DE19742912A1 - Dye mixture giving luminous colour with high contrast for signal or warning clothing - Google Patents

Abstract

Dye mixtures based on red and yellow disperse dyes have a position in a colour area given by points with co-ordinates (x, y) (0.655, 0.344), (0.579, 0.341), (0.606, 0.314) and (0.690, 0.310); and a minimum luminous density factor beta > 0.25 0.40, based on measurements of (semi)synthetic materials treated with the mixture. Also claimed is a method of dyeing (semi)synthetic materials in a dyebath to which the dyes are added as a mixture or separately.

Description

The present invention relates to new dye mixtures which essentially contain yellow and red disperse dyes and which, when measuring synthetic or semi-synthetic materials treated with them, their color locus in one by corner points with the following coordinates x and y

have a spanned color space and a minimum luminance factor β <0.25 <0.40, their use for dyeing or printing ken of synthetic or semi-synthetic materials as well a method of dyeing synthetic or semi-synthetic Materials.

The abnormality of signal or warning clothing is indicated by a high contrast between clothing and the background against which the clothes are seen, shaped. It is due to large areas of the eye-catching material. When selecting the signal or warning colors, the user must know the prevailing background, urban or rural environment where protection is sought, take into account and choose the colors so that the required con trast is reached.

From EP-A-42 090 and DE-A-34 47 794 are already Mixtures of dyes known as Signal or Warnfar ben should be used.

However, it has been shown that the materials of the prior art Technology still have disadvantages. So their color location lies outside of the color space spanned by the mentioned corner points.

The object of the present invention was now to create new dye Mixtures containing disperse dyes to provide the itself in an advantageous manner for the production of signal and warning clothing, the treated with the dye mixtures Material should no longer have the disadvantages mentioned above.  

Accordingly, the dye specified in the introduction mixtures found.

For the color space defined by the corner points with the above Coordinates x and y is stretched, as well as the minimum light density factor β is common in this technique Terms familiar to a person skilled in the art. They are in the euro European standard EN 471 "Warning clothing" (1994) and those mentioned there References to which express reference is made here treated.

Synthetic materials are e.g. B. polyester, polyamide or Polycarbonates. Materials in texti are particularly worth mentioning form, such as fibers, yarns, threads, knitwear, woven goods or Non-wovens made of polyester, modified polyester, e.g. B. anionic modified polyester, blended fabric of polyester with cellulose, Cotton, viscose or wool (semi-synthetic materials), or polyamide.

The red and yellow disperse dyes come in particular from the class of benzopyran and naphthalimide dyes.

Suitable yellow disperse dyes obey z. B. formulas I or II

wherein
R ¹ and R ² are each independently of the other C ₁ -C ₁₃ alkyl,
Q is a residue of the formula

in the
n for 1 or 2,
R ^{3 is} hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogen, cyano, nitro, carbamoyl, C ₁ -C ₄ mono- or dialkylcarbamoyl, sulfamoyl or C ₁ -C ₄ mono- or dialkylsulfamoyl,
R ^{4 is} hydrogen or C ₁ -C ₆ alkyl and
X represents imino, C ₁ -C ₄ -alkylimino, oxygen or sulfur,
L ¹ C ₁ -C ₁₃ alkyl, which is optionally interrupted by one to three oxygen atoms in ether function and can be substituted by hydroxy, or phenyl and
L ^{2 is} C ₁ -C ₆ alkyl.

Suitable red disperse dyes obey z. B. formulas III or IV

wherein
R ¹ , R ² , R ³ , X and n each have the meaning given above and
Y oxygen or imino and
Z mean cyano or carbamoyl.

All alkyl radicals occurring in the formulas mentioned here can be both straight and branched.

When substituted alkyl groups in the formulas mentioned here occur, they usually have one or two, preferred have a substituent.

Residues L ¹ , L ² , R ¹ , R ² , R ³ and R ⁴ are e.g. B. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neophenyl, tert-pentyl, hexyl or 2-methylpentyl.

R ¹ and R ² are, for. B. heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl or isotridecyl. [The designations isooctyl, isononyl, isodecyl and isotridecyl are trivial designations and come from the alcohols obtained after the oxo synthesis (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. Al, pages 290 to 293, and Vol. A 10, pages 284 and 285).]

R ³ are still z. B. methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyl oxy, neopentyloxy, tert-pentyloxy, hexyloxy, fluorine, chlorine, bromine, mono- or dimethylcarbamoyl, mono- or diethylcarbonyl , Mono- or dipropylcarbamoyl, mono- or diisopropylcarbonyl, mono- or dibutylcarbamoyl, N-methyl-N-butylcarbamoyl, mono- or dimethylsulfamoyl, mono- or diethylsulfamoyl, mono- or dipropylsulfamoyl, mono- or diisopropylsulfamoyoyl or mono N-methyl-N-ethylsulfamoyl.

L ¹ are still z. B. 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4 -Methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-butoxy butyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4, 7-dioxaoctyl, 4,7-dioxanonyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2- or 4-hydroxybutyl, 5-hydroxypentyl or 6-hydroxyhexyl.

X residues are e.g. B. methylimino, ethylimino, propylimino, iso propylimino or butylimino.

Preferred yellow disperse dyes are those of the formula I in which R ¹ and R ^{2 are} each C ₁ -C ₄ alkyl, in particular ethyl.

Preferred yellow disperse dyes are furthermore those of the formula II in which L ^{1 is} C ₁ -C ₄ -alkyl, which is optionally simply substituted by hydroxy, and L ^{2 is} methyl or ethyl.

Preferred yellow disperse dyes are also those of the formula Ia, Ib or Ic

wherein R ¹ , R ² and R ³ each have the meaning given above and X is imino, oxygen or sulfur.

Preferred red disperse dyes are those of the formula IIIa

in which R ¹ , R ² and Y each have the meaning given above.

Preferred red disperse dyes are also those of the formula IVa

in which R ¹ , R ² and Y each have the meaning given above.

Dye mixtures containing as red dispersers are preferred ion dyes at least one dye of formula IV, preferably of the formula IVa, in which Y is oxygen.

Dye mixtures containing red are also preferred Disperse dyes a dye of formula IV, preferably of the formula IVa, in which Y is oxygen and a dye of the formula IV, preferably of the formula IVa, in which Y means imino tet.

Dye mixtures containing red are also preferred Disperse dyes a dye of formula IV, preferably of the formula IVa, in which Y is oxygen, a dye of Formula IV, preferably of formula IVa, in which Y is imino and a dye of the formula III, preferably of the formula IIIa.

Dye mixtures containing red are particularly preferred Disperse dyes at least one dye of the formula IVa, in which Y means oxygen, and as a yellow dispersion paint substances, at least one dye of the formula Ia, Ib and / or Ic.  

In addition, dye mixtures are preferred in which the Mi partners from a combination of the above selected components are selected.

In the dye mixtures according to the invention, the Weight fraction of the red disperse dyes as a rule 50 up to 90% by weight, preferably 55 to 85% by weight and in particular 70 to 85 wt .-% and that of the yellow disperse dyes 10 to 50% by weight, preferably 15 to 45% by weight and in particular 15 to 30 wt .-%, each based on the total weight of the red and yellow disperse dyes, the total proportion of color fabric of course results in 100%.

Dye mixtures in which the Weight fraction of the red disperse dyes of the formula IV, where rin Y means oxygen, 45 to 80 wt .-%, that of the red dis persion dyes of the formula IIIa 5 to 45 wt .-% and that of yellow disperse dyes 10 to 20 wt .-%, each based on the total weight of the red and yellow disperse dyes is, the total proportion of dyes of course 100% results.

Further constituents of the dye mixtures according to the invention can e.g. B. conventional aids, such as commercial dispersants medium, adjusting agent or defoaming agent or water.

Preferred are dye mixtures that have a minimum have luminance factor β <0.30 <0.40.

Preference is further given to such dye mixtures which mentioned conditions for color locus and minimum luminance factor meet before and after xenon radiation. Regarding the out "Xenon radiation" is also referred to EN 471 here taken.

The new dye mixtures are produced in themselves known way by mixing the mixing partners. You can the red and yellow disperse dyes in bulk can be mixed directly with one another. However, it is also possible the red and yellow disperse dyes in the form of dye to mix preparations. Furthermore can also Mixtures by mixing dyes, at least of which one in substance and at least one as a dye preparation is present.  

Another possibility is the invention Generate dye mixtures in situ, d. H. the mix part ner separately in the dyeing liquor, where the Then form mixtures. This in turn can be done as well hen that the mixture partners in substance and / or as a color fabric preparation for the dye liquor. The addition in the form of Dye preparations are preferred.

Another subject of the present application is therefore a Process for dyeing synthetic or semi-synthetic Materials that are characterized in that the synthe tables or semi-synthetic materials in the dyeing liquor treated the dye mixtures according to the invention, wherein either the dye mixtures are added to the dye liquor or the Dye mixtures by adding the red and yellow separately Disperse dyes are generated in situ in the dyeing liquor.

In the contained in the dye mixtures according to the invention Dyes are generally known per se Products. They are for example in the in EP-A-42 090 zi documents or described in US-A-3 880 869.

The dye mixtures according to the invention are advantageous way for dyeing or printing synthetic or semi-synthetic materials (also by means of the ink jet process rens). The dyeing and printing conditions are known per se and include dyeing in supercritical carbon dioxide.

The new dye mixtures have the particular advantage that in their application for the production of signal and warning bran products that have a pronounced luminosity point.

The following examples are intended to explain the invention in more detail.

The following dyes were used in the form of preparations dung.

Dye 1

(as a 15% by weight preparation)

Dye 2

Dianix® Brilliant Yellow H10GF-FS (Mitsubishi Kasei Corp., Tokyo) (Commercial preparation)

Dye 3

Resolin® Brilliant Yellow 10GN 400% (Bayer AG, Leverkusen) (Commercial preparation)

Dye 4

(as a 20% by weight preparation)

Dye 5

(as a 20% by weight preparation)

Dye 6

Resolin® Brilliant Red FFB 50% (Bayer AG, Leverkusen) (Commercial preparation)

A1) HT process (in situ generation of the dye mixture)

W ¹ % by weight of red dye (as preparation), W ² % by weight of yellow dye (as preparation), each based on the weight of the polyester fabric and 10 g of polyester fabric, are placed in 200 ml of a dyeing liquor at a temperature of 50 ° C given, the pH of which is adjusted to 4.5 using acetic acid. It is treated for 5 minutes at 50 ° C., then the temperature of the liquor is raised to 130 ° C. within 30 minutes, kept at this temperature for 60 minutes and then allowed to cool to 60 ° C. within 20 minutes.

The dyed polyester fabric is then oxidatively treated by placing it in 200 ml of a liquor containing 2 ml / l 50% by weight sodium hydroxide solution, 5 ml 30% by weight aqueous Hydrogen peroxide and 1 m / l of a commercially available peroxide contains stabilizers, treated at 90 ° C. Eventually rinsed the tissue, neutralized with dilute acetic acid, rinsed again and dried.

A2) HT process (Dye mixture is added to the dye liquor)

The procedure is analogous to A1). The dye liquor contains W% by weight, based on the polyester fabric, dye mixture.

B1) Thermosol process (in situ generation of the dye mixture)

Z ¹ g / l of red dye (as preparation) and Z ² g / l of yellow dye (as preparation) are placed in a padding liquor containing 2 g / l of a commercially available wetting agent based on a phosphoric acid ester and 10 g / l of a commercially available antimigration agent based on an acrylic acid / acrylamide copolymer. This liquor is applied with a liquor absorption of 50% to polyester-cotton blend (80:20) using a padder. Intermediate drying with air circulation at 100 ° C follows. Thereafter, thermosolation is carried out at 220 ° C. for 60 seconds.

B2) Thermosol process (Dye mixture is added to the dye liquor)

The procedure is analogous to B1). The block fleet contains Z g / l, based on the polyester fabric, dye mixture.

Similar favorable results are obtained if the dyeing process described under A1) is carried out using a mixture of two red dyes [W ¹ % by weight and W ³ % by weight (in each case as a preparation)] and a yellow solid [W ² % by weight]. -% (as preparation)], whereby the information relates in each case to the weight of the polyester fabric.

The individual test data are shown in Tables 1 and 2 below refer to. The values relating to the amount of dyes each apply to the dye preparation used.  

Claims (8)

1. dye mixtures which essentially contain red and yellow dispersion dyes and which, when measuring synthetic or semisynthetic materials treated with them, their color locus in one by corner points with the following coordinates x and y
have a spanned color space and a minimum luminance factor β <0.25 <0.40. 2. dye mixtures according to claim 1, characterized in that they have a minimum luminance factor β <0.30 <0.40 point. 3. dye mixtures according to claim 1, characterized in that they have the conditions for color locus and minimum luminance factor before and after xenon radiation. 4. dye mixtures according to claim 1, characterized in that the weight fraction of the red disperse dyes 50 to 90 wt .-% and that of the yellow disperse dyes 10 to 50 wt .-%, each based on the total weight of the red and yellow disperse dyes. 5. dye mixtures according to claim 1, characterized in that they contain yellow disperse dyes which have the formulas I or II
obey what
R ¹ and R ² are each independently of the other C ₁ -C ₁₃ alkyl,
Q is a residue of the formula
in the
n for 1 or 2,
R ^{3 is} hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogen, cyano, nitro, carbamoyl, C ₁ -C ₄ mono- or dialkyl carbamoyl, sulfamoyl or C ₁ -C ₄ mono - or dialkyl sulfamoyl,
R ^{4 is} hydrogen or C ₁ -C ₆ alkyl and
X represents imino, C ₁ -C ₄ -alkylimino, oxygen or sulfur,
L ¹ C ₁ -C ₁₃ alkyl, which is optionally interrupted by one to three oxygen atoms in ether function and can be substituted by hydroxyl, or phenyl and L ² C ₁ -C ₆ alkyl. 6. dye mixture according to claim 1, characterized in that they contain red disperse dyes which have the formulas III or IV
obey what
n 1 or 2,
R ¹ and R ² are each independently of the other C ₁ -C ₁₃ alkyl,
R ^{3 is} hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogen, cyano, nitro, carbamoyl, C ₁ -C ₄ mono- or dialkyl carbamoyl, sulfamoyl or C ₁ -C ₄ mono- or dialkyl sulfamoyl,
Y oxygen or imino and
Z mean cyano or carbamoyl. 7. Process for dyeing synthetic or semi-synthetic Materials, characterized in that the syntheti or semi-synthetic materials in the dyeing liquor treated with the dye mixtures according to claim 1, wherein either the dye mixtures are added to the dye liquor or the dye mixtures by adding the red ones separately and yellow disperse dyes in the dye liquor in situ generated. 8. Use of the dye mixtures according to claim 1 for dyeing or synthetic or semi-synthetic printing Materials.