DE2625386A1 - Dyestuff mixt. contg. catalytic fading inhibitor - of single oxygen-deactivating type, pref. nickel complex or diazabicyclooctane - Google Patents

Abstract

Dyestuff with reduced catalytic fading contains >=2 dyestuff components and, as fading inhibitor, a singlet O-deactivating substance (I). (I) pref. is a commercial antioxidant and antiozonant, esp. a Ni complex or diazabicyclo 2.2.2 -octane. Claimed Ni complexes are Ni(II) salicylaldehyde-oxime complexes, e.g. Ni (II) -(N-dodecylformimdoyl)-phenyl Ni (II) thiobisphenolato complexes, e.g. Ni (II) amino(i,2-thiobis (4, tert.-octyl)phenolate, Ni (II) 2-hydroxy-5-methlbenzophenone, Ni (II) di-n-butyldithiocarbamate (Ia) or Ni (II) dithiobenzil. In an example, Ni (II) di-n-butyldithiocarbamate prevented fading of a mixt. of C.I. Acid Yellow 127 and C.I Acid Violet, 47, in an ethylcellulose film at a conc. of 2.5 mole/mole dye.

Description

Dyes 1 with reduced catalytic fading,

Staining processes and inhibitors to reduce the catalytic Fading The invention relates to dyes with reduced catalytic fading, the at least two dye components, for example a blue and a yellow component, as well as a fade inhibitor.

The invention also relates to a dyeing method in which to reduce catalytic fading of the dyed material, a fading inhibitor is used.

Finally, the invention relates to the use of certain substances as an inhibitor to reduce catalytic fading.

A number of fastness properties play a role in the development of new dyes a great wool. One of them is the lightfastness, which is essential for the dye and textile chemist is of great importance. The requirements for light fastness are extraordinary high. ; an expected that sicfl a colored vlextilmeterial even after months Sun exposure does not change the color quality. In modern textile dyeing However, numerous color nuances can only be achieved by mixing different dyes, some of which come from different classes of dyes. this leads to a particular problem. The lightfastness of the components in the mixture can be quite different from that of the individual paraffins. Examples of this are yellow-blue combinations in which either the blue component or the gel component accelerated or catalytically faded.

At the DT-OS 2 000 688 a method is already known that concerned with the problem described. Here is taught the textile fibers during of dyeing or then with an orbho-hydroxybenzoic acid substituted in the 3-, 4- and / or 5-position, to treat one of its salts or an ester or a halide of this acid. This teaching is obviously purely empirical.

Since the mechanism underlying catalytic bleaching is was not recognized, the active substance group could neither functionally delimited can still be specifically found and optimized in terms of effectiveness.

A quantitative statement about the effectiveness of the proposed Fabrics weren't made.

The object of the present invention is to provide dyes and dyeing processes and to indicate inhibitors with which the catalytic bleaching is practically complete can be avoided.

This task cannot be solved without first clarifying it to have won the eschanism which is the cause of the catalytic bleaching is. For this purpose, extensive experiments were carried out, mainly based on spectroscopic Investigations were based and will not be discussed here in detail. in the The result was found that the catalytic bleaching was essentially due to a sensitized photooxygenation is based. Below is a mechanism of interaction to understand in which a dye component (which acts as a sensitizer) under Absorption of a photon corresponding to its parbe in its first singlet state is stimulated, which is then with considerable probability in the first converts excited triplet state. These triplet excited states of the sensitizer react with molecular oxygen, the presence of which does not prevent in practice can be. The molecular oxygen gets out of the triplet ground state into an excited singlet state, which is highly reactive, and leads to a conversion with the second dye component tends. This implementation presents itself visually as Fading.

The invention is based on the knowledge that the catalytic Bleaching can largely be prevented if the caused by the sensitizer Singlet oxygen is deactivated so quickly that the reaction with the second Dye component than competing Mechanism unlikely will. In this way, the energy transmission chain between the sensitizer and fading component interrupted.

Accordingly, the present invention teaches to solve the above The task described in general the use of a singlet oxygen deactivator Substance as an inhibitor.

Singlet oxygen-deactivating substances are from oxygen research known. For example, see the publications by A. Zweig and W.A.

Henderson Jr. in "Journal of polymer Science", 13, p. 933 (1975), D.J. Carlsson,. Suprunchuk and D.M. Wiles in Can. J. Chem., 52, p. 3728 (1974), and J.P. Guillory, C.F. Cook in "Journal of Polymer Science", 11, p. 1927 (1973) pointed out. These essays provide information about the effectiveness of the substances concerned.

The singlet oxygen-deactivating substance is preferably a commercially available antioxidant and antiozonant.

This can be a nickel complex. In particular, can the substance can be selected from the group consisting of Ni (II) o- (N-dodecylformimidoyl) phenol, Ni (II) o- (N-phenylformimidoyl) phenol, Ni (II) 2'-hydroxyacetophenone oxime, Ni (II) amino (2,2'-thiobis (4-tert.-octyl) phenolate), Contains Ni (II) din-butyldithiocarbamate and Ni (II) dithiobenzil.

The inhibitor can also seln diazabicyclo [2.2.2] octane.

A dye according to the invention is characterized in that the The inhibitor contained in it is a singlet oxygen-deactivating substance Advantageous embodiments of such a dye are in the claims 2 to 7.

A dyeing method according to the present invention is characterized in that that the dyeing bath through which the material to be dyed is passed has a singlet oxygen deactivator Substance is added. Advantageous embodiments of this method are in the claims 9 to 14 described.

A coloring method according to the present invention can also thereby be characterized in that the material to be dyed is passed through a special bath that contains a singlet oxygen-deactivating substance. Advantageous embodiments this method are described in claims 16-19.

The invention is illustrated in the pole end on the basis of experiments with reference to the drawing explains in more detail; 1 shows typical absorption spectra of a Dye mixture with blue and yellow components before and after bleaching; Fig. 2 the inhibitory effect 7 as a function of the added concentration p for a typical system of dye mixture and inhibitor.

I Sample preparation For the quantitative determination of the absorption spectra and the fading rates, the dye mixtures with their respective inhibitor additives cannot be examined on the textile fabric. Rather, it was initially necessary an equivalent matrix for the dyes, on the one hand in the color behavior comes as close as possible to the textile materials, and which, on the other hand, become thin, Can process penetrable films.

Ethyl cellulose films have proven to be suitable.

Films were used for the exposure tests described below made of this material, in which the dyes and optionally the Addition of inhibitor are homogeneously distributed. This is done as follows: The dyes and optionally the inhibitors are in a mixture of ethanol-butanol solved. Ethyl cellulose polymers are stirred into this solution so that the solution contains a total of 104 polymers. Stir in over a longer period of time until it is guaranteed is that there is a homogeneous distribution. After that, the viscous solution will rise A flat glass plate is applied and drawn into a pilm of a defined thickness. Man leaves the solvent then evaporate and retain as slowly as possible on this journey a clear film suitable for the measurement, which is in the middle range has an almost constant layer thickness. Such films were made of all dyes and all dye mixtures. For the fading measurement are off larger pieces of pilm with a template circular pieces with a diameter cut out 2.5 cm. These circular disks are based on the outermost points a sample holder stuck on in the xenotest device.

The concentration of dye in the film is determined so that the molar The extinction coefficient in solution is set equal to that in the film.

The following applies: Emax Film Film Film dFilm ## max solution Emax Film = extinction maximum in the film dFilm = film thickness in cm #max solution maximum molar extinction coefficient in l # Mol-1 # cm-1 cFilm = dye concentration in the film in Mol # l-1 As far as possible This measurement method and the underlying assumptions result in errors, affect them at most the absolute value of the concentration data. The resulting margins of error are only of scientific, not practical, interest. Otherwise stay the relative concentration ratios of all determined by this method Errors unaffected. The qualitative functional dependency of the evaluated variables from the concentration remains independent of any errors in the absolute size right.

II Determination of the fading rates To determine the fading rates the films with the respective dye mixtures were placed in a commercially available spectrophotometer brought. The corresponding absorption spectrum was recorded there before the bleaching began recorded. The sample was then exposed to light typically for about 23 hours exposed to a commercial xenon lamp of 1,500 watts. This radiation was enough usually to achieve an easily detectable bleaching. This became quantitative determined by repeating the absorption measurement.

III The systems investigated There were mainly tests on dye mixtures made with yellow and blue components, in which the yellow component is in the mixture accelerated fading.

The dyes were in detail: 1. Yellow component: a) C.I. acid Yellow 127 b) C.I. Acid Yellow 29 c) O.I. Disperse Yellow 50 2nd blue component: a) C.I. Acid Red 43 b) d.I. Acid Violet 47 c) C.I. Acid Green 25 d) C.I. Disperse Blue 56 The dye names correspond to the international ones Color Index (C.I.). The term "blue component" is a collective term for darker dye components whose subjective color impression is not necessarily "blue" must be, but includes green, red, red-violet and blue.

The aforementioned Parben were obtained from Sandoz AG Basel. The combinations studied were: C.I. Acid Yellow 127 + O.I. Acid Red 143 + C.I. Acid Violet 47 + O.I. Acid Green 25 + C.I. Disperse Blue 56 C.I. Acid Yellow 29 + C.I. Acid Red 143 + C.I. Acid Violet 47 + C.I. Acid Green 25 + C.I. Disperse Blue 56 0.1. Disperse Yellow 50 + O.I. Acid Red 143 + C.I. Acid Violet 47 + C.I. Acid Green 25 + O.I. Disperse Blue 56 These combinations became the majority of the in the claims listed inhibitors added, so that the effectiveness for the entire claimed area is secured. For selected inhibitors it was additionally investigated the effectiveness as a function of the concentration added.

IV Definitions: 1. The effectiveness of an inhibitor addition is determined by expresses an efficiency T which is defined as follows: rate of fading without inhib. - Fading rate with inhib.

# = () # 100 Fading rate without inhibitor The efficiency is given in percent printed out. An efficiency 7 = 0% thus means that the addition of inhibitor does the could not affect catalytic fading.

An efficiency n # = 100% indicates that the addition of inhibitor is the catalytic Could completely prevent fading.

2. The concentration of the added inhibitor becomes physical sensibly based on the amount of yellow component present, its catalytic Should prevent fading. It is therefore: Mole inhibitor ß = Mole yellow component 3. The fading rates of the individual dye components were defined as that Change in absorbance cm maximum of the corresponding absorption band. The corresponding Wavelengths are: C.I. Acid Yellow 127 410 nm 0.1. Acid Yellow 29 385 nm C.I. Disperse Yellow 50 360 lirn C.I. Acid Red 143 530 nm C.I. Acid Violet 47 530 nm C.I. acid Green 25 640 nm C.I. Disperse Blue 56 620 nm For the pure blue components the change in absorbance at 410, 385, 360 nm was also measured. Under the Assume that these absorbance changes are equal to the blue components in the mixture are as in the pure state, the fading rates of the yellow components were calculated.

The following applies: total fading rate at xxx nm = fading rate of the yellow component at xxx nm + bleaching rate of the blue.

at xxx nm xxx = 410, 385, 360.

V Experimental Examples: 1. Comparative Experiments First, the fading rates were of pure dyes. For this purpose, samples were made in the manner described under I above Way made; the fading rates were determined in the manner described under II. The results are summarized in Table 1: Table 1 Concentration Bleaching rate [Mol # 1-1] [%] C.I. Acid Yellow 127 7.4 # 10-3 31 C.I. Acid Yellow 29 4.3 # 10-3 37 C.I. Disperse Yellow 50 5.9 # 10-3 19 C.I. Acid Red 143 3.3 # 10-3 15 C.I. Acid Violet 47 1.1 # 10-2 24 C.I. Acid Green 25 2.2 # 10-2 21 C.I. Disperse Blue 56 9.6 # 10-2 17 Thereafter Corresponding measurements were carried out on dye mixtures.

The concentrations of the dyes in the mixtures became about the same Chosen as large as the concentrations in the measurement with the individual dyes.

The results are summarized in Table 2: Table 2 Bleaching # Fade-out

the yellow the blue.

[%] [%] C.I. Acid Yellow 127 + C.I. Acid Red 143 72 11 + O.I. acid Violet 47 92 21 + C.I. Acid Green 25 72 20 + C.I. Disperse Blue 56 96 11 C.I. acid Yellow 29 + 0.1. Acid Red 143 49 22 + C.I. Acid Violet 47 89 25 + C.I. Acid Green 25 51 23 + C.I. Disperse Blue 56 71 14 O.I. Disperse Yellow 50 + O.I. Acid Red 143 50 8 + C.I. Acid Violet 47 68 31 + C.I. Acid Green 25 52 20 + O.I. Disperse Blue 56 59 18 It can be seen that the yellow component in the mixture with the blue component fades much more strongly than isolated. This effect is called catalytic Known to be fading or yellowing.

The relationships are also clear from FIG. 1, which are typical Represents absorption spectra.

The curves belong to the system Acid Yellow 127 + Acid Violet 47. The The dashed curve shows the absorption spectrum, the dash-dotted curve the absorption spectrum after fading.

It can be seen that the blue component also decreases the absorbance experiences. This effect is not due to catalytic bleaching and is not covered by the present invention. What is striking, however, is that striking change in the spectrum at the one indicated by the double arrow Place: The absorption band of the yellow component with a maximum at 410 nm disappears practically complete. This accelerated fading, which the parbs do not only lets it fade but also changes the color value, can with the present Invention are prevented.

2. Experiments with Various Inhibitors The present invention can be realized with all singlet oxygen deactivating substances. Examples of this are given in the literature cited and in the examples listed. Since all tested inhibitors behave qualitatively the same and their effectiveness corresponds roughly to what can be expected from the publications only two characteristic experiments are described below.

a) The inhibitor used was Ni (II) di-n-butyldithiocarbamate. He stands here as an example of the Mickel complexes described in the literature. the The dye mixture used was Acid Yellow 127 + Acid Violet 47.

A comparative sample was prepared according to the method described above, which did not contain any inhibitor additive. A sample that was otherwise produced in the same way contained Ni (II) di-n-butyldithiocarbamate (abbreviation NBO) in a concentration of about p = 4.5.

The evaluation of the degree of inhibitor was carried out in the above under II described way. The result was a value of 10Q.

That means: The catalytic bleaching could be caused by the addition of NBC are practically completely prevented.

b) As an example of the group that does not belong to the nickel complexes of singlet oxygen-deactivating substances is diazabicyclo [2.2.2] octane (abbreviation DABCO). The dye mixture used was again Acid Yellow 127 + Acid Violet 47.

The Pestimmaung of the inhibitor efficiency 9 happened the same as with Experiment a) described above with BC, the result was a value # # 30%.

The concentration in this case was approximately = 1.

This result is indicated in Pigur 2 by an empty dot shown. The comparison with the solid curve for the inhibitor NBC shows that NBC is about 2.5 times more effective than DABCO at the same concentration. This matches with about the theoretical expectation.

3. Experiments with different inhibitor concentrations: The knowledge the mechanism of interaction that leads to catalytic bleaching a theoretical prediction of how the inhibitory effect # # depends on the concentration X depends on the added inhibitor: After that, # should be a function that starts with increasing ß increases monotonically between the values 0 (ß = 0) and = 100% o (ß = ßmax).

Inhibitor additions at which the concentration exceeded t ax will therefore bring practically no further improvement.

The theoretical prediction is confirmed by the experiments. There If all inhibitors behave qualitatively in the same way, the description here suffices a single series of experiments.

8 samples were produced according to the method described under I above, which were largely identical except for the inhibitor concentration. That used The system was again Acid Yellow 127 + Acid Violet 47. The one in various concentrations added inhibitor was again NBC. The inhibitory effect was determined again as described above under II.

The determined characteristic data are summarized in Table 3: Table 3 # 9 # 10-3 5 # 10-2 6.7 # 10-2 10-1 3.6 # 10-1 5 # 10-1 2.5 5 # 5% 16% 24% 37% 76% 80% 100% 100% These results are illustrated in FIG. It is recognizable, that the theoretically expected increase in the inhibitory effect # between the inhibitor concentrations 10-3 3 and 10 Mol / Eol plays. The practically interesting area is, as can be seen, in the concentration range between 10 2 and 1 arol / mol. It should be noted that in practice one will often be satisfied with an inhibitory effect that is below 100. When choosing the inhibitor action, economic ones are usually also considered Cost-benefit considerations play a role by the present invention cannot be detected.

Curves for inhibitors with poorer efficiency than NEC, for example for Dfii: BC0, which is flatter, also shown in FIG. 2, differentiate but not qualitatively different from the curve according to FIG. 2.

From the above explanation, it can be seen that the invention is a great one Provides a variety of substances that reduce catalytic fading are suitable. These substances can be based on procedural and economic The knowledge of the theoretical relationships makes it is not only possible to find suitable substances in a targeted manner; it can also be done in advance It can be estimated how good the effectiveness of the selected substance will be: All the more stronger the singlet oxygen deactivating effect (known from the literature) is, the more suitable the substance is as an inhibitor according to the present invention.

It will often be useful to use the dye itself during the Add the appropriate amount of inhibitor to manufacture. However, as between dye and inhibitor no chemical reaction needs to take place and a physical, if a narrow mixture is sufficient, the Inhibitor of the dye can also be added later, for example in the dye bath. In the end it is also conceivable that the inhibitor is in a special bath through which the material to be dyed is carried out before or after the actual dyeing.

Claims (24)

Claims 1. Dye with reduced catalytic fading, which contains at least two dye components as well as a bleaching ingredient, characterized in that the inhibitor lives a singular »oxygen-deactivating Substance is. 2. Dye according to claim 1, characterized gekennzeichn.et that the inhibitor is a commercially available antioxidant and antiozonant. 3. Dye according to claim 2, characterized in that the inhibitor is a nickel complex. 4. Dye according to claim 3, characterized in that the inhibitor from the group of Ni (II) salicylaldehyde oxime complexes, for example Ni (II) o- (N-dodecylformimidoyl) phenol, or from the group of Ni (II) thiobisphenolato complexes, for example Ni (II) amino (2,2'-thiobis (4-tert.-octyl) phenolate), or from the nickel complexes Ni (II) 2-hydroxy-5-methylbenzophenone, Ni (II) di-n-butyldithiocarbamate, Ni (II) dithiobenzil is selected. 5. Dye according to claim 1, characterized in that the inhibitor Is diazabicyclo [2.2.2] octane. 6. Dye according to one of claims 1 to 5, characterized in that that the concentration p of the inhibitor is between 10-3 3 and 10 ol inhibitor per mole catalytically fading dye component is. 7. Dye according to one of claims 1 to 5, characterized in that that the concentration β of the inhibitor is between 10-2 and 1 mole inhibitor per mole catalytically bleaching dye component. 8. Colorings that reduce catalytic fading of the dyed material a fading inhibitor is used, characterized in that the dyebath through which the dyed material is passed, a singlet oxygen-deactivating Substance is added. 9. dyeing method according to claim 8, characterized in that a commercial antioxidant and antiozonant is added. 10. dyeing method according to claim 9, characterized in that a Nickel complex is added. ii. Dyeing method according to claim 10, characterized in that a Substance from the group of Ti (II) salicylaldehyde oxime complexes, for example Ni (II) -o- (N-dodecylformimidoyl) phenol, or from the group of Ni (II) thiobisphenolato complexes, for example Ni (II) amino (2,2'-thiobis (4-tert.-octyl) phenolate), or from the nickel complexes Ni (II) 2-hydroxy-5-methylbenzophenone, Ni (II) di-n-butyldithiocarbamate, Ni (II) dithiobenzil is added. 12. coloring process according to claim 8, characterized in that diazabicyclo [2.2.2] octane is admitted. 13. Dyeing method according to one of claims 8 to 12, characterized in that that the concentration ß of the inhibitor in the dye bath at a value between 10 3 and 10 moles of inhibitor per mole of catalytically bleaching dye is held. 14. Dyeing method according to one of claims 8 to 12, characterized in that that the concentration ß P of the inhibitor in the dye bath on a different between 10 2 and maintaining 1 mole of inhibitor per oil of catalytically fading dye. 15. Dyeing process in which to reduce catalytic fading of the dyed material a fading inhibitor is used, characterized in that the dyed material is passed through a special bath that has a singlet oxygen-deactivating bath Contains substance. 16. The method according to claim 15, characterized in that the special Bath contains a commercially available antioxidant and antiozonant. 17. The method according to claim 16, characterized in that the special Bath contains a nickel complex. 18. The method according to claim 17, characterized in that the special Bath a substance from the group of Ni (II) salicylaldehyde oxime complexes, for example Ni (II) o- (N-dodecylformimidoyl) phenol, or from the group of Ni (II) thiobisphenolato complexes, for example Ni (II) amino (2,2'-thiobis (4-tert.-octyl) phenolate), or from the nickel complexes Ni (II) 2-hydroxy-5-methylbenzophenone, Ni (II) di-n-butyldithiocarbamate, Ni (II) dithiobenzil contains. 19. The method according to claim 15, characterized in that the special Bad contains diazabicyclo [2.2.2] octane. 20. Use of a singlet oxygen-deactivating substance as an inhibitor to reduce catalytic fading. 21. Use of a commercially available antioxidant and antiozonant as An inhibitor according to claim 20. 22. Use of a nickel complex as an inhibitor according to claim 21. 23. Use of a substance from the group of Ni (II) salicylaldehyde oxime complexes, for example Ni (II) o- (N-dodecylformimidoyl) phenol, or from the group of i (II) -thiobisphenolato complexes, for example Ni (II) amino (2,2'-thiobls (4-tert-octyl) phenolate), or from the nickel complexes Ni (II) 2-hydroxy-5-methylbenzophenone, Ni (II) di-n-butyldithiocarbamate> Ni (II) dithiobenzil as an inhibitor according to claim 22. 24. Use of diazabicyclo [2.2.2] octane as an inhibitor according to claim 20th