CN100577787C - laundry treatment composition - Google Patents
laundry treatment composition Download PDFInfo
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- CN100577787C CN100577787C CN200580038122A CN200580038122A CN100577787C CN 100577787 C CN100577787 C CN 100577787C CN 200580038122 A CN200580038122 A CN 200580038122A CN 200580038122 A CN200580038122 A CN 200580038122A CN 100577787 C CN100577787 C CN 100577787C
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- Prior art keywords
- laundry treatment
- treatment compositions
- reactive
- anchor
- chromophore
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
本发明提供包含表面活性剂和水解活性染料的洗衣处理组合物。本发明也要求保护处理纺织品的方法，所述方法包括用水解染料的水溶液处理纺织品，漂洗和干燥纺织品。This invention provides a laundry treatment composition comprising a surfactant and a hydrolyzed reactive dye. This invention also claims protection for a method of treating textiles, the method comprising treating the textiles with an aqueous solution of the hydrolyzed dye, rinsing the textiles, and drying the textiles.
Description
Technical field
The present invention relates to contain the laundry treatment compositions of dyestuff.
Background of invention
Reactive dyestuffs are to have the painted compound that one or more can form the functional group of covalent linkage with suitable substrate (normally cotton or other cellulosic fibre).The common active group of reactive dyestuffs is a chlorotriazine base, a Cyanuric trifluoride base and 2-sulfo group oxygen base ethylsulfonyl.The common chromophore of reactive dyestuffs is azo, anthraquinone, phthalocyanine, first
And triphendioxazine (triphendioaxazine).
Reactive dyestuffs contain can with textile fibres in exist-OH ,-SH and-the concrete functional group of the generation addition of NH2 group or substitution reaction.The result of these concrete functional group character is stimulation/sensitization that reactive dyestuffs can cause respiratory tract and skin.Illustrate on evidence that also they cause contact dermatitis, allergic conjunctivitis, rhinitis, occupational asthma and other transformation reactions.
Summary of the invention
We have found that hydrolysed reactive dye can be used for giving shading value to textiles and compares the danger that reduces respiratory tract and skin irritation/sensitization simultaneously with reactive dyestuffs.
The active group of reactive dyestuffs is hydrolyzed under water and high pH value.We find that the reactive dyestuffs of hydrolysis are direct to cotton also under normal wash conditions.
The invention provides on the one hand the laundry treatment compositions of the tensio-active agent of the hydrolysed reactive dye that contains 0.0001 to 0.1% weight and 2 to 60% weight.
The invention provides the method for handling textiles on the other hand, this method may further comprise the steps: (i) handle textiles with the aqueous solution of hydrolysed reactive dye, this aqueous solution comprises the hydrolysed reactive dye of 10ppb to 1ppm and the tensio-active agent of 0.2g/L to 3g/L; (ii) rinsing and dry textiles.Most preferably the concentration of hydrolysed reactive dye is 100ppb to 500ppb.The present invention also extends to aqueous solutions employed in the method.
" unitary dose " used herein is for being used to wash, nurse one's health or the concrete amount of the laundry treatment compositions of necessary treatment step type.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
Can think that reactive dyestuffs are made up of the chromophore that is connected to anchor part, chromophore can be directly connected to anchor or by bridge linkage group.Chromophore is used to provide color, and anchor is used to be attached to textile substrate.
The remarkable advantage that reactive dyestuffs are better than substantive dyestuff is simpler for their chemical structure, and their absorption band is narrower, and dyeing/shading value is brighter; Industrial Dyes (industrial dye), K.Hunger ed.Wiley-VCH 2003 ISBN 3-527-30426-6.Yet Mammals contact reactive dyestuffs cause the stimulation and/or the sensitization of respiratory tract and/or skin.In addition, because sedimentation effect is low, wash conditions is undesirable to the deposition of dyestuff.
About reduce stimulating and/or sensitization, the preferably independent anchor group hydrolysis of each of each reactive dyestuffs so that the most active group hydrolysis of dyestuff anchor group.About this point, the term hydrolysed reactive dye comprises fully and the reactive dyestuffs of partial hydrolysis.
Reactive dyestuffs can contain more than an anchor.If dyestuff contains more than an anchor, each causes that the anchor of stimulation and/or sensitization needs hydrolysis to arrive above-mentioned degree so.
Being used for dyestuff of the present invention comprises the chromophore of covalent bonding and anchor and available following mode and represents: chromophore-anchor.Connection between chromophore and the anchor preferably by-NH-CO-,-NH-, NHCO-CH2CH2-,-NH-CO-or-N=N-provides.
Preferably when the laundry treatment compositions of " unitary dose " was dissolved in the water, the ionic strength of the moisture laundry treatment compositions that obtains was 0.001 to 0.5, more preferably 0.02 to 0.2.
Preferably, hydrolysed reactive dye contains the chromophore's part that is covalently bonded to anchor group, and anchor group is bonded to cotton, and anchor group is selected from: hetero-aromatic ring, preferred package contains nitrogen heteroatom, contain at least one be covalently bonded to hetero-aromatic ring-the OH substituting group and
Anchor group preferably has following form:
Wherein:
N is 1-3;
X is selected from :-Cl ,-F, NHR, quaternary ammonium group ,-OR and-OH;
R is selected from: aryl, benzyl, C1-C6-alkyl; Wherein at least one X is-OH.R be preferably selected from naphthyl, phenyl and-CH3.Most preferably anchor group is selected from:
Preferred chromophore is selected from: azo, anthraquinone, phthalocyanine, first
And triphendioxazine.
Preferred chromophore is connected to the anchor of hydrolysis by bridging, described bridge is selected from-NH-CO-,-NH-, NHCO-CH2CH2-,-NH-CO-and-N=N-.
Most preferred hydrolysed reactive dye is hydrolysed reactive red 2, hydrolysed reactive blue 4, hydrolysed reactive black 5 and hydrolysed reactive blue 19.
Balance carrier and additive component
Except that the hydrolysis reactive dyestuffs, laundry treatment compositions comprises balance carrier and additive component to 100% weight combinations thing.
For example, these can be tensio-active agent, builder, whipping agent, defoamer, solvent, fluorescent agent, SYNTHETIC OPTICAL WHITNER and enzyme.These components use and amount makes composition work, depend on economy, environmental factors and composition purposes.
Composition can comprise tensio-active agent and other optional conventional detergent ingredients.Composition also can comprise the enzyme detergent composition, and described enzyme detergent composition comprises one or more tensio-active agents based on the 0.1-50% weight of total detergent composition.This surfactant system can contain one or more anion surfactants of 0-95% weight and one or more nonionogenic tensides of 5 to 100% weight.Surfactant system can contain both sexes or zwitterionic detergent compounds in addition, but because their cost is higher, this also unconventional requirement.Enzyme detergent composition of the present invention generally uses with about 0.05 to 2% weight water dilution.
Composition preferably contains 2 to 60% weight tensio-active agents, most preferably 10 to 30% weight.Usually, the optional self-described of the nonionic of surfactant system and anion surfactant is in " Surface Active Agents (tensio-active agent) " Vol.1, by Schwartz﹠amp; Perry, Interscience 1949, Vol.2 by Schwartz, Perry﹠amp; Berch, Interscience 1958, current version or " Tenside-Taschenbuch " of " McCutcheon ' sEmulsifiers and Detergents " that publishes by Manufacturing Confectioners Company, H.Stache, 2nd Edn., Carl Hauser Verlag, 1981 tensio-active agent.
The nonionic detergent compounds that available is suitable specifically comprises compound (for example fatty alcohol, acid, acid amides or alkylphenol) and the oxyalkylene with hydrophobic grouping and active hydrogen atom, particularly independent oxyethane or with the reaction product of propylene oxide.Concrete nonionic detergent compounds is C
6-C
22Alkylphenol-ethylene oxide condensate (general 5 to 25 EO, i.e. 5 to 25 ethylene oxide units of per molecule) and uncle or secondary straight or branched C
8-C
18The condensation product of fatty alcohol and oxyethane (general 5 to 40 EO).
The anionic detergent immunomodulator compounds that available is suitable is generally to have and contains about 8 to the organic sulfuric acid of the alkyl of about 22 carbon atoms and the water-soluble alkali metal salts of sulfonic acid, and the term alkyl comprises the moieties of senior acyl group.The example of suitable synthetic anionic detergent compound is sodium alkyl sulfate and alkylsurfuric acid potassium, particularly by the senior C of sulfation from for example butter or Oleum Cocois generation
8-C
18Those that alcohol obtains, C
9-C
20Sodium alkyl benzene sulfonate and potassium, particularly C
10-C
15The linear secondary sodium alkyl benzene sulfonate, alkyl glycerol base ether sodium sulfate is especially derived from the higher alcohols of butter or Oleum Cocois with derived from those ethers of the synthol of oil.The preferred anionic surfactants detergent compound is C
11-C
15Sodium alkyl benzene sulfonate and C
12-C
18Sodium alkyl sulfate.Available for example is described in those tensio-active agents (showing the resistance to saltouing) of EP-A-328 177 (Unilever) in addition, is described in alkyl polyglycoside tensio-active agent and the alkyl list glycosides of EP-A-070 074.
The preferred surfactants system is the mixture of negatively charged ion and nonionic detergent active materials, particularly the group and the example of negatively charged ion of pointing out in EP-A-346 995 (Unilever) and nonionogenic tenside.Particularly preferred surfactant system is C
16-C
18Primary alconol sulfuric acid an alkali metal salt and C
12-C
15The mixture of primary alconol 3-7EO ethoxylate.
Preferred nonionic detergent is to be higher than 10% of surfactant system, and for example the amount of 25-90% weight exists.About 5% amount to about 40% weight that for example anion surfactant can surfactant system exists.
Cation compound
When being used as fabric regulator, the present invention need contain cation compound.
Most preferred is quaternary ammonium compound.
Advantageously quaternary ammonium compound is for having at least one C
12-C
22The quaternary ammonium compound of alkyl chain.
Preferably quaternary ammonium compound has following formula:
R wherein
1Be C
12To C
22The alkyl or alkenyl chain; R
2, R
3And R
4Independently be selected from C
1-C
4Alkyl chain, X
-Be compatible negatively charged ion.The preferred compound of this class is a quaternary ammonium compound cetyltrimethylammonium base quaternary ammonium.
Being used for the second class material of the present invention is the quaternary ammonium of said structure, wherein R
1And R
2Independently be selected from C
12To C
22The alkyl or alkenyl chain; R
3And R
4Independently be selected from C
1-C
4Alkyl chain, X
-Be compatible negatively charged ion.
In the detergent composition of claim 1 (ii) cationic substance be at least 2: 1 with the (iv) ratio of anion surfactant.
Other suitable quaternary ammonium compound is disclosed in EP 0 239 910 (Proctor andGamble).
Preferably the ratio of positively charged ion and nonionogenic tenside is 1: 100 to 50: 50, more preferably 1: 50 to 20: 50.
Cation compound can composition total weight 0.02% weight to 20% weight exist.
The preferred cationic compound can composition total weight 0.05% weight to 15% weight exist, more preferably compositing range is 0.2% weight to 5% weight, most preferably the composition scope is 0.4% weight to 2.5% weight.
If product is a liquid, preferably the cats product level is 0.05% weight to 10% weight of composition total weight.The preferred cationic compound can composition total weight 0.2% weight to 5% weight, most preferably the amount of 0.4% weight to 2.5% weight exists.
If product is a solid, preferably the cats product level is 0.05% weight to 15% weight of composition total weight.Preferred compositing range is 0.2% weight to 10% weight of composition total weight, and most preferably the composition scope is 0.9% weight to 3.0% weight.
Albic material
Laundry treatment compositions can comprise albic material.For example, albic material can be selected from perborate and percarbonate.These peroxyl species (peroxyl species) can further strengthen by using activator (as TAED or SNOBS).Perhaps or in addition, transition-metal catalyst can use with peroxyl species.When bleaching is undertaken by atmosphericoxygen,, there is not peroxyl species can use transition-metal catalyst referring to for example WO02/48301 yet.Optical white (comprising the singlet oxygen optical white) can use with laundry treatment compositions.Preferred optical white is a vitamin K.
Fluorescent agent
Laundry treatment compositions preferably comprises fluorescent agent (white dyes).Fluorescent agent is for knowing a lot of so commercially available getting of fluorescent agent.Usually, these fluorescent agents provide with its an alkali metal salt (as sodium salt) form and use.The fluorescent agent total amount that is used for the carrying out washing treatment composition is generally 0.005-2% weight, more preferably 0.01 to 0.1% weight.Preferred fluorescent agent type is: the distyryl biphenol compound, Tinopal (trade mark) CBS-X for example, diamines stilbene disulfonic acid compound is as Tinopal DMS pure Xtra and Blankophor (trade mark) HRH, and pyrazoline compounds, as Blankophor SN.Preferred fluorescent agent is 2-(4-styryl-3-sulfo group phenyl)-2H-naphthols [1,2-d] triazole sodium salt, 4,4 '-it is two that { [(4-anilino-6-(N-methyl-N-2-hydroxyethyl) amino-1,3,5-triazine-2-yl)] amino } stilbene-2-2 '-disulfonic acid disodium, 4,4 '-two { [(4-anilino-6-morpholino-1,3,5-triazine-2-yl)] amino } stilbene-2-2 '-disulfonic acid disodium and 4,4 '-two (2-sulfo group styryl) biphenyl disodium salt.
Embodiment
Embodiment 1: deposit on cotton
Carry out following experiment and determine the substantivity of dyestuff.Preparation 0.1% weight reactive dyestuffs solution in the damping fluid of pH=10, this solution is placed four angel's active group hydrolysis in the room temperature dark place.The water stock solution of preparation 1.5g/L neutralizing treatment powder.Washing powder contains the impurity and the water of 18%NaLAS, 73% salt (silicate, Tri sodium Phosphate, vitriol, carbonate), 3% small amounts of material (comprising perborate, fluorescent agent and enzyme), surplus.Solution is divided into the 60ml aliquots containig and hydrolysed reactive dye is added this solution, and the maximum absorption place optical density(OD) that obtains at visible wavelength 400 to 700nm dyestuffs is the solution of about 1 (the 5cm journey is long).With UV-visible light light-splitting instrumentation amount optical density(OD).The cotton (available from Phoenic Calico) through bleaching, non-mercerising are handled, the woven non-mercerising of non-fluorescence is handled of a heavy 1.3g is placed solution in room temperature (20 ℃).This piece cloth is represented faint yellow cotton.Cloth was soaked 45 minutes, and stirred solution is 10 minutes then, and rinsing is also dry.Then measure the optical density(OD) of solution once more and calculate the amount of dye that cloth absorbs.
The results are shown in following table.
| Dyestuff | On cotton, deposit % |
| Hydrolysed reactive red 2 | 11.6 |
| Hydrolysed reactive blue 4 | 17.9 |
| Hydrolysed reactive black 5 | 18.3 |
| Hydrolysed reactive blue 19 | 22.0 |
Reactive red 2[17804-49-8] representative have following structure the dichlorotriazine based azo dyes:
The dichlorotriazine base anthraquinone dye that reactive blue 4 [13324-20-4] representative has following structure:
Two anchor vinylsulfonyl azoic dyestuffs that reactive black 5 [17095-24-8] representative has following structure:
The vinylsulfonyl anthraquinone dye that Reactive Blue 19 100 [2580-78-1] representative has following structure:
Find that all dyestuffs are direct to Cottonopolis.
Embodiment 2: deposit on nylon
Adopt the deposition of method measurement on nylon fabrics similar to Example 1, difference is to adopt nylon as fabric.
The results are shown in following table.
| Dyestuff | On nylon, deposit % |
| Hydrolysed reactive red 2 | 0.7 |
| Hydrolysed reactive blue 4 | 2.3 |
| Hydrolysed reactive black 5 | 4.0 |
| Hydrolysed reactive blue 19 | 5.60 |
Find that some hydrolised dyes are direct to nylon.
Claims (18)
1. laundry treatment compositions, described composition comprises the tensio-active agent of the hydrolysed reactive dye and 2 to 60% weight of 0.0001 to 0.1% weight,
Wherein hydrolysed reactive dye comprises the chromophore's part that is covalently bonded to anchor group, and described anchor group and cotton knot close, described anchor group be selected from have at least one be covalently bonded to hetero-aromatic ring-the substituent hetero-aromatic ring of OH and
2. the laundry treatment compositions of claim 1, wherein hetero-aromatic ring contains nitrogen heteroatom.
3. the laundry treatment compositions of claim 2, wherein anchor group has following form:
Wherein:
N is 1-3;
X is selected from :-Cl ,-F, NHR, quaternary ammonium group ,-OR and-OH;
R is selected from: aryl, benzyl, C1-C6-alkyl; Wherein at least one X is-OH.
4. the laundry treatment compositions of claim 3, wherein R be selected from naphthyl, phenyl and-CH3.
5. each laundry treatment compositions in the claim 1 to 4, wherein chromophore is selected from azo, anthraquinone, phthalocyanine, first
And triphendioxazine.
6. each laundry treatment compositions in the claim 1 to 4, wherein anchor partly is selected from:
7. each laundry treatment compositions in the claim 1 to 4, wherein chromophore is connected to the anchor of hydrolysis by bridging, described bridge is selected from :-NH-CO-,-NH-, NHCO-CH2CH2-,-NH-CO-and-N=N-.
8. the laundry treatment compositions of claim 1, wherein hydrolysed reactive dye is selected from the hydrolysate of reactive red 2, reactive blue 4, reactive black 5 and Reactive Blue 19 100.
9. each laundry treatment compositions in the claim 1 to 4, wherein laundry treatment compositions comprises the fluorescent agent of 0.005 to 2% weight.
10. method of handling textiles said method comprising the steps of:
(i) handle textiles with the aqueous solution of hydrolysed reactive dye, the described aqueous solution comprises the hydrolysed reactive dye of 10ppb to 1ppm and the tensio-active agent of 0.2g/L to 3g/L; With
(ii) rinsing and dry textiles,
Wherein hydrolysed reactive dye comprises the chromophore's part that is covalently bonded to anchor group, and described anchor group and cotton knot close, described anchor group be selected from have at least one be covalently bonded to hetero-aromatic ring-the substituent hetero-aromatic ring of OH and
11. the method for claim 10, wherein hetero-aromatic ring contains nitrogen heteroatom.
12. the method for claim 11, wherein anchor group has following form:
Wherein:
N is 1-3;
X is selected from :-Cl ,-F, NHR, quaternary ammonium group ,-OR and-OH;
R is selected from: aryl, benzyl, C1-C6-alkyl; Wherein at least one X is-OH.
13. the method for claim 12, wherein R be selected from naphthyl, phenyl and-CH3.
14. each method in the claim 10 to 13, wherein chromophore is selected from azo, anthraquinone, phthalocyanine, first
And triphendioxazine.
15. each method in the claim 10 to 13, wherein anchor partly is selected from:
16. each method in the claim 10 to 13, wherein chromophore is connected to the anchor of hydrolysis by bridging, and described bridge is selected from :-NH-CO-,-NH-, NHCO-CH2CH2-,-NH-CO-and-N=N-.
17. the method for claim 10, wherein hydrolysed reactive dye is selected from the hydrolysate of reactive red 2, reactive blue 4, reactive black 5 and Reactive Blue 19 100.
18. the method for claim 10, wherein the aqueous solution has 0.001 to 0.5 ionic strength.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB0420203.2A GB0420203D0 (en) | 2004-09-11 | 2004-09-11 | Laundry treatment compositions |
| GB0420203.2 | 2004-09-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101056971A CN101056971A (en) | 2007-10-17 |
| CN100577787C true CN100577787C (en) | 2010-01-06 |
Family
ID=33186867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200580038122A Expired - Fee Related CN100577787C (en) | 2004-09-11 | 2005-08-15 | laundry treatment composition |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP1794274B2 (en) |
| CN (1) | CN100577787C (en) |
| AR (1) | AR053967A1 (en) |
| AT (1) | ATE390476T1 (en) |
| BR (1) | BRPI0515066A (en) |
| DE (1) | DE602005005702T2 (en) |
| ES (1) | ES2301042T3 (en) |
| GB (1) | GB0420203D0 (en) |
| WO (1) | WO2006027086A1 (en) |
| ZA (1) | ZA200701947B (en) |
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| US3960744A (en) * | 1973-11-29 | 1976-06-01 | Kao Soap Co., Ltd. | Powder detergent composition |
| US5770552A (en) * | 1997-03-13 | 1998-06-23 | Milliken Research Corporation | Laundry detergent composition containing poly(oxyalkylene)-substituted reactive dye colorant |
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| GB2094826B (en) † | 1981-03-05 | 1985-06-12 | Kao Corp | Cellulase enzyme detergent composition |
| US6126700A (en) † | 1999-01-20 | 2000-10-03 | Everlight Usa, Inc. | Black dye composition |
| ATE391166T1 (en) * | 2003-06-18 | 2008-04-15 | Unilever Nv | BLUE AND RED BLEACH |
-
2004
- 2004-09-11 GB GBGB0420203.2A patent/GB0420203D0/en not_active Ceased
-
2005
- 2005-08-15 BR BRPI0515066-3A patent/BRPI0515066A/en not_active Application Discontinuation
- 2005-08-15 ES ES05771350T patent/ES2301042T3/en not_active Expired - Lifetime
- 2005-08-15 ZA ZA200701947A patent/ZA200701947B/en unknown
- 2005-08-15 DE DE602005005702T patent/DE602005005702T2/en not_active Expired - Lifetime
- 2005-08-15 WO PCT/EP2005/008861 patent/WO2006027086A1/en not_active Ceased
- 2005-08-15 CN CN200580038122A patent/CN100577787C/en not_active Expired - Fee Related
- 2005-08-15 AT AT05771350T patent/ATE390476T1/en not_active IP Right Cessation
- 2005-08-15 EP EP05771350.5A patent/EP1794274B2/en not_active Expired - Lifetime
- 2005-09-08 AR ARP050103747A patent/AR053967A1/en active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3960744A (en) * | 1973-11-29 | 1976-06-01 | Kao Soap Co., Ltd. | Powder detergent composition |
| US5770552A (en) * | 1997-03-13 | 1998-06-23 | Milliken Research Corporation | Laundry detergent composition containing poly(oxyalkylene)-substituted reactive dye colorant |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1794274B2 (en) | 2019-12-18 |
| AR053967A1 (en) | 2007-05-30 |
| GB0420203D0 (en) | 2004-10-13 |
| WO2006027086A1 (en) | 2006-03-16 |
| DE602005005702D1 (en) | 2008-05-08 |
| ES2301042T3 (en) | 2008-06-16 |
| DE602005005702T2 (en) | 2009-04-09 |
| EP1794274B1 (en) | 2008-03-26 |
| BRPI0515066A (en) | 2008-07-01 |
| CN101056971A (en) | 2007-10-17 |
| EP1794274A1 (en) | 2007-06-13 |
| ATE390476T1 (en) | 2008-04-15 |
| ZA200701947B (en) | 2008-07-30 |
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