DE2721763A1 - DISAZO COMPOUNDS DERIVED FROM 1-PHENYLPYRAZOLE-5-ON-3-ACETIC ACID AND PROCESSES FOR COLORING OR PRINTING OF TEXTILES AND DYED OR PRINTED TEXTILES - Google Patents

Description

DR. STEPHAN G. BESZEDES PATENT ADVOCATE

- «10 ~

8060 ÜACHAU NEAR MUNICH

PO8TFACH ti ··

AM HEIDEWEQ 2

TELEPHONE: DACHAU 4STt

Potocheckkonto MOnchtn (BLZ 700 100 W) Account no. 138 * 71

Bank account no. 906 370 b * l of the Kralt- und Stadt- DMhM-Inctoradorf (BU 1 * 01114 ·) (VIA Bayarltch · UndMbMk

P 974

description

for patent application

AZIENDE COLORI NAZIONALI APFINI ACNA S.p.A.

Milano, Italy

concerning

Disazo compounds derived from 1-phenylpyrazol-5-one-3-acetic acid and processes for dyeing or printing textiles and dyed or printed textiles

The invention relates to new disazo compounds which are primarily used for dyeing or printing of textiles, in particular cellulose materials which swell with water and their mixtures with synthetic materials, especially polyester / cotton mixtures, in golden yellow to orange shades are suitable, as well as a method for dyeing or printing textiles with them and thus obtained

709847/1109

dyed or printed textiles.

The term "cellulosic materials" is used in this text in the broadest sense, that is, as well as modified celluloses, such as rayon or viscose silk and acetate silk, to be understood comprehensively.

There are already processes for dyeing polyester / cotton mixed fibers, which comprise more than 1 stage, the mixture components in separate stages with different Dyes are known to be colored. However, these methods have serious disadvantages such as the complexity of the Implementation, the possibility of mutual overstaining respectively staining and the need to use substantial amounts of dye. One of those dyeing methods is for example in U.S. Patent 3,313,590 described.

Processes for dyeing polyester / cellulose -Mixed fibers, in which the property of the cellulose material to swell in response to the action of water, made use of is and therefore the mixture in 1 stage with only 1 water-insoluble or sparingly soluble dye, which in particular Solvents such as polyols, ether derivatives thereof or esters of organic acids is dissolved, colored becomes known. One such method is described, for example, in U.S. Patent 3,706,525.

The dyes to be used according to the last-mentioned process should meet the following important requirements:

Good affinity for polyester fibers.

Good affinity for cellulose fibers swollen with mixtures of water and solvents ^

Ability to provide uniform colors or prints on both fibers.

Ability to provide sunlightfast, rubfast and washfast dyeings or prints.

The invention is therefore based on the object, while eliminating the disadvantages of the prior art, new compounds, which have proven to be superior dyes for textiles, especially for dyeing or printing with Water-swellable cellulose materials and their mixtures with synthetic materials, especially polyester / cotton or polyester / rayon mixed fibers, according to the above-described process engineering, that is, under essentially conventional operating conditions of the "Thermosol" - -Type suitable to create in the presence of special solvents.

In the course of investigations on disazo dyes derived from 1-phenylpyrazol-5-one and free from water-solubilizing groups, it has now surprisingly been found that the choice of the chemical leading to dyes for dyeing and printing polyester / cellulose mixed fibers according to the process technology described above Structure is very critical.

709847/1109

It has been observed that, although a number of dyes having a specific chemical structure, that is laid down in the following disazo compounds according to the invention can be used with success for dyeing and printing, in particular of polyester / cellulose mixtures, in contrast, however, other dyes with a color tone similar to the color tone of the former and a structure very close to its structure lead to unsatisfactory results when dyeing and printing the mixtures mentioned: They have a low affinity, an inadequate hiding power with respect to the polyester / cellulose mixtures and a low rub fastness and / or Resistance to wet treatments.

The invention relates to disazo compounds of the general formula derived from i-phenylpyrazol-5-one-3-acetic acid

709847/1109

272 \> 63

! 25

709847/1 109

wherein

Χ, ι »Xp ι Χχ and χ that are the same or different

can be, for hydrogen, methyl radicals or methoxy radicals stand,

Y chlorine, bromine or a methyl

rest means and

η is 0, 1 or 2.

The disazo compounds of the present invention are dyes with golden yellow to orange shades, which surprisingly have a good affinity for both components of polyester / cellulose mixtures and have the ability to give very uniform and permanent dyeings and prints.

Preferred dyes according to the invention are those of the formulas

709847/1109

709847/1109

! Π -β-

OO • I

W ο:

709847/1109

IB

709847/1109

709847/1109

Ti

H H 272Ί7Θ3

709847/1109

W Ο:

• JZ5

709847/1109

The disazo compounds according to the invention can be prepared by diazotizing an aminoazobenzene of the formula

H-N- /

NH.

wherein X ^, X ₂ and X are as defined above, in an acidic medium to the corresponding diazoazobenzene, coupling the latter with an i-phenylpyrazol ^ -one - ^ - acetic acid derivative of the formula

- OH

709847/1109

wherein Y and η are as defined above, to the corresponding disazo compound and subsequent condensation of the latter in the absence of solvents with an amine of the formula

XII

where X ^ is defined as above.

The invention also relates to a method for dyeing or printing textiles, in particular yarns made from water-swellable cellulose materials or their mixtures with synthetic materials, especially polyester / cotton mixed fibers, which is characterized in that the dye (s) 1 or more of the above disazo compounds of the formula I, preferably in the presence of water and a solvent, in particular a polyol, an ether derivative of such and / or an ester of an organic acid, is or are used

709847/1109

The invention also relates to colored or printed textiles, in particular cellulose materials and their mixtures with synthetic materials, whole especially polyester / cotton blended fibers, which are characterized by having 1 or more of the above Disazo compounds of the formula I are colored or printed.

The dyes according to the invention can be used in the presence of suitable dispersants, for example sodium lignosulfonate or a condensate of formaldehyde and Schaffer's acid (Saltra SS), to a particle size of ground about 1 iu and on mixed fibers in the form of an aqueous Paste with the addition of a high-boiling solvent usually used for such a procedure, for example a polyethylene glycol ether, to be applied

The dyeings and prints can be heat set for 1 minute at about C and removed for removal fixed dye can be soaped.

200 ⁰ C thermoset and not to remove any

The dyes according to the invention are for dyeing mixtures of 65 to 80% by weight and polyethylene terephthalate 20 to 35% by weight of cotton are particularly useful.

The invention is explained in more detail with reference to the following examples, which are not to be interpreted as limiting. The authenticity tests were carried out according to UNI standards. The percent fixation values given in the examples are the ratios of the dye permanently retained by the fiber to the dye used. The hiding power is the degree of distribution of the dye on the two fibers.

709847/1109 - 16 -

example 1

There were 8.0 parts by weight of a dye of the formula

709847/1109 _ _1? _

3 <o

709847/1109

2721783

with 8 parts by weight of a condensate of formaldehyde and Schaffer's acid (Saltra SS), 12 parts by weight of ethylene glycol and 105 parts by weight of water micro-refined. From this Mixtures were made by adding 100 parts by weight of a polyoxyethylene glycol monomethyl ether (Molecular weight = about 350), 37 parts by weight sodium alginate and 730 parts by weight of water 1,000 parts by weight of a printing paste. This paste was made from a yarn polyester / cotton mixed fiber cleaned for printing and then allowed to air dry (about 20 minutes) with a Applied ratio of polyester to cotton of 65:35.

The fixation of the dye on the two fibers that made up the mixture was carried out in a "Thermosol" Device performed at 200 ° C for 60 seconds. The heat-set print was subjected to a 3-stage curing treatment subject to:

a) Wash cold.

b) Soaping (10 minutes at 90 ° C using 1 g / l Diapon T).

c) rinsing.

A print with an orange hue with a color intensity or strength of about - ^ E.C.E, obtain. With this color intensity the following data could be determined:

709847/1109

- 19 -

Opacity to the mixture: good. Fixation:> 90%.

Dry rub fastness / wet rub fastness: 4 to 5/4 ·· Sunlight fastness: 5 ·
Wash fastness at 60 ⁰ C: 4/4 to 5Λ up. 5

The third property is the first value (before the slash) the dry rub fastness and the second value (after the slash) the wet rub fastness and for the latter property, the first value (before the first slash) of the change in the hue of the Mixture, the second value (between the slashes) the discoloration on the polyester and the third value (after the second Slash) is assigned to the discoloration of the cotton.

The dye was prepared in the following way:

τ. There were 4.2 parts by weight of p-aminoazotoluene with 10 cnr

Hydrochloric acid (d = 1.18) and 40 cm * water heated to the boil.

After cooling to 5 to 10 ⁰ C and diluting the composition it was diazotized by gradual addition of 1.4 parts by weight of sodium nitrite in 10 cm of water.

After stirring or shaking for a further 1 hour, the solution of the diazo compound obtained was clarified and at 5 to 10 ° C in a solution of 4.8 parts by weight of 1-phenyl-2-pyrazol-5-one-3-acetic acid in 30 cm * acetic acid and 50 cm water poured in.

709847/1109

- 20 '-

- 20 -

During the coupling, the pH was kept at 4 to 5 by adding sodium acetate in the form of crystals.

After 1 hour of stirring or shaking at 5 to 1O ⁰ C was filtered and the precipitate was washed with water and dried. There were 8.8 parts by weight of the dye intermediate of the formula

708847/1109

MO

27217S3

t = fc

* 3

ft I S3

SZi

KN

Γ *

709847/1109

obtain.

8.0 parts by weight of this intermediate were then used for 2 hours
Treated aniline.

Product for 2 hours at 180 ⁰ C with 20 parts by weight

Finally the solution was poured into 200 cnr water and the pH was brought to 5 to 6 by adding hydrochloric acid (d ■ 1.18). It became 30 minutes long stirred or shaken and then filtered and the filter cake was washed with water and dried,

6.4 parts by weight of the dye of the formula II were obtained in this way.

Example 2

The material used in Example 1 was exactly the same according to the procedure described in Example 1, but using the dye of the formula

709847 / 1tO9 - 23 -

H H H

2721783

709847/1109

27217Θ3

printed.

There was thus obtained a print with a yellow-orange hue, the data of which at the obtained color intensity (about £ ECE) were as follows.

Opacity to the mixture: excellent. Fixation: 94%.

Dry rub / wet rub fastness: 4/3 to 4. sun light fastness: 5 to 6. wash fastness at 60 ⁰ C: V3 / 3 to. 4

For the third property, the first value (before the slash) is the dry rub fastness and the second value (after the slash) is the wet rub fastness, and for the latter property, the first value (before the first slash) is the change in the color of the mixture, the second The value (between the slashes) is assigned to the discoloration on the polyester and the third value (after the second slash) is assigned to the discoloration of the cotton.

The dye was prepared according to a procedure analogous to the procedure described in Example 1.

709847/1109 -25-

Example 3

The material used in Example 1 was exactly the same as the procedure described in Example 1, but using the dye of the formula

709847/1109

- 26 -

Mb

CM I

709847/1109

printed.

Thus, there was obtained a print having a yellow-orange hue, the data of which at the obtained color intensity (approx . £ ECE) were as follows.

Opacity to the mixture: excellent. Fixation:> 90%.

Dry rub / wet rub fastness: 4.3 to 4 solar light fastness: 5 to 6 wash fastness at 60 ⁰ C: 4/3 to 4/4 to fifth

For the third property, the first value (before the slash) is the dry rub fastness and the
second value (after the slash) of the wet rub fastness and for the latter property the first value (before
the first slash) the change in the color of the
Mixture, the second value (between the slashes) is assigned to the discoloration of the polyester and the third value (after the second slash) to the discoloration of the cotton.

The dye was prepared according to a procedure analogous to the procedure described in Example 1.

- 28 -709847/1109

Example 4 -

The material used in Example 1 was exactly the same as the procedure described in Example 1, but using the dye of the formula

709847/1109

«Ft

70 9 847/1109

printed.

Thus, there was obtained a print with an orange hue, the data of which at the obtained color intensity (about - ^ ECE) were as follows .

Opacity to the mixture: good. Fixation: 95%.

Fastness to dry rub / fastness to wet rub: 4/4. Fastness to sunlight: 5 to 6. Fastness to washing at 60 ^° C.: 4/4 to 5/4 to 5.

The third property is the first value (before the slash) the dry rub fastness and the second value (after the slash) the wet rub fastness and for the latter property, the first value (before the first slash) of the change in the hue of the Mixture, the second value (between the slashes) the discoloration on the polyester and the third value (after the second Slash) is assigned to the discoloration of the cotton.

The dye was prepared according to a procedure analogous to the procedure described in Example 1.

- 31 -709847/1109

27217G3

Example 5

The material used in Example 1 was exactly the same as the procedure described in Example 1, however using the dye of the formula

709847/1109 - 32 -

5Λ

rc »rc *

w ο:

9847/1109

printed.

So became a print with an orange hue, its

Xl

Data when the obtained color intensity (about - * ECE) was as follows .

Opacity to the mixture: good. Fixation:> 90%.

Fastness to dry rub / fastness to wet rub: 4 to 5/4. Sunlight fastness: 5 to 6. Fastness to washing at 60 ° C: 3 to 4 / 3Λ.

For the third property, the first value (before the slash) is the dry rub fastness and the second value (after the slash) of the wet rub fastness and for the latter property the first value (before the first slash) the change in the shade of the mixture, the second value (between the slashes) the Discoloration on the polyester and the third value (after the second slash) assigned to the discoloration on the cotton.

The dye was prepared according to a procedure analogous to the procedure described in Example 1.

709847/1109

Example 6

The material used in Example 1 was exactly the same as the procedure described in Example 1, however using the dye of the formula

- 35 709847/1109

5Η

ο:

525 I.

WHERE

! ζ; η

SS

709B47 / 1

printed.

Thus, a print with an orange-brown hue, the data of which at the obtained color intensity (about 4 E.C.E.) were as follows.

Opacity to the mixture: good. Fixation:> 90%.

Fastness to dry rub / fastness to wet rub: 4 to 5/4 ·· Sunlight fastness: 5 ·
Fastness to washing at 60 ^° C.: 3 to VV ^.

For the third property, the first value (before the slash) is the dry rub fastness and the second value (after the slash) of the wet rub fastness and for the latter property the first value (before the first slash) the change in the shade of the mixture, the second value (between the slashes) the Discoloration on the polyester and the third value (after the second Slash) is assigned to the discoloration of the cotton.

The dye was prepared according to a procedure analogous to the procedure described in Example Λ.

- 57-709847 / 1109

-w-

Example 7

The material used in Example 1 was exactly the same as the procedure described in Example 1, however using the dye of the formula

- 38 -

709847/1109

7 O 9 8 A 7/1 1 O 9

27217S3

printed.

Thus, a print having a yellow-orange hue, the data of which at the obtained color intensity (about · * ECE) were as follows.

Opacity to the mixture: good. Fixation:> 90%.

Dry rub fastness / wet rub fastness: 4/3 to 4. Sunlight fastness: 5
Fastness to washing at 60 ⁰ G: 4 / V4 to 5

The third property is the first value (before the slash) the dry rub fastness and the second value (after the slash) the wet rub fastness and for the latter property, the first value (before the first slash) of the change in the hue of the Mixture, the second value (between the slashes) the discoloration on the polyester and the third value (after the second Slash) is assigned to the discoloration of the cotton.

The dye was prepared according to one of those described in Example 1 Procedure analogous procedure produced.

- 40 -

709847/1109

Example 8

The material used in Example 1 was exactly the same as the procedure described in Example 1, but using the dye of the formula

709847/1109

Where

709847/1109

printed .

A print with an orange hue, the data of which at the obtained color intensity (approximately -κ ECE) were as follows , was thus obtained.

Opacity to the mixture: good. Fixation:> 90%

Dry rub / wet rub fastness: sun light fastness: 5 to 6. wash fastness at 60 ⁰ C: VV ^ up. 5

For the third property, the first value (before the slash) is the dry rub fastness and the second value (after the slash) of the wet rub fastness and for the latter property the first value (before the first slash) the change in the shade of the mixture, the second value (between the slashes) the Discoloration on the polyester and the third value (after the second slash) assigned to the discoloration on the cotton.

The dye was prepared according to a procedure analogous to the procedure described in Example 1.

- 43 7098 / »7/1109

Comparative Examples A, B, C and D.

For comparison, the disazopyrazolone dyes compiled in the following table with shades from yellow to orange and a structure similar to that of the compounds according to the invention were used under identical conditions to those given in the preceding examples. The results obtained are placed in the following order: opacity to the polyester / cotton blend, dye affinity (percentage fixation), dry rub / wet rub fastness, fastness to washing at 60 ⁰ C and sun light fastness.

709847/1109

- 44 table

Ver dye 0 Il 2 "5 i j) DeckShig- Affi Wet rub Washing Sun gleddis- // \\ TVT-TT // \\ un r> r \ η u I »
HO ISHLt geyii— nity authenticity/ real n- atipiel V y ix -. Ii V / ^ · "- ■" I
I. above that (Per /Dry- Ness I ^ O
co
00 ! he blooms /
/ Cotton- centu
ale rub-proof
Ness at
6O ⁰ C real-
Ness -J -Mixture Fixie tion) O A. middle
moderate 5A to 5 ⁵ IM IN THE 763

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ORIGINAL INSPECTED

The third from the last vertical column is the above Table the first value (before the slash) of the dry rub fastness The second value (after the slash) is the wet rub fastness and in the penultimate vertical column of the table above is the first value (before the first slash ^ of the change in the shade of the mixture, the second value (between the slashes) of the discoloration on the polyester and the third value (after the second slash) the. Discoloration associated with the cotton.

The table above clearly shows that the dyes according to the invention are by far superior to the comparison dyes.

Patent pending 709847/1109

Claims (1)

Patent claims 1.) Derived from 1-phenylpyrazol-5-one-3-acetic acid Disazo compounds of the general formula - 50 -709B47 / 1109 ιΛ I 709847/1109 wherein X ,. , Xp, X, and X ^, the same or different can be, for hydrogen, methyl radicals or methoxy radicals stand, Y chlorine, bromine or one Methyl radical means and η is 0, 1 or 2. 2.) Dieazo compound according to claim 1 of the formula - 52 70980/1109 cvj ο: 709847/1109 3 ·) Disazo compound according to claim 1 of the formula - 54 -709847/1109 -fe- IfN 709847/1109 - 95 l ·.) Disazo compound according to claim 1 of the formula 709847/1109 -β- IN m ι 709847/1109 9 27217G3 - 57 - 5.) disazo compound according to claim 1 of the formula 70 9 847/1109 • S3 S3 ft κ \ 98 4 7/1109 ΛΛ 6.) disazo compound according to claim 1 of the formula - 60 - 709847/1109 27217G3 709847/1109 7 ·) Dieazo compound according to claim 1 of the formula 709847/1109 VO 709847/1109 - 65 - θ.) Diβaζο connection according to claim 1 of the formula 709847/1109 -Ib- H H us 709847/1109 9.) disazo compound according to claim 1 of the formula - 66 - 709847/1 109 -YES 7098A7 / 1109 272Π63 10.) A method for dyeing or printing textiles, in particular yarns made from water-swellable cellulose materials or their mixtures with synthetic materials, especially polyester / cotton mixed fibers, characterized in that the dye (s) 1 or more disazo compounds according to claim 1 to 9i, preferably in the presence of water and a solvent, in particular a polyol, an ether derivative of such and / or an ester of an organic acid. 11.) Dyed or printed textiles, in particular cellulose materials and their mixtures with synthetic materials, especially polyester / cotton mixed fibers, characterized that they are colored or printed with 1 or more disazo compounds according to claims 1 to 9 are. 709847/1109