EP0382138B1 - Auxiliary mixture and its use in dyeing synthetic fibrous materials - Google Patents
Auxiliary mixture and its use in dyeing synthetic fibrous materials Download PDFInfo
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- EP0382138B1 EP0382138B1 EP90102212A EP90102212A EP0382138B1 EP 0382138 B1 EP0382138 B1 EP 0382138B1 EP 90102212 A EP90102212 A EP 90102212A EP 90102212 A EP90102212 A EP 90102212A EP 0382138 B1 EP0382138 B1 EP 0382138B1
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
- D06P1/613—Polyethers without nitrogen
- D06P1/6131—Addition products of hydroxyl groups-containing compounds with oxiranes
- D06P1/6133—Addition products of hydroxyl groups-containing compounds with oxiranes from araliphatic or aliphatic alcohols
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
- D06P1/613—Polyethers without nitrogen
- D06P1/6131—Addition products of hydroxyl groups-containing compounds with oxiranes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
- D06P1/613—Polyethers without nitrogen
- D06P1/6131—Addition products of hydroxyl groups-containing compounds with oxiranes
- D06P1/6135—Addition products of hydroxyl groups-containing compounds with oxiranes from aromatic alcohols or from phenols, naphthols
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/54—Polyesters using dispersed dyestuffs
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/922—Polyester fiber
Definitions
- the present invention relates to a new combination of auxiliaries and their use as dyeing auxiliaries in the dyeing of synthetic fibers, in particular polyester fibers.
- the new dyeing aid not only ensures the penetration of the dye into the material, but also serves to promote the migration of the dyes, thereby improving the levelness and increasing the color yield.
- the dyeing aid according to the invention advantageously contains 10 to 50 percent by weight of component (A), 10 to 40 percent by weight of component (B) and 10 to 70 percent by weight of component (C). Not only component (C) but both component (A) and component (B) can be present as a single compound or in the form of a mixture.
- substituent Y in formula (1) represents an alkyl group, it can be straight-chain or branched.
- alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, isononyl or n-dodecyl.
- Aryl conveniently means phenyl.
- the phenyl radical can be substituted once or twice by halogen, lower alkyl or lower alkoxy.
- Lower alkyl and lower alkoxy in the definition of the radicals of the compounds of the formula (1) are those groups or group components which have 1 to 5, in particular 1 to 3, carbon atoms.
- Examples of such groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl or methoxy, ethoxy, isopropoxy, isobutoxy or tert-butoxy.
- Halogen means for example fluorine, bromine or preferably chlorine.
- Y in the meaning of aralkyl advantageously has a total of 7 to 9 carbon atoms and generally stands for benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, ⁇ -phenethyl, ⁇ -tolylethyl or phenisopropyl.
- the substituent Y is preferably C4-C10 alkyl or especially ⁇ -methylbenzyl. are preferred of the ethylene glycol, propylene ethylene glycol or ethylene propylene glycol type; the former is particularly preferred. n is preferably 4 to 40.
- the acid residue X is derived, for example, from low molecular weight dicarboxylic acids, such as of maleic acid, succinic acid or sulfosuccinic acid, and is connected to the alkyleneoxy part of the molecule via an ester bridge.
- X is derived from inorganic polybasic acids, such as sulfuric acid or orthophosphoric acid.
- the acid residue X can be in the form of a free acid or in salt form, i.e. e.g. as an alkali metal, ammonium or amine salt.
- alkali metal, ammonium or amine salts are lithium, sodium, potassium, ammonium, trimethylamine, diethylamine, ethanolamine, diethanolamine or triethanolamine salts.
- Alkali metal salts or triethanolamine salts are preferred.
- the mono- or diethanolamine salts can be etherified further with 1 to 4 oxethylene units.
- Preferred acid esters of component (A) correspond to the formula wherein Y1 C4-C12-alkyl, phenyl, tolyl or preferably tolyl-C1-C3-alkyl or phenyl-C1-C3-alkyl, such as ⁇ -methyl or ⁇ , ⁇ -dimethylbenzyl, X1 is an acid residue which is derived from sulfuric acid or preferably o-phosphoric acid, and m are 1 to 3 and n1 4 to 40.
- acidic esters are preferably in the form of sodium, potassium, ammonium, diethylamine, triethylamine, diethanolamine or triethanolamine salts.
- the acid esters of the formula (1) or (2) which are suitable as components (A) are prepared by adding alkylene oxide (ethylene oxide or propylene oxide) to a phenol compound which is by definition substituted and the adduct with a polybasic oxygen acid or a functional derivative of this acid , such as Acid anhydrides, acid halides, acid esters or acid amides are converted into the acidic esters and, if appropriate, the acidic ester obtained into the abovementioned salts.
- these functional derivatives are phosphorus pentoxide, phosphorus oxytrichloride, chlorosulfonic acid or sulfamic acid. Both the alkylene oxide addition and the esterification can be carried out by known methods.
- Well-suited components (A) are acidic esters or their salts of a polyadduct of 4 to 40 moles of ethylene oxide with 1 mole of a phenol which has at least one C4-C12-alkyl group, a phenyl group, a tolyl group, an ⁇ -tolylethyl group, a benzyl group, a has ⁇ -methylbenzyl group or an ⁇ , ⁇ -dimethylbenzyl group, such as Butylphenol, Tributylphenol, Octylphenol, Nonylphenol, Dinonylphenol, o-Phenylphenol, Benzylphenol, Dibenzylphenol, ⁇ -Tolylethylphenol, Dibenzyl- (nonyl) -phenol, ⁇ -Methylbenzylphenol, Bis- ( ⁇ -Methylbenzyl) -phenol or Tris- ( ⁇ -methylbenzyl) ) -phenol, whereby these acidic esters can be used individually or
- the phosphoric acid esters are expediently present as mixtures of the corresponding salts of a mono- and diester.
- the styrene addition products are prepared in a known manner, preferably in the presence of catalysts, such as sulfuric acid or p-toluenesulfonic acid.
- catalysts such as sulfuric acid or p-toluenesulfonic acid.
- Suitable styrenes are advantageously styrene, ⁇ -methylstyrene or vinyltoluene (4-methylstyrene).
- examples of the phenols are phenol, cresols or xylenols.
- Acidic phosphoric acid esters (mono- and diesters) or sulfuric acid esters or their salts of oxyalkylation products of the formula are very particularly preferred wherein m is 1 to 3 and n2 is 12 to 30.
- the nonionic surfactant used as component (B) is advantageously an alkylene oxide addition product of 2 to 100 moles of alkylene oxide, e.g. Ethylene oxide and / or propylene oxide, on 1 mol of an aliphatic monoalcohol with at least 4 carbon atoms, a 3- to 6-valent aliphatic alcohol with preferably 3 to 6 carbon atoms, one optionally by C4-C12-alkyl, phenyl, ⁇ -tolylethyl, benzyl, ⁇ -methylbenzyl or ⁇ , ⁇ -dimethylbenzyl substituted phenol or a fatty acid with 8 to 22 carbon atoms.
- alkylene oxide addition product 2 to 100 moles of alkylene oxide, e.g. Ethylene oxide and / or propylene oxide, on 1 mol of an aliphatic monoalcohol with at least 4 carbon atoms, a 3- to 6-valent aliphatic alcohol with preferably 3 to 6 carbon atoms
- oxyalkylation products of the formula (3) derived from styrene addition products are particularly preferred as nonionic surfactants.
- the compounds of formula (4) can by reacting the adduct of the formula with a fatty acid W-COOH or by reacting an alcoholic or phenolic compound R-OH with a fatty acid ester of the formula getting produced.
- the compounds of the formula (5) are reaction products from addition products of the formula Formaldehyde or a formaldehyde-releasing compound, for example paraformaldehyde and a fatty acid ester of the formula and are partially described in Japanese Patent Application Laid-Open No. 83-18486. Compounds not mentioned there which fall under formula (5) can be prepared accordingly, the reaction conditions mentioned in the Japanese laid-open specification leading to the desired products of the formula (5).
- the compounds of formula (6) are prepared by adding styrene oxide to the polyethylene glycol ether of the formula attaches.
- the aliphatic or aromatic carboxylic acid esters used as component (C) can be mono- or dicarboxylic acid diesters which are prepared by esterifying aliphatic or aromatic mono- or dicarboxylic acids of 3 to 12 carbon atoms with aliphatic monoalcohols of 4 to 22 carbon atoms or araliphatic alcohols, especially benzyl alcohol will.
- C1-C12 alkyl esters of propionic acid lactic acid, butyric acid, hydroxybutyric acid, valeric acid, caproic acid, 2-ethylhexanoic acid, malonic acid, maleic acid, adipic acid, benzoic acid, 2-hydroxy- or 4-hydroxybenzoic acid or phthalic acid and especially benzoic acid-C8 -C12-alkyl esters or especially aryl benzoates.
- component (C) are:
- 2-ethylhexyl propionate n-octyl lactic acid, 2-ethylhexyl lactate, 2-ethylhexyl 2-ethylhexanoate, di-2-ethylhexyl maleate, di-2-ethylhexyl adipate, methyl benzoate, butyl benzoate, 2-benzoate ethylhexyl ester, benzoic acid decyl ester, benzoic acid dodecyl ester, benzoic acid phenyl ester, benzoic acid 2-methylphenyl ester, benzoic acid benzyl ester, benzoic acid phenoxyethyl ester or phthalic acid dimethyl ester.
- Benzyl benzoate is particularly preferred as component (C).
- the dyeing auxiliaries according to the invention can additionally contain, as component (D) in the form of a polar solvent, water and / or water-miscible organic solvents.
- a polar solvent water and / or water-miscible organic solvents.
- water-miscible organic solvents are aliphatic C1-C4 alcohols, e.g. Methanol, ethanol or the propanols; Ketones, e.g. Acetone, methyl ethyl ketone, cyclohexanone, diacetone alcohol, ethers such as e.g.
- auxiliary mixtures according to the invention advantageously contain, based in each case on the entire mixture, 10 to 40 percent by weight of component (A) 15 to 50 percent by weight of component (B) 20 to 70 percent by weight of component (C) 0 to 40 percent by weight of component (D).
- the new dyeing aid preparations can be prepared by simply stirring the components (A), (B), (C) and, if appropriate, (D), giving homogeneous mixtures which are notable for good transport and storage stability.
- the dyeing auxiliaries according to the invention are in particular very stable at higher temperatures up to 130 ° C. when used in dye baths.
- the dyeing aid according to the invention is used in the dyeing of synthetic fibers, in particular textile material containing polyester fibers.
- the dyeing process is carried out in the usual way.
- the dyeing aid according to the invention is slowly introduced into an aqueous bath with stirring, after which the liquor with the addition of the dye is provided for dyeing.
- the present invention accordingly also relates to a process for dyeing synthetic fiber material, in particular polyester fibers with disperse dyes.
- the process is characterized in that this material is colored in the presence of the auxiliary mixture according to the invention.
- the amounts used in which the auxiliary combination according to the invention is added to the dye baths range from 0.5 to 10%, preferably 1 to 5%, of the weight of the goods.
- fiber material in particular textile material that can be dyed in the presence of the new auxiliary mixture, e.g. Cellulose ester fibers, such as cellulose 2 1/2 acetate fibers and triacetate fibers and particularly linear polyester fibers, should be mentioned.
- Cellulose ester fibers such as cellulose 2 1/2 acetate fibers and triacetate fibers and particularly linear polyester fibers
- Linear polyester fibers are to be understood as synthetic fibers which e.g. can be obtained by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane, and also copolymers of terephthalic and isophthalic acid and ethylene glycol.
- the linear polyester used almost exclusively in the textile industry so far consists of terephthalic acid and ethylene glycol.
- the fiber materials can also be used as a mixed fabric with one another or with other fibers, for example mixtures of polyacrylonitrile / polyester, polyamide / polyester, polyester / cotton, polyester / viscose and polyester / wool.
- the textile material to be dyed can be in various stages of processing. Examples include: loose material, piece goods, such as knitted or woven fabrics, yarn in the form of a wrap or muff.
- the latter can have winding densities of 200 to 600 g / dm3, in particular 400 to 450 g / dm3.
- the disperse dyes to be used which are only sparingly soluble in water and are largely present in the dye liquor in the form of a fine dispersion, can belong to a wide variety of dye classes, for example the acridone, azo, anthraquinone, coumarin, methine, Perinone, naphthoquinoneimine, quinophthalone, styryl or nitro dyes.
- the amount of dyes to be added to the liquor depends on the desired color strength; In general, amounts of 0.01 to 10, preferably 0.05 to 5 percent by weight, based on the textile material used, have proven successful.
- the dye baths can contain, in addition to the dyes and the auxiliary mixture according to the invention, oligomer inhibitors, anti-foaming agents (e.g. silicone oils or ethylene bis fatty acid amides), wrinkle-free agents and preferably dispersants.
- oligomer inhibitors e.g. silicone oils or ethylene bis fatty acid amides
- wrinkle-free agents e.g. silicone oils or ethylene bis fatty acid amides
- dispersants e.g. silicone oils or ethylene bis fatty acid amides
- the dispersants are used primarily to achieve a good fine distribution of the disperse dyes.
- the dispersants generally used for dyeing with disperse dyes are suitable.
- the dispersants used are preferably sulfated or phosphated adducts of 15 to 100 moles of ethylene oxide or preferably propylene oxide with polyhydric aliphatic alcohols containing 2 to 6 carbon atoms, such as ethylene glycol, glycerol or pentaerythritol or with at least two amino groups or one amino group and one hydroxyl group with amines having 2 up to 9 carbon atoms and alkylsulfonates with 10 to 20 carbon atoms in the alkyl chain, alkylbenzenesulfonates with straight-chain or branched alkyl chain with 8 to 20 carbon atoms in the alkyl chain, such as, for example, nonyl or dodecylbenzenesulfonate, 1,3,5,7-tetramethyloctylbenzenesulfonate or octadecylbenzenesulfonate, and also alkylnaphthalenesulfonates
- Lignin sulfonates polyphosphates and preferably formaldehyde condensation products of aromatic sulfonic acids, formaldehyde and optionally mono- or bifunctional phenols, such as e.g. from cresol, ⁇ -naphtholsulfonic acid and formaldehyde, from benzenesulfonic acid, formaldehyde and naphthalenesulfonic acid, from naphthalenesulfonic acid and formaldehyde or from naphthalenesulfonic acid, dihydroxydiphenyl sulfone and formaldehyde.
- the disodium salt of di- or tri- (6-sulfonaphthyl-2-) methane is preferred.
- anionic dispersants can also be used.
- the anionic dispersants are normally in the form of their alkali metal salts, ammonium salts or amine salts. These dispersants are preferably used in an amount of 0.5 to 8 g / l of liquor.
- the dyebaths can also contain conventional additives, advantageously electrolytes such as salts, for example sodium sulfate, ammonium sulfate, sodium or ammonium phosphates or polyphosphates, metal chlorides or nitrates such as calcium chloride, magnesium chloride or calcium nitrates, ammonium acetate or sodium acetate and / or acids, for example mineral acids, such as sulfuric acid or phosphoric acid, or organic acids, suitably lower aliphatic carboxylic acids, such as formic, acetic, citric or oxalic acid.
- the acids serve primarily to adjust the pH of the liquors used according to the invention, which is generally 4 to 6.5, preferably 4.5 to 6.
- dyeing can also take place in the alkaline range. (pH 7 to 10)
- the dyeings are advantageously carried out from an aqueous liquor using the exhaust process.
- the liquor ratio can accordingly be chosen within a wide range, for example 1: 3 to 1: 100, preferably 1: 7 to 1:50.
- the temperature at which dyeing is carried out is at least 70 ° C and usually it is not higher than 140 ° C. It is preferably in the range from 80 to 135 ° C.
- Linear polyester fibers and cellulose triacetate fibers are preferably dyed by the so-called high-temperature process in closed and expediently also pressure-resistant apparatus at temperatures above 100 ° C., preferably between 110 and 135 ° C., and optionally under pressure.
- closed vessels for example, circulation apparatuses such as cross-wound or tree dyeing machines, reel runners, jet or drum dyeing machines, jet or muff dyeing machines, paddles or jiggers are suitable.
- Cellulose-2 1/2 acetate fibers are preferably dyed at temperatures of 80-85 ° C.
- the dyeing process can be carried out by either briefly treating the material to be dyed first with the auxiliary mixture and then dyeing it, or preferably treating it simultaneously with the auxiliary mixture and the dye.
- the material to be dyed is preferably allowed to run for 5-10 minutes at 40-80 ° C. in a bath which contains the dye, the auxiliary mixture and, if appropriate, further additives and is adjusted to a pH of 4.5 to 10, the temperature increases within 15 to 45 minutes to 110 to 135 ° C, preferably 125-130 ° C and the dye liquor 15 to 90 minutes, preferably 30 to 60 minutes, at this temperature.
- the dyeings are completed by cooling the dye liquor to 60 to 90 ° C., rinsing the dyeings with water and, if appropriate, cleaning in a customary manner in an alkaline medium under reductive conditions. The dyeings are then rinsed again and dried.
- parts mean parts by weight and percentages are percentages by weight.
- the liquor is then heated to 128 ° C. in the course of 40 minutes and the goods are dyed at this temperature for 60 minutes. During the heating phase, no increase in the differential pressure between inside and outside is found in the material block.
- the liquor is then cooled to 70 ° C. and the substrate is reductively cleaned, rinsed and dried as usual. A strong, level, orange coloration is obtained, which is distinguished by good coloring and good fastness properties.
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Abstract
Description
Die vorliegende Erfindung betrifft eine neue Hilfsmittelkombination und ihre Verwendung als Färbereihilfsmittel beim Färben von synthetischen Fasern, insbesondere Polyesterfasern.The present invention relates to a new combination of auxiliaries and their use as dyeing auxiliaries in the dyeing of synthetic fibers, in particular polyester fibers.
Das neue Färbereihilfsmittel sorgt nicht nur für das Eindringen des Farbstoffes in das Material, sondern es dient auch zur Förderung der Migration der Farbstoffe, wobei eine Verbesserung der Egalität und eine Steigerung der Farbausbeute erreicht wird.The new dyeing aid not only ensures the penetration of the dye into the material, but also serves to promote the migration of the dyes, thereby improving the levelness and increasing the color yield.
Es sind bereits aus der DE-A 2 941 763 Färbereihilfsmittel für das Färben von synthetischen Fasermaterialien bekannt, die Tetralin und/oder ein Alkylbenzol als Komponente (a), ein anionisches Tensid als Komponente (b) und ein nichtaromatisches und mit Wasser nicht mischbares Lösungsmittel als Komponente (c) aufweisen und gegebenenfalls noch ein polares Lösungsmittel und/oder ein nichtionogenes Tensid enthalten. Diese vermögen jedoch nicht alle anwendungstechnischen Anforderungen zu erfüllen.It is already known from DE-A 2 941 763 dyeing aids for dyeing synthetic fiber materials that contain tetralin and / or an alkylbenzene as component (a), an anionic surfactant as component (b) and a non-aromatic and water-immiscible solvent have as component (c) and optionally also contain a polar solvent and / or a nonionic surfactant. However, these are unable to meet all the application requirements.
Die erfindungsgemässe Hilfsmittelkombination ist dadurch gekennzeichnet, dass sie
- (A) einen sauren Ester oder dessen Salze eines Alkylenoxidadduktes der Formel
X den Säurerest einer anorganischen, Sauerstoff enthaltenden Säure oder den Rest einer organischen Säure und
Y C₁-C₁₂-Alkyl, Aryl oder Aralkyl bedeuten,
"Alkylen" für den Ethylenrest oder Propylenrest steht und
m 1 bis 3, m₁ 1 oder 2 und n 4 bis 50 sind, - (B) ein nichtionogenes, Polyglykolethergruppen aufweisendes Tensid und
- (C) einen aliphatischen oder aromatischen Carbonsäureester enthält, ausgenommen Färbereihilfsmittelgemische, die Alkylbenzol, Tetralin oder nichtaromatische, mit Wasser nicht mischbare Lösungsmittel aufweisen.
- (A) an acidic ester or its salts of an alkylene oxide adduct of the formula
X is the acid residue of an inorganic, oxygen-containing acid or the rest of an organic acid and
Y is C₁-C₁₂-alkyl, aryl or aralkyl,
"Alkylene" stands for the ethylene radical or propylene radical and
m are 1 to 3, m₁ 1 or 2 and n are 4 to 50, - (B) a nonionic surfactant containing polyglycol ether groups and
- (C) contains an aliphatic or aromatic carboxylic acid ester, with the exception of dyeing aid mixtures which contain alkylbenzene, tetralin or non-aromatic, water-immiscible solvents.
Die Ausnahmebestimmung berieht sich auf solche Färbereihilfsmittelgemische, wie sie aus der zuvor erwähnten DE-A- 2 941 763 bekannt sind.The exception is based on such dyeing aid mixtures as are known from the aforementioned DE-A-2 941 763.
Vorteilhafterweise enthält das erfindungsgemässe Färbereihilfsmittel 10 bis 50 Gewichtsprozent der Komponente (A), 10 bis 40 Gewichtsprozent der Komponente (B) und 10 bis 70 Gewichtsprozent der Komponente (C). Nicht nur Komponente (C) sondern sowohl Komponente (A) als auch Komponente (B) können als Einzelverbindung oder in Form eines Gemisches vorhanden sein.The dyeing aid according to the invention advantageously contains 10 to 50 percent by weight of component (A), 10 to 40 percent by weight of component (B) and 10 to 70 percent by weight of component (C). Not only component (C) but both component (A) and component (B) can be present as a single compound or in the form of a mixture.
Stellt der Substituent Y in Formel (1) eine Alkylgruppe dar, so kann sie geradkettig oder verzweigt sein. Beispiele solcher Alkylreste sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, sek.Butyl, tert.Butyl, n-Pentyl, Isopentyl, tert.Pentyl, n-Hexyl, 2-Ethylhexyl, n-Heptyl, n-Octyl, Isooctyl, n-Nonyl, Isononyl oder n-Dodecyl.If the substituent Y in formula (1) represents an alkyl group, it can be straight-chain or branched. Examples of such alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, isononyl or n-dodecyl.
"Aryl" bedeutet zweckmässigerweise Phenyl. Der Phenylrest kann durch Halogen, Niederalkyl oder Niederalkoxy einfach oder zweifach substituiert sein."Aryl" conveniently means phenyl. The phenyl radical can be substituted once or twice by halogen, lower alkyl or lower alkoxy.
Niederalkyl und Niederalkoxy stellen bei der Definition der Reste der Verbindungen der Formel (1) solche Gruppen oder Gruppenbestandteile dar, die 1 bis 5, insbesondere 1 bis 3 Kohlenstoffatome aufweisen. Beispiele für derartige Gruppen sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, sek.Butyl, tert.Butyl, Amyl, Isoamyl oder tert.Amyl bzw. Methoxy, Ethoxy, Isopropoxy, Isobutoxy oder tert.Butoxy.Lower alkyl and lower alkoxy in the definition of the radicals of the compounds of the formula (1) are those groups or group components which have 1 to 5, in particular 1 to 3, carbon atoms. Examples of such groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl or methoxy, ethoxy, isopropoxy, isobutoxy or tert-butoxy.
Halogen bedeutet beispielsweise Fluor, Brom oder vorzugsweise Chlor.Halogen means for example fluorine, bromine or preferably chlorine.
Y in der Bedeutung von Aralkyl weist vorteilhafterweise insgesamt 7 bis 9 Kohlenstoffatome auf und steht in der Regel für Benzyl, α-Methylbenzyl, α,α-Dimethylbenzyl, β-Phenethyl, α-Tolylethyl oder Phenisopropyl.Y in the meaning of aralkyl advantageously has a total of 7 to 9 carbon atoms and generally stands for benzyl, α-methylbenzyl, α, α-dimethylbenzyl, β-phenethyl, α-tolylethyl or phenisopropyl.
Der Substituent Y ist vorzugsweise C₄-C₁₀-Alkyl oder besonders α-Methylbenzyl.
sind bevorzugt vom Ethylenglykol-, Propylenethylenglykol- oder Ethylenpropylenglykol-Typus; besonders bevorzugt ist ersterer.
n ist bevorzugt 4 bis 40.The substituent Y is preferably C₄-C₁₀ alkyl or especially α-methylbenzyl.
are preferred of the ethylene glycol, propylene ethylene glycol or ethylene propylene glycol type; the former is particularly preferred.
n is preferably 4 to 40.
Der Säurerest X leitet sich beispielsweise von niedermolekularen Dicarbonsäuren ab, wie z.B. von Maleinsäure, Bernsteinsäure oder Sulfobernsteinsäure, und ist über eine Esterbrücke mit dem Alkylenoxyteil des Moleküls verbunden. Insbesondere leitet sich X jedoch von anorganischen mehrbasischen Säuren, wie Schwefelsäure oder Orthophosphorsäure ab.The acid residue X is derived, for example, from low molecular weight dicarboxylic acids, such as of maleic acid, succinic acid or sulfosuccinic acid, and is connected to the alkyleneoxy part of the molecule via an ester bridge. In particular, however, X is derived from inorganic polybasic acids, such as sulfuric acid or orthophosphoric acid.
Der Säurerest X kann als freie Säure oder in Salzform, d.h. z.B. als Alkalimetall-, Ammonium- oder Aminsalz, vorliegen. Beispiele für solche Salze sind Lithium-, Natrium-, Kalium-, Ammonium-, Trimethylamin-, Diethylamin-, Ethanolamin-, Diethanolamin- oder Triethanolaminsalze. Bevorzugt sind Alkalimetallsalze oder Triethanolaminsalze. Die Mono- bzw. Diethanolaminsalze können noch weiter mit 1 bis 4 Oxethylen-Einheiten verethert sein.The acid residue X can be in the form of a free acid or in salt form, i.e. e.g. as an alkali metal, ammonium or amine salt. Examples of such salts are lithium, sodium, potassium, ammonium, trimethylamine, diethylamine, ethanolamine, diethanolamine or triethanolamine salts. Alkali metal salts or triethanolamine salts are preferred. The mono- or diethanolamine salts can be etherified further with 1 to 4 oxethylene units.
Bevorzugte saure Ester der Komponente (A) entsprechen der Formel
worin Y₁ C₄-C₁₂-Alkyl, Phenyl, Tolyl oder vorzugsweise Tolyl-C₁-C₃-alkyl oder Phenyl-C₁-C₃-alkyl, wie z.B. α-Methyl- oder α,α-Dimethylbenzyl bedeutet,
X₁ ein Säurerest ist, der sich von Schwefelsäure oder vorzugsweise o-Phosphorsäure ableitet, und
m 1 bis 3 und n₁ 4 bis 40 sind.Preferred acid esters of component (A) correspond to the formula
wherein Y₁ C₄-C₁₂-alkyl, phenyl, tolyl or preferably tolyl-C₁-C₃-alkyl or phenyl-C₁-C₃-alkyl, such as α-methyl or α, α-dimethylbenzyl,
X₁ is an acid residue which is derived from sulfuric acid or preferably o-phosphoric acid, and
m are 1 to 3 and n₁ 4 to 40.
Diese sauren Ester liegen vorzugsweise als Natrium-, Kalium-, Ammonium-, Diethylamin-, Triethylamin, Diethanolamin- oder Triethanolaminsalze vor.These acidic esters are preferably in the form of sodium, potassium, ammonium, diethylamine, triethylamine, diethanolamine or triethanolamine salts.
Die als Kompomente (A) in Frage kommenden sauren Ester der Formel (1) oder (2) werden hergestellt, indem man Alkylenoxyd (Ethylenoxid oder Propylenoxid) an eine definitionsgemäss substituierte Phenolverbindung anlagert und das Anlagerungsprodukt mit einer mehrbasischen Sauerstoffsäure oder einem funktionellen Derivat dieser Säure, wie z.B. Säureanhydride, Säurehalogenide, Säureester oder Säureamide in die sauren Ester und gegebenenfalls den erhaltenen sauren Ester in die obengenannten Salze überführt. Als Beispiele dieser funktionellen Derivate seien Phosphorpentoxid, Phosphoroxytrichlorid, Chlorsulfonsäure oder Sulfaminsäure genannt. Sowohl die Alkylenoxidanlagerung als auch die Veresterung können nach bekannten Methoden durchgeführt werden.The acid esters of the formula (1) or (2) which are suitable as components (A) are prepared by adding alkylene oxide (ethylene oxide or propylene oxide) to a phenol compound which is by definition substituted and the adduct with a polybasic oxygen acid or a functional derivative of this acid , such as Acid anhydrides, acid halides, acid esters or acid amides are converted into the acidic esters and, if appropriate, the acidic ester obtained into the abovementioned salts. Examples of these functional derivatives are phosphorus pentoxide, phosphorus oxytrichloride, chlorosulfonic acid or sulfamic acid. Both the alkylene oxide addition and the esterification can be carried out by known methods.
Gut geeignete Komponenten (A) sind saure Ester oder deren Salze eines Polyadduktes von 4 bis 40 Mol Ethylenoxid an 1 Mol eines Phenols, das mindestens eine C₄-C₁₂-Alkylgruppe, eine Phenylgruppe, eine Tolylgruppe, eine α-Tolylethylgruppe, eine Benzylgruppe, eine α-Methylbenzylgruppe oder eine α,α-Dimethylbenzylgruppe aufweist, wie z.B. Butylphenol, Tributylphenol, Octylphenol, Nonylphenol, Dinonylphenol, o-Phenylphenol, Benzylphenol, Dibenzylphenol, α-Tolylethylphenol, Dibenzyl-(nonyl)-phenol, α-Methylbenzylphenol, Bis-(α-Methylbenzyl)-phenol oder Tris-(α-methylbenzyl)-phenol, wobei diese sauren Ester einzeln oder in Mischung verwendet werden können.Well-suited components (A) are acidic esters or their salts of a polyadduct of 4 to 40 moles of ethylene oxide with 1 mole of a phenol which has at least one C₄-C₁₂-alkyl group, a phenyl group, a tolyl group, an α-tolylethyl group, a benzyl group, a has α-methylbenzyl group or an α, α-dimethylbenzyl group, such as Butylphenol, Tributylphenol, Octylphenol, Nonylphenol, Dinonylphenol, o-Phenylphenol, Benzylphenol, Dibenzylphenol, α-Tolylethylphenol, Dibenzyl- (nonyl) -phenol, α-Methylbenzylphenol, Bis- (α-Methylbenzyl) -phenol or Tris- (α-methylbenzyl) ) -phenol, whereby these acidic esters can be used individually or in a mixture.
Von besonderem Interesse sind saure Phosphorsäureester oder Schwefelsäureester der Addukte von 8 bis 30 Mol Ethylenoxid an 1 Mol 4-Nonylphenol oder besonders an 1 Mol von Verbindungen, die durch Anlagerung von 1 bis 3 Mol von Styrolen an 1 Mol Phenole hergestellt werden, wobei die Phosphorsäureester zweckmässigerweise als Gemische der entsprechenden Salze eines Mono- und Diesters vorhanden sind.Of particular interest are acidic phosphoric acid esters or sulfuric acid esters of the adducts of 8 to 30 moles of ethylene oxide with 1 mole of 4-nonylphenol or especially with 1 mole of compounds which are prepared by the addition of 1 to 3 moles of styrenes to 1 mole of phenols, the phosphoric acid esters are expediently present as mixtures of the corresponding salts of a mono- and diester.
Die Herstellung der Styrolanlagerungsprodukte erfolgt in bekannter Weise vorzugsweise in Gegenwart von Katalysatoren, wie Schwefelsäure oder p-Toluolsulfonsäure. Als Styrole kommen zweckmässigerweise Styrol, α-Methylstyrol oder Vinyltoluol (4-Methylstyrol) in Betracht. Beispiele für die Phenole sind Phenol, Kresole oder Xylenole.The styrene addition products are prepared in a known manner, preferably in the presence of catalysts, such as sulfuric acid or p-toluenesulfonic acid. Suitable styrenes are advantageously styrene, α-methylstyrene or vinyltoluene (4-methylstyrene). Examples of the phenols are phenol, cresols or xylenols.
Ganz besonders bevorzugt sind saure Phosphorsäureester (Mono- und Diester) oder Schwefelsäureester oder deren Salze von Oxalkylierungsprodukten der Formel
worin m 1 bis 3 und n₂ 12 bis 30 bedeuten.Acidic phosphoric acid esters (mono- and diesters) or sulfuric acid esters or their salts of oxyalkylation products of the formula are very particularly preferred
wherein m is 1 to 3 and n₂ is 12 to 30.
Als Beispiele für Oxalkylierungsprodukte der Formeln (2) und (3) seien im einzelnen genannt:
- Oxalkylierungsprodukt mit 18 Ethylenoxideinheiten des Anlagerungsproduktes von 2 Mol Styrol an 1 Mol Phenol
- Oxalkylierungsprodukt mit 18 Ethylenoxideinheiten des Anlagerungsproduktes von 3 Mol Styrol an 1 Mol Phenol
- Oxalkylierungsprodukt mit 27 Ethylenoxideinheiten des Anlagerungsproduktes von 2 Mol 4-Methylstyrol an 1 Mol Phenol
- Oxalkylierungsprodukt mit 17 Ethylenoxideinheiten des Anlagerungsproduktes von 3 Mol 4-Methylstyrol an 1 Mol Phenol
- Oxalkylierungsprodukt mit 18 Ethylenoxideinheiten des Gemisches aus einem Anlagerungsprodukt von 2 Mol Styrol an 1 Mol Phenol und einem Anlagerungsprodukt von 3 Mol Styrol an 1 Mol Phenol
- Oxalkylierungsprodukt mit 13 Ethylenoxideinheiten des Gemisches aus einem Anlagerungsprodukt von 2 Mol Styrol an 1 Mol Phenol und einem Anlagerungsprodukt von 3 Mol Styrol an 1 Mol Phenol.
- Oxalkylation product with 18 ethylene oxide units of the adduct of 2 moles of styrene with 1 mole of phenol
- Oxalkylation product with 18 ethylene oxide units of the adduct of 3 moles of styrene with 1 mole of phenol
- Oxalkylation product with 27 ethylene oxide units of the adduct of 2 moles of 4-methylstyrene with 1 mole of phenol
- Oxalkylation product with 17 ethylene oxide units of the adduct of 3 moles of 4-methylstyrene with 1 mole of phenol
- Oxalkylation product with 18 ethylene oxide units of the mixture of an adduct of 2 moles of styrene with 1 mole of phenol and an adduct of 3 moles of styrene with 1 mole of phenol
- Oxalkylation product with 13 ethylene oxide units of the mixture of an adduct of 2 moles of styrene with 1 mole of phenol and an adduct of 3 moles of styrene with 1 mole of phenol.
Das als Komponente (B) verwendete nichtionogene Tensid ist vorteilhafterweise ein Alkylenoxydanlagerungsprodukt von 2 bis 100 Mol Alkylenoxyd, z.B. Ethylenoxyd und/oder Propylenoxyd, an 1 Mol eines aliphatischen Monoalkohols mit mindestens 4 Kohlenstoffatomen, eines 3- bis 6-wertigen aliphatischen Alkohols mit vorzugsweise 3 bis 6 Kohlenstoffatomen, eines gegebenenfalls durch C₄-C₁₂-Alkyl, Phenyl, α-Tolylethyl, Benzyl, α-Methylbenzyl oder α,α-Dimethylbenzyl substituierten Phenols oder einer Fettsäure mit 8 bis 22 Kohlenstoffatomen.The nonionic surfactant used as component (B) is advantageously an alkylene oxide addition product of 2 to 100 moles of alkylene oxide, e.g. Ethylene oxide and / or propylene oxide, on 1 mol of an aliphatic monoalcohol with at least 4 carbon atoms, a 3- to 6-valent aliphatic alcohol with preferably 3 to 6 carbon atoms, one optionally by C₄-C₁₂-alkyl, phenyl, α-tolylethyl, benzyl, α-methylbenzyl or α, α-dimethylbenzyl substituted phenol or a fatty acid with 8 to 22 carbon atoms.
Als nichtionogene Tenside seien beispielsweise genannt:
- Anlagerungsprodukte von vorzugsweise 2 bis 80 Mol Alkylenoxyd, insbesondere Ethylenoxyd, wobei einzelne Ethylenoxydeinheiten durch substituierte Epoxyde, wie Styroloxyd und/oder Propylenoxyd, ersetzt sein können, an höhere ungesättigte oder gesättigte Monoalkohole, Fettsäuren, Fettamine oder Fettamide mit jeweils 8 bis 22 Kohlenstoffatomen oder an Benzylalkohole, Phenylphenole, Benzylphenole, β-Phenethylphenole, α-Methylbenzylphenole, α,α-Dimethylbenzylphenole, α-Tolylethylphenole oder Alkylphenole, deren Alkylreste mindestens 4 Kohlenstoffatome aufweisen;
- Alkylenoxyd-, insbesondere Ethylenoxyd- und/oder Propylenoxyd-Kondensationsprodukte (Blockpolymerisate);
- Ethylenoxyd-Propylenoxyd-Addukte an Fettamine oder Diamine, vor allem Ethylendiamin;
- Umsetzungsprodukte aus einer 8 bis 22 Kohlenstoffatome aufweisenden Fettsäure und einem primären oder sekundären, mindestens eine Hydroxyniederalkyl- oder Niederalkoxyniederalkylgruppe aufweisenden Amin oder Alkylenoxyd-Anlagerungsprodukte dieser hydroxyalkylgruppenhaltigen Umsetzungsprodukte, wobei die Umsetzung so erfolgt, dass das molekulare Mengenverhältnis zwischen Hydroxyalkylamin und Fettsäure 1:1 und grösser als 1, z.B. 1:1 bis 2:1 sein kann, und
- Sorbitanester vorzugsweise mit C₆-₂₄-Fettsäureestergruppen oder polyethoxylierte Sorbitanester, wie z.B. Polyoxethylen-Sorbitanmonolaurat bzw. -monooleat oder -monostearat mit jeweils 4 bis 20 Ethylenoxideinheiten oder Polyoxethylen-Sorbitantrioleat mit 4 bis 20 Ethylenoxideinheiten.
- Anlagerungsprodukte von Propylenoxyd an einen drei- bis sechswertigen aliphatischen Alkohol von 3 bis 6 Kohlenstoffatomen, z.B. Glycerin oder Pentaerythrit, wobei die Polypropylenoxyaddukte ein durchschnittliches Molekulargewicht von 250 bis 1800, vorzugsweise 400 bis 900, aufweisen;
- Fettalkoholpolyglykolmischether, insbesondere Anlagerungsprodukte von 3 bis 30 Mol Ethylenoxid und 3 bis 30 Mol Propylenoxid an aliphatische Monoalkohole von 8 bis 22 Kohlenstoffatomen, vorzugsweise Alkanole von 8 bis 16 Kohlenstoffatomen.
- Addition products of preferably 2 to 80 mol of alkylene oxide, in particular ethylene oxide, it being possible for individual ethylene oxide units to be replaced by substituted epoxides, such as styrene oxide and / or propylene oxide, with higher unsaturated or saturated monoalcohols, fatty acids, fatty amines or fatty amides each having 8 to 22 carbon atoms or an Benzyl alcohols, phenylphenols, benzylphenols, β-phenethylphenols, α-methylbenzylphenols, α, α-dimethylbenzylphenols, α-tolylethylphenols or alkylphenols, the alkyl radicals of which have at least 4 carbon atoms;
- Alkylene oxide, in particular ethylene oxide and / or propylene oxide condensation products (block polymers);
- Ethylene oxide-propylene oxide adducts with fatty amines or diamines, especially ethylenediamine;
- Reaction products from a fatty acid containing 8 to 22 carbon atoms and a primary or secondary amine or alkylene oxide addition products containing these hydroxyalkyl group-containing reaction products, which have at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group, the reaction taking place in such a way that the molecular quantitative ratio between hydroxyalkylamine and fatty acid is 1: 1 and greater than 1, for example 1: 1 to 2: 1, and
- Sorbitan esters preferably with C₆-₂₄ fatty acid ester groups or polyethoxylated sorbitan esters, such as polyoxethylene sorbitan monolaurate or monooleate or monostearate, each with 4 to 20 ethylene oxide units or polyoxethylene sorbitan trioleate with 4 to 20 ethylene oxide units.
- Addition products of propylene oxide onto a trihydric to hexavalent aliphatic alcohol of 3 to 6 carbon atoms, for example glycerol or pentaerythritol, the polypropyleneoxy adducts having an average molecular weight of 250 to 1800, preferably 400 to 900;
- Fatty alcohol polyglycol mixed ethers, in particular addition products of 3 to 30 moles of ethylene oxide and 3 to 30 moles of propylene oxide with aliphatic monoalcohols of 8 to 22 carbon atoms, preferably alkanols of 8 to 16 carbon atoms.
Davon sind obengenannte von Styrolanlagerungsprodukten abgeleitete Oxalkylierungsprodukte der Formel (3) als nichtionische Tenside besonders bevorzugt.Of these, the above-mentioned oxyalkylation products of the formula (3) derived from styrene addition products are particularly preferred as nonionic surfactants.
Weitere besonders bevorzugte nichtionogene Tenside können durch die Formel
oder durch die Formel
dargestellt werden, worin
- R
- einen Alkyl- oder Alkenylrest mit jeweils 8 bis 24 Kohlenstoffatomen oder einen Rest der Formel
- W
- einen aliphatischen Rest mit 8 bis 30 Kohlenstoffatomen und
- z
- 1 bis 25 bedeuten und
- Y, m, n und "Alkylen"
- die oben angegebene Bedeutung haben.
or by the formula
are shown in what
- R
- an alkyl or alkenyl radical each having 8 to 24 carbon atoms or a radical of the formula
- W
- an aliphatic radical having 8 to 30 carbon atoms and
- e.g.
- 1 to 25 mean and
- Y, m, n and "alkylene"
- have the meaning given above.
Die Verbindungen der Formel (4) können durch Umsetzung des Anlagerungsproduktes der Formel
mit einer Fettsäure W-COOH oder durch Umsetzung einer alkoholischen oder phenolischen Verbindung R-OH mit einem Fettsäureester der Formel
hergestellt werden. Die Verbindungen der Formel (5) sind Umsetzungsprodukte aus Anlagerungsprodukten der Formel
Formaldehyd oder einer Formaldehyd abgebenden Verbindung, z.B. Paraformaldehyd und einem Fettsäureester der Formel
und werden teilweise in der japanischen Offenlegungsschrift JP-A-83-18486 beschrieben. Dort nicht genannte Verbindungen, die unter Formel (5) fallen, lassen sich entsprechend herstellen, wobei die in der japanischen Offenlegungsschrift genannten Reaktionsbedingungen zu den gewünschten Produkten der Formel (5) führen.The compounds of formula (4) can by reacting the adduct of the formula
with a fatty acid W-COOH or by reacting an alcoholic or phenolic compound R-OH with a fatty acid ester of the formula
getting produced. The compounds of the formula (5) are reaction products from addition products of the formula
Formaldehyde or a formaldehyde-releasing compound, for example paraformaldehyde and a fatty acid ester of the formula
and are partially described in Japanese Patent Application Laid-Open No. 83-18486. Compounds not mentioned there which fall under formula (5) can be prepared accordingly, the reaction conditions mentioned in the Japanese laid-open specification leading to the desired products of the formula (5).
Gut geeignete Komponenten (B) entsprechen auch der Formel
worin
- R₁
- Alkyl oder Alkenyl mit jeweils 8 bis 22 Kohlenstoffatomen, von Z₁ und Z₂ eines Phenyl und das andere Wasserstoff und
- m'
- 4 bis 80 bedeuten.
wherein
- R₁
- Alkyl or alkenyl each having 8 to 22 carbon atoms, of Z₁ and Z₂ a phenyl and the other hydrogen and
- m '
- 4 to 80 mean.
Die Verbindungen der Formel (6) werden hergestellt, indem man Styroloxid an den Polyethylenglykolether der Formel
anlagert.The compounds of formula (6) are prepared by adding styrene oxide to the polyethylene glycol ether of the formula
attaches.
Die als Komponente (C) verwendeten aliphatischen oder aromatischen Carbonsäureester können Mono- oder Dicarbonsäurediester darstellen, die durch Veresterung von aliphatischen oder aromatischen Mono- oder Dicarbonsäuren von 3 bis 12 Kohlenstoffatomen mit aliphatischen Monoalkoholen von 4 bis 22 Kohlenstoffatomen oder araliphatischen Alkoholen, vor allem Benzylalkohol hergestellt werden.
Im Vordergrund des Interesses stehen C₁-C₁₂-Alkylester von Propionsäure, Milchsäure, Buttersäure, Hydroxybuttersäure, Valeriansäure, Capronsäure, 2-Ethylhexansäure, Malonsäure, Maleinsäure, Adipinsäure, Benzoesäure, 2-Hydroxy- oder 4-Hydroxybenzoesäure oder Phthalsäure und insbesondere Benzoesäure-C₈-C₁₂-alkylester oder vor allem Benzoesäurearalkylester. Als Beispiele für derartige Komponente (C) seien im einzelnen genannt:The aliphatic or aromatic carboxylic acid esters used as component (C) can be mono- or dicarboxylic acid diesters which are prepared by esterifying aliphatic or aromatic mono- or dicarboxylic acids of 3 to 12 carbon atoms with aliphatic monoalcohols of 4 to 22 carbon atoms or araliphatic alcohols, especially benzyl alcohol will.
Of primary interest are C₁-C₁₂ alkyl esters of propionic acid, lactic acid, butyric acid, hydroxybutyric acid, valeric acid, caproic acid, 2-ethylhexanoic acid, malonic acid, maleic acid, adipic acid, benzoic acid, 2-hydroxy- or 4-hydroxybenzoic acid or phthalic acid and especially benzoic acid-C₈ -C₁₂-alkyl esters or especially aryl benzoates. Examples of such component (C) are:
Propionsäure-2-ethylhexylester, Milchsäure-n-octylester, Milchsäure-2-ethylhexylester, 2-Ethylhexansäure-2-ethylhexylester, Maleinsäure-di-2-ethylhexylester, Adipinsäure-di-2-ethylhexylester, Benzoesäuremethylester, Benzoesäurebutylester, Benzoesäure-2-ethylhexylester, Benzoesäuredecylester, Benzoesäuredodecylester, Benzoesäurephenylester, Benzoesäure-2-methylphenylester, Benzoesäurebenzylester, Benzoesäurephenoxyethylester oder Phthalsäuredimethylester.
Benzoesäurebenzylester ist als Komponente (C) besonders bevorzugt.2-ethylhexyl propionate, n-octyl lactic acid, 2-ethylhexyl lactate, 2-ethylhexyl 2-ethylhexanoate, di-2-ethylhexyl maleate, di-2-ethylhexyl adipate, methyl benzoate, butyl benzoate, 2-benzoate ethylhexyl ester, benzoic acid decyl ester, benzoic acid dodecyl ester, benzoic acid phenyl ester, benzoic acid 2-methylphenyl ester, benzoic acid benzyl ester, benzoic acid phenoxyethyl ester or phthalic acid dimethyl ester.
Benzyl benzoate is particularly preferred as component (C).
Die erfindungsgemässen Färbereihilfsmittel können zusätzlich als Komponente (D) in Form eines polaren Lösungsmittels Wasser und/oder mit Wasser mischbare organische Lösungsmittel enthalten. Ein solcher Zusatz dient dazu, um die Homogenität der Zubereitung zu verbessern. Beispiele von mit Wasser mischbaren organischen Lösungsmitteln sind aliphatische C₁-C₄-Alkohole, wie z.B. Methanol, Ethanol oder die Propanole; Ketone, wie z.B. Aceton, Methylethylketon, Cyclohexanon, Diacetonalkohol, Ether, wie z.B. Diisopropylether, Dioxan, Tetrahydrofuran; Ethylenglykol, Propylenglykol, Monoalkylether von Glykolen, wie z.B Ethylenglykolmonomethyl-, -ethyl- und -butylether und Diethylenglykolmonomethyl- oder -ethylether, ferner Tetrahydrofurfurylalkohol, Pyridin, Acetonitril, γ-Butyrolacton, N,N-Dimethylformamid, N,N-Dimethylacetamid, Tetramethylharnstoff oder Tetramethylensulfon. Auch Mischungen der genannten Lösungsmittel können verwendet werden.The dyeing auxiliaries according to the invention can additionally contain, as component (D) in the form of a polar solvent, water and / or water-miscible organic solvents. Such an addition serves to improve the homogeneity of the preparation. Examples of water-miscible organic solvents are aliphatic C₁-C₄ alcohols, e.g. Methanol, ethanol or the propanols; Ketones, e.g. Acetone, methyl ethyl ketone, cyclohexanone, diacetone alcohol, ethers such as e.g. Diisopropyl ether, dioxane, tetrahydrofuran; Ethylene glycol, propylene glycol, monoalkyl ethers of glycols, such as, for example, ethylene glycol monomethyl, ethyl and butyl ether and diethylene glycol monomethyl or ethyl ether, also tetrahydrofurfuryl alcohol, pyridine, acetonitrile, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylamethylamine or tetramethylene sulfone. Mixtures of the solvents mentioned can also be used.
Die erfindungsgemässen Hilfsmittelgemische enthalten mit Vorteil, jeweils bezogen auf das gesamte Gemisch,
10 bis 40 Gewichtsprozent der Komponente (A)
15 bis 50 Gewichtsprozent der Komponente (B)
20 bis 70 Gewichtsprozent der Komponente (C)
0 bis 40 Gewichtsprozent der Komponente (D).The auxiliary mixtures according to the invention advantageously contain, based in each case on the entire mixture,
10 to 40 percent by weight of component (A)
15 to 50 percent by weight of component (B)
20 to 70 percent by weight of component (C)
0 to 40 percent by weight of component (D).
Die neuen Färbereihilfsmittelzubereitungen können durch einfaches Verrühren der genannten Komponenten (A), (B), (C) und gegebenenfalls (D) hergestellt werden, wobei homogene Mischungen erhalten werden, die sich durch gute Transport- und Lagerstabilität auszeichnen. Die erfindungsgemässen Färbereihilfsmittel sind insbesondere sehr stabil bei höheren Temperaturen bis zu 130°C, wenn sie in Färbebädern eingesetzt werden.The new dyeing aid preparations can be prepared by simply stirring the components (A), (B), (C) and, if appropriate, (D), giving homogeneous mixtures which are notable for good transport and storage stability. The dyeing auxiliaries according to the invention are in particular very stable at higher temperatures up to 130 ° C. when used in dye baths.
Verwendung findet das erfindungsgemässe Färbereihilfsmittel je nach dem Farbstoff beim Färben von Synthesefasern, insbesondere Polyesterfasern enthaltendem Textilmaterial. Das Färbeverfahren wird jeweils in üblicher Weise durchgeführt. Das erfindungsgemässe Färbereihilfsmittel wird in ein wässriges Bad langsam unter Rühren eingetragen, wonach die Flotte mit dem Zusatz vom Farbstoff zum Färben bereitgestellt ist.Depending on the dye, the dyeing aid according to the invention is used in the dyeing of synthetic fibers, in particular textile material containing polyester fibers. The dyeing process is carried out in the usual way. The dyeing aid according to the invention is slowly introduced into an aqueous bath with stirring, after which the liquor with the addition of the dye is provided for dyeing.
Gegenstand der vorliegenden Erfindung ist demnach auch ein Verfahren zum Färben von synthetischem Fasermaterial, besonders Polyesterfasern mit Dispersionsfarbstoffen. Das Verfahren ist dadurch gekennzeichnet, dass man dieses Material in Gegenwart des erfindungsgemässen Hilfsmittelgemisches färbt.The present invention accordingly also relates to a process for dyeing synthetic fiber material, in particular polyester fibers with disperse dyes. The process is characterized in that this material is colored in the presence of the auxiliary mixture according to the invention.
Die Einsatzmengen, in denen die erfindungsgemässe Hilfsmittelkombination den Färbebädern zugesetzt wird, bewegen sich von 0,5 bis 10 %, vorzugsweise 1 bis 5 % vom Warengewicht.The amounts used in which the auxiliary combination according to the invention is added to the dye baths range from 0.5 to 10%, preferably 1 to 5%, of the weight of the goods.
Als Fasermaterial, insbesondere Textilmaterial, das in Gegenwart des neuen Hilfsmittelgemisches gefärbt werden kann, sind z.B. Celluloseesterfasern, wie Cellulose-2 1/2-acetatfasern und -triacetatfasern und besonders lineare Polyesterfasern zu erwähnen.As fiber material, in particular textile material that can be dyed in the presence of the new auxiliary mixture, e.g. Cellulose ester fibers, such as cellulose 2 1/2 acetate fibers and triacetate fibers and particularly linear polyester fibers, should be mentioned.
Unter linearen Polyesterfasern sind dabei Synthesefasern zu verstehen, die z.B. durch Kondensation von Terephthalsäure mit Ethylenglykol oder von Isophthalsäure oder Terephthalsäure mit 1,4-Bis-(hydroxymethyl)-cyclohexan erhalten werden, sowie Mischpolymere aus Terephthal- und Isophthalsäure und Ethylenglykol. Der in der Textilindustrie bisher fast ausschliesslich eingesetzte lineare Polyester besteht aus Terephthalsäure und Ethylenglykol.Linear polyester fibers are to be understood as synthetic fibers which e.g. can be obtained by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane, and also copolymers of terephthalic and isophthalic acid and ethylene glycol. The linear polyester used almost exclusively in the textile industry so far consists of terephthalic acid and ethylene glycol.
Die Fasermaterialien können auch als Mischgewebe unter sich oder mit anderen Fasern, z.B. Mischungen aus Polyacrylnitril/Polyester, Polyamid/Polyester, Polyester/Baumwolle, Polyester/Viskose und Polyester/Wolle, verwendet werden.The fiber materials can also be used as a mixed fabric with one another or with other fibers, for example mixtures of polyacrylonitrile / polyester, polyamide / polyester, polyester / cotton, polyester / viscose and polyester / wool.
Das zu färbende Textilmaterial kann sich in verschiedenen Verarbeitungsstadien befinden. Beispielsweise kommen in Betracht: loses Material, Stückware, wie Gewirke oder Gewebe, Garn in Wickel- oder Muff-Form. Letztere können Wickeldichten von 200 bis 600 g/dm³, insbesondere 400 bis 450 g/dm³, aufweisen.The textile material to be dyed can be in various stages of processing. Examples include: loose material, piece goods, such as knitted or woven fabrics, yarn in the form of a wrap or muff. The latter can have winding densities of 200 to 600 g / dm³, in particular 400 to 450 g / dm³.
Die zu verwendenden Dispersionsfarbstoffe, die in Wasser nur sehr wenig löslich sind und in der Färbeflotte zum grössten Teil in Form einer feinen Dispersion vorliegen, können den verschiedensten Farbstoffklassen angehören, beispielsweise den Acridon-, Azo-, Anthrachinon-, Cumarin-, Methin-, Perinon-, Naphthochinonimin-, Chinophthalon-, Styryl- oder Nitrofarbstoffen.The disperse dyes to be used, which are only sparingly soluble in water and are largely present in the dye liquor in the form of a fine dispersion, can belong to a wide variety of dye classes, for example the acridone, azo, anthraquinone, coumarin, methine, Perinone, naphthoquinoneimine, quinophthalone, styryl or nitro dyes.
Die Menge der der Flotte zuzusetzenden Farbstoffe richtet sich nach der gewünschten Farbstärke; im allgemeinen haben sich Mengen von 0,01 bis 10, vorzugsweise 0,05 bis 5 Gewichtsprozent, bezogen auf das eingesetzte Textilmaterial, bewährt.The amount of dyes to be added to the liquor depends on the desired color strength; In general, amounts of 0.01 to 10, preferably 0.05 to 5 percent by weight, based on the textile material used, have proven successful.
Die Farbbäder können je nach dem zu behandelnden Textilmaterial neben den Farbstoffen und dem erfindungsgemässen Hilfsmittelgemisch, Oligomereninhibitoren, Antischaummittel (z.B. Siliconöle oder Ethylenbisfettsäureamide), Faltenfreimittel und vorzugsweise Dispergiermittel enthalten.Depending on the textile material to be treated, the dye baths can contain, in addition to the dyes and the auxiliary mixture according to the invention, oligomer inhibitors, anti-foaming agents (e.g. silicone oils or ethylene bis fatty acid amides), wrinkle-free agents and preferably dispersants.
Die Dispergiermittel dienen vor allem zur Erzielung einer guten Feinverteilung der Dispersionsfarbstoffe. Es kommen die beim Färben mit Dispersionsfarbstoffen allgemein gebräuchlichen Dispergatoren in Frage.The dispersants are used primarily to achieve a good fine distribution of the disperse dyes. The dispersants generally used for dyeing with disperse dyes are suitable.
Als Dispergiermittel kommen vorzugsweise sulfatierte oder phosphatierte Anlagerungsprodukte von 15 bis 100 Mol Ethylenoxid oder vorzugsweise Propylenoxid an mehrwertige, 2 bis 6 Kohlenstoffatome aufweisende aliphatische Alkohole, wie z.B. Ethylenglykol, Glycerin oder Pentaerythrit oder an mindestens zwei Aminogruppen oder eine Aminogruppe und eine Hydroxylgruppe aufweisende Amine mit 2 bis 9 Kohlenstoffatomen sowie Alkylsulfonate mit 10 bis 20 Kohlenstoffatomen in der Alkylkette, Alkylbenzolsulfonate mit geradkettiger oder verzweigter Alkylkette mit 8 bis 20 Kohlenstoffatomen in der Alkylkette, wie z.B. Nonyl- oder Dodecylbenzolsulfonat, 1,3,5,7-Tetramethyloctylbenzolsulfonat oder Octadecylbenzolsulfonat, sowie Alkylnaphthalinsulfonate oder Sulfobernsteinsäureester, wie z.B. Natriumdioctylsulfosuccinat oder Natrium-di-2-ethylhexylsulfosuccinat, in Betracht.The dispersants used are preferably sulfated or phosphated adducts of 15 to 100 moles of ethylene oxide or preferably propylene oxide with polyhydric aliphatic alcohols containing 2 to 6 carbon atoms, such as ethylene glycol, glycerol or pentaerythritol or with at least two amino groups or one amino group and one hydroxyl group with amines having 2 up to 9 carbon atoms and alkylsulfonates with 10 to 20 carbon atoms in the alkyl chain, alkylbenzenesulfonates with straight-chain or branched alkyl chain with 8 to 20 carbon atoms in the alkyl chain, such as, for example, nonyl or dodecylbenzenesulfonate, 1,3,5,7-tetramethyloctylbenzenesulfonate or octadecylbenzenesulfonate, and also alkylnaphthalenesulfonates or sulfosuccinic acid esters, such as, for example, sodium dioctylsulfosuccinate or sodium di-2-ethylhexylsulfosuccinate.
Besonders günstig haben sich als anionische Dispergiermittel Ligninsulfonate, Polyphosphate und vorzugsweise Formaldehyd-Kondensationsprodukte aus aromatischen Sulfonsäuren, Formaldehyd und gegebenenfalls mono- oder bifunktionellen Phenolen, wie z.B. aus Kresol, β-Naphtholsulfonsäure und Formaldehyd, aus Benzolsulfonsäure, Formaldehyd und Naphthalinsulfonsäure, aus Naphthalinsulfonsäure und Formaldehyd oder aus Naphthalinsulfonsäure, Dihydroxydiphenylsulfon und Formaldehyd erwiesen. Bevorzugt ist das Dinatriumsalz des Di- oder Tri-(6-sulfonaphthyl-2-)methans.Lignin sulfonates, polyphosphates and preferably formaldehyde condensation products of aromatic sulfonic acids, formaldehyde and optionally mono- or bifunctional phenols, such as e.g. from cresol, β-naphtholsulfonic acid and formaldehyde, from benzenesulfonic acid, formaldehyde and naphthalenesulfonic acid, from naphthalenesulfonic acid and formaldehyde or from naphthalenesulfonic acid, dihydroxydiphenyl sulfone and formaldehyde. The disodium salt of di- or tri- (6-sulfonaphthyl-2-) methane is preferred.
Es können auch Gemische von anionischen Dispergiermitteln zum Einsatz kommen. Normalerweise liegen die anionischen Dispergiermittel in Form ihrer Alkalimetallsalze, Ammoniumsalze oder Aminsalze vor. Diese Dispergiermittel werden vorzugsweise in einer Menge von 0,5 bis 8 g/l Flotte verwendet.Mixtures of anionic dispersants can also be used. The anionic dispersants are normally in the form of their alkali metal salts, ammonium salts or amine salts. These dispersants are preferably used in an amount of 0.5 to 8 g / l of liquor.
Die Färbebäder können auch übliche Zusätze, zweckmässig Elektrolyte wie Salze, z.B. Natriumsulfat, Ammoniumsulfat, Natrium- oder Ammoniumphosphate oder -polyphosphate, Metallchloride oder -nitrate wie Calciumchlorid, Magnesiumchlorid bzw. Calciumnitrate, Ammoniumacetat oder Natriumacetat und/oder Säuren, z.B. Mineralsäuren, wie Schwefelsäure oder Phosphorsäure, oder organische Säuren, zweckmässig niedere aliphatische Carbonsäuren, wie Ameisen-, Essig-, Zitronen- oder Oxalsäure enthalten. Die Säuren dienen vor allem der Einstellung des pH-Wertes der erfindungsgemäss verwendeten Flotten, der in der Regel 4 bis 6,5, vorzugsweise 4,5 bis 6, beträgt. In bestimmten Fällen kann aber auch im alkalischen Bereich gefärbt werden. (pH 7 bis 10)
Die Färbungen erfolgen mit Vorteil aus wässriger Flotte nach dem Ausziehverfahren. Das Flottenverhältnis kann dementsprechend innerhalb eines weiten Bereiches gewählt werden, z.B. 1:3 bis 1:100, vorzugsweise 1:7 bis 1:50. Die Temperatur, bei der gefärbt wird, beträgt mindestens 70°C und in der Regel ist sie nicht höher als 140°C. Vorzugsweise liegt sie im Bereich von 80 bis 135°C.The dyebaths can also contain conventional additives, advantageously electrolytes such as salts, for example sodium sulfate, ammonium sulfate, sodium or ammonium phosphates or polyphosphates, metal chlorides or nitrates such as calcium chloride, magnesium chloride or calcium nitrates, ammonium acetate or sodium acetate and / or acids, for example mineral acids, such as sulfuric acid or phosphoric acid, or organic acids, suitably lower aliphatic carboxylic acids, such as formic, acetic, citric or oxalic acid. The acids serve primarily to adjust the pH of the liquors used according to the invention, which is generally 4 to 6.5, preferably 4.5 to 6. In certain cases, dyeing can also take place in the alkaline range. (pH 7 to 10)
The dyeings are advantageously carried out from an aqueous liquor using the exhaust process. The liquor ratio can accordingly be chosen within a wide range, for example 1: 3 to 1: 100, preferably 1: 7 to 1:50. The temperature at which dyeing is carried out is at least 70 ° C and usually it is not higher than 140 ° C. It is preferably in the range from 80 to 135 ° C.
Lineare Polyesterfasern und Cellulosetriacetatfasern färbt man vorzugsweise nach dem sogenannten Hochtemperaturverfahren in geschlossenen und zweckmässigerweise auch druckbeständigen Apparaturen bei Temperaturen von über 100°C, bevorzugt zwischen 110 und 135°C, und gegebenenfalls unter Druck. Als geschlossene Gefässe eignen sich beispielsweise Zirkulationsapparaturen wie Kreuzspul- oder Baumfärbeapparate, Haspelkufen, Düsen- oder Trommelfärbemaschinen, Jet- oder Muff-Färbeapparate, Paddeln oder Jigger.Linear polyester fibers and cellulose triacetate fibers are preferably dyed by the so-called high-temperature process in closed and expediently also pressure-resistant apparatus at temperatures above 100 ° C., preferably between 110 and 135 ° C., and optionally under pressure. As closed vessels, for example, circulation apparatuses such as cross-wound or tree dyeing machines, reel runners, jet or drum dyeing machines, jet or muff dyeing machines, paddles or jiggers are suitable.
Cellulose-2 1/2-acetatfasern färbt man vorzugsweise bei Temperaturen von 80-85°C.Cellulose-2 1/2 acetate fibers are preferably dyed at temperatures of 80-85 ° C.
Das Färbeverfahren kann so durchgeführt werden, dass man das Färbegut entweder zuerst mit dem Hilfsmittelgemisch kurz behandelt und anschliessend färbt oder vorzugsweise gleichzeitig mit dem Hilfsmittelgemisch und dem Farbstoff behandelt.The dyeing process can be carried out by either briefly treating the material to be dyed first with the auxiliary mixture and then dyeing it, or preferably treating it simultaneously with the auxiliary mixture and the dye.
Vorzugsweise lässt man das Färbegut während 5-10 Minuten bei 40-80°C im Bad, das den Farbstoff, das Hilfsmittelgemisch und gegebenenfalls weitere Zusätze enthält und auf einen pH-Wert von 4,5 bis 10 eingestellt ist, vorlaufen, steigert die Temperatur innerhalb von 15 bis 45 Minuten auf 110 bis 135°C, vorzugsweise 125-130°C und belässt die Färbeflotte 15 bis 90 Minuten, vorzugsweise 30 bis 60 Minuten, bei dieser Temperatur.The material to be dyed is preferably allowed to run for 5-10 minutes at 40-80 ° C. in a bath which contains the dye, the auxiliary mixture and, if appropriate, further additives and is adjusted to a pH of 4.5 to 10, the temperature increases within 15 to 45 minutes to 110 to 135 ° C, preferably 125-130 ° C and the dye liquor 15 to 90 minutes, preferably 30 to 60 minutes, at this temperature.
Die Fertigstellung der Färbungen erfolgt durch Abkühlen der Färbeflotte auf 60 bis 90°C, Spülen der Färbungen mit Wasser und gegebenenfalls durch Reinigung auf übliche Weise im alkalischen Medium unter reduktiven Bedingungen. Die Färbungen werden dann wiederum gespült und getrocknet.The dyeings are completed by cooling the dye liquor to 60 to 90 ° C., rinsing the dyeings with water and, if appropriate, cleaning in a customary manner in an alkaline medium under reductive conditions. The dyeings are then rinsed again and dried.
Man erhält auf synthetischem Fasermaterial, insbesondere auf linearen Polyesterfasern, gleichmässige und farbkräftige Ausfärbungen, die sich zudem durch gute Lichtechtheit und Reibechtheiten auszeichnen. Während des Färbens bleibt die Färbeflotte stabil und entstehen keine Ablagerungen im Inneren der Färbeapparaturen.On synthetic fiber material, in particular on linear polyester fibers, uniform and vivid colorations are obtained, which are furthermore distinguished by good light fastness and rub fastness. During the dyeing process, the dyeing liquor remains stable and there are no deposits inside the dyeing equipment.
In den folgenden Herstellungsvorschriften und Anwendungsbeispielen bedeuten Teile Gewichtsteile und die Prozentangaben Gewichtsprozente.In the following manufacturing instructions and application examples, parts mean parts by weight and percentages are percentages by weight.
229 g Tristyrylphenol-polyethylenglykolether mit 11 Oxiethyleneinheiten werden mit 92,5 g Oelsäurediethylenglykolester, 8,7 g Paraformaldehyd und 2,3 g Salzsäure (37 %) während 7 Stunden bei 120-130°C kondensiert. Dabei wird das entstehende Wasser über einen absteigenden Kühler aus dem Reaktionsgemisch entfernt. Man erhält ein braunes, viskoses Produkt, welches der Formel
entspricht und telquel als Komponente (B) eingesetzt wird.229 g of tristyrylphenol polyethylene glycol ether with 11 oxiethylene units are condensed with 92.5 g of oleic acid diethylene glycol ester, 8.7 g of paraformaldehyde and 2.3 g of hydrochloric acid (37%) at 120-130 ° C. for 7 hours. The water formed is removed from the reaction mixture via a descending cooler. A brown, viscous product is obtained, which has the formula
corresponds and telquel is used as component (B).
164,7 g des Anlagerungsproduktes von 20 Mol Ethylenoxid an 1 Mol p-Nonylphenol werden mit 45,75 g Kokosfettsäure-diethylenglykolester, 5,2 g Paraformaldehyd und 1,4 g Salzsäure (37 %) in Stickstoffatmosphäre langsam auf 120-130°C erwärmt. Dabei wird innerhalb von 24 Stunden das entstehende Wasser über einen absteigenden Kühler entfernt. Man erhält ein braunes, viskoses Produkt, das der Formel
entspricht und telquel als Komponente (B) eingesetzt wird.164.7 g of the adduct of 20 moles of ethylene oxide and 1 mole of p-nonylphenol are slowly increased to 120-130 ° C. in a nitrogen atmosphere with 45.75 g of coconut fatty acid diethylene glycol ester, 5.2 g of paraformaldehyde and 1.4 g of hydrochloric acid (37%) warmed up. The resulting water is removed via a descending cooler within 24 hours. A brown, viscous product is obtained, that of the formula
corresponds and telquel is used as component (B).
Auf ähnliche Art und Weise wie in den Vorschriften 1 und 2 beschrieben werden unter Verwendung der entsprechenden Ausgangsstoffe die Verbindungen der Formel
hergestellt.
produced.
75 g 2,6-Distyryl-4-nonylphenol werden mit 150 g Oelsäurepolyethylenglykolester mit 13,6 Oxiethyleneinheiten und 1,5 g Schwefelsäure (96 %) 6 1/2 Stunden bei 130-160°C gerührt. Das entstehende Wasser wird über einen absteigenden Kühler aus dem Reaktionsgemisch entfernt. Man erhält ein braunes, viskoses Produkt, das der Formel
entspricht und telquel als Komponente (B) eingesetzt wird.75 g of 2,6-distyryl-4-nonylphenol are stirred with 150 g of oleic acid polyethylene glycol ester with 13.6 oxyethylene units and 1.5 g of sulfuric acid (96%) at 130-160 ° C. for 6 1/2 hours. The water formed is removed from the reaction mixture via a descending cooler. A brown, viscous product is obtained, that of the formula
corresponds and telquel is used as component (B).
164,7 g des Anlagerungsproduktes von 20 Mol Ethylenoxid an 1 Mol p-Nonylphenol werden mit 32,55 g Kokosfettsäure und 0,5 g p-Toluolsulfonsäure in Stickstoffatmosphäre auf 155-160°C erwärmt. Das entstehende Wasser wird über einen absteigenden Kühler aus dem Reaktionsgemisch entfernt. Die Reaktion dauert 24 Stunden. Man erhält ein hellbraunes Produkt, das der Formel
entspricht und telquel als Komponente (B) eingesetzt wird.164.7 g of the adduct of 20 moles of ethylene oxide with 1 mole of p-nonylphenol are heated to 155-160 ° C. in a nitrogen atmosphere using 32.55 g of coconut fatty acid and 0.5 g of p-toluenesulfonic acid. The water formed is removed from the reaction mixture via a descending cooler. The reaction takes 24 hours. A light brown product is obtained, that of the formula
corresponds and telquel is used as component (B).
Auf ähnliche Art und Weise wie in den Vorschriften 10 und 11 beschrieben, werden unter Verwendung der entsprechenden Ausgangsstoffe die folgenden Verbindungen der Formel
hergestellt.
produced.
Beispiel 1: 100 Teile eines Polyestergewebes werden in ein 60°C warmes Bad gegeben, das 1500 Teile Wasser, 2 g/l Ammoniumsulfat, 2,5 Teile eines Farbstoffes der Formel
und 2 Teile einer Hilfsmittelformulierung (P₁) bestehend aus
- 12
- Teilen des Natriumsalzes des sauren Schwefelsäureesters des Oxalkylierungsproduktes von 18 Mol Ethylenoxid an 1 Mol des Anlagerungsproduktes von 3 Mol Styrol an 1 Mol Phenol
- 12
- Teilen des Oxalkylierungsproduktes von 18 Mol Ethylenoxid an 1 Mol des Anlagerungsproduktes von 3 Mol Styrol an 1 Mol Phenol
- 16
- Teilen des Anlagerungsproduktes von 36 Mol Ethylenoxid an 1 Mol Stearylalkohol und
- 60
- Teilen Benzoesäurebenzylester
enthält und mit Ameisensäure auf pH 5 gestellt ist. Man erhitzt die Flotte, bei ständiger Zirkulation, innerhalb von 30 Minuten auf 130°C und färbt bei dieser Temperatur 60 Minuten. Alsdann wird die Flotte abgekühlt, abgelassen und die Ware gespült und getrocknet. Man erhält eine egale und reibechte brillante Rotfärbung mit einer hohen Farbstoffausbeute. Die übliche reduktive Nachreinigung ist nicht erforderlich. Example 1 : 100 parts of a polyester fabric are placed in a 60 ° C bath containing 1500 parts of water, 2 g / l ammonium sulfate, 2.5 parts of a dye of the formula
and 2 parts of an auxiliary formulation (P₁) consisting of
- 12th
- Share the sodium salt of the acidic sulfuric acid ester of the oxyalkylation product of 18 moles of ethylene oxide with 1 mole of the adduct of 3 moles of styrene with 1 mole of phenol
- 12th
- Share the oxyalkylation product of 18 moles of ethylene oxide with 1 mole of the adduct of 3 moles of styrene with 1 mole of phenol
- 16
- Share the adduct of 36 moles of ethylene oxide with 1 mole of stearyl alcohol and
- 60
- Parts of benzoate
contains and is adjusted to pH 5 with formic acid. The liquor is heated, with constant circulation, to 130 ° C. within 30 minutes and dyed at this temperature for 60 minutes. The liquor is then cooled, drained and the goods rinsed and dried. A level and rub-fast brilliant red color with a high dye yield is obtained. The usual reductive post-cleaning is not necessary.
Beispiel 2: 100 Teile einer Wirkware aus texturierten Polyesterfasern werden in eine Jet-Färbeanlage, die 1500 Teile 60°C warmes Wasser, 2 Teile Ammoniumsulfat, 2,9 Teile des Farbstoffes der Formel
2,6 Teile des Farbstoffes der Formel
0,8 Teile des Farbstoffes der Formel
und 2 Teile einer Hilfsmittelformulierung (P₂) bestehend aus
- 20
- Teilen des Natriumsalzes des sauren Schwefelsäureesters des Oxalkylierungsproduktes von 18 Mol Ethylenoxid an 1 Mol des Anlagerungsproduktes von 3 Mol Styrol an 1 Mol Phenol,
- 20
- Teilen des Oxalkylierungsproduktes von 18 Mol Ethylenoxid an 1 Mol des Anlagerungsproduktes von 3 Mol Styrol an 1 Mol Phenol und
- 60
- Teilen Benzoesäurebenzylester
enthält und deren Färbeflotte mit Ameisensäure auf pH 5 gestellt ist, eingebracht. Danach wird die Flotte im Verlaufe von 30 Minuten auf 130°C erhitzt, worauf 60 Minuten bei dieser Temperatur gefärbt wird. Während dieser Zeit wird kein störendes Schäumen beobachtet. Anschliessend wird die Flotte auf 70°C abgekühlt und das Substrat wie üblich reduktiv gereinigt, gespült und getrocknet. Man erhält eine egale und echte Braunfärbung mit einer ausgezeichneten Durchfärbung der Ware. Example 2 : 100 parts of a knitted fabric made of textured polyester fibers are placed in a jet dyeing machine which contains 1500 parts of water at 60 ° C., 2 parts of ammonium sulfate, 2.9 parts of the dye of the formula
2.6 parts of the dye of the formula
0.8 parts of the dye of the formula
and 2 parts of an auxiliary formulation (P₂) consisting of
- 20th
- Dividing the sodium salt of the acidic sulfuric acid ester of the oxyalkylation product of 18 mol of ethylene oxide with 1 mol of the adduct of 3 mol of styrene with 1 mol of phenol,
- 20th
- Share the oxyalkylation product of 18 moles of ethylene oxide with 1 mole of the adduct of 3 moles of styrene with 1 mole of phenol and
- 60
- Parts of benzoate
contains and the dye liquor is adjusted to pH 5 with formic acid. The liquor is then heated to 130 ° C. in the course of 30 minutes, after which dyeing is carried out for 60 minutes. No disturbing foaming is observed during this time. The liquor is then cooled to 70 ° C. and the substrate is reductively cleaned, rinsed and dried as usual. You get a level and real brown color with an excellent coloring of the goods.
Beispiel 3: 100 Teile eines Wickelkörpers aus texturierten Polyestergarnen werden in einen HT-Färbeapparat, welcher 800 Teile 40°C warmes Wasser, 2 Teile Ammoniumsulfat, 4 Teile eines Farbstoffes der Formel
und 2 Teile einer Hilfsmittelformulierung (P₃) aus
- 24
- Teilen Natriumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 35 Mol Ethylenoxid an 1 Mol Nonylphenol,
- 16
- Teilen des Anlagerungsproduktes von 36 Mol Ethylenoxid an 1 Mol Stearylalkohol und
- 60
- Teilen Benzoesäurebenzylester enthält und dessen Flotte mit
Ameisensäure auf pH 5 eingestellt ist, eingebracht. Example 3 : 100 parts of a bobbin made of textured polyester yarns are placed in an HT dyeing machine which contains 800 parts of 40 ° C. warm water, 2 parts of ammonium sulfate, 4 parts of a dye of the formula
and 2 parts of an auxiliary formulation (P₃)
- 24th
- Parts of sodium salt of the acidic sulfuric acid ester of the adduct of 35 moles of ethylene oxide and 1 mole of nonylphenol,
- 16
- Share the adduct of 36 moles of ethylene oxide with 1 mole of stearyl alcohol and
- 60
- Parts of benzoic acid contains and its fleet with
Formic acid is adjusted to pH 5.
Danach wird die Flotte im Verlaufe von 40 Minuten auf 128°C erhitzt und die Ware 60 Minuten bei dieser Temperatur gefärbt. Während der Aufheizphase wird im Materialblock kein Anstieg des Differenzdruckes zwischen Innen und Aussen festgestellt. Anschliessend wird die Flotte auf 70°C abgekühlt und das Substrat wie üblich reduktiv gereinigt, gespült und getrocknet. Man erhält eine farbstarke, egale, orange Färbung, die sich durch gute Durchfärbung und gute Echtheiten auszeichnet.The liquor is then heated to 128 ° C. in the course of 40 minutes and the goods are dyed at this temperature for 60 minutes. During the heating phase, no increase in the differential pressure between inside and outside is found in the material block. The liquor is then cooled to 70 ° C. and the substrate is reductively cleaned, rinsed and dried as usual. A strong, level, orange coloration is obtained, which is distinguished by good coloring and good fastness properties.
Verwendet man in Beispiel 3 anstelle der Hilfsmittelformulierung (P₃) die gleiche Menge der folgenden Zubereitungen, so erhält man ebenfalls jeweils eine farbstarke und echte orange Färbung.
- (P₄) Zubereitung bestehend aus
- 20
- Teilen Triethanolaminsalz eines Gemisches von Mono- und Diesterphosphat eines Oxalkylierungsproduktes mit 18 Ethylenoxideinheiten des Anlagerungsproduktes von 2,5 bis 3 Mol Styrol an 1 Mol Phenol
- 20
- Teilen eines Oxalkylierungsproduktes von 18 Mol Ethylenoxid mit 1 Mol eines Anlagerungsproduktes von 2,5 bis 3 Mol Styrol an 1 Mol Phenol und
- 60
- Teilen Benzoesäurebenzylester.
- (P₅) Zubereitung bestehend aus
- 16
- Teilen Natriumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 35 Mol Ethylenoxid an 1 Mol Nonylphenol
- 24
- Teilen der gemäss Vorschrift 1 hergestellten Verbindung der Formel (11) und
- 60
- Teilen Benzoesäurebenzylester.
- (P₆) Zubereitung bestehend aus
- 16
- Teilen Natriumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 35 Mol Ethylenoxid an 1 Mol Nonylphenol
- 24
- Teilen der gemäss Vorschrift 11 hergestellten Verbindung der Formel (15) und
- 60
- Teilen Benzoesäurebenzylester.
- (P₇) Zubereitung bestehend aus
- 16
- Teilen Natriumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 35 Mol Ethylenoxid an 1 Mol Nonylphenol
- 24
- Teilen des Anlagerungsproduktes von 36 Mol Ethylenoxid an 1 Mol Stearylalkohol und
- 60
- Teilen Propionsäure-2-ethylhexylester.
- (P₈) Zubereitung bestehend aus
- 16
- Teilen Natriumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 35 Mol Ethylenoxid an 1 Mol Nonylphenol
- 24
- Teilen des Anlagerungsproduktes von 36 Mol Ethylenoxid an 1 Mol Stearylalkohol und
- 60
- Teilen Milchsäure-n-octylester.
- (P₉) Zubereitung bestehend aus
- 12
- Teilen des Natriumsalzes des sauren Schwefelsäureesters des Oxalkylierungsproduktes von 18 Mol Ethylenoxid an 1 Mol des Anlagerungsproduktes von 3 Mol Styrol an 1 Mol Phenol
- 12
- Teilen des Oxalkylierungsproduktes von 18 Mol Ethylenoxid an 1 Mol des Anlagerungsproduktes von 3 Mol Styrol an 1 Mol Phenol
- 60
- Teilen Benzoesäuredodecylester.
- (P₁₀) Zubereitung bestehend aus
- 12
- Teilen des Natriumsalzes des sauren Schwefelsäureesters des Oxalkylierungsproduktes von 18 Mol Ethylenoxid an 1 Mol des Anlagerungsproduktes von 3 Mol Styrol an 1 Mol Phenol
- 12
- Teilen des Oxalkylierungsproduktes von 18 Mol Ethylenoxid an 1 Mol des Anlagerungsproduktes von 3 Mol Styrol an 1 Mol Phenol
- 60
- Teilen Benzoesäuredecylester.
- (P₄) preparation consisting of
- 20th
- Parts of triethanolamine salt of a mixture of mono- and diester phosphate of an oxyalkylation product with 18 ethylene oxide units of the adduct of 2.5 to 3 moles of styrene and 1 mole of phenol
- 20th
- Share an oxyalkylation product of 18 moles of ethylene oxide with 1 mole of an adduct of 2.5 to 3 moles of styrene with 1 mole of phenol and
- 60
- Parts of benzoate.
- (P₅) preparation consisting of
- 16
- Parts of sodium salt of the acidic sulfuric acid ester of the adduct of 35 moles of ethylene oxide and 1 mole of nonylphenol
- 24th
- Parts of the compound of formula (11) and prepared according to regulation 1
- 60
- Parts of benzoate.
- (P₆) preparation consisting of
- 16
- Parts of sodium salt of the acidic sulfuric acid ester of the adduct of 35 moles of ethylene oxide and 1 mole of nonylphenol
- 24th
- Parts of the compound of formula (15) and prepared according to regulation 11
- 60
- Parts of benzoate.
- (P₇) preparation consisting of
- 16
- Parts of sodium salt of the acidic sulfuric acid ester of the adduct of 35 moles of ethylene oxide and 1 mole of nonylphenol
- 24th
- Share the adduct of 36 moles of ethylene oxide with 1 mole of stearyl alcohol and
- 60
- Parts of 2-ethylhexyl propionate.
- (P₈) preparation consisting of
- 16
- Parts of sodium salt of the acidic sulfuric acid ester of the adduct of 35 moles of ethylene oxide and 1 mole of nonylphenol
- 24th
- Share the adduct of 36 moles of ethylene oxide with 1 mole of stearyl alcohol and
- 60
- Parts of lactic acid n-octyl ester.
- (P₉) preparation consisting of
- 12th
- Share the sodium salt of the acidic sulfuric acid ester of the oxyalkylation product of 18 moles of ethylene oxide with 1 mole of the adduct of 3 moles of styrene with 1 mole of phenol
- 12th
- Share the oxyalkylation product of 18 moles of ethylene oxide with 1 mole of the adduct of 3 moles of styrene with 1 mole of phenol
- 60
- Share dodecyl benzoate.
- (P₁₀) preparation consisting of
- 12th
- Share the sodium salt of the acidic sulfuric acid ester of the oxyalkylation product of 18 moles of ethylene oxide with 1 mole of the adduct of 3 moles of styrene with 1 mole of phenol
- 12th
- Share the oxyalkylation product of 18 moles of ethylene oxide with 1 mole of the adduct of 3 moles of styrene with 1 mole of phenol
- 60
- Share decyl benzoate.
Claims (20)
- A process for preparing a mixture of dyeing assistants which comprises(A) an acid ester, or salts thereof, of an alkylene oxide adduct of the formula(B) a nonionic surfactant containing polyglycol ether groups, and(C) an aliphatic or aromatic carboxylic acid ester, with the exception of mixtures of dyeing assistants comprising alkylbenzene, tetralin or nonaromatic, water-immiscible solvents, wherein the components (A), (B) and (C) are mixed with one another.
- A process according to claim 1, wherein Y in the formula (1) is C₄-C₁₀alkyl or α-methylbenzyl.
- A process according to either of claims 1 and 2, wherein the acid radical X in the formula (1) is derived from sulfuric acid or orthophosphoric acid.
- A process according to any one of claims 1 to 3, wherein n in the formula (1) is 4 to 40.
- A process according to any one of claims 1 to 4, wherein V in the formula (1) is hydrogen.
- A process according to claim 1, wherein the component (A) is an acid phosphoric acid ester or sulfuric acid ester, or salts thereof, of an alkoxylation product of 8 to 30 moles of ethylene oxide added onto 1 mole of a compound which has been prepared by the addition of 1 to 3 moles of styrene, α-methylstyrene or vinyltoluene onto 1 mole of phenol, cresol or xylenol.
- A process according to any one of claims 1 to 8, wherein the component (B) is an alkylene oxide adduct of 2 to 100 moles of alkylene oxide onto 1 mole of an aliphatic monoalcohol having at least 4 carbon atoms, of a trihydric to hexahydric aliphatic alcohol having 3 to 6 carbon atoms, of a phenol which is unsubstituted or substituted by C₄-C₁₂alkyl, phenyl, α-tolylethyl, benzyl, α-methylbenzyl or α,α-dimethylbenzyl, or of a fatty acid having 8 to 22 carbon atoms.
- A process according to any one of claims 1 to 8, wherein the component (B) is a compound of the formula
R is an alkyl or alkenyl radical having in each case 8 to 24 carbon atoms or a radical of the formula
W is an aliphatic radical having 8 to 30 carbon atoms and Y, m, n and "alkylene" are as defined in claim 1. - A process according to any one of claims 1 to 13, wherein the component (C) is a monocarboxylic or dicarboxylic acid ester formed from an aliphatic or aromatic monocarboxylic or dicarboxylic acid having 3 to 12 carbon atoms and an aliphatic monoalcohol of 4 to 22 carbon atoms or an araliphatic alcohol.
- A process according to any one of claims 1 to 14, wherein the component (C) is benzyl benzoate.
- A process according to any one of claims 1 to 14, wherein the component (C) is a C₈-C₁₂alkyl benzoate.
- A process according to any one of claims 1 to 16, to which a polar solvent as a component (D) is additionally admixed.
- A process according to any one of claims 1 to 17, which relates to a mixture comprising, relative to the whole mixture,
10 to 40 per cent by weight of the component (A)
15 to 50 per cent by weight of the component (B)
20 to 70 per cent by weight of the component (C)
0 to 40 per cent by weight of the component (D). - The use of the mixture of assistants according to any one of claims 1 to 18 in the dyeing of synthetic fibre materials, in particular polyester fibres.
- A process for dyeing textile material containing polyester fibres by means of disperse dyes, which comprises dyeing this material in the presence of the mixture of assistants according to any one of claims 1 to 18.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH43089 | 1989-02-08 | ||
CH430/89 | 1989-02-08 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0382138A1 EP0382138A1 (en) | 1990-08-16 |
EP0382138B1 true EP0382138B1 (en) | 1994-08-24 |
Family
ID=4186843
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90102212A Expired - Lifetime EP0382138B1 (en) | 1989-02-08 | 1990-02-05 | Auxiliary mixture and its use in dyeing synthetic fibrous materials |
Country Status (12)
Country | Link |
---|---|
US (1) | US5009668A (en) |
EP (1) | EP0382138B1 (en) |
JP (1) | JPH07111031B2 (en) |
AT (1) | ATE110425T1 (en) |
AU (1) | AU605703B2 (en) |
CA (1) | CA2009382C (en) |
DE (1) | DE59006864D1 (en) |
DK (1) | DK0382138T3 (en) |
ES (1) | ES2058621T3 (en) |
IL (1) | IL93283A (en) |
MX (1) | MX173670B (en) |
ZA (1) | ZA90901B (en) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5223177A (en) * | 1989-01-09 | 1993-06-29 | Ciba-Geigy Corporation | Alkali-resistant foam suppressant which is free from silicone oil |
EP0420807A1 (en) * | 1989-09-27 | 1991-04-03 | Ciba-Geigy Ag | Addition products of alkylene and styrene oxide on arylalkanols |
US6113656A (en) * | 1995-01-17 | 2000-09-05 | Milliken & Company | Method of dyeing low pill polyester |
EP0879277B1 (en) * | 1996-01-19 | 2001-10-17 | Unilever Plc | Non-cationic systems for dryer sheets |
DE19638566A1 (en) * | 1996-09-20 | 1998-03-26 | Clariant Gmbh | Use of aryloxypolyglycol ethers as leveling and dispersing agents |
TW459022B (en) * | 1996-10-31 | 2001-10-11 | Bayer Ag | Pigment preparation useful for ink-jet printing, dispersing mixture used therein and ink-jet printing method |
US6245138B1 (en) | 1997-10-20 | 2001-06-12 | Bayer Aktiengesellschaft | Pigment preparations useful for ink-jet printing |
DE102005013781A1 (en) * | 2005-03-22 | 2006-09-28 | Basf Ag | Process for dyeing textiles with vat dye |
DE102005018932A1 (en) * | 2005-04-22 | 2006-10-26 | Basf Ag | Process for dyeing polyester-containing textile with disperse dye |
US7261742B2 (en) * | 2005-10-13 | 2007-08-28 | S.C. Johnson & Son, Inc. | Method of deodorizing a textile |
US7407922B2 (en) * | 2005-10-13 | 2008-08-05 | S.C. Johnson & Son, Inc. | Deodorizing compositions |
US10011703B2 (en) * | 2012-03-09 | 2018-07-03 | Ethox Chemicals, Llc | Water borne epoxy resin dispersions and epoxy hardener compositions |
WO2014022991A1 (en) * | 2012-08-08 | 2014-02-13 | 日华化学株式会社 | Dyeing assistant for polyester fibre and method for dyeing polyester fibre using same, and method for manufacturing dyed material |
CN103741522A (en) * | 2013-12-14 | 2014-04-23 | 常熟市淼泉盛达助剂厂 | Fabric dispersive dye leveler |
JP6214388B2 (en) * | 2013-12-25 | 2017-10-18 | 日華化学株式会社 | Dyeing assistant for fiber and method for producing dyed product |
US9915028B1 (en) * | 2016-09-15 | 2018-03-13 | Ronald Tyler Daugherty | Dye additive and process for dyeing aramid fibers |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3728078A (en) * | 1971-10-18 | 1973-04-17 | Gaf Corp | Textile dye carrier emulsifier composition and process for dyeing polyesters therewith |
JPS5012036B2 (en) * | 1971-12-18 | 1975-05-08 | ||
JPS5370175A (en) * | 1976-11-26 | 1978-06-22 | Sanyo Chemical Ind Ltd | Dyeing aid for hydrohobic synthetic fiber with dye transfer property |
CH637432A5 (en) * | 1978-10-19 | 1983-07-29 | Ciba Geigy Ag | Dyeing assistant suitable for use in the dyeing of synthetic fibre materials |
US4252534A (en) * | 1978-10-19 | 1981-02-24 | Ciba-Geigy Corporation | Dyeing assistants and their use in dyeing synthetic fibre material |
JPS57176267A (en) * | 1981-04-21 | 1982-10-29 | Sumitomo Chemical Co | Dyeing of hydrophobic fiber |
EP0197001B1 (en) * | 1985-03-07 | 1988-10-19 | Ciba-Geigy Ag | Auxiliary mixture and its use as a dyeing auxiliary or textile auxiliary |
EP0414631A1 (en) * | 1989-02-22 | 1991-02-27 | Ciba-Geigy Ag | Auxiliary agent mixture and its use in dyeing polyester fibre materials |
-
1990
- 1990-02-05 AT AT90102212T patent/ATE110425T1/en not_active IP Right Cessation
- 1990-02-05 DE DE59006864T patent/DE59006864D1/en not_active Expired - Fee Related
- 1990-02-05 EP EP90102212A patent/EP0382138B1/en not_active Expired - Lifetime
- 1990-02-05 DK DK90102212.9T patent/DK0382138T3/en active
- 1990-02-05 ES ES90102212T patent/ES2058621T3/en not_active Expired - Lifetime
- 1990-02-06 IL IL93283A patent/IL93283A/en not_active IP Right Cessation
- 1990-02-06 CA CA002009382A patent/CA2009382C/en not_active Expired - Fee Related
- 1990-02-07 ZA ZA90901A patent/ZA90901B/en unknown
- 1990-02-07 AU AU49220/90A patent/AU605703B2/en not_active Ceased
- 1990-02-07 MX MX019412A patent/MX173670B/en unknown
- 1990-02-08 JP JP2027309A patent/JPH07111031B2/en not_active Expired - Fee Related
- 1990-02-08 US US07/476,997 patent/US5009668A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
CA2009382A1 (en) | 1990-08-08 |
JPH07111031B2 (en) | 1995-11-29 |
IL93283A (en) | 1993-01-31 |
IL93283A0 (en) | 1990-11-29 |
ES2058621T3 (en) | 1994-11-01 |
EP0382138A1 (en) | 1990-08-16 |
MX173670B (en) | 1994-03-22 |
DE59006864D1 (en) | 1994-09-29 |
DK0382138T3 (en) | 1994-09-19 |
ZA90901B (en) | 1990-09-26 |
CA2009382C (en) | 1995-12-12 |
AU605703B2 (en) | 1991-01-17 |
US5009668A (en) | 1991-04-23 |
JPH02242981A (en) | 1990-09-27 |
AU4922090A (en) | 1990-08-23 |
ATE110425T1 (en) | 1994-09-15 |
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