JP2612945B2 - Carrier for dyeing hydrophobic fiber materials - Google Patents

Description

The present invention relates to a carrier for dyeing a polyester material, preferably with a disperse dye, in the presence of a carrier, to a component thereof and to a method for dyeing the same.

Known carriers used to dye polyesters for textile applications include halogenobenzene, halogenotoluene, N-alkylphthalimide, aromatic carboxylic esters, methylnaphthalene, diphenyl, diphenylester, naphtholether, phenolether and hydroxy. And diphenyl. However, these compounds have disadvantages. For example, the above carrier types have a strong intrinsic odor except for N-alkylphthalimide. Methylnaphthalene and hydroxydiphenyl have an adverse effect on sunlight fastness. Diphenyl esters have the disadvantage that their function as carriers depends largely on the structure of the disperse dyes used, and therefore often results in non-reproducible dyeing. N-alkylphthalimides significantly reduce their ability to act as carriers at dyeing temperatures below 98 ° C., thereby limiting their use to only those temperatures that cannot be achieved with open-type dyeing equipment.
Phthalates and benzoates have to be used in large quantities because of their limitations on their function as carriers and their ability to dye uniformly.

It is an object of the present invention to provide highly active halogen-free carriers which can be dyed as uniformly as possible when used in small amounts. At the same time, the resulting dyeings should meet the requirements of high firmness and should not stain the accompanying fibers when dyeing fiber blends.

It has been found that this object can be realized by using a mixture of alkylalkoxybenzoate or N-alkylphthalimide and a mixture thereof or a mixture of arylalkoxybenzoate and N-alkylphthalimide as a carrier. In some cases, the alkyl, allyl, and alkoxy radicals can also have substituents conventional in the chemistry of textile auxiliaries.

The alkoxy benzoate is represented by the following formula, In the formula, R represents a C ₁ -C ₇ -alkyl group, which can be substituted with a phenyl group or a phenyl group, which is a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -alkoxy group. Alternatively C ₁ -C ₄ - alkoxy it can be substituted with a carbonyl group, and R ¹ is C ₁ -C ₄ - represents an alkyl group, which may be substituted by OH groups.

Substituent -OR ¹ is of the ortho-position or para-position is preferred.

Phthalimide has the following formula: In the formula, X represents a C ₁ -C ₇ -alkyl group.

The weight ratio of N-alkylphthalimide to benzoate is from 0.5 to 12 to 1.

Since the carrier according to the invention is insoluble in water, it is preferably added to the dyeing liquor in the form of a component comprising an emulsifier or dispersant and a solvent (if appropriate).

If the alkoxybenzoic esters (I) are used in the form of their alkyl esters, the preparations made therefrom have the following composition: 1) Formula (I) 40-98 (as alkyl esters), in particular
It is preferred to have 60-90 weight percent, 2) emulsifiers 2-30, especially 10-20 weight percent, and 3) solvent 0-10 weight percent.

 Preferred formulations of the carrier mixture are: 1) Formula (I) 8-58, especially 10-45 weight percent; 2) Formula (II) 40-90, especially 45-80 weight percent; 3) Emulsifiers 2-30, especially 10-20 weight percent, and 4) 0-10 weight percent solvent.

The components 1) to 4) can also be used as a mixture.

Specific examples of the preferred compound (I), n-C ₁ -C ₄ - alkyl ortho / para-methoxybenzoate, n-C ₁ -C ₄ - alkyl ortho / para-ethoxy benzoate and n-C ₁ -C _4, - alkyl Ortho / parahydroxyethoxybenzoate.

Specific examples of the preferred compound (II) is a straight-chain or branched-like C ₃ -C _5-N-alkyl phthalimide.

As the emulsifier 3), nonionic and anionic emulsifiers are preferred.

Examples of suitable emulsifiers include: a) oxyethylated oils (eg, castor oil or soybean oil), oxyethylated alcohols, alkylphenol polyglycol ethers, or phenylalkylphenol polyglycol ethers and b) alkali metals A mixture of an alkaline earth metal and / or an organic ammonium sulfonate containing at least 10 carbon atoms (eg dodecylbenzenesulfonic acid, diisobutylnaphthalenesulfonic acid, alpha-sulfo-fatty acid and lysine oleylmethyl tauride). is there.

Solvents 4) that make the viscosity of the carrier mixture appropriate and can be used include, for example, alkanols, glycols,
Ketone, N-substituted caprolactam or ether.

Particularly preferred components of the carrier are: 1) Formula (I) having 70-90 weight percent or formula (I)
2) 15 to 30 moles of ethylene oxide or C ₁₆ -C ₂₂ -fatty alcohol, octylphenol, nonylphenol or castor oil or soybean oil. 5 to 50 moles of ethylene oxide and / or propylene oxide or alkali metal, alkaline earth metal, ammonium salt of dodecylbenzenesulfonic acid or mono-, di- or tri-ethanol salt of dodecylbenzenesulfonic acid in phenylethylphenol The additive contains from 5 to 20 weight percent.

Since the mixture of carriers according to the invention is compatible with other carriers, it can also be used in mixtures with other known carriers.

Disperse dyes used for dyeing are commonly used for dyeing polyesters (for example, "Color Sample" in Third Edition (1971)).
(Colour Index), Vol. 2, pages 2483-2471). Dyeing in the presence of the carrier according to the invention is carried out by the usual discontinuous steps when dyeing with disperse dyes. The general process and the high temperature process performed at 98 ° C are
It may be said that such a process.

The carrier mixtures according to the invention are also suitable for dyeing polyester / wool and polyester / cotton mixed fibers. This is because the use of the carrier mixture prevents the discoloration of wool and cotton inside stains.

Various types (STRUCTUR)
ES), for example, polyester woven yarn (THREAD), fiber (FIBRE), woven fabric (WOVEN FABRIC), nittofabric (KNITTED FABRIC), film (FILM), and foil (FOIL) (eg, polyterephthalic acid glycol ester) Alternatively, by using a disperse dye of polyester mixed with FABRIC, deep and excellent uniform dyeing can be achieved. Staining is 90
It can be performed at a temperature of 140140 ° C. Industrially, 90
It is preferred to work at ~ 105 ° C. Another advantage of the carrier component is its very good activity below the boiling point. For a pure N-alkylphthalimide carrier, for example,
Doesn't work very well at 95 ° C. In the case of the open-type dyeing apparatus, the temperature is hardly exceeded in practice.

The amount of the mixture of carriers (I) and (II) required for staining can in each case be readily determined by preliminary experiments. At a typical liquid ratio of 1 to 5 to 1 to 40 (LIQUOR RATIO), an amount of 1 to 7 grams per liter of stain has been found to be generally adequate.

The use of N-alkylphthalimides as carriers for dyeing polyesters is known and described in DE 1,769,210.

The use of mixtures of N-alkylphthalimides with disubstituted benzoates is also described in DE 1,769,210.
No.

It should be mentioned as surprising that the mixtures according to the invention have a dye-promoting effect which is superior to the sum of the individual effects. This significant increase in its activity has not been demonstrated in known mixtures (for example, salicylic acid compounds containing alkyl groups and N-alkylphthalimides described in German Patent Specification 1,769,210). The mixing ratios at which significant effects are achieved here depend on the components of the carrier mixture and can in each case be determined by preliminary experiments.

Example 1 A yarn of polyester fiber was heated to 60 ° C. and, per liter, 0.25 g of a dye of the formula: Concentrate of naphthalene sulfonate and formaldehyde
2 g, sodium dihydrogen phosphate 2 g and carrier 3 g having the following composition (the composition is ethyl 4-methoxybenzoate)
2.55 g, 0.25 g of a mixture of tri- (methylphenylethyl) -phenol and about 15 mol of ethylene oxide, 0.20 g of monoethanolamine salt of dodecylbenzenesulfonic acid
g) into a bath at a liquid ratio of 1:40.

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 that temperature for 60 minutes. It is dyed blue uniformly.

Examples 2 to 11 Staining was carried out as described in Example 1 and in each example, Example 2: 2.55 g of n-propyl 4-methoxybenzoate tri- (methylphenylethyl) -phenol and about 0.25 g of a mixture with 15 mol of ethylene oxide and 0.20 g of monoethanolamine salt of dodecylbenzenesulfonic acid, Example 3: 2.50 g of ethyl 3-methoxybenzoate, about 15 mol of tri- (methylphenylethyl) -phenol 0.29 g of a mixture with ethylene oxide and 0.21 g of monoethanolamine salt of dodecylbenzenesulfonic acid, Example 4: 2.55 g of phenyl 2-methoxybenzoate, tri- (methylphenylethyl) -phenol and about 50 mol of ethylene oxide And calcium dodecylbenzenesulfonate (70% in butanol) 0.18 g, Example 5: 2.50 g of 4-methoxybenzoate, 0.28 g of tri- (methylphenylethyl) -phenol and about 15 mol of ethylene oxide and 0.22 g of monoethanolamine salt of dodecylbenzenesulfonic acid, Example 6: 0.90 g of ethyl 4-methoxybenzoate 1.65 g of N-butylphthalimide, 0.22 g of a mixture of castor oil and about 30 mol of ethylene oxide, monoethanolamine salt of dodecylbenzenesulfonic acid
0.18 g and 0.05 g of a mixture of stearyl alcohol and about 8 moles of ethylene oxide. Example 7: 1.05 g of n-butyl 4-ethoxybenzoate, 1.50 g of N-butylphthalimide, tri- (methylphenylethyl) -phenol and 0.25 g of a mixture with about 15 mol of ethylene oxide and 0.20 g of the monoethanolamine salt of dodecylbenzenesulfonic acid, Example 8: 1.05 g of cresyl 4-methoxybenzoate, N-alkylphthalimide (alkyl = 50% n-butyl, 1.50 g of 30% propyl and 20% ethyl), 0.25 g of a mixture of tri- (methylphenylethyl) -phenol and about 15 mol of ethylene oxide and 0.20 g of monoethanolamine salt of dodecylbenzenesulfonic acid, Example 9: methyl 0.50 g of 2-methoxybenzoate, 2.05 g of N-butylphthalimide, about 30 moles of ethanol with castor oil 0.30 g of a mixture of lenoxide and 0.15 g of calcium dodecylbenzenesulfonate (70% in butanol), Example 10: 1.05 g of ethyl 2-methoxybenzoate, N-alkylphthalimide (alkyl = 50% n-butyl, 30% propyl 1.50 g of 20% ethyl), 0.25 g of a mixture of tri- (methylphenylethyl) -phenol and about 15 mol of ethylene oxide and 0.20 g of monoethanolamine salt of dodecylbenzenesulfonic acid, Example 11: ethyl 4- 1.55 g of ethoxybenzoate, N-alkylphthalimide (alkyl = 70% n-butyl, 30% n-butyl
Propyl) 1.20 g, tri- (methylphenylethyl)-
Mixture of phenol and about 15 moles of ethylene oxide
A carrier having a composition of 0.25 g and 0.20 g of a monoethanolamine salt of dodecylbenzenesulfonic acid is used.

 In each example, the dye is blue and uniformly dyed.

The carrier activity of the carrier mixtures of Examples 6 to 11 is determined by comparison to the color depth obtained. The amounts of carrier mixture and alkoxybenzoate (I) required to obtain the same color depth are given in the following table. The amounts given are expressed as 100 with the amount of N-alkylphthalimide (II).
A small amount of the mixture shows more effective carrier activity than the respective components.

Example 12 (Comparative Example with West German Patent Specification No. 1,769,210) A yarn of polyester fiber was heated to 60 ° C., in which, per liter, 0.25 g of a dye of the formula Concentrate of naphthalene sulfonate and formaldehyde
2 g, sodium hydrogen phosphate 2 g and carrier with the following composition
3 g (the composition is 1.80 g of N-alkylphthalimide (alkyl = 60% butyl and 40% propyl), 0.7 g of ethyl ortho-cresate, tri- (methylphenylethyl) -phenol and about 15 moles of ethylene oxide (B) containing a mixture of 0.25 g of a mixture of the above and 0.20 g of a monoethanolamine salt of dodecylbenzenesulfonic acid
ath) at a liquid ratio of 1:40.

The pH of the bath is adjusted to pH 4.5-5 with acetic acid. After this, the bath is heated to 98 ° C. and kept at that temperature for 60 minutes.
Stained blue uniformly. The carrier activity was determined as described above (N-alkylphthalimide (II) = 10
0).

In contrast to the carrier mixture of the invention, this mixture comprises:
There was no significant increase in carrier activity compared to the respective components.

Example 13 Several woven fabrics, the warp and the weft of which consist of spun polyester yarn, were placed in a bath heated to 50 ° C. with a liquid ratio of 40: 1.
In the bath, 0.2 g of a dye of the following formula per liter: Concentrate of naphthalene sulfonate and formaldehyde
2 g of sodium dihydrogen phosphate, 2.5 g of a carrier having the following composition (the composition is 1.65 g of N-alkylphthalimide (alkyl = 60% butyl and 40% propyl), ethyl 4-methoxybenzoate) 0.90 g, 0.25 g of a mixture of tri- (methylphenylethyl) -phenol and about 15 mol of ethylene oxide, and monoethanolamine salt of dodecylbenzenesulfonic acid
0.20g).

The pH of the bath is adjusted to pH 4.5-5 with acetic acid. The dyeing liquor is then heated to the boiling point and kept at this temperature for one hour. It is dyed red uniformly enough.

Example 14 1 g of the disperse dye according to Example 14, 1 liter of the spun polyester fiber at a liquid ratio of 1 to 15 per liter, and 0.03 dye per "Color Sample 2nd Edition (1956), Vol. 3, No. 12790" g,
Concentrate of naphthalene sulfonate and formaldehyde
2 g, sodium dihydrogen phosphate 2 g and the carrier of Example 13 3.5 g
In a staining solution containing The pH of the bath is acetic acid
The pH is adjusted to 4.5-5. The solution is gradually heated to 98 ° C. and the treatment is performed at this temperature for 1 hour. Dark reddish brown staining is performed.

 The main features and aspects of the present invention are as follows.

1. Alkyl alkoxy benzoate or N
A mixture of alkyl phthalimides or a mixture of arylalkoxybenzoates and N-alkyl phthalimides, wherein said alkyl, aryl and alkoxy radicals can further have the usual substituents in the chemistry of textile auxiliaries, hydrophobicity A carrier for dyeing fiber materials.

2. The alkoxybenzoic acid ester contained in the carrier has the following formula (I): In the formula, R represents a C ₁ -C ₇ -alkyl group (which can be substituted with a phenyl group) or a phenyl group (a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -alkoxy group or a C ₁ -C ₄ group). ₄ −
R ¹ represents a C ₁ -C ₄ -alkyl group (which can be substituted with an OH group), and R ¹ represents a phthalimide contained in the carrier. The following formula (II) Wherein the X represents a C ₁ -C ₇ -alkyl group.

3. alkyl alkoxy benzoate, n-C ₁ -C ₄ - alkyl ortho / para - methoxybenzoate, n-C ₁
-C ₄ - alkyl ortho / para - ethoxy benzoate and n-C ₁ -C _4, - alkyl ortho / para - carrier according to claim 1, characterized in that the hydroxy ethoxy benzoate.

4. The carrier according to the above 1, wherein the weight ratio of phthalimide to alkoxybenzoate is 0.5 to 12: 1.

5. 8-58 weight percent alkoxy benzoate,
A carrier comprising 40-90% by weight of an N-alkylphthalimide, 2-30% by weight of an emulsifier, and 0-10% by weight of a solvent.

6. The carrier of claim 1 comprising 40-98 weight percent alkylalkoxybenzoate, 2-30 weight percent emulsifier, and 0-10 weight percent solvent.

7. A method for dyeing a hydrophobic fiber material, wherein the dyeing is performed in the presence of the carrier according to the above 1.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Heinz Ulrich Blanch Germany Day 5068 Ordenter Le Amgoishuerde 35 (72) Inventor Karlhans Jakopus Germany Day 5060 Bergisch Gradbach And Andeuchz 55 ( 72) Inventor Klaus-Data Schulz, Federal Republic of Germany, Day 4019 Monheim Half-Arbskell 24 (72) Inventor Karl-Heintz Patsson, Federal Republic of Germany, Day 5090 Reef Elksen 1 Würzknerschützler 6 (56) References JP-A-61-174483 (JP, A) JP-A-61-102490 (JP, A) JP-B-46-19949 (JP, B1)

Claims (2)

(57) [Claims] (1) Expression In the formula, R represents a C ₁ -C ₇ -alkyl group (which can be substituted with a phenyl group) or a phenyl group (a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -alkoxy group or a C ₁ -C ₄ group). ₄ - alkoxy may be substituted with a carbonyl group) represents and R ¹ is C ₁ -C ₄ - and represents an alkyl group (may be substituted with an OH group), an alkoxy benzoates of the formula Wherein X represents a C ₁ -C ₇ -alkyl group, comprising a mixture with phthalimide, wherein the weight ratio of phthalimide to alkoxybenzoate is from 0.5 to 12: 1.
A carrier for dyeing a hydrophobic fiber material, characterized in that: 2. A method for dyeing a hydrophobic fiber material, wherein the dyeing is performed in the presence of the carrier according to claim 1.