CA2283218A1 - Textile treatment - Google Patents

Abstract

A compound of formula (I) wherein: R1 and R2 each independently represents arylamino, diphenylamino, benzylamino or dibenzylamino, and Z represents a leaving group. In general the group -SO2-CH2-CH2-Z is a blocked vinylsulphone and in some cases it is advantageous to use the free vinylsulphone. The leaving group Z may comprise, for example, sulphato (-OSO3-), S-thiosulphato (SSO3-), Sarcosine, N-methyltaurine, N,N-dialkyl acetate (-O-CO-CH3), acyloxy (O-CO-R, where R is alkyl e,g, C1-C5), phosphato (-OPO-3), or a halogen. Activation of the leaving group is usually by means of heating in slightly acidic baths to produce the fibre reactive vinylsulphone. Alternatively the free reactive vinylsulphone may be pre-formed and applied to the fabric as a dispersion. The compounds of the invention contain more aromatic rings which are not substituted with vinylsulphone groups which has been found to improve pi-bonding. In addition the pi system of the present invention is planar, which has been found to be crucial to increasing the affinity of the fibres to disperse dyes as well as imparting shrink resistance and other properties to the fabric.

Description

TEXT I LE TREATMENT
This invention relates to a method of treating textiles and in particular relates to a method for treating cellulosic, keratinous and polyamide textiles to increase their affinity for disperse dyes, and novel compounds therefor.
Keratinous fibres such as wool, natural polyamides such as silk and natural cellulosic fibres such as cotton do not normally exhibit any marked affinity for disperse dyestuffs. Again attempts to dye these fibres with disperse dyes result in poor colour yields, dull shades and poor wet and light fastness.
Disperse dyestuffs are used largely with synthetic fibres such as polyesters and are therefore commonly available. Furthermore, disperse dyes are often sublimable and form the basis of the well known "transfer printing" process in which papers are printed with a design using disperse dye and these papers may then be subsequently used to colour the textile fabric merely by placing the paper and the fabric together and heating in a press for a short period of time, typically half a minute at 180-220°C
(French Patent No. 1,223,330).
Synthetic polyamide fibres ("nylon") have apparent adequate affinity for disperse dyes but the wash fastness of dyeings and prints of these dyes on this substrate is inadequate, indicating that the actual dye-fibre interactions are weak.
The invention seeks to provide a method of increasing the affinity of these fibres for disperse dyes and to allow deeply coloured, high wet-fast dyeings and prints to be produced. The invention also seeks to provide novel compounds useful in this method. US-A-4563189 discloses certain arylating agents for this purpose. The present invention represents an improvement in the agents claimed therein. The compounds of the invention may in addition impart shrink resistance and easy care properties to the fabric.
In accordance with the present invention there is provided a compound of the formula:
~Z
' N
~~ N~\ SO C
N+-l-0 It: ~ S~~y ~ ~' LW
(I) wherein . R1 and RZ each, independently, represent arylamino, diphenylamino, benzylamino or dibenzylamino, and Z represents a leaving group.
In general the group -SOZ-CHZ-CHZ-Z is a blocked vinylsulphone and in some cases it is advantageous to use the free vinylsulphone.
The leaving group Z may comprise, for example, sulphato (-OS03-), S-thiosulphato (-SS03-), Sarcosine, N-methyltaurine, N,N-dialkyl acetate (-O-CO-CH3), acyloxy (-O-CO-R, where R is alkyl e,g, C,-CS), phosphato (-OPO-3), or a halogen. Activation of the leaving group is usually by means of heating in slightly acidic baths to produce the fibre reactive vinylsulphone. Alternatively the free reactive vinylsulphone may be pre-formed and applied to the fabric as a dispersion.
The compounds of the invention are arylating agents improved with respect to US-A-4563189 in that the compounds contain more aromatic rings which are not substituted with vinylsulphone groups which has been found to improve pi-bonding. In addition the pi system of the present invention is planar, which has been found to be crucial to increasing the affinity of the fibres to disperse dyes as well as imparting shrink resistance and other properties to the fabric. Subject to the foregoing, the compounds R1 and R2, and the aromatic ring shown in Formula I, may be substituted by substituents not interfering with the reactive moiety, e.g. by alkyl or alkoxy groups or by chlorine atoms.
The fibre reactive arylating agents of general formula I may be prepared by condensation of a halogenoheterocyclic compound of general formula IA.
v.
Y
(IA) wherein Hal represents a chlorine, bromine or fluorine atom and two of the Yes represent nitrogen atoms and the other Y nitrogen or a carbon atom carrying a hydrogen atom or a chlorine atom or a cyano group, with an amine of general formula HZN-Ar-SOZ-CHZCHZZ, where Ar is an aromatic ring, and reacting the product with an aromatic amine of general formula IB and then with a further amine of general formula IB:-D-Ar-NHZ
(IB) where Ar is an aromatic ring, and D is hydrogen, halogen, cyano, substituted amino, alkyl, alkoxy, aryl or alkylaryl.
As examples of halogenoheterocyclic compounds there may be mentioned cyanuric chloride, cyanuric bromide, cyanuric fluoride, trif luoro pyrimidine, trichloropyrimidine, tetrachloropyrimidine, 5-chloro-2,4,6-trifluoropyrimidine and 5-cyano-2,4,6-trichloro-pyrimidine.
As examples of amines of general formula IB there may be mentioned aniline, p-chloroaniline, 2,5-dichloroaniline, p-anisidine, p-phenetidine, p-toluidine, 2,4-dimethylaniline;
2,4,5-trimethylaniline, p-butylaniline, p-dodecylaniline, p-aminoacetanilide, N-methylaniline, N-butylaniline, p-aminobenzonitrile, p-benzylaniline, 4-aminobiphenyl, a-naphthylamine, 2-ethoxy-1-aminonaphthalene.
The invention further provides a method of treating natural (proteinaceous, polyamide and cellulosic) textile fibres and synthetic polyamide fibres to enhance their affinity for disperse dyestuffs which comprises treating the fibres with an aqueous solution or aqueous dispersion of fibre reactive arylating agent of formula (I) or, alternatively, applying a dispersion of the pre-formed reactive vinylsulphone form of the arylating agent.
In order to improve the photostability of both the arylated substrate and the dyed, arylated substrate, it is preferred to employ a fibre substantive, sulphonated benzophenone W absorber either in the formulation or as an after treatment.
In the treatment, one or two of the vinyl sulphone or blocked vinyl sulphone groupings present in the arylating agent react with nucleophilic centres present in the fibre causing the arylating agent to become covalently bound into the fibre.
Such treatment involves reacting the fibre reactive arylating agent with the textile material under conditions of pH and temperature analogous to those used in the application of reactive dyes to textile materials. Such conditions are well known to those skilled in the art. It is particularly advantageous if Z is an anionic, water solubilising group since the arylating agent is then compatible with the anionic dispersions of disperse dyes available commercially. To ensure maximum light fastness of the dyeings it is also preferred to include a water soluble W absorber (e.g. Uvinul MS-40[BASF -sulfonated benzophenone) in the formulation.
The treatment can be carried out prior to or simultaneously with dye application.
According to a further aspect of the invention there is provided a composition comprising: a disperse dye, an anionic dispersing agent, and an arylating agent as defined above.
The arylating agent contains one or more benzene residues and is covalently bonded to the fibre by nucleophilic addition at the vinylsulphone group. One such preferred compound has the formula:
~ ~NN-~O Sfly_ CNzc~IZ- G'S ~3 .. I C
I I
i'~ ,J
~/
(II) Alternatively, the sulphato group can be replaced by an S-thiosulphato group, a phosphato group,~a sarcosinate group or an N-methyl-taurine residue.
The amount of arylating agent employed is preferably between 2 and 20% on weight of fibre (o.w.f).
A particularly useful arylating agent has the structure of formula (II) above.
This compound is water soluble, anionic and extremely reactive to silk, wool and nylon under neutral to slightly acidic conditions;
its substantivity for these fibres is also excellent. In the case of the polyamide fibres, if co-applied with a disperse dye, e.g. at about pH 6.5, by the simple procedure of raising to the boil and boiling one hour, dyeings of excellent brilliance, colour yield (water-white dye-bath exhaustion) and colour fastness are achieved. Alternatively co-application by padding processes may be carried out, fixation of the disperse dye and arylating agent occurring simultaneously on drying, or steaming:
Fixation on cotton is promoted under alkaline conditions e.g.
pH10.5 for 1 hour at 60°C.
The preferred amino-triazinyl reactive arylating agents may be applied either by exhaustion from long liquors, or by padding.
In the former case the arylating agent is dissolved or dispersed in water, optionally in the presence of an anionic dispersing agent and a buffer. The textile material may be immersed in the bath which is raised to the necessary treatment temperature and held at this temperature for a period of, for example, from 10 minutes to 2 hours. Where the arylating agent is applied by padding, the agent is dispersed or dissolved in water optionally together with a swelling agent for the textiles, for example urea and a thickener. If cellulosic fibres are to be treated, then an alkali such as trisodium phosphate should also be included in the liquor. The fabric or material may be padded, steamed or baked to fix the reagent and then rinsed to remove unfixed arylating agent; alternatively the fabric or material may be padded with the reactive agent, batched for periods up to 48 hours to allow reaction to occur and then rinsed to remove unfixed reagent. In a further aspect of the invention the agent may simply be applied by a pad~dry procedure and fixed during the sublimation transfer printing process (30 secs - 60 secs at 180-210°C) .
The arylating agent may conveniently be any suitable compound according to formula (I) (or its free vinysulphone form) which contains at least two benzene rings and a reactive, optionally blocked, vinylsulphone group. Such compounds are conveniently prepared by the reaction of water insoluble halo-s-triazines with selected aromatic amines containing blocked vinylsulphone residues. The reaction products become water soluble by virtue of an introduced sulphato or S-thiosulphato residue. The following scheme describes this general reaction:

y .~ X
ll ~ H2~-~ S~,z CKZcHZ ~
~ N
KN- A~- O
J, i ~
_~,~
t HX
J
HN-a~_~
(III) Wherein Ar, Z and D have the meanings ascribed hereinabove, and X is a halogen. In particular, D may be hydrogen, phenyl or phenyl amide or combinations thereof. If required, excellent dispersions of the free vinylsulphone form may be prepared by heating the water soluble versions at 98°C, pH 8, for 15 minutes in the presence of an anionic dispersant (e. g. lignin sulphate).
Compounds (II) and (III) are anionic in character and have substantivity for wool, silk and nylon fibres from neutral to weakly alkaline baths. This has numerous advantages in that the nucleophilicity of the reactive sites in the fibres increases with increasing pH and it is thus easier to covalently bind the sorbed reactive agent than if the agent were sorbed under strong acidic conditions.
Nucleophiles available for the addition reaction with the vinylsulphone residue depend on the fibre to be treated. In wool there are highly reactive thiol residues, slightly less reactive amino residues and much lower reactivity hydroxyl groups. Silk contains amino and hydroxy nucleophiles but the concentration of amino groups in silk is low compared with wool.
Cotton contains relatively weak cellulosate nucleophiles; the C6 primary hydroxyl group and the CZ secondary hydroxyl group in the anhydro-glucose monomer units have been identified as being reactive to reactive dyes and are expected to be involved in covalent reactions with the preferred reactive arylating agents.
However, it is important to adjust the pH of the baths to between pH 10-12 in order to generate sufficiently nucleophilic cellulosate anions which will then react with the vinylsulphone.
The reaction of these arylating agents with fibre nucleophiles may be summarized:
- ~( -NH -- C ~~ \ C - ~ ~ ~ S~z~ C~1" ~1.. + ~ ' ~IW
ll N
v\ L, J
K N _ ~_ 7 ~- Ar - N~ _ L~/~~ ~ -- y --~~~U -- S °Z - C t~ z a tiL -~-~N
N~ ~
H N _ ,.s.r - O
Where fb is the nucleophilic residue.
The compounds of the invention are also useful in the tanning of leather, and the preparation of paper for printing. They may also be used in wood treatments to render the wood more hydrophobic and receptive to subsequent treatment e.g. with dyes, preservatives, etc. In addition they may be used for hair treatments e.g. prior to colouring with disperse dyes, and may give improved heat settability.

The invention will be illustrated further by the following non-limiting Examples.
Pret~aration of Fibre Arylating A . ents The chemicals used throughout the following preparations were laboratory grade unless otherwise stated.

Sodium 1-12,4-dianilino-s-triazin-6y1)-aminobenzene-3 sulphatoethylsulphone ~(FAA100~
Aminobenzene-3-sulphatoethylsulphone (0.1 mole) was dissolved in water (200n1s) and the pH adjusted to 5.5 with sodium carbonate.
This solution was then cooled to 0-5°C in an ice/salt bath. To this vigorously stirred solution was added dropwise a solution of cyanuric chloride (0.1 mole) in acetone (100m1s). The pH was maintained at pH 5.5 by additions of sodium bicarbonate solution as required, whilst maintaining the temperature at 0-5°C. The reaction was judged to be complete after about 45 minutes when no further change in pH was observed. The ice bath was removed and replaced with a heating mantle. The temperature was raised to 35°C, and aniline (0.1 mole) was dripped into the solution.
Again the pH was maintained at pH 5.5 with additions of sodium carbonate solution, as required. The reaction was judged to be complete after about 45 minutes when no further changes was observed in the pH of the mixture. The reaction temperature was raised to 90°C, and a further equivalent of aniline (0.1 mole) was added dropwise, as before, while maintaining the pH at 5.5.
The reaction was again judged to be complete after about 45 minutes when no further change in pH was observed. The product a was isolated by the addition of 20% w/v sodium chloride. The off-white solid this isolated was filtered and dried under vacuum overnight. The product was found to have good water solubility at room temperature.

SO~CZHi0S03 CI CI
H N + H~K 0-SeC~ H _i S07C~H~OS03 =o~ ~
C ! ~K~C I C I ~H~H 1t ~ + H C I
~KH~ KH
C h w SO=C~Hi0SG3 Kc~
90~C (( )}--KH~k~r:k' ~ + ?HC I

Sodium 1-(2.4-dianilino-s-triazin-6v1)-aminobenzene-4-sulphatoethvlsulphone (FAA200) The method of Example 1 was followed, but in this case aminobenzene-4-sulphatoethylsulphone (0.1 mole) was used in place of aminobenzene-3-sulphatoethylsulphone, and the pH was maintained below 5 during the final stage of the synthesis. A
water soluble product was again produced.

Sodium 1-~2-anilino-4-aminocarbazole-s-triazin-6v1)-aminobenzene-4-sulbhatoethylsulphone (FAA300) The method of Example 2 was followed, but in this case 3-aminocarbazole (0.1 mole) was used in place of aniline for the second substitution at 35°C. A water soluble product was produced.

Sodium 1-~2-anilino-4-aminophenol-s-triazin-6y1)-aminobenzene-4-sulnhatoeth_ylsulphone (FAA400) The method of Example 2 was followed, but .in this case 0-aminophenol (2x 0.1 mole) was used in place of aniline. A water soluble product was produced.

Evaluation of Fibre Arylating Agents EgAMPLE 5 A range of commercially available disperse dyes was selected and applied at 2% owf to the wool fabric in the presence of 5% and 10% owf of FAA100. The dyebaths were buffered to pH7 using sodium acetate/acetic acid buffers (3g1-'). Hydrogen peroxide (2m1/1,27%w/v) and Briquest 422-33N (2m1/1, Albright & Wilson Ltd) was also added to the dyebaths in order to prevent reduction of the disperse dyes during the dyeing process.
100°C
2°C/min 60 mins A = Fibre Arylating Agent B = Buffer (pH7)/Peroxide (2m1/1) mins C = Dyes 40°C D = Fabric 1 t t t A B C D
Method for Fibre Arylation/Disperse Dyeing of Wool The following table give the trade names of the dyes used:
D a No Trade Name , " C.I.Number 1 Serene Dis arse Red 50 Dis arse Red 50 2 Serene Dis arse Scarlet M3L5 -3 Serene Disperse Oran a 25 Dis arse Orange 25 4 Serene Dis arse Blue BGFN -5 Serene Dis arse Violet Dis arse Violet 6 Dispersol Red D-38 {Zeneca) Dis arse Red 167:1 7 Dis ersol Na D-3GR (Zeneca Dis arse Blue 79:1 8 Dis ersol Red B-2B (Zeneca) Disperse Red 60 9 Dispersol Yellow C-5G (Zeneca) Disperse Yellow 119 On completion of the dyeing, the fabrics were washed thoroughly in hot {50°C), soapy water to remove any surface dye. The range of dyes was also applied to 100% polyester fabric at 2% owf depth of shade under normal disperse dyeing conditions (45 mins. at 130°C, pH6) in order to produce a range of standards for comparison with the wool fabric dyeings.
The depth of shade of the resultant dyeings was assessed by measuring the summed, visually weighted K/S function, fk. This is a more relevant figure than the K/S of the dyed fabric at the absorption maximum, since the latter does not take into account any hue change, fk is a much more accurate representation of the experience of the observer, taking into account as it does the entire visible spectrum.
WOOL DYEINGS

Dye PES 0% 5% 10%
Std. FAA 100 FAA 100 FAA 100 1 159.3 50.3 120.0 169.6 2 149.7 43.9 123.4 159.7 3 130.8 22.6 42.1 82.6 4 37.8 11.9 30.8 34.0 74.0 14.4 20.7 28.1 6 127.3 47.6 105.9 128.4 I

7 136.1 37.4 81.2 117.1 8 72.1 14.7 21.3 32.3 9 72.7 11.5 51.3 59.8 fk Values of Wool and Polyester Disperse Dyeings As the above figures demonstrate, the application of the FAA100 results in a significant improvement in depth of shade over the untreated fabric. The resultant disperse dyed wool fabrics were similar in depth of shade to the dyed polyester fabric standards.
Increasing the level of arylating agent from 5% owf to 10% owf results in even deeper dyeings, with almost total exhaustion of the disperse dyebaths.

A range of commercially available disperse dyes was selected and applied at 2% owf to 60/40 wool/polyester fabric in the presence of 5% owf and 10%owf FAA100. The dyebaths were buffered to pH7 using sodium acetate/acetic acid buffers (3g1-'). Hydrogen peroxide (2m1/1, 27%w/v) and Briquest 422-33N (2m1/1, Albright &
Wilson Ltd) was also added to the dyebaths as per Example 5. On completion of the dyeing, the fabrics were washed thoroughly in hot (50°C), soapy water to remove any surface dye. The range of dyes was also applied to 100% polyester fabric at 2% owf depth of shade under normal disperse dyeing conditions (45 mins. at 13o°C, pH6) in order to produce a range of standards for comparison with the wool blend dyeings. The depth of shade of the resultant dyeings was assessed by measuring the K/S function, fk for each sample.
12 0°C
2°C/min 40 mins A = Fibre Arylating Agent/Dyes B = Buffer (pH7) mins C = Peroxide/Briquest (2m1/1) 60°C D = Fabric i T T T
w A B C D
Method for Fibre Arylation/Disperse Dyeing of Wool/Polyester Blend The dyeings thus produced were subjected to wash fastness. testing (IS02) and dry rub testing. The following table gives the trade names of the dyes used:
Dye No Trade Name C.I.Number 1 Serene Dis erse Red 202 Disperse Red 202 2 Serene Disperse Oran a 30 Disperse Orange 30 3 Serene Disperse Yellow 114 Disperse Yellow 114 4 Serene Dis erse Yellow ERF -Serene Disperse Blue BGFN -6 Serene Disperse Violet 26 Disperse Violet 26 7 Serene Disperse Black BGLS -8 Dispersol Red D-3B (Zeneca) Disperse Red 167:1 9 Dis ersol Yellow B-6G (Zeneca) Disperse Yellow 218 Dis ersol Navy D-3G (Zeneca) Disperse Blue 79:1 I1 Dispersol Navy ZF (Zeneca) -12 Dispersol Black ZF (Zeneca) -13 Dispersol Red C-BN (Zeneca) Dis erse Red 356 14 Dis ersol Scarlet D-SF(Zeneca) Disperse Red 367 Dispersol Red 4G PC (Zeneca) -16 Dispersol Yellow 7G PC(Zeneca) -17 Dis ersol Blue R PC (Zeneca) -18 Dis ersol Brown 3G PC (Zeneca) -19 Dispersol Black R PC (Zeneca) -Dis ersol Navy G PC (Zeneca) -21 Dis ersol Na 5R PC (Zeneca) -22 Dispersol Orange G PC (Zeneca) -23 Dis ersol Rubine 3B PC(Zeneca) -24 Polycron Yellow 10GF Disperse Yellow 82 (Hollida s) Polycron Blue GLP (Hollidays) Dis erse Blue 60 26 polycron Brill. Red G Disperse Red 277 (Hollidays) WOOL/POLYESTER
DYEINGS

Dye PES 0% 5% 10%
Std. FAA 100 FAA 100 FAA 100 1 139.1 69.9 109.3 111.3 2 120.4 63.7 80.0 87.12 3 69.0 28.4 54.4 58.8 4 78.2 35.1 47.2 51.4 5 37.8 26.1 42.6 40.4 6 74.0 30.8 40.5 59.3 7 132.5 61.5 124.3 129.2 8 127.3 72.7 120.6 118.5 9 78.2 50.0 79.3 77.9 10 136.1 94.5 128.2 126.6 11 149.7 71.9 129.1 133.6 12 151.3 99.8 104.6 112.1 13 70.9 15.1 24.6 35.0 14 68.7 23.3 36.7 58.9 15 114.6 54.8 79.7 95.2 16 68.5 12.0 44.9 55.0 17 109.1 18.9 47.9 59.3 18 117.2 43.4 56.5 61.4 19 105.3 61.7 95,7 93,g 110.1 61.5 129.5 119.9 21 101.2 51.2 117.9 110.2 22 55.6 38.4 64.1 61.7 23 105.7 47.5 124.6 117.0 24 57.3 39.3 47.3 49.2 39.6 19.2 23.2 25.8 26 33.4 25.1 31.3 37.9 fk Values of Wool/Polyester Disperse Dyeings The above f figures demonstrate a considerable improvement in depth -of shade of the FAA treated fabrics over the untreated fabric.
An average increase in K/S (fk) of 72% is observed for the 5% owf treated fabric over the untreated fabric, with some dyes showing increases in the depth of shade in excess of 100% (dyes 7, 16, 17, 20, 21, 23). Increasing the Level of FAA applied to 10% owf results in the average % increase in depth of shade rising 96% "
(i.e. doubling the amount of FAA applied only results in an increase in the depth of shade of 33%) and in some dyes (5, 8, 9, 10, 19, 20, 21, 22, 23) better colour yields were obtained a the 5% level. In general the dyeings were also brighter at the lower FAA level. It would thus seem that an application level of around 5% Owf is the ideal FAA level for the purpose of disperse dyeing wool/polyester blend fabric.
FASTNESS TESTING
The results of wash testing (IS02) on the dyed treated fabric (5%
and 10% owf FAA100) are given below. SDC multifibre test fabric was used for the tests, and ISO Grey Scales were used to evaluate staining and change in colour. Staining on nylon adjacent is quoted as this was the most critical. As may be seen from the figures, staining on nylon is generally around 3-4 with both 5%
and 10% owf FAA 100. Colour change is on average 4-5, again for both FAA application levels. Dry rub testing was performed on the dyed fabrics, and produced extremely good results on the 5%
owf FAA treated samples (4-5 in all cases) . Rub test results on the 10% owf FAA treated fabrics were generally around 1 point lower (worse) on the grey scale compared to the 5% FAA samples.
This suggests that at this higher application level surface deposition of the dye is becoming a problem. This would also account for the previously noted decrease in brightness of the dyeings at the higher FAA level.

Dye Staining Colour Staining Colour on Nylon Change on Nylon Change 5% FAA 100 5% FAA 100 10% FAA 10% FAA 100 Wash Fastness Test Results for FAA-Treated, Disperse Dyed Wool/Polyester Fabric (Dyes as previously coded) I00% wool fabric was treated at pH 7 in a bath containing 10%owf FAA100. The bath temperature was raised to the boil and maintained at this temperature for 1 hour. The fabric was then removed from the bath and rinsed thoroughly in cold water. As a control, an identical sample of wool fabric was similarly treated, but in the absence of the FAA100. After drying, the FAA
treated wool exhibited much better handling properties than the untreated sample: the control fabric was harsh, considerably yellowed and showed evidence of shrinkage during the treatment.
In contrast, the FAA treated wool exhibited no such harshness, yellowing or shrinkage.

The method of Example 5 was followed, but using FAA200 (see example 2) as the arylating agent. Again, dyeings of excellent depth and brightness were produced which exhibited good fastness to both wet and dry treatments.

The method of Example 6 was followed, but using FAA200 (see example 2) as the arylating agent. Again, dyeings of excellent depth and brightness were produced which exhibited good fastness to both wet and dry treatments.

The method of Example 6 was followed, but using FAA300 (see example 3) as the arylating agent. Again, dyeings of excellent depth and brightness were produced which exhibited good fastness to both wet and dry treatments.

The method of Example 6 was followed, but using FAA400 (see example 4) as the arylating agent. Again, dyeings of excellent depth and brightness were produced which exhibited good fastness to both wet and dry treatments.

The method of Example 6 was followed, but in this case the initial dyebath was set at pH 5, and the dyebath temperature was held at 80°C for 10 minutes. At the end of this period the bath pH was readjusted to 6.5 - 7 and the temperature raised to 120°C
for 40 minutes, as before. The dyeings thus produced were extremely level, and of an excellent depth and brightness.
Again the dyeings showed excellent fastness to both wet and dry treatments.

The method of Example 6 was followed, but in this case the disperse dye (2% owf) and FAA200 (5% owf) was applied to a 60/40 wool/polyester yarn package. In addition, 5g1-1 Matexil DA-AC
(I.C.I) dispersant was added at the start of the dyeing. The resultant level dyeing was of an excellent depth and brightness, with almost total exhaustion of the disperse dyebath and no evidence of surface deposition of the dye/FAA on the package surf ace .

A range of commercially available disperse dyes was selected and applied at 2% owf to 100% wool fabric in the presence of a dispersion of 5% owf of the activated vinylsulphone form of FAA200. This was achieved as follows. The calculated amount of the water-soluble arylating agent was dissolved in water in the presence of 20% w/w of an anionic dispersing agent, Matexil DA-AC (I.C.I.). The pH of the solution was adjusted to pH8 and the temperature was then raised to the boil and held for 1 hour.
The resulting fine FAA dispersion was used in the disperse dyeing of the wool fabric, following the method of Example 5. The resulting dyeings were of excellent depth and brightness, and exhibited good fastness to both wet and dry treatments.

A range of commercially available disperse dyes was selected and applied at 2% owf to 60/40 wool/polyester fabric in the presence of a dispersion of 3% owf of the activated vinylsulphone form of FAA200. The activated FAA200 dispersion was prepared as outlined in Example 14, and the wool/polyester fabric was disperse dyed following the method of Example 6. The resulting dyeings were of exceptional depth and brightness and exhibited excellent fastness to both wet and dry treatments.

The method of Example 15 was followed, but in this case the disperse dye (2% owf) and activated FAA200 dispersion (3% owf) was applied to a 60/40 wool/polyester yarn package. The dyeing method was adjusted as follows: on reaching a temperature of 80°C, the dyebath was held at this temperature for 20 minutes.
The temperature was then raised to 120°C and held for 40 minutes as before. The resultant level dyeing was of an excellent depth and brightness, with total exhaustion of the disperse dyebath.
Again, the dyeing exhibited excellent fastness to both wet and dry treatments.

100% wool fabric was treated in a bath at pH 6, containing either 5%, 10% or 15% owfFAA200 hydrogen peroxide (2m1/1) and Briquest 422-33N (2m1/1). The bath temperature was raised to the boil and maintained at this temperature for 1 hour. The fabric was then removed from the bath and rinsed thoroughly in hot (50°C) running water. A sample of each treated fabric was then immersed in a bath at pH 3 and at 80°C, containting 5g/1 Uvinul MS-40 (BASF), a water soluble benzophenone-based UV absorber.
The samples were treated thus for 20 minutes, then removed from the bath and rinsed in warm water. After dying, all the wool samples (both with and without Uvinul MS-40 aftertreatments) were subjected to light fastness testing to Standard 5 using SDC Blue Wool Standards in a Microscal Light Fastness Tester.
On removal from the light fastness tester it was noted that all the samples which had not been aftertreated with the Uvinul MS-40 were subject to quite severe photoyellowing, while those which had been given the Uvinul MS-40 aftertreatment displayed very little, if any, photoyellowing.

A range of commercially available disperse dyes (Teratop from CIBA) was selected and applied at 2% owf to 60/40 wool/polyester fabric in the presence of 5% owf FAA200. The dyebaths were buffered to pH6 (sodium acetate/acetic acid buffer), and hydrogen peroxide/Briquest 422-33N ws added to the dyebaths as per Example 5. The dyeing was commenced at 40°C, raising to 80°C at 2°C/min, holding at this temperature for 20 minutes and then raising to 120°C at 2°C/min. The dyebaths were maintained at this temperature for 40 minutes. On completion of the dyeings, the dyed fabric was removed from the dyebaths and rinsed thoroughly in hot (50°C) running water. A sample of each dyed fabric was then immersed in a bath at pH3 and at 80°C, containing 5g/1 Uvinul MS-40 (BASF). The samples were treated thus for 20 minutes, then removed from the bath and rinsed in warm water.
After drying, all the samples (both with and without Uvinul MS-40 aftertreatments) were subjected to light fastness testing to Standard 5 using SDC Blue Wool Standards inla Microscal Light Fastness Tester.

The following table lists the disperse dyes used in this example:
DYE NO. TRADE C. I.
NAME NUMBER

1 Teratop Yellow GWL -2 Teratop Violet BL Disperse Violet 3 Teratop Pink 2GLA Disperse Red 86 4 Teratop Blue HLB -Teratop Navy 2RLA Disperse Blue 77 6 Teratop Red GSLA Disperse Red 279 7 Teratop Black RLA-02 -8 Teratop Blue BGE Disperse Blue 60 9 Teratop Blue BLF Disperse Blue 56+62 Teratop Yellow NFG -11 Teratop Red HLR -12 Teratop Blue GLF -13 Teratop Pink 3G -The following light fastness values were obtained:
DYE NO. 5% owfFAA200 ONLY 5%owfFAA200 + Uvinul MS-40 Light Fastness Values of Wool/Polyester Disperse Dyeings The above figures demonstrate the importance of the UV absorber in the system where good light fastness of the resulting dyed fabric is required. The inclusion of the UV absorber results in dyed fabrics with an average light fastness of 5 (measured against Blue Wool Standards), whereas without the UV absorber the average light fastness value is 4.

100% wool fabric was treated at pH6 in a bath containing 5%, 10%, 15% and 20% owf FAA200 and hydrogen peroxide/Briquest 422-33N
(2m1/1). The fabric was entered into the bath at 40°C and the bath temperature raised to the boil at 2°C/min. The bath was maintained at this temperature for 1 hour, after which the fabric was removed and washed thoroughly in warm (50°C) running water.
The treated fabrics were subjected to three consecutive Wascator 5A wash cycles (IWS Test Method 31), equivalent to 25-30 domestic Woolmark wash cycles, and the fabric area shrinkage measured.
These results were compared with untreated wool fabric which was washed alongside the treated fabrics, and are shown in the following table and graph:
1 Wash Cycle 2 Wash Cycles - 3 Wash Cycles - % Area -Area Shrinkage % Area Shrinkage Shrinkage Untreated 8.4 16.2 23.2 5%FAA200 5.0 10.8 14.9 10%FAA200 3.6 7.1 15%FAA200 2.3 5,0 ~,1 20%FAA200 2.0 4.1 6.3 Area Shrinkage for FAA200-Treated Wool Fabric i i a~
v~
~o ~ 15 -c L

Area Shrinkage for FAA200-Treated Wool Fabric (After 3 Wash Circles ) After three wash cycles the untreated fabric has shrunk by over 23%, while the fabric treated with 20o FAA200 has shrunk by only 6.3%. This equates to a 73o reduction in fabric area shrinkage clearly demonstrating the effect of the arylating agent.

°r6 FAA200

Claims (21)

25

1. A compound of the formula:
wherein : R1 and R2 each, independently, represent arylamino, diphenylamino, benzylamino or dibenzylamino, and Z represents a leaving group.

2. A compound as claimed in claim 1 in which the group -SO2-CH2-CH2-Z is a blocked vinylsulphone or a free vinylsulphone.

3. A compound as claimed in claim 2 in which the leaving group Z comprises sulphato (-OSO3-), S-thiosulphato (-SSO3-), Sarcosine, N-methyltaurine, N,N-dialkyl acetate (-O-CO-CH3), acyloxy (-O-CO-R, where R is alkyl e,g, C1-C5), phosphato (-OPO-3), or a halogen.

4. A compound as claimed in any of claims 1 to3 in which the compounds R1 and R2, and the aromatic ring shown in Formula I, are substituted by substituents not interfering with the reactive moiety, e.g. by alkyl or alkoxy groups or by chlorine atoms.

5. A compound according to claim 1 in which the arylating agent contains one or more benzene residues and is covalently bonded to the fibre by nucleophilic addition at the vinylsulphone group.

6. A compound according to claim 5 having the formula:

7. A compound according to claim 5 wherein the sulphato group is replaced by an S-thiosulphato group, a phosphato group, a sarcosinate group or an N-methyl-taurine residue.

8. A method of making fibre reactive arylating agents of general formula I which comprises condensation of a halogenoheterocyclic compound of general formula IA
wherein Hal represents a chlorine, bromine or fluorine atom and two of the Y's represent nitrogen atoms and the other Y nitrogen or a carbon atom carrying a hydrogen atom or a chlorine atom or a cyano group, with an amine of general formula H2N-Ar-SO2-CH2CH2Z, where Ar is an aromatic ring, and reacting the product with an aromatic amine of general formula IB and then with a further amine of general formula IB:-D-Ar-NH2 (IB) where Ar is an aromatic ring, and D is hydrogen, halogen, cyano, substituted amino, alkyl, alkoxy, aryl or alkylaryl.

9. A method as claimed in claim 8 wherein the halogenoheterocyclic compounds are selected from cyanuric chloride, cyanuric bromide, cyanuric fluoride, trifluoro pyrimidine, trichloropyrimidine, tetrachloropyrimidine, 5-chloro-2,4,6-trifluoropyrimidine and 5-cyano-2,4,6-trichloro-pyrimidine.

10. A method as claimed in either of claims 8 or 9 wherein the amines of general formula IB there are selected from aniline, p-chloroaniline, 2,5-dichloroaniline, p-anisidine, p-phenetidine, p-toluidine, 2,4-dimethylaniline, 2,4,5-trimethylaniline, p-butylaniline, p-dodecylaniline, p-aminoacetanilide, N-methylaniline, N-butylaniline, p-aminobenzonitrile, p-benzylaniline, 4-aminobiphenyl, .alpha.-naphthylamine, 2-ethoxy-1-aminonaphthalene.

11. A method of treating natural (proteinaceous, polyamide and cellulosic) textile fibres and synthetic polyamide fibres to enhance their affinity for disperse dyestuffs which comprises treating the fibres with an aqueous solution or aqueous dispersion of fibre reactive arylating agent of formula (I) or, alternatively, applying a dispersion of the pre-formed reactive vinylsulphone form of the arylating agent.

12. A method as claimed in claim 11 wherein the fibre reactive arylating agent is reacted with the textile material under conditions of pH and temperature analogous to those used in the application of reactive dyes to textile materials.

13. A method as claimed in any of claims 10 or 11 in which the treatment is carried out prior to or simultaneously with dye application.

14. A method as claimed in any of claims 10 to 13 in which a fibre substantive, sulphonated benzophenone uv absorber is employed to increase the photostability of the treated product.

15. A method as claimed in claim 14 in which the UV absorber is applied simultaneously or as an aftertreatment.

16. A method as claimed in any of claims 11 to 15 wherein the amount of arylating agent employed is between 2 and 20% on weight of fibre (o.w.f).

17. A method as claimed in any of claims 11 to 16 in which amino-triazinyl reactive arylating agents are applied either by exhaustion from long liquors, or by padding.

18. A method as claimed in claim 17 in which the arylating agent is applied from long liquor and is dissolved or dispersed in water, optionally in the presence of an anionic dispersing agent and a buffer, the textile material is immersed in the bath which is raised to the necessary treatment temperature and held at this temperature for a period of from 10 minutes to 2 hours.

19. A method as claimed in claim 17 wherein the arylating agent is applied by padding and the agent is dispersed or dissolved in water optionally together with a swelling agent for the textiles, for example urea, and a thickener.

20. A method according to claim 17 wherein the agent is applied by a pad~dry procedure and fixed during the sublimation transfer printing process (30 secs - 60 secs at 180-210°C).

21. A composition comprising: a disperse dye, an anionic dispersing agent, and an arylating agent according to any of claims 1 to 7.