FR2667627A1 - PROCESS FOR THE AFTER-TREATMENT OF DYED SUBSTRATES WITH ANIONIC DYES. - Google Patents

Abstract

The present invention relates to a process for post-treatment of substrates chosen from synthetic polyamides, cellulose, cellulose derivatives and leather, dyed with anionic dyes, a process according to which the dyed substrate is subjected to a post-treatment. treatment with a solution or dispersion comprising one or more compounds containing a sterically hindered amino group and / or a sterically hindered amino group which has been protonated.

Description

The subject of the present invention is a process for post-processing of

  substrates of synthetic polyamides, cellulose or cellulose derivatives (including paper and cotton) and leather, which have been dyed with anionic dyes. The invention relates in particular to a process for post-processing the substrates chosen from

  synthetic polyamides, cellulose, cellulose derivatives and leather, dyed with anionic dyes, process according to which the dyed substrate is subjected to a post-treatment with a solution or a dispersion comprising one or more compounds containing a sterically hindered amino group and / or a sterically hindered amino group which has been protonated. Compounds containing a sterically hindered amino group and / or a steric amino group-

  ment congested which has been protonated, are designated below HALS compounds (Hindered Amine Light Stabilizer). The preferred HALS compounds are those containing one or more groups of formula a) to e) above.

  after / P, / R 2 R r / '2 R i \ ZN, (2) () Ac) (

2 '

3 2

  o R 1 signifies hydrogen or a C1-C4 alkyl, C2-C4 alkenyl, -CO-C1 alkyl

  C 1-C 4 or -CO-C 2 -C 4 alkenyl, preferably

  hydrogen or a C1-C4 alkyl group, each R 2 independently signifies a C1-C5 alkyl group (preferably a methyl group),

I I.

  -Y means a residue of formula -CO-N * or 1 * -N-CO, the carbon atom and the nitrogen atom being placed so that together with the carbon atoms to which Y is attached and the oxygen atom linking said carbon atoms, a 5-membered ring is formed, the atoms marked with an asterisk being attached to the carbon atom carrying R 3, each R 3 independently signifies hydrogen or a

  C1-C4 alkyl group, or a sub-

  stituant R 3 signifies a phenyl group and the other signifies hydrogen or a group

  C1-C4 alkyl, or both

  stituants R 3 together form a group

- (CH 2) 11

  Preferably, said amino groups

  sterically hindered are linked to a carbon residue

  cyclic in aromatic character via an ester or amide group or are attached by an amino, imino or ether group to a heterocyclic residue (of

  preferably a triazine group).

  Particularly preferred HALS compounds

  are those chosen from the compounds of formula 1 to 29.

R 4 R 4

4 4

  2 ((CO-R 4) n 3 2,3-Bis- (2 ', 2', 6 t, 6 '- tettramethylpiperidine-4' -yl-amino) -quinoxaline, 4 1,4-Bis- (2 r, 2 ', 6 t, 6 t-tetramethylpiperidine-4, -yl-amino) -phthalazine, 2-Chloro-4,6-bis- (2 t, 2 t, 6', 6 _-t 4 tramethylpiperidine- 4 ty 1-amino) - pyrimidine, 6 2,5-Dichloro-4,6-bis- (2,, 2 ', 6,, 6 _-t'traméthylpiprdine_ 4, _ylamino) _ pyrimidine,

  7 2-Fluoro-5-chloro-4,6-bis- (2 ', 2 t, 6 t, 6 _-tetramethyl'piperidine-4' -yl-

  amino) -pyrimidine, 8 2,4,6-Tri- (2 t, 2 f, 6 t, 6 '-tetramethyl piperidine-4, -yl-amino) -pyrimidine,

  9 to 2,4,6-Tri- (2 ', 2 r, 6,, 6-tetramethylpiperidine-4' -yl-amino) -5chloro-

  pyrimidine, 2,4-Bis- (2 ', 2', 6 ', 6' -tetramethylpiperidine-4 '-ylamino) -quinazoline,

CH 3 NH-CO-NH-R, '

CH 3 N-C 0-N-R 4

CH 3

11 / \

CH 3 NH-CO-NH-R 4 "

) I Y NY

NH-R '

lky lènè e: n C 2-C 3-N <N

NH-R 4 '

- (NH-R) 3

- (CO-O-R 7) 3

  - (- NE- al kylene 6 in C 2 Cj to OC 0-R 6) 3 12. 13. 14. 15. 16. CO-N (NH-'alkylene in C 2-C 3-0-C 0- R 9) 3

- (C 0-NH-R 8) 3

  R 4 '-NH-CO CO-4 f I-R' CO R 4 '-Ni H-C C 0-NH-R 4

R 4 -N C O -NH-R 4 ') 3

  <, - (CO-Nl HR 4 ') 3 - (C 0-O-Rs) 3 - (- HN-alkylene and C 2-C 3-0-CO- R 8) 3 N <N 17. 18. 19. 20. 21. 22. 23.

N N

- (CO-NH-R'4) 4

24.

R '-NH-CO 1

t o

CO-NH-R

CO-NH-R 7

26.

(/ 9 - (CO-NH-R 7) 3

CO-O- (CH 2) 3-R 10

27.

CO-O- (CH 2) 3-R 10

28 c-o (CH 2)

CO-O (CH 2) 3-R 10

29 N

  ys Ny -E NH-CH 2 CH 2-0-CO-R 9 l 3 o n means 2, 3 or 4,

  R 4 signifies a 2,2,6,6-tetramethylpiperidine group

  4-yl-4-amino, 2,2,6,6-tetramethylpiperidine-4-yl-

  oxy, 1,2,2,6,6-pentamethylpiperidine-4-yl-amino or 1,2,2,6,6pentamethylpiperidine-4-yl-oxy, R 4 'signifies a group of formula a) above,

  R 5 means halogen or has one of the meanings

  cations given for R 4, independently of R 4, R 6 signifies a group of formula d),

  R 7 signifies a 1,2,2,6,6-pentamethyl-piper group

  ridine-4-yle, R 8 means a group of formula b), R 9 means a group of formula e), R 10 means a group of formula c), o -Y means I CO-N- *, the group CO being attached to the piperidine ring, I RIO 'signifies a group of formula c), o -Y signifies

I * I

  -N-CO, the atom -N being attached to the piperidine ring, and in all the groups of formula a) to e), R 1 and R 3 signify hydrogen and each R 2 signifies a methyl group. As examples of compounds of formula 1, we

  may quote 2,4-bis (2 ', 2', 6 ', 6' -tetramethyl-

  piperidine-4-yl-amino) -6-chlorotriazine (compound 30) and

  2,4,6-tris (2 ', 2', 6 ', 6' -tetramethyl-piperidine-4-yl-

amino) triazine (compound 31).

  As examples of compounds of formula 2, mention may be made of the following compounds 32 and 36:

  32 Tri- (2 ', 2', 6 ', 6' -tetramethylpiperidine-4 '-yl) -

amide of trimesinic acid,

  33 Tri- (2 ', 2', 6 ', 6' -tetramethylpiperidine-4 '-yl) -

trimellitic acid amide,

  34 The di- (2 ', 2', 6 ', 6' -tetramethylpiperidine-4 '-yl-

  aminocarbonyl-paraphenylene) -amide of terephthalic acid,

  Di- (2 ', 2', 6 ', 6' -tetramethylpiperidine-4 '-yl) -

isophthalic acid amide,

  36 Di- (2 ', 2', 6 ', 6' -tetramethylpiperidine-4 'yl) -

amide of terephthalic acid.

  More preferably, the HALS compounds are

  those containing a group of formula a) such as

  finite above, preferably when R 1 means

hydrogen or a methyl group.

  Particularly preferred compounds are

  those having one or more 2,2,6,6-tetramethyl-

  piperidine-4-yl or 1,2,2,6,6-pentamethyl-piperidine-

  4-yle, especially those of formula 1 or 2 such as

defined above.

  The HALS compounds mentioned in the present application are known and can be prepared according to known methods from known compounds, for example by reacting the appropriate acid chloride with the appropriate amine or alcohol or by reacting triazine , pyrimidine, quinoxaline or

  halogenated phthalazine suitable with the appropriate amine

  prayed. Before the post-treatment according to the invention, the substrates can be dyed according to the usual methods with anionic dyes in the medium

  aqueous Substrates can be inter-

  media intended to be transformed into finished products

  or finished textile materials made of poly-

  synthetic, cotton, cellulose or derivatives amide

  cellulose, especially poly-

  synthetic amide which can be used in the form of granules or in other forms having a large specific surface area. Said substrates can be treated with aqueous solutions or dispersions

  HALS compounds indicated above.

  In the process of the invention, the sterically hindered amino groups generally have a tendency to form salts with the anionic dyes, which makes it possible to improve the migration properties (keeping migration to a minimum makes it possible

  improve the fastness to washing).

  The substrate used in the process of the invention is preferably a synthetic polyamide

  in the form of powder or granules, which are

  then forms into fibers or other forms.

  Sterically hindered amino groups can also be present in protonated form,

  for example when an amino group sterically

  conbred is protonated by an acid (HC 1, acetic acid

  etc) or a C 1 -C 4 alkyl halide.

  After dyeing, the HALS compounds

  mentioned above can be applied depending on the pro-

  yielded by exhaustion or by padding (using a scarf), in the form of a solution of an aqueous dispersion The bath ratio for the post-treatment can vary within wide limits, and is understood to include

preferably between 1:10 and 1:80.

  The amount of HALS compound applied to the substrate is preferably between 0.05 and 10%, more preferably between 0.5 and 3% relative to the total weight of the substrate, or between 1 and 10% relative

the weight of the dye used.

  The following examples illustrate the invention

  without in any way limiting its scope.

Example 1:

  Polyamide 6 granules (Grilon A 22, from the company Emser Werke AG) having a relative solvent viscosity of 2.01 are dyed with 10% (relative to the total weight of the substrate) of the dye CI Acid Blue 129 to a bath ratio of 1: 3 while maintaining the bath

  weakly acidic with 4 g / liter of sodium phosphate.

  Dyeing is carried out for 2 hours at

  boiling The colored granules are filtered

  sultants, washed with cold water and subjected to post-treatment in an aqueous bath, the ratio of the granules to the bath being 1: 2 and the bath containing 0.5

  part of 2,4-bis (2 ', 2', 6 ', 6' -tetramethylpiperidine-

  -4 '-yl-amino) -6-chlorotriazine (compound 30) which has been protonated with HC 1 The bath is heated for 1 hour at 60 ° C., then the granules are filtered, washed,

  dry them and file them in fibers.

  The resulting fibers are dyed intense blue and exhibit excellent fastness to light and improved fastness to washing by

  compared to fibers which have not been subjected to post-

processing of the invention.

Examples 2-35:

  We proceed as described in Example 1, but

  instead of 2,4-bis (2 ', 2', 6 ', 6' -tetramethyl-

  piperidine-4 'yl-amino) -6-chlorotriazine (compound 30), an equivalent amount of any of the compounds of formula 3 to 29 and 31 to 36 defined above is used. One can proceed as described in Examples 1 to 35, but instead of the dye CI Acid Blue 129, an equivalent amount of one or more of the following dyes is used: CI Acid Blue 25, 40, 72, 106, 126, 227, 230, 278, 280 and 296, CI Acid Yellow 59, 112, 114, 127 and 129, CI Acid Red 261 and 404, C. I Acid Green 40, CI Acid Orange 82, CI Acid Violet 66, CI Acid Brown 28, 30 and 289, CI Acid Black 58 and 115, CI Solvant Yellow 83, CI Solvent Red 90: 1, 91 and 92 CI Solvent Black 45

Claims (10)

  1 A process for post-treatment of the substrates chosen from synthetic polyamides, cellulose, cellulose derivatives and leather, dyed with anionic dyes, characterized in that the dyed substrate is subjected to a post-treatment with a solution or dispersion comprising one or   several compounds containing a steric amino group-   mentally congested and / or a sterically amino group conbred which was protonated.   2 A process according to claim 1, characterized in that the compounds containing a sterically hindered amino group and / or a sterically hindered amino group which has been protonated are chosen from those containing one or more groups of formula a) to e) below R RR R R 2 2 'I 3   (a) (O) (c) (d) (î), where R 1 signifies hydrogen or C 1 -C 4 alkyl, C 2 -C 4 alkenyl, -CO- C 1 -C alkyl 4 or -CO-C 2 -C 4 alkenyl, each R 2 independently signifies a C 1 -C 5 alkyl group, -Y signifies a residue of formula -CO-N * or 1 * -N-CO, the atom of carbon and the nitrogen atom being placed so that together with the carbon atoms to which Y is attached and the oxygen atom linking said carbon atoms, a 5-membered ring is formed, the atoms marked an asterisk being attached to the carbon atom carrying R 3, each R 3 independently signifies hydrogen or a   C 1 -C 4 alkyl group, or a sub-   stituant R 3 signifies a phenyl group and the other signifies hydrogen or a group   C 1 -C 4 alkyl, or both   stituants R 3 together form a group - (CH 2) 1 l-.   3 A process according to claim 1, characterized in that the compounds containing a sterically hindered amino group and / or a sterically hindered amino group which has been protonated are chosen from the compounds of formula 1 to 30: N N R 4 R 4   2 (CO-R 4) n 3 2,3-Bis- (2 ', 2,, 6,, 6, tetramethylpiperidine-4, -yl-amino) -quinoxaline, 4 1,4-Bis- (2', 2 ', 6', 6 'tetramethylpiperi-dine-4' -yl-amino) -phthal azine, 2-Chloro-4,6bis- (2 ', 2', 6 ', 6' -têtramethylp ipéridine-4 '-yl -amino) - pyrimidine, 6 2,5-Dichloro-4,6-bis- (2 ', 2', 6 ', 6' -tét ramethyl pi p éri di ne-4 '-yl -amfiho) - pyrimidine, 7 2-Fluoro-5-chloro-4,6-bis- (2 ', 2', 6 ', 6 -tetramethylpippridine-44-yl - amino) -pyrimidine, 8 2,4,6- Tri- (2' , 2 ', 6', 6 '-tetramethylpitridit ei-4' -yl-amino) -pyrftrfdtne, 9 2 p 46-Tri- (22 N 6,6-ttramethylpiperidine-4 '-yl-amino) -5-chloro - pyrimidine, 2,4-Bis- (2 ', 2', 6 ', 6' -tetramethylpiperidine-4 '-yl- amino) -quinazoline, CH 3 CH 3 CH NH-CO-NH-R 4 ' rUS T s H-PIR 4 ' L / YH-'NH 4 o-NH-al kyl ne in C 2-C 3-N-_ N \ N -R 4 '3 NK-R 4 'y - (NH-R 7) 3 11. 12. 13. 14. I_ N (CO-O-R 7) 3   - (- Nl = -al kylene in C 2-C 3-0-CO 0-R 6) 3 - (NHI-alky 11 ne in C 2-C 3-0CO-R 9) 3 - (C O O-NH-R 8) 3 - (CO-NH-R'4) 4 R 4 '-NI-CO CO-Ni-R' R 4 '-N-4 o Co R '-NH-C O CO-NH-R 4' 4 -4 (C 0-NH-R 4 ') - (GO-NB-R 4 ') 3   15. 16. 17. N A N- 18. 19. K 20. 21. 22. - (CO-O-RS) 3   N i: N - (- HN-al ky 1 lne -en C 2-C 3-0-CO-R 8) 3 Q R 4 -N'-co-C O RI O CO-NH-R CO-NH-R 7 -x - (CO-NH-R?) 3 / = CO-O- (CH 2) 3-R 10 CO-O (CH 2) 3-RO 10 NOT 2 Y 3 1 CO-0 (CH 2) 3-R 10   CO-O (Cz 2) 3-Rlo + NH-CH 2 CH 2-0-CO-Rg l 3 23. 24. 25. 26. 27. 28. 29. 2,4-Bis- (2 t, 21 , 6 ', 6-tetramethyl-piperidin-4' -y 7 amino) - quinazoline, we mean 2, 3 or 4,   R 4 signifies a 2,2,6,6-tetramethylpiperidine group   4-yl-4-amino, 2,2,6,6-tetramethylpiperidine-4-yl-   oxy, 1,2,2,6,6-pentamethylpiperidine-4-yl-amino or 1,2,2,6,6pentamethylpiperidine-4-yl-oxy, R 4 'signifies a group of formula a) above,   R 5 means halogen or has one of the meanings   cations given for R 4, independently of R 4, R 6 signifies a group of formula d),   R 7 signifies a 1,2,2,6,6-pentamethyl-piper group   ridine-4-yle, R 8 means a group of formula b), R 9 means a group of formula e), R 10 O means a group of formula c), o -Y means CO-N- *, the group CO being attached to the piperidine ring, R 10 o 'signifies a group of formula c), o -Y signifies t * I - -N-CO, the -N atom being attached to the piperidine ring, and in all the groups of formula a ) to e), R 1 and R 3 signify hydrogen and each R 2 signifies a methyl group. 4 A process according to claim 1, characterized in that the compounds containing a sterically hindered amino group and / or a sterically hindered amino group which has been protonated are chosen from the compounds of formula 1 or 2: %N / A R 4 R 4 2 (CO-R 4) n or   R 4 signifies a 2,2,6,6-tetramethylpiperidine group   4-yl-4-amino, 2,2,6,6-tetramethylpiperidine-4-yl-   oxy, 1,2,2,6,6-pentamethylpiperidine-4-yl-amino or 1,2,2,6,6pentamethylpiperidine-4-yl-oxy,   R 5 means halogen or has one of the meanings   cations given for R 4, independently of R 4, and n signifies 2, 3 or 4, A process according to claim 4, characterized in that the compound of formula 1 is   2,4-bis (2 ', 2', 6 ', 6' -tetramethylpiperidine-4-yl-amino) -   6-chlorotriazine or 2,4,6-tris (2 ', 2', 6 ', 6' -tétra-   methyl-piperidine-4-yl-amino) triazine.   6 A process according to claim 4, characterized in that the compound of formula 2 is chosen from the following compounds:   Tri- (2 ', 2', 6 ', 6' -tetramethylpiperidine-4 '-yl) - amide of trimesinic acid,   Tri- (2 ', 2', 6 ', 6' -tetramethylpiperidine-4 '-yl) - trimellitic acid amide,   Di- (2 ', 2', 6 ', 6' -tetramethylpiperidine-4 '-yl-   aminocarbonyl-paraphenylene) -amide of terephthalic acid,   Di- (2 ', 2', 6 ', 6' -tetramethylpiperidine-4 '-yl) - amide of isophthalic acid, and   Di- (2 ', 2', 6 ', 6' -tetramethylpiperidine-4 'yl) - amide of terephthalic acid.   7 A substrate, characterized in that it has been dyed with an anionic dye and subjected to a post-treatment with a compound as defined in one   any of claims 1 to 6.   8 A substrate according to claim 7,   characterized in that it is polyamide.   9 A substrate according to claim 8, characterized in that it is in the form of powder, granules or fibers. el