EP0379954B1 - Carrier for dyeing hydrophobic fibre materials - Google Patents

Carrier for dyeing hydrophobic fibre materials Download PDF

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Publication number
EP0379954B1
EP0379954B1 EP90100893A EP90100893A EP0379954B1 EP 0379954 B1 EP0379954 B1 EP 0379954B1 EP 90100893 A EP90100893 A EP 90100893A EP 90100893 A EP90100893 A EP 90100893A EP 0379954 B1 EP0379954 B1 EP 0379954B1
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Prior art keywords
alkyl
carrier
dyeing
substituted
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EP90100893A
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German (de)
French (fr)
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EP0379954A2 (en
EP0379954A3 (en
Inventor
Frank Dr. Bartkowiak
Hans Dr. Schulze
Willi Dr. Schössler
Heinz Ulrich Dr. Blank
Karlhans Dipl.-Ing. Jakobs
Klaus-Dieter Schultz
Karl-Heinz Dr. Passon
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Bayer AG
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Bayer AG
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Classifications

    • 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
    • D06P1/64—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 low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/649—Compounds containing carbonamide, thiocarbonamide or guanyl groups
    • D06P1/6495—Compounds containing carbonamide -RCON= (R=H or hydrocarbons)
    • D06P1/6498—Compounds containing -CONCO-, e.g. phthalimides, hydantoine; Compounds containing RCONHSO2R (R=H or hydrocarbon)
    • 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
    • D06P1/64—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 low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65125—Compounds containing ester groups

Definitions

  • the invention relates to carriers, their preparations and processes for dyeing preferably polyester materials with disperse dyes in the presence of these carriers.
  • Known carriers used in textile practice for dyeing polyester include halogenobenzenes, halogen toluenes, N-alkylphthalimides, aromatic carboxylic acid esters, methylnaphthalene, diphenyl, diphenyl ether, naphthol ether, phenol ether and oxydiphenyls.
  • these connections have disadvantages.
  • the carrier types mentioned - with the exception of N-alkylphthalimides - have a strong intrinsic odor. Methylnaphthalene and the oxydiphenyls adversely affect the lightfastness of the dyeings.
  • Diphenyl ether has the disadvantage that its carrier activity depends strongly on the constitution of the disperse dye used and therefore often no reproducible colorations are obtained.
  • N-alkylphthalimides show a strong drop in the carrier effect at dyeing temperatures below 98 ° C., which indicates their use in higher regions, in the open regions Dyeing equipment limits this temperature is not reached.
  • Phthalic acid esters and benzoic acid esters have only a limited carrier effect and a limited leveling capacity and therefore require high amounts.
  • the object of the present invention is to provide highly effective, halogen-free carriers which bring about the most level possible coloring with a small amount used.
  • the dyeing obtained should meet high authenticity requirements, and the dyeing of mixed fibers should not result in soiling of the accompanying fiber.
  • the substituent -OR1 is in the o- or p-position.
  • the carriers according to the invention are water-insoluble, they are preferably added to the dyeing liquors in the form of preparations which contain emulsifiers or dispersants and, if appropriate, solvents.
  • components 1.) - 4.) can also be used as mixtures.
  • Examples of preferred compounds (I) are: o / p-methoxybenzoic acid-n-C1-C4-alkyl esters, o / p-ethoxybenzoic acid-n-C1-C4-alkyl esters and o / p-Hydroxyethoxybenzoic acid n-C1-C4 alkyl ester.
  • Examples of preferred compounds (II) are straight-chain or branched C3-C5-N-alkylphthalimides.
  • Nonionic and anionic emulsifiers are preferred as emulsifiers 3.).
  • emulsifiers are mixtures of a) ethoxylated oils, such as castor oil or soybean oil, ethoxylated alcohols, alkylphenol polyglycol ethers or phenylalkylphenol polyglycol ethers, b) alkali metal, alkaline earth metal and / or ammonium salts of organic sulfonic acids containing at least 10 carbon atoms, such as dodecylbenzenesulfonic acid, Sulfo fatty acids and ricinoleyl methyl tauride.
  • ethoxylated oils such as castor oil or soybean oil, ethoxylated alcohols, alkylphenol polyglycol ethers or phenylalkylphenol polyglycol ethers
  • z. B. alkanols, glycols, ketones, N-substituted caprolactams or ethers can be used.
  • the carrier mixtures according to the invention are well compatible with other carriers, they can also be used in a mixture with known other carriers.
  • the disperse dyes used for dyeing are the disperse dyes usually used for dyeing polyesters, as described, for example, in "Color Index” Vol. 2, pp. 2483-2741, 3rd edition (1971).
  • the dyeing in the presence of the carriers according to the invention is carried out according to the batchwise methods customary for dyeing with disperse dyes; the usual process operating at 98 ° C. and the high-temperature process may be mentioned as such.
  • the carrier blends according to the invention are also suitable for dyeing polyester / wool and polyester / cotton blended fabrics, because when they are used the soiling of the wool and cotton content is avoided by the disperse dyes.
  • the coloring can be carried out at temperatures of 90-140 ° C, the preferred industrial use being at 90-105 ° C.
  • An additional advantage of the carrier settings described is the very good effectiveness below cooking temperature, which pure N-alkylphthalimide carriers do not show, e.g. B. at 95 ° C, which are often not exceeded under practical conditions with open dyeing machines.
  • the amounts of the mixture of carriers (I) and (II) required to carry out the dyeing can easily be determined from case to case by preliminary tests. In general, amounts of 1 to 7 g per liter of dye liquor have proven themselves in the usual liquor ratios of 1: 5 to 1:40.
  • N-alkylphthalimides as carriers in dyeing polyester is known and is described in DE-C-1 769 210.
  • DE-C-1 769 210 also discloses the use of mixtures of N-alkylphthalimides with disubstituted benzoic acid esters.
  • the mixtures according to the invention have a higher color-accelerating effect than the sum of the individual effects.
  • This synergistic increase in the effectiveness is not shown by the mixtures known hitherto (for example the mixtures of N-alkylphthalimides described in DE-C-1 769 210 with salicylic acid compounds containing alkyl groups).
  • the mixing ratio at which the synergistic optimum is present depends on the components of the carrier mixtures and can easily be determined in individual cases by preliminary tests.
  • Yarns made of polyester fibers are placed in a liquor ratio of 1:40 in a bath heated to 60 ° C, containing 0.25 g of a dye of the formula per liter
  • the pH of the bath is adjusted to pH 4.5-5 with acetic acid.
  • the bath is then heated to 98 ° C. and held at this temperature for 60 minutes. A uniform blue color is obtained.
  • the carrier effectiveness of the carrier mixtures of Examples 2-7 is determined by comparing the color depths achieved.
  • the small amounts of the mixtures demonstrate their more advantageous carrier activity compared to the individual components.
  • Example 8 (comparative example to DE-PS 1 769 210)
  • Yarns made of polyester fibers are placed in a liquor ratio of 1:40 in a bath heated to 60 ° C, which contains 0.25 g of a dye of the formula per liter
  • the pH of the bath is adjusted to pH 4.5-5 with acetic acid.
  • the bath is then heated to 98 ° C. and held at this temperature for 60 minutes. You get an even blue color.
  • this mixture shows no synergistic increase in carrier effectiveness compared to the individual components.
  • Piece goods consisting of polyester spun fiber in warp and weft are placed in a liquor ratio of 1:40 in a bath heated to 50 ° C, containing 0.2 g of a dye of the formula per liter
  • the pH of the bath is adjusted to pH 4.5-5 with acetic acid.
  • the dye liquor is then brought to the boiling temperature and kept at this temperature for one hour. A full, even red color is achieved.
  • Polyester staple fibers are introduced into a dyeing liquor in a liquor ratio of 1:15, which contains 1 g of a disperse dye according to Example 9, 0.03 g of a dye according to Color Index, 2nd edition (1956) Volume 3, No. 12790, 2 per liter g of a condensation product of naphthalene sulfonate and formaldehyde, 2 g of sodium dihydrogen phosphate and 3.5 g of a carrier setting of Example 13.
  • the pH of the bath is adjusted to pH 4.5-5 with acetic acid.
  • the liquor is slowly heated to 98 ° C. and treated at this temperature for one hour. A dark reddish brown color is obtained.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Indole Compounds (AREA)

Description

Die Erfindung betrifft Carrier, ihre Zubereitungen und Verfahren zum Färben von vorzugsweise Polyestermaterialien mit Dispersionsfarbstoffen in Gegenwart dieser Carrier.The invention relates to carriers, their preparations and processes for dyeing preferably polyester materials with disperse dyes in the presence of these carriers.

Zu den bekannten Carriern, die in der textilen Praxis beim Färben von Polyester verwendet werden, gehören Halogenbenzole, Halogentoluole, N-Alkylphthalimide, aromatische Carbonsäureester, Methylnaphthalin, Diphenyl, Diphenylether, Naphtholether, Phenolether und Oxydiphenyle. Diese Verbindungen haben jedoch Nachteile. Beispielsweise besitzen die genannten Carriertypen - mit Ausnahme der N-Alkylphthalimide - einen starken Eigengeruch. Methylnaphthalin und die Oxydiphenyle beeinflussen nachteilig die Lichtechtheit der Färbungen. Diphenylether hat den Nachteil, daß seine Carrierwirksamkeit stark von der Konstitution des verwendeten Dispersionsfarbstoffes abhängt und deshalb oft keine reproduzierbaren Färbungen erhalten werden. N-Alkylphthalimide zeigen bei Färbetemperaturen unterhalb 98°C einen starken Abfall der Carrierwirkung, was ihre Verwendung in höher gelegenen Regionen, in den bei offenen Färbeapparaturen diese Temperatur nicht erreicht wird, einschränkt. Phthalsäureester und Benzoesäureester besitzen nur eine begrenzte Carrierwirkung und ein begrenztes Egalisiervermögen und erfordern deshalb hohe Einsatzmengen.Known carriers used in textile practice for dyeing polyester include halogenobenzenes, halogen toluenes, N-alkylphthalimides, aromatic carboxylic acid esters, methylnaphthalene, diphenyl, diphenyl ether, naphthol ether, phenol ether and oxydiphenyls. However, these connections have disadvantages. For example, the carrier types mentioned - with the exception of N-alkylphthalimides - have a strong intrinsic odor. Methylnaphthalene and the oxydiphenyls adversely affect the lightfastness of the dyeings. Diphenyl ether has the disadvantage that its carrier activity depends strongly on the constitution of the disperse dye used and therefore often no reproducible colorations are obtained. N-alkylphthalimides show a strong drop in the carrier effect at dyeing temperatures below 98 ° C., which indicates their use in higher regions, in the open regions Dyeing equipment limits this temperature is not reached. Phthalic acid esters and benzoic acid esters have only a limited carrier effect and a limited leveling capacity and therefore require high amounts.

Aufgabe der vorliegenden Erfindung ist es, hochwirksame, halogenfreie Carrier zur Verfügung zu stellen, die mit geringer Einsatzmenge eine möglichst egale Färbung bewirken. Gleichzeitig soll die erzielte Färbung hohen Echtheitsansprüchen genügen, und bei der Färbung von Mischfasern soll keine Anschmutzung der Begleitfaser erfolgen.The object of the present invention is to provide highly effective, halogen-free carriers which bring about the most level possible coloring with a small amount used. At the same time, the dyeing obtained should meet high authenticity requirements, and the dyeing of mixed fibers should not result in soiling of the accompanying fiber.

Es wurde nun gefunden, daß man diese Aufgabe dadurch lösen kann, daß man als Carrier solche einsetzt, die Alkoxybenzoesäureester der Formel

Figure imgb0001

worin

R
C₁-C₇-Alkyl, das durch Phenyl substituiert sein kann, oder Phenyl, das durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder C₁-C₄-Alkoxycarbonyl substituiert sein kann und
R¹
C₁-C₄-Alkyl, das durch OH substituiert sein kann, bedeuten,
im Gemisch mit Phthalimiden der Formel
Figure imgb0002

worin
X
C₁-C₇-Alkyl bedeutet,

enthalten, wobei das bevorzugte Gewichtsverhältnis von N-Alkylphthalimiden zu den Benzoesäureestern bei 0,5 - 12 : 1 liegt.It has now been found that this problem can be solved by using carriers as carriers, the alkoxybenzoic acid esters of the formula
Figure imgb0001
wherein
R
C₁-C₇-alkyl, which may be substituted by phenyl, or phenyl, which may be substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkoxycarbonyl and
R¹
C₁-C₄-alkyl, which may be substituted by OH, mean
in a mixture with phthalimides of the formula
Figure imgb0002

wherein
X
C₁-C₇ alkyl means

included, the preferred weight ratio of N-alkylphthalimides to the benzoic acid esters being 0.5-12: 1.

Vorzugsweise steht der Substituent -OR₁ in o- oder p-Stellung.Preferably, the substituent -OR₁ is in the o- or p-position.

Da die erfindungsgemäßen Carrier wasserunlöslich sind, werden sie vorzugsweise in Form von Zubereitungen, die Emulgier- oder Dispergiermittel und gegebenenfalls Lösungsmittel enthalten, den Färbeflotten zugesetzt.Since the carriers according to the invention are water-insoluble, they are preferably added to the dyeing liquors in the form of preparations which contain emulsifiers or dispersants and, if appropriate, solvents.

Bevorzugte Zubereitungen von Carriermischungen sind:

  • 1.) 8-58, insbesondere 10-45 Gew.-% (I),
  • 2.) 40-90, insbesondere 45-80 Gew.-% (II),
  • 3.) 2-30, insbesondere 10-20 Gew.-% eines Emulgators und
  • 4.) 0-10 Gew.-% eines Lösungsmittels
Preferred preparations of carrier mixtures are:
  • 1.) 8-58, in particular 10-45% by weight (I),
  • 2.) 40-90, in particular 45-80% by weight (II),
  • 3.) 2-30, in particular 10-20 wt .-% of an emulsifier and
  • 4.) 0-10% by weight of a solvent

Im übrigen können die Komponenten 1.) - 4.) auch als Mischungen eingesetzt werden.Otherwise, components 1.) - 4.) can also be used as mixtures.

Beispiele für bevorzugte Verbindungen (I) sind:
o/p-Methoxybenzoesäure-n-C₁-C₄-alkylester,
o/p-Ethoxybenzoesäure-n-C₁-C₄-alkylester und
o/p-Hydroxyethoxybenzoesäure-n-C₁-C₄-alkylester.Examples of preferred compounds (I) are:
o / p-methoxybenzoic acid-n-C₁-C₄-alkyl esters,
o / p-ethoxybenzoic acid-n-C₁-C₄-alkyl esters and
o / p-Hydroxyethoxybenzoic acid n-C₁-C₄ alkyl ester.

Beispiele für bevorzugte Verbindungen (II) sind gradkettige oder verzweigte C₃-C₅-N-Alkylphthalimide.Examples of preferred compounds (II) are straight-chain or branched C₃-C₅-N-alkylphthalimides.

Als Emulgatoren 3.) werden nichtionische und anionische Emulgatoren bevorzugt.Nonionic and anionic emulsifiers are preferred as emulsifiers 3.).

Beispiele geeigneter Emulgatoren, sind Gemische aus a) oxethylierten Ölen, wie Rizinusöl oder Sojaöl, oxethylierten Alkoholen, Alkylphenolpolyglykolethern oder Phenylalkylphenolpolyglykolethern, b) Alkali-, Erdalkali- und /oder Ammoniumsalzen organischer, mindestens 10 Kohlenstoffatome aufweisender Sulfonsäuren, wie Dodecylbenzolsulfonsäure, Diisobutylnaphthalinsulfonsäure, alpha-Sulfofettsäuren und Rizinoleylmethyltaurid.Examples of suitable emulsifiers are mixtures of a) ethoxylated oils, such as castor oil or soybean oil, ethoxylated alcohols, alkylphenol polyglycol ethers or phenylalkylphenol polyglycol ethers, b) alkali metal, alkaline earth metal and / or ammonium salts of organic sulfonic acids containing at least 10 carbon atoms, such as dodecylbenzenesulfonic acid, Sulfo fatty acids and ricinoleyl methyl tauride.

Als Lösungsmittel 4.), die gegebenenfalls die Viskosität der Formulierung verbessern, können z. B. Alkanole, Glykole, Ketone, N-substituierte Caprolactame oder Ether verwendet werden.As a solvent 4.), which may improve the viscosity of the formulation, z. B. alkanols, glycols, ketones, N-substituted caprolactams or ethers can be used.

Besonders bevorzugte Carrier-Zubereitungen enthalten entweder

  • 1.) 10-40 Gew.-% (I) und 50-75 Gew.-% (II) sowie
  • 2.) 5-20 Gew.-% eines Additionsproduktes von 15-30 mol Ethylenoxid an Rizinus- oder Sojaöl, von 5-50 mol Ethylenoxid und/oder Propylenoxid an C₁₆-C₂₂-Fettalkohole, Octyl- oder Nonylphenol oder Phenylethylphenol, Alkali-, Erdalkali-, Ammonium- oder Mono-, Di- oder Triethanolaminsalze der Dodecylbenzolsulfonsäure.
Particularly preferred carrier preparations contain either
  • 1.) 10-40 wt .-% (I) and 50-75 wt .-% (II) as well
  • 2.) 5-20% by weight of an addition product of 15-30 mol ethylene oxide with castor or soybean oil, with 5-50 mol ethylene oxide and / or propylene oxide with C₁₆-C₂₂ fatty alcohols, octyl or nonylphenol or phenylethylphenol, alkali , Alkaline earth metal, ammonium or mono-, di- or triethanolamine salts of dodecylbenzenesulfonic acid.

Da die erfindungsgemäßen Carrier-Mischungen gut verträglich mit anderen Carriern sind, können sie auch in Mischung mit bekannten anderen Carriern verwendet werden.Since the carrier mixtures according to the invention are well compatible with other carriers, they can also be used in a mixture with known other carriers.

Die zur Färbung verwendeten Dispersionsfarbstoffe sind die üblicherweise zum Färben von Polyestern verwendeten Dispersionsfarbstoffe, wie sie beispielsweise im "Colour Index" Vol. 2, S. 2483-2741, 3. Edition (1971) beschrieben sind. Das Färben in Gegenwart der erfindungsgemäßen Carrier wird nach den für das Färben mit Dispersionsfarbstoffen üblichen diskontinuierlichen Verfahren durchgeführt; als solche seien das übliche bei 98°C arbeitende Verfahren und das Hochtemperatur-Verfahren genannt.The disperse dyes used for dyeing are the disperse dyes usually used for dyeing polyesters, as described, for example, in "Color Index" Vol. 2, pp. 2483-2741, 3rd edition (1971). The dyeing in the presence of the carriers according to the invention is carried out according to the batchwise methods customary for dyeing with disperse dyes; the usual process operating at 98 ° C. and the high-temperature process may be mentioned as such.

Die erfindungsgemäßen Carrier-Mischungen eignen sich auch zum Färben von Polyester/Wolle- und Polyester/Baumwolle-Mischgeweben, weil bei ihrer Verwendung die Anschmutzung des Woll- und Baumwolleanteils durch die Dispersionsfarbstoffe vermieden wird.The carrier blends according to the invention are also suitable for dyeing polyester / wool and polyester / cotton blended fabrics, because when they are used the soiling of the wool and cotton content is avoided by the disperse dyes.

Mit Hilfe der Carrier-Mischungen gelingt es, Gebilde, z. B. Fäden, Fasern, Gewebe, Gewirke, Filme und Folien aus Polyestern, wie Polyterephthalsäureglykolestern, oder Polyester-Mischgewebe mit Dispersionsfarbstoffen in tiefen Tönen und hervorragend gleichmäßig zu färben. Die Färbung kann bei Temperaturen von 90-140°C durchgeführt werden, wobei die bevorzugte technische Verwendung bei 90-105°C erfolgt. Ein zusätzlicher Vorteil der beschriebenen Carrier-Einstellungen ist die sehr gute Wirksamkeit unterhalb Kochtemperatur, die reine N-Alkylphthalimid-Carrier nicht zeigen, z. B. bei 95°C, die häufig unter Praxisbedingungen bei offenen Färbeapparaturen nicht überschritten werden.With the help of carrier mixtures it is possible to form, z. B. threads, fibers, fabrics, knitted fabrics, films and foils made of polyesters, such as polyterephthalic acid glycol esters, or polyester blended fabrics with disperse dyes in deep shades and excellent to dye evenly. The coloring can be carried out at temperatures of 90-140 ° C, the preferred industrial use being at 90-105 ° C. An additional advantage of the carrier settings described is the very good effectiveness below cooking temperature, which pure N-alkylphthalimide carriers do not show, e.g. B. at 95 ° C, which are often not exceeded under practical conditions with open dyeing machines.

Die zur Durchführung der Färbung erforderlichen Mengen der Mischung der Carrier (I) und (II) lassen sich durch Vorversuche von Fall zu Fall leicht ermitteln. Im allgemeinen haben sich Mengen von 1 bis 7 g je Liter Färbeflotte bei den üblichen Flottenverhältnissen von 1:5 bis 1:40 bewährt.The amounts of the mixture of carriers (I) and (II) required to carry out the dyeing can easily be determined from case to case by preliminary tests. In general, amounts of 1 to 7 g per liter of dye liquor have proven themselves in the usual liquor ratios of 1: 5 to 1:40.

Die Verwendung von N-Alkylphthalimiden als Carrier beim Färben von Polyester ist bekannt und in DE-C- 1 769 210 beschrieben.The use of N-alkylphthalimides as carriers in dyeing polyester is known and is described in DE-C-1 769 210.

Aus der DE-C- 1 769 210 ist auch die Verwendung von Mischungen von N-Alkylphthalimiden mit disubstituierten Benzoesäureestern bekannt.DE-C-1 769 210 also discloses the use of mixtures of N-alkylphthalimides with disubstituted benzoic acid esters.

Es ist als ausgesprochen überraschend zu bezeichnen, daß die erfindungsgemäßen Mischungen eine höhere färbebeschleunigende Wirkung aufweisen, als es der Summe der Einzelwirkungen entspricht. Diese synergistische Erhöhung der Wirksamkeiten zeigen die bisher bekannten Mischungen (z. B. die in der DE-C- 1 769 210 beschriebenen Mischungen von N-Alkylphthalimiden mit alkylgruppenhaltigen Salicylsäure-Verbindungen) nicht. Das Mischungsverhältnis, bei dem das synergistische Optimum vorliegt, ist dabei von den Komponenten der Carrier-Mischungen abhängig und ist im Einzelfall durch Vorversuche leicht zu ermitteln.It can be described as extremely surprising that the mixtures according to the invention have a higher color-accelerating effect than the sum of the individual effects. This synergistic increase in the effectiveness is not shown by the mixtures known hitherto (for example the mixtures of N-alkylphthalimides described in DE-C-1 769 210 with salicylic acid compounds containing alkyl groups). The mixing ratio at which the synergistic optimum is present depends on the components of the carrier mixtures and can easily be determined in individual cases by preliminary tests.

Beispiel 1example 1

Garne aus Polyesterfasern werden im Flottenverhältnis von 1:40 in ein auf 60°C erwärmtes Bad eingebracht, das je Liter 0,25 g eines Farbstoffes der Formel

Figure imgb0003
Yarns made of polyester fibers are placed in a liquor ratio of 1:40 in a bath heated to 60 ° C, containing 0.25 g of a dye of the formula per liter
Figure imgb0003

2 g eines Kondensationsprodukts aus Naphthalinsulfonat und Formaldehyd, 2 g Natriumdihydrogenphosphat und 3 g einer Carrier-Einstellung der Beispiele 2-7 enthält:2 g of a condensation product of naphthalene sulfonate and formaldehyde, 2 g of sodium dihydrogen phosphate and 3 g of a carrier setting of Examples 2-7 contains:

Der pH-Wert des Bades wird mit Essigsäure auf pH 4,5-5 eingestellt. Dann wird das Bad auf 98°C erhitzt und 60 Minuten bei dieser Temperatur gehalten. Man erhält eine gleichmäßige Blaufärbung.The pH of the bath is adjusted to pH 4.5-5 with acetic acid. The bath is then heated to 98 ° C. and held at this temperature for 60 minutes. A uniform blue color is obtained.

Beispiel 2-7Example 2-7

Die Färbung wird wie in Beispiel 1 beschrieben durchgeführt, wobei man Carrier-Einstellungen folgender Zusammensetzungen verwendet:The dyeing is carried out as described in Example 1, using carrier settings of the following compositions:

Bspl. 2:Ex. 2:

0,90 g0.90 g
4-Methoxybenzoesäureethylester4-methoxybenzoic acid ethyl ester
1,65 g1.65 g
N-ButylphthalimidN-butyl phthalimide
0,22 g0.22 g
Rizinusöl mit ca. 30 mol EOCastor oil with approx. 30 mol EO
0,18 g0.18 g
Monoethanolaminsalz der DodecylbenzolsulfonsäureMonoethanolamine salt of dodecylbenzenesulfonic acid
0,05 g0.05 g
Stearylalkohol mit ca. 8 mol EOStearyl alcohol with approx. 8 mol EO
Bspl. 3:Ex. 3:

1,05 g1.05 g
4-Ethoxybenzoesäure-n-butylester4-Ethoxybenzoic acid n-butyl ester
1,50 g1.50 g
N-ButylphthalimidN-butyl phthalimide
0,25 g0.25 g
Tri-(methylphenylethyl)-phenol mit ca. 15 mol EOTri- (methylphenylethyl) phenol with approx. 15 mol EO
0,20 g0.20 g
Monoethanolaminsalz der DodecylbenzolsulfonsäureMonoethanolamine salt of dodecylbenzenesulfonic acid
Bspl. 4:Ex. 4:

1,05 g1.05 g
4-Methoxybenzoesäurekresylester4-Methoxybenzoic acid cresyl ester
1,50 g1.50 g
N-Alkylphthalimide (Alkyl = 50 % n-Butyl, 30 % Propyl, 20 % Ethyl)N-alkylphthalimides (alkyl = 50% n-butyl, 30% propyl, 20% ethyl)
0,25 g0.25 g
Tri-(methylphenylethyl)-phenol mit ca. 15 mol EOTri- (methylphenylethyl) phenol with approx. 15 mol EO
0,20 g0.20 g
Monoethanolaminsalz der DodecylbenzolsulfonsäureMonoethanolamine salt of dodecylbenzenesulfonic acid
Bspl. 5:Ex. 5:

0,50 g0.50 g
2-Methoxybenzoesäuremethylester2-methoxybenzoic acid methyl ester
2,05 g2.05 g
N-ButylphthalimidN-butyl phthalimide
0,30 g0.30 g
Rizinusöl mit ca. 30 mol EOCastor oil with approx. 30 mol EO
0,15 g0.15 g
Calciumdodecylbenzolsulfonat (70 % in Butanol)Calcium dodecylbenzenesulfonate (70% in butanol)
Bspl. 6:Ex. 6:

1,05 g1.05 g
2-Methoxybenzoesäureethylester2-methoxybenzoic acid ethyl ester
1,50 g1.50 g
N-Alkylphthalimide (Alkyl = 50 % n-Butyl, 30 % Propyl, 20 % Ethyl)N-alkylphthalimides (alkyl = 50% n-butyl, 30% propyl, 20% ethyl)
0,25 g0.25 g
Tri-(methylphenylethyl)-phenol mit ca. 15 mol EOTri- (methylphenylethyl) phenol with approx. 15 mol EO
0,20 g0.20 g
Monoethanolaminsalz der DodecylbenzolsulfonsäureMonoethanolamine salt of dodecylbenzenesulfonic acid
Bspl. 7:Ex. 7:

1,55 g1.55 g
4-Ethoxybenzoesäureethylester4-Ethoxybenzoic acid ethyl ester
1,20 g1.20 g
N-Alkylphthalimide (Alkyl = 70 % n-Butyl, 30 % n-Propyl)N-alkylphthalimides (alkyl = 70% n-butyl, 30% n-propyl)
0,25 g0.25 g
Tri-(methylphenylethyl)-phenol mit ca. 15 mol EOTri- (methylphenylethyl) phenol with approx. 15 mol EO
0,20 g0.20 g
Monoethanolaminsalz der DodecylbenzolsulfonsäureMonoethanolamine salt of dodecylbenzenesulfonic acid

Man erhält jeweils eine gleichmäßige Blaufärbung.A uniform blue color is obtained in each case.

Die Bestimmung der Carrierwirksamkeit der Carriermischungen der Beispiele 2-7 erfolgt durch Vergleich der erzielten Farbtiefen. In der folgenden Tabelle wird die Menge an Carriermischung und an Alkoxybenzoesäureester (I) angegeben, die zur Erzielung gleicher Farbtiefen erforderlich ist. Die Mengenangabe ist bezogen auf die Menge an N-Alkylphthalimid (II) = 100. Die geringen Mengen der Mischungen belegen ihre vorteilhaftere Carrierwirksamkeit gegenüber den Einzelkomponenten.

Figure imgb0004
The carrier effectiveness of the carrier mixtures of Examples 2-7 is determined by comparing the color depths achieved. The following table shows the amount of carrier mixture and of alkoxybenzoic acid ester (I) required to achieve the same depth of color. The amount is based on the amount of N-alkylphthalimide (II) = 100. The small amounts of the mixtures demonstrate their more advantageous carrier activity compared to the individual components.
Figure imgb0004

Beispiel 8 (Vergleichsbeispiel zu DE-PS 1 769 210)Example 8 (comparative example to DE-PS 1 769 210)

Garne aus Polyesterfasern werden im Flottenverhältnis von 1:40 in ein auf 60°C erwärmtes Bad eingebracht, das je Liter 0,25 g eines Farbstoffs der Formel

Figure imgb0005
Yarns made of polyester fibers are placed in a liquor ratio of 1:40 in a bath heated to 60 ° C, which contains 0.25 g of a dye of the formula per liter
Figure imgb0005

2 g eines Kondensationsprodukts aus Naphthalinsulfonat und Formaldehyd, 2 g Natriumhydrogenphosphat und 3 g einer Carrier-Einstellung folgender Zusammensetzung enthält:

1,80 g
N-Alkylphthalimide (Alkyl = 60 % Butyl, 40 % Propyl)
0,75 g
o-Kresotinsäureethylester
0,25 g
Tri-(methylphenylethyl)-phenol mit ca. 15 mol EO
0,20 g
Monoethanolaminsalz der Dodecylbenzolsulfonsäure.
2 g of a condensation product of naphthalene sulfonate and formaldehyde, 2 g of sodium hydrogen phosphate and 3 g of a carrier setting contains the following composition:
1.80 g
N-alkylphthalimides (alkyl = 60% butyl, 40% propyl)
0.75 g
ethyl o-cresotate
0.25 g
Tri- (methylphenylethyl) phenol with approx. 15 mol EO
0.20 g
Monoethanolamine salt of dodecylbenzenesulfonic acid.

Der pH-Wert des Bades wird mit Essigsäure auf pH 4,5-5 eingestellt. Dann wird das Bad auf 98°C erhitzt und 60 Minuten bei dieser Temperatur gehalten. Man erhält eine gleichmäßige Blaufärbung. Die Bestimmung der Carrierwirksamkeit erfolgte wie vorstehend beschrieben (N-Alkylphthalimide (II) = 100).

Figure imgb0006
The pH of the bath is adjusted to pH 4.5-5 with acetic acid. The bath is then heated to 98 ° C. and held at this temperature for 60 minutes. You get an even blue color. The carrier effectiveness was determined as described above (N-alkylphthalimide (II) = 100).
Figure imgb0006

Diese Mischung zeigt im Gegensatz zu den beanspruchten Carriermischungen keine synergistische Erhöhung der Carrierwirksamkeit im Vergleich zu den Einzelkomponenten.In contrast to the carrier mixtures claimed, this mixture shows no synergistic increase in carrier effectiveness compared to the individual components.

Beispiel 9Example 9

Stückware, die in Kette und Schuß aus Polyester-Spinnfaser besteht, wird im Flottenverhältnis von 1:40 in ein auf 50°C erwärmtes Bad gegeben, das je Liter 0,2 g eines Farbstoffs der Formel

Figure imgb0007
Piece goods consisting of polyester spun fiber in warp and weft are placed in a liquor ratio of 1:40 in a bath heated to 50 ° C, containing 0.2 g of a dye of the formula per liter
Figure imgb0007

2 g eines Kondensationsprodukts aus Naphthalinsulfonat und Formaldehyd, 2 g Natriumdihydrogenphosphat und 2,5 g einer Carrier-Einstellung folgender Zusammensetzung enthält:

1,65 g
N-Alkylphthalimide (Alkyl = 60 % Butyl, 40 % Propyl)
0,90 g
4-Methoxybenzoesäureethylester
0,25 g
Tri-(methylphenylethyl)-phenol mit ca. 15 mol EO
0,20 g
Monoethanolaminsalz der Dodecylbenzolsulfonsäure.
2 g of a condensation product of naphthalene sulfonate and formaldehyde, 2 g of sodium dihydrogen phosphate and 2.5 g a carrier setting with the following composition:
1.65 g
N-alkylphthalimides (alkyl = 60% butyl, 40% propyl)
0.90 g
4-methoxybenzoic acid ethyl ester
0.25 g
Tri- (methylphenylethyl) phenol with approx. 15 mol EO
0.20 g
Monoethanolamine salt of dodecylbenzenesulfonic acid.

Der pH-Wert des Bades wird mit Essigsäure auf pH 4,5-5 eingestellt. Die Färbeflotte wird dann auf Kochtemperatur gebracht und eine Stunde bei dieser Temperatur gehalten. Es wird eine volle, gleichmäßige Rotfärbung erzielt.The pH of the bath is adjusted to pH 4.5-5 with acetic acid. The dye liquor is then brought to the boiling temperature and kept at this temperature for one hour. A full, even red color is achieved.

Beispiel 10Example 10

Polyester-Spinnfasern werden im Flottenverhältnis von 1:15 in eine Färbeflotte eingebracht, die je Liter 1 g eines Dispersionsfarbstoffs nach Beispiel 9, 0,03 g eines Farbstoffs gemäß Colour Index, 2. Auflage (1956) Band 3, Nr. 12790, 2 g eines Kondensationsprodukts aus Naphthalinsulfonat und Formaldehyd, 2 g Natriumdihydrogenphosphat und 3,5 g einer Carrier-Einstellung des Beispiels 13 enthält. Der pH-Wert des Bades wird mit Essigsäure auf pH 4,5-5 eingestellt. Man erhitzt die Flotte langsam auf 98°C und behandelt eine Stunde bei dieser Temperatur. Man erhält eine dunkle Rotbraunfärbung.Polyester staple fibers are introduced into a dyeing liquor in a liquor ratio of 1:15, which contains 1 g of a disperse dye according to Example 9, 0.03 g of a dye according to Color Index, 2nd edition (1956) Volume 3, No. 12790, 2 per liter g of a condensation product of naphthalene sulfonate and formaldehyde, 2 g of sodium dihydrogen phosphate and 3.5 g of a carrier setting of Example 13. The pH of the bath is adjusted to pH 4.5-5 with acetic acid. The liquor is slowly heated to 98 ° C. and treated at this temperature for one hour. A dark reddish brown color is obtained.

Claims (4)

  1. Carriers for dyeing hydrophobic fibre materials, which contain alkoxybenzoic acid enters of the formula
    Figure imgb0012
     wherein
    R   denotes C₁-C₇-alkyl, which can be substituted by phenyl, or phenyl, which can be substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkoxycarbonyl, and
    R₁   denotes C₁-C₄-alkyl, which can be substituted by OH,
    in a mixture with phthalimides of the formula
    Figure imgb0013
     wherein
    X   denotes C₁-C₇-alkyl,
    the weight ratio of the phthalimides to the alkoxybenzoic acid esters being 0.5-12:1.
  2. Carriers according to Claim 1, characterised in that the alkyl alkoxybenzoates they contain are
    n-C₁-C₄-alkyl o/p-methoxybenzoates,
    n-C₁-C₄-alkyl o/p-ethoxybenzoates and
    n-C₁-C₄-alkyl o/p-hydroxybenzoates.
  3. Carrier formulations, characterised in that they contain
    8-58 % by weight of alkoxybenzoic acid esters of the formula
    Figure imgb0014
     wherein
    R   denotes C₁-C₇-alkyl, which can be substituted by phenyl, or phenyl, which can be substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkoxycarbonyl and
    R₁   denotes C₁-C₄-alkyl, which can be substituted by OH,
    40-90 % by weight of N-alkylphthalimide of the formula
    Figure imgb0015
     wherein
    X   denotes C₁-C₇-alkyl,
    2-30 % by weight of emulsifier and
    0-10 % by weight of solvent.
  4. Process for dyeing hydrophobic fibre materials, characterised in that dyeing in carried out in the presence of carriers according to Claim 1.
EP90100893A 1989-01-25 1990-01-17 Carrier for dyeing hydrophobic fibre materials Expired - Lifetime EP0379954B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3902052A DE3902052A1 (en) 1989-01-25 1989-01-25 CARRIER FOR DYING HYDROPHOBIC FIBER MATERIALS
DE3902052 1989-01-25

Publications (3)

Publication Number Publication Date
EP0379954A2 EP0379954A2 (en) 1990-08-01
EP0379954A3 EP0379954A3 (en) 1991-08-14
EP0379954B1 true EP0379954B1 (en) 1993-08-18

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JP (1) JP2612945B2 (en)
DE (2) DE3902052A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2037597B1 (en) * 1990-08-27 1994-03-16 Sandoz Ag IMPROVEMENTS IN OR RELATED TO ORGANIC COMPOUNDS.
JPH09319104A (en) * 1996-05-24 1997-12-12 Ricoh Co Ltd Electrophotographic photoreceptor
JP5629104B2 (en) * 2010-03-24 2014-11-19 株式会社クラレ Method for dyeing polyetherimide fiber and dyed product thereof
CA2850126C (en) * 2011-09-29 2019-07-30 Dow Global Technologies Llc Formulations having benzoate dye carriers for meta-aramid articles

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Publication number Priority date Publication date Assignee Title
US2881045A (en) * 1954-06-17 1959-04-07 American Cyanamid Co Method of dyeing synthetic fibrous materials
FR1140000A (en) * 1955-01-05 1957-07-09 Hoechst Ag Process for dyeing articles made of polyester fibers with a high degree of polymerization
DE1769210A1 (en) * 1968-04-20 1970-12-17 Bayer Ag Printing and coloring processes
DE2244239A1 (en) * 1972-09-08 1974-03-14 Bayer Ag Dyeing polyesters in multicolour effects - by treating or printing with aqs bath or paste containing carrier and dyeing with dispersion dyestuff without adding carrier

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts Band 98, Nr.16, 1983, Zusammenfassung Nr. 127634p. *
Chemical Abstracts Band 98, Nr.16, 1983, Zusammenfassung Nr.127632m. *

Also Published As

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JPH02229280A (en) 1990-09-12
DE3902052A1 (en) 1990-07-26
EP0379954A2 (en) 1990-08-01
DE59002352D1 (en) 1993-09-23
JP2612945B2 (en) 1997-05-21
EP0379954A3 (en) 1991-08-14

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