JPS6321986A - Method for improving light fastness of polyamide dyed article - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION It relates to a method for improving the lightfastness of dyeings of textile materials for dyeings by the use of copper compounds.

The light fastness of automotive seat covers, carpets and other interior interior items must meet very high standards, which, as is known, cannot be fully met by many commercially available dyes alone.

The reason is that, in addition to DIN 54,003 and 54,004, it has also become necessary to provide high lightfastness under the action of intense heat, measured by high temperature light irradiation according to DIN 75,202 (draft). Because there is.

Therefore, to meet this standard, previous proposals have used complex compounds of a wide variety of copper compounds, such as Schiff bases, 0-hydroxybenzophenone and oximes, in addition to many other lightfastness improvers. Including (EP-
A-51,188 and -113,856).

Nevertheless, these auxiliaries have not yet been able to fully meet the high requirements of automobile manufacturers, since the effects achieved are not completely sufficient. Moreover, some auxiliaries have undesirable colors of their own and/or are relatively expensive due to the complexity of the synthesis process.

Finally, a particular disadvantage is the fact that the action of the above-mentioned classes of substances decreases with increasing concentration, which limits the possible applications.

It has now surprisingly been found that when a 1:2 copper-lead body of the formula is used as an auxiliary agent, very fast dyeings can be obtained, virtually without the above-mentioned disadvantages. In the above formula, R and R2 independently represent H, O) (or OW, and X, ~X. independently represent H.W, ○H, halogen,
C.N. NH2, NVW. S○, H. C00H. COOW
, CONVW Mataha C O N H .

and two adjacent groups xl to X, can also jointly form the remainder of a fused benzene ring, where W represents C1 to Cll alkyl and V represents W or H However, the secondary substituents described above for X1 to Xll are
The condition is that at most two benzene groups appear in one benzene group.

Suitable halogen atoms are F. Br, especially CI. Suitable alkyl groups are straight-chain or branched and saturated or unsaturated.

The acid groups mentioned above can also be present in the form of salts.

Preferred compounds of formula I are of the symmetrical type.

Particularly preferred are formula I in which X and X6 are C.

~C1o-alkyl or chlorine compounds and x in the formula
This is a compound in which 2 and Xγ represent ○H, while the remaining X groups represent hydrogen.

Very particular preference is given to compounds of formula I which have the general and preferred meanings given above when R, and R2 represent ○H.

Examples of compounds to be used according to the invention are: a) salicylic acid, b) 5-methylsalicylic acid (p-cresotic acid), c)
) 5-t-butylsalicylic acid, d) 5-chlorosalicylic acid, e) 5-t-octylsalicylic acid, f) 2,4-dihydroxybenzoic acid (β-resorcylic acid), g) 2-hydroxynaphthalene-1-carvone Acid (2
-hydroxy-1-naphthoic acid), h) 4-hydroxy-1,3-benzenedicarboxylic acid (4-hydroxy-isophthalic acid), i) salicylaldehyde, j) 5-chlorosalicylaldehyde, k) 3-methoxysalicyl It is a 1:2 complex of copper with an aldehyde.

The copper complexes according to the invention can also be obtained from mixtures of aromatic 0-hydroxycarboxylic acids.

The amount used is 0.01 to 3 by weight, preferably 0.05 to 0.
．． 2% (relative to polyamide).

The production of the Cu complex according to the invention can be carried out by using known methods to prepare an alkali metal salt of an aromatic 0-hydroxycarboxylic acid in an aqueous medium, for example CuCl2, Cu5O, .5H20
, Cu (○A C> 2 ・H2O or CuC○s・
This is accomplished by reacting with a copper(I[) salt, such as Cu 2 (OH) 2 . 1+2Cu of salicylic acid
Complexes are described, for example, in "Gmelin's Handbook of Inorganic Chemistry"(Gmelin's Handbook of Inorganic Chemistry)
nnorFIanischen Chemie), 8th
Edition, Verlagk Hiemi Weinheim 1961,
System number 60. It is written on pages 800-804.

Dyeing of polyamide fibers using not only azo metal complex dyes and anthraquinone dyes but also acid dyes is only 1 yen! can be built. Preference is given to metal complex dyes, especially 1=2 chromium or 1:2 cobalt inscriptions of azo compounds, many of which are described in the literature and are commercially available. These dyes can also contain 1-2 sulfo groups.

The treatment of the polyamide material with the copper compound to be used according to the invention can be carried out before, during or after dyeing, preferably during dyeing.

Copper compounds, which are usually prepared separately, are used in finely dispersed form, such as those obtained, for example, by grinding in the presence of customary dispersants, unless they are water-soluble.

In one particular embodiment of the process according to the invention, the process is carried out not by treating the fiber material directly with a solid, isolated copper compound, but from the corresponding starting material, in principle in any order. It is carried out as a single container process by producing the auxiliaries in situ on the fibers.

In that variant, the fibers are first dyed with a dye liquor containing, in addition to dyes and other common dyeing aids, a metal-free compound of formula Process. Formula (I) without any cocatalyst
It is preferable to use a compound of The dyeings that can be obtained with the copper complexes to be used according to the invention are:
Even at relatively high concentrations of this auxiliary, which do not cause any discoloration on the fibers, it is distinguished by a high stability against high temperature light irradiation according to DIN 75.202.

Already, DE-A-2,000,688 also discloses salicylic acid derivatives as dyeing acid auxiliaries. However, in this case these compounds are used for a completely different purpose, namely to avoid catalytic fading effects.

It has not been recognized hitherto that Cu complexes have a particularly remarkable lightfastness-enhancing effect, especially as 1:2 complexes. Surprisingly, the 1:1 complex is less effective; other metal salts of aromatic hydroxycarboxylic acids are even less effective.

In the examples below, parts are by weight.

Example 1 Preparation of disalyl □ body 138 g of salicylic acid was mixed with 100 g of NaO at a concentration of 40%.
Dissolve in 500 ml of water by adding H. Then 125 g CuS○ in 350 nN H2C, -582
0 was added dropwise at 50°C, and the mixture was stirred at 50°C for 1 hour.

By filtration, 160 g of copper complex in the form of green crystals with a Cu content of 18% are obtained. Decomposition temperature〉300℃
. Infrared subektor maximum 3230cm-', 1680c
m-'.

Example 2 2 moles of 5-tert-butylsalicylic acid, 2 moles of NaOH and 1 mole of CuSO4.
Copper di-t-butylsalicylate is obtained from 5 H20 in the form of green crystals with a Cu content of 14%.

Example 3 Dilythyl copper 55'-disulfone PNa1234g2
-Hydroxy-5-sulfobenzoic acid and 80g NaOH
Dissolve in 620 g of water.

125g Cu5O, 5H20 in 350n+N water
dropwise and then heated at 50°C for 1 hour.

As a result, an aqueous solution of copper disalicylate 5,5'-disulfonate Na salt with a concentration of approximately 22% is obtained, which in that form can be used for the stabilization of dyeings of polyamides.

Example 4 61g salicylaldehyde and 20g NaOH at 350g
62°5g of Cu in 175mN water
A solution of SO4.5 H20 is added dropwise at room temperature. Suction filtration and drying give about 70 g of green crystals with a Cu content of 18.4%.

Decomposition temperature >300°C.

Example 5 100 parts of nylon-6 fiber material are introduced into 200 parts of an aqueous dye liquor containing 0.08 part of the copper complex of Preparation Example 1 and 0.15 part of the dyestuff of the formula. A pH value of 8 is achieved by adding sodium and disodium phosphate. The material to be dyed is stirred, then the liquid temperature is gradually raised to 98-100°C and left at that temperature for 60 minutes.

The dyed item is then removed from the dye bath, washed and dried.

This dyeing, together with a comparison dyeing prepared without the copper complex described above, is exposed to a thermal light irradiation test according to DIN 75,202 (draft).The dyeing shows excellent lightfastness.

Example 6 The dye solution was not pH 8, but pHed with sodium phosphate and acetic acid.
Standardization to H5.5 achieves a similar improvement in stability to thermal light irradiation.

Example 7 1.0 part of nylon 6 material is introduced into 2000 parts of an aqueous dye liquor containing 0.15 parts of the copper complex described in Example 1 and 15 parts of a dye of the formula.

The pH of the dye liquor is brought to 5.5 using a mixture of sodium phosphate and acetic acid. The nylon material is treated for 1 hour at 98-1 oo'c, washed and dried.

The dyeings thus prepared exhibit significantly better lightfastness than dyeings prepared without the copper complexes mentioned above.

Example 8 The dyeings prepared in Examples 5 to 7 were then incubated at 180°C for 3
Even when heat-setting for 0 seconds, the improvement in lightfastness is completely preserved.

Example 9 The dyed products prepared in Examples 5 to 7 were dyed at pH 8 or p) (5
i, '5, and when treated with the corresponding II mixture in an aqueous medium at 98-100[deg.] C. for 30 minutes, the improvement in lightfastness is completely preserved.

Example 10 In the case of the dyed products prepared in Examples 5 to 7, EP-A-
Application Example 2a of 51,188 and EP-A-113,
In contrast to the dyeings described in Application Examples 1a and 2 of 856, the shade is hardly affected compared to the dyeings prepared without the above copper complex.

When repeating the procedure described in Examples 5 to 7 but using the copper compound described in Preparation Example 2, a significant improvement in heat-light fastness is achieved not only at pH 8 but also at pH 5.5. .

Example 11 (comparative example) When repeating the procedure described in Examples 5-7 except using the 1:1 copper slithylic acid complex described in the literature, pH 8 and
In both liquors No. 5 and No. 5, only a slight improvement in heat-light fastness is achieved.

Example 12 A nylon-6 dyeing, prepared in a customary manner from a long liquor using the dye "Acid Yellow 151" (C, 1, 14906), after finishing and drying, is processed as follows: The dyeing is processed as follows: The pad-mangle is impregnated with a 20% strength aqueous dispersion of 0.7 g/l of the copper complex described in 1 above. The wet weight increase is 70%.

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

The dyed product prepared in this way was dyed according to DIN75°202 (
When exposed to light according to the scheme), it exhibits significantly better lightfastness compared to untreated dyeings.

Example 13 In the dye baths of Examples 5 to 7 or the impregnating bath of Example ρ112, instead of using the copper complex as in Production Example 1, 1:1.8 to 1
An improvement in lightfastness also occurs when using a molar ratio of copper sulfate and sodium salicylate of :3.

Example 14 (comparative example) Instead of the fj4 complex of Example 1, 0 for the fiber subtype
When dyeing as described in Examples 5 to 7 but using the corresponding Zinc complex or zinc complex in an amount of 61%, pH 5,
No improvement in lightfastness is achieved in either the pH 5 or pH 8 dye liquors.

The dyeing behaves as if no light stabilizer had been added to the dye liquor.

Claims (1)

[Claims] 1. The copper compound used has the formula I ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R_1 and R_2 independently represent H, OH or OW, and X_1 to X_8 are mutually Regardless of H, W, OH, halogen, CN, NH_2, NVW, SO_3H, COOH,
COOW, CONVW or CONH_2, and two adjacent groups X_1 to X_8 can jointly form the remaining members of a fused benzene ring, where W represents C_1 to C_1_■alkyl and V is W or H, provided that the above secondary substituents for X_1 to X_8 occur at most twice in one benzene ring, in a 1:2 complex of an aromatic hydroxycarbonyl compound of A method for lightfastness of polyamide dyeings by the use of copper compounds, characterized in that: 2. Process according to claim 1, characterized in that from 0.01 to 3% (based on the weight of the fibers) of copper compounds are used. 2. Process according to claim 1, characterized in that a 1:2 copper compound of 3, salicylic acid, 5-methylsalicylic acid, 5-tert-butylsalicylic acid, 5-chlorosalicylic acid or naphthoic acid is used. 2. Process according to claim 1, characterized in that a 1:2 copper compound of 4, salicylaldehyde or 5-chlorosalicylaldehyde is used. 5. Process according to claim 1, characterized in that a 1:2 copper compound of salicylic acid is used. 6. The method according to claim 1, characterized in that a copper compound is added to the dye bath. 7. The method according to claim 1, characterized in that the polyamide dyed product is improved with a metal complex dye. 8. The method according to claim 1, characterized in that the dyed product of synthetic polyamide is improved.