EP1347091B1 - Dyeing assistant - Google Patents

Abstract

A novel ester (I) is the reaction product of: (i) benzoic acid (optionally substituted by 1-4C alkyl, 1-4C alkoxy, halogen, OH, NH2 and/or NO2); with (ii) phenol which is optionally substituted by 1-4C alkyl, 1-4C alkoxy, halogen, NH2 and/or NO2 and which has been reacted with 0.5-6 mols. alkylene oxide per mol. OH group in the phenol. An Independent claim is also included for a dyeing aid including by wt. (A) the novel ester (I) (20-60%) and (B) an ester (20-60%) of benzoic acid (optionally substituted by 1-4C alkyl, 1-4C alkoxy, halogen, OH, NH2 and/or NO2) with a 2-12C diol.

Description

The invention relates to the use of a special composition as a leveling agent.

In the dyeing of, in particular, polyester fiber materials, such as polyethylene terephthalate (PET), with disperse dyes, auxiliaries (dyeing auxiliaries) are generally added to the dyebath in order to obtain, for example, to promote a uniform distribution of the dyes in textiles (leveling agent). Such dyeing aids are generally compositions containing nonionic and anionic dispersants, nonionic emulsifying surfactants and swelling agents.

The use of non-ionic and anionic dispersants avoids dye deposits on the product. The emulsifying nonionic surfactants are responsible for both the emulsification of the water-insoluble product portions and the uniform coating of the dyes on the fiber. Of great importance are the swelling substances, in particular with regard to migration, diffusion acceleration, migrating action, synchronizing effect and affinity differences.

The swelling substances used include methyl cresotinate, methyl salicylate, phthalic acid alkyl esters, N-alkylphthalimides and methyl benzoate and benzoic acid esters with dihydric or polyhydric alcohols. The latter benzoic acid esters are described, for example, in DE 32 46 383 A1 and US Pat. No. 4,516,979. Aliphatic dialcohols, glycerol and pentaerythritol are used as polyhydric alcohols. However, the aforementioned products have the serious disadvantages that they are either potentially teratogenic (phthalic acid ester) or else odor-intensive or less effective.

From DE 31 39 562 A1 textile processing compositions are known, wherein a cycloaliphatic diester with the formula given in DE 31 39 562 A1 can be used in combination with a high-boiling aromatic ester for fiber finishing and textile processing compositions.

US 4,708,719 describes a disperse dye concentrate for use in non-aqueous solvent systems in which a disperse dye is admixed with a cycloaliphatic ester, a high boiling aromatic ester or a high boiling point alkylphenol ester of an aliphatic or aromatic monocarboxylic acid or a phosphoric acid, all with those disclosed in US 4,708,719 Formulas, is used.

The present invention is therefore based on the object to provide the use of a special composition as a leveling agent, which does not have the aforementioned disadvantages.

• (a) 20 Gew.-% bis 60 Gew.-%, insbesondere etwa 30 Gew.-%, bezogen auf die Zusammensetzung, Ester von mit C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, wie F, Cl oder Br, OH, NH₂ und/oder NO₂ substituierter oder unsubstituierter Benzoesäure und C₂-C₁₂-Diol und
• (b) 20 Gew.-% bis 60 Gew.-%, insbesondere etwa 30 Gew.-%, bezogen auf die Zusammensetzung, Ester von mit C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, wie F, Cl oder Br, OH, NH₂ und/oder NO₂ substituierter oder unsubstituierter Benzoesäure und mit C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, wie F, Cl oder Br, NH₂ und/oder NO₂ substituiertem oder unsubstituiertem Phenol, das mit 0,5 bis 6 Mol Alkylenoxid pro Mol OH-Gruppe des Phenols umgesetzt ist.

According to the invention, this is achieved by the use of a composition as a leveling agent, comprising

• (A) 20 wt .-% to 60 wt .-%, in particular about 30 wt .-%, based on the composition, esters of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, such as F, Cl or Br, OH, NH ₂ and / or NO ₂ substituted or unsubstituted benzoic acid and C ₂ -C ₁₂ diol and
• (B) 20 wt .-% to 60 wt .-%, in particular about 30 wt .-%, based on the composition, esters of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, such as F, Cl or Br, OH, NH ₂ and / or NO ₂ substituted or unsubstituted benzoic acid and with C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen, such as F, Cl or Br, NH ₂ and / or NO ₂ substituted or unsubstituted phenol reacted with from 0.5 to 6 moles of alkylene oxide per mole of OH group of the phenol.

The present invention is based on the completely surprising finding that the addition of the benzoic acid ester (b) significantly increases the effect of the benzoic acid esters (a) and thus allows for very low leveling and migration effects with simultaneous low odor, as previously among the low-odor types only from the Phthalic acid esters were known. In contrast to the potentially teratogenic phthalic acid esters, however, the benzoic acid esters (a) and (b) according to the current state of knowledge do not have a reproduction-impairing effect.

The composition used in the invention causes the dye to penetrate very well and very quickly into the fiber and diffuse within the fiber (migration). The result is a very good dye yield (diffusion acceleration) and, due to the increased intrafibrillar dye migration (migrating effect), an excellent level dyeing.

Furthermore, even during the heating and absorption phase, the synchronous diffusion of disperse dyes, even with different diffusion coefficients, is made possible (synchronizing effect), which results in a level dyeing.

When using the composition according to the invention with pronounced swelling and thus migration-promoting properties, it is also possible in particular to compensate for extremely unequally colored parts subsequently, as it were by blank staining with product use.

Another special feature of the composition used according to the invention is the compensation or at least the attenuation of material-related, i. fibermorphology-related staining differences (affinity differences), even in the case of large molecular weight and so-called "high energy" dyes.

Finally, the solvent character of the esters (a) and (b) present in the composition used according to the invention, in particular in combination with the emulsifying action of nonionic surfactants, also enables a crude dyeing of various processing states without separate additives.

As stated above, can be used as the acid component of the aforementioned benzoic unsubstituted or substituted benzoic acid. In this case, the benzoic acid may be 1 or more, e.g. 2 or 3, have the aforementioned substituents. These can be arranged in the o, p and m positions, based on the carboxyl group.

The alcohol component of the benzoic acid ester (a) is a C ₂ -C ₁₂ diol. These are aliphatic or alicyclic compounds containing two hydroxy groups in the molecule. For the purposes of the present invention, diols also include ether alcohols, ie compounds having two hydroxy groups, which additionally have 1 or more ether function (s). Examples of the C ₂ -C ₁₂ diols are glycol, diethylene glycol, propylene glycol, dipropylene glycol and butanediol. Particular preference is given to diethylene glycol, since this results in a particularly good activity of the composition according to the invention with regard to its properties as dyeing auxiliaries.

In a preferred embodiment of the composition used according to the invention, the degree of esterification of the benzoic acid ester (a) is 1.8-2.0 mol of acid per mole of diol. As a result, a particularly high proportion of aromatics is obtained in a favorable manner, which has an advantageous effect on the effectiveness of the composition used according to the invention as a leveling agent. Furthermore, if any, there is only a very small residual level of free acid present, thereby minimizing the hazards caused by acids.

For the ester (b), the above-defined unsubstituted or substituted benzoic acid is used. As the alcohol component for the ester (b), a compound obtainable by reacting phenol with alkylene oxide is used. In this reaction, the alkylene oxide reacts with OH groups of the phenol, resulting in new to the alkylene oxide going back OH groups. At this the binding of benzoic acid takes place. The

Phenol may contain 1 or more, for example 2 or 3, OH groups. In the case of several OH groups on the phenol can either only 1 OH group or it can all OH groups with have been reacted with the alkylene oxide. The phenol may be unsubstituted or substituted as above. It may have 1 or more, for example 2 or 3, substituents. The substituents can be in the o, p and m positions, based on the OH group.

The phenol was reacted before the ester formation with the substituted or unsubstituted benzoic acid with 0.5-6 moles of alkylene oxide per mole of OH group of the phenol. By an alkylene oxide are meant oxiranes, i. saturated three-membered, oxygen-containing heterocyclic compounds. They can have 2 to 6 carbon atoms. Examples of the alkylene oxides are ethylene oxide (EO), propylene oxide and butylene oxide. It is also possible to use mixtures of 2 or more alkylene oxides for reaction with the phenol.

As noted above, the phenol is occupied by 0.5-6 moles of alkylene oxide derived units per mole of OH. Particularly preferred are 0.5-1.5 moles of alkylene oxide, especially 1.2 moles of alkylene oxide. By means of these amounts of the alkylene oxide, a particularly good effectiveness of the composition according to the invention as a leveling agent is achieved. In particular, the agent has a high aromatic content, whereby a particularly advantageous interaction with polyester threads is achieved.

In a preferred embodiment of the present invention, the degree of esterification of the benzoic acid ester (b) is 0.3-1.0, more preferably 0.5-0.8 mole of acid per mole of alcohol component. This degree of esterification achieves a high aromatic content and thus a particularly good activity of the composition according to the invention as a dyeing auxiliaries. Furthermore, the residual free acid content is minimized, thereby also reducing the hazards resulting from the corrosive properties of an acid.

The esters present in the composition used according to the invention can be prepared in a customary manner, for example by reacting the alcohol components with the benzoic acid components, for example by acid catalysis at elevated temperatures, for example 120-130 ° C. The preparation of the two ester components (a) and (b) for the composition used according to the invention can be carried out in 1 reaction vessel in which the benzoic acid components and the two alcohol components are combined in appropriate proportions. In this way, the benzoic acid esters (a) and (b) required for the composition used in the present invention can be obtained in a particularly simple manner, which is advantageous from a commercial standpoint.

The composition used in the present invention may contain, in addition to the above-described ingredients, nonionic emulsifiers, anionic emulsifiers, sizing agents, and mixtures of two or more thereof. Fatty acid ethoxylates and / or ethoxylated vegetable or animal fats or oils can be used as nonionic emulsifier. In the fatty acid ethoxylates unsaturated fatty acids with chain lengths C12-C22, coated with, for example, 4-12 moles of alkylene oxide, in particular ethylene oxide, are preferred. A particularly preferred representative thereof is oleic acid with 4-8 moles of ethylene oxide. For the oils, an ethoxylated castor oil coated with 30-60 moles of ethylene oxide is preferably used. By these compounds, a particularly good emulsification is achieved. Suitable anionic emulsifiers are C1-C20 alkylbenzenesulfonic acids, in particular dodecylbenzenesulfonic acid, and / or phosphated fatty alcohol ethoxylates (C6-C16 alkyl chain length, 2-12 moles of ethylene oxide) are advantageously used. By this a very good emulsification is achieved. If a C1-C20 alkylbenzenesulfonic acid is used, the amount is, for example, 1-5% by weight, based on the composition used according to the invention. The acidic anionic emulsifiers can be neutralized with customary bases, for example alkali metal hydroxide and / or alkanolamines, in particular monoethanolamine (pH about 7). By this neutralization a particularly safe and easy handling of the composition used in the invention is possible.

Furthermore, the composition used according to the invention may have an adjusting agent. Examples thereof are lower glycols or alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, butyl diglycol, diacetone alcohol, hexylene glycol and isopropanol. It is also possible to use mixtures of two or more of these. The adjusting agents make the turbid products clear, which is advantageous in terms of the acceptance of the buyers of such dyeing auxiliaries.

Furthermore, the composition used in the invention may have the above-mentioned in connection with the ester (b) phenols, which were reacted with alkylene oxide. These act as swelling substances, whereby a particularly good effectiveness of the composition used according to the invention as a leveling agent is achieved.

The amount of the aforementioned emulsifiers may in each case be from 10% by weight to 40% by weight, in particular from 15% by weight to 20% by weight, based on the composition used according to the invention. The adjusting agent may be present in an amount of 1% by weight to 10% by weight, in particular 3% by weight to 5% by weight. The amount of phenol reacted with alkylene oxide is e.g. 5 wt .-% to 15 wt .-%, in particular about 10 wt .-%, based on the composition used in the invention.

The rest of the composition used according to the invention can form water.

The composition used according to the invention can be prepared in a particularly simple manner by combining the individual components. This combination can be done with stirring, whereby at the same time a good mixing of the ingredients is achieved.

The composition used according to the invention is ideally suited as a leveling agent. It may be added to the dyebath in amounts of from 0.5 g / l to 3.0 g / l, preferably about 1.0 g / l, to the degassing bath in amounts of from 1 g / l to 3.0 g / l, preferably about 2 , 0 g / l, are added. By these amounts, a particularly good effectiveness of the composition used according to the invention as a leveling agent is achieved with regard to the economy.

The composition used according to the invention is ideally suited as a leveling agent, in particular when dyeing polyester, preferably polyethylene terephthalate. The composition used according to the invention can be used particularly well in the high-temperature dyeing of polyester fibers. Such high temperature dyeing may e.g. be carried out at about 100 ° C in an autoclave.

The composition used in the invention can be used to particular advantage in various problematic cases when dyeing PET fiber materials and their blends with other fibers where other PET leveling agents fail or are not effective enough.

• Färben unkritischer PET-Materialien jeglicher Aufmachung/Bearbeitungsform mit geringen Egalisiermittelmengen;
• Egalfärben kritischer Aufmachungsformen/Bearbeitungszustände von PET-Fasaern, wie dicht gepackte Garn- und Stückbaumwickelkörper, hoch gedrehte und oder gereckte Zwirne/Stick- und Nähgarne sowie andere technische Garne;
• gewisser Ausgleich von durch Texturier-, Verstreckungs- und Thermofixierungsschwankung verursachten kristallinitätsbedingten bzw. affinitätsbedingten Differenzen im PET-Fasermaterial jeglichen Bearbeitungszustandes und jeglicher Aufmachungsform;
• gutes nachträgliches Ausegalisieren ungleichmäßiger Färbungen von PET (allein oder in Mischung mit anderen Fasern), unabhängig von Aufmachungsform und Bearbeitungszustand, und
• simultanes Färben und Waschen von PET-Garn, Masche, Garment und Flocke, bei denen präparationsbedingte Ölauflagen vorliegen, die normalerweise ein vorgängiges Waschen oder die Mitverwendung eines separaten Wasch- und Emulgiermittels im Färbebad erfordern würden.

In particular, the composition used according to the invention can be used in the following processes:

• Dyeing uncritical PET materials of any presentation / processing form with low leveling agent amounts;
• Dyeing of critical packaging / processing conditions of PET fibers, such as tightly packed twine and part tree wrap bodies, twisted and / or drawn twines / embroidery and sewing threads and other technical yarns;
• some balance of differences in crystallinity and affinity caused by texturing, stretching and heat setting variation in the PET fiber material of any state of processing and any form of presentation;
• good subsequent Auslegalisieren uneven dyeings of PET (alone or in combination with other fibers), regardless of packaging and processing state, and
• simultaneous dyeing and washing of PET yarn, mesh, garment and flake, in which there are preparation-based oil spills that would normally require a prior washing or the use of a separate washing and emulsifying agent in the dyebath.

The ester used as component (b) in the composition used in the present invention is more specifically defined above. It is obtainable by reacting with C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, OH, NH and / or NO ₂ substituted or unsubstituted benzoic acid with a substituted or unsubstituted phenol with 0.5 6 moles of alkylene oxide per mole of OH group of the phenol was reacted. This ester is already defined in more detail above in connection with the composition used according to the invention.

The present invention will be further illustrated by the following examples, but without being limited thereto.

Preparation Examples Example 1:

In a 4-necked reaction flask equipped with stirrer, contact thermometer, water separator, reflux condenser and gas feed tube, 16 parts of an ethoxylated phenol (1.2 units derived from EO), 10 parts of diethylene glycol, 32 parts of benzoic acid and 0.5 parts are added under nitrogen Sulfuric acid heated under reflux for 3 hours. The calculated amount of water splits off.

Following the reaction, the solution successively 9 parts of ethoxylated phenol (1.2 units derived from EO), 5 parts of a phosphated fatty alcohol based on alkyl chain length C10, coated with 10 moles of ethylene oxide, 1 part dodecylbenzenesulfonic acid, 17 parts of a castor oil occupied with 40 moles of EO and 13 parts of water were added. Thereafter, the pH is adjusted to neutral with about 1 part of monoethanolamine.

Example 2:

In a 4-necked reaction flask equipped with stirrer, contact thermometer, water separator, reflux condenser and gas feed tube, under nitrogen, 18 parts of an ethoxylated phenol (see Example 1 above), 12 parts of diethylene glycol, 35 parts Benzoic acid and 0.5 parts of sulfuric acid heated under reflux for 3 hours. The calculated amount of water splits off.

Following the reaction, 9 parts of ethoxylated phenol (see above), 3 parts of dodecylbenzenesulfonic acid, 20 parts of a castor oil coated with 40 moles of EO, and 5 parts of water are added successively to the solution. Thereafter, the pH is adjusted to neutral with about 3 parts of monoethanolamine.

Application examples: Example 3:

100 parts of a polyester lining fabric, pre-desized, wound on perforated support, are treated in a tree dyeing machine with a cold liquor containing 0.2 parts of an emulsified polydimethylsiloxane-based deaerator in 800 parts of permutate water for 5 minutes.

• 1,2 Teile einer Dispersfarbstofftrichromie, bestehend aus
  48 Teile Foron Gelbbraun SE-RL
  22 Teile Foron Rot SE-RL
  30 Teile Foron Blau SE-RL

Thereafter, the liquor is heated to 50 ° C with maximum gradient and there 1.5 parts of the inventive composition of Example 1, 1.0 parts of a liquid dispersant based on dodecylbenzenesulfonate and naphthalenemethanesulfonate polycondensate and 1.0 parts of sodium acetate added. The pH is then adjusted to 4.5 with acetic acid (60%) and after a further 10 min at 50 ° C, the dye is added:

• 1.2 parts of a disperse dye trichromatic, consisting of
  48 parts Foron yellow brown SE-RL
  22 parts Foron Red SE-RL
  30 parts Foron Blue SE-RL

After a further 10 min at 50 ° C is heated at 2 ° C / min to 100 ° C and at 1.5 ° C / min to 130 ° C, there lingered for 40 min and cooled to 80 ° C at 2 ° C / min ,

Then it is drained off and, as is known to the person skilled in the art, reductively purified, giving a perfectly level and true coloration in this way.

Is used instead of the product according to Example 1
1.5 parts of the product according to Example 2
you get comparable good results.

Example 4:

100 parts of a Dyelix Yellow HF-4G (0.15 part), Dianix Red HF-G (0.2 part) and Dianix Blue HF-2G (0.07 part) Dyes in advance, in medium shade, slightly colored polyester circular knit fabric Yarn is spun on an aerodynamic piece dyeing machine with a liquor containing 1.0 parts of the inventive composition according to Example 1 and 2.0 parts of a polyacrylamide solution-based inhibitor in 500 parts of water emulsified with 0.5 ° dH.

After heating at 3 ° C / min to 135 ° C is there for 30 minutes and then cooled at 2 ° C / min to 100 and further at 1.5 ° C / min to 75 ° C.

This gives a perfect Ausegalisierung the originally cloudy color without significant change in color.

Is used instead of the product according to Example 1
2.0 parts of the product according to Example 2
you get comparable good results.

Example 5:

100 parts of a non-prewash, stretched polyester sewing yarn with known (DSC-proven) draw differences and consequently high unegradability hazard is blended with a liquor containing 0.1 part of a triisobutyl phosphate formulation deaerator, 1.0 part of a acrylic copolymer based penetration enhancer , 5 parts of an acid buffer based on citric acid, formic acid and Napthalinmethansulfonatpolykondensatmischung and 2.5 parts of the composition of the invention according to Ex. 1 in 950 parts of water at 40 ° C with 2 ° dH added.

After 10 minutes at 40 ° C, 2.1 parts of a Farbstofftrichromie containing
25 parts Terasil yellow 4 G
50 parts Terasil Red 5 G
25 parts Terasil Blue 3 RL-02 150%
After a further 10 min, the mixture is left at 40 ° C. within 25 minutes at 90 ° C., and then heated to 130 ° C. within 45 minutes. There is 60 minutes lingering.

The completion, including cooling, reductive post-purification and post-avivage, especially with regard to oligomer minimization, is known to the person skilled in the art and needs no further explanation here.

Obtained by this application a perfectly through-dyed and self-dyed polyester sewing thread. The original preparation pads are eliminated.

Is used instead of the product according to Example 1
2.5 parts of the product according to Example 2
you get comparable good results.

Example 6:

To 100 parts of a polyester microfibre felting knit, a liquor containing 1.5 parts of a lubricant based on a mixture of acrylic copolymer and ethoxylated caproclactam and 1.0 part of a naphthalene methanesulfonate-based dispersant, 0.9 parts, is added to a round-magazine jet The inventive composition according to Example 1, 1.0 parts of a sequestering agent based on Hydroxyethandiphosphonsäure, 1.0 parts of sodium acetate and 0.6 parts of acetic acid (60%) in 1400 parts of water, 7 ° dH added, mixed at 25 ° C. ,

After heating to 50 ° C., 0.8 parts of disperse dye trichromatic acid containing
37 parts Foron Yellow Brown RD-2RS
58 parts Foron Brillantrot RD-BR
05 parts Foron Blue RD-GLF,
and heated to 130 ° C at 2 ° C / min. There is lingered for 30 min and after cooling to 80 ° C at 2 ° C / min for 10 min reductive in the dyebath using a specific Sulfinsäurederivates cleaned.

Obtained by this Schnellfärbeverfahren a perfectly level and true color.

Is used instead of the product according to Example 1
0.9 parts of the product according to Example 2
you get comparable good results.

Claims (6)

1. Use of a composition as a levelling agent, the composition comprising, by weight of the composition:

   (a) 20 % to 60 % of an ester of benzoic acid substituted with C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen, OH, NH₂ and/or NO₂, or of unsubstituted benzoic acid, and a C₂-C₁₂ diol, and

   (b) 20 % to 60 % of an ester of benzoic acid substituted with C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen, OH, NH₂ and/or NO₂ or of unsubstituted benzoic acid, and of phenol substituted with C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen, OH, NH₂ and/or NO₂, or of unsubstituted phenol, the phenol being reacted with 0.5 to 6 moles of alkylene oxide per mole of OH group of said phenol.
2. Use according to claim 1, wherein the C₂-C₁₂ diol comprises glycol, diethylene glycol, propylene glycol, dipropylene glycol or butandiol.
3. Use according to any one of the preceding claims, wherein the ester (a) has a degree of esterification of 1.8 to 2.0 moles of acid per mole of diol.
4. Use according to any one of the preceding claims, wherein said phenol is reacted with 0.5 to 1.5 moles of alkylene oxide per mole of the OH group of the phenol.
5. Use according to any one of the preceding claims, wherein the ester (b) has a degree of esterification of 0.3 to 1.0 moles of acid per molecule of alcohol.
6. Use according to any one of the preceding claims, wherein the composition further includes non-ionogenic and/or anionic emulsifiers or regulating substances.