DE3622864A1 - METHOD FOR IMPROVING THE LIGHT FASTNESS OF POLYAMIDE COLORS - Google Patents

Description

The invention relates to a method for improving light fastness of dyeings on polyamide fiber materials, especially textile materials for the Automotive sector, using copper compounds.

The lightfastness of seat covers, carpets and other lining materials for motor vehicles As is well known, the highest demands are made with numerous commercially available dyes alone cannot be satisfied.

In addition to the "normal" light fastness according to DIN 54 003 and 54 004 is also a high lightfastness strong heat exposure, as they have recently determined by hot exposure in accordance with DIN 75 202 (draft) becomes.  

To meet this standard, there are already numerous other light fastness improvers diverse Copper compounds, such as complex compounds from (Schiff bases, o-hydroxybenzophenones and oximes (see EP-A 51 88 and 113 856).

After that, these aids could not fully meet the high demands of automobile manufacturers because the effects achieved were not quite sufficient. Some of the tools also have an undesirable one Own color and / or are because of their elaborate Production method relatively expensive.

Finally, the fact that the effect of the substance classes mentioned above higher concentrations decrease, so that their application possibilities are limited.

It has now surprisingly been found that largely without these disadvantages, very lightfast dyeings arrives when 1: 2 copper complexes are used as an aid of the formula

used where

R₁ and R₂ independently of one another H, OH or OW and X₁-X₈ independently of one another H, W, OH, halogen, CN, NH₂, NVW, SO₃H, COOH, COOW, CONVW or CONH₂ mean and two neighboring residues X₁-X₈also the remaining links together can form a condensed benzene ring,

in which

W for C₁-C₁₈ alkyl and V stands for W or H,

with the proviso that the above for X₁-X₈ Second order substituents at most twice in a benzene residue occur.

Suitable halogen atoms are F, Br and especially Cl. Suitable alkyl radicals are straight-chain or branched and optionally unsaturated. The acid groups mentioned can also be in salt form are available.

Preferred compounds of formula I are symmetrical Guys.

Particularly preferred are those of the formula I in which X₃ and Y₆ are C₁-C₁₀ alkyl or chlorine and such this formula, wherein X₂ and X₇ are OH, the remaining X radicals are hydrogen.  

Compounds of the formula I are very particularly preferred with the above general and preferred Meanings in which R₁ and R₂ = OH.

Examples of the compounds to be used according to the invention are 1: 2 complexes of copper with

a) salicylic acid b) 5-methylsalicylic acid (p-cresotinic acid) c) 5-tert-butylsalicylic acid d) 5-chlorosalicylic acid e) 5-tert-octylsalicylic acid f) 2,4-dihydroxybenzoic acid ( β- resorcylic acid) g) 2- Hydroxynaphtaline-1-carboxylic acid (2-hydroxy-1-naphthoic acid) h) 4-hydroxy-1,3-benzenedicarboxylic acid (4-hydroxyisophthalic acid) i) salicylaldehyde j) 5-chlorosalicylaldehyde k) 3-methoxysalicylaldehyde.

The copper complexes according to the invention can also consist of Obtain mixtures of aromatic o-hydroxycarboxylic acids will. The amount used is 0.01 to 3, preferably 0.05 to 0.2% by weight (based on polyamide).

The Cu complexes according to the invention are produced in a manner known per se by implementing Alkali salts of aromatic o-hydroxycarboxylic acids in aqueous medium, with a copper (II) salt, such as. B. CuCl₂, CuSO₄, 5 H₂O, Cu (OAc) ₂ · H₂O or CuCO₃ · Cu (OH) ₂.  

1: 2 Cu complexes of salicylic acid are e.g. B. in Gmelins Handbook of inorganic chemistry 8th edition, publisher Chemie Weinheim 1961, system no. 60, pages 800-804 described.

The dyeings on polyamide fibers can be done in conventional Way with both azo metal complex dyes and Anthraquinone dyes as well as with acid dyes be generated. The metal complex dyes are preferred, especially the 1: 2 chromium or 1: 2 cobalt complexes of azo compounds described in the literature in described in large numbers and are commercially available. These dyes can also contain 1 to 2 sulfo groups.

The treatment of the polyamide materials with the invention copper compounds to be used can during or after, preferably during coloring, respectively.

The copper connections normally produced separately if they are not water soluble, come in finely divided form, as obtained by grinding in the presence The usual dispersant is used.

According to a special embodiment of the invention This process is practically in a "stew" performed by not using the fiber materials directly with the copper connections insulated in solid form treated, but - in principle in any Sequence - in situ from the corresponding starting materials generated on the fiber.  

In this variant, the fibers are first covered with a Dyeing liquor, in addition to the dye and, if necessary usual dyeing aids the metal-free compounds contain the formula I, colored and then treated with a copper (II) salt solution. Preferably the compounds of formula I are without any Co-catalysts used. The with the invention available copper complexes to be used Colorings are characterized by high durability against hot light radiation according to DIN 75 202, whereby no discoloration, even with higher doses of these aids the fiber enters.

DE-A-2 000 688 already contains salicylic acid derivatives known as dyeing aid. However these connections are there for a completely different one Purpose, namely to avoid the so-called catalytic Fading effect.

Nor was it recognized that the Cu complexes an outstanding light fastness improving effect own and of these in particular the 1: 2 complexes. Surprisingly, 1: 1 complexes do not achieve that State of the art. Other metal salts more aromatic Hydroxycarboxylic acids are much weaker.

In the examples below, "parts" mean Parts by weight.  

example 1 Manufacture of disalicylate copper

138 g of salicylic acid are added in 500 ml of water dissolved in 100 g of 40% NaOH. Then you drip at 50 ° C a solution of 125 g CuSO₄ · 5 H₂O in 350 ml H₂O add and stir at 50 ° C for 1 hour. After filtering off 160 g of copper complex are obtained as green crystals with a Cu content of 18%.

Example 2

Di-p-tert-butylsalicylate copper are made from 2-mol 5- tert-butylsalicylic acid, 2 mol NaHO and 1 mol CuSO₄ · 5 H₂O following the procedure of Example 1 as green crystals obtained with a Cu content of 14%.

Example 3 Disalicylate-copper-5,5′-disulfonic acid sodium salt

234 g of 2-hydroxybenzoic acid 5-sulfonic acid and 80 g of NaOH are dissolved in 620 g of water. Then you drop one Solution of 125 g of CuSO₄ · 5 H₂O in 350 ml of water and heated to 50 ° C for 1 hour. You get a dark green, approx. 22% aqueous solution of disalicylate copper 5,5′- disulfonic acid sodium salt used in this form for stabilization of polyamide dyeings can be used.  

Example 4

61 g salicylaldehyde and 20 g NaOH become 350 ml Dissolved water and at room temperature with a solution of 62.5 g of CuSO₄ · 5 H₂O in 175 ml of water. To Vacuuming and drying gives about 70g of green crystals with a Cu content of 18.4%.

Example 5

100 parts of polyamide 6 fiber material are made into 2000 parts aqueous dye liquor entered the 0.08 parts of Copper complex of preparation example 1 and 0.15 Parts of the dye of the formula

contains. By adding mono- and disodium phosphate a pH of 8 is set. Then the Liquor temperature slowly while moving the material to be dyed increased to 98 to 100 ° C and 60 minutes at this temperature leave.

The dye is then removed from the dye bath, rinsed and dried.  

The coloring is done together with one without the mentioned Comparative staining prepared according to the copper complex Draft DIN 75 202 exposed to hot exposure. The Coloring thus produced shows excellent lightfastness.

Example 6

An equally good improvement in resistance to Hot exposure is obtained when the liquor is not at pH 8, but with monosodium phosphate and acetic acid pH 5.5 is adjusted.

Example 7

100 parts of polyamide 6 material are made in 2000 parts aqueous dye liquor entered, the 0.15 parts of the in Example 1 copper complex described and 0.15 parts of the dye of the formula

contain.  

The dye liquor is adjusted to pH 5.5 with the aid of a Buffer mixture of monotriumphosphate and acetic acid set. Treated at 98 to 100 ° C for one hour, rinses and dries.

The coloring produced in this way shows a clearly better one Lightfastness as one without the copper complex mentioned manufactured.

Example 8

Are those prepared according to Examples 5 to 7 Dyeings then heat set at 180 ° C. for 30 seconds, so the light fastness improvement remains full receive.

Example 9

Are those prepared according to Examples 5 to 7 Colorings at pH 8 or at pH 5.5 adjusted with the appropriate buffer mixtures, during 30 minutes at Treated 98 to 100 ° C in an aqueous medium, the remains Lightfastness improvement fully preserved.

Example 10

In the coloring produced according to Examples 5 to 7 is the hue compared to those without the above Copper complex produced stains practically not  influenced, in contrast to those in EP-A-51 188, application example 2a and EP-A-113 856, application examples 1a and 2 colorings listed.

If the procedure is as described in Examples 5 to 7, however, that described in Preparation Example 2 Copper compound used is obtained both at pH 8 as well as at pH 5.5 a significant improvement in Hot light fastness.

Example 11 (comparative example)

If the procedure is as described in Examples 5 to 7, however, the known 1: 1 copper salicylate The complex becomes both at pH 8 and at pH 5.5 Dyeing liquor only a little improvement in hot light fastness achieved.

Example 12

A well-known made from a long fleet Polyamide 6 dyeing with the dye "Acid Yellow 151" (C.I. 14906 is finished and dried like treated as follows:

The coloring is 0.7 g / l of a 20% aqueous Dispersion of the copper complex described in Example 1 impregnated on the foulard. The wet weight gain is 70%.  

After impregnation is dried at 120 ° C and then heat set at 180 ° C. for 30 seconds.

The coloring treated in this way has, according to draft DIN 75 202 exposed, a significantly better lightfastness compared the untreated staining.

Example 13

Is placed the dye bath according to Examples 5 to 7 or Impregnation bath from example 12 instead of the copper complex, from preparation example 1 copper sulfate and sodium salicylate in a molar ratio of 1: 1.8 to 1: 3, this will also improve the light fastness achieved.

Example 14 (comparative example)

If dyeing is carried out as described in Examples 5 to 7, however instead of the copper complex from Example 1 the Corresponding nickel or zinc complex based on 0.1% used on the fiber weight, so you get neither at pH 5.5 still at pH 8 of the dye liquor an improvement in lightfastness.

The colors behave as if there is no light stabilizer added to the dye liquor.

Claims (8)

1. Process for improving the light fastness of polyamide dyeings by using copper compounds, characterized in that the copper compounds are the 1: 2 complexes of aromatic hydroxycarbonyl compounds of the formula (I) uses, in which R₁ and R₂ independently of one another are H, OH, or OW and X₁-X₈ independently of one another H, W, OH, halogen, CN, NH₂, NVW, SO₃H, COOH, COOW, CONVW or CONH₂ and two adjacent radicals X₁-X₈ also together mean the can form remaining members of a fused-on benzene ring, where W stands for C₁-C₈-alkyl and V for W or H, with the proviso that the second-order substituents mentioned above for X₁-X₈ occur at most twice in a benzene radical. 2. The method according to claim 1, characterized in that that 0.01 to 3% (based on the fiber weight) the copper compound used. 3. The method according to claim 1, characterized in that the 1: 2 copper compounds of salicylic acid, 5-methylsalicylic acid, 5-tert-butylsalicylic acid, 5-chlorosalicylic acid or naphthoic acid is used. 4. The method according to claim 1, characterized in that the 1: 2 copper compound of salicylaldehyde or 5-chlorosalicylaldehyde is used. 5. The method according to claim 1, characterized in that the 1: 2 copper compound of salicylic acid used. 6. The method according to claim 1, characterized in that the copper compounds the dye bath adds.   7. The method according to claim 1, characterized in that polyamide dyeings of metal complex dyes improved. 8. The method according to claim 1, characterized in that one can dye synthetic polyamides improved.