CN101878291A - Performance ingredients in film particles - Google Patents

Performance ingredients in film particles Download PDF

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Publication number
CN101878291A
CN101878291A CN2008801117706A CN200880111770A CN101878291A CN 101878291 A CN101878291 A CN 101878291A CN 2008801117706 A CN2008801117706 A CN 2008801117706A CN 200880111770 A CN200880111770 A CN 200880111770A CN 101878291 A CN101878291 A CN 101878291A
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CN
China
Prior art keywords
detergent composition
film particles
film
granular detergent
preferred
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Pending
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CN2008801117706A
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Chinese (zh)
Inventor
S·N·巴彻勒
J·库特罗纳
R·G·范德里尔
K·B·吉尔斯
E·L·M·莱姆珀斯
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Unilever PLC
Unilever NV
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Unilever NV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/02—Floating bodies of detergents or of soaps
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0063—Photo- activating compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0084—Antioxidants; Free-radical scavengers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents

Abstract

A granular detergent composition comprising a plurality of film particles, each film particle comprising at least 30% polymer and 0.01 to 1wt% of a benefit ingredient selected from the group comprising: shading dye,shading pigment, photobleach, fluorescer, antioxidant,transition metal catalyst and mixtures thereof characterised in that the cross sectional area ofeach film particle is between 4mm2 and 100mm2.

Description

Functional component in the film particles
The present invention relates to contain the granular detergent composition of many film particles (a plurality of film particles).
Background
The known particulate that in particulate state laundry detergent (1aundry detergent) composition, contains visual contrast.But contrast particulate transmitting function composition or can offer user's visual cues thing (visual cue) simply.
In US 4082682, in washing powder, add the elongated soap particulate that small portion has contrasting colour.The contrast particulate contains the fluorescent agent of non-woven substantive dyestuff.This powder comprises washing assistant (detergency builder) compound.The soap particulate helps the composition de-sludging and reduces foam.Because the soap particulate may sink on the fabric, do not make fabric coloring that they contacted just become the advantage of the regulation of particulate.
In GB2358403A, the powder detergent composition with most of white or light particles is dried sneaks into than the mean particle size at least one dimension of small part significantly greater than the lamelliform visual contrast thing (lamellar visuallycontrasting bodies) of the mean particle size of white or light particles.Embodiment adopts correlated circle or the star by the film preparation of colored water soluble polymer.The visual contrast thing can be chosen wantonly and contain the washing function composition.
WO2006/079416 proposes to adopt the high resolution film particles as the visual cues thing.Hint may comprise functional component in film, such as, tensio-active agent, spices, antioxidant, defoamer.Embodiment in this application compared contain 0.1% weight by the visual cues thing of polyvinyl alcohol preparation with by the washing powder of the visual cues thing of gum arabic preparation.Suitably, can select by 1400 μ m sieve but the film particles by 500 μ m sieve.
The known particulate sensitive composition for preparing as separately that in washing powder, adds.This process can be described as dry blending or back feed (post dosing).
US4176079 describes a kind of selective back feed particle.Enzyme is incorporated in the water-soluble film, the function film of making like this is cut into square, rectangle or strip, and adds in the washing powder.Typical film binder component is 48.7% polyvinyl alcohol and 43.8% nonionogenic tenside (equilibrium water and enzyme).The surface-area of cutting function film additive is 300mm 2
US 2005/0075261A1 relates in the specific polyvinyl alcohol polymer particulate matrix of 20-95% and contains activeconstituents, the water-soluble and/or water dispersible particulate of preferred enzyme.This embodiment is by applying shear action (chopping action) preparation particulate to extruding bar.This will be tending towards making granular (sphere) particulate.Other activeconstituents in suggestion is included in the 0.1-55% level comprises: SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, whitening agent and optical white.Size range is 200 μ m-2000 μ m, preferred 250 μ m-800 μ m.In (cylindric) particulate of being extruded embodiment not chopped, it is long that it can reach 20mm at the most, but preferably long less than 1mm, and preferred size-grade distribution is 100 μ m-800 μ m.
The a large amount of problems that still have the application that relates to the film particles in granular detergent composition, especially the particulate state laundry detergent.
Subject matter is the visual cues film particles that preparation helps cleaning.Surprisingly, we have been found that now the clear and definite useful composition by sending film particles obtains new benefit.
Summary of the invention
According to the present invention, a kind of granular detergent composition that comprises many film particles is provided, each film particles comprises the following beneficiating ingredient that is selected from of at least 30% polymkeric substance and 0.01-1% weight: masking dye, shelter pigment, optical white, fluorescent agent, antioxidant, transition-metal catalyst and composition thereof, the thickness that is characterised in that each film particles less than the cross-sectional area of 0.5mm and each film particles between 4mm 2-100mm 2Between.
Detailed Description Of The Invention
The particulate state laundry detergent compositions mainly is made up of tensio-active agent and ionogen.Exemplary surfactants comprises linear alkyl benzene sulfonate, primary alcohol sulfate,, linear alcohol ethoxy sulfate and fatty alcohol ethoxylate.Typical ionogen is an inorganic raw material, such as, sodium sulfate, sodium-chlor, tripoly phosphate sodium STPP, yellow soda ash, silicon-dioxide and zeolite, and organic raw material, such as, polycarboxylate and citric acid.
For producing extra washing benefit, can comprise low-level beneficiating ingredient; Be fluorescent agent, masking dye, optical white, antioxidant and catalyzer.When with extremely low-level, when the composition that typically is less than 0.1% weight adds this class beneficiating ingredient, be have maximum cost-benefit.Beneficiating ingredient is usually by granulating, again through after the reinforced granular composition that enters.This must cause the localization of high density beneficiating ingredient, and this may have problems, if they have an opportunity the dissolving or be distributed to washings before the contact some fabric.This problem is caused by the high local concentrations of beneficiating ingredient, but not cause the opportunity that is discharged by it.This problem appears in lower molecular weight beneficiating ingredient especially easily, when occurring with high concentration, if especially when disengaging than the solvability of beneficiating ingredient and/or dispersed higher carrier substrate, can damage fabric.
One or more beneficiating ingredients are encapsulated in the solution that this problem is provided in the soluble polymeric film particulate.The film particles of the preferred 0.05-1.0% weight of the amount of beneficiating ingredient in the film particles.
As seen the non-woven substantive dyestuff makes film particles satisfactorily, and it is given it and is different from particulate contrast color, the rest part of described granulometric composition granular composition.
Granular detergent composition than film particles light color advantageously comprises some fluorescent agent and/or masking dye in particle, produce higher contrast gradient between particle and film particles.
Preferably when being dissolved in deionized water, granular detergent composition is high alkalinity.Under 25 ℃, 0.1% solution＞pH 10.5.For reaching this pH, granular detergent composition can advantageously comprise silicate and/or carbonate.
Film particles is more preferably near neutral pH, is contained in wherein one or more beneficiating ingredients with protection.When being dissolved in deionized water when forming 0.1% solution, its pH is 3-9, preferred 6-8.
Although many soluble polymers can be suitable for being included in the film particles, preferred polymer raw material is a polyvinyl alcohol.For improving its solvability and helping comprising easily beneficiating ingredient, wish that film particles further comprises the tensio-active agent of 5-50% weight.The preferred surfactants content of film particles is at least 5% weight anion surfactant, most preferably alkyl-sulphate.
Preferred film composite is to comprise those of polymkeric substance and tensio-active agent.Except job element (performance ingredient), the also optional tinting material that comprises as the preferred component of film.
Other optional composition has: help to prepare the additive of film, for example, releasing agent and water.Except the effect of relative humidity of its control film, water also helps to make film plastic and regulate its solvability.
The water-soluble film of the optional self-forming polymkeric substance of polymkeric substance, in particular for the preparation washing powder those.Preferred polymkeric substance is included under the temperature anywhere of 293-333K scope, under agitation in 30 minutes fully dissolving and/be scattered in the polymkeric substance in the water.
Preferred water-soluble polymers is to be cast into those of film or solid piece, for example, and as Davidson and Sittig, as described in the Water-Soluble Resins, Van Nostrand ReinholdCompany, New York (1968).Preferred water soluble resin comprises polyvinyl alcohol, ether of cellulose, poly-epoxy hexane, starch, polyvinylpyrrolidone, polyacrylamide, polyvinyl methyl ether-maleic anhydride, polymaleic anhydride, styrene-maleic anhydride, Natvosol, Vltra tears, polyoxyethylene glycol, carboxymethyl cellulose, polyacrylate, alginate, acrylamide copolymer, guar gum, casein, ethene-maleic anhydride resin series, polymine, Type 3U, ethylmethylcellulose, hydroxyethylmethyl-cellulose, sugar.The polyvinyl alcohol film-forming resin of preferred low-molecular weight water-soluble.
The molecular-weight average that is preferred for the polyvinyl alcohol of this paper is approximately 1,000-1, and 000,000, preferred 5,000-250,000, for example 15,000-150,000.Hydrolysis or alcoholysis are defined as the per-cent of finishing reaction, wherein the acetate groups on the resin by hydroxyl ,-the OH group replaces.To water miscible polyvinyl alcohol film-forming resin, the hydrolysis degree of the polyvinyl alcohol film-forming resin of 60-99% (hydrolysis range) is preferred, and preferred hydrolysis degree is about 70-90%.Most preferred hydrolysis degree is 80-89%.Such as used in this application, term " polyvinyl alcohol " comprises the polyvinyl acetate compound with hydrolysis level disclosed herein.
The another kind of polymkeric substance that is suitable for is a PVA (PVOH) FILM, by the polyvinyl alcohol copolymer preparation with the comonomer that contains carboxylicesters functional group.
Only when relative humidity (RH) surpassed granular detergent composition fully, the PVA of preference ranking just absorbed water.Thereby it protects other thin film composition to avoid by water decomposition and the unlikely bleeding of soluble dye.
The visual cues film particles can comprise 10-80% polymkeric substance or polymeric blends.
Although can adopt any suitable tensio-active agent or surfactant system, tensio-active agent is preferably anion surfactant, if especially granular composition comprises washing assistant (builder).
The anion surfactant that is suitable for comprises those that those skilled in the art know.The example of high bubble (high-foaming) sulfonate or sulfated surfactant comprises alkylbenzene sulfonate, and especially alkyl chain length is C 3-C 15Linear alkyl benzene sulfonate; Primary and secondary alkyl-sulphate, especially C 8-C 15Primary alkyl sulphates; Alkene sulfonate; Alkylxylene sulfonate; Dialkyl sulfosuccinates; And fatty sulfonate.Common particular certain cancers.
Further information is provided in open document, for example, and " tensio-active agent and the washing composition " of Schwartz, Perry and Berch, volume I and II.
The preferred anionic surfactants tensio-active agent is an alkylbenzene sulfonate, linear alkyl benzene sulfonate (LAS) more especially, and it is preferably with 12-24% weight, and more preferably the amount of 12-22% weight and particularly 15-22% weight exists.
Even more preferably primary alcohol sulfate, (PAS), particularly C 8-C 18, preferred C 12-C 15Primary alcohol sulfate.Particularly preferred tensio-active agent is with the primary alcohol sulfate, of the chain length of 12 carbon (PAS).Can adopt and contain the visual cues film particles of 50%PAS at the most.
Film can comprise second kind of tensio-active agent in addition.Second kind of tensio-active agent preferably selected amphoterics, zwitterionics, nonionogenic tenside and ethoxylation anion surfactant.
Preferred second kind of tensio-active agent of amphoteric is amine oxide.Most preferred amine oxide is cocounut oil (coco) dimethylamine oxide compound.
Preferred zwitterionic second kind of tensio-active agent is trimethyl-glycine, and amido betaine especially, for example, and cocamidopropyl betaine.
Preferred second kind of tensio-active agent of nonionic comprises the primary and secondary alcohol ethoxylate, especially makes C with average every mol of alcohol 1-20 moles of ethylene oxide 8-C 20The Fatty Alcohol(C12-C14 and C12-C18) ethoxylation, and more particularly make C with average every mol of alcohol 1-10 moles of ethylene oxide 10-C 15The primary and secondary alcohol ethoxyization.
Preferred second kind of tensio-active agent of ethoxylation negatively charged ion comprises sulfated alkyl ether (sulfated ethoxylated alcohol).
Be suitable for second kind of tensio-active agent doing in the visual cues thing of the present invention and also have C 8-C 18Alkyl monoethanol amide, for example, coconut monoethanol amide.
The second kind of surfactant system that is used for film particles can comprise the cats product that (for example is less than 5% film) on a small quantity in addition.
90% weight at the most, preferred 75% weight at the most, most preferably the level of 60% weight comprises tensio-active agent in film at the most.
The visual cues thing must be easy to discover in washings and in the background of relative detergent formulations, and is therefore, preferably colored.The direct tinting material of non-woven can 0.001-0.5% weight, and the level of preferred 0.1-0.3% weight film is included in the film composite.
The tinting material that is suitable for comprises any those of colored washings or powder of being used for.Yellow, blueness, pansy, purple, redness, orange, green, pink are preferred colors.
For making its cleaning product obtain the most effective use, many human consumers are immersed in its clothing in the laundry detergent compositions solution.Usually clothing is put into water, spill laundry detergent compositions in the above, clothing is placed 2-200 minute again.In this program, the particulate state laundry detergent compositions may not dissolve fully, the situation that beneficiating ingredient is stained the clothing fabric may occur.Stain relate to particulate not exclusively dissolving form partial high density with the beneficiating ingredient that contact with the clothing fabric subsequently, so this high density may form colloid with the excessive beneficiating ingredient in part, and then is suppressed and can not further disperses or dissolves.This problem is the most outstanding and obvious during with dyestuff and optical white, and wherein color spot appears on the fabric of clothing clearly.This phenomenon has also reduced the effectiveness of beneficiating ingredient, because be not that whole compositions all are used for washing.
Can be by beneficiating ingredient being incorporated into soluble polymeric thing film, film is cut into is less than 100mm again 2The discrete fragment of little cross-sectional area, overcome this problem.Such film particles also can satisfy the requirement of visual cues thing, if they also comprise dyestuff.The flower that can be by film particles being cut into wounded in the battle lobe or the shape of the natural object of certain other this class are further strengthened their functions as the visual cues thing.Cross-sectional area should be 4mm at least 2The cross-sectional area of our indication is that the real surface of planar film particulate one side is long-pending.
Film particles has makes the additional advantage of often responsive beneficiating ingredient away from the alkaline laundry detergent compositions of active (aggressive) high pH.It offers the visual cues thing that there is beneficiating ingredient clearly in the user.What want especially is that when at first being added in the water, film particles can be floating.This has increased the visibility of used film particles, also can help to reduce because of the dissolving that takes place on the surface at first to stain or other infringement of fabric, and this may be away from most of fabric that will wash.Floating for guaranteeing film particles, preferably its relative density is lower than 0.8, more preferably less than 0.5 with most preferably be lower than 0.4.
Thickness with flat film of film particles is maximum 0.5mm.Preferably less than 0.3mm, 0.2mm most preferably.Film has relative homogeneous thickness, to produce foreseeable dissolution characteristics.Thickness fills poor (thickness tolerance) for maximum adds deduct 20%, preferably adds deduct 10%.
Masking dye
For fabric is pure white, very preferably film particles comprises the beneficiating ingredient that is selected from masking dye and pigment of 0.01-1% weight.
Masking dye or pigment are selected from:
Pigment
Pigment is the coloured particle of preferred 0.05-10 micron size, and it is dissolved in the water-bearing media that contains tensio-active agent hardly.Preferred pigment is blueness or purple.
Can adopt mineral dye such as, Pigment blue 29 or pigment violet 15, yet, preferred pigment dyestuff.
Can adopt pigment blue 1,1:2,1:3,2,2:1,2:2,3,4,5,7,10,10:1,11,12,13,14,15,15:1,15:2,15:3,15:4,15:6,18,19,20,21,22,23,25,26,27,28,29,30,31,32,34,35,36,57,58,59,60,61,61:1,62,63,64,65,66,67,69,71,72,73,74,75,80,83 and pigment violet 3,3:1,3:3,3:4,5,7:1,8,9,11,12,13,14,15,16,18,19,23,25,27,28,29,31,35,37,39,41,43,44,45,47,48,50,54,55 and 56.
Preferred pigment dyestuff is pigment violet 1,1:1,1:2,2,3,5:1,13,19,23,25,27,31,32,37,39,42,44,50 and pigment blue 1,2,9,10,14,15,15:1,15:2,15:3,15:4,15:6,16,18,19,24:1,25,56,60,61,62,66,75,79 and 80.
Preferred pigment is pigment violet 3,13,23,27,37,39, pigment blue 14,25,66 and 75.
Pigment Violet 23 most preferably.
Figure GPA00001099121600081
Pigment Violet 23
Also can adopt white pigment; If granular detergent composition is dark, for example green or blue, these are especially suitable.The white pigment that is suitable for is listed in Colour Index (dyers and colorist association and U.S. fabric chemist and colorist association 2002), and Pigment white 1 to Pigment white 35 can be used to make petal to bleach.Preferred pigments is white 18, Pigment white 26, Pigment white 27, Pigment white 6, Pigment white 4 and Metallic stearates, and metal wherein is selected from Ba, Ca, Mg or Zn.
White pigment is specified in ' industrial mineral dye ' (3 editions, 2005G.Buxbaum, G.Pfaff edits, Wiley VCH) and comprise TiO 2, zinc white (ZnO), zinc sulphide and lithopone.
Substantive dyestuff
Directly purple and sun blue dyestuff even more preferably than pigment.Preferably, dyestuff is two or trisazo dye.Not preferred carcinogenic p-diaminodiphenyl (benzidene) radical dye.
Most preferably, substantive dyestuff is the direct purple with following structure:
Figure GPA00001099121600091
Wherein
R 1It is hydrogen or alkyl
R 2Be hydrogen, alkyl or replacement or unsubstituted aryl, preferred phenyl;
R 3And R 4Independent is hydrogen or alkyl;
X and Y independently are hydrogen, alkyl or alkoxyl group, and dyestuff preferably has X=methyl and Y=methoxyl group.
N is 0,1 or 2, preferred 1 or 2.
Preferred dyestuff is directly purple 7, directly purple 9, directly purple 11, directly purple 26, directly purple 31, directly purple 35, directly purple 40, directly purple 41, directly purple 51 and directly purple 99.
In another embodiment, substantive dyestuff can be covalently bound to optical white (photobleach), for example, and described in WO2006/024612.
Acid dye
Cotton acid dye (Cotton substantive acid dyes) brings benefit to cotton-containing fabrics.Preferred dyestuff and dye mixture are blue or purple.Preferred acid dye has:
(i) azines, dyestuff wherein has following cored structure:
Figure GPA00001099121600101
R wherein a, R b, R cAnd R dBe selected from: H, side chain or straight chain C 1-C 7-alkyl chain, benzyl, phenyl and naphthyl; Dyestuff is by at least one SO 3 -Or-COO -Group replaces, the B not electronegative group of ring or its salt; Can further be substituted the formation naphthyl with the A ring; Dyestuff is chosen wantonly and is selected from following group replacement: amine, methyl, ethyl, hydroxyl, methoxyl group, oxyethyl group, phenoxy group, Cl, Br, I, F and NO 2
Preferred azines has: acid indigo plant 98, acid purple 50 and acid blue 59, more preferably sour purple 50 and acid blue 98.
(ii) acid purple 17, sour purple 50, acid black 1, sour red 51, sour red 17 and sour blue 29.
Hydrophobic dye
Beneficiating ingredient can comprise and is selected from one or more following hydrophobic dyes: benzo two furans (benzodifuranes), methine (methine), tritane, naphthalimide (napthalimides), pyrazoles, naphthoquinones (napthoquinone), anthraquinone and monoazo-dyes or diazotizing dyes chromophoric group.Hydrophobic dye is the dyestuff that does not contain any charged water soluble group.Hydrophobic dye can be selected from dispersion agent and solvent dye.Preferred blue and violanthrene quinone and single nitrogen dyestuff.
Preferred dyestuff comprises solvent violet (solvent violet) 13, dispersion agent purple (disperseviolet) 27, dispersion agent purple 26, dispersion agent purple 28, dispersion agent purple 63 and dispersion agent purple 77.
Basic dyestuff
Basic dyestuff is the organic dye with clean positive charge.They are deposited on the cotton.They have special effectiveness when being used for the composition of main cation tensio-active agent.Dyestuff can be selected from the purple and blue dyestuff of alkali of the alkali of listing in Colour Index.Preferred examples comprises triarylmethane basic dyestuff, methane basic dyestuff, anthraquinone basic dyestuff, alkali indigo plant 16, alkali indigo plant 65, alkali indigo plant 66, alkali indigo plant 67, alkali indigo plant 71, alkali indigo plant 159, alkali purple 19, alkali purple 35, alkali purple 38, alkali purple 48; Alkali indigo plant 3, alkali indigo plant 75, alkali indigo plant 95, alkali indigo plant 122, alkali indigo plant 124, alkali indigo plant 141.
Also can described in WO 2007/084729, adopt blue and purple thiazole list nitrogen dyestuff (mono-azo dyes).
Reactive dyestuffs
Reactive dyestuffs are to contain the dyestuff that can also can dyestuff be linked to cellulosic organic group with fibrin reaction with covalent linkage.They are deposited on the cotton.Active group preferably is hydrolyzed, perhaps dyestuff with organism, such as, polymer reaction is so that be attached to this material with dyestuff.Dyestuff can be selected from the reactive violet and the reactive blue dye of listing in the Colour Index.Example has Reactive Blue 19 100, Reactive blue 163, Reactive blue 182 and Reactive blue, Reactive blue 96.
Dye conjugates
By acid or basic dyestuff being connected directly to polymkeric substance or particle formation dye conjugates through physical force.According to selected polymkeric substance or particle, they are deposited on cotton and the synthetics.In WO2006/055787, describe to some extent.They can be used as beneficiating ingredient but are not preferred.
Optical white
Pure white and the cleaning for fabric, the beneficiating ingredient in the film particles preferably comprises the optical white of 0.01-1% weight.
Preferred singlet oxygen light-SYNTHETIC OPTICAL WHITNER.
Singlet oxygen light-SYNTHETIC OPTICAL WHITNER (PB) function is as follows:
PB+ light → PB *
PB *+ 3O 3→PB+ 1O 2
Light-SYNTHETIC OPTICAL WHITNER molecular absorption light also reaches excited electronic state PB *This excited electronic state is by the triplet oxygen in the environment, 3O 2Quencher forms singlet 1O 2Singlet oxygen is the high reactivity SYNTHETIC OPTICAL WHITNER.
Singlet oxygen light-the SYNTHETIC OPTICAL WHITNER that is suitable for can be selected from, the water soluble metal phthalocyanine compound, and the phthalocyanine compound that particularly metallizes, metal wherein are Zn or A1-Z1, Z1 wherein is halogenide, sulfate radical, nitrate radical, carboxylate radical, alkanol acid group or hydroxyl ion.Phthalocyanine preferably has the 1-4 covalently bound with it SO 3X group, X wherein are basic metal or ammonium ion.This compounds is described among the WO2005/014769.
Preferred particularly based on the xanthene type dye of following structure:
Figure GPA00001099121600121
Dyestuff wherein can be replaced by halogen and other element/group.Particularly preferred example has Food Red (Food Red) 14 and Rose Bengale B, Phloxin B, eosin W or W S.
The quantum yield that photosensitization generates singlet oxygen can be found in J.Phys.Chem.Ref.Data 1993,22 volumes, 1 phase, 113-262 page or leaf.The quantum yield that the singlet oxygen of measuring in organic solvent or D2O forms is preferably greater than 0.05, more preferably greater than 0.1.
Other singlet oxygen generates compound and comprises chlorophyll, tonka bean camphor, porphyrin, myohaemoglobin, riboflavin, bilirubin and methylenum coeruleum.
Fluorescent agent
For fabric is pure white, film particles preferably comprises the fluorescent reagent (fluorescent agent) of 0.01-1% weight as beneficiating ingredient.
Fluorescent agent is known, and much this class fluorescent agent can obtain by commercially available.Usually with its an alkali metal salt, for example the form of sodium salt provides and uses these fluorescent agents.The total amount that is used for one or more fluorescent agents of laundry detergent compositions is a 0.005-2% weight, more preferably 0.01-0.1% weight.Preferred fluorescent agent has: 2 (4-styryl-3-sulfophenyl)-2H-naphthols [1,2-d] triazole sodium (sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d] triazole), 4,4 '-two { [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazine-2-yl)] amino } Stilbene base (stilbeno)-2-2 ' disulfonic acid disodium, 4,4 '-two [(4-anilinos-6-morpholino-1,3,5-triazine-2-yl) amino] Stilbene-2-2 ' disulfonic acid disodium and 4,4 '-two (2-sulphur styryl) biphenyl disodium.
Antioxidant
Film particles preferably comprises the antioxidant of 0.01-1% weight as beneficiating ingredient, to prolong the life-span of fabric.
If antioxidant is present in the film particles, bleaching catalyst (being not optical white) should not exist.
Be applicable to that antioxidizing agent of the present invention is the alkylating phenol with following general formula:
Wherein R is a C1-C22 straight or branched alkyl, preferable methyl or side chain C3-C6 alkyl; The C3-C6 alkoxyl group, preferred methoxyl group; R1 is the C3-C6 branched-chain alkyl, the preferred tertiary butyl; X is 1 or 2.Preferably as the hindered phenol compound of antioxidant.
Be applicable to that another kind of antioxidant of the present invention is cumarone or the 1-benzopyran derivatives with following formula:
Figure GPA00001099121600132
Wherein R1 and R2 each independently can be joined together to form C5-C6 cyclic hydrocarbon radical part for alkyl or R1 and R2; B is not for existing or being CH2; R4 is the C1-C6 alkyl; R 5Be hydrogen or-C (O) R3, R3 wherein is hydrogen or C1-C19 alkyl; R6 is the C1-C6 alkyl; R7 is hydrogen or C1-C6 alkyl; X is-CH 2OH or-CH 2A, wherein A is the phenyl of nitrogenous unit, phenyl or replacement.Preferred nitrogenous A unit comprises amino, pyrrolidino, piperidino-(1-position only), morpholino, Piperazino, and composition thereof.
Other antioxidant that is suitable for is found as follows.The derivative of alpha-tocopherol, 5,8-dimethyl tocol, Gamma-Tocopherol, Delta-Tocopherol and alkyl gallates, especially Stabilizer GA 8 and lauryl gallate.
Another example that is suitable for antioxidant is (HALS) class of hindered amine as light stabilizer (light stabilisers), particularly based on 2,2,6, and those of 6-tetramethyl pyridine (pipiridines).
The limiting examples that is applicable to antioxidant of the present invention comprises phenol, particularly 2, and 6-two-tert-butyl phenol, 2,6-di-t-butyl-4-sylvan, 2 and the mixture of the 3-tertiary butyl-4-methoxyl group phenol.Can adopt the mixture of antioxidant, especially as at, such those mixture of for example finding among the WO02/072746 with collaborative antioxidant action.
Bleaching catalyst
Film particles preferably comprises the transition-metal catalyst of 0.01-1% weight, as the beneficiating ingredient of strengthening cleaning fabric.
Catalyzer is preferably formed from the part that contains with 3-5 nitrogen-atoms of transition-metal coordination.Especially preferably contain the substituent part of pyridine.In the transition metal, preferred especially Fe and Mn ion.
Part preferably is the complex form of following general formula (A1):
[M aL kX n]Y m????(A1)
Wherein:
M represents to be selected from Mn (II)-(III)-(IV)-(V), Cu (I)-(II)-(III), Fe (II)-(III)-(IV)-(V), Co (I)-(II)-(III), Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), Mo (II)-(III)-(IV)-(V)-(VI) and W (IV)-(V)-(VI), be preferably selected from Fe (II)-(III)-(IV)-(V), Mn (II)-(III)-(IV)-(V) or Co (I)-(II)-(III), the most preferably metal of Fe (II)-(III)-(IV)-(V) or Mn (II)-(III)-(IV)-(V); L represents part as described herein or its analogue protonated or deprotonation; X represent to be selected from can with the ligand (coordinatingspecies) of metal with any single, double or three charged negatively charged ion and any neutral molecule of single, double or three dentation mode coordinate, be preferably selected from O 2-, RBO 2 2-, RCOO -, RCONR -, OH -, NO 3 -, NO, S 2-, RS -, PO 4 3-, PO 3OR 3-, H 2O, CO 3 2-, HCO 3 -, ROH, N (R) 3, ROO -, O 2 2-, O 2 -, RCN, Cl -, Br -, OCN -, SCN -, CN -, N 3 -, F -, I -, RO -, ClO 4 -And CF 3SO 3 -And more preferably be selected from O 2-, RBO 2 2-, RCOO -, OH -, NO 3 -, S 2-, RS -, PO 3 4-, H 2O, CO 3 2-, HCO 3 -, ROH, N (R) 3, Cl -, Br -, OCN -, SCN -, RCN, N 3 -, F -, I -, RO -, ClO 4 -And CF 3SO 3 -
Y represents any non-coordination counter ion, is preferably selected from ClO 4 -, BR 4 -, [MX 4] -, [MX 4] 2-, PF 6 -, RCOO -, NO 3 -, RO -, N +(R) 4, ROO -, O 2 2-, O 2 -, Cl -, Br -, F -, I -, CF 3SO 3 -, S 2O 6 2-, OCN -, SCN -, H 2O, RBO 2 2-, BF 4 -And BPh 4 -, more preferably from ClO 4 -, BR 4 -, [FeCl 4] -, PF 6 -, RCOO -, NO 3 -, RO -, N +(R) 4, Cl -, Br -, F -, I -, CF 3SO 3 -, S 2O 6 2-, OCN -, SCN -, H 2O and BF 4 -
A represents 1-10, the integer of preferred 1-4;
K represents the integer of 1-10;
N represents 1-10, the integer of preferred 1-4;
M represents 0 or 1-20, the integer of preferred 1-8; With
Each R independently represent to be selected from hydrogen, hydroxyl ,-R ' and-group of OR ', wherein R '=alkyl, thiazolinyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl or carbonyl derivative group, R ' is optional to be replaced by one or more E of functional group, wherein E independently represent to be selected from-F ,-Cl ,-Br ,-I ,-OH ,-O R ' ,-NH 2,-NHR ' ,-N (R ') 2,-N (R ') 3 +,-C (O) R ' ,-OC (O) R ' ,-COOH ,-COO " (Na +, K +) ,-COOR ' ,-C (O) NH 2,-C (O) NHR ' ,-C (O) N (R ') 2, heteroaryl ,-R ' ,-SR ' ,-SH ,-P (R ') 2,-P (O) (R ') 2,-P (O) (OH) 2,-P (O) (OR ') 2,-NO 2,-SO 3H ,-SO 3-(Na +, K +) ,-S (O) 2R ' ,-NHC (O) R ' and-functional group of N (R ') C (O) R ', wherein R ' representative ring alkyl, aryl, arylalkyl or optional quilt-F ,-Cl ,-Br ,-alkyl of I replacement ,-NH 3 +,-SO 3H ,-SO 3-(Na +, K +) ,-COOH ,-COO-(Na +, K +) ,-P (O) is (OH) 2Or-P (O) (O -(Na +, K +)) 2And the preferred independent expression hydrogen of each R, the optional alkyl that replaces or the optional aryl that replaces, more preferably hydrogen or optional phenyl, naphthyl or the C that replaces 1-4-alkyl.
Electric charge z on the complex compound that counter ion Y balance in the formula (A1) is become by ligand L, metal M and ligand X-shaped.Therefore, if electric charge z is positive, Y just may be a negatively charged ion, such as, RCOO -, BPh 4 -, ClO 4 -, BF 4 -, PF 6 -, RSO 3 -, RSO 4 -, SO 4 2-, NO 3 -, F -, Cl -, Br -Or I -, and R is hydrogen, the optional alkyl that replaces or the optional aryl that replaces.If z bears, Y just may be common positively charged ion, such as, basic metal, alkaline-earth metal or (alkyl) ammonium cation.
The counter ion Y that is suitable for comprise cause forming the shelf-stable solid those.The preferred counter ion of preferred metal complex are selected from R 7COO -, ClO 4 -, BF 4 -, PF 6 -, RSO 3 -(CF especially 3SO 3 -), RSO 4 -, SO 4 2-, NO 3 -, F -, Cl -, Br -And I -, wherein R represents hydrogen or optional phenyl, naphthyl or the C that replaces 1-C 4Alkyl.
It below is preferred part.Part with following formula:
Figure GPA00001099121600161
Above part and complex compound thereof are described in WO 02/088289, US 6,800,775 and US2005/0209920.
Part with following formula:
Figure GPA00001099121600162
In ring texture, R1-R4 can be identical or different, is H and straight or branched, replacement or unsubstituted C 1-C 20Alkyl, alkylaryl, alkenyl or alkynyl.As selection, contraposition R group can form bridge jointly, the optimal ethylene bridge and
Figure GPA00001099121600171
Part can be substituted in due course.For example, they can be by sulfonic acid and hydroxy-acid group; Amine; Quaternary amine; Alkyl and alkoxyl group are such as methyl, methoxyl group, ethyl and oxyethyl group; Halogen; CN; And NO 2Replace.
Preferred part has formula:
Figure GPA00001099121600172
R wherein 1Independently be selected from H and straight or branched, replacement or do not replace C 1-C 20Alkyl, alkylaryl, alkenyl or alkynyl.R 1Be preferably methyl, most preferably ethyl.
Preferred part has following form:
Wherein-NR 6R 7Be selected from-NMe 2, NEt 2,-N (i-Pr) 2,
Figure GPA00001099121600181
The etheno of band uncle nitrogen is preferably by alkyl, preferably by methyl substituted.Alkyl is most preferably in the α position of the dicyclo nitrogen of band uncle nitrogen.
Referring now to following non-limiting example, further describe the present invention.
Embodiment 1
Be prepared as follows the film that contains [inferior nitro (nitrolo) three (2,1-second two basic oxygen bases)] three [propyl alcohol] salt of direct purple 9:
Under 60 ℃, make 30% solution of polymkeric substance (polyvinyl alcohol) and tensio-active agent (lauryl ether sulfate) be dissolved in water.After dissolving fully, add 0.8% direct purple 9 [inferior nitrotrimethylolmethane (2,1-second two basic oxygen bases)] three [propyl alcohol] salt and dissolving.Sheet glass at 24x34cm expands into thin layer with this final solution, and dry down in 70-90 ℃ in drying oven.
Behind complete drying, take off the film that is generated from sheet glass, and be cut into the film particles shape of wanting.
When film particles is dissolved in water when becoming 0.284% weight solution, solution has 0.875 photoabsorption at 550nm (1cm path length).
Embodiment 2
By aqueous dye solutions being mixed and dry with yellow soda ash, preparation contains the sodium carbonate particle of [inferior nitrotrimethylolmethane (2,1-second two basic oxygen bases)] three [propyl alcohol] salt of direct purple 9 of 0.1% weight of demarcation.Dyestuff is the pure white effective sequestering agent beneficiating ingredient of fabric.
When particle is dissolved in water when preparing 1.83% weight solution, solution is located 0.442 optical absorption at 550nm (1cm path length).Therefore, the film particles that calculates unit weight contains than particle and Duos dyestuff more than 13 times.
Embodiment 3
Prepare three part of 3 gram washing powder sample.Washing powder contains 18% weight LAS sodium, 73% weight salt (silicate, tripoly phosphate sodium STPP, sodium sulfate, yellow soda ash), and remaining is impure water and a small amount of thing (enzyme and fluorescent agent).With A, B and C on three identified as samples.The carbonate particle that adds the embodiment 2 of 0.100g to A.Add the film particles that 0.011g contains the embodiment 1 of dyestuff beneficiating ingredient to B.The film particles that adds the embodiment 1 of 0.084g to C.Like this, the amount of masking dye beneficiating ingredient is A in the sample: B: C is 1: 1.4: 11 a ratio.
In Embodiment B and C, it is 5-6mm that dye film is cut into cross-sectional area 2Film particles.
Before use, each sample of thorough mixing.
(non-mercerised) white woven shikifugi cloth sheet that 1.7g is handled through the not mercerising of bleaching places beaker, makes fabric fill up the bottom of beaker with the single plane layer.To wherein adding the 100ml softening water, again sample A is sprinkled upon above the cloth.Stir solution gently for a moment, placed again 5 minutes.Take out cloth, fully twice of rinsing and placement are dry.
With sample B and C repeated experiments.
Cloth one drying is just to the number count of the dyestuff stain on the cloth.The results are shown in the table 1.
Table 1
Embodiment Big stain quantity Speckle quantity
??A ??18 ??106
??B ??0 ??2
??C ??7 ??3
The diameter of big stain is greater than 1mm.The diameter of speckle is less than 1mm.
Although sample B and C contain more dyestuff than A, stain significantly reduces.
The granular laundry composition A of example, B, C, D
Composition ??A ??B ??C ??D
?NaLAS ??15 ??20 ??10 ??12
?NI(7EO) ??- ??- ??- ??8
Tripoly phosphate sodium STPP ??7 ??15 ??- ??-
Soap ??- ??- ??- ??1
Zeolite A24 ??- ??- ??- ??17
Water glass ??5 ??4 ??5 ??1
Yellow soda ash ??23 ??20 ??30 ??20
Sodium sulfate ??40 ??30 ??40 ??20
Carboxymethyl cellulose ??0.2 ??0.3 ??- ??0.5
Percarbonate ??- ??3 ??- ??10
??TAED ??- ??0.8 ??- ??4
Proteolytic enzyme ??0.005 ??0.01 ??- ??0.005
Spices ??0.15 ??0.1 ??0.1 ??0.2
Spices (lobe) ??0.01 ??- ??0.03 ??0.05
Lobe * * ??1 ??0.5 ??0.1 ??2
Amylase (lobe) ??0.001 ??0.003 ??- ??-
Composition ??A ??B ??C ??D
Cellulase ??- ??0.003 ??- ??-
Fluorescent agent ??0.1 ??0.15 ??0.05 ??0.3
Directly purple 9 (lobes) ??0.0002 ??0.0005 ??- ??0.0004
Direct purple 99 ??- ??- ??0.0003 ??-
Direct purple 13 ??- ??0.002 ??- ??-
Directly purple 13 (lobes) ??- ??- ??0.001 ??0.004
Food Red 14 (lobe) ??0.001 ??- ??- ??-
The sulfonation zinc phthalocyanine phthalocyanine optical white ??0.002 ??0.004 ??- ??-
Water/frame matter/a small amount of thing Resistates Resistates Resistates Resistates
The * lobe is that cross-sectional area is 10-20mm 2Film particles, and film composition is made up of primary alkyl sulphates tensio-active agent and polyvinyl alcohol polymer.
The amount that this row provides comprises a small amount of beneficiating ingredient that is included in the film particles, and is indicated by " (lobe) " respectively.
Per-cent with pure enzyme provides enzyme level.Provide direct purple 9, the direct level of purple 99, solvent violet 13 and sulfonation zinc phthalocyanine phthalocyanine optical white with pure dye.NI (7EO) refers to R-(OCH 2CH 2) nOH, R wherein is C 12-C 15Alkyl chain and n be 7.

Claims (10)

1. granular detergent composition that comprises many film particles, each film particles comprises the following beneficiating ingredient that is selected from of at least 30% polymkeric substance and 0.01-1% weight: masking dye, shelter pigment, optical white, fluorescent agent, antioxidant, transition-metal catalyst and composition thereof, the cross-sectional area that is characterised in that each film particles is at 4mm 2-100mm 2Between.
2. according to the granular detergent composition of claim 1, wherein film particles because of the non-woven substantive dyestuff of giving its contrasting colour that are different from granular detergent composition as seen.
3. according to the granular detergent composition of claim 2, wherein fluorescent agent in the particle and/or masking dye make the higher contrast of generation between particle and the film particles.
4. according to the granular detergent composition of each aforementioned claim, composition wherein is strong basicity (0.1% solution under 25 ℃ for＞pH 10.5) and when being dissolved in independently when forming 0.1% solution in the deionized water when being dissolved in deionized water, the pH of film particles is 3-9, preferred 6-8.
5. according to the granular detergent composition of claim 4, granular laundry powder wherein comprises silicate and/or carbonate.
6. according to the granular detergent composition of each aforementioned claim, wherein the polymkeric substance in the film particles comprises polyvinyl alcohol.
7. according to the granular detergent composition of each aforementioned claim, film particles wherein also contains the tensio-active agent of 5-50% weight.
8. according to the granular detergent composition of claim 7, tensio-active agent wherein contains the anion surfactant of at least 5% weight, preferred alkyl vitriol.
9. according to the granular detergent composition of each aforementioned claim, film particles wherein comprises the masking dye as beneficiating ingredient.
10. according to the granular detergent composition of each aforementioned claim, wherein film particles is from the dissolvable film feedstock production that floats on the formed lotion liquid of dissolved particles shape detergent composition.
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Application publication date: 20101103