IL42961A

IL42961A - Process for modifying keratinous textiles and fibres

Info

Publication number: IL42961A
Application number: IL42961A
Authority: IL
Original assignee: Ciba Geigy Ag; Iws Nominee Co Ltd
Priority date: 1972-09-01
Filing date: 1973-08-13
Publication date: 1976-07-30
Also published as: CH1244173A4; IE38188L; ZA736017B; CA1012310A; IL42961A0; AU5958173A; SU529810A3; BE804300A; ES418377A1; JPS49124395A; CH573503B5; FR2198022A1; IT990436B; BR7306795D0; IE38188B1; GB1435085A; DE2343620A1; FR2198022B1; NL7312070A

Claims

WHAT WE CLAIM IS;

1. A process for finishing keratinous material which comprises (1) treating the material with a polyene having, per average molecule, at least two ethylenic double bonds each 3 to an oxygen, nitrogen, or sulphur atom, (2) curing the polyene on the material by reaction with a polymercaptan containing, per average molecule, at least two mercaptan groups and having the following features (a) the sum of its mercaptan groups and of the said ethylenic double bonds in the polyene is more than 4, (b) it contains in the molecule (i) either the residue of a polyhydric alcohol after removal of its alcoholic hydroxyl groups or the polyacyl residue of a polycarboxyl c acid (ii) bound to such a residue, through ether oxygen or ester oxygen atoms, at least two chains each containing either the residue of a dihydric alcohol after removal of both of its hydroxyl groups or the diacyl residue of a dicarboxylxc acid (iii) bound, through ether oxygen or ester oxygen atoms, to the said residues of a dihydric alcohol or a dicarboxylxc acid, eit er- 311 acyl residue of an aliphatic mercaptancarboxylic acid or a residue of an aliphatic mercaptanalcohol after removal of a hydroxyl grou , the combined weight of the polyene and the polymercaptan being from 0.5 to 15% by weight of the keratinous material treated.

2. Process according to claim 1, in which the sum of the mercaptan groups in the polymercaptan and of the aaid ethylenic double bonds in the polyene is from 5 to 8.

3. Process according to claim 1 or 2 , in which the amount of polymercaptan is such as to supply from 0.8 to 1.2 inercaptan groups per ethylenic double bond of the polyene.

4. Process according to any of claims 1 to 3, in which the treated fabric is heated at a temperature in the range 35° to 180°C.

5. Process according to any of claims 1 to 4 , in which the polymercaptan and the polyene are applied from an organic solvent.

6. Process according to any of claims 1 to 4 , in which the polymercaptan and the polyene are applied from an aqueous emulsion by exhaus tion.

7. Process according to any of claims 1 to 6 , in which the polyene has a molecular weight in the range 250 to 10000.

8. Process according to any of claims 1 to 7, in which the polyene contains at least two ethylenic double bonds each a to a carbonyloxy group.

9. Process according to claim 8, in which the polyene is of the formula I -(0-alkylene) where a is zero or a positive integer of value such that the average molecular weight of the polyene does not exceed 10000, b is zero or 1. is an integer of at least 1, R denotes the radical remaining after removal of c OH groups from a compound having at least _c alcoholic hydroxyl groups or the acyl radical remaining after removal of _c OH groups from a compound having at least COOH group3, each 'alkylene' group contains a chain of at least 2 and at most 6 carbon atoms between consecutive oxygen atoms, 1 3 R represents a group of formula -OH or -00CR , 2 R represents -H, an acyl group, or the residue, after removal 2 of an -OH group, of an alcohol, with the provisos that R and R do not 2 both represent acyl if and b_ both denote zero and that R does not represent -H if b is 1, and 3 R represents -H or a monovalent hydrocarbon group which may bear carboxyl or alkoxycarbonyl substituents , there being a total of at least two ethylenic bonds a to 2 carbonyloxy groups in the group R, and/or in the groups R , and/or in 3 . the be groups R if present.

10. Process according to claim .9 , in which c is 2 or 3.

11. · Process according to claim 9, in which R^ denotes a group of formula - CO - C - CHR5 I» where denotes -H, -CI, -Br, or alkyl, and denotes -H, -COOH, or a group of the formula where and ]> have the meanings assigned in claim 9 and ^ denotes -H, an alkyl, aryl, aralkyl or alkenyl hydrocarbon group, or an aliphatic, aromatic or araliphatic acyl group, such that the group ^ contains not more than 24 carbon atoms.

12. Process according to any of claims 9 to 11 in which R represents a group containing from 2 to 16 carbon atoms and bearing either one -COOH group or one alkoxycarbonyl group containing from 1 to 13 carbon atoms.

13. Process according to any of claims "9 to 12 in which R represents an aliphatic radical containing up to 60 carbon atoms.

14. Process according to claim "8, in which the polyene is of the formula where R denotes the radical remaining after removal of j: OH groups from a compound having at least c phenolic hydroxy1 groups, a and b have the meanings assigned in claim 9., c has the meaning assigned in claim or 10., ' alkylene* has the meaning assigned in claim 9 or 11., R has the meaning assigned in claim .9 , R2 has the meaning assigned in any of claims 9 , 12 , and 13. , and 3 R has the meaning assigned in any of claims !9. and "12.

15. Process according to claim 14, in which R represents a radical of the formula atoms, R denotes a carbon-carbon bond, an alkylene hydrocarbon group of from 1 to 4 carbon atoms, or an ether oxygen atom, and u is en integer of from to * .

16. Process according to any of claims 1 to 15, in which the polymercaptan has an average molecular weight of at least 400 and at most 10000.

17. Process according to claim 16, in which the polymercaptan is of the general formula where alkylene* has the meanings assigned in claim d 'is an integer of from 2 to 6," e_ is zero or a positive integer such that (d + e) equals at most 6, f is a positive integer and may have different values in each of the l and chains , j» is zero or 1, q R represents the radical of a polyhydric alcohol after removal of (d + e) alcoholic hydroxyl groups, and X represents an aliphatic radical containing at least one merea tan group.

18. Process according to claim 17 , n which the polymercaptan is also of the formula where R , jd, ji, and _f have the meanings assigned in claim - 17 , ' alkylene' has the meaning assigned in claim 9, and lx is an integer of from 1 to 24.

19. Process according to claim 18 , in which the polymercaptan is of the formula SH CH (OC J0H,)„ OCOCH-SH o f t CH2 (OC3H6)f OCOCH2SH where f has the meaning assigned in claim 17 , having a olecular weight within the range 700 to 6000.

20. Process according to claim 17 , in which the polymercaptan is of the formul where denotes -OH or -(O-alkylene) OH, R , d, e, and _f have the meanings assigned in claim 17, 'alkylene* has the meaning assigned in claim '9, and n is an integer of at least 1 and may have different values in each of the _d chains.

21. Process according to claim 20, in which the polymercaptan is also of the formula CH„ - (0C,H,) 0CH CHCH_SH _> O f OH CH2 - (OC3H6) .^CH2CHCH2SH OH where f has the meaning assigned in claim 17 ,the molecular weight of the polymercaptan being at least 700 and at most 6000.

22. Process according to claim 16,in which the polymercaptan is a polyester of the average formula W-^_ (0)rC0(0)qZ(0)qC0(0)rYSH^ where and _r are zero or 1 but are not the same. £ is a positive integer of at most 6, Z represents a divalent organic radical, linked through a carbon atom or carbon atoms thereof to the indicated -0- or -CO- uni Y represents a divalent organic radical, linked through a carbon atom or carbon atoms thereof to the indicated -SH group and -0- or -CO- units, and represents an organic radical which mu&t contain at least one -SH group when p is 1, linked through a carbon atom or carbon atoms thereof to the indicated -0- or -CO- units.

23. Process according to claim 22, in which the polymercaptan is also substantially of one of the formulae 13 Γ 12 16 I R " †- C0-0-R~ O-CO- SHj a 13r Γ 12 Ί 16 1 R ij.0 † CO-R -CO-O-R -0 -U CO-R' SH 13- f 12 11 1 15 Ί R CO-J- 0-R" ' -O-CO-R CO -†- 0-R SHj 13 Γ Γ 12 1 11 1 η R -lO† CO-R -CO-O-R" -0 -tC0-R COO-R SHj where 11 m # denotes the residue of an aliphatic, cycloaliphatic, or aromatic dicarboxylic acid after removal of the two -COOH groups, 1? R denotes the residue of an aliphatic, araliphatic, or cycloaliphatic diol after removal of the two hydroxyl groups, 13 R denotes an organic radical containing at least two carbon atoms and directly linked through carbon atoms thereof to the indicated mercaptan-terminated ester chains, denotes the residue of an aliphatic, cycloaliphatic, or aromatic dicarboxylic acid containing a mercaptan group, after removal of the -COOH groups, t is an integer of at least 1, s is an integer of at least 2, R^SH denotes the residue of a monomerca tanmonohydric alcohol after the removal of an alcoholic hydroxyl group, and R^SH denotes the residue of a monomercaptanmonocarboxylic acid after the removal of a carboxyl group.

24. Process according to any of claims 1 to 13 and 16 to 23, in which the polyene and polymercaptan are employed in the presence of a Br^nsted base as catalyst.

25. Process according to any of claims 1 to 23, in which the polyene and polymercaptan are employed in the presence of a Br^nsted acid or a free-radical catalyst.

26. Keratinous material bearing thereon from 0.5 to 15% by weight, calculated on the weight of the keratinous material, of a product comprising a polyene as defined in any of claims 1, 7 to 15, cured with a polymercaptan as defined in any of claims 1, 16 to 24.

27. Keratinous material treated by a process as claimed in any of claims 1 to 25.