EP0364792B1 - Carrier for dyeing polyester materials - Google Patents

Description

The invention relates to carriers, their preparations and processes for dyeing 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. However, these connections have disadvantages. All compounds, with the exception of the 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 sharp drop in the dyeing temperature below 98 ° C. Carrier effect, which limits their use in higher regions, where this temperature is not reached with open dyeing machines. 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. 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.

worin
   R C₁-C₇-Alkyl; Phenyl, Benzyl oder Phenylethyl, die durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder C₁-C₄-Alkoxycarbonyl substituiert sein können.
   R¹ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkylcarbonyloxy, Hydroxy oder C₁-C₄-Alkoxycarbonyl,
   m 0 oder 1,
   n 0 oder 1, wobei m und n nicht gleichzeitig 0 sind,
   enthalten,
   gelöst wird. Diese Mischungen von Carrierwirkstoffen zeigen gegenüber den Einzelkomponenten eine synergistische Erhöhung der färbebeschleunigenden Wirkung.It has now been found that this object is achieved with the carriers according to the invention, which are a mixture of N-alkylphthalimides (I) and compounds of the general formula

wherein
R is C₁-C₇ alkyl; Phenyl, benzyl or phenylethyl, which can be substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkoxycarbonyl.
R¹ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyloxy, hydroxy or C₁-C₄-alkoxycarbonyl,
m 0 or 1,
n is 0 or 1, where m and n are not simultaneously 0,
contain,
is solved. These mixtures of carrier active substances show a synergistic increase in the color-accelerating effect compared to the individual components.

The preferred weight ratio of N-alkylphthalimides (I) to the compounds (II) is 0.5-12: 1.

Since the carrier mixtures 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.

• 1.) 40-90, insbesondere 45-80 Gew.-% (I),
• 2.) 8-58, insbesondere 10-45 Gew.-% (II),
• 3.) 2-30, insbesondere 10-20 Gew.-% eines Emulgators und
• 4.) 0-10 Gew.-% eines Lösungsmittels

enthalten. Dabei können die Komponenten 1.) - 4.) auch als Mischungen eingesetzt werden.Carrier mixtures which are preferred

• 1.) 40-90, in particular 45-80% by weight (I),
• 2.) 8-58, in particular 10-45% by weight (II),
• 3.) 2-30, in particular 10-20 wt .-% of an emulsifier and
• 4.) 0-10% by weight of a solvent

contain. Components 1.) - 4.) can also be used as mixtures.

N-alkylphthalimides (I) are understood to mean, in particular, straight-chain or branched alkyl radicals (C1-C6) on the nitrogen-substituted phthalimides or mixtures thereof which, for. B. can be prepared by the reaction of phthalic anhydride or phthalic acid esters with amines. The carriers can therefore contain phthalic acid amides and esters due to the manufacturing process.

Examples of the compounds (II) are aromatic monocarboxylic acid esters (e.g. esters of benzoic acid, methylbenzoic acid, salicylic acid), dicarboxylic acid esters (e.g. esters of terephthalic acid or phthalic acid), carbonates (e.g. diphenyl carbonate) and ethers (e.g. B. diphenyl ether or ditolyether). As alcohol components of the esters such. B. C₁-C₆ alkanols, phenols and benzyl alcohol.

Nonionic and anionic emulsifiers are preferred as emulsifiers 3.).

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 sulphonic acids having at least 10 carbon atoms, such as dodecylbenzenesulfonic acid, diodecylbenzenesulphonic acid, and dodecylbenzenesulphonic acid -Sulfo fatty acids and ricinoleyl methyl tauride.

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.

• 1.) 50-75 Gew.-% eines N-Alkylphthalimids mit gradkettigem oder verzweigtem Alkylrest mit 3-5 C-Atomen,
• 2.) 10-40 Gew.-% eines C₁-C₄-Alkyl-, Phenyl- oder Benzylesters der Benzoe-, Methylbenzoe-, Terephthal-, Phthal- oder Salicylsäure oder Diphenylcarbonat, Diphenylether oder Ditolylether und
• 3.) 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.

Contain particularly preferred carriers

• 1.) 50-75% by weight of an N-alkylphthalimide with a straight-chain or branched alkyl radical with 3-5 C atoms,
• 2.) 10-40 wt .-% of a C₁-C₄ alkyl, phenyl or benzyl ester of benzoic, methylbenzoic, terephthalic, phthalic or salicylic acid or diphenyl carbonate, diphenyl ether or ditolyl ether and
• 3.) 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.

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.

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.

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 dyeing can be carried out at temperatures of 90-140 ° C, the preferred industrial application being at 90-150 ° C. An additional advantage of the carrier settings described is the very good effectiveness below cooking temperature, which pure N-alkyl phthalimide carriers do not show, e.g. B. at 95 ° C, which is 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.

The use of components (I) and (II) as carriers in dyeing polyester is known.

So z. B. the use of N-alkylphthalimides in DE-C-1 769 210, the use of phthalic acid esters in US-A-4 032 291 and the use of benzoic acid esters in DE-A-2 348 363. DE-C-1 769 210 also discloses the use of mixtures of N-alkylphthalimides with disubstituted benzoic acid esters.

Surprisingly, it has now been found that the mixtures according to the invention have a higher color-accelerating effect than corresponds to 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.

example 1

2 g eines Kondensationsprodukts aus Naphthalinsulfonat und Formaldehyd, 2 g Natriumdihydrogenphosphat und 3 g einer Carrier-Einstellung folgender Zusammensetzung enthält:
   1,80 g N-Alkylphthalimide (Alkyl= 50 % n-Butyl, 50 % n-Propyl)
   0,75 g 4-Methylbenzoesäuremethylester
   0,25 g eines Additionsprodukts von Tri-(methylphenylethyl)-phenol mit ca. 15 mol EO
   0,20 g Monoethanolaminsalz der Dodecylbenzolsulfonsäure.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

2 g of a condensation product of naphthalene sulfonate and formaldehyde, 2 g of sodium dihydrogen phosphate and 3 g of a carrier setting contains the following composition:
1.80 g N-alkylphthalimides (alkyl = 50% n-butyl, 50% n-propyl)
0.75 g of methyl 4-methylbenzoate
0.25 g of an addition product of tri- (methylphenylethyl) phenol with approx. 15 mol EO
0.20 g monoethanolamine salt of dodecylbenzenesulfonic acid.

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.

Example 2-12

The dyeing is carried out as described in Example 1, using carrier settings of the following compositions:

Example 2:

1.65 g of N-butyl phthalimide
0.90 g of 4-methylbenzoic acid ethyl ester
0.20 g calcium dodecylbenzenesulfonate (70% in butanol)
0.20 g castor oil with approx. 30 mol EO
0.05 g stearyl alcohol hexaethylene glycol ether

Example 3:

2.25 g of N-butyl phthalimide
0.30 g dimethyl terephthalate
0.25 g tri- (methylphenylethyl) phenol with approx. 15 mol EO
0.20 g monoethanolamine salt of dodecylbenzenesulfonic acid

Example 4:

1.50 g of N-butyl phthalimide
1.05 g of methyl salicylic acid
0.25 g tri- (methylphenylethyl) phenol with approx. 15 mol EO
0.20 g monoethanolamine salt of dodecylbenzenesulfonic acid

Example 5:

1.50 g N-alkylphthalimide (alkyl = 50% n-butyl, 30% propyl, 20% ethyl)
1.05 g benzyl benzoate
0.25 g di- (phenylethyl) phenol with approx. 10 mol EO
0.20 g monoethanolamine salt of dodecylbenzenesulfonic acid

Example 6:

1.80 g N-alkylphthalimide (alkyl = 70% butyl, 30% propyl)
0.75 g n-butyl benzoate
0.30 g castor oil with approx. 30 mol EO
0.15 g calcium dodecylbenzenesulfonate (70% in butanol)

Example 7:

2.10 g of N-butyl phthalimide
0.45 g phenyl benzoate
0.30 g di- (methylphenylethyl) phenol with approx. 12 mol EO
0.15 g calcium dodecylbenzenesulfonate (70% in butanol)

Example 8:

1.50 g of N-butyl phthalimide
1.05 g diphenyl ether
0.30 g di- (phenylethyl) phenol with approx. 10 mol EO
0.15 g monoethanolamine salt of dodecylbenzenesulfonic acid

Example 9:

1.90 g N-alkylphthalimide (alkyl = 50% butyl, 30% propyl, 20% ethyl)
0.65 g diphenyl carbonate
0.25 g tri- (methylphenylethyl) phenol with approx. 15 mol EO
0.20 g monoethanolamine salt of dodecylbenzenesulfonic acid

Example 10:

2.10 g of N-butyl phthalimide
0.45 g of 2-methylbenzoic acid butyl ester
0.25 g tri- (methylphenylethyl) phenol with approx. 15 mol EO
0.20 g monoethanolamine salt of dodecylbenzenesulfonic acid

Example 11:

1.50 g N-alkylphthalimide (alkyl = 60% n-butyl, 40% n-propyl)
1.05 g of 3-methylbenzoic acid ethyl ester
0.25 g tri- (methylphenylethyl) phenol with approx. 15 mol EO
0.20 g monoethanolamine salt of dodecylbenzenesulfonic acid

Example 12:

1.50 g of N-butyl phthalimide
1.05 g ditolyl ether
0.25 g tri- (methylphenylethyl) phenol with approx. 15 mol EO
0.20 g monoethanolamine salt of dodecylbenzenesulfonic acid

A uniform blue color is obtained in each case.

The carrier effectiveness of the carrier mixtures of Examples 1-12 is determined by comparing the color depths achieved. The following table shows the amount of carrier mixture and of ester / ether (II) required to achieve the same depth of color. The amount is based on the amount of N-alkylphthalimide (I) = 100. The small amounts of the mixtures demonstrate their more advantageous carrier activity compared to the individual components.

Example 13 (comparative example to DE-C-1 769 210)

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.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

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 of N-alkylphthalimides (alkyl = 60% butyl, 40% propyl)
0.75 g of ethyl o-cresotate
0.25 g tri- (methylphenylethyl) phenol with approx. 15 mol EO
0.20 g monoethanolamine salt of dodecylbenzenesulfonic acid.

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. Carrier effectiveness was determined as described above ((I) = 100).

In contrast to the carrier mixtures claimed, this mixture shows no synergistic increase in carrier effectiveness compared to the individual components.

Example 14

2 g eines Kondensationsprodukts aus Naphthalinsulfonat und Formaldehyd, 2 g Natriumdihydrogenphosphat und 2,5 g einer Carrier-Einstellung folgender Zusammensetzung enthält:
   1,80 g N-alkylphthalimide (Alkyl = 60 % Butyl, 40 % Propyl)
   0,75 g 4-Methylbenzoesäuremethylester
   0,25 g Tri-(methylphenylethyl)-phenol mit ca. 15 mol EO
   0,20 g Monoethanolaminsalz der Dodecylbenzolsulfonsäure.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

2 g of a condensation product of naphthalene sulfonate and formaldehyde, 2 g of sodium dihydrogen phosphate and 2.5 g of a carrier setting contains the following composition:
1.80 g N-alkylphthalimide (alkyl = 60% butyl, 40% propyl)
0.75 g of methyl 4-methylbenzoate
0.25 g tri- (methylphenylethyl) phenol with approx. 15 mol EO
0.20 g monoethanolamine salt of dodecylbenzenesulfonic acid.

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.

Example 15

Polyester staple fibers are introduced in a liquor ratio of 1:15 into a dyeing liquor containing 1 g of a disperse dye according to Example 14 per liter, 0.03 g of a dye according to the Color Index, 2nd edition (1956) Volume 3, No. 12790, 2nd 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 14. 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 (5)

1. Carrier mixture containing N-alkylphthalimides (1) and compounds of the general formula

   

   in which
      R denotes C₁-C₇-alkyl; phenyl, benzyl or phenylethyl, which can be substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkoxy- carbonyl,
      R¹ denotes hydrogen, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyloxy, hydroxyl or C₁-C₄-alkoxycarbonyl,
      m denotes 0 or 1,
      n denotes 0 or 1, m and n not being 0 at the same time.
2. Carrier mixture according to Claim 1, containing components (I) and (II) in a weight ratio of 0.5 - 12 : 1.
3. Carrier mixture according to Claim 1, containing

   1.) 40-90% by weight of (I),

   2.) 8-58% by weight of (II),

   3.) 2-30% by weight of an emulsifier and

   4.) 0-10% by weight of a solvent.
4. Carrier mixture according to Claim 1, containing

   1.) 50-75% by weight of an N-alkylphthalimide which has a straight-chain or branched alkyl radical of 3-5 C atoms,

   2.) 10-40% by weight of a C₁-C₄-alkyl, phenyl or benzyl ester of benzoic, methylbenzoic, terephthalic, phthalic or salicylic acid or diphenyl carbonate, diphenyl ether or ditolyl ether and

   3.) 5-20% by weight of an addition product of 15-30 mol of ethylene oxide with castor oil or soya bean oil, of 5-50 mol of ethylene oxide and/or propylene oxide with C₁₆-C₂₂-fatty alcohols, octylphenol or nonylphenol or phenylethylphenol, alkali metal salts, alkaline earth metal salts, ammonium salts or (di)ethanolamine salts of dodecylbenzenesulfonic acid.
5. Process for dyeing polyester materials with disperse dyestuffs in the presence of carrier mixtures of Claim 1.