EP1724333A1 - Process for the treatment of textile fibre materials - Google Patents
Process for the treatment of textile fibre materials Download PDFInfo
- Publication number
- EP1724333A1 EP1724333A1 EP06118810A EP06118810A EP1724333A1 EP 1724333 A1 EP1724333 A1 EP 1724333A1 EP 06118810 A EP06118810 A EP 06118810A EP 06118810 A EP06118810 A EP 06118810A EP 1724333 A1 EP1724333 A1 EP 1724333A1
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- EP
- European Patent Office
- Prior art keywords
- peroxide
- detergent
- weight
- compound
- activator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- XZTREEKDSMOYDA-BQYQJAHWSA-L CCN(CCO)c1nc(Nc2cc(S([O-])(=O)=O)c(/C=C/c(ccc(Nc3nc(OC)nc(N(CC)CCO)n3)c3)c3S([O-])(=O)=O)cc2)nc(OC)n1 Chemical compound CCN(CCO)c1nc(Nc2cc(S([O-])(=O)=O)c(/C=C/c(ccc(Nc3nc(OC)nc(N(CC)CCO)n3)c3)c3S([O-])(=O)=O)cc2)nc(OC)n1 XZTREEKDSMOYDA-BQYQJAHWSA-L 0.000 description 1
- PMXWIVKOPPTVEC-ONEGZZNKSA-L COc1nc(Cl)nc(Nc2ccc(/C=C/c(ccc(Nc3nc(OC)nc(Cl)n3)c3)c3S([O-])(=O)=O)c(S([O-])(=O)=O)c2)n1 Chemical compound COc1nc(Cl)nc(Nc2ccc(/C=C/c(ccc(Nc3nc(OC)nc(Cl)n3)c3)c3S([O-])(=O)=O)c(S([O-])(=O)=O)c2)n1 PMXWIVKOPPTVEC-ONEGZZNKSA-L 0.000 description 1
- BKGUERUEBWCOMX-ONEGZZNKSA-L COc1nc(N2CCOCC2)nc(Nc2ccc(/C=C/c(ccc(Nc3nc(OC)nc(N4CCOCC4)n3)c3)c3S([O-])(=O)=O)c(S([O-])(=O)=O)c2)n1 Chemical compound COc1nc(N2CCOCC2)nc(Nc2ccc(/C=C/c(ccc(Nc3nc(OC)nc(N4CCOCC4)n3)c3)c3S([O-])(=O)=O)c(S([O-])(=O)=O)c2)n1 BKGUERUEBWCOMX-ONEGZZNKSA-L 0.000 description 1
Classifications
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- 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
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- 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
-
- 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
- C11D3/3907—Organic 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
Definitions
- the present invention is directed to detergent formulations containing certain fluorescent whitening agents and a peroxide, a peroxide activator and/or a bleaching catalyst.
- the present invention provides, as a first aspect, a detergent composition comprising at least one compound of formula or wherein M is hydrogen or cation, and wherein the detergent contains a peroxide, a peroxide activator and/or a bleaching catalyst.
- the cation M is preferably an alkali metal atom, an alkaline earth metal atom, ammonium or a cation formed from an amine.
- Preferred are Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C 1 -C 4 alkylammonium, mono-, di- or tri-C 2 -C 4 -hydroxyalkylammonium or ammonium that is di- or tri-substituted with a mixture of C 1 -C 4 -alkyl and C 2 -C 4 -hydroxyalkyl groups.
- Highly preferred is sodium.
- Compounds of formulae (1), (2), (3) and (4) can for example be prepared by first reacting cyanuric chloride with methanol, reacting the product obtained with 4,4'-diaminostilbene-2,2'-disulfonic acid and then reacting the intermediate with the corresponding amines.
- the detergent compositions used preferably comprise
- detergent compositions used comprise
- an amount of compounds of formulae (1), (2), (3) or (4) of 0.001-5%, especially an amount of 0.01-5% is used. Highly preferred is an amount of 0.05-5%, especially 0.05 to 2%.
- amounts given in percent are to be understood as being percent by weight, based on the total weight, unless otherwise stated.
- the detergent may be formulated as a solid, as an aqueous liquid comprising, e.g., 5-50, preferably 10-35% water or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 wt.% of water, and based on a suspension of a builder in a non-ionic surfactant, as described, e.g., in GB-A-2158454 .
- the anionic surfactant component may be, e.g., an alkylbenzenesulfonate, an alkylsulfate, an alkylethersulfate, an olefinsulfonate, an alkanesulfonate, a fatty acid salt, an alkyl or alkenyl ether carboxylate or an ⁇ -sulfofatty acid salt or an ester thereof.
- alkylbenzenesulfonates having 10 to 20 carbon atoms in the alkyl group
- alkylsulfates having 8 to 18 carbon atoms
- alkylethersulfates having 8 to 18 carbon atoms
- fatty acid salts being derived from palm oil or tallow and having 8 to 18 carbon atoms.
- the average molar number of ethylene oxide added in the alkylethersulfate is preferably 1 to 20, preferably 1 to 10.
- the salts are preferably derived from an alkaline metal like sodium and potassium, especially sodium.
- alkali metal sarcosinates of formula R-CO(R 1 )CH 2 COOM 1 in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R 1 is C 1 -C 4 alkyl and M 1 is alkali metal, especially sodium.
- the nonionic surfactant component may be, e.g., primary and secondary alcohol ethoxylates, especially the C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
- the total amount of anionic surfactant and nonionic surfactant is preferably 5-50% by weight, preferably 5-40% by weight and more preferably 5-30% by weight. As to these surfactants it is preferred that the lower limit is 10% by weight.
- the builder component may be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate or disilicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of these.
- Preferred silicates are crystalline layered sodium silicates of the formula NaHSi m O 2m+1 .pH 2 O or Na 2 Si m O 2m+1 .pH 2 O in which m is a number from 1.9 to 4 and p is 0 to 20.
- Preferred aluminosilicates are the commercially-available synthetic materials designated as Zeolites A, B, X, and HS, or mixtures of these. Zeolite A is preferred.
- Preferred polycarboxylates include hydroxypolycarboxylates, in particular citrates, polyacrylates and their copolymers with maleic anhydride.
- Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetra-acetic acid.
- Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
- the amount of builders is preferably 5-70% by weight, preferably 5-60% by weight and more preferably 10-60% by weight. As to the builders it is preferred that the lower limit is 15% by weight, especially 20% by weight.
- Suitable peroxide components include, for example, the organic and inorganic peroxides (like sodium peroxides) known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 5 to 95°C.
- the organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 3, preferably 6 to 20, carbon atoms; in particular diperoxydicarboxylates having 6 to 12 C atoms, such as diperoxyperazelates, diperoxypersebacates, diperoxyphthalates and/or diperoxydodecanedioates, especially their corresponding free acids, are of interest.
- very active inorganic peroxides such as persulphate, perborate and/or percarbonate. It is, of course, also possible to employ mixtures of organic and/or inorganic peroxides.
- the amount of peroxide is preferably 0.5-30% by weight, preferably 1-20% by weight and more preferably 1-15% by weight.
- the lower limit is preferably 2% by weight, especially 5% by weight.
- the peroxides are preferably activated by the inclusion of a bleach activator.
- a bleach activator Preferred are such compounds that, under perhydrolysis conditions, yield unsubstituted or substituted perbenzo- and/or peroxo-carboxylic acids having from 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms.
- Suitable compounds include those that carry O- and/or N-acyl groups having the said number of carbon atoms and/or unsubstituted or substituted benzoyl groups.
- polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N,N-diacetyl-N,N-dimethyl-urea (DDU), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), compounds of formula wherein R is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R' is linear or branched (C 7 -C 15 )alkyl; also activators that are known under the names SNOBS, SLOBS, NOBS and DOBA, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran
- the amount of bleach activator is preferably 0-10% by weight, preferably 0-8% by weight.
- the lower limit is preferably 0.5% by weight, especially 1% by weight.
- Bleaching catalysts which may be added, include, e.g., enzymatic peroxide precursors and/or metal complexes.
- Preferred metal complexes are manganese, cobalt or iron complexes such as manganese or iron phthalocyanines or the complexes described in EP-A-0509787 .
- the amount is preferably 0.005 to 2% by weight, more preferably 0.01 to 2% by weight, especially 0.05 to 2% by weight. Highly preferred is an amount of 0.1-2% by weight.
- bleaching catalysts As examples for bleaching catalysts the following are mentioned:
- the detergent can optionally contain enzymes. Enzymes can be added to detergents for stain removal.
- the enzymes usually improve the performance on stains that are either protein- or starch-based, such as those caused by blood, milk, grass or fruit juices.
- Preferred enzymes are cellulases, proteases, amylases and lipases.
- Preferred enzymes are cellulases and proteases, especially proteases.
- Cellulases are enzymes which act on cellulose and its derivatives and hydrolyze them into glucose, cellobiose, cellooligosaccharide. Cellulases remove dirt and have the effect of mitigating the roughness to the touch. Examples of enzymes to be used include, but are by no means limited to, the following:
- the enzymes can optionally be present in the detergent.
- the enzymes are usually present in an amount of 0.01-5% by weight, preferably 0.05-5% and more preferably 0.1-4% by weight, based on the total weight of the detergent.
- Further preferred additives for the detergents according to the invention are polymers that, during the washing of textiles, inhibit staining caused by dyes in the washing liquor that have been released from the textiles under the washing conditions (dye fixing agents, dye transfer inhibitors).
- Such polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine N-oxides which may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range from 5000 to 60 000, more especially from 10 000 to 50 000.
- Such polymers are usually used in an amount of from 0.01 to 5 %, preferably 0.05 to 5 % by weight, especially 0.1 to 2 % by weight, based on the total weight of the detergent.
- Preferred polymers are those given in WO-A-02/02865 (see especially page 1, last paragraph and page 2, first paragraph).
- the detergents used will usually contain one or more auxiliaries such as soil suspending agents, for example sodium carboxymethylcellulose; salts for adjusting the pH, for example alkali or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and granulating properties, for example sodium sulphate; perfumes; and also, if appropriate, antistatic and softening agents; such as smectite clays; photobleaching agents; pigments; and/or shading agents.
- auxiliaries can be present in an amount of, for example, 0.1 to 20% by weight, preferably 0.5 to 10 % by weight, especially 0.5 to 5 % by weight, based on the total weight of the detergent.
- the detergent compositions can take a variety of physical forms including powder, granular, tablet and liquid forms. Examples thereof are conventional powder heavy-duty detergents, compact and supercompact heavy-duty detergents and tablets, like heavy-duty detergent tablets.
- One important physical form is the so-called concentrated granular form adapted to be added to a washing machine.
- compact detergents Of importance are also the so-called compact (or supercompact) detergents.
- compact detergents In the field of detergent manufacture, a trend has developed recently towards the production of compact detergents which contain increased amounts of active substance. In order to minimize energy expenditure during the washing process, the compact detergents are required to operate efficiently at temperatures as low as 40°C, or even at room temperatures, e.g. at 25°C.
- Such detergents usually contain only low amounts of fillers or processing aids, like sodium sulfate or sodium chloride.
- the amount of such fillers is usually 0-10% by weight, preferably 0-5 % by weight, especially 0-1 % by weight, based on the total weight of the detergent.
- Such detergents usually have a bulk density of 650-1000 g/I, preferably 700-1000 g/I and especially 750-1000 g/I.
- the detergents can also be present in the form of tablets. Relevant characteristics of tablets are ease of dispensing and convenience in handling. Tablets are the most compact delivery of solid detergents and have a bulk density of, for example, 0.9 to 1.3 kg/litre. To enable fast disintegration laundry detergent tablets generally contain special disintegrants:
- the detergent may also be formulated as a an aqueous liquid comprising 5-50, preferably 10-35% water or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 wt.% of water.
- Non-aqueous liiquid detergent compositions can contain other solvents as carriers.
- Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
- Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
- the compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
- the detergents can also be present as the so-called "unit liquid dose" form.
- This detergent treatment of textiles can be conducted as a domestic treatment in normal washing machines.
- the textile fibres treated may be natural or synthetic fibres or mixtures thereof.
- natural fibres include vegetable fibres such as cotton, viscose, flax, rayon or linen, preferably cotton and animal fibres such as wool, mohair, cashmere, angora and silk, preferably wool.
- Synthetic fibres include polyester, polyamide and polyacrylonitrile fibres.
- Preferred textile fibres are cotton, polyamide and wool fibres, especially cotton fibres.
- textile fibres treated according to the method of the present invention have a density of less than 200 g/m 2 .
- the process is usually conducted in the temperature range of from 5 to 100°C, especially 5 to 60°C.
- Preferred is a temperature range of 5 to 40°C, especially 5 to 35°C and more preferably 5 to 30°C.
- the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 11. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
- Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accordance with the invention.
- an effective amount of the detergent composition it is meant, e.g., from 20 g to 300 g of product dissolved or dispersed in a wash solution of volume from 5 to 85 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Examples are
- the liquor ratio is preferably 1:4 to 1:40, especially 1:4 to 1:15. Highly preferred is a liquor ratio of 1:4 to 1:10, especially 1:5 to 1:9.
- a further object of the present invention is to provide a process for the domestic washing treatment of a textile fibre material wherein the textile fibre material is contacted with an aqueous solution of a detergent comprising a compound of formula (1) as defined above, and wherein the detergent contains a peroxide, a peroxide activator and/or a bleaching catalyst, and wherein the temperature of the solution is between 5°C and 40°C, preferably between 5°C and 30°C, throughout the process.
- the compounds used according to the present invention are particularly advantageous in that they exhibit not only extremely high whitening ability, but, in addition, in many cases highly desirable water solubilities and also possess excellent white aspects in the solid state.
- a further advantage of the present invention is that the detergent composition delivers improved whiteness performance and fabric feel. Furthermore the compounds show very good results with respect to exhaustion properties.
- the compounds have the advantage that they are also effective in the presence of active chlorine donors, such as, for example, hypochlorite and can be used without substantial loss of the effects in washing baths with non-ionic washing agents, for example alkylphenol polyglycol ethers.
- active chlorine donors such as, for example, hypochlorite
- non-ionic washing agents for example alkylphenol polyglycol ethers.
- perborate or peracids and activators for example tetraacetylglycoluril or ethylenediamine-tetraacetic acid are the compounds stable both in pulverulent washing agent and in washing baths. In addition, they impart a brilliant appearance in daylight.
- a wash liquor is prepared by dissolving 0.8 g of a washing powder in 200 ml of tap water. 10 g of bleached cotton fabric is added to the bath and washed at 40°C over 15 minutes and then rinsed, spin-dried and ironed at 160°C.
- washing powders A and B are used (amounts given in the following Tables 3a and 3b are in g): Table 3a (Ingredients of washing powders A and B) A B Sodium laurylbenzene-sulfonate (LAS) 10g 10g Sodium lauryl ether sulfate (AES) 3g 3g Dobanol 23-6.5 (nonionic alcoholethoxylate) 4g 4g Sodium tripolyphosphate 30g ----- Zeolite A ----- 20g Sodium carbonate 15g 15g Sodium silicate 5g 5g Sodium sulfate 11g 17g Sodium perborate monohydrate 10g 10g TAED 3g 3g Polycarboxylate (co-builder) ----- 4g Carboxymethylcellulose 2g 2g Perfume 0.1g 0.1g Water 5g 5g Fluorescent whitener used Xg Xg Table 3b (Washing powders used) Amount of fluorescent whitener used Washing powder Compound of Prep.
- a wash liquor is prepared by dissolving 0.8 g of a washing powder in 200 ml of tap water. 10 g of bleached cotton fabric is added to the bath and washed at 30°C over 15 minutes and then rinsed, spin-dried and ironed at 160°C.
- washing powders are used (amounts given in the following Tables 4a and 4b are percent by weight, based on the total weight of the detergent): Table 4a (Ingredients of washing powders C and D) C D Sodium laurylbenzene-sulfonate (LAS) 8% 8% Sodium lauryl ether sulfate (AES) 3% 3% Dobanol 23-6.5 ( on-ionic alcoholethoxylate) 5% 5% 5% Zeolite A 20% 20% Polycarboxylate (co-builder) 5% 5% Soda ash 18% 18% Sodium silicate 4% 4% Sodium sulfate 5% 5% Hydroxyethanediphosphonic acid (complexing agent) 0.5% 0.5% Cellulase 1.5% ----- Protease ----- 1.5% Carboxymethylcellulose 1% 1% Sodium perborate monohydrate 15% 15% TAED 5% 5% Soap 2% 2% Fluorescent whitener used X% X%
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Abstract
Description
- The present invention is directed to detergent formulations containing certain fluorescent whitening agents and a peroxide, a peroxide activator and/or a bleaching catalyst.
- It is commonly known to use fluorescent whitening agents in detergent formulations. They exhaust during the treatment on to the material to be washed and, by virtue of their special light absorption/emission property, result in elimination of the yellowish shades.
- However there is still a need to find improved fluorescent whitening agents for this application. It has now been found that the following compounds of formulae (1), (2), (3) or (4) possess superior properties with regard to, for example, solubility, build-up properties, light-fastness degree of whiteness, and also possess excellent white aspects in the solid state. The whiteness properties, like whiteness maintenance, can even be enhanced by the use of of compounds of formulae (1), (2), (3) or (4) in detergents containing a peroxide, a peroxide activator and/or a bleaching catalyst. Favourable results are even obtained at low washing temperatures.
-
- The cation M is preferably an alkali metal atom, an alkaline earth metal atom, ammonium or a cation formed from an amine. Preferred are Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C1-C4alkylammonium, mono-, di- or tri-C2-C4-hydroxyalkylammonium or ammonium that is di- or tri-substituted with a mixture of C1-C4-alkyl and C2-C4-hydroxyalkyl groups. Highly preferred is sodium.
- The compounds of formulae (1), (2), (3) and (4) are known or can be prepared in analogy to known processes.
- Compounds of formulae (1), (2), (3) and (4) can for example be prepared by first reacting cyanuric chloride with methanol, reacting the product obtained with 4,4'-diaminostilbene-2,2'-disulfonic acid and then reacting the intermediate with the corresponding amines.
- The detergent compositions used preferably comprise
- i) 1-70% of an anionic surfactant and/or a nonionic surfactant;
- ii) 0-75% of a builder;
- iii) 0.5-30% of a peroxide;
- iv) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst ;
- v) 0.001-5% of a compound of formulae (1), (2), (3) or (4); and
- vi) 0-5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.
- More preferably the detergent compositions used comprise
- i) 5-70% of an anionic surfactant and/or a nonionic surfactant;
- ii) 5-70% of a builder;
- iii) 0.5-30% of a peroxide;
- iv) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst;
- v) 0.01-5% of a compound of formulae (1), (2), (3) or (4); and
- vi) 0.05-5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.
- In general, an amount of compounds of formulae (1), (2), (3) or (4) of 0.001-5%, especially an amount of 0.01-5% is used. Highly preferred is an amount of 0.05-5%, especially 0.05 to 2%. In general, amounts given in percent are to be understood as being percent by weight, based on the total weight, unless otherwise stated.
- The detergent may be formulated as a solid, as an aqueous liquid comprising, e.g., 5-50, preferably 10-35% water or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 wt.% of water, and based on a suspension of a builder in a non-ionic surfactant, as described, e.g., in
GB-A-2158454 - The anionic surfactant component may be, e.g., an alkylbenzenesulfonate, an alkylsulfate, an alkylethersulfate, an olefinsulfonate, an alkanesulfonate, a fatty acid salt, an alkyl or alkenyl ether carboxylate or an α-sulfofatty acid salt or an ester thereof. Preferred are alkylbenzenesulfonates having 10 to 20 carbon atoms in the alkyl group, alkylsulfates having 8 to 18 carbon atoms, alkylethersulfates having 8 to 18 carbon atoms, and fatty acid salts being derived from palm oil or tallow and having 8 to 18 carbon atoms. The average molar number of ethylene oxide added in the alkylethersulfate is preferably 1 to 20, preferably 1 to 10. The salts are preferably derived from an alkaline metal like sodium and potassium, especially sodium. Highly preferred carboxylates are alkali metal sarcosinates of formula R-CO(R1)CH2COOM1 in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R1 is C1-C4 alkyl and M1 is alkali metal, especially sodium.
- The nonionic surfactant component may be, e.g., primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
- The total amount of anionic surfactant and nonionic surfactant is preferably 5-50% by weight, preferably 5-40% by weight and more preferably 5-30% by weight. As to these surfactants it is preferred that the lower limit is 10% by weight.
- The builder component may be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate or disilicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of these.
Preferred silicates are crystalline layered sodium silicates of the formula NaHSimO2m+1.pH2O or Na2SimO2m+1.pH2O in which m is a number from 1.9 to 4 and p is 0 to 20.
Preferred aluminosilicates are the commercially-available synthetic materials designated as Zeolites A, B, X, and HS, or mixtures of these. Zeolite A is preferred.
Preferred polycarboxylates include hydroxypolycarboxylates, in particular citrates, polyacrylates and their copolymers with maleic anhydride.
Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetra-acetic acid.
Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates. - The amount of builders is preferably 5-70% by weight, preferably 5-60% by weight and more preferably 10-60% by weight. As to the builders it is preferred that the lower limit is 15% by weight, especially 20% by weight.
- Suitable peroxide components include, for example, the organic and inorganic peroxides (like sodium peroxides) known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 5 to 95°C.
In particular, the organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 3, preferably 6 to 20, carbon atoms; in particular diperoxydicarboxylates having 6 to 12 C atoms, such as diperoxyperazelates, diperoxypersebacates, diperoxyphthalates and/or diperoxydodecanedioates, especially their corresponding free acids, are of interest. It is preferred, however, to employ very active inorganic peroxides, such as persulphate, perborate and/or percarbonate. It is, of course, also possible to employ mixtures of organic and/or inorganic peroxides. - The amount of peroxide is preferably 0.5-30% by weight, preferably 1-20% by weight and more preferably 1-15% by weight. In case a peroxide is used, the lower limit is preferably 2% by weight, especially 5% by weight.
- The peroxides, especially the inorganic peroxides, are preferably activated by the inclusion of a bleach activator. Preferred are such compounds that, under perhydrolysis conditions, yield unsubstituted or substituted perbenzo- and/or peroxo-carboxylic acids having from 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms. Suitable compounds include those that carry O- and/or N-acyl groups having the said number of carbon atoms and/or unsubstituted or substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N,N-diacetyl-N,N-dimethyl-urea (DDU), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), compounds of formula
German Patent Application DE-A-44 43 177 may also be used. Nitrile compounds that form peroxyimidic acids with peroxides are also suitable as bleach activators. Preferred are tetraacetyl ethylenediamine and nonoyloxybenzene sulfonate. - The amount of bleach activator is preferably 0-10% by weight, preferably 0-8% by weight. In case a bleach activator is used, the lower limit is preferably 0.5% by weight, especially 1% by weight.
- Bleaching catalysts, which may be added, include, e.g., enzymatic peroxide precursors and/or metal complexes. Preferred metal complexes are manganese, cobalt or iron complexes such as manganese or iron phthalocyanines or the complexes described in
EP-A-0509787 . In case a bleaching catalyst is used the amount is preferably 0.005 to 2% by weight, more preferably 0.01 to 2% by weight, especially 0.05 to 2% by weight. Highly preferred is an amount of 0.1-2% by weight. - As examples for bleaching catalysts the following are mentioned:
-
WO-A-95/30681 -
WO-A-01/09276 -
WO-A-01/05925 -
WO-A-02/088289 - Furthermore, the detergent can optionally contain enzymes. Enzymes can be added to detergents for stain removal. The enzymes usually improve the performance on stains that are either protein- or starch-based, such as those caused by blood, milk, grass or fruit juices. Preferred enzymes are cellulases, proteases, amylases and lipases. Preferred enzymes are cellulases and proteases, especially proteases. Cellulases are enzymes which act on cellulose and its derivatives and hydrolyze them into glucose, cellobiose, cellooligosaccharide. Cellulases remove dirt and have the effect of mitigating the roughness to the touch. Examples of enzymes to be used include, but are by no means limited to, the following:
- proteases as given in
US-B-6,242,405 , column 14, lines 21 to 32; - lipases as given in
US-B-6,242,405 , column 14, lines 33 to 46; - amylases as given in
US-B-6,242,405 , column 14, lines 47 to 56; and - cellulases as given in
US-B-6,242,405 , column 14, lines 57 to 64. - The enzymes can optionally be present in the detergent. When used, the enzymes are usually present in an amount of 0.01-5% by weight, preferably 0.05-5% and more preferably 0.1-4% by weight, based on the total weight of the detergent.
- Further preferred additives for the detergents according to the invention are polymers that, during the washing of textiles, inhibit staining caused by dyes in the washing liquor that have been released from the textiles under the washing conditions (dye fixing agents, dye transfer inhibitors). Such polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine N-oxides which may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range from 5000 to 60 000, more especially from 10 000 to 50 000. Such polymers are usually used in an amount of from 0.01 to 5 %, preferably 0.05 to 5 % by weight, especially 0.1 to 2 % by weight, based on the total weight of the detergent. Preferred polymers are those given in
WO-A-02/02865 - The detergents used will usually contain one or more auxiliaries such as soil suspending agents, for example sodium carboxymethylcellulose; salts for adjusting the pH, for example alkali or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and granulating properties, for example sodium sulphate; perfumes; and also, if appropriate, antistatic and softening agents; such as smectite clays; photobleaching agents; pigments; and/or shading agents. These constituents should, of course, be stable to any bleaching system employed. Such auxiliaries can be present in an amount of, for example, 0.1 to 20% by weight, preferably 0.5 to 10 % by weight, especially 0.5 to 5 % by weight, based on the total weight of the detergent.
- The detergent compositions can take a variety of physical forms including powder, granular, tablet and liquid forms. Examples thereof are conventional powder heavy-duty detergents, compact and supercompact heavy-duty detergents and tablets, like heavy-duty detergent tablets. One important physical form is the so-called concentrated granular form adapted to be added to a washing machine.
- Of importance are also the so-called compact (or supercompact) detergents. In the field of detergent manufacture, a trend has developed recently towards the production of compact detergents which contain increased amounts of active substance. In order to minimize energy expenditure during the washing process, the compact detergents are required to operate efficiently at temperatures as low as 40°C, or even at room temperatures, e.g. at 25°C. Such detergents usually contain only low amounts of fillers or processing aids, like sodium sulfate or sodium chloride. The amount of such fillers is usually 0-10% by weight, preferably 0-5 % by weight, especially 0-1 % by weight, based on the total weight of the detergent. Such detergents usually have a bulk density of 650-1000 g/I, preferably 700-1000 g/I and especially 750-1000 g/I.
- The detergents can also be present in the form of tablets. Relevant characteristics of tablets are ease of dispensing and convenience in handling. Tablets are the most compact delivery of solid detergents and have a bulk density of, for example, 0.9 to 1.3 kg/litre. To enable fast disintegration laundry detergent tablets generally contain special disintegrants:
- Effervescents such as carbonate/hydrogencarbonate/citric acid;
- swelling agents like cellulose, carboxymethyl cellulose, cross-linked poly(N-vinylpyrrollidone);
- quickly dissolving materials such as Na (K) acetate, or Na (K) citrate;
- rapidly dissolving water-soluble rigid coating such as dicarboxy acids.
- The detergent may also be formulated as a an aqueous liquid comprising 5-50, preferably 10-35% water or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 wt.% of water. Non-aqueous liiquid detergent compositions can contain other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The compositions may contain from 5% to 90%, typically 10% to 50% of such carriers. The detergents can also be present as the so-called "unit liquid dose" form.
- This detergent treatment of textiles can be conducted as a domestic treatment in normal washing machines.
- The textile fibres treated may be natural or synthetic fibres or mixtures thereof. Examples of natural fibres include vegetable fibres such as cotton, viscose, flax, rayon or linen, preferably cotton and animal fibres such as wool, mohair, cashmere, angora and silk, preferably wool. Synthetic fibres include polyester, polyamide and polyacrylonitrile fibres. Preferred textile fibres are cotton, polyamide and wool fibres, especially cotton fibres. Preferably, textile fibres treated according to the method of the present invention have a density of less than 200 g/m2.
- According to this process usually an amount of 0.01 to 3.0% by weight, especially 0.05 to 3.0% by weight, based on the weight of the textile fibre material, of a compound of formulae (1), (2), (3) or (4) is used.
- The process is usually conducted in the temperature range of from 5 to 100°C, especially 5 to 60°C. Preferred is a temperature range of 5 to 40°C, especially 5 to 35°C and more preferably 5 to 30°C.
- The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 11. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
- Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accordance with the invention. By an effective amount of the detergent composition it is meant, e.g., from 20 g to 300 g of product dissolved or dispersed in a wash solution of volume from 5 to 85 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Examples are
- top-loading, vertical axis U.S.-type automatic washing machines using about 45 to 83 liters of water in the wash bath, a wash cycle of about 10 to about 14 minutes and a wash water temperature of about 10 to about 50°C;
- front-loading, horizontal-axis European-type automatic washing machine using about 8 to 15 liters of water in the wash bath, a wash cycle of about 10 to about 60 minutes and a wash water temperature of about 30 to about 95°C;
- top-loading, vertical-axis Japanese-type automatic washing machine using about 26 to 52 liters of water in the wash bath, a wash cycle of about 8 to about 15 minutes and a wash water temperature of about 5 to about 25°C.
- The liquor ratio is preferably 1:4 to 1:40, especially 1:4 to 1:15. Highly preferred is a liquor ratio of 1:4 to 1:10, especially 1:5 to 1:9.
- A further object of the present invention is to provide a process for the domestic washing treatment of a textile fibre material wherein the textile fibre material is contacted with an aqueous solution of a detergent comprising a compound of formula (1) as defined above, and wherein the detergent contains a peroxide, a peroxide activator and/or a bleaching catalyst, and wherein the temperature of the solution is between 5°C and 40°C, preferably between 5°C and 30°C, throughout the process.
- As to the compounds of formulae (1), (2), (3) or (4) as well as for the detergents and the washing process the definitions and preferences given above apply.
- The compounds used according to the present invention are particularly advantageous in that they exhibit not only extremely high whitening ability, but, in addition, in many cases highly desirable water solubilities and also possess excellent white aspects in the solid state. A further advantage of the present invention is that the detergent composition delivers improved whiteness performance and fabric feel. Furthermore the compounds show very good results with respect to exhaustion properties.
- The compounds have the advantage that they are also effective in the presence of active chlorine donors, such as, for example, hypochlorite and can be used without substantial loss of the effects in washing baths with non-ionic washing agents, for example alkylphenol polyglycol ethers. Also in the presence of perborate or peracids and activators, for example tetraacetylglycoluril or ethylenediamine-tetraacetic acid are the compounds stable both in pulverulent washing agent and in washing baths. In addition, they impart a brilliant appearance in daylight.
- The following Examples serve to illustrate the invention; parts and percentages are by weight, unless otherwise stated.
-
- In a 1 litre flask 0.05 mole of the compound of formula
- The following compounds of formula
Table 2 Example X 2 -N(CH2CH3)CH2CH2OH 3 4 -N(CH2CH2OH)2 - A wash liquor is prepared by dissolving 0.8 g of a washing powder in 200 ml of tap water. 10 g of bleached cotton fabric is added to the bath and washed at 40°C over 15 minutes and then rinsed, spin-dried and ironed at 160°C.
- The following washing powders A and B are used (amounts given in the following Tables 3a and 3b are in g):
Table 3a (Ingredients of washing powders A and B) A B Sodium laurylbenzene-sulfonate (LAS) 10g 10g Sodium lauryl ether sulfate (AES) 3g 3g Dobanol 23-6.5 (nonionic alcoholethoxylate) 4g 4g Sodium tripolyphosphate 30g ----- Zeolite A ----- 20g Sodium carbonate 15g 15g Sodium silicate 5g 5g Sodium sulfate 11g 17g Sodium perborate monohydrate 10g 10g TAED 3g 3g Polycarboxylate (co-builder) ----- 4g Carboxymethylcellulose 2g 2g Perfume 0.1g 0.1g Water 5g 5g Fluorescent whitener used Xg Xg Table 3b (Washing powders used) Amount of fluorescent whitener used Washing powder Compound of Prep. Ex. 1 0.3g B Compound of Prep. Ex. 2 0.2g A - The cotton fabrics washed with the detergents given in Table 3b according to the general procedure show good whiteness properties.
- A wash liquor is prepared by dissolving 0.8 g of a washing powder in 200 ml of tap water. 10 g of bleached cotton fabric is added to the bath and washed at 30°C over 15 minutes and then rinsed, spin-dried and ironed at 160°C.
- The following washing powders are used (amounts given in the following Tables 4a and 4b are percent by weight, based on the total weight of the detergent):
Table 4a (Ingredients of washing powders C and D) C D Sodium laurylbenzene-sulfonate (LAS) 8% 8% Sodium lauryl ether sulfate (AES) 3% 3% Dobanol 23-6.5 ( on-ionic alcoholethoxylate) 5% 5% Zeolite A 20% 20% Polycarboxylate (co-builder) 5% 5% Soda ash 18% 18% Sodium silicate 4% 4% Sodium sulfate 5% 5% Hydroxyethanediphosphonic acid (complexing agent) 0.5% 0.5% Cellulase 1.5% ----- Protease ----- 1.5% Carboxymethylcellulose 1% 1% Sodium perborate monohydrate 15% 15% TAED 5% 5% Soap 2% 2% Fluorescent whitener used X% X% - In each of the above detergents a sufficient amount of water is used to give 100%.
Table 4b (Washing powders used) Amount of fluorescent whitener used Washing powder Compound of Prep. Ex. 2 0.4% C Compound of Prep. Ex. 4 0.3% C - The cotton fabrices washed with the detergents given in Table 4b according to the general procedure show good whiteness properties.
Claims (17)
- A composition according to claim 1, wherein M is hydrogen, an alkaline- or alkaline earth-metal, or ammonium, preferably sodium.
- A composition according to claim 1 or 2, comprisingi) 1-70% of an anionic surfactant and/or a nonionic surfactant;ii) 0-75% of a builder;iii) 0.5-30% of a peroxide;iv) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst;v) 0.001-5% of a compound of formula (1), (2), (3) or (4); andvi) 0-5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.
- A composition according to any of claims 1 to 3, comprisingi) 5-70% of an anionic surfactant and/or a nonionic surfactant;ii) 5-70% of a builder;iii) 0.5-30% of a peroxide;iv) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst;v) 0.01-5% of a compound of formula (1), (2), (3) or (4); andvi) 0.05-5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.
- A composition according to any of claims 1 to 4, wherein the composition comprises at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.
- A composition according to claim 5, wherein the enzyme is a protease enzyme.
- A composition according to any of claims 1 to 6, wherein the composition comprises a peroxide.
- A composition according to any of claims 1 to 7, wherein the composition comprises a peroxide and a peroxide activator.
- A composition according to claim 8, wherein the peroxide activator is TAED.
- A process for the domestic washing treatment of a textile fibre material wherein the textile fibre material is contacted with an aqueous solution of a detergent comprising a compound of formula
and wherein the detergent contains a peroxide, a peroxide activator and/or a bleaching catalyst,
and wherein the temperature of the solution is between 5°C and 40°C, preferably between 5°C and 30°C, throughout the process. - A process according to claim 10, wherein M is hydrogen, an alkaline- or alkaline earth-metal, or ammonium, preferably sodium.
- A process according to claim 10 or 11, wherein the textile fibre materials are treated with 0.05 to 3.0% by weight, based on the weight of the textile fibre material, of the compound of formulae (1), (2), (3) or (4).
- A process according to any of claims 10 to 12, wherein the detergent comprises at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.
- A process according to claim 13, wherein the enzyme is a protease enzyme.
- A process according to any of claims 10 to 14, wherein the detergent comprises a peroxide.
- A process according to any of claims 10 to 15, wherein the detergent comprises a peroxide and a peroxide activator.
- A process according to claim 16, wherein the peroxide activator is TAED.
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EP06118810A EP1724333A1 (en) | 2002-02-25 | 2003-02-18 | Process for the treatment of textile fibre materials |
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EP02405136 | 2002-02-25 | ||
EP02405876 | 2002-10-11 | ||
EP06118810A EP1724333A1 (en) | 2002-02-25 | 2003-02-18 | Process for the treatment of textile fibre materials |
EP03706527A EP1478724B1 (en) | 2002-02-25 | 2003-02-18 | Process for the treatment of textile fibre materials |
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EP06118810A Withdrawn EP1724333A1 (en) | 2002-02-25 | 2003-02-18 | Process for the treatment of textile fibre materials |
EP06118792.8A Expired - Lifetime EP1715029B1 (en) | 2002-02-25 | 2003-02-18 | Process for the treatment of textile fibre materials |
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EP03706527A Expired - Lifetime EP1478724B1 (en) | 2002-02-25 | 2003-02-18 | Process for the treatment of textile fibre materials |
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EP (4) | EP1485460B1 (en) |
JP (2) | JP4567975B2 (en) |
CN (2) | CN1294248C (en) |
AR (3) | AR038582A1 (en) |
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AU (2) | AU2003208870B2 (en) |
BR (3) | BRPI0306187B1 (en) |
DE (2) | DE60308485T2 (en) |
ES (3) | ES2271529T3 (en) |
TW (2) | TWI324177B (en) |
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DE60308485T2 (en) * | 2002-02-25 | 2007-09-06 | Ciba Speciality Chemicals Holding Inc. | PROCESS FOR THE TREATMENT OF TEXTILE FIBER MATERIALS |
ATE359352T1 (en) | 2003-03-24 | 2007-05-15 | Ciba Sc Holding Ag | DETERGENT COMPOSITIONS |
US7585333B2 (en) | 2004-01-20 | 2009-09-08 | Ciba Specialty Chemicals Corporation | Triazinylaminostilbene disulphonic acid mixtures |
CN1973026A (en) * | 2004-04-20 | 2007-05-30 | 西巴特殊化学制品控股公司 | Amphoteric flourescent whitening agents in detergent formulations |
ES2404533T3 (en) * | 2004-08-30 | 2013-05-28 | Basf Se | Matting Process |
WO2007135003A1 (en) * | 2006-05-23 | 2007-11-29 | Ciba Holding Inc. | A detergent composition for textile fibre materials |
CN104801511B (en) * | 2014-01-26 | 2018-09-18 | 艺康美国股份有限公司 | Ex-situ cleaning process and clean-in-place system |
PE20211336A1 (en) | 2014-01-31 | 2021-07-26 | Goldcorp Inc | PROCESS FOR THE SEPARATION AND RECOVERY OF METAL SULFIDES FROM A MIXED SULFIDE MINE OR CONCENTRATE |
CN105001671A (en) * | 2015-06-29 | 2015-10-28 | 纳爱斯丽水日化有限公司 | Compound brightening agent and washing agent composition containing compound brightening agent |
CN107857738A (en) * | 2017-11-28 | 2018-03-30 | 贺州学院 | The synthesis and application of hexadecylamino pyrrolotriazine derivatives |
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