CN101068914A

CN101068914A - Laundry treatment compositions

Info

Publication number: CN101068914A
Application number: CNA2005800394905A
Authority: CN
Inventors: S·N·巴切洛尔; J·M·伯德; A·P·查普尔; P·格雷厄姆; A·夸迪尔
Original assignee: Unilever NV
Current assignee: Unilever PLC; Unilever NV
Priority date: 2004-11-22
Filing date: 2005-09-05
Publication date: 2007-11-07
Also published as: CA2588068A1; ATE487784T1; WO2006053598A1; EP1814974B1; EP1814974A1; DE602005024709D1; ZA200704091B; AR051963A1; ES2354367T3

Abstract

The present invention provides a granule comprising one or more shading dyes solubilized in a non-ionic surfactant. The granule, for use in laundry compositions, has reduced spotting properties.

Description

Laundry treatment compositions

Technical field

The present invention relates to contain the laundry treatment compositions of dyestuff.

Background of invention

The WO02/10327 of Unilever discloses use sodium-chlor and has reduced the fabric contamination.

The US 6 of Unilever, 696,400 disclose the speck composition that is used for granular laundry detergent compositions, wherein contain porous and granular carrier and the photofading agent based on activeconstituents of 0.01wt% at least, described composition is with high bearing capacity particulate material in small, broken bits and/or water-soluble material stratification.

For powder coloring being provided or, dyestuff being used for detergent powder to the painted benefit of white fabrics.A kind of shortcoming of these powder is under certain conditions, on the fabric of handling with detergent powder local spotization can take place.

Summary of the invention

We have found that the fabric spotting for the dyestuff that reduces and/or prevention is not expected causes can be applied to nonionogenic tenside in the nonionogenic tenside soluble dye under wash conditions.Particularly, the present invention is applicable to the dyestuff to the fabric substantive dyeing.

In one aspect of the invention, provide the particle that comprises following material:

(i) nonionogenic tenside of 5～40wt% wherein has been dissolved with the dyestuff of 0.0001～5%wt%, and wherein the solubleness of dyestuff in nonionogenic tenside is at least 0.01wt%;

The (ii) solid carrier of 20～90wt%;

The (iii) wedding agent of 0～20wt%; With

The (iv) optical white of 0～1wt%.

The amount that preferably is dissolved in the dyestuff of nonionogenic tenside is 0.1～2wt%.The solubleness of preferred described dyestuff in nonionogenic tenside is at least 0.1wt%, more preferably 1wt%, and more preferred 5wt% at least.

Solvability at this dyestuff that relates to is the solvability of measuring down at 25 ℃.

The visual effect of preferred coloring agent in human eye is that the peak absorbtivity wavelength on fabric is the monogenetic dyestuff of 550nm～650nm.Most preferably outward appearance is blue or violaceous dyestuff or its mixture.Preferred described dyestuff is those dyestuffs to fabric (particularly cotton and polyester) substantive dyeing.

On the other hand, the invention provides particulate laundry composition that contains as defined herein and the method for handling textiles.

On the other hand, the invention provides granulating method, may further comprise the steps:

(i) dyestuff with 0.0001～5wt% (preferred 1wt%) is dissolved in the nonionogenic tenside of 5～40wt%, and the solubleness of described dyestuff in nonionogenic tenside is at least 0.1wt%;

(ii) dyestuff and nonionic surfactant solution are mixed with the solid carrier of 20～90wt%; With

The (iii) mixture that obtains by step (II) of granulation.

Step (ii) and/or step (iii) in, preferably use the tackiness agent outside the nonionogenic tenside.

As used herein " unitary dose " be used to wash, the concrete amount of laundry treatment compositions that adjustment or essential treatment step type are used.Described unitary dose can be powder, particle or the tablet of definite volume or the form of unit dose detergent liquid.

Detailed Description Of The Invention

The nonionogenic tenside soluble dye

Be used for the dyestuff of particle of the present invention or the solubleness % of dye mixture in nonionogenic tenside or its mixture and need be 0.1wt% at least.

Preferred homogencous dyes or for the dyestuff of dye mixture is that peak absorbtivity wavelength on textiles is the homogencous dyes of 550nm～650nm in the visual effect on the human eye, most preferably 570nm～630nm.This visual effect provides the blueness that makes the human consumer be perceived as white subsequently to violaceous outward appearance.The dyestuff that is preferred for pigmented polyester is that hydrophobic dye and the dyestuff that is preferred for painted cotton are: hydrolysed reactive dye; Matching stain; And substantive dyestuff.

The dyestuff of following discloses can use separately or with the present invention's mixing use, and these dyestuffs are to provide for example, but are preferred dyestuffs.

Hydrophobic dye

It is uncharged organic compound in 7～11 the aqueous solution greater than 1000L/mol/cm and in the pH value that hydrophobic dye is defined as at maximum optical extinction coefficient under the wavelength of 400～750nm.Hydrophobic dye lacks the polarity solubilizing group.Particularly, described hydrophobic dye does not contain any sulfonic acid, carboxylic acid or quaternary ammonium group.Preferred coloring agent chromophore is selected from: azo; Anthraquinone; Phthalocyanine; Benzo two furans; Quinophthalone; The azepine thiophene; Azobenzthiazole and tritane chromophore.Most preferred chromophore is azo and anthraquinone dye chromophore.

In solvent and dispersed dye class dyestuff, can find the example of various hydrophobic dyestuff.

The tone of white clothes is regulated and can be used any color to carry out, and this depends on human consumer's hobby.Blue and pansy is particularly preferred tone, thereby preferred coloring agent or dye mixture are those dyestuffs or the dye mixtures that produces blueness or pansy tone on white.Can use multiple The suitable solvent and dispersed dye.Yet detailed toxicologic study shows that many described dyestuffs are possible carcinogenic substances, and for example EX-SF DISPERSE BLUE EX-SF 300 1.Not preferred this dyestuff.Dyestuff preferably can be selected from those solvent that is used for makeup and dispersed dye.For example by European Union's cited those in instruction 76/768/EEC Annex IV part 1.For example, 63 DISPERSE Violet 63 rowland 27 and solvent violet rowland 13.

The azo hydrophobic dye that is preferred among the present invention is: EX-SF DISPERSE BLUE EX-SF 300

10,11,12,21,30,33,36,38,42,43,44,47,79,79:1,79:2,79:3,82,85,88,90,94,96,100,101,102,106,106:1,121,122,124,125,128,130,133,137,138,139,142,146,148,149,165,165:1,165:2,165:3,171,173,174,175,177,183,187,189,193,194,200,201,202,205,206,207,209,210,211,212,219,220,222,224,225,248,252,253,254,255,256,257,258,259,260,264,265,266,267,268,269,270,278,279,281,283,284,285,286,287,290,291,294,295,301,303,304,305,313,315,316,317,319,321,322,324,328,330,333,335,336,337,338,339,340,341,342,343,344,345,346,351,352,353,355,356,358,360,366,367,368,369,371,373,374,375,376 and 378,63 DISPERSE Violet 63 rowland 2,3,5,6,7,9,10,12,13,16,24,25,33,39,42,43,45,48,49,50,53,54,55,58,60,63,66,69,75,76,77,82,86,88,91,92,93,93:1,94,95,96,97,98,99,100,102,103,104,106 or 107, Dianix violet cc and CAS-No are 42783-06-2,210758-04-6,104366-25-8,122063-39-2,167940-11-6,52239-04-0,105076-77-5, the dyestuff of 84425-43-4 and 87606-56-2.

The anthraquinone hydrophobic dye that is preferred among the present invention is:

Solvent violet rowland 11,13,14,15,15,26,28,29,30,31,32,33,34,26,37,38,40,41,42,45,48,59; Solvent blue 19 1,12,13,14,15,17,18,19,20,21,22,35,36,40,41,45,59,59:1,63,65,68,69,78,90; 63 DISPERSE Violet 63 rowland 1,4,8,11,11:1,14,15,17,22,26,27,28,29,34,35,36,38,41,44,46,47,51,56,57,59,60,61,62,64,65,67,68,70,71,72,78,79,81,83,84,85,87,89,105; EX-SF DISPERSE BLUE EX-SF 300 2,3,3:2,8,9,13,13:1,14,16,17,18,19,22,23,24,26,27.28,31,32,34,35,40,45,52,53,54,55,, 56,60,61,62,64,65,68,70,72,73,76,77,80,81,83,84,86,87,89,91,93,95,97,98,103,104,105,107,108,109,11,112,113,114,115,116,117,118,119,123,126,127,131,132,134,136,140,141,144,145,147,150,151,152,153,154,155,156,158,159,160,161,162,163,164,166,167,168,169,170,176,179,180,180:1,181,182,184,185,190,191,192,196,197,198,199,203,204,213,214,215,216,217,218,223,226,227,228,229,230,231,232,234,235,236,237,238,239,240,241,242,243,244,245,246,247,249,252,261,262,263,271,272,273,274,275,276,277,289,282,288,289,292,293,296,297,298,299,300,302,306,307,308,309,310,311,312,314,318,320,323,325,326,327,331,332,334,347,350,359,361,363,372,377 and 379.

Other preferred (non--azo) (non--anthraquinone) hydrophobic dye that is used for the present invention is: EX-SF DISPERSE BLUE EX-SF 300 250,354,364,366, solvent violet rowland 8, solvent blue 43, solvent blue 57, Lumogen F Blau 650 and Lumogen F violet 570.

Hydrolysed reactive dye

Can think that reactive dyestuffs are made up of the chromophore that is connected with anchor portion.Described chromophore can directly be connected on the anchor portion or through the bridge joint group and be connected on the anchor portion.Chromophore is used to provide color, is connected textile substrates with anchor portion.

Reactive pigment is that with respect to the remarkable advantage of substantive dyestuff their chemical structure is more simple, their absorption band is more narrow and dyeing/tone is regulated more bright; IndustrialDyes, K.Hunger chief editor, Wiley-VCH 2003ISBN 3-527-30426-6.Yet Mammals contacts with reactive dyestuffs and can cause respiratory tract and/or skin are produced stimulation and/or sensibilized.In addition, because sedimentation effect is low, therefore unsatisfactory to the wash conditions of deposition of dye.

Considering reduce to stimulate and/or sensibilized, and preferably each anchoring group to various reactive dyestuffs is hydrolyzed, thereby makes the active group of described dyestuff anchoring group obtain hydrolysis.Just in this respect, term " hydrolysed reactive dye " comprises fully and the reactive dyestuffs of partial hydrolysis.

Described reactive dyestuffs can have more than an anchoring group.If described dyestuff has more than an anchoring group, need so each is helped to stimulate and/or the anchoring group of sensibilized is hydrolyzed into above-mentioned degree.

Described hydrolised dye comprises covalently bound chromophore and anchoring group, and can be expressed as following mode: chromophore-anchoring group.Connection between preferred chromophore and the anchoring group by-NH-CO-,-NH-, NHCO-CH ₂CH ₂-,-NH-CO-or-N=N-provides.

Preferred described hydrolysed reactive dye contains covalently bound chromophore's part to anchoring group, described anchoring group is used for connecting cotton, described anchoring group is selected from: hetero-aromatic ring, preferably contain nitrogen heteroatom, have at least one covalently bound to assorted aromatic nucleus-the OH substituting group and

Preferred described anchoring group is following form:

Wherein:

N gets 1～3 numerical value;

X is selected from :-Cl ,-F, NHR, quaternary ammonium group ,-OR and-OH;

R is selected from: aryl, benzyl, C1-C6-alkyl; With, wherein at least one X is-OH.Preferred R be selected from naphthyl, phenyl and-CH ₃Most preferably described anchoring group is selected from:

Preferred described chromophore is selected from: azo, anthraquinone, phthalocyanine, first And triphendioaxazine.

Preferred described chromophore is connected on the hydrolysis anchoring group by being selected from following bridging :-NH-CO-,-NH-, NHCO-CH ₂CH ₂-,-NH-CO-and-N=N-.

Most preferably described hydrolysed reactive dye is hydrolysed reactive red 2, hydrolysed reactive blue 4, hydrolysed reactive black 5 and hydrolysed reactive blue 19.

Matching stain

It below is preferred matching stain class.

This group comprises the blueness and the pansy matching stain of following structure:

Wherein at least one is necessary for aryl among X and the Y, preferred two all is aryl, described aryl can be benzyl or the naphthyl that replaces, it can be replaced by water-insoluble group (such as alkyl or alkoxyl group or aryloxy), X and Y cannot be replaced by water soluble group (such as sulfonate radical or carboxylate radical), and most preferably wherein X is that benzyl and the Y that nitro replaces is benzyl.

This group comprises the carmoisine of following structure:

Wherein B is can be by the naphthyl or the benzyl of water-insoluble group (such as alkyl or alkoxyl group or aryloxy) replacement, and B cannot be replaced by water soluble group (such as sulfonate radical or carboxylate radical).

The group of following structure:

Wherein:

Naphthyl a kind of be selected from following about the location of ring under by two SO ₃-group replaces:

7,8; 6,8; 5,8; 4,8; 3,8; 7,6; 7,5; 7,4; 7,3; 6,5; 6,4; 5,4; 5,3 and 4,3;

B is the aryl that is selected from phenyl and naphthyl, and described aryl is independently selected from following group and replaces: one-NH ₂Group; One-NH-Ph group; One-N=N-C6H5; One-N=N-C10H7 group; One or more-OMe; With one or more-Me.

The group of following structure:

Wherein:

X is selected from-OH and-NH ₂

R is selected from-CH ₃With-OCH ₃

N is selected from 0,1,2 and 3 integer; With

A ring among ring A, B and the C is replaced by a sulfonate radical.

Below be the example of the preferred acidic dyestuff that can use with the present invention: acid black 24, acid blue 25, acid blue 29, Acid Black 1, Acid blue 113, azogeramine 7, Xylene Red 51, Xylene Red 73, acid red 88 and acid red 87, Xylene Red 91, acid red 92, Xylene Red 94 and acid violet rowland 17.

Substantive dyestuff

It below is the example of the substantive dyestuff that can use with the present invention.

Preferred substantive dyestuff is selected from the group that following formula contains three-azo sun blue dyestuff:

Wherein at least two in A, B and the C naphthyl ring are replaced by sulfonate group, and the C ring can be in the 5-position by NH ₂Perhaps the NHPh group replaces, and X is by the benzyl that replaces up to two sulfonate group or naphthyl ring and can be on 2 be replaced by the OH group and can also be by NH ₂Perhaps the NHPh group replaces.

Other preferred substantive dyestuff is selected from the group that following formula contains the direct pansy dyestuff of two-azo:

Wherein Z is H or phenyl, preferably encircles A and is replaced by methyl and methoxyl group on the position shown in the arrow, and ring A can also be the naphthyl ring, and Y group is benzyl or naphthyl ring, and it is replaced by sulfate groups and can be replaced by the methyl list or two replacements.

The limiting examples of these dyestuffs is direct violet 5,7,9,11,31 and 51.Other limiting examples of these dyestuffs also is a sun blue 34,70,71,72,75,78,82 and 120.Preferred described dyestuff is direct violet 9.

The blend fiber dye mixture

Pledge clothes when being blend fiber, for example, polyester cotton preferably is direct staining to the dyestuff on each respective fiber because otherwise even the white of passing fiber wire all can not be maintained.Thus, described particle can contain different dyestuffs or dye mixture, thus make contain that the tone that is used for polyester that particulate laundry composition of the present invention comprises 0.001～0.01wt% regulates hydrophobic dye and/or 0.001～0.01wt% one or more be selected from other dyestuff that following cotton substantive dyeing tone is regulated dyestuff: hydrolysed reactive dye; Matching stain; And substantive dyestuff.Disclosed dyestuff level is provided by the dyestuff in the particle as defined herein in this laundry composition.About above-mentioned, most preferably the whole dyestuffs in the laundry composition are 0.001～0.01wt%.

Preferably under the wavelength of 400～750nm, the maximum optical extinction coefficient of dyestuff is greater than 1000L/mol/cm.The level of corresponding dyestuff in composition is in harmonious proportion and will makes the deposition of dyestuff on polyester and cotton obtain aesthstic coupling.The peak absorbtivity wavelength of preferred coloring agent is 550nm～650nm, preferred 570nm～630nm.Can use altogether eye is had dye combinations as the homogencous dyes visual effect, its peak absorbtivity wavelength on polyester or cotton is 550nm～650nm, preferred 570nm～630nm.This can for example obtain preparation by mixing redness and green-blue dyes, thereby obtains blueness or pansy tone.The specific examples of matching stain is the mixture of azogeramine 7, acid red 88, Xylene Red 51 and/or Xylene Red 73 and Acid Black 1 and/or acid blue 25.For cotton and polyester substantive dyeing dyestuff, need the identical spectra parameter.

Nonionogenic tenside

Preferred nonionic is, for example, and the alcohol of polyethoxylated, the alkylphenol of ethoxylation, anhydro sorbitol and oxyalkylated Isosorbide Dinitrate.The example of preferred nonionic surfactants is that trade mark is " Neodol " by the alcohol of the polyethoxylated of Shell Chemical Company manufacturing and sale.The example of preferred Neodols is Neodol 25-7, and it is the alcohol of 12～15 carbon chain length and the mixture of about 7 the ethylene oxide groups of per molecule; Neodol23-65 has the C12-13 mixture of about 6.5 mole ethylene oxides; Neodol 25-9 has the C12-13 mixture of about 9 mole ethylene oxides; With Neodol 45-7, the mixture of C14-15 and about seven mole ethylene oxides.Other can be used for nonionic surface active agent of the present invention and comprises that trimethylammonium nonyl polyglycol ether is (such as the product by Union Carbide Corporation produce and market, trade mark is Tergitol), Rohm and Haas octylphenoxy polyethoxy ethanol and the Volpo S 10 (such as Brij 76 and Brij 97, the Registering product of Atlas Chemical Co) sold with trade mark Triton.It is about 13 that preferred its hydrophilic-lipophilic balance (HLB) is lower than, and more preferably less than 10.

When using agglomeration process and preferably its mesolite and/or clay are as carrier, the ratio of preferred vector and tensio-active agent is about 1: 1～10: 1, more preferably from about 2: 1～5: 1.Use non-ionic surfactant mixture equally within the scope of the invention.Most preferably described nonionogenic tenside is the tensio-active agent of ethoxylation.

Carrier

Described carrier can be water/tensio-active agent soluble carrier or water/tensio-active agent insolubility carrier.The example of preferably water/tensio-active agent soluble carrier is yellow soda ash, sodium sulfate, sodium-chlor and Trisodium Citrate.Yet preferred described carrier is water/tensio-active agent insolubility carrier, and thus, preferred vector is zeolite (for example, zeolite 4A and zeolite MAP), clay and mineral substance; Clay most preferably.Preferred described clay is a bentonite.

Particle

Preferred described particulate maximum width is 180～1000 microns.This is by the ability reflection of described particle by the classification screen cloth.

Fluorescent agent

Most preferably described particle contains fluorescent agent (white dyes).Fluorescent agent is that fluorescent agent and the multiple described fluorescent agent known can buy in market.Usually, these fluorescent agents all provide with their form of an alkali metal salt (for example, sodium salt) and use.The total amount that is used for the fluorescent agent of laundry treatment compositions is generally 0.005～2wt%, more preferably 0.01～0.1wt%.Preferred fluorescent agent classification is: two-styrylbiphenyl based compound (for example, (Tinopal (trade mark) CBS-X), diamines stilbene disulfonic acid compound (for example, Tinopal DMS pure Xtra and Blankophor (trade mark) HRH) and pyrazoline compounds (for example Blankophor SN).Preferred white dyes is: 2-(4-styryl-3-sulfo group phenyl)-2H-naphtho-[1,2-d] triazole sodium, 4,4 '-two { [(4-anilino-6-(N-methyl-N-2-hydroxyethyl) amino-1,3,5-triazines-2-yl)] amino } Stilbene-2,2 '-disulfonic acid disodium, 4,4 '-two { [(4-anilino-6-morpholino-1,3,5-triazines-2-yl)] amino } Stilbene-2,2 '-disulfonic acid disodium and 4,4 '-two (2-sulfo group styryl (sulfoslyryl)) xenyl disodium.

Optical white

Described particle can also contain optical white, and described optical white is the compound that absorbs the light of 290～750nm.By absorbing light, optical white produces the active substance that can bleach stain with high quantum production rate (＞0.05), such as simple oxygen or free radical.The example of optical white is a free radical photo-initiation, such as the dyestuff (such as metallized phthalocyanine (the commercially available trade name of CIBA is TINOLUX)) of vitamin K3 and the simple oxygen of generation.

Laundry detergent composition

Particle of the present invention self can be laundry detergent composition.Opposite and preferred, particle of the present invention can mix with other pharmaceutical adjunct and carrier, thereby forms laundry detergent composition.These other pharmaceutical adjuncts and carrier can comprise, eliminate polymkeric substance, SPC-D, activator, transition-metal catalyst, sequestrant, dye transfer inhibition polymkeric substance and optical brightener such as above-mentioned listed component, nonionogenic tenside, cats product and anion surfactant, washing assistant, enzyme, defoamer, dirt.Preferably include the laundry detergent composition that contains the particulate dyestuff and make that the level of dyestuff is 0.00005～0.01wt% in total detergent composition particle, preferred 0.001～0.01wt%.

Test

Embodiment 1

Acid Black 1 is dissolved in the COCO 7EO nonionogenic tenside, thereby makes that its concentration is 1wt%.Dyestuff/NI solution (2.5g) is joined in the 10g bentonite powder and with its thorough mixing.On this level, mixture remains the easy mobility powder.Then, 40% solution with 3gSokalan CP5 polymers soln carries out granulation to the gained powder.Then, in 80 ℃ baking oven, the gained particle is carried out drying, and at last it is sieved, thereby obtain 180～1000 microns particle.

These particulate anhydrous compositions, particle A is:

Component	wt(g)	% by weight
Component	wt(g)	% by weight	Dyestuff	0.025g	0.18
NI	2.475	18.1	Dyestuff	0.025g	0.18
NI	2.475	18.1	Bentonite	10g	73.0
CP5	1.2g	8.8	Bentonite	10g	73.0

The comparative particle of no nonionogenic tenside is prepared in the following manner: the 0.025g dyestuff is mixed with the 10g bentonite; with 4g CP5 solution said mixture is carried out granulation then; under 80 ℃, the gained particle is carried out granulation once more; at last it is sieved, thereby obtain 180～1000 microns particle.

Thus, described particulate anhydrous composition, particle B is:

Component	wt(g)	% by weight
Component	wt(g)	% by weight	Dyestuff	0.025g	0.215
Bentonite	10g	86.0	Dyestuff	0.025g	0.215
Bentonite	10g	86.0	CP5	1.6g	13.8

Embodiment 2

Join the particle of embodiment 1 in the neutralizing treatment powder separately and with its thorough mixing, be 0.004% powder by weight thereby obtain final dyestuff level.Described washing powder contains 18%NaLAS, 73% salt (silicate, tripoly phosphate sodium STPP, vitriol, carbonate), and 3% contains the accessory constituent of perborate, white dyes and enzyme and the impurity and the water of residual content.

The non-mercerising processing of the braiding cotton that the white of a slice 20 * 20cm is bleached places the aqueous solution, makes that this cloth ratio smooth and fluid and cloth is 3: 1.The 10g powder is spread upon on the cloth and it was placed 30 minutes.Then to this cloth fully clean, dry and the number of visible coating spot counted.Gained the results are shown in following.

Powder with particle A has 62 spots.Powder with particle B has 385 spots.

Dye granule with nonionogenic tenside has demonstrated spot significantly still less.

Embodiment 3

Repeat the test of embodiment 1 and 2, but be to use direct violet 51 as dyestuff.

Gained the results are shown in following.

Powder with particle category-A has 2 spots.Powder with particle category-B has 78 spots.

Dye granule with nonionogenic tenside (category-A) has demonstrated spot significantly still less.

Embodiment 4

Particle C as described below and D make according to the mode similar to embodiment 1, but are to use the component of different concns.In all scenario, all be to use the Acid Black 1 dyestuff.For particle E, bentonite is replaced by zeolite (4A).

Particle C

Component	wt(g)	% by weight
Component	wt(g)	% by weight	Acid Black 1	0.025	0.16
Nonionic	4.975	31.4	Acid Black 1	0.025	0.16
Nonionic	4.975	31.4	Bentonite	10	63.1
CP5	0.84	5.3	Bentonite	10	63.1

Particle D

Component	wt(g)	% by weight
Component	wt(g)	% by weight	Acid Black 1	0.05g	0.32
Nonionic	4.95g	31.3	Acid Black 1	0.05g	0.32
Nonionic	4.95g	31.3	Bentonite	10g	63.1
CP5	0.84g	5.3	Bentonite	10g	63.1

Particle E

Component	wt(g)	% by weight
Component	wt(g)	% by weight	Acid Black 1	0.069	0.22
Nonionic	6.83	22.1	Acid Black 1	0.069	0.22
Nonionic	6.83	22.1	Zeolite 4A	24	77.7

Embodiment 5

Use the particle of making among the embodiment 5 to repeat the test of embodiment 2.

Powder with particle C class has 54 spots.

Powder with particle D class has 62 spots.

Powder with particle E class has 123 spots.

Particle C and D contain the nonionogenic tenside of promising about particle A (embodiment 1) twice level, but its spot is approaching.C compares with particle, and particle D has the dyestuff of double strength, and (dosage level is half weight in laundry detergent composition thus), but have similar load.Particle E based on zeolite has shown the spot still less than particle B, and but particle B does not have nonionogenic tenside has more clay particle.

Embodiment 6

In order to check the relative performance of dye granule, just to the average color transmission aspect of cotton, preparation 60ml has the corresponding particulate 1g/L of 0.5g/L alkali (base) powder solution.In this solution, 2g braiding cotton is washed, it is cleaned and drying, utilize reflectance spectrometer that it is compared with using the cotton that adds the solution washing of dye granule in addition, the difference table on the color is shown Δ E.

Gained the results are shown in the following table.

Particle	ΔE
Particle	ΔE	A	5.2
B	5.0	A	5.2
B	5.0	C	3.5
D	6.9	C	3.5
D	6.9	E	5.4

Should be pointed out that in the test of particle D the dyestuff of adding is the twice in other particle.Just, have the particle of the nonionogenic tenside of lower level to the even color transmission aspect of cloth, A and E are the same with the particle that does not have nonionogenic tenside (B) good.Higher levels of non-ionic particle C and D with respect to the dyestuff of unit weight, transmit color still less.

Embodiment 7

Solvent violet rowland 13 is dissolved in the COCO 7EO nonionogenic tenside, thereby obtains the solution of 1%wt.Dyestuff/NI solution (2.5g) is joined in the 10g bentonite powder and with its thorough mixing.On this level, mixture remains the easy mobility powder.Then, 40% solution with 3g Sokalan CP5 polymers soln carries out granulation as wedding agent to the gained powder.Then, in 80 ℃ baking oven, the gained particle is carried out drying, and at last it is sieved, thereby obtain 180～1000 microns particle.

These particulate anhydrous compositions are:

Embodiment 8

The test of repetition embodiment 7 still at first is dissolved in solvent violet rowland 13 in the COCO 3EO nonionogenic tenside, thereby obtains the solution of 1wt%.

Embodiment 9

Prepare the mixture of solid solvent violet 13 and coco 7EO nonionogenic tenside, thereby obtain the dyestuff of 1%wt.In lab oven at, in Glass Containers, said mixture is heated to 80 ℃.With this mixture melt, thereby form dye solution, then it is poured on the zeolite A24 carrier solid in the Sirman high-shear mixer, and in proportion it is carried out thorough mixing, described ratio agglomerated effect maximization.As known in the art, add the solid agglomeration that liquid wedding agent very little causes part only to exist, cause wet material or slurry group to form and add excessive wedding agent.

Component	wt(g)	% by weight
Component	wt(g)	% by weight	The SV13 dyestuff	0.4	0.29
NI7EO	39.6	28.9	The SV13 dyestuff	0.4	0.29
NI7EO	39.6	28.9	Zeolite A24	100	71.4

The gained particle is sieved, thus remove excessive material (＞1000um), and it is stored in the sealed vessel.

Embodiment 10

Repeat to be similar to the test of embodiment 9, but be to use the dyestuff Disperse Blue-79: 1.The common concentration of the mixture of dyestuff and solvent is lower, is 0.4～0.6%wt.In view of the above, the particle of formation has following component.

Component	wt(g)	% by weight
Component	wt(g)	% by weight	The DB79:1 dyestuff	0.2	0.14
NI7EO	39.8	28.9	The DB79:1 dyestuff	0.2	0.14
NI7EO	39.8	28.9	Zeolite A24	100	71.4

The particle of embodiment 6～10 has demonstrated less spot and polyester has been had good dyestuff transmission.

Preparation and embodiment 7 and 8 similar other particles, but be to use yellow soda ash rather than zeolite.Prepare particle similar to Example 9, but the mixture (1: 2) of zeolite/light soda ash ash is used as carrier substance.

Join the particle of embodiment 7～10 in the neutralizing treatment powder separately and with its thorough mixing, be 0.001～0.004% powder by weight thereby obtain final dyestuff level.Described washing powder contains 18%NaLAS, 73% salt (silicate, tripoly phosphate sodium STPP, vitriol, carbonate), and 3% contains the accessory constituent of perborate, white dyes and enzyme and the impurity and the water of residual content.

Join the particle of embodiment 7～10 in the neutralizing treatment powder separately and with its thorough mixing, be 0.0005～0.002% powder by weight thereby obtain final dyestuff level.Described laundry powder contains 10%NaLAS, the 5%7EO nonionogenic tenside, 1% soap, 17% zeolite A24,12% percarbonate, 4%TAED, 40% salt (sodium sulfate, yellow soda ash), surplus is white dyes, enzyme, antiredeposition reagent, moisture content, perfume compound, (multivalence) sequestrant, anti-ashing reagent, defoamer and dispersion agent.

Claims

(according to the modification of the 19th of treaty)

1, a kind of particle comprises:

(i) nonionogenic tenside of 5～40wt% wherein is dissolved with the dyestuff of 0.0001～5%wt%, and the solubleness of wherein said dyestuff in nonionogenic tenside is at least 0.01wt%;

The (ii) solid carrier of 20～90wt%;

The (iii) wedding agent of 0～20wt%; With

The (iv) optical white of 0～1wt%,

Wherein said dyestuff is selected from: hydrophobic dye; Hydrolysed reactive dye; Matching stain; And substantive dyestuff,

Be selected from wherein said matching stain: the blueness of following structure and pansy matching stain

Wherein at least one is necessary for aryl among X and the Y, preferred two all is aryl, described aryl can be benzyl or the naphthyl that replaces, benzyl or naphthyl can be replaced by non-water solubilization radical, such as alkyl or alkoxyl group or aryloxy, X and Y cannot be replaced by the water solubilization radical, and such as sulfonate radical or carboxylate radical, most preferably wherein X is that benzyl and the Y that nitro replaces is benzyl;

The carmoisine of following structure:

Wherein B is naphthyl or benzyl, and they can be replaced by non-water solubilization radical, and such as alkyl or alkoxyl group or aryloxy, B cannot be replaced by the water solubilization radical, such as sulfonate radical or carboxylate radical;

The group of following structure:

Wherein:

Naphthyl a kind of be selected from following about the location of ring on by two SO ₃-group replaces: 7,8; 6,8; 5,8; 4,8; 3,8; 7,6; 7,5; 7,4; 7,3; 6,5; 6,4; 5,4; 5,3 and 4,3;

B is the aryl that is selected from phenyl and naphthyl, and described aryl is independently selected from following group and replaces: one-NH ₂Group; One-NH-Ph group; One-N=N-C6H5; One-N=N-C10H7 group; One or more-OMe; With one or more-Me;

The group of following structure:

Wherein:

X is selected from-OH and-NH ₂R is selected from-CH ₃With-OCH ₃N is selected from 0,1,2 and 3 integer; Replaced by a sulfonate group with a ring among ring A, B and the C;

Wherein said substantive dyestuff is selected from:

The trisazo-sun blue dyestuff of following formula:

Wherein at least two in A, B and the C naphthyl ring are replaced by sulfonate group, and the C ring can be in the 5-position by NH ₂Perhaps the NHPh group replaces, and X is by the benzyl or the naphthyl ring that replace up to two sulfonate group, and can be on 2 be replaced by the OH group and can also be by NH ₂Perhaps the NHPh group replaces;

With,

The direct violet dyestuff of two azos of following formula:

2, according to the particle of claim 1, wherein said particle comprises the nonionogenic tenside of 10～25wt%.

3, according to the particle of claim 1 or 2, the water insoluble and tensio-active agent of wherein said solid carrier.

4, according to any one particle of claim formerly, wherein dyestuff is to the fabric substantive dyeing, and it is the homogencous dyes of 550nm～650nm as the peak absorbtivity wavelength on textiles to the visual effect on the human eye.

5, according to any one particle of claim formerly, the amount of wherein said wedding agent is 2～10wt%.

6, according to any one particle of claim formerly, wherein said carrier is selected from zeolite, clay and mineral substance.

7, according to the particle of claim 6, wherein said carrier is selected from bentonite, zeolite 4A and zeolite MAP.

8, according to any one particle of claim formerly, wherein said wedding agent is selected from polyacrylic ester, polyoxyethylene glycol and polyacrylic ester/maleate copolymer.

9, according to any one particle of claim formerly, wherein the ratio of carrier and tensio-active agent is about 1: 1～10: 1.

10, according to the particle of claim 9, wherein the ratio of carrier and tensio-active agent is about 2: 1～5: 1.

11, according to each particle of claim 1～10, wherein said dyestuff is hydrophobic dye and the mixture that is selected from following dyestuff: hydrolysed reactive dye; Matching stain; And substantive dyestuff.

12, according to any one particle of claim formerly, wherein said hydrophobic dye is solvent dye or dispersed dyestuff.

13, according to each particle of claim 1～10, wherein said hydrophobic dye is selected from: Disperse Blue-79: 1, solvent black 3, solvent violet rowland 13, solvent blue 59, solvent blue 35, solvent red 24, Red-1 200, EX-SF DISPERSE BLUE EX-SF 300 3 and EX-SF DISPERSE BLUE EX-SF 300 106.

14, according to each particle of claim 1～10, wherein said dyestuff is selected from: acid black 24, acid blue 25, acid blue 29, Acid Black 1, Acid blue 113, azogeramine 7, Xylene Red 51, Xylene Red 73, acid red 88 and acid red 87, Xylene Red 91, acid red 92, Xylene Red 94, directly violet 9 and acid violet rowland 17.

15, according to the particle of claim 14, wherein said dyestuff is direct violet 9.

16, containing just like any one defined particulate laundry detergent composition of claim formerly, in total detergent composition, is 0.00005～0.01wt% from the dyestuff level in the particle wherein.

17, according to claim 16 comprise the particulate laundry detergent composition, in total detergent composition, be 0.001～0.01wt% wherein from the dyestuff level in the particle.

18, a kind of granulating method may further comprise the steps:

(i) dyestuff with 0.0001～1% weight percent is dissolved in the nonionogenic tenside of 5～40wt%, and the solubleness of wherein said dyestuff in nonionogenic tenside is at least 0.1wt%;

(ii) described dyestuff and nonionic surfactant solution are mixed with the solid carrier of 20～90wt%; With

(iii) carry out granulation to being obtained from step mixture (ii).

Claims

1, a kind of particle comprises:

The (ii) solid carrier of 20～90wt%;

The (iii) wedding agent of 0～20wt%; With

The (iv) optical white of 0～1wt%.

11, according to each particle of claim 1～10, wherein said dyestuff is selected from: hydrophobic dye; Hydrolysed reactive dye; Matching stain; And substantive dyestuff.

12, according to each particle of claim 1～10, wherein said dyestuff is hydrophobic dye and the mixture that is selected from following dyestuff: hydrolysed reactive dye; Matching stain; And substantive dyestuff.

13, according to any one particle of claim formerly, wherein said hydrophobic dye is solvent dye or dispersed dyestuff.

14, according to each particle of claim 1～10, wherein said hydrophobic dye is selected from: Disperse Blue-79: 1, solvent black 3, solvent violet rowland 13, solvent blue 59, solvent blue 35, solvent red 24, Red-1 200, EX-SF DISPERSE BLUE EX-SF 300 3 and EX-SF DISPERSE BLUE EX-SF 300 106.

15, according to each particle of claim 1～10, wherein said dyestuff is selected from: acid black 24, acid blue 25, acid blue 29, Acid Black 1, Acid blue 113, azogeramine 7, Xylene Red 51, Xylene Red 73, acid red 88 and acid red 87, Xylene Red 91, acid red 92, Xylene Red 94, directly violet 9 and acid violet rowland 17.

18, a kind of granulating method may further comprise the steps:

(iii) carry out granulation to being obtained from step mixture (ii).