WO1996028603A1

WO1996028603A1 - Improving the light-fastness of dyes on polyamide fibres

Info

Publication number: WO1996028603A1
Application number: PCT/EP1996/000897
Authority: WO
Inventors: Frank Schlegel; Claudius Brinkmann; Martin Jöllenbeck
Original assignee: Ciba Specialty Chemicals Holding Inc.
Priority date: 1995-03-15
Filing date: 1996-03-04
Publication date: 1996-09-19
Also published as: AU4944896A

Abstract

The description relates to a process for improving the light-fastness of dyed polyamide fibre materials in which the polyamide fibres material is treated in an aqueous bath with an auxiliary selected from the group of (a) acid esters or their salt of the formula (1) R-O-(CH2-CH2-O)n-X, (b) a compound of formula (2) and (c) a compound of formula (3) in which the variables have the meanings given in the claims.

Description

Improving the lightfastness of dyeings on polyamide fibers

The present invention relates to a method for improving the lightfastness of dyeings on polyamide fiber materials and to the polyamide fiber material treated therewith.

Dyes on polyamide fiber materials, which are colored with disperse, acid or 1: 2 metal complex dyes, tend to photochemical instability. This is partly due to the dyeing aids usually added when dyeing polyamide, e.g. by leveling agents, caused or intensified.

There is therefore a need for auxiliaries which improve the photochemical stability of polyamide dyeings without adversely affecting the effectiveness of the dyeing auxiliaries which are obligatory for the dyeing process.

It has now surprisingly been found that certain anionic compounds meet these requirements.

The invention therefore relates to a process for improving the light fastness of dyed polyamide fiber materials, which is characterized in that the polyamide fiber material is selected from the group with an auxiliary

(a) acidic ester or its salt of the formula

R - O - (CH ₂ -CH ₂ -0) _n - X (1)

in which R is straight-chain or branched C ₆ -C ₂₄ alkyl or singly or multiply by C _r C ₁₂ alkyl, phenyl, which in turn can be substituted by halogen, C ₁ -C alkyl or C _r C ₄ alkoxy, or C ₇ -C ₀ aralkyl-substituted phenyl, n is a number from 0 to 20 and X represents the acid residue of an inorganic, oxygen-containing acid or an organic acid,

(b) Compound of the formula SO ₃ γ

wherein Rι means straight-chain or branched C ₆ -C ₂₄ alkyl and Y is hydrogen or a cation, and

(c) Compound of the formula

wherein Rj and Rj 'each independently represent straight-chain or branched -C ^ alkyl, Y is hydrogen or a cation, and p and q independently of one another each represent the number 0 or 1, treated from an aqueous bath.

As C ₆ -C ₂₄ alkyl, R is, for example, straight-chain or branched hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosicos, or docosyl Tetracosyl. R is preferably alkylrcst for straight-chain or branched C ₈ -C ₈ alkyl.

Suitable C _] -C ₁₂ alkyl substituents on the phenyl radical R are, for example, methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, n-, iso- or tert-pentyl , n-hexyl, 2-ethylhexyl, n-heptyl, n- or iso-octyl, n- or iso-nonyl or n-dodecyl.

Suitable phenyl substituents on the phenyl radical R are, for example, unsubstituted or halogen, which is generally to be understood to mean, for example, fluorine, chlorine or bromine, C _r C -alkyl, which is generally methyl, ethyl, n- or iso-propyl or n-, iso-, sec - or teπ.-butyl is to be understood, or phenyl substituted by C _r C ₄ -alkoxy, which generally comprises methoxy, ethoxy, n- or iso-propoxy or n-, iso-, sec- or tert-butoxy.

Suitable aralkyl radicals on the phenyl radical R are, for example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, β-phenethyl, α-tolylethyl or phenisopropyl.

R preferably represents straight-chain or branched Cg-C _j g-alkyl or phenyl, which is mono- or polysubstituted by C _r C ₁₂ -alkyl or C ₇ -CQ-aralkyl. R particularly preferably represents straight-chain or branched Cg-Cjg-alkyl or phenyl which is mono- or polysubstituted by C ₄ -C ₁₀ -alkyl or α-methylbenzyl.

n represents an integer or fraction from 0 to 20 and preferably from 1 to 20.

The acid residue X derives e.g. from an inorganic polybasic acid, e.g. of sulfuric acid or o-phosphoric acid, or of an organic acid, e.g. from a low molecular weight dicarboxylic acid such as maleic acid, succinic acid or sulfosuccinic acid. If X is the acid residue of sulfuric acid, the compounds of formula (1) are optionally present as a mixture of the corresponding mono- and diester. If X is the remainder of o-phosphoric acid, the compounds of the formula (1) are optionally in the form of a mixture of the corresponding mono- and diesters or mono-, di- and triesters.

Acid residue X can be in the form of a free acid or in salt form, e.g. as an alkali metal, ammonium or salt of an organic amine. Examples of such salts are lithium, sodium, potassium, ammonium, trimethylammonium, diethylammonium, ethanol-ammonium, diethanolammonium or triethanolammonium salts or mixtures thereof. The acid residue X is preferably in the form of the sodium, potassium, ammonium, diethylammonium, triethylammonium, diethanolammonium or triethanolammonium salt.

Preferred as auxiliary (a) is an acidic ester or its salt of the formula (1) given above, in which R is straight-chain or branched C ₈ -C ₁₈ -alkyl or phenyl, which is mono- or polysubstituted by C _r C ₁₂ -alkyl or C ₇ -C ₉ aralkyl is substituted, n is a number from 0 to 20, and X is an acid residue which is derived from sulfuric acid or o-phosphoric acid.

Particularly preferred as auxiliary (a) is an acid ester or its salt of the above formula (1) wherein R represents straight-chain or branched Cg-C ₁₈ alkyl or phenyl which is mono- or polysubstituted by C ₁ -C ₄ -alkyl or α-methylbenzyl is substituted, n is an integer or fraction from 1 to 20, and X is Is an acid residue that is derived from sulfuric acid or o-phosphoric acid.

The auxiliaries (a) are known or can be obtained in a manner known per se. Their synthesis can e.g. take place by adding ethylene oxide to a compound of the formula R-OH, in which R has the meaning given above, and the adduct with an inorganic, oxygen-containing acid, an organic acid or a functional derivative of these acids, e.g. the acid anhydride, acid halide, acid ester or acid amide.

The auxiliaries according to (a) can, in addition to the compound of the formula (1), also additionally the starting products for their synthesis, for example the alcohol of the formula RO- (CH ₂ -CH ₂ -O) _n -H, where R and n are each the same as above have the meaning given, or the inorganic, oxygen-containing acid or organic acid (H) _t -X, where X has the meaning given above and t is the number 1, 2 or 3,.

In the auxiliaries according to (b) and (c), the meanings and preferences given previously for R as C ₆ -C ₂₄ alkyl apply independently for R _j and R _j '. If Y is a cation, it can be, for example, an alkali metal or ammonium cation or the cation of an organic amine. Examples of such cations are the lithium, sodium, potassium, ammonium, trimethylammonium, diethylammonium, ethanolammonium, diethanolammonium or triethanolammonium cation or mixtures thereof.

Preferred auxiliaries according to (b) or (c) are compounds of the formula (2) or (3), in which R _j and R _j 'are each independently of the other C ₆ -Cιg-alkyl and Y is hydrogen or the sodium, potassium or Ammonium cation mean.

The compounds of the formulas (2) and (3) are known or can be obtained by methods known per se.

The method according to the invention can be carried out using one or more different auxiliaries (a), (b) and / or (c).

The application of the auxiliaries (a), (b) or (c) according to the invention can take place before, during or after the dyeing by an exhaust or continuous process. The auxiliary (a), (b) or (c) is in the aqueous treatment bath or dye bath, for example in an amount of 0.001 to 5 g 1 liquor, preferably 0.005 to 3 g / 1 liquor and particularly preferably 0.01 to 1.5 g / 1 liquor.

The auxiliary (a), (b) or (c) is preferably applied during the dyeing process, which can be carried out in a manner known per se.

When dyeing using the exhaust process, the liquor ratio can be selected within a wide range, e.g. 1: 3 to 1: 100, preferably 1:10 to 1:40. It is convenient to work at a temperature of 20 to 120 ° C, preferably 40 to 100 ° C.

When dyeing according to the continuous process, the liquor application is expediently 40-700, preferably 40-500% by weight. The chamfer material is then subjected to a heat treatment process in order to fix the applied dyes. This fixation can also be done using the cold-dwell method.

The heat treatment for fixing the dyes is preferably carried out by a steaming process with treatment in a steamer with possibly superheated steam at a temperature of 98 to 105 ° C during e.g. 1-7, preferably 1-5 minutes. The dyes can be fixed in accordance with the cold residence process by storing the impregnated and preferably rolled-up goods at room temperature (15 to 30 ° C) e.g. during 3 to 24 hours, the cold residence time being known to depend on the dye.

In addition to the dye, one or more auxiliaries (a), (b) or (c) and water, the dyeing liquor or padding liquor can contain other conventional constituents, e.g. Contain salts, acids, bases, buffers, surfactants or leveling agents.

After the dyeing process has ended or the dye has been fixed, the dyeings produced are washed and dried in the customary manner.

According to the present invention, dyeings having good general fastness properties and in particular good light fastness are obtained. The method is particularly suitable for dyeing polyamide fiber materials in the presence of a leveling agent, where the aid (a), (b) or (c) at least compensates or overcompensates the negative effect of the leveling agent on the light fastness.

Suitable colorations to be stabilized according to the invention are those which are: Dispersion, acid or metal complex dyes, especially azo, anthraquinone, 1,2-metal complex dyes, for example 1: 2-chromium, 1: 2-cobalt complex dyes or Cu complex dyes are produced.

Examples of such dyes are described in Color Index, 3rd edition, 1971, volume 4, and the supplements thereto.

Synthetic polyamide, e.g. Understood polyamide-6, polyamide-6,6 or polyamide-12, as well as modified polyamide, e.g. known as low dyeing, regular dyeing, or deep dyeing polyamide or basic dyeable polyamide. In addition to the pure polyamide fibers, fiber mixtures made of polyurethane and polyamide are also considered, e.g. Tricot material made of polyamide / polyurethane in the mixing ratio up to approx. 70:30. In principle, the pure or mixed polyamide material can be in a wide variety of processing forms, e.g. as fiber, yarn, fabric, knitted fabric, fleece or pile material. Yarn is preferred.

The following examples illustrate the invention. Parts mean parts by weight and percentages percentages by weight.

EXAMPLE 1 0.22 part of the phosphoric acid partial ester of the compound of the formula is converted into 2000 parts of demineralized water at room temperature

C ₁₃ H ₂₇ - O - (CH ₂ -CH ₂ -0) ₃ - H

(Reaction product of phosphorus pentoxide with the ethoxylation product of 3 ethylene oxide units on a C ₁₃ alkanol, containing mono- and diesters and unreacted C ^ alkanol) and 2 parts of monosodium phosphate and 2 parts of disodium phosphate and the pH to 4 with acetic acid. 5 set. Then a dye mixture of 0.02 parts of a dye in the form of the free acid of the compound of the formula

corresponds to

0.025 parts of a dye in the form of the free acid of the compound of the formula

corresponds, and

0.06 part of a dye which is in the form of the free acid of the compound of the formula

corresponds, addieπ. The dye solution obtained is mixed with 100 parts of polyamide 6.6 woven tricot and heated at a constant rate of 1.5 ° C./min to a temperature of approximately 96 ° C. The mixture is kept at this temperature for 45 minutes, then cooled to 50 ° C. at a constant rate of 3 ° C./min and the material to be dyed is removed, which is rinsed with water and then dried. A fabric dyed in a brown shade is obtained which has good general fastness properties and in particular good light fastness. Example la: One proceeds as described in Example 1 and uses 0.44 parts instead of 0.22 parts of the phosphoric acid partial ester of the compound of the formula

C _{] 3} H ₂₇ - O - (CH ₂ -CH ₂ -O) ₃ - H,

a color with a further improved light fastness is obtained.

Comparative Example 1: The procedure described in Example 1 is followed and the dyeing is carried out without the 0.22 part of the phosphoric acid partial ester of the compound of the formula

C ₁₃ H ₂₇ - O - (CH ₂ -CH ₂ -O) ₃ - H

through, a color with a significantly lower light fastness is obtained.

Example 2: One enables as described in Example 1 and is added to the dyebath together with the 0.22 part of the phosphoric acid partial ester of the compound of the formula

C ₁₃ H ₂₇ - O - (CH ₂ -CH ₂ -0) ₃ - H

the following components:

0.13 parts of sodium dodecylbenzenesulfonic acid salt

0.07 part ethoxylation product of 6 ethylene oxide units to a mixture of

Oleyl alcohol and cetyl alcohol 0.26 parts compound of the formula

SO _g Na

0.12 part 30% sodium hydroxide solution.

The coloration obtained also has good lightfastness.

Comparative Example 2: The procedure is as described in Example 2 and the dyeing is carried out without the 0.22 part of the phosphoric acid partial ester of the compound of the formula C ₁₃ H ₂₇ - 0 - (CH CH ₂ -O) ₃ - H

through, a color with a significantly lower light fastness is obtained.

Examples 3-4: Are as described in Examples 1 or 2 and use a dye mixture consisting of 0.03 parts of the dye in the form of the free acid of the compound of the formula used instead of the dye mixture used

corresponds to

0.007 parts of the dye, which is in the form of the free acid of the compound of the formula

corresponds, and

0.078 parts of the dye, which is in the form of the free acid of the compound of the formula

corresponds to dyeings are also obtained in a brown shade with good general fastness properties and in particular good light fastness.

EXAMPLE 5 0.15 part of the phosphoric acid partial ester of n-octanol, 0.09 part of 30% sodium hydroxide are added to 2000 parts of demineralized water at room temperature. solution, 0.026 parts of a solution consisting of 75% by weight of 01eyl-di (2-hydroxyethyl) methylammonium chloride and 25% by weight of isopropanol, as well as 2 parts of monosodium phosphate and 2 parts of disodium phosphate, and the pH was adjusted to 4 with acetic acid, 5 set. Subsequently, a dye mixture of 0.02 parts of a dye in the form of the free acid of the compound of the formula

corresponds to

0.02 part of a dye in the form of the free acid of the compound of the formula

corresponds to

0.023 parts of a dye in the form of the free acid of the compound of the film

corresponds, and

0.023 parts of a dye in the form of the free acid of the compound of the formula

corresponds, addieπ. The dye solution obtained is mixed with 100 parts of polyamide 6.6 woven tricot and heated at a constant rate of 1.5 ° C./min to a temperature of approximately 96 ° C. The mixture is kept at this temperature for 45 minutes, then cooled to 50 ° C. at a constant rate of 3 ° C./min, and the material to be dyed is washed with water and then dried. A fabric dyed in a brown shade is obtained which has good general fastness properties and in particular good light fastness.

Comparative Example 5: As described in Example 5, the dyeing is carried out (i) without the 0.15 part of the phosphoric acid partial ester of n-octanol or (ii) without the 0.15 part of the phosphoric acid partial ester of n-octanol and without the 0.026 part through the solution consisting of 75% by weight of 01eyl-di (2-hydroxyethyl) methylammonium chloride and 25% by weight of isopropanol, dyeings with a significantly lower light fastness are obtained.

EXAMPLES 6-9: Compatible as described in Example 5 and, instead of the 7.5 parts of the phosphoric acid partial ester of n-octanol, the auxiliaries specified below and the amounts of sodium hydroxide solution and 01eyl-di (2-hydroxyethyl) methylammonium chloride given below are used in isopropanol, dyeings with good general fastness properties and in particular good light fastness are also obtained.

6-0.3 parts of a mixture of the phosphoric acid partial esters of the compounds of

Formula nC ₁₂ H ₂₅ - O - (CH ₂ -CH ₂ -0) ₃ - H and nC ₁₄ H ₂₉ - O - (CH ₂ -CH ₂ -O) ₃ - H

(Reaction products of phosphorus pentoxide with the ethoxylation product of 3 ethylene oxide units on a mixture of lauryl alcohol and Myristyl alcohol, each containing the mono- and diester and unreacted C ₁₂ and C ₁₄ alkanol);

- 0.052 parts of a solution consisting of 75% by weight oleyl-di (2-hydroxyethyl) methylammonium chloride and 25% by weight isopropanol;

- 0.08 parts of 30% sodium hydroxide solution.

- 0.3 parts of bis-tridecyl sulfosuccinate, sodium salt

- 0 parts of 30% sodium hydroxide solution.

- 0.3 parts of hexadecyl-diphenyloxide disulfonic acid, sodium salt;

- 0 parts of 30% sodium hydroxide solution.

- 0.3 parts of ammonium salt of the sulfuric acid partial ester of the compound of formula

(Reaction product of sulfamic acid with the ethoxylation product of 16 ethylene oxide units on a statistical mixture of bis- and tris (α-methylbenzyl) phenol;

0.052 parts of a solution consisting of 75% by weight oleyl-di (2-hydroxyethyl) methylammonium chloride and 25% by weight isopropanol;

- 0.004 parts of 30% sodium hydroxide solution.

Claims

claims

1. A process for improving the light fastness of dyed polyamide fiber materials, characterized in that the polyamide fiber material is selected with an auxiliary from group (a) acidic ester or its salt of a compound of the formula

R - O - (CH ₂ -CH ₂ -O) _n - X (1)

in which R is straight-chain or branched -C ^ alkyl or singly or multiply by C _r C ₁₂ alkyl, phenyl, which in turn can be substituted by halogen, C 1 -C ₄ alkyl or C _r C ₄ alkoxy, or C ₇ - C ₉ aralkyl-substituted phenyl, n is a number from 0 to 20 and X represents the acid residue of an inorganic, oxygen-containing acid or an organic acid, (b) compound of the formula

SO ₃ YR - OC - OV CH - CO - R, (2),

¹ II II ¹

O O

wherein Ri is straight-chain or branched C ₆ -C ₂₄ alkyl and Y is hydrogen or a cation, and

(c) Compound of the formula

wherein R _j and R _j 'independently of one another each represent straight-chain or branched C ₆ -C ₂₄ alkyl, Y is hydrogen or a cation, and p and q independently of one another each represent the number 0 or 1, treated from an aqueous bath.

2. The method according to claim 1, characterized in that at least one acidic ester or its salt of the formula (1) according to (a) given in claim 1 is used as auxiliary.

3. The method according to any one of claims 1 and 2, characterized in that R in formula (1) for straight-chain or branched Cg-C _j g-alkyl or phenyl, which is mono- or multiple by CC ₁ alkyl or C ^ C aralkyl is substituted.

4. The method according to any one of claims 1 to 3, characterized in that R in formula (1) for straight-chain or branched C -C _j g alkyl or phenyl, which is mono- or polysilicon by C ₄ -C ₁₀ alkyl or α- Methylbenzyl is substituted.

5. The method according to any one of claims 1 to 4, characterized in that X in formula (1) represents the acid residue of sulfuric acid or preferably of o-phosphoric acid.

6. The method according to any one of claims 1 and 5, characterized in that n in the aid according to (a) is a number from 1 to 20.

7. The method according to claim 2, characterized in that one uses an acidic ester or its salt of the formula (1) given in claim 1, wherein R is straight-chain or branched C ₈ -C ₁₈ alkyl or phenyl, which is simple or is substituted several times by C _r C ₁ alkyl or C ₇ -C ₉ aralkyl, n is a number from 0 to 20, and X is an acid residue which is derived from sulfuric acid or o-phosphoric acid.

8. The method according to claim 2, characterized in that the auxiliary (a) in addition to the compound of formula (1) the corresponding alcohol of the formula R-0 (CH ₂ -CH ₂ -0) _n -H and an inorganic, oxygen Containing acid (H) _t -X, wherein R, X and n each have the meaning given in claim 1 and t represents the number 1, 2 or 3.

9. The method according to any one of claims 1 to 8, characterized in that the polyamide fiber material is treated with the auxiliary by adding it to the dye bath during dyeing according to an exhaust or continuous process.

10. Use of an auxiliary agent selected from group (a) acid ester or its salt of a compound of the formula

R - O - (CH ₂ -CH ₂ -O) _n - X (1)

wherein R is straight-chain or branched C ₆ -C ₂ alkyl or singly or multiply by C _j -C ₁₂ alkyl, phenyl, which in turn can be substituted by halogen, C _j - alkyl or C ₁ -C ₄ alkoxy, or C- -Cg-Anύkyl substituted phenyl, n is a number from 0 to 20 and X represents the acid residue of an inorganic, oxygen-containing acid or an organic acid, (b) compound of the formula

SO ₃ YIR - OC - CH - CH - CO - R, (2),

¹ II II ¹

O O

wherein Rj denotes straight-chain or branched C ₆ -C ₂₄ alkyl and Y is hydrogen or a cation, and

(c) Compound of the formula

R

wherein R _j and R _j 'independently of one another each represent straight-chain or branched C ₆ -C ₂₄ alkyl, Y is hydrogen or a cation, and p and q independently of one another each represent the number 0 or 1, in order to improve the light fastness of dyeings Polyamide fiber material.

1 1. The dyeings treated according to the method of claim 1 on polyamide fibers.

FD 4.1 / LIP