WO1991010006A1

WO1991010006A1 - Textile treatment

Info

Publication number: WO1991010006A1
Application number: PCT/AU1991/000001
Authority: WO
Inventors: Arthur David Fisher; Jorg Binz; Dieter Reinehr; Sven Strunk
Original assignee: Invicta Group Industries Pty Ltd
Priority date: 1990-01-02
Filing date: 1991-01-02
Publication date: 1991-07-11
Also published as: AU6974491A

Abstract

Process for treating textile fibre material to be stain resisting by treatment of the fibre material with an aqueous liquor containing (A) a compound of formula (I), wherein X is halogen, Y is -O-, -S- or -NRo, where Ro is hydrogen or C1-C4-alkyl, and R is an unsubstituted phenyl or naphthyl radical or a phenyl or naphthyl radical or one which is substituted by C1-C4-alkyl, -SO3M- or -COOM groups, where M is hydrogen or an alkali metal, alkaline earth metal or ammonium cation, and (B) a stain resisting agent having one or more MSO3 groups.

Description

Textile Treatment;

The present invention relates to a process and composition for treating textiles, an aqueous liquor to carry out the process as well as the treated material.

The textile treatment composition may be a textile stain-resistance composition. The textile treatment composition is also preferably a composition which provides improved stain-resistant properties and/or improved twist retention and/or improved wearability.

When used herein, the term "textile" refers to both textiles which are comprised of natural fibres and/or synthetic fibres, for example wool, cotton and nylon and also blends of natural fibres and synthetic fibres. The reference to textiles herein includes all textiles to which the method and composition according to the invention is found suitable.

It is well known that wool fibre material can be treated with sulfonated compounds so as to protect the material against soiling by oily foods or aqueous beverages which have been dyed with synthetic dyes, as for example FD & CRed 40. See for example U.S. 4,699,812 and 4,857,392. However, the stain resisting effect is inadequate.

It has now been found that this disadvantage can be eliminated if the wool fibre material is treated with a mixture of stain resisting materials (stain blockers) and colourless reactive compounds.

The present invention, therefore, provides a process for treating a textile fibre material to make it stain resisting wherein the fibre material is treated with an aqueous liquor which contains

(A) a compound of the formula

Y-R

wherein X is halogen, Y is -0-, -S- or -NR -, where R o o is hydrogen or C,-C.-alkyl and R is an unsubstituted phenyl or naphthyl radical or one which is substituted by C₁-C₄-alkyl, ^_S03^{M or} -COOM groups, where M is hydrogen or an alkali metal, alkaline earth metal or an ammonium cation, and

(B) a stain resisting agent having one or more MSO_-^~ groups .

The invention also provides a composition for treating a textile to make it stain resistant comprising

(A) a compound of the formula

Y-R

wherein X is halogen, Y is -0-, -S- or -NRo-, where Ro is hydrogen or C, -C.-alkyl, and R is an unsubstitued phenyl or naphthyl radical or one which is substituted by C,-C₄-alkyl, -SO.-M- or -COOM groups, where M is hydrogen, or an alkali metal, alkaline earth metal or ammonium cation; and (B) * a stain resisting agent having one or more MS0₃ groups .

X as halogen signifies fluorine, bromine and preferably chlorine. Y is preferably ^J -NRo-, where Ro as C,-C₄-alkyl signifies methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or ter-butyl. R is preferably hydrogen.

The C,-C -alkyl radical as substituent of a phenyl- or naphthyl radical, assumes the significance given above for R , and especially that of methyl. M as alkali metal cation signifies preferably the sodium or potassium cation; as alkaline earth metal cation the calcium or magnesium cation and as ammonium cation one of the formula

^NR1^R2^R3^R4 where

R,, R_, R₃ and R₄ signify, independently from each other, hydrogen, C,-C₄-alkyl β-hydroxy-C₁-C₄-alkyl or a cyclohexyl radical, where at least two of these residues can form a carbon- or heterocyclic ring system. C 1--C4.-alkyl radicals R1, , R2„, R_3 or R4. assume the significance given above to R . β-hydroxy-C,-C₄~alkyl radicals ^Rι^{-R are} for example hydroxyethyl, β-hydroxypropyl and β-hydroxybutyl. Carbon and heterocyclic ring systems which are formed by at least two of the radicals ^R-ι-^R ₄ with the N-atom to which they are bound, are for ^• example cyclohexylamine, dicyclohexylamine or morpholine.

Substituted phenyl radicals R are preferably substituted, by a ^εo ₃ ^M group, or by a C,-C₄-alkyl radical and a ^S0 ₃ ^M group. C,-C₄-alkyl and M assume the significance given above.

The compounds of formula (1) are known as such, for example, from US-A-3,743 ,477 or V.A. Bell, D.M. Lewis and M.T. Pailthorpe, JSDC, Vol 100, 223-231 (1984) and can be produced according to the process described in the US-A-3,278,253, ie. by condensation of 2,4, 6-trichloro-s- triazine with an amine HNR R, an alcohol HOR or a mercaptan HSR, where R and R have the significance given above.

The stain^' resisting agents containing MSO--group(s) , which can be employed as component (B) are preferably (I) anionic aromatic syntanes and (II) aliphatic sulfonic acid with 8 to 24 C-atoms.

They following are, for example, mentioned as aromatic syntanes:

(a) polymeric condensation products which consist essentially of repeating units of the formula: OH

R where R in each unit is either the same or different and signifies a radical selected from

where X signifies hydrogen or a cation such as NH , Na,

K. Such agents are, for example, condensation products of phenol sulfonic acid and dihydroxy diphenylsulfone with formaldehyde or condensation products of naphthalene sulfonic acid^' and dihydroxy diphenylsulfone with formaldehyde and .sulfonated naphthol, phenol or cresol (cf. for example US-A-4,680,212; EP-A-0242,495 or EP-O 235

989). These products are also used as stain resisting agents and wet fastness improvers. Other agents can, for example be found in A.Chwala and V.Anger "Handbuch der

Testilhilfsmittel" (Handbook for Textile Aids), 6/8 Verlag

Chemie, Weinheim, New York (1977)-.

(b) Condensation products from naphthalene sulfonic acid and formaldehyde; (c) Formaldehyde condensation products of sulfonic group containing aromatic hydroxy compounds with aralkyl halogenides.

(d) Urea-formaldehyde condensation products of phenols and phenol sulfonic acids; (e) Reaction product of phenol and a sulfonation agent, wherein the mole ratio phenol: (SO_) is (1):(1.1

- 2.2);

(f) Condensation products of sulfonated diaryl ether and formaldehyde; (g) Condensation products of sulfonated di- or ter-phenylene and formaldeyde;

(h) Condensation products of 4,4 '-dihydroxy diphenyl sulfone and sulfonated 4,4'-dihydro diphenyl sulfone with formaldehyde and (i) Formaldehyde condensation products of diarylether .sulfonic acid and 4,4'-dihydroxy diphenyl sulfone.

The condensation products of the types (a), (b) and (f)-(i) are well known, for example from Ullmann's

Enzyklopaedie der Technischen Chemie, Vol 16, (4), 140

(1979) and can be produced according to processes described in the references given therein.

Condensation products of the type (c) and their production are known from GB-C-986621.

Condensation products of the type (d) and their production are known from GB-C-890160 and 935678.

The reaction product of the type (e) and its production is known from EP-A-0215205. These reaction products can be condensed according to known methods to products of the type (d) (cf. for example GB-C-683084) .

Aliphatic sulfonic (II) acids to be mentioned are C_-C₂₄-alkyl or C₈-C₂₄-alkenyl sulfonic acids. The alkenyl sulfonic acids are simply unsaturated paraffin sulfonic acids. The aliphatic sulfonic acids can be straight chain or preferably branch chain. Branching is preferred on the C-atom which carries the sulfonic group, ie. secondary alkyl- or alkenyl sulfonic acids are preferred. The following can, for example be used as alkyl and alkenyl radicals for these aliphatic sulfonic acids: octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, oktadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl as well as their single unsaturated analogues, such as octenyl, nonenyl, decenyl, ^' undecenyl etc.

The 1-octane, 1-nonane, 1-decane, 1-undecane, 1-dodecane, 1-tetradecane, 1-octadecane and 1-eicosane sulfonic acid can be considered, for example, as straight chain sulfonic acids (II). The 2-octane, 3-octane, 4-octane, 5,5-dirnethyl-2-hexane-, 5,6,7-trimethyl-3- dodecane- and 4,6,9,10-tetramethyl-2-undecane sulfonic acid can be named as saturated, branched sulfonic acids. As unsaturated, straight chain or branched sulfonic acids (II) the following can be considered; 2-dodecene-l-, 3-dodecene-l-, 4-dodecene-l-, 11-dodecene-l-, 4-dodecene-2-, ^' ll-dodecene-3-, ll-dodecene-5-, 10-methyl-lO-undecene-l-, 10-methyl-10-undecene-2-, 8,9,-diraethyl-9-decene-l- and

5,5-dimethyl-7-decene-l-sulfonic acid.

The above mentioned aliphatic sulfonic acids are, for example, known from US-A-4,699,812 and can be produced according to well known methods, for example, by sulfoxidation of alkanes with SO- and 0„ under pressure in the presence of peroxides or by the addition of SO- to alkenes.

In a preferred embodiment of the process according to the invention a textile fibre material is treated with a liquor containing the compound of the formula (I) as component (A) , and as component (B) either a condensation product of naphthalene sulfonic acid and dihydro diphenylsulfone with formaldehyde and sulfonated naphthol, phenol or cresol. Especially preferred liquors contain as component (A) the sodium salt of 4-[(4' ,6'-dichloro-s-triazine-2'-yl) amiήo]-benzene sulfonic acid) or the 2-[(4',6'-dichloro-s- triazine-2'yl)amino]-naphthalene-1,5-disulfonic acid and as component (B) a condensation product of phenyl sulfonic acid and dihydroxy diphenylsulfone with formaldehyde or the ammonium salt of a condensation product of naphthalene sulfonic acid and formaldehyde.

The components (A) and (B) are used in the weight ratio of (A) : (B) of 1 : 1 to 15 : 1. The components are added to the liquor one after the other where the period between the two additions is not decisive. They can also be added simultaneously (continuous process) .

Wool fibre material is especially suitable for treatment according to the invention. Wool fibre material is considered to be a material which is available in the most varied forms of fabrication, such as, for example, fibre, thread, woven fabric, knitted fabric and especially gauze. The wool fibre material to be treated according to the invention can be ^"undyed or dyed. Coloured woollen material has been dyed with anionic dyes.

The following can, for example, be named as anionic dyes: salts of metal containing or metal free mono-, di- or polyazo dyes including the formazan dyes as well as the anthraquinone-, xanthene-, nitro, triphenyl methane-, naphthoquinone imine- and phthalocyanine dyes. The anionic character of these dyes can be caused by metal complex formation alone and/o preferably by acid, salt forming substituents such as carboxylic acid groups, sulfuric acid- and phosphonic acid ester groups, phosphonic acid .groups or sulfonic acid groups. These dyes can also have in their molecule so-called reactive groupings which enter into a covalent bond with the material to be dyed. Preferred are acid, metal free dyes which have a single sulfonic acid group, or else reactive dyes with preferably at least two sulfonic acid groups.

Mixtures of the anionic dyes can also be used. For example dye mixtures of at least 2 or 3 components can be used.

The liquor which can be used according to the invention contains the component (A) which is to be used in quantities of 2-20, preferably 5 to 10% by weight and the. component (B) in quantities of 1-10, preferably 2-6% by weight, where the quantities are based on the weight of the wool. This liquor can also contain other additives, such as are used in the dying of textile fibres.

The treatment of the fibre material can be carried out by batches or as a continuous process of after treatment.

The following examples illustrate the invention. Parts signify parts by weight, and percents are percent .by weight. Example 1: A sample of lOg of a woollen carpet yarn is treated in the dye apparatus with a liquor in the liquor ratio of 1:30 which contains 7.5%* of the sodium . s.aIt of 4-[ (4 ' ,6'-dichloro-s- triazin-2'-yl)amino] benzene sulfonic acid (a) 10% NaCl. The pH of the liquor is adjusted to 5.5 with acetic acid.

(* all percentage figures are based on the weight of material) The liquor is heated to 98°C, the previously moistened sample is immersed in the liquor and treatment is carried out for 30 minutes at this temperature. After this 3.75% of the ammonium salt of a condensation product of naphthalene sulfonic acid, dihydroxy diphenylsulfone and formaldehyde (b) is added to the treatment bath, and treatment is continued for 30 minutes at 98°C. Subsequently the material is rinsed and dried. Example 2: The procedure is the same as in Example 1, however instead of the benzene sulfonic acid derivative specified there, 7.5% 2~[(4' ,6'-dichloro-s-triazin- 2'-yl)amino] naphthalene-1,5 disulfonic acid (c)is used. Example 3: The procedure is the same as in Example 1, however, instead of the condensation product specified there, 3.75% of a condensation product of phenol sulfonic acid and dihydroxy diphenyl sulfone with 0.4 mole of formaldehyde (d) is used. Example 4: The procedure is the same as in Example 1, however, instead of the woollen carpet yarn a sample of lOg

2 of a woollen carpet of 350g/m is used and instead of the benzene sulfonic acid derivative, 7.5% of the naphthalene-1,5-disulfonic acid derivative of Example 2 is used, and instead of the condensation product of Example 1, the condensation product of Example 3 is used.

Example 5: The procedure is the same as in Example 4, however, instead of the naphthalene-1,5-disulfonic acid derivative, 7% of the derivative according to example 1 is used and instead of the condensation product of Example 3, 3.5% of the condensation product of phenol sulfonic acid and dihydroxy diphenylsulfone with 0.58 moles formaldehyde (e) is used.

Example 6: The procedure is the same as in Example 1, however, instead of the benzene sulfonic acid derivative, 7.0% of the naphthalene-1,5-disulfonic acid derivative of Example 2 is used, and instead of the condensation product of Example 1 3.5% of the condensation product according to Example 5 is used. Comparative Examples A-F

Six samples of woollen carpet yarn of lOg each are treated with liquor in the liquor ratio of 1:30 which contain

10% NaCl and each

7.5% of the component (a) or (b) or 3.75% of the component (c) , (d) or (e) , respectively not a single component.

The pH value of the liquors is adjusted to 5.5 with acetic acid.

The moistened samples are then immersed in the liquors which have been heated to 98°C and treatment is carried out for 60 minutes at this temperature. Subsequently, the samples are rinsed cold and dried.

The samples which were dressed according to the Examples 1 to 6 and the comparative Examples A to F are each separately immersed at a liquor ratio of 1:20 in a liquor at 20°C which contains 80mg/L of the acid dye FD & C Red 40 and 0.5 g/L of citric acid (pH 3) and are kept there for 15 minutes at this temperature. After this they are rinsed cold for 5 minutes and are dried at 60°C.

The results are summarised in Table 1. Table 1

Sample Evaluation of Evaluation of the according to the dyeing stain resistance

Example 1 none good Example 2 none good Example 3 none good Example 4 none good Example 5 none good Example 6 none good

Example A clearly moderate Example B clearly moderate Example C clearly moderate Example D clearly moderate Example E clearly moderate Example F clearly poor Example 7: A specimen of lOg of a wool carpet yarn is dyed with a solution which, relative to the mass of the yarn, contains 0.026% of the dye with the formula

0.02% of the dye with the formula

0.038% of the dye with the formula

10.0% sodium sulfate decahydrate

7.5% of the component (a) of Example 1 and

3.75% of the component (d) of Example 3 The pH of the dye liquor is adjusted to 5 with acetic acid.

The pre-moistened sample is immersed in the liquor which has been heated to 40°C, and the temperature is then raised to 80°C over a period of 30 minutes and dyeing proceeds at that temperature for an hour. After that the sample is cooled down over a period of 10 minutes to 60°C, and is then rinsed in running water and is subsequently dried. Comparative Example G

A second sample is dyed and after treated as described, in a further dye liquor which, however, does not contain the components (a) and (d) .

The samples so obtained are tested on their stain resistance as in the comparative samples A-F.

The results are summarised in Table II:

Table II

Sample Evaluation according to of dye acceptance of stain resistance

Example 7 none good Example G strong poor

Claims

Claims :

1. A process for treating a textile fibre material to make it stain resisting wherein the fibre material is treated with an aqueous liquor which contains (A) a compound of the formula

Y-R

wherein X is halogen, Y is -O-, -S- or -NR -, where R o o is hydrogen or C,-C₄-alkyl, and R is an unsubstituted phenyl or naphthyl radical or one which is substituted by C--C₄-alkyl, -S0₃M- or -COOM groups, where M is hydrogen, or an alkali metal, alkaline earth metal or ammonium cation, and

(B) a stain resisting agent having one or more MSO_ groups .

2. A process according to claim 1, wherein X is chlorine, bromine or fluorine, Y is -NH- and R is an unsubstituted phenyl or phenyl which is substituted by a -SO„M-group or by a C,-C₄-alkyl radical and a -SO,M-group, or an unsubstituted naphthyl, or one substituted by one or two -SO_M-groups .

3. A process according to claim 1 wherein compound (B) is selected from the following:

(I) anionic aromatic syntanes and

(II) aliphatic sulfonic acids with 8 to 24 C-atoms.

4. A process according to claim 3 wherein a polymeric condensation product is used as anionic aromatic syntane (I), which consists essentially of units of the formula

OH

R wherein Z in each unit is either the same or different and signifies hydrogen or a radical selected from

wherein X signifies hydrogen or a cation such as NH , Na, K.

5. A process according to- claim 3 wherein a condensation product of phenolsulfonic acid and dihydroxy diphenylsulfone with formaldehyde is used as aromatic syntane (I) .

6. A process according to claim 3, wherein a condensation product of naphthalenesulfonic acid and dihydroxy diphenylsulfone with formaldehyde is used as aromatic syntane (I).

7. A process according to claim 3, wherein a condensation product of formaldehyde and sulfonated naphthol, phenol or cresol is used as aromatic syntane (I).

8. A process according to claim 3, wherein a C₈-C₂₄-alkyl or C₈-C₂₄-alkenyl sulfonic acid is used as aliphatic sulfonic acid (II) .

9. A process according to claim 1, wherein a compound according to claim 2 is used as component (A) and a condensation product according to claim 5 is used as component (B) .^•

10. A process according to claim 1, wherein a compound according to claim 2 is used as component (A) and a condensation product according to claim 6 is used as component (B) .

11. A process according to claim 9, wherein the sodium salt of 4-[(4 ' , 6'-dichloro-s-triazine-2'yl)amino]-benzene sulfonic acid is^" used as component (A) and a condensation product of phenol sulfonic acid and dihydroxy diphenylsulfone with formaldehyde is used as component (B) .

12. A process according to claim 11, wherein the ammonium salt of a condensation product of naphthalene sulfonic acid and dihydroxy diphenysulfone with formaldehyde is used as component (B) .

13. A process according to claim 9, wherein 2-[(4 ' ,6'-dichloro-s-triazine-2'yl)amino]naphthalene-1,5- disulfonic acid is used as component (A) and a condensation product of naphthalene _ sulfonic acid and dihydroxy diphenylsulfone with formaldehyde as component (B) .

14. A process according to claim 13, wherein the ammonium salt of a condensation product of naphthalene sulfonic acid and dihydroxy diphenylsulfone with formaldehyde is used as component (B) .

15. A process according to claim 1, characterised by the fact that the treatment is carried out as a batch process or continuously, as an after treatment.

16. A process according to one of claims 1 to 15, characterised by the fact that the liquor contains the components (A) and (B) in .a weight ratio (A):(B) of 1:1 to 15:1.

17. A process according to any one of claims 1 to 14 wherein the textile fibre material is wool.

18. A textile fibre material, which has been dressed to be stain resisting according to claim 1, which has on the material 2 to 20% by weight of component (A) and 1 to 10% of the component (B) , both based on the weight of the material.

19. A -process according to claim 17 wherein the textile fibre material is a woollen carpet material.

20. A textile which has been treated by a process according to claim 1.

21. A composition for treating a textile to make it stain resistant comprising

(A) a compound of the formula

Y-R

wherein X is halogen,- Y is -0-, -S- or -NR -, where R is hydrogen or C,-C₄-alkyl, and R is an unsubstitued phenyl or naphthyl radical or one which can be further substituted by -SO-M- or -COOM groups, where M is hydrogen, or an alkali metal, alkaline earth metal or ammonium cation; and

(B) a stain resisting agent having one or more S0₃ groups.

22. A composition according to claim 21, wherein X is chlorine, bromine or fluorine, Y is -NH- and R is an unsubstituted phenyl or phenyl which is substituted by a -SO-M-group or by a C C-,--CC₄„--aallkkyyll rraaddiiccaall and a -SO-.M-group, or an unsubstituted naphthyl, or one substituted by one or two -SO-M-groups.

23. A composition according to claim 22, wherein compound (B) is selected from the following:

(i) anionic aromatic syntanes and (ii) aliphatic sulfonic acids with 8 to 24 C-atoms.

24. A composition according to claim 23, wherein a polymeric condensation product is used as anionic aromatic syntane (I), which consists essentially of units of the formula

OH

wherein X signifies hydrogen or a cation such as NH₃, Na,

K.

25. A composition according to claim 24, wherein a condensation product of phenolsulfonic acid and dihydroxy diphenylsulfone with formaldehyde is used as aromatic syntane (I) .

26. A composition according to claim 25, wherein a condensation product of naphthalenesulfonic acid and dihydroxy diphenylsulfone with formaldehyde is used as aromatic syntane (I) .

27. A composition according to claim 26, wherein a condensation product of formaldehyde and sulfonated naphthol, phenol or cresol is used as aromatic syntane (I).

28. A composition according to claim 27, wherein a C₈-C₂₄-alkyl or C₈-C₂₄-alkenyl sulfonic acid is used as aliphatic sulfonic acid (II).

29. A composition according to claim 28, wherein a compound according to claim 2 is used as component (A) and a condensation product according to claim 5 is used as component (B) .

30. A composition according to claim 29, wherein a compound according to claim 2 is used as component (A) and a condensation product according to claim 6 is used as component (B) .

31. A composition according to claim 30, wherein the sodium salt of 4-[(4',6'-dichloro-s-triazine-2'yl)amino]- benzene sulfonic acid is used as component (A) and a condensation product of phenol sulfonic acid and dihydroxy diphenylsulfone with formaldehyde is used as component (B) .

32. A composition according to claim 31, wherein the ammonium salt of a condensation product of naphthalene sulfonic acid and dihydroxy diphenysulfone with formaldehyde is used as component (B) .

33. A composition according to claim 32, wherein 2-[(4 ' ,6'-dichloro-s-triazine-2'yl)amino]naphthalene-1,5- disulfonic acid is' used as component (A) and a condensation product ^' of naphthalene sulfonic acid and dihydroxy diphenylsulfone with formaldehyde as component (B) .

34. A composition according to claim 33, wherein the ammonium salt of a condensation product of naphthalene sulfonic acid and dihydroxy diphenylsulfone with formaldehyde is used as component (B) .