FR2556013A1 - PROCESS FOR POST-PROCESSING TINTED OR PRINTED CELLULOSIC SUBSTRATES - Google Patents

Abstract

THE OBJECT OF THE INVENTION IS THE USE OF COMPOUNDS RESPONDING TO THE FORMULA (CF DRAWING IN BOPI) IN WHICH R REPRESENTS AN ALIPHATIC REMAIN IN CC, R REPRESENTS A SALICYL GROUP POSSIBLY SUBSTITUTE, EACH R REPRESENTS INDEPENDENTLY HYDROGENE OR A GROUP POSSIBLE SUBSTITUTE, N MEANS 0 OR A WHOLE NUMBER OF 1 TO 10, EACH X INDEPENDENTLY REPRESENTS A -CH- OR -CH- GROUP, THE MOLECULE MUST CONTAIN FROM 1 TO 5 SALICYL GROUPS POSSIBLY SUBSTITUTED, IN THE FORM OF A FREE BASE OR IN THE FORM OF A FREE BASE PROTONEE OR QUATERNIZED, AS POST-TREATMENT AGENTS FOR DYED OR PRINTED TEXTILE SUBSTRATES CONTAINING CELLULOSIC FIBERS.

Description

2556 0 1 3

  The present invention relates to the use of

  phenolamines as post-treatment agents for cell substrates

  dyed or printed beads, as well as a post-treatment process

  of these substrates using these compounds.

  The invention relates more particularly to the use of compounds of formula I

R - N - X - NH-R2

i n N-2 ()

R3

  in which R1 represents a C6-C22 aliphatic radical, R2 represents a group of formula (a) OH

OH

  Each R3 independently represents hydrogen or a group of formula (a), each R4 independently represents hydrogen or a C1-C12 alkyl group, each R5 independently represents hydrogen, chlorine or an alkyl group; C1-C12, cycloalkyl or phenyl, n means O or an integer of from 1 to 10, each X independently represents a -C2H4- or -C3H6- group, the molecule to contain from 1 to 5 groups of formula (a), as a free base or in protonated or quaternized form, as post-treatment agents for dyed textile substrates or

  printed matter comprising cellulosic fibers.

  The invention also includes a post-process

  treatment of a dyed or printed textile substrate comprising cellulosic fibers, process according to which a compound of formula I as defined is applied to the dyed or printed substrate

previously.

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  The aliphatic radical represented by R 1 can be saturated or unsaturated. It preferably represents an alkyl group

  C6-C22 or linear or branched C6-C22 alkenyl, more preferably

  C12-C18 alkyl or C12-C18 alkenyl, in particular cetyl, stearyl or a mixture of C14-C18 alkyl and / or alkenyl groups derived from natural fatty acids.

such as tallow fatty acid.

  Any alkyl group represented by R4 or R5 may be straight or branched chain and preferably means an alkyl group

  C1-C4, in particular a methyl or ethyl group.

  The cycloalkyl group represented by R5 means

preferably a cyclohexyl group.

  When R4 is an alkyl group, it is located

  preferably in the ortho or meta position with respect to the hydroxy group.

  When R5 has a meaning other than hydrogen, it is preferably in the para position relative to the hydroxy group. Of

  preferably, R4 and R5 each signify hydrogen.

  The group of formula (a) preferably means a salicyl group. When X means a -C3H6- group, it can be

linear or branched.

  n preferably means an integer of 1 to 10. n

  more preferably means 1, 2, 3 or 4, especially 3 or 4.

  Preferred compounds of formula I are those wherein R 1 is C 12 -C 18 alkyl or alkenyl

  C12-C18, R2 is a salicyl group, each R3 is independently

  especially hydrogen or a salicyl group, X is -C3H6- and n is 1, 2, 3 or 4, the molecule containing 1, 3 or 4 salicyl groups. Other preferred compounds of formula I are those wherein R 1 is cetyl, stearyl or fatty

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  tallow, R2 is salicyl, X is -C3H6-

  and either n is 3 and R3 is a salicyl group, or n is 4 and one of R3 is hydrogen and the other symbols

  R3 each means a salicyl group.

  The nature of the anion of protonated or quaternized compounds of formula I is not critical. Preferred anions are halide ions, for example Cl- or Br-, and benzenesulfonate, p-toluenesulfonate, formate, sulfate, methylsulfate and phosphate ions,

  more preferably Cl- and formiate ions, especially Cl-.

  Compounds of formula I in which n is an integer of 1 to 10, in free base form or in the form of

  protonated or quaternized, are new and part of the

  vention. The compounds of formula I, in free base form or in protonated or quaternized form, can be prepared by reacting one mole of an amine of formula II ## STR2 ## wherein R 1, X and n are as defined above, or a mixture of amines of formula II, with 1 mole percent of formaldehyde and 1 to n + 1 mole of a compound of formula III

H- - <(III)

  R5 wherein R4 and R5 are as defined above, or a mixture of compounds of formula III, formaldehyde and the compound of formula III each being reacted in equimolar amounts, recovering the resulting compounds of formula I in the form of

  free base or in protonated or quaternized form.

  The reaction can be carried out according to the known methods, for example according to the Mannicho condensation. The compounds of formula I obtained in free base form can be converted according to the known methods into one.

  protonated or quaternized form, and vice versa.

  The compounds of formula I in free base form can be protonated by reaction with an organic acid or

  mineral, for example benzenesulfonic acid, p-toluene acid,

  sulfonic acid, hydrochloric acid, hydrobromic acid, phosphoric acid etc ..., or quaternized by reaction with a quaternizing agent, for example dimethyl sulfate, methyl chloride, benzyl chloride, etc. Depending on the amount of acid or quaternizing agent used, it is possible to protonate or quaternize one, more or all of the basic nitrogen atoms

  present in the molecule, following the value of n.

  The compounds of formula I, in free base form or in protonated or quaternized form, can be in the form of liquid, paste or solid. They can be purified according to

known methods.

  The compounds of formula I, in free base form or in protonated or quaternized form, are useful as post-treatment agents for dyed or printed textile substrates, in particular for improving the wet fastness in an oxidizing medium of dyes or prints made on substrates

  textiles comprising cellulosic fibers.

  Cellulosic textile substrates include those made, wholly or in part, of natural and / or regenerated cellulose, preferably cotton. The substrates may be in any of the usual forms, for example, yarns, woven or knitted articles, finished articles, etc. According to the process of the invention, the compounds of formula I are applied to a textile substrate which has been dyed or printed

  according to known methods with direct or reactive dyes.

  The textile substrate is advantageously washed or rinsed after

fixing of the dyes.

  The application of the compounds of formula I on the dyed or printed textile substrate can be carried out according to the methods

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  known, for example by impregnation, for example by padding, or by the method of exhaustion. The bath ratio is suitably between 0.7: 1 and 60: 1. The application can be carried out at a temperature between room temperature and 100 C. In the case of impregnation, the fixing is carried out according to the known methods at a temperature between

  room temperature and about 180 C.

  The application of the compounds of formula I may advantageously

  be carried out at a pH of between 4 and 7, in the presence of a

  basic compound, for example sodium trichloroacetate.

  The treatment bath suitably contains 0.1 to 10 g / liter of a compound of formula I, preferably 0.5 to g / liter when the compound of formula I is applied by the depletion method. The padding solutions suitably contain from 1 to 100 g / liter, preferably from 10 to 10 g / liter, most preferably from 10 to 60 g / liter of a compound of formula I. According to their solubility in water, the compounds of formula I can be added as such to the treatment bath or be mixed first with a solubilizer, for example a glycol such as ethylene glycol or a glycolic monoether, for example ether

  butyl ether of diethylene glycol or the propyl ether of ethylene-

  glycol. After treatment with a compound of formula I, it is dried

the textile substrate.

  Wet fastness in an oxidizing environment is of increasing importance today, as running water for washing has an increasing chlorine content and swimming pool water has a high chlorine content. The dyes or the impressions on the cellulose obtained with the usual dyes are sensitive to the harmful action of the cnlorée water and this action is even stronger when the articles

  are washed in hot water. The method according to the invention of

  treatment with the compounds of formula I of dyed or printed cellulosic substrates, makes it possible to avoid these drawbacks, the solidities

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  wet in an oxidizing medium being improved by the method of

  the invention, in particular the solidities with chlorinated water.

  The following examples illustrate the present invention without in any way limiting its scope. In these examples, parts and percentages are by weight unless otherwise indicated, and

  temperatures are given in degrees Celsius.

Example 1I

  455 parts of the amine of formula

H37C18 (NH-CH2-CH2-CH2 + 4NH2

  and 376 parts of phenol in a flask equipped with a reflux condenser and heated to 90.degree. Paraformaldehyde is then added portionwise to the stirring mixture and the temperature is maintained below 100. After stirring for 5 hours at a temperature between 95 and 100, the water resulting from the reaction is distilled off at 80 and at about 20 mm Hg. The mixture is then brought to atmospheric pressure and the mixture is heated to 85 with vigorous stirring. To this mixture is first added slowly 341 parts of concentrated hydrochloric acid (pH, 3) and then 978 parts of ethylene glycol. After cooling to about 20 minutes stirring, the pH of the resulting product is adjusted to 3, if necessary. The resulting phenolamine of formula HO

- HO

H37C18 (N-CH2-CH2) 4- NH-CH2

  Wherein one of the substituents R is hydrogen and the others each means a salicyl group, can be used as such in the form of a solution in ethylene glycol for the post-treatment of cellulosic substrates

dyed or printed.

  By proceeding as described in Example 1 but using the amines, phenol and formaldehyde in such quantities

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  as indicated in the following table, other phenolamines of formula I can be prepared.

BOARD

  Ex. Amine Moles of Moles Transformation into.

  No. Phenol CH20 salt with 2 C16Hl3-NH 2 1NH2 lmole dimothyl sulphate

3 C12H25NH2 1 mole do.

  4 fatty amine tallow 1 I lmole do.

  in C14-C18 C18H37-NH-C36-NHNH2 11.1 mole do.

  C18H37- (NH-C3H6) 2 -NH2 11.1 mole do.

: 7 do. - 1 - 1 lmole do.

  8 C18H37 (NHC3H6) 3- NH2 1 1 lmoIe do.

9 do. 1 1 mole do.

  10 C 18 H 37 (NHC 3 H 6) 4 NH 2 1 mole of HCOOH. 1 1 1mole.d 'HC1

12 remains fat of tallow

  (NHC3H6) 4-NH2 1 i1 (NHC 3H6) 4-NH 2 1 1 1 molece dimethylsulphate

13 C18H37-NHC3H6NHC2H4-

NHC3H6NH2 1 1 lmole do.

  14 fatty amine tallow 1 i1 free base

C12H25-NHC3H6 (NHC2H4) 2

NHC3H6NH2 1 l Imole d CH3Ci

16 remains tall fat ---

  (NHC3H6) 4-NH2 2 2 free base 17 do. 1 free base 18 C18-H37- (NHC3H6) 4NH2 4 4 Imoled 'HC - _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _loe'C Application example A Dyes a cotton fabric bleached for 90 minutes to

    in an aqueous dye bath containing 1.9% C.I.

  Reactive Red 123 (based on the weight of the fabric in the dry state) and, for 1000 parts, 50 parts of calcined sodium sulfate and 20 parts of calcined sodium carbonate. The bath ratio is 1:20. After dyeing, the fabric is rinsed thoroughly with warm water and cold water. The fabric is then boiled for 20 minutes with a solution containing, for 1000 parts, 0.5 part of a commercial detergent based on a carboxymethylated alkylene oxide adduct and rinse with hot water. The resulting tissue is then treated at room temperature for 20 minutes with an aqueous bath containing, per 1000 parts, 3 parts of the product obtained in Example-1. The bath ratio is 1:20. After drying, a scarlet red dye having good fastness to 83 'chlorinated water is obtained (test

according to SNV standard 195.828).

  Good results are obtained when the post-

  treatment of the dye with the reactive dye is carried out with the products of Examples 2 to 18 in place of the product of

Example 1

  Application Example B Cotton knitted and mercerized articles were dyed for 60 minutes at 98 'in an aqueous dye bath containing 1% CI Reactive Blue 79 dye (based on the weight of dry articles) and, per 1000 parts, 60 parts of sodium chloride, 15 parts of calcined sodium carbonate and 1 part of

  sodium m-nitro-benzenesulfonate. The bath ratio is 1:40.

  After dyeing, rinse thoroughly with hot and cold water. They are then soaped and rinsed

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  As described in Example A above, the articles are then treated for 20 minutes at 98 with an aqueous bath containing, for 1000 parts, 1.5 parts of the compound of Example 13 (without ethylene glycol) and 5 parts of trichloroacetate. sodium. The bath ratio is 1:20. After drying, a blue dye with excellent fastness to chlorinated water (according to SNV standard 195.822) is obtained. Solidities with chlorinated water are also good after

  two washes at 60 (according to SNV standard 195.813).

  Application Example C Knitted and bleached cotton articles are dyed for 60 minutes to 40 minutes in an aqueous dye bath containing 0.33% CI Reactive Orange dye 91 based on weight 0.40% CI Reactive Red 184 dye in the 0.20% CI CI Reactive Blue 184 - dry state and, per 1000 parts, 60 parts of calcined sodium sulfate, 1 part of calcined sodium carbonate, and 2 parts (by volume) of sodium

at 36%.

The bath ratio is 1:20.

  The articles are then rinsed, soaped and

  subject to post-processing as shown in Example B above.

  The resulting beige dye has good solidities -

with chlorinated water.

  Application Example D A bleached cotton fabric was dyed according to the method of Example A described above but using the following dyes: 6.4% CI dye Reactive Yellow 25 based on weight 3.5% dye CI Reactive Red 147 items in the state

  1.4% C.I. Reactive Blue 193 sec.

  After rinsing, soaping and rinsing, the articles are treated for 20 minutes at 60 with an aqueous bath containing, per 1000 parts, 2 parts of the compound of Example 18.

bath is 1:20.

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  The resulting dye has very good fastness to chlorinated water at 83.degree. This property remains after 3 successive washes in

chlorinated water.

  Similar good results are obtained when the dyed substrate is padded with an absorption rate of 80% in an aqueous bath containing, per 1000 parts, 20 parts of the

Example 18, and dried at 120.

  Application Example E Bleached cotton cretonne was dyed for 90 minutes at 98 in an aqueous dye bath containing 2% CI Direct Red 207 based on the weight of the substrate in the dry state and 15 parts of sulfate. calcined sodium per 1000

  parts. The bath ratio is 1:20.

  After rinsing thoroughly with cold water, the substrate is treated for 15 minutes at 60 with an aqueous bath containing, per 1000 parts, 2 parts of the compound of Example 16 (without

ethylene glycol) and dried.

  The resulting burgundy dye has good

solidity with chlorinated water.

  The same good results are obtained when the substrate dyed with 3% C.I. Direct Blue 199 is subjected to the same post-treatment. By proceeding as indicated in Examples B to D but using the compounds of the other examples, dyes are obtained.

  having good fastness to chlorinated water.

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Claims (14)

  1. The use of the compounds of formula I R ,, (- N -X NH-R2   R3 wherein R1 represents a C6-C22 aliphatic radical, R2 represents a group of formula (a) OH -CH2-R (a) 2 R 5   each R3 is independently hydrogen or a group of formula (a), each R4 is independently hydrogen or C1-C12 alkyl, each R5 is independently hydrogen, chlorine or C1-C12 alkyl; , cycloalkyl or phenyl, n is O or an integer of from 1 to 10, each X independently represents a C2H4- or -C3H6- group, the molecule to contain from 1 to 5 groups of formula (a), in the form of a base free or in protonated or quaternized form, as post-treatment agents for dyed textile substrates or   printed matter comprising cellulosic fibers.   2. A process for the post-treatment of a dyed or printed textile substrate comprising cellulosic fibers, characterized in that a compound of formula I as specified in claim 1 is applied to the dyed or printed substrate in the form of based   free or in protonated or quaternized form.   3. A method according to claim 2, characterized in   that, in formula 1, n means an integer of I to 10.   4. A process according to claim 3, characterized in that what n means 1, 2, 3 or 4.   5. A method according to any of the claims   2 to 4, characterized in that, in formula I, R 1 is C 12 -C 18 alkyl or C 12 -C 18 alkenyl, R 2 is salicyl, each R 3 is independently hydrogen or a salicyl group, X means -C3H6- and n means 1, 2, 3 or 4, the   molecule containing 1, 3 or 4 salicyl groups.   6. A process according to claim 5 wherein R1 is cetyl, stearyl or tallow fatty, R2 is salicyl, X is -C3H6- and n is 3 and R3 is salicyl group, where n is 4 and one of R3 stands for hydrogen and the other R3 symbols   each mean a salicyl group.   7. A process according to claim 6, characterized in that the compound of formula I has the formula HO ## STR2 ## in which one of the substituents R denotes hydrogen. and the   others each mean a salicyl group.   8. A process according to any of the claims   2 to 6, characterized in that the dyed or printed substrate is   made partly or wholly of natural or   Nereus. 9. A dyed or printed substrate made in whole or in part of cellulosic fibers, characterized in that it is   treated according to the method specified in any of the claims cations 2 to 8. 2556 0 1 3   10. A compound of formula I R N -X - NH -R2 () R1 n H- 2 R3   in which R1 represents a C6-C22 aliphatic radical, R2 represents a group of formula (a) OH   -CH 2 (a) R 5 each R 3 is independently hydrogen or a group of formula (a), each R 4 is independently hydrogen or a C 1 -C 12 alkyl group, each R 5 independently is hydrogen, chlorine or a C1-C12 alkyl, cycloalkyl or phenyl group, n means an integer from 1 to 10, each X independently represents a -C2H4- or -C3H6- group, the molecule to contain from 1 to 5 groups of formula (a),   as a free base or in protonated or quaternized form.   11. A compound according to claim 10, characterized in that R1 is a C12-C18 alkyl or C12-C18 alkenyl group, R2 is a salicyl group, each R3 is   independently of hydrogen or a salicyl group, X is -C3H6-   and n is 1, 2, 3 or 4, the molecule containing 1, 3 or 4 groups salicyl.   12. A compound according to claim 11 wherein R1 is cetyl, stearyl or tallow fatty, R2 is salicyl, X is -C3H6- and n is 3 and R3 is a group. salicyl, where n stands for 4 and one of R3 stands for hydrogen and other R3 symbols   each mean a salicyl group.   13. A compound according to claim 12, characterized in that it corresponds to the formula HO H37C18 (N-CH2-CH2-CH2) 4- NH-CH2   R in which one of the substituents R signifies hydrogen and the   others each mean a salicyl group.   A process for the preparation of the compounds of the formula I as claimed in claim 10, which comprises the reaction of one mole of an amine of the formula II R 1 (- NH-X -N 2 II   wherein R 1, X and n are as defined in the claim, or a mixture of amines of formula II, with 1 to n + 1 moles of formaldehyde and 1 to n + 1 moles of a compound of formula III HO 4 (III)   HO4 R5 wherein R4 and R5 are as defined in claim 10, or a mixture of compounds of formula III, formaldehyde and the compound of formula III each being reacted in equimolar amounts, and recovery of the resulting compounds from formula I in form   free base or in protonated or quaternized form.