EP0557730A1 - Bleach regulating compositions and bleaching process therefrom - Google Patents
Bleach regulating compositions and bleaching process therefrom Download PDFInfo
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- EP0557730A1 EP0557730A1 EP93101290A EP93101290A EP0557730A1 EP 0557730 A1 EP0557730 A1 EP 0557730A1 EP 93101290 A EP93101290 A EP 93101290A EP 93101290 A EP93101290 A EP 93101290A EP 0557730 A1 EP0557730 A1 EP 0557730A1
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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
- C11D3/3937—Stabilising 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
- C11D3/3937—Stabilising agents
- C11D3/394—Organic compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
Definitions
- the invention relates to bleach regulator (stabilizer) compositions for bleaching with H2O2 containing gluconic acid, nitrilotriacetic acid and magnesium in ionic form, to which a content of citric acid can also occur.
- bleach regulators are used in aqueous, alkaline solution.
- Natural vegetable fibers such as cotton, sisal, jute, etc. contain raw waxes, fats and other plant components that cause a yellowish-brown coloring of the fibers. This means that not all of the desired colors are possible; Colorings are also uneven.
- a treatment of these fibers is therefore carried out in which bleaching and washing are combined.
- Such a treatment can be applied to the fibers of the named origin, to yarns made therefrom and to Woven, knitted or non-woven of such fibers. This treatment can also be applied to mixtures of such fibers with synthetic fibers and products made therefrom.
- So-called bleaching liquors which contain water, hydrogen peroxide, wetting / washing and emulsifying agents, alkali for adjusting the pH and H 2 O 2 regulators (stabilizers) are used for carrying out the combined treatment mentioned.
- Na silicate and inorganic phosphates for example, have long been used as regulators. Because of the over-fertilization of the waste water, the inorganic phosphates were later replaced by (poly) -phosphonates. However, these phosphonates are difficult or not at all degradable and thus pollute the waste water again in a different way.
- EDTA biodegradable ethylenediamine tetraacetic acid
- Ingredient a) is preferably present in an amount of 0.1 to 10 parts by weight, particularly preferably 0.1 to 8 parts by weight.
- component b) is present in an amount of 10 to 150 parts by weight, particularly preferably 15 to 120 parts by weight.
- component c) is present in an amount of 4 to 12 parts by weight, particularly preferably 4 to 8 parts by weight.
- component d) is present in an amount of 4 to 30 parts by weight, particularly preferably 5 to 25 parts by weight.
- the bleach regulator compositions according to the invention are used in aqueous, alkaline solution.
- the components a), b), c) and d) are present together in an amount of 10 to 60% by weight, preferably 25 to 40% by weight, based on the total aqueous, alkaline solution.
- an alkali hydroxide is added until a pH of 7.5 to 14 is reached.
- Such a wide pH range up to a strongly alkaline setting is fundamentally possible because alkali must be added to the bleaching liquor to which the bleaching regulator compositions according to the invention are added.
- a lower pH has proven to be more favorable.
- a pH of 7.5 to 12.5, particularly preferably 7.5 to 12, is therefore preferably carried out.
- sodium hydroxide is preferred as the alkali hydroxide, although in principle KOH or LiOH are also possible; it can be used both in solid form and in the easy-to-handle aqueous solution with, for example, 10 to 60% by weight.
- the invention further relates to a method for bleaching natural vegetable fibers or their mixtures with synthetic fibers or of yarns, fabrics, knitted fabrics or nonwovens made from such fibers or their mixtures in bleaching liquors, the water, alkali, hydrogen peroxide, wetting, washing and emulsifying agents as well as bleach regulators, which is characterized in that compositions of the type described above are used as bleach regulators.
- the process according to the invention can be carried out in a number of different embodiments, all of which are known to the person skilled in the art as prior art: bleaching in a long liquor (discontinuous or continuous); Block Cold Dwell Process (KKV); Pad steam process; Pad roll process and others.
- Natural vegetable fibers for example cotton, jute, linen or regenerated cellulose, as well as animal fibers, such as silk and wool, and their mixtures with synthetics can be bleached according to the invention.
- Vegetable fibers are preferred, particularly preferably cotton and mixtures thereof.
- a bleach regulator composition according to the invention is used in addition to water, alkali hydroxide, wetting agents, detergents and emulsifiers and hydrogen peroxide.
- hydrogen peroxide is present in an amount of 0.5-100 ml / l.
- the alkali metal hydroxide is added in an amount and added so that a pH of 7.5 to 14 is maintained in the bleaching liquor becomes.
- Wetting, washing and emulsifying agents are those which are known to the person skilled in the art in this field.
- anionic, cationic or non-ionic surfactants are individual substances or mixtures of the known anionic, cationic or non-ionic surfactants; it is preferably anionic or nonionic surfactants, such as fatty acids and their salts, fatty acid alkyl esters, fatty alcohols, fatty alcohol polyglycol ethers, glycerols, alkyl aromatic sulfonic acids and others
- these surfactants are selected and put together in such a way that the undesirable accompanying substances of the natural vegetable fibers, such as fats, waxes and other plant components (e.g. residues of seed capsules etc.) are removed.
- Demineralized water or a customary made-up water which has a different degree of hardness depending on the occurrence, can be used as water.
- the bleach regulator compositions serve as stabilizers for the hydrogen peroxide. It regulates the release of oxygen to bleach the fibers.
- Gluconic acid, nitrilotriacetic acid and optionally citric acid are used for the complexation and "masking" of alkaline earth metals, in particular the troublesome Ca ions and heavy metals.
- the complexing effect of the mixture of gluconic acid and nitrilotriacetic acid is sufficient.
- citric acid is additionally used; gluconic acid and nitrilotriacetic acid can be used both as free acid and Alkali salt (preferably as sodium salt) can be used.
- Citric acid if it is used, can also be used as alkali metal salt or as free acid.
- citric acid is used as the technically available citric acid monohydrate.
- Magnesium ions and calcium ions as an example of alkaline earth ions and iron as an example of heavy metal ions that are to be complexed are natural components of the commonly available process water. Alkaline earth metal ions and heavy metal ions can also be introduced as impurities in the natural vegetable fibers to be bleached. When deionized water is used, both the calcium to be complexed and the magnesium desired as a co-stabilizer are missing, while the constituents introduced by impurities in the natural vegetable fibers must still be taken into account.
- the amount of gluconic acid, nitrilotriacetic acid and, if citric acid is used, citric acid can therefore be worked in the lower part of the stated quantity range, while the missing magnesium is compensated for by working in the upper part of the specified quantity range.
- bleach regulator compositions according to the invention are able to cover the entire described field of application.
- the phosphonates used earlier or still today and considered to be irreplaceable are not biodegradable and pollute the waste water.
- the EDTA which is also not degradable, also pollutes the water due to the risk of remobilization of the heavy metal ions.
- a typical bleach regulator composition is obtained by combining 28% by weight of an aqueous sodium gluconate solution (60%), 5% by weight of nitrilotriacetic acid trisodium salt, 8% by weight of citric acid monohydrate and 2% by weight of magnesium oxide and 6% by weight 50% sodium hydroxide solution. The rest (51% by weight) is demineralized water. The composition had a pH of 7.5.
- Typical bleaching liquors consist of
- composition of a regulator according to the invention is:
- the composition has a pH of 7.5.
- Another bleach regulator composition is obtained from 80 parts by weight of citric acid monohydrate 20 parts by weight of MgO 280 parts by weight of Naglusol (gluconic acid / Na gluconate, 60%) 50 parts by weight of nitrilotriacetic acid Na3 salt 106 parts by weight of sodium hydroxide solution (50%) 464 parts by weight of demineralized water.
- the composition has a pH of 11.2.
Abstract
Description
Die Erfindung betrifft Bleichregulator(Stabilisator)-Zuammensetzungen für die Bleiche mit H₂O₂ mit einem Gehalt an Gluconsäure, Nitrilotriessigsäure und Magnesium in ionischer Form, zu denen weiterhin ein Gehalt an Zitronensäure treten kann. Solche Bleichregulatoren werden in wäßriger, alkalisch eingestellter Lösung eingesetzt.The invention relates to bleach regulator (stabilizer) compositions for bleaching with H₂O₂ containing gluconic acid, nitrilotriacetic acid and magnesium in ionic form, to which a content of citric acid can also occur. Such bleach regulators are used in aqueous, alkaline solution.
Natürliche pflanzliche Fasern, wie Baumwolle, Sisal, Jute u.a. enthalten in roher Form Wachse, Fette und andere Pflanzenbestandteile, die eine gelblich-braune Färbung der Faser verursachen. Dadurch sind nicht alle gewünschten Einfärbungen möglich; Einfärbungen fallen zudem unegal aus. Zur Entfernung der unerwünschten nicht-faserigen Bestandteile und zum Zerstören der die gelblich-braune Färbung hervorrufenden Stoffe wird daher eine Behandlung dieser Fasern vorgenommen, in der Bleichen und Waschen kombiniert sind. Eine solche Behandlung kann angewandt werden auf die Fasern der genannten Herkunft, auf daraus hergestellte Garne und auf Gewebe, Gewirke oder Vliese solcher Fasern. Diese Behandlung kann weiterhin angewandt werden auf Gemische solcher Fasern mit synthetischen Fasern und daraus hergestellte Erzeugnisse.Natural vegetable fibers, such as cotton, sisal, jute, etc. contain raw waxes, fats and other plant components that cause a yellowish-brown coloring of the fibers. This means that not all of the desired colors are possible; Colorings are also uneven. In order to remove the undesirable non-fibrous components and to destroy the substances which give rise to the yellowish-brown color, a treatment of these fibers is therefore carried out in which bleaching and washing are combined. Such a treatment can be applied to the fibers of the named origin, to yarns made therefrom and to Woven, knitted or non-woven of such fibers. This treatment can also be applied to mixtures of such fibers with synthetic fibers and products made therefrom.
Für die Durchführung der genannten kombinierten Behandlung werden sogenannte Bleichflotten eingesetzt, die Wasser, Wasserstoffperoxid, Netz-/Wasch- und Emulgiermittel, Alkali zur pH-Einstellung und H₂O₂-Regulatoren (Stabilisatoren) enthalten. Als Regulatoren wurden lange Zeit beispielsweise Na-Silikat und anorganische Phosphate eingesetzt. Wegen der Überdüngung der Abwässer wurden später die anorganischen Phosphate durch (Poly)-Phosphonate ersetzt. Diese Phosphonate sind jedoch schwer oder gar nicht abbaubar und belasten somit in einer anderen Weise erneut die Abwässer. Auch die biologisch nicht abbaubare Ethylendiamin-tetraessigsäure (EDTA), die zudem vom Klärschlamm nicht absorbiert wird, ist bedenklich in ihrem Einsatz als H₂O₂-Regulator. Bei EDTA ist zudem eine Remobilisierung von Schwermetallen nicht völlig ausgeschlossen.So-called bleaching liquors which contain water, hydrogen peroxide, wetting / washing and emulsifying agents, alkali for adjusting the pH and H 2 O 2 regulators (stabilizers) are used for carrying out the combined treatment mentioned. Na silicate and inorganic phosphates, for example, have long been used as regulators. Because of the over-fertilization of the waste water, the inorganic phosphates were later replaced by (poly) -phosphonates. However, these phosphonates are difficult or not at all degradable and thus pollute the waste water again in a different way. The biodegradable ethylenediamine tetraacetic acid (EDTA), which is also not absorbed by the sewage sludge, is questionable in its use as an H₂O₂ regulator. With EDTA, the remobilization of heavy metals is not completely excluded.
Es bestand daher der Wunsch, völlig phosphorfreie und EDTA-freie Bleichregulatoren (Stabilisatoren) zur Verfügung zu stellen. Die Entwicklung zeigte jedoch bisher, daß es nicht möglich zu sein schien, auf Phosphate oder Phosphonate oder EDTA in solchen Regulatoren zu verzichten.There was therefore a desire to provide completely phosphorus-free and EDTA-free bleach regulators (stabilizers). However, the development so far has shown that it did not seem possible to dispense with phosphates or phosphonates or EDTA in such regulators.
Es wurden nun Bleichregulator-Zusammensetzungen, die in wäßriger, alkalisch eingestellter Lösung eingesetzt werden, gefunden, die in wasser- und alkalifreier Form aus
- a) 0,1 bis 20 Gew.-Teilen Magnesium-Ionen, gerechnet als MgO,
- b) 3 bis 200 Gew.-Teilen Gluconsäure, gerechnet als freie Säure,
- c) 3 bis 25 Gew.-Teilen Nitrilotriessigsäure, gerechnet als freie Säure, und
- d) 0 bis 40 Gew.-Teilen Zitronensäure, gerechnet als Zitronensäure-monohydrat,
- a) 0.1 to 20 parts by weight of magnesium ions, calculated as MgO,
- b) 3 to 200 parts by weight of gluconic acid, calculated as free acid,
- c) 3 to 25 parts by weight of nitrilotriacetic acid, calculated as free acid, and
- d) 0 to 40 parts by weight of citric acid, calculated as citric acid monohydrate,
In bevorzugter Weise liegt der Bestandteil a) in einer Menge von 0,1 bis 10 Gew.-Teilen, besonders bevorzugt 0,1 bis 8 Gew.-Teilen vor.Ingredient a) is preferably present in an amount of 0.1 to 10 parts by weight, particularly preferably 0.1 to 8 parts by weight.
In weiterhin bevorzugter Weise liegt der Bestandteil b) in einer Menge von 10 bis 150 Gew.-Teilen, besonders bevorzugt 15 bis 120 Gew.-Teilen vor.In a further preferred manner, component b) is present in an amount of 10 to 150 parts by weight, particularly preferably 15 to 120 parts by weight.
In weiterhin bevorzugter Weise liegt der Bestandteil c) in einer Menge von 4 bis 12 Gew.-Teilen, besonders bevorzugt 4 bis 8 Gew.-Teilen vor.In a further preferred manner, component c) is present in an amount of 4 to 12 parts by weight, particularly preferably 4 to 8 parts by weight.
In weiterhin bevorzugter Weise liegt der Bestandteil d) in einer Menge von 4 bis 30 Gew.-Teilen, besonders bevorzugt 5 bis 25 Gew.-Teilen vor.In a further preferred manner, component d) is present in an amount of 4 to 30 parts by weight, particularly preferably 5 to 25 parts by weight.
Die erfindungsgemäßen Bleichregulator-Zusammensetzungen werden in wäßriger, alkalisch eingestellter Lösung eingesetzt. Hierbei liegen die Bestandteile a), b), c) und d) zusammen in einer Menge von 10 bis 60 Gew.-%, bevorzugt 25 bis 40 Gew.-%, bezogen auf die gesamte wäßrige, alkalisch eingestellte Lösung, vor. Zur alkalischen Einstellung wird ein Alkalihydroxid bis zur Erreichung eines pH-Wertes von 7,5 bis 14 zugesetzt. Ein solch weiter pH-Bereich bis zu einer stark alkalischen Einstellung ist grundsätzlich möglich, weil in der Bleichflotte, der die erfindungsgemäßen Bleichregulator-Zusammensetzungen zugesetzt werden, ohnehin Alkali zugesetzt werden muß. Zur Erhöhung der Lagerstabilität der erfindungsgemäßen Bleichregulator-Zusammensetzungen allein hat sich jedoch ein niedrigerer pH-Wert als günstiger erwiesen. Daher wird in bevorzugter Weise ein pH-Wert von 7,5 bis 12,5, besonders bevorzugt 7,5 bis 12 vorgenommen.The bleach regulator compositions according to the invention are used in aqueous, alkaline solution. The components a), b), c) and d) are present together in an amount of 10 to 60% by weight, preferably 25 to 40% by weight, based on the total aqueous, alkaline solution. For alkaline adjustment, an alkali hydroxide is added until a pH of 7.5 to 14 is reached. Such a wide pH range up to a strongly alkaline setting is fundamentally possible because alkali must be added to the bleaching liquor to which the bleaching regulator compositions according to the invention are added. To increase the storage stability of the bleach regulator compositions according to the invention alone, however, a lower pH has proven to be more favorable. A pH of 7.5 to 12.5, particularly preferably 7.5 to 12, is therefore preferably carried out.
Als Alkalihydroxid ist aus Preisgründen das Natriumhydroxid bevorzugt, wenngleich grundsätzlich auch KOH oder LiOH möglich sind; es kann sowohl in fester Form als auch in der gut handhabbaren wäßrigen Lösung mit beispielsweise 10 bis 60 Gew.-% eingesetzt werden.For reasons of price, sodium hydroxide is preferred as the alkali hydroxide, although in principle KOH or LiOH are also possible; it can be used both in solid form and in the easy-to-handle aqueous solution with, for example, 10 to 60% by weight.
Die Erfindung betrifft weiterhin ein Verfahren zum Bleichen von natürlichen pflanzlichen Fasern oder ihren Gemischen mit synthetischen Fasern oder von Garnen, Geweben, Gewirken oder Vliesen aus solchen Fasern oder ihren Gemischen in Bleichflotten, die Wasser, Alkali, Wasserstoffperoxid, Netz-, Wasch- und Emulgiermittel sowie Bleichregulatoren enthalten, das dadurch gekennzeichnet ist, daß als Bleichregulatoren Zusammensetzungen der oben beschriebenen Art eingesetzt werden.The invention further relates to a method for bleaching natural vegetable fibers or their mixtures with synthetic fibers or of yarns, fabrics, knitted fabrics or nonwovens made from such fibers or their mixtures in bleaching liquors, the water, alkali, hydrogen peroxide, wetting, washing and emulsifying agents as well as bleach regulators, which is characterized in that compositions of the type described above are used as bleach regulators.
Das erfindungsgemäße Verfahren kann in einer Reihe verschiedener Ausführungsformen durchgeführt werden, die alle dem Fachmann als Stand der Technik geläufig sind: Bleichen in langer Flotte (Diskontinue oder Kontinue); Klotz-Kaltverweil-Verfahren (KKV); Pad Steam-Verfahren; Pad Roll-Verfahren und andere.The process according to the invention can be carried out in a number of different embodiments, all of which are known to the person skilled in the art as prior art: bleaching in a long liquor (discontinuous or continuous); Block Cold Dwell Process (KKV); Pad steam process; Pad roll process and others.
Natürliche pflanzliche Fasern, beispielsweise Baumwolle, Jute, Leinen oder Regenerat-Cellulose, sowie tierische Fasern, wie Seide und Wolle, sowie deren Mischungen mit Synthetics können erfindungsgemäß gebleicht werden. Bevorzugt seien pflanzliche Fasern, besonders bevorzugt Baumwolle und deren Mischungen genannt.Natural vegetable fibers, for example cotton, jute, linen or regenerated cellulose, as well as animal fibers, such as silk and wool, and their mixtures with synthetics can be bleached according to the invention. Vegetable fibers are preferred, particularly preferably cotton and mixtures thereof.
In den im erfindungsgemäßen Verfahren einzusetzenden Bleichflotten wird neben Wasser, Alkalihydroxid, Netz-, Wasch- und Emulgiermitteln und Wasserstoffperoxid eine erfindungsgemäße Bleichregulator-Zusammensetzung eingesetzt. Hierbei liegt Wasserstoffperoxid je nach Verfahren in einer Menge von 0,5-100 ml/l vor. Das Alkalihydroxid wird in einer Menge zugesetzt und nachgesetzt, daß ein pH-Wert von 7,5 bis 14 in der Bleichflotte aufrechterhalten wird. Netz-, Wasch-und Emulgiermittel sind solche, die dem auf diesem Gebiet tätigen Fachmann bekannt sind. Es handelt sich hierbei um Einzelstoffe oder Gemische aus den bekannten anionischen, kationischen oder nicht-ionischen Tensiden; bevorzugt handelt es sich um anionische oder nicht-ionische Tenside, wie Fettsäuren und deren Salze, Fettsäurealkylester, Fettalkohole, Fettalkohol-polyglykolether, Glyzerine, Alkylaromat-sulfonsäuren u.a.In the bleaching liquors to be used in the process according to the invention, in addition to water, alkali hydroxide, wetting agents, detergents and emulsifiers and hydrogen peroxide, a bleach regulator composition according to the invention is used. Depending on the process, hydrogen peroxide is present in an amount of 0.5-100 ml / l. The alkali metal hydroxide is added in an amount and added so that a pH of 7.5 to 14 is maintained in the bleaching liquor becomes. Wetting, washing and emulsifying agents are those which are known to the person skilled in the art in this field. These are individual substances or mixtures of the known anionic, cationic or non-ionic surfactants; it is preferably anionic or nonionic surfactants, such as fatty acids and their salts, fatty acid alkyl esters, fatty alcohols, fatty alcohol polyglycol ethers, glycerols, alkyl aromatic sulfonic acids and others
In einer dem Fachmann bekannten Weise werden diese Tenside so gewählt und zusammengestellt, daß die unerwünschten Begleitstoffe der natürlichen pflanzlichen Fasern, wie Fette, Wachse und andere Pflanzenbestandteile (z.B. Reste von Samenkapseln u.a.) entfernt werden. Als Wasser kann vollentsalztes Wasser oder ein in üblicher Weise bereitgestelltes Brauchwasser, das je nach Vorkommen einen unterschiedlichen Härtegrad hat, eingesetzt werden.In a manner known to the person skilled in the art, these surfactants are selected and put together in such a way that the undesirable accompanying substances of the natural vegetable fibers, such as fats, waxes and other plant components (e.g. residues of seed capsules etc.) are removed. Demineralized water or a customary made-up water, which has a different degree of hardness depending on the occurrence, can be used as water.
Die Bleichregulator-Zusammensetzungen dienen als Stabilisatoren für das Wasserstoffperoxid. Dabei wird die Abgabe des Sauerstoffs zum Bleichen der Fasern reguliert. Gluconsäure, Nitrilotriessigsäure und gegebenenfalls Zitronensäure dienen der Komplexierung und "Maskierung" von Erdalkalimetallen, insbesondere der störenden Ca-Ionen und von Schwermetallen.The bleach regulator compositions serve as stabilizers for the hydrogen peroxide. It regulates the release of oxygen to bleach the fibers. Gluconic acid, nitrilotriacetic acid and optionally citric acid are used for the complexation and "masking" of alkaline earth metals, in particular the troublesome Ca ions and heavy metals.
Grundsätzlich ist die komplexierende Wirkung des Gemisches aus Gluconsäure und Nitrilotriessigsäure ausreichend, In vielen Fallen ist es jedoch günstig und stellt daher eine vorteilhafte Variante der erfindungsgemäßen Bleichregulator-Zusammensetzungen dar, daß zusätzlich Zitronensäure eingesetzt wird, Gluconsäure und Nitrilotriessigsäure können sowohl als freie Säure als auch als Alkalisalz (bevorzugt als Natriumsalz) eingesetzt werden, Auch Zitronensäure, sofern sie zum Einsatz kommt, kann als Alkalimetallsalz oder als freie Säure eingesetzt werden. In bevorzugter Form wird die Zitronensäure als das technisch verfügbare Zitronensäuremonohydrat eingesetzt.Basically, the complexing effect of the mixture of gluconic acid and nitrilotriacetic acid is sufficient. In many cases, however, it is cheap and therefore represents an advantageous variant of the bleaching regulator compositions according to the invention that citric acid is additionally used; gluconic acid and nitrilotriacetic acid can be used both as free acid and Alkali salt (preferably as sodium salt) can be used. Citric acid, if it is used, can also be used as alkali metal salt or as free acid. In a preferred form, citric acid is used as the technically available citric acid monohydrate.
Magnesiumionen und Calciumionen als Beispiel für Erdalkaliionen sowie Eisen als Beispiel für Schwermetallionen, die komplexiert werden sollen, sind natürliche Bestandteile des üblicherweise verfügbaren Brauchwassers. Erdalkaliionen und Schwermetallionen können ferner als Verunreinigungen der zu bleichenden natürlichen pflanzlichen Fasern eingebracht werden. Beim Einsatz von vollentsalztem Wasser fehlt sowohl das zu komplexierende Calcium als auch das als Co-Stabilisator gewünschte Magnesium, während die durch Verunreinigungen der natürlichen pflanzlichen Fasern eingeschleppten Bestandteile weiterhin zu berücksichtigen sind. Bei Verwendung von vollentsalztem Wasser kann man daher bei der Menge an Gluconsäure, Nitrilotriessigsäure und, falls Zitronensäure eingesetzt wird, an Zitronensäure im unteren Teil der angegebenen Mengenbereiche arbeiten, während das fehlende Magnesium dadurch ausgeglichen wird, daß man im oberen Teil des angegebenen Mengenbereiches arbeitet.Magnesium ions and calcium ions as an example of alkaline earth ions and iron as an example of heavy metal ions that are to be complexed are natural components of the commonly available process water. Alkaline earth metal ions and heavy metal ions can also be introduced as impurities in the natural vegetable fibers to be bleached. When deionized water is used, both the calcium to be complexed and the magnesium desired as a co-stabilizer are missing, while the constituents introduced by impurities in the natural vegetable fibers must still be taken into account. When deionized water is used, the amount of gluconic acid, nitrilotriacetic acid and, if citric acid is used, citric acid can therefore be worked in the lower part of the stated quantity range, while the missing magnesium is compensated for by working in the upper part of the specified quantity range.
Diese Abhängigkeiten unter Berücksichtigung des zur Verfügung stehenden Wassers und der Qualität der zu bleichenden Faser sind dem Fachmann bekannt. Die erfindungsgemäßen Bleichregulator-Zusammensetzungen sind in der Lage, den gesamten beschriebenen Anwendungsbereich zu überdecken.These dependencies, taking into account the available water and the quality of the fiber to be bleached, are known to the person skilled in the art. The bleach regulator compositions according to the invention are able to cover the entire described field of application.
Die Herstellung der erfindungsgemäßen Bleichregulator-Zusammensetzungen geschieht durch einfaches Zusammengeben, beispielsweise in folgender Reihenfolge bei folgender typischer Zusammensetzung:
- 1. 200 Gew.-Teile entsalztes H₂O werden vorgelegt;
- 2. 80 Gew.-Teile Zitronensäure-Monohydrat werden gelöst;
- 3. 20 Gew.-Teile MgO werden gelöst;
- 4. 280 Gew.-Teile Gluconsäure/Na-Gluconat (60 %ig) werden gelöst;
- 5. 50 Gew.-Teile Nitrilotriessigsäure-trinatriumsalz werden gelöst;
- 6. 106 Gew.-Teile NaOH (50 %ig) werden zugesetzt (pH-Wert bei 8,5-9) und
- 7. 264 Gew.-Teile entsalztes Wasser werden als Rest zu 1000 Gew.-Teilen zugesetzt.
- 1. 200 parts by weight of desalted H₂O are presented;
- 2. 80 parts by weight of citric acid monohydrate are dissolved;
- 3. 20 parts by weight of MgO are dissolved;
- 4. 280 parts by weight of gluconic acid / Na gluconate (60%) are dissolved;
- 5. 50 parts by weight of trisodium nitrilotriacetic acid salt are dissolved;
- 6. 106 parts by weight of NaOH (50%) are added (pH at 8.5-9) and
- 7. 264 parts by weight of demineralized water are added to 1000 parts by weight of the remainder.
Um einwandfrei färbbare Materialien zu erzielen, ist es meist erforderlich, über das Bleichen hinaus noch weitere Behandlungsstufen vor- bzw. nachzuschalten:
- Sengen, Abbrennen der abstehenden Faserenden, um eine glatte Oberfläche zu erzielen. Dies ist üblicherweise der 1. Arbeitsgang.
- Abkochen, Beuchen, d.h. heiße Alkalibehandlung mit dem Ziel einer Vor-Extraktion der Faserbegleitsubstanzen bzw. Aufquellung der Fasern und der Samenschalen der Baumwolle. Dies wird meist vor dem Bleichen durchgeführt.
- Laugieren, Merzerisieren, Behandlung mit hoch konzentrierten Alkali mehr oder weniger unter Spannung des Materiales zur Erzielung einer starken Faserquellung und damit Glanz sowie Eliminierung der unreifen bzw. toten Baumwollanteile, welche sich nicht oder schlecht anfärben lassen. Dies kann vor oder nach dem Bleichen durchgeführt werden.
- Säure-Extraktion, wird vor dem Bleichen durchgeführt, wenn extrem hohe Mengen an Schwermetallen vorliegen (Brauchwasser und/oder Fasersubstrat). Die Komplexbildner des Bleichregulators wären überfordert.
- Ferner kommen zur Erzielung sehr hoher Weißgrade auch weitere Bleichverfahren vor oder nach der Wasserstoffperoxid-Bleiche zur Anwendung. z.B.
- Natriumhypochlorit-Bleiche
- Natriumchlorit-Bleiche
- reduktive Bleiche
- Singe, burn off the protruding fiber ends to achieve a smooth surface. This is usually the first step.
- Boil, boil, ie hot alkali treatment with the aim of pre-extraction of the accompanying fibers or swelling of the fibers and the seed shells of the cotton. This is usually done before bleaching.
- Leaching, mercerizing, treatment with highly concentrated alkali more or less under tension of the material to achieve a strong fiber swelling and thus shine as well as elimination of the immature or dead cotton parts, which are difficult or impossible to dye. This can be done before or after bleaching.
- Acid extraction, is carried out before bleaching when there are extremely high amounts of heavy metals (process water and / or fiber substrate). The complexing agents of the bleach regulator would be overwhelmed.
- Furthermore, other bleaching methods are used before or after hydrogen peroxide bleaching to achieve very high whiteness levels. e.g.
- Sodium hypochlorite bleach
- Sodium chlorite bleach
- reductive bleaching
Bei Verwendung von Wasserglas (Natriumsilikat) als Stabilisator treten besonders in Verbindung mit Ca-Salzen unlösliche Ca-Silikat-Ablagerungen auf Maschine und Material auf, dies trifft bei Verwendung des beschriebenen, erfindungsgemäßen Regulators nicht zu.When using water glass (sodium silicate) as a stabilizer, insoluble calcium silicate deposits occur on the machine and material, especially in connection with calcium salts; this does not apply when the regulator according to the invention described is used.
Die früher bzw. noch heute verwendeten und als unersetzlich geltenden Phosphonate sind biologisch nicht abbaubar und belasten die Abwässer. Das ebenfalls nicht abbaubare EDTA belastet die Gewässer darüber hinaus noch wegen der Gefahr der Remobilisierung der Schwermetallionen.The phosphonates used earlier or still today and considered to be irreplaceable are not biodegradable and pollute the waste water. The EDTA, which is also not degradable, also pollutes the water due to the risk of remobilization of the heavy metal ions.
Eine typische Bleichregulator-Zusammensetzung erhält man durch Zusammengeben von 28 Gew.-% einer wäßrigen Natrium-gluconatlösung (60 %ig), 5 Gew.-% Nitrilotriessigsäure-trinatriumsalz, 8 Gew.-% Zitronensäure-monohydrat, 2 Gew.-% Magnesiumoxid und 6 Gew.-% 50 %iger Natronlauge. Der Rest (51 Gew.-%) ist voll entsalztes Wasser. Die Zusammensetzung hatte einen pH-Wert von 7,5.A typical bleach regulator composition is obtained by combining 28% by weight of an aqueous sodium gluconate solution (60%), 5% by weight of nitrilotriacetic acid trisodium salt, 8% by weight of citric acid monohydrate and 2% by weight of magnesium oxide and 6% by weight 50% sodium hydroxide solution. The rest (51% by weight) is demineralized water. The composition had a pH of 7.5.
Typische Bleichflotten bestehen aus
Eine weitere typische Variante einer Zusammensetzung eines erfindungsgemäßen Regulators ist:
Die Zusammensetzung hat einen pH-Wert von 7,5.The composition has a pH of 7.5.
Erfindungsgemäßer Bleichregulator ohne Zitronensäure
Mit Bleichflotten, welche keinen Regulator enthielten, wurden nach den o.g. Bedingungen gleiches Material gebleicht und im Vergleich zu o.g. Werten folgende Resultate gefunden:
In Kochversuchen mit einer typischen Bleichrezeptur am Rückflußkühler unter Belastung der Bleichflotte mit Eisensalz (Fe⁺⁺⁺Sulfat 1:1000) wurde die Wirksamkeit des erfindungsgemäßen Regulators demonstriert:The effectiveness of the regulator according to the invention was demonstrated in cooking tests with a typical bleaching formulation on a reflux condenser while the bleaching liquor was loaded with iron salt (Fe⁺⁺⁺Sulfate 1: 1000):
200 ml einer Bleichflotte mit folgender Zusammensetzung wurden 30 min am Rückflußkühler gekocht und die Gehalte an Wasserstoffperoxid nach 15 und 30 min. ermittelt (Versuch a mit erfindungsgemäßem Regulator; Versuch b ohne Regulator).
Eine weitere Bleichregulator-Zusammensetzung erhält man aus
80 Gew.-Teilen Citronensäure-Monohydrat
20 Gew.-Teilen MgO
280 Gew.-Teilen Naglusol (Gluconsäure/Na-gluconat, 60 %)
50 Gew.-Teilen Nitrilotriessigsäure-Na₃-salz
106 Gew.-Teilen Natronlauge (50 %)
464 Gew.-Teilen entsalztes Wasser.Another bleach regulator composition is obtained from
80 parts by weight of citric acid monohydrate
20 parts by weight of MgO
280 parts by weight of Naglusol (gluconic acid / Na gluconate, 60%)
50 parts by weight of nitrilotriacetic acid Na₃ salt
106 parts by weight of sodium hydroxide solution (50%)
464 parts by weight of demineralized water.
Die Zusammensetzung hat einen pH-Wert von 11,2.The composition has a pH of 11.2.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4203797A DE4203797A1 (en) | 1992-02-10 | 1992-02-10 | BLEACH REGULATOR COMPOSITIONS AND BLEACHING METHOD THEREFOR |
| DE4203797 | 1992-02-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0557730A1 true EP0557730A1 (en) | 1993-09-01 |
| EP0557730B1 EP0557730B1 (en) | 1997-07-16 |
Family
ID=6451317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93101290A Expired - Lifetime EP0557730B1 (en) | 1992-02-10 | 1993-01-28 | Bleach regulating compositions and bleaching process therefrom |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5510055A (en) |
| EP (1) | EP0557730B1 (en) |
| JP (1) | JPH061998A (en) |
| CA (1) | CA2088952A1 (en) |
| DE (2) | DE4203797A1 (en) |
| ZA (1) | ZA93886B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0628655A1 (en) * | 1993-06-11 | 1994-12-14 | Ciba-Geigy Ag | Bleaching aids |
| WO1996005354A1 (en) * | 1994-08-10 | 1996-02-22 | Woellner-Silikat Gmbh | Concentrate of stabilisers for aqueous bleaching and treating solutions based on hydrogen peroxide and/or other inorganic and/or organic peroxo compounds |
| US5646271A (en) * | 1993-06-11 | 1997-07-08 | Ciba-Geigy Corporation | Bleaching auxiliary |
| EP0940495A1 (en) * | 1998-03-05 | 1999-09-08 | Bayer Aktiengesellschaft | Simultaneous washing and bleaching of natural fibres and textiles containing the same |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4344029A1 (en) * | 1993-12-23 | 1995-06-29 | Grillo Werke Ag | Copolymers of unsaturated carboxylic acids, process for their preparation and their use |
| DE19810885A1 (en) * | 1998-03-13 | 1999-10-07 | Henkel Kgaa | Process for the gentle bleaching of textile fabrics |
| SI2029800T1 (en) | 2006-06-08 | 2013-07-31 | National Research Council Of Canada | Extraction of hemp fibers |
| AU2009337704B2 (en) | 2009-01-13 | 2014-02-20 | National Research Council Of Canada | Enzymatic preparation of plant fibers |
| JP2014037476A (en) * | 2012-08-14 | 2014-02-27 | Kinboshi Inc | Detergent composition |
| EP3409265A1 (en) * | 2017-05-29 | 2018-12-05 | Basf Se | Method for the preparation of brightly coloured disalt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2927082A (en) * | 1956-01-19 | 1960-03-01 | Du Pont | Peroxide bleaching compositions and their use |
| US3345303A (en) * | 1964-12-08 | 1967-10-03 | Shell Oil Co | Bleaching composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3766078A (en) * | 1971-06-03 | 1973-10-16 | Monsanto Co | Processes for stabilizing peroxy solutions |
| BE795085A (en) * | 1972-03-10 | 1973-05-29 | Benckiser Knapsack Gmbh | PROCESS FOR BLEACHING CELLULOSIC FIBERS SINGLE OR IN MIXTURE WITH SYNTHETIC FIBERS |
| FR2323631A1 (en) * | 1975-09-15 | 1977-04-08 | Ugine Kuhlmann | MIXED STAFF STABLE IN LIXIVIEL MIXTURE |
| DE3545909A1 (en) * | 1985-12-23 | 1987-06-25 | Henkel Kgaa | SILICATE- AND MAGNESIUM-FREE ACTIVE SUBSTANCE MIXTURES |
| DE4208106B4 (en) * | 1991-03-20 | 2006-10-05 | Clariant Finance (Bvi) Ltd. | Pretreatment of textile fiber material |
| US5362412A (en) * | 1991-04-17 | 1994-11-08 | Hampshire Chemical Corp. | Biodegradable bleach stabilizers for detergents |
-
1992
- 1992-02-10 DE DE4203797A patent/DE4203797A1/en not_active Withdrawn
-
1993
- 1993-01-28 DE DE59306905T patent/DE59306905D1/en not_active Expired - Fee Related
- 1993-01-28 EP EP93101290A patent/EP0557730B1/en not_active Expired - Lifetime
- 1993-02-05 CA CA002088952A patent/CA2088952A1/en not_active Abandoned
- 1993-02-05 JP JP5040743A patent/JPH061998A/en active Pending
- 1993-02-09 ZA ZA93886A patent/ZA93886B/en unknown
-
1995
- 1995-02-17 US US08/391,376 patent/US5510055A/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2927082A (en) * | 1956-01-19 | 1960-03-01 | Du Pont | Peroxide bleaching compositions and their use |
| US3345303A (en) * | 1964-12-08 | 1967-10-03 | Shell Oil Co | Bleaching composition |
Non-Patent Citations (2)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 78, no. 12, 26. März 1973, Columbus, Ohio, US; abstract no. 73587, KAKINUMA, KAZUMI ET AL. 'Bleaching of cellulose fiber textiles with hydrogen peroxide and hydroxycarboxylic acid' * |
| CHEMICAL ABSTRACTS, vol. 84, no. 18, 3. Mai 1976, Columbus, Ohio, US; abstract no. 123349, YOTSUYA, MINORU ET AL. 'Bleaching of textiles' * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0628655A1 (en) * | 1993-06-11 | 1994-12-14 | Ciba-Geigy Ag | Bleaching aids |
| US5646271A (en) * | 1993-06-11 | 1997-07-08 | Ciba-Geigy Corporation | Bleaching auxiliary |
| US5670082A (en) * | 1993-06-11 | 1997-09-23 | Ciba-Geigy Corporation | Bleaching auxiliary |
| WO1996005354A1 (en) * | 1994-08-10 | 1996-02-22 | Woellner-Silikat Gmbh | Concentrate of stabilisers for aqueous bleaching and treating solutions based on hydrogen peroxide and/or other inorganic and/or organic peroxo compounds |
| EP0940495A1 (en) * | 1998-03-05 | 1999-09-08 | Bayer Aktiengesellschaft | Simultaneous washing and bleaching of natural fibres and textiles containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2088952A1 (en) | 1993-08-11 |
| DE59306905D1 (en) | 1997-08-21 |
| EP0557730B1 (en) | 1997-07-16 |
| US5510055A (en) | 1996-04-23 |
| DE4203797A1 (en) | 1993-08-12 |
| JPH061998A (en) | 1994-01-11 |
| ZA93886B (en) | 1993-09-23 |
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