i.e. wherein n=0's is above-mentioned The surfactant of ethoxylated alkyl sulfates chemical formula.Unethoxylated alkyl sulfate also can be added separately to the present invention Compositions in and be used as or for any anionic surfactant component that can exist.Non-alkoxylate (such as, non-second Epoxide) the object lesson of alkyl ether sulfate surfactant be the C by longer chain₈-C₂₀The sulfation of fatty alcohol Those prepared.Conventional primary salt surfactant has formula: ROSO₃-M⁺, wherein R is typically linear C₈- C₂₀Hydrocarbyl group, it can be straight or branched, and M is soluble in the cation of water.In one aspect, R is C₁₀-C₁₅Alkyl, And M is alkali metal, more specifically R is C₁₂-C₁₄Alkyl, and M is sodium.

The concrete non-limitative example of anion surfactant available herein includes: a) C₁₁-C₁₈Alkyl benzene sulphonate Salt (LAS)；b)C₁₀-C₂₀Side chain and random primary alkyl sulphates (AS)；C) there is formula (I) and the C of (II)₁₀-C₁₈Secondary (2,3) Alkyl sulfate: the M in its Chinese style (I) and (II) is hydrogen or provides electroneutral cation, and either with surfactant Or all M unit relevant with adjuvant ingredient can be hydrogen atom or cation, and this depends on what technical staff was separated Form or use the relative pH of system of described compound, the non-limitative example of suitable cation include sodium, potassium, ammonium and Mixture, x is at least about 7 or the integer of at least about 9, and y is at least 8 or the integer of at least about 9；d)C₁₀-C₁₈Alkyl alkoxy sulfur Hydrochlorate (AE_xS), wherein x is 1-30；e)C₁₀-C₁₈Alkyl alkoxy carboxylates, in one aspect, including 1-5 ethyoxyl list Unit；F) the mid chain branched alkyl base sulfate as discussed in United States Patent (USP) 6,020,303 and United States Patent (USP) 6,040,443；G) as Mid chain branched alkyl base alkoxy sulfate discussed in United States Patent (USP) 6,008,181 and United States Patent (USP) 6,020,303；H) exist WO99/05243、WO99/05242、WO99/05244、WO99/05082、WO99/05084、WO99/05241、WO99/07656、 Modified alkylbenzene sulfonates (MLAS) discussed in WO00/23549 and WO00/23548；I) methylmesylate (MES)；And j) α- Alkene sulfonate (AOS).

It is any that suitable nonionic surfactant available herein can include being generally used in detergent product Conventional nonionic surfactant.These include alkoxy fatty alcohols and amine oxide surfactant.In one aspect, it is used for In detergent product herein is those normally liquid nonionic surfactants.

Alcohol alkoxide nonionic surfactant is included with suitable nonionic surfactant in this article.Alcohol alkane Oxide corresponds to the material of below formula: R¹(C_mH_2mO)_nOH, wherein R¹It is C₈-C₁₆Alkyl group, m is that 2-4, n are about 2- 12.In one aspect, R¹Being alkyl, it can be primary alkyl or secondary alkyl, and described alkyl group includes about 9 to 15 carbon atoms Or about 10 to 14 carbon atoms.In one aspect, alkoxy fatty alcohols can also be to comprise about 2 to 12 epoxies of per molecule Ethane part or the ethoxylation material of about 3 to 10 ethylene oxide moieties of per molecule.

Can be used for the alkoxy fatty alcohols material in liquid detergent composition herein generally would have about 3 to 17, Hydrophilic-lipophilic balance (HLB) of about 6 to 15 or about 8 to 15.Alkoxy fatty alcohols nonionic surfactant by Shell Chemical Company commercially sells with trade name Neodol and Dobanol.

The nonionic surfactant of another kind of suitable type available herein includes amine oxide surfactant.Amine oxide It it is the material of generally referred in the art as " semi-polarity " nonionic surfactant.Amine oxide has below formula: R (EO)_x(PO)_y(BO)_zN(O)(CH₂R’)₂·qH₂O.In the formula, R is the hydrocarbyl portion of relative long-chain, its can be saturated or Unsaturated, straight or branched, and 8 to 20,10 to 16 carbon atoms, or C can be comprised₁₂-C₁₆Primary alkyl.R ' is short Chain part, in one aspect, R ' be selected from hydrogen, methyl and--CH₂OH.When x+y+z is not 0, EO is ethyleneoxy, and PO is Propenyloxy group, and BO is butenyloxy.Amine oxide surfactant is interpreted C_12-14Alkyl dimethyl amine oxide.

The non-limitative example of nonionic surfactant includes: a) C₁₂-C₁₈Alkyl ethoxylate, such as, from Shell'sNonionic surfactant；b)C₆-C₁₂Alkyl phenolic alkoxy thing, wherein alcoxylates list Unit is the mixture of ethyleneoxy and propyleneoxy units；c)C₁₂-C₁₈Alcohol and C₆-C₁₂Alkyl phenol and ethylene oxide/propylene oxide The condensation substance of block polymer, such as from BASF'sd)C₁₄-C₂₂Mid-chain branched alcohols, BA, such as United States Patent (USP) 6, Discussed in 150,322；e)C₁₄-C₂₂Mid chain branched alkyl based alkoxylation thing, BAE_x, wherein x is 1-30, such as United States Patent (USP) 6, 153,577, discussed in United States Patent (USP) 6,020,303 and United States Patent (USP) 6,093,856；F) alkyl polysaccharide, such as in January, 1986 Within 26th, authorize discussed in the United States Patent (USP) 4,565,647 of Llenado；Especially such as United States Patent (USP) 4,483,780 and the U.S. Alkyl polysaccharide discussed in patent 4,483,779；G) polyhydroxy fatty acid amide, such as United States Patent (USP) 5,332,528, WO92/ 06162, discussed in WO93/19146, WO91/19038 and WO94/09099；And h) ether capped poly-(o-alkylation) alcohol Surfactant, such as United States Patent (USP) 6, discussed in 482,994 and WO01/42408.

In laundry detergent composition herein, washing performance surface active agent composition can include anion and nonionic table The combination of face surfactant material.When belonging to this situation, anion surfactant and the weight of nonionic surfactant Ratio typically 10:90 to 90:10, is more typically 30:70 to 70:30.

Cationic surfactant is well known in the present art, and its non-limitative example includes quaternary ammonium surfactant Agent, it can have up to 26 carbon atoms.Other example includes a) alkoxy quaternary ammonium (AQA) surfactant, as the U.S. is special Discussed in profit 6,136,769；B) dimethyl hydroxy ethyl quaternary ammonium, such as United States Patent (USP) 6, discussed in 004,922；C) polyamine Cationic surfactant, in WO98/35002, WO98/35003, WO98/35004, WO98/35005 and WO98/35006 Discussed；D) cationic ester surfactant, such as United States Patent (USP) 4,228,042,4,239,660,4,239,529 and the U.S. special Discussed in profit 6,002,844；And e) amino surfactants, such as United States Patent (USP) 6, institute in 221,825 and WO00/47708 Discuss, especially amidopropyldimethylamine (APA).

The non-limitative example of zwitterionic surfactant includes the derivant of secondary amine and tertiary amine, heterocyclic secondary and tertiary amine Derivant, or quaternary ammonium, season or the derivant of tertiary sulfonium compound.See December in 1975 and authorize Laughlin's etc. on 30th United States Patent (USP) 3,929, the 678, the 19th hurdle the 38th row to the 22nd hurdle the 48th row, about the example of zwitterionic surfactant；Sweet Dish alkali, including alkyl dimethyl betaine and coco dimethyl amido propyl betaine, C₈-C₁₈(in one aspect, C₁₂- C₁₈) amine oxide and sulfo group and hydroxy betaines, such as N-alkyl-N, N-dimethyl ammino-1-propane sulfonic acid ester, wherein alkyl base Group can be C₈-C₁₈, or C₁₀-C₁₄。

The non-limitative example of amphoteric surfactant includes the aliphatic derivatives of secondary amine or tertiary amine, or heterocyclic secondary and The aliphatic derivatives of tertiary amine, wherein aliphatic group can be straight or branched.One of aliphatic series substituent group includes at least about 8 carbon Atom, typically about 8 to about 18 carbon atoms, and at least one includes anionic water solubilizing group, such as, carboxyl, sulphur Acid group, sulfate radical.See December in 1975 and within 30th, authorize United States Patent (USP) the 3,929,678, the 19th hurdle 18-of Laughlin et al. 35 row, about the example of amphoteric surfactant.

Aqueous on-surface-active liquid-carrier

As it has been described above, fabric care composition can be the solid form of tablet or particle form, include but not limited to granule, Thin slice, tablet etc., or compositions can be liquid form.Liquid detergent composition can include aqueous on-surface-active liquid Carrier.Generally, the amount of the aqueous on-surface-active liquid-carrier used in compositions herein can effectively be dissolved, be suspended Or dispersive composition component.Such as, liquid detergent composition can include pact based on total liquid detergent composition weight The aqueous on-surface-active liquid-carrier of 5% to about 90%, about 10% to about 70% or about 20% to about 70%.

The aqueous on-surface-active liquid-carrier of most cost-effective type is usually water.Therefore, aqueous on-surface-active liquid Major part (if not all) is generally made up of by body carrier water.Although being that the purpose of the present invention also can be by other type of water Forming ionisable polymer such as alkanol, glycol, other polyhydric alcohol, ether, amine etc. add conduct in liquid detergent composition routinely to Cosolvent or stabilizer, the application of this water miscible liquid would generally be minimized to reduce the cost of compositions.Therefore, originally The water liquid carrier component of the detergent product of literary composition is typically included and arrives by about the 5% of liquid detergent composition weight The water that the concentration of about 90% or about 5% to about 70% exists.

Bleach

The Cleasing compositions of the bleach present invention can include one or more bleachs.Suitably bleach (urge by non-bleached Agent) include photobleaching agent, bleach-activating, hydrogen peroxide, hydrogen peroxide source, preformed peracid and mixture thereof. In general, when a bleaching agent is used, the compositions of the present invention can include based on theme Cleasing compositions weight about 0.1% to about The bleach of 50% or the most about 1% to about 25%.The suitably example of bleach includes:

(1) photobleaching agent, such as sulfonate zinc phthalocyanine；

(2) preformed peracid: suitable preformed peracid includes but not limited to selected from percarboxylic acids and salt, mistake Carbonic acid and salt thereof, cross imidic acid and salt, permonosulphuric acid (peroxymonosulfuric acid) and salt is (such as,) and the compound of mixture.Suitably percarboxylic acids include having the hydrophobic of formula R-(C=O) O-O-M and Hydrophilic peracids, wherein R is alkyl, and it is optionally side chain, and when this peracid is hydrophobicity, described alkyl has 6-14 Carbon atom or 8 to 12 carbon atoms, and when this peracid is hydrophilic, described alkyl have less than 6 carbon atoms or Even less than 4 carbon atoms；And M is counter ion counterionsl gegenions, such as, sodium, potassium or hydrogen.

(3) hydrogen peroxide source, such as, Inorganic perhydrate (perhydrate, perhydrates) salt, including alkali gold Belong to salt, such as perboric acid (usually monohydrate or tetrahydrate), percarbonic acid, persulfuric acid, peroxophosphoric acid, cross silicic acid sodium salt and Its mixture.In one aspect of the invention, Inorganic perhydrate salt is selected from perboric acid, the sodium salt of percarbonic acid and mixture thereof. When deployed, Inorganic perhydrate salt generally exists with the amount of 0.05-40wt% or 1-30wt% of entire combination thing, and Usually used as can applied crystalline solid join in such compositions.Suitably coating includes, inorganic salt such as alkali gold The silicate, carbonate or the borate that belong to or its mixture, or organic material such as water solublity or water-dispersible polymers, Wax, oil or fat soap；With

(4) bleach-activating of formula R-(C=O)-L, wherein R is alkyl, and it is optionally side chain, when this bleach activating When agent is hydrophobicity, described alkyl has 6-14 carbon atom or 8 to 12 carbon atoms, and when this bleach activator is parent During aqueous, described alkyl has less than 6 carbon atoms or even less than 4 carbon atoms；And L is leaving group.Suitably from The example removing group is benzoic acid and derivant especially benzene sulfonate thereof.Suitably bleach-activating includes lauroyl hydroxyl Base benzene sulfonate, oxybenzene sulphonate, capryl hydroxy benzoic acid or its salt, 3,5,5-trimethyl hexanoyloxybenzene benzene Sulfonate, tetra acetyl ethylene diamine (TAED) and pelargonyl group phenolsulfonate (NOBS).Suitably bleach-activating also exists WO98/17767 discloses.Although any suitable bleach-activating can be used, in one aspect of the invention, theme cleaning group Compound can include NOBS, TAED or its mixture.

When it is present, peracid and/or bleach-activating generally arrive to about 60wt%, about 0.5 with based on compositions about 0.1 The amount of about 40wt% or the most about 0.6 to about 10wt% is present in compositions.One or more hydrophobicity peracid or its before Body can be used in combination with one or more hydrophilic peracids or its precursor.

The amount of hydrogen peroxide source and peracid or bleach-activating be selectable such that available oxygen (from hydrogen peroxide source) with The mol ratio of peracid is 1:1 to 35:1, or even 2:1 to 10:1.

Bleaching auxiliary compounds compositions herein can include that one or more bleach auxiliary compounds.Bleaching auxiliaryization Compound provides bleaching effect of raising in lower temperature is applied.Bleaching assistant and conventional peroxide bleaching source synergism To provide the bleaching effect strengthened.This is typically by being formed in situ active oxygen-transfer agent such as bisoxirane, oxa-nitrogen Heterocycle propane or oxaziridine salt realize.Or, preformed bis-epoxy propane, oxazepine ring can be used Propane and oxaziridine salt.

Suitably bleaching auxiliary compounds used according to the invention be net charge be about+3 to about-3 cationic imines, Both sexes example imines, anionic imine and/or polyion imines and mixture thereof.These imines bleaching auxiliary chemical combination of the present invention Thing includes those of following universal architecture:

Wherein R¹-R⁴Can be hydrogen or unsubstituted or substituted selected from phenyl, aryl, heterocycle, alkyl and group of naphthene base Group.

Suitably bleaching auxiliary compounds includes amphion bleaching assistant, and it is in United States Patent (USP) 5,576,282 and 5, Described in 718,614.Other bleaching auxiliary compounds is included in United States Patent (USP) 5,360,569；5,442,066；5,478,357； 5,370,826；5,482,515；5,550,256；With WO94/13351, WO95/13352 and WO95/13353 described in sun from Sub-bleaching assistant.

Peroxygen source is well known in the present art and peroxygen source employed in the present invention can include any known in these Source, including per-compound and when the compound of peroxide that provide effective dose under the conditions of the use of consumer on the spot. Peroxygen source can include hydrogen peroxide source, crosses acid anion by what the reaction of hydrogen peroxide source Yu bleach-activating was formed in situ, Preformed peracid compound, or the mixture of suitable peroxygen source.Certainly, it will be appreciated by persons skilled in the art that other Peroxygen source also may be utilized without departing from the scope of the present invention.Bleaching auxiliary compounds is when it is present generally and the drift of the present invention The collaborative use of peroxygen source in white system.

Enzyme bleaching enzymatic system is used as bleach.Hydrogen peroxide also can be by starting in washing and/or rinse cycle Time or during it add can generate the enzymatic system (that is, enzyme and substrate thereof) of hydrogen peroxide and exist.Such enzymatic system Disclosed in the european patent application 91202655.6 that on October 9th, 1991 submits to.

The compositions and methods of the invention can utilize other optional bleaching system, such as ozone, chlorine dioxide etc..With smelly Oxygen bleaching can be by being about 20 to about 300g/m by ozone content³Introduce reality in the solution that contact with fabric containing ozone gas Existing.Gas in solution: liquor ratio should keep about 1:2.5 to about 1:6.United States Patent (USP) 5,346,588 describes one and utilizes ozone As the method for the replacement scheme of conventional bleaching system, the document is incorporated herein by.

In one aspect, fabric-softening active matter (" FSA ") is to be suitable for the quaternary ammonium compounds of softening fabrics in rinse step Thing.In one aspect, FSA is by fatty acid and the amino obtaining the single-, two-mixture with (in one aspect) three ester compounds The product of alcohol is formed.On the other hand, FSA includes one or more softening agent quaternary ammonium compounds, such as, but not limited to list Alkyl quaternary ammonium compound, diamides base quaternary ammonium compound and diester quat or a combination thereof.

In one aspect of the invention, FSA includes diester quaternary ammonium (hereinafter referred to as " DQA ") compound composition.At this Some bright aspect, DQA compound composition also comprise to diamides base FSAs and with mixing amido link and ester bond and The description of the FSAs of aforementioned diester linkage, the most referred to as DQA.

The DQA (" DQA (1) ") being suitable in the CFSC of the present invention the first type as FSA includes having following formula Compound:

{R_4-m–N⁺–[(CH₂)_n–Y–R¹]_m}X^-

The most each R substituent is hydrogen, short chain C₁-C₆(such as C₁-C₃) alkyl or hydroxyalkyl group (such as, methyl, second Base, propyl group, ethoxy etc.), poly-(C_2-3Alkoxyl) (such as, polyethoxy group), benzyl or its mixture；Each m be 2 or 3；Each n is 1 to about 4, or 2；Each Y is-O-(O) C-,-C (O)-O-,-NR-C (O)-or-C (O)-NR-, and can accept Be that each Y may be the same or different；When Y be-O-(O) C-or-NR-C (O)-time, each R¹In carbon number add 1 sum and be C₁₂-C₂₂Or C₁₄-C₂₀, each R¹It is alkyl or substituted hydrocarbon radical；For R¹Acceptable is that it is unsaturated or saturated and props up Chain or straight chain, and in an aspect, it is straight chain；For each R¹Acceptable be its be identical or different, And generally these are identical；And X-can be the anion that any softening agent is compatible, suitable anion include chloride ion, Bromide ion, methylsulfate, ethyl sulphate, sulfate radical, phosphate radical and nitrate anion, in one aspect anion be chloride ion or Methylsulfate.Suitably DQA compound is generally by by such as MDEA (methyl diethanolamine) and the alkane of TEA (triethanolamine) Hydramine is prepared with fatty acid response.Some materials generally obtained by this reaction include N, N-bis-(acyl group-oxygen ethyl)-N, N-alkyl dimethyl ammonium chloride or N, N-bis-(acyl group-oxygen ethyl)-N, N-dimethyl hydroxyethyl (methylsulfuric acid) ammonium, wherein carboxyl groups obtains From Animal fat, unsaturated and polyunsaturated fatty acid (such as, Adeps Bovis seu Bubali, hardened tallow, oleic acid and/or partially hydrogenated fat Acid), derive from vegetable oil and/or partially hydrogenated vegetable oil (such as Canola oil, safflower oil, Oleum Arachidis hypogaeae semen, Oleum Helianthi, Semen Maydis Oil, soybean oil, tall oil, Testa oryzae oil, Petiolus Trachycarpi oil etc.).

Suitably the non-limitative example of fatty acid is in United States Patent (USP) 5, lists, see the 4th hurdle 45-66 row in 759,990. In one aspect, FSA includes other active matters in addition to DQA (1) or DQA.In yet other aspects, FSA only includes DQA (1) or DQA, and without or be substantially free of other quaternary ammonium compound any or other active matter.At still another aspect, FSA includes the precursor amine for producing DQA.

In another aspect of this invention, FSA includes the compound being designated DTTMAC, and it includes following formula:

[R_4-m–N(⁺)–R¹ _m]A^-

The most each m is 2 or 3, each R¹It is C₆-C₂₂Or C₁₄-C₂₀But not more than one less than about C₁₂Other is the most at least It is about alkyl or the substituted hydrocarbon radical substituent group of 16, such as, C₁₀-C₂₀(unsaturated alkyl, including many unsaturated alkane for alkyl or alkenyl Base, otherwise referred to as " alkylidene "), in one aspect, C₁₂-C₁₈Alkyl or alkenyl, and be side chain or non-branched.One Individual aspect, the iodine number (IV) of FSA is about 1 to 70；Each R is hydrogen or short chain C₁-C₆Or C₁-C₃Alkyl or hydroxyalkyl group (example As, methyl, ethyl, propyl group, ethoxy etc.), benzyl or (R²O)_2-4H, the most each R²It is C_1-6Alkylidene group；And A-is soft The anion that agent is compatible, suitable anion include chloride ion, bromide ion, methylsulfate, ethyl sulphate, sulfate radical, Phosphate radical or nitrate anion；In one aspect, anion is chloride ion or methylsulfate.

The example of these FSA includes dialkyl dimethyl ammonium salt and two alkylidene dimethyl ammoniums, such as two Adeps Bovis seu Bubali diformazan Base (methylsulfuric acid) ammonium and two tallow dimethyl (methylsulfuric acid) ammonium.Commercially available two alkylidenes two that can be used in the present invention The example of methyl ammonium salt is dihydrogenated tallow alkyl dimethyl ammonium chloride and two tallow dimethyl ammonium chloride, and it can be respectively with trade name442 Hes470 obtain from Degussa.In one aspect, FSA includes in addition to DTTMAC Other active matters.In yet other aspects, FSA only includes the compound of DTTMAC, and without or be substantially free of any other Quaternary ammonium compound or other active matter.

In one aspect, FSA be included in U.S. Patent Publication No. 2004/0204337A1 (on October 14th, 2004 is open, Authorize Corona et al., 30-79 section) described in FSA.On the other hand, FSA is U.S. Patent Publication No. 2004/ 0229769A1 (on November 18th, 2005 is open, authorizes Smith et al., 26-31 section)；Or United States Patent (USP) 6,494,920 the (the 1st Hurdle the 51st row and following etc., describes " esterquats " or quaternized fatty acid triethanolamine ester salts in detail) in retouched The person of stating.

In one aspect, at least one in following of FSA: two tallowoyl base ethyl alkyl dimethyl ammonium chlorides, dihydro Change tallowoyl base ethyl alkyl dimethyl ammonium chloride, two tallow dimethyl ammonium chloride, two tallowoyl base ethyl dimethyl (methyl sulfur Acid) ammonium, dihydrogenated tallow dimethylbenzylammonium ammonium chloride, dihydrogenated tallow dimethylbenzylammonium ammonium chloride or its group Close.

In one aspect, FSA may also include the chemical composition of amide containing.The example of the compound containing diamides include but Be not limited to methyl two (tallow amido ethyl)-2-ethoxy (methylsulfuric acid) ammonium (can with trade name Varisoft110 and Varisoft222 derives from Degussa).The example of amide containing ester compounds is that [2-is (hard for N-[3-(stearoyl amino) propyl group]-N- Acyl epoxide) ethyoxyl) ethyl]-N-methylamine.

The fabric softening compositions added when another aspect provides rinsing, it also includes cationic starch. Cationic starch is disclosed in US2004/0204337A1.In one aspect, the fabric softening compositions added during rinsing includes Account for described fabric softening compositions weight about 0.1% to about 7% cationic starch.In one aspect, cationic starch is Derive from the HCP401 of National Starch.

The compositions of the washing assisant present invention can include one or more detergent builders or adjuvant systems.When it is present, Compositions is typically included the auxiliary agent of at least about 1%, or about 5wt% or 10wt% is to about 80wt%, 50wt% or even The described washing assisant of 30wt%.Washing assisant includes but not limited to the alkali metal salt of polyphosphoric acid, ammonium salt and alkanol ammonium salt, silicic acid Alkali metal salt, carbonic acid alkaline-earth metal and alkali metal salt, aluminosilicate washing assisant, Polycarboxylate compounds, ether hydroxyl polycarboxylic acids Ester, maleic anhydride and ethylene or the copolymer of vinyl methyl ether, phloroglucinol-2,4,6-trisulfonic acids, and carboxymethyl Oxysuccinic acid, the various alkali metal salts of poly-acetic acid, ammonium salt and substituted ammonium salt (such as ethylenediaminetetraacetic acid and nitrilotriacetic acid(NTA)), And polycarboxylate such as mellic acid., succinic acid, hydroxyl disuccinic acid, poly, benzene 1,3,5-tricarboxylic acid, carboxy-methoxy Base succinic acid and soluble-salt thereof.

Chelating agen compositions herein the most optionally comprises one or more copper, ferrum and/or manganese chelating agen.If made With, chelating agen generally will account for the about 0.1wt% to about 15wt% of compositions herein, or even accounts for the pact of compositions herein 3.0wt% to about 15wt%.

The compositions of the dye transfer inhibitor present invention may also include one or more dye transfer inhibitors.Suitably Polymeric dye transfer inhibitor includes but not limited to polyvinyl pyrrolidone polymers, polyamine N-oxide pllymers, N-ethylene Ketopyrrolidine and the copolymer of N-vinyl imidazol, polyvinyl carbazole alkanone and polyvinyl imidazole or its mixture.When being present in this Time in the compositions of literary composition, dye transfer inhibitor with about the 0.0001% of Cleasing compositions weight, about 0.01%, about 0.05% arrives The level of about the 10% of Cleasing compositions weight, about 2% or the most about 1% exists.

The compositions of the dispersant present invention also can comprise dispersant.Suitably water-soluble organic materials is homopolymerization or copolymerization Acid or its salt, wherein said polycarboxylic acids can include at least two carboxyl free radical, they by not more than two carbon atoms that This is separately.

Compositions described in enzyme can include that one or more provide clean-up performance and/or the detergent enzyme of fabric care benefits. Suitably the example of enzyme include but not limited to hemicellulase, peroxidase, protease, cellulase, xylosidase, lipase, Phospholipase, esterase, at, pectase, keratan sulfate enzyme, reductase, oxidase, phenol peroxidase, lipoxidase, Ligninase, pullulanase (pullulanase), tannase, pentosanase, malanase, 1,4 beta-glucanase, Arabic half poly-breast Carbohydrase, hyaluronidase, chondroitinase, laccase and amylase or its mixture.Typical combination be conventional available enzyme such as protease, Lipase, at and/or cellulase combine diastatic combination.

Enzyme stabilizers can be stablized by multiple technologies for the enzyme of compositions (such as, detergent).Enzyme used herein Can come steady by existing for the water-soluble source of these ions of enzyme offer calcium ion and/or magnesium ion in the final composition Fixed.

The preparation method of fabric care composition

The fabric care composition of the present invention can be configured to any suitable form and by appointing selected by formulator Where prepared by method, and its non-limiting example is disclosed in the embodiment of applicant and in following document: U.S.5, and 879,584； U.S.5,691,297；U.S.5,574,005；U.S.5,569,645；U.S.5,565,422；U.S.5,516,448；U.S.5, 489,392；U.S.5, in 486,303, all documents are incorporated herein by.

Liquid detergent composition is surfactant, Toner and the aqueous solution of other composition that some is optional or uniformly Dispersion liquid or the form of suspension, some of which generally can be solid form, its normally liquid with compositions group Deciliter also, described normally liquid component such as liquid alcohol ethoxylate nonionic surfactant, water liquid carrier With other normally liquid optional components any.Such solution, dispersion liquid or suspension will be mutually the most stable, And it is generally of about 100 to 600cps or about 150 viscosity arriving 400cps scope.For the purpose of the present invention, use Brookfield LVDV-II+ viscometer apparatus uses #21 spindle to measure viscosity.

Liquid detergent composition herein can be prepared as follows: its component is closed with any convenient order And, and by mixing, such as, the component combination of stirring gained is to form mutually stable liquid detergent composition.Preparing this During kind of compositions, define and comprise at least most of or even almost all liquid component (such as, non-ionic surface Activating agent, on-surface-active liquid-carrier and other optional liquid component) fluid matrix, and by this liquid group Close and give shear agitation and liquid component is sufficiently mixed.Such as, can be efficiently used and quickly stir with what mechanical agitator was carried out Mix.While keeping shear agitation, most any anion surfactant and the composition of solid form can be added. Continue mixture is stirred, and if it is required, the stirring to mixture can be strengthened at this moment, to form solution or insoluble Property solid phase particles uniform dispersion in the liquid phase.Adding the material of some or all solid forms to this stirred Mixture in after, add and to be contained in the granule of any enzyme material therein, such as, enzyme grain.As described previously group The variant of compound preparation procedure, one or more solid constituents can as with one or more liquid components of small part premix Grain solution or serosity and be added in the mixture that stirred.After with the addition of all of composition component, will be to mixing The stirring of thing proceeds the time that be enough to form the compositions with required viscosity and phase stability characteristics.Generally this will include The stirring of about 30 to 60 minutes.

Formed liquid detergent composition an aspect, Toner first merge with one or more liquid components with Form Toner pre-composition, and this Toner pre-composition is added to the major part comprising remaining component of laundry detergent composition In the composite preparation of (being greater than 50wt%, more specifically more than 70wt%, the most more specifically more than 90wt%). Such as, in method described above, the final stage that Toner pre-composition and enzyme component are all added in component is added.At another Aspect, Toner was encapsulated before adding composition of detergent to, and encapsulated Toner is suspended in structuring liquid In body, and suspension is added in the most composite preparation containing remaining component of laundry detergent composition.

As it was previously stated, composition of detergent can be solid form.Suitably solid form includes tablet and particle form, Such as, granulated particles, thin slice or tablet.Form the multiple technologies of composition of detergent of such solid form in this area In be known, and can be used herein.In one aspect, such as when compositions is granulated particles when, Toner There is provided in granular form, optionally comprise other but not all component of laundry detergent composition.Toner granule with comprise Other granule of one or more of remaining component of laundry detergent composition merges.Further, optionally, laundry detergent compositions is comprised Other but the Toner of not all component of compositions can provide with encapsulated form, and Toner encapsulation object with comprise clothes washing The granule of other component of major part of agent compositions merges.

The compositions of the present invention of preparation as mentioned before can be used for being formed in fabric laundering process the aqueous used Wash solution.Generally, this compositions of effective dose is added in water, such as, at conventional fabric washing automatic washing machine In, form such Aqueous wash solution.Then the Aqueous wash solution being consequently formed is contacted with the fabric washed with it, It is typically under agitation.Add in water with form the effective dose of liquid detergent composition of this paper of Aqueous wash solution can Including being enough to be formed in Aqueous wash solution about 500 to 7, the amount of the compositions of 000ppm, or in Aqueous wash solution The composition of detergent of about 1,000 this paper arriving 3,000ppm will be provided.

Using method

Some consumer products disclosed herein can be used for cleaning or process fabric face position etc..Generally by least one Point position and undiluted form or the consumer products of applicant diluted in liquid (such as wash liquid) contact, and subsequently may be used Optionally by the washing of this position and/or rinsing.In one aspect, position is optionally washed and/or rinses, with consumer products The contact of aspect, subsequently optionally wash and/or rinse.For the purpose of the present invention, washing include but not limited to clean and Mechanical agitation.Fabric mainly can include any fabric that can wash or process under the conditions of normal consumer uses.Can include The liquid of disclosed compositions can have the pH of about 3 to about 11.5.Such compositions is generally with the most about 500ppm Concentration to about 15,000ppm uses.When cleaning solvent is water, water temperature is typically about 5 DEG C to about 90 DEG C, and when position includes During fabric, water is typically about 1:1 to about 30:1 with the ratio of fabric.One or more preceding methods are used to obtain treated position Put.

In one aspect, disclose process and/or cleaning surface or the method for fabric, comprise the steps: optionally washing And/or rinse described surface or fabric, make described surface or fabric connect with any fabric care composition of this disclosure Touch, then optionally washing and/or rinse described surface and/or fabric, the most optionally make described surface or fabric drying, and/or Actively it is dried described surface or fabric.

Embodiment

Following example are provided for being explained further the Toner of the present invention；But, they are not necessarily to be construed as right Invention defined in claims herein is any limitation as.It is true that those skilled in the art are it will be apparent that can be to the present invention Make various modification and transformation without departing from the scope of the present invention or spirit.Unless otherwise indicated, these embodiments are given All parts and percentages be by weight.

Sample preparation and method of testing

A. prepared by sample

Utilize following general step to prepare the thiophene azo dye of the present invention.

The preparation of (+)-2,3-Epoxy-1-propanol material

Under room temperature, 18 parts of N-ethyl-meta-aminotoluenes, 52 parts of isopropyl glycidyl ethers and 50 parts of toluene are added 200mL circle In end flask.Mixture is refluxed overnight.Remove solvent and thick for gained material is used for next step.The most as described herein to this A little materials are alkylated.

The preparation of alkoxylate intermediate

General step method A of alkoxylate:

Intermediate-type 1, initial single position polymer

Under room temperature, 18 parts of N-ethyl-meta-aminotoluenes, 14 parts of acetic acid and 20 parts of water are added in 200mL stainless steel autoclave. 11 parts of oxirane are added within a few hours.To react after at room temperature keeping 24 hours, container will add 0.2 part of NaOH also It is heated to 125 DEG C.Then, in 1 hour, oxirane is added.React after 125 DEG C persistently carry out other 3 hours, vacuum Remove the EO of residual.Being then cooled to room temperature, the intermediate of gained is succinic acid viscous liquid.By controlling in synthesis The amount of oxirane, can realize constant EO average.

Intermediate-type 2, initial double-chain polymer

Under room temperature, 18 parts of 2-methoxyl group-5-monomethylaniline .s, 14 parts of acetic acid and 20 parts of water are added 200mL stainless steel autoclave In.22 parts of oxirane are added within a few hours.To react after at room temperature keeping 24 hours, container will add 0.2 part NaOH is also heated to 125 DEG C.Then, in 1 hour, 40 parts of oxirane are added.Reaction persistently carries out other 3 hours at 125 DEG C Afterwards, vacuum removes the EO of residual.Being then cooled to room temperature, the intermediate of gained is succinic acid viscous liquid.By Synthesis controls the amount of oxirane, constant EO average can be realized.

General step-method B of alkoxylate

By 18 parts of aniline, 60 parts of list-bromo-Polyethylene Glycol-200,20 parts of NaHCO under room temperature₃200mL is added with 50 parts of toluene In round-bottomed flask.Reactant mixture is heated to 80 DEG C, continues 5 hours.Filter salt, remove molten from filtrate by low-pressure distillation Agent.Crude product is without being further purified and for next step.

Also can utilize list-bromo-list-chlorine glycol, prepare halogenated products directly utilizing above-mentioned identical step.

The general step of colorant synthesis

All colours is prepared according to identical general step.

The color intermediate synthesis of embodiment 1

2 parts of Amino-thiophene and 30 parts of phosphoric acid are added in 200mL glass flask and are cooled to 0-5 DEG C.It is slowly added 1 part Solid NaNO₂, keep temperature less than 10 DEG C.When the interpolation for diazo-reaction completes, stir the mixture for 30 minutes, and The sodium nitrite of excess is consumed by adding 0.3 part of sulfamic acid.Add enough sulfamic acids, until Starch iodide paper carries For negative findings.Add in 5 parts of meta-aminotoluene ethoxylation compound coupling agents flask extremely containing 100mL water, and cool the temperature to 5 ℃.Prepared diazol is added slowly in above-mentioned solution carry out coupling reaction.Carefully temperature is not made to be higher than 10 DEG C.Complete After becoming diazonium salt solution to add, reaction is made to be slowly reached room temperature in 1 hour.Then with in sodium hydroxide and mixture carrying out It is separated.Then with methanol lysate layer and filter to remove excess salt.Evaporation filtrate, and make the product of this reaction this moment Prepare application.

Acid anhydride adds to colorant

Embodiment 1

8 parts of succinic anhydrides are added in 25 parts of thiophene azobenzene polymer coloring agent.Reaction is heated to 85 DEG C, continues 12 little Time, it is then cooled to room temperature.Utilize sodium hydroxide by the pH regulator of mixture to 7, removed from mixture by rotary evaporation Water.Obtain the required product of Quantitative yield, as surveyed by HPLC.

Embodiment 3

Embodiment 4

8 parts of maleic anhydrides are added in 25 parts of thiophene azobenzene polymer coloring agent.Reaction is heated to 85 DEG C, continues 12 little Time, it is then cooled to room temperature.Utilize sodium hydroxide by the pH regulator of mixture to 7, removed from mixture by rotary evaporation Water.Obtain the required product of Quantitative yield, as surveyed by HPLC.

Embodiment 5

8 parts of phthalic anhydrides are added in 25 parts of thiophene azobenzene polymer coloring agent.Reaction is heated to 85 DEG C, continues 12 hours, it is then cooled to room temperature.Utilize sodium hydroxide by the pH regulator of mixture to 7, by rotary evaporation from mixture Remove water.Obtain the required product of Quantitative yield, as surveyed by HPLC.

Embodiment 7

8 parts of hexahydrophthalic anhydrides are added in 25 parts of thiophene azobenzene polymer coloring agent.Reaction is heated to 85 DEG C, Continue 12 hours, be then cooled to room temperature.Utilize sodium hydroxide by the pH regulator of mixture to 7, by rotary evaporation from mixing Thing is removed water.Obtain the required product of Quantitative yield, as surveyed by HPLC.

Embodiment 6

8 parts of allyl succinic anhydride are added in 25 parts of thiophene azobenzene polymer coloring agent.Reaction is heated to 85 DEG C, holds Continuous 12 hours, it is then cooled to room temperature.Utilize sodium hydroxide by the pH regulator of mixture to 7, by rotary evaporation from mixture Middle removal water.Obtain the required product of Quantitative yield, as surveyed by HPLC.

Embodiment 8

8 parts of octyl group-succinic anhydrides are added in 25 parts of thiophene azobenzene polymer coloring agent.Reaction is heated to 85 DEG C, holds Continuous 12 hours, it is then cooled to room temperature.Utilize sodium hydroxide by the pH regulator of mixture to 7, by rotary evaporation from mixture Middle removal water.Obtain the required product of Quantitative yield, as surveyed by HPLC.

Embodiment 10

Embodiment 11

Embodiment 12

Embodiment 14

Embodiment 13

Embodiment 15

Embodiment 17

Embodiment 18

Embodiment 19

Embodiment 21

Embodiment 24

Embodiment 25

Embodiment 34

Embodiment 44

Embodiment 45

16 parts of hexahydro-phthalic anhydrides are added in 25 parts of thiophene azobenzene polymer coloring agent.Reaction is heated to 85 DEG C, continue 12 hours, be then cooled to room temperature.Utilize sodium hydroxide by the pH regulator of mixture to 7, by rotary evaporation from mixed Compound is removed water.Obtain the required product of Quantitative yield, as surveyed by HPLC.

B. method of testing

I. extinction coefficient assay method

Utilize methanol that 0.1000 gram of pigment sample is diluted to the volume of 100ml volumetric flask.This solution of 2ml is transferred to Two 100ml volumetric flasks and with methanol dilution to scale.Spectrophotometer is utilized to measure the absorbance of institute's extended color in 1cm pond And λ_max。

λ_maxDirectly read from spectrum.

The MW of extinction coefficient=((absorbance/quality used) × 5)/colorant

Exemplary detergent formulations

Preparation 1a 11: liquid detergent preparation

Table 7A and 7B provides containing at least one thiophene azo dye of the present invention as the liquid detergent system of Toner The embodiment of agent.Described preparation is shown in table 7A with preparation 1a-1f, is suitable in table 7B with preparation 1g-11.

Table 7A comprises the liquid detergent preparation of Toner of the present invention

Table 7B-comprises the liquid detergent preparation of Toner of the present invention

The footnote of preparation 1a l:

¹Diethylene-triamine pentaacetic acid sodium salt

²Diethylenetriamine pentamethylenophosphonic acid sodium salt

³Disodium edta

⁴For regulating the dyestuff of the not dizzy dye of the not dizzy dye (non-tinting) of preparation color

⁵Fine and close formula, is dosage unit (unitized dose) at polyvinyl alcohol film intermediate package

⁶From table 6, thiophene azo carboxylate's Toner of embodiment 1-21, preferably have colouring effect of 10 and 30- The washing clearance of 85%

⁷From table 6, thiophene azo carboxylate's Toner of embodiment 22-48, preferably have colouring effect of 10 and 30- The washing clearance of 85%

⁸Acusol OP301

Preparation 2a 2e: granular detergent formulation

Table 8 provides the granulated detergent as Toner of the thiophene azo carboxylate's dyestuff containing at least one present invention The embodiment of preparation.Preparation is expressed as 2a 2e in table 8.

The table 8 granular detergent formulation containing Toner of the present invention

The footnote of preparation 2a-e:

¹From table 6, thiophene azo carboxylate's Toner of embodiment 1-21, preferably have colouring effect of 10 and 30- The washing clearance of 85%

²From table 6, thiophene azo carboxylate's Toner of embodiment 22-48, preferably have colouring effect of 10 and 30- The washing clearance of 85%

Example fabric care composition

Preparation 3a 3d: liquid fabric care composition

Table 9 provides thiophene azo carboxylate's dyestuff containing at least one present invention and protects as the liquid fabric of Toner The embodiment of reason compositions.Described compositions is expressed as preparation 3a-3d in table 9.

Table 9 includes the liquid fabric care composition of Toner of the present invention

The footnote of preparation 3a-d:

^aN, N-bis-(tallowoyl base ethyl)-N, N-alkyl dimethyl ammonium chloride.

^bBased on common corn starch or the cationic starch of potato starch, comprise the amylose of 25% to 95%, and Substitution value is 0.02 to 0.09, and the value that its viscosity is measured as water mobility (Water Fluidity) is 50-84.

^cOxirane and the copolymer of terephthalate, have such as US5, institute in the 15th hurdle 1-5 row in 574,179 The chemical formula stated, the most each X is methyl, and each n is 40, and u is 4, each R¹Essentially Isosorbide-5-Nitrae-phenylen moiety, each R²Base This is ethylidene, 1,2-propylene moieties or its mixture.

^dDiethylene-triamine pentaacetic acid.

^e KATHONCG is available from Rohm and Haas Co..

^fSilicone antifoaming agent can derive from Dow Corning Corp. with trade name DC2310.

^gFrom table 6, thiophene azo carboxylate's Toner of embodiment 1-21, preferably have colouring effect of 10 and 30- The washing clearance of 85%.

^hFrom table 6, thiophene azo carboxylate's Toner of embodiment 22-48, preferably have colouring effect of 10 and 30- The washing clearance of 85%.

ⁱFrom table 6, thiophene azo carboxylate's Toner of embodiment 1-48, preferably have colouring effect of 10 and 30- The washing clearance of 85%

^j4,4 '-two-(2-sulfostyryl) biphenyl disodiums, are available from Ciba Specialty Chemicals.

^kCocomethylammonium ethoxylation [15] ammonium chloride, is available from Akzo Nobel.

Size disclosed herein and value are understood not to be limited strictly to described exact numerical.On the contrary, unless additionally Illustrating, each this size refers to described value and the function equivalence scope around this value.Such as, it is disclosed as " 40mm " Size refers to " about 40mm ".

All Files cited in the detailed description is incorporated herein by its relevant portion；Any file is drawn Recognize that it constitutes prior art relative to the present invention with should not be construed as.Any implication of term in this document or definition with In the case of any implication of the same term in the file being incorporated by reference into or definition conflict, presents is assigned to this art Implication or the definition of language are taken the lead.

Although explaining and describing certain aspects of the present disclosure, it is obvious to a person skilled in the art that can do Go out multiple other change and modify without departing from the spirit and scope of the present invention.Therefore claims are intended to contain fall into All these changes in the scope of the invention and modification.

Claims

1. a compositions, it comprises and has the thiophene azo carboxylate's dyestuff selected from following structural formula:

2. compositions as claimed in claim 1, wherein said thiophene azo carboxylate's dyestuff has selected from following structural formula,

3. compositions as claimed in claim 1, wherein said thiophene azo carboxylate's dyestuff is at the wavelength of 400nm to 750nm In the range of there are in methanol solution the maximum extinction coefficient more than 1000L/mol/cm.

4. compositions as claimed in claim 3, wherein said thiophene azo carboxylate's dyestuff is at the wavelength of 540nm to 630nm In the range of there are the maximum extinction coefficient of 20,000 to 100,000L/mol/cm.

5. compositions as claimed in claim 4, wherein said thiophene azo carboxylate's dyestuff is at the wavelength of 560nm to 610nm In the range of there are the maximum extinction coefficient of 20,000 to 65,000L/mol/cm.