KR20000075922A - Textile treatment - Google Patents

Abstract

This invention is a compound of following formula (I).

(I)

Here, R ¹ and R ² each represent an arylamino, diphenylamino, benzylamino or dibenzylamino group, and Z is a leaving group. Generally the group -SO ₂ -CH ₂ -CH ₂ -Z is a blocked vinylsulfone and in some cases it is advantageous to use free vinylsulfones. The leaving group Z is, for example, sulfatoethylsulfonyl (-OSO ₃ ^-), S- thio sulfatoethylsulfonyl (-SSO ₃ ^-), Sako new (Sarcosine), N- methyl taurine, N, N- di-alkyl acetate ( -O-CO-CH _3), and acyloxy (-O-CO-R, wherein, R is alkyl, e.g., C ₁ -C _5), phosphine sulfatoethylsulfonyl (-OPO ₃ ^-), or formed of a halogen Can be. The activity of the leaving group generally produces fiber reactive vinylsulfone by heating in some acid bath. Optionally, the free reactive vinylsulfone can be preformed and applied to the fiber as a dispersant. Compounds of the present invention include one or more aromatic rings where the compound is not substituted with vinylsulfone which may improve pi-bonding. In addition, the pi system of the present invention is planar, which is known to be important by increasing the affinity of the fibers for disperse dyes as well as imparting shrinkage resistance and other properties to the fibers.

Description

Textile treatment

Keratinous fibers such as wool, natural polyamides such as silk and natural cellulosic fibers such as cotton do not generally exhibit any characteristic affinity for disperse dyes. Retrying to dye these fibers with disperse dyes results in poor color yield, dull shades, and poor wet and light fastness. Disperse dyes are widely used in synthetic fibers such as polyesters and are therefore generally useful. In addition, disperse dyes are often sublimated and form the basis of the well-known "transfer printing" process of printing designs on paper using dyes, which then place the paper and fabric together, It can be used one after the other mainly for coloring textile fabrics by heating in pressure at 180-220 ° C. for a period of time, typically 0.5 minutes (French Patent No. 1,223,330).

Synthetic polyamide fibers (“nylons”) have moderate affinity for disperse dyes, but the wash fastness of dyeing and the printing of these dyes on substrates are not appropriate, which is in fact weak in dye-fiber interactions. Indicates.

The present invention provides a method for improving the affinity of these fibers for disperse dyes and for producing highly wet and high wet-fast dyeing and printed materials. The present invention also provides novel compounds useful in these methods. US-A-4563189 describes certain arylating agents for this purpose. The present invention represents an improvement in the formulations claimed herein. The compounds of the present invention further impart shrinkage resistance and facilitate property management of the fibers.

The present invention relates to a textile processing method. More particularly, it relates to a process for treating cellulose, keratin and polyamide textiles to increase their affinity for disperse dyes and novel compounds therefor.

According to the present invention there is provided a compound of formula (I).

Equation I

Here, R ¹ and R ² each represent an arylamino, diphenylamino, benzylamino or dibenzylamino group, and Z is a leaving group.

In general, the group —SO ₂ —CH ₂ —CH ₂ —Z is a blocked vinylsulfone, and in some cases, it is advantageous to use free vinylsulfones. The leaving group Z is, for example, sulfatoethylsulfonyl (-OSO ₃ ^-), S- thio sulfatoethylsulfonyl (-SSO ₃ ^-), Sako new (Sarcosine), N- methyl taurine, N, N- di-alkyl acetate ( -O-CO-CH _3), and acyloxy (-O-CO-R, wherein, R is alkyl, e.g., C ₁ -C _5), phosphine sulfatoethylsulfonyl (-OPO ₃ ^-), or formed of a halogen Can be. The activity of the leaving group generally produces fiber reactive vinylsulfone by heating in a slight acid bath. Optionally, the free reactive vinylsulfone may be preformed and applied to the fabric as a dispersant.

The compounds of the present invention are improved arylating agents for US-A-4563189 which describe that the compound contains one or more aromatic rings that are not substituted with vinylsulfone which can improve pi-bonding. In addition, the pi system of the present invention has been found to be planar, which not only increases the affinity of the fibers for disperse dyes but also imparts shrinkage resistance to the fabric and other properties. In the above, the compounds R ¹ and R ² and the aromatic rings shown in formula I may be substituted by substituents which do not interfere with the reactive moiety, for example alkyl or alkoxy groups or chlorine atoms.

The fiber reactive arylating agent of formula I condenses the halogenoheterocyclic compound of formula IA with the amine of formula H ₂ N-Ar-SO ₂ -CH ₂ CH ₂ Z, wherein Ar is an aromatic ring , A product having an aromatic amine of formula IB can be prepared by reacting with another amine of formula IB.

Formula IA

Here, Hal represents a chlorine, bromine or fluorine atom, two of Y represents a nitrogen atom, and the other Y represents a nitrogen or carbon atom having a hydrogen atom, or a chlorine atom or a cyano group.

Formula IB

D-Ar-NH ₂

Wherein Ar is an aromatic ring and D is hydrogen, halogen, cyano, substituted amino, alkyl, alkoxy, aryl or alkylaryl.

Examples of the halogenoheterocyclic compound include cyanuric chloride, cyanuric bromide, cyanuric fluoride, trifluoropyrimidine, trichloropyrimidine, tetrachloropyrimidine, 5-chloro-2,4,6-trifluoropyripy. Midine and 5-cyano-2,4-6-trichloropyrimidine.

Examples of amines of general formula IB include aniline, p-chloroaniline, 2,5-dichloroaniline, p-anisidine, p-phenetidine, p-toluidine, 2,4-dimethylaniline, 2,4,5- Trimethylaniline, p-butylaniline, p-dodecylaniline, p-acetanilide, N-methylaniline, N-butylaniline, p-aminobenzonitrile, p-benzylaniline, 4-aminobiphenyl, α-naphthyl Amine and 2-ethoxy-1-aminonaphthalene are mentioned.

The present invention also provides an aqueous solution or aqueous dispersion of a fiber reactive arylating agent of formula (I) to increase the affinity for natural (protein, polyamide and cellulose) textile fibers and synthetic polyamide fibers to their disperse dyes. Or a dispersant in the form of a preformed reactive vinylsulfone of an arylating agent.

In order to improve the light stability of both the arylated and dyed and arylated substrates, it is preferred that the sulfonated benzophenone UV adsorbent of the fiber material be provided either during manufacture or as a post treatment.

In the treatment, one or two vinylsulfone or blocked vinyl sulfone groups present in the arylating agent react with the nucleophilic center present in the fiber to cause the arylating agent to covalently bond with the fiber. Such treatments include reacting the fiber reactive arylating agent under pH and temperature conditions similar to those used to apply textile materials and reactive dyes to textile materials. Such conditions are well known to those skilled in the art. Particularly preferred when Z is an anionic water soluble group, the arylating agent is particularly preferred since it is compatible with the anionic dispersants of commercially available disperse dyes. In order to ensure maximum light resistance of dyeing, it is also preferred that water-soluble UV adsorbents are included in the preparation (eg Uvinul. MS-40 [BASF] -sulfonated benzophenone).

The treatment can be done before or simultaneously with the application of the dye.

According to another aspect of the invention, there is provided a composition consisting of a disperse dye, an anionic dispersant and an arylating agent as defined above.

The arylating agent comprises at least one benzene moiety and is covalently bound to the fiber by nucleophilic addition in a vinylsulfone group. Such a preferable compound has the following formula.

Equation II

Optionally, the sulfato group can be replaced by an S-thiosulfato group, a phosphate group, a sacosinate group or an N-methyl-taurine residue.

The amount of arylating agent provided is preferably from 2 to 20% by weight of the fiber.

In particular, useful arylating agents have the structure of formula (II) above.

The compounds are extremely reactive to silk, wool and nylon under water soluble, anionic and neutral to weakly acidic conditions, and their substantivity to these fibers is also excellent. In the case of polyamide fibers, when applied with disperse dyes, for example by a simple method of raising the temperature until boiling at pH about 6.5 and holding at that temperature for 1 hour, excellent brilliance, color yield ) (Water-white dye-bath consumption) and color fastness are obtained. Optionally, co-application by a padding process can be done by immobilization or thickening of the disperse dyes and arylating agents that occur simultaneously with the dyeing. Immobilization on cotton is promoted at 60 ° C. for 1 hour at alkaline conditions, for example pH 10.5.

Preferred amino-triazinyl reactive arylating agents can be applied from the long liquor by exhaustion or by padding. In the former case, the arylating agent is dissolved or dispersed in water, optionally in the presence of an anionic dispersant and a buffer. The textile material may be warmed to the required processing temperature and soaked in a bath kept at this temperature for a period of time, for example for 10 minutes to 2 hours. When arylating agents are applied by padding, the formulations are dispersed or dissolved in water, optionally with swelling agents for textiles such as urea and thickening agents. When cellulose fibers are treated, alkalis such as trisodium phosphate must also be included in the liquid. The fabric or material is padded to fix the reactant, steamed, baked and then washed to remove the unfixed arylating agent. Optionally the fabric or material is padded with a reactive agent and treated to allow reaction for up to 48 hours and then washed to remove unfixed reactant. In another aspect of the invention, the formulation is simply applied by a pad-dry procedure and fixed during the sublimation transfer printing process (30 seconds-60 seconds at 180-210 ° C.).

The arylating agent can be conveniently made into any suitable compound according to formula (I) (or in its free vinylsulfone form), which comprises an optionally blocked vinylsulfone group reactive with at least two benzene rings. Such compounds are conveniently prepared by reacting a water soluble halo-s-triazine with a selected aromatic amine comprising blocked vinylsulfone residues. The reaction product becomes water soluble by the introduced sulfato or S-thiosulfato residues. The following scheme illustrates this reaction.

Scheme III

Here, Ar, Z and D have the above meaning, and X is halogen. In particular, D is hydrogen, phenyl or phenyl amide or a combination thereof. If desired, a good dispersible free vinylsulfone form can be prepared by heating the water soluble version at 98 ° C., pH 8, for 15 minutes in the presence of an anionic dispersant (eg lignin sulfate).

Compounds (II) and (III) are anionic in nature and have realism to wool, silk and nylon fibers in neutral to about alkaline baths. This has a great advantage in that the nucleophilicity of the reactive site in the fiber increases with increasing pH, and therefore it is easier to covalently bind the absorbed reactive agent than when the agent is absorbed under strong acidic conditions.

Useful nucleophiles for addition reactions to vinylsulfone residues depend on the fibers being treated. In the parent, there are high reactive thiol residues, slightly less reactive amino residues and much lower reactive hydroxyl groups. Silk includes amino and hydroxy nucleophiles but the concentration of amino groups in the silk is low compared to the parent. Cotton contains relatively weak cellulosate nucleophiles. It is confirmed that the C ₆ primary hydroxyl group and the C ₂ secondary hydroxyl group in the anhydroglucose monomer unit become reactive with the reactive dye and are included in the covalent reaction with the preferred reactive arylating agent. However, adjusting the pH of the bath to 10-12 is important for producing sufficiently nucleophilic cellulose acetate anions that are subsequently reacted with vinylsulfone.

Reaction of these alkylating agents and fiber nucleophiles is shown below.

Is a nucleophilic moiety.

The compounds of the invention are also useful for tanning leather and for the production of printing paper. They are more hydrophobic and can be used in wood treatment to provide wood that is well accepted for treatment with post-treatments such as dyes, preservatives and the like. In addition, they can be used before hair treatment, for example coloring with disperse dyes, and improved heat fixation is provided.

The invention is illustrated in more detail by the following non-limiting examples.

Preparation of Fiber Arylating Agent

Chemicals used throughout the following manufacturing are laboratory grade unless otherwise indicated

Example 1

1- (2,4-Dianilino-s-triazin-6yl) -aminobenzene-3-sulfatoethylsulfone sodium (FAA100)

Aminobenzene-3-sulfatoethylsulfone (0.1 mol) was dissolved in water (200 nls) and the pH was 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 cyanuric chloride solution dissolved in acetone (100 mls). Sodium bicarbonate solution was added as needed to maintain the temperature at 0-5 ° C. while maintaining the pH at 5.5. The reaction was judged complete after about 45 minutes, when no 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 mol) was added dropwise into the solution. Again, sodium carbonate solution was added if necessary to maintain the pH at 5.5. The reaction was judged complete after 45 minutes, when the pH of the mixture was no longer observed to change. The reaction temperature was raised to 90 ° C. and an equivalent aniline (0.1 mol) was further added dropwise as before while maintaining the pH at 5.5. The reaction was judged complete again after 45 minutes, when no further pH change was observed. The product was isolated by addition of 20% by weight sodium chloride. The isolated off-white solid product was filtered and dried overnight under vacuum. This product was found to have good water solubility at room temperature.

FAA-100

Example 2

1- (2,4-Dianilino-s-triazin-6yl) -aminobenzene-4-sulfatoethylsulfone sodium (FAA200)

Example 1 except that aminobenzene-4-sulfatoethylsulfone (0.1 mole) was used in place of aminobenzene-3-sulfatoethylsulfone and the pH was maintained below 5 during the final stage of the synthesis I followed the way. The water soluble product was prepared again.

Example 3

1- (2-anilino-4-aminocarbazole-s-triazin-6yl) -aminobenzene-4-sulfatoethylsulfone sodium (FAA300)

The method of Example 2 was followed except that 3-aminocarbazole (0.1 mole) was used at 35 ° C. instead of aniline for secondary substitution. The water soluble product was prepared again.

Example 4

1- (2-anilino-4-aminophenol-s-triazin-6yl) -aminobenzene-4-sulfatoethylsulfone sodium (FAA400)

The method of Example 2 was followed except that o-aminophenol (2 x 0.1 mole) was used instead of aniline. The water soluble product was prepared again.

Evaluation of Fiber Arylating Agent

Example 5

A range of commercially available disperse dyes was selected and applied at 2 fibers by weight in wool in the presence of 5 fibers and 10 fibers by weight of FAA. The dye bath was buffered to pH 7 using sodium acetate / acetic acid buffer (3 g / L). In order to prevent reduction of the disperse dye during the dyeing process, hydrogen peroxide (2 mL / 1.27 weight / vol.%) And Briquest 422-33N (2 mL / L, manufactured by All-Blive & Wilson, Inc.) were added to the dye bath. Added.

Method for fiber arylation / dispersion dyeing of wool

The following table shows the trade names of the dyes used.

Dye number Trade name C.I.Number One Serene Disperse Red 50 Disperse Red 50 2 Serene Disperse Scarlet M3L5 - 3 Serene Disperse Orange 25 Disperse Orange 25 4 Serene Disperse Blue BGFN - 5 Serene Disperse Violet Disperse Violet 6 Dispersol Red D-3B (Zeneca) Disperse Red 167: 1 7 Dispersol Navy D-3GR (Zeneca) Disperse Blue 79: 1 8 Dispersol Red B-2B (Zeneca) Disperse Red 60 9 Dispersol Yellow C-5G (Zeneca) Disperse Yellow 119

Upon completion of the dye, the fabric was washed thoroughly with hot (50 ° C.) soapy water to remove other surface dyes. In order to make a range of specimens for comparison with wool dyeing, the dyes in this range were also 100% in 2 fiber weight% depth of shade under normal dispersion dyeing conditions (45 min at 130 ° C., pH 6). Applied to polyester fabrics.

The tint of the obtained dye was evaluated by measuring f _k , which is a summed and visually weighted K / S function. This is a more relevant value than the K / S of the dyed fabric at the absorption maximum, since the latter does not consider any hue shift, and f _k is a more accurate representation of the observer's experience, considering that this is the entire visible spectrum to be.

Dyed hair dyes PES Std. 0% FAA 100 5% FAA 100 10% FAA 100 One 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 5 74.0 14.4 20.7 28.1 6 127.3 47.6 105.9 128.4 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

F _k value of wool and polyester dispersion dyeing

As the above figures demonstrate, the application of FAA100 is significantly improved in lightness over untreated fabrics. The dispersed dyed wool obtained was similar in lightness to the dyed polyester fabric specimens. Increasing the acylating agent concentration from 5% by weight to 10% by weight results in a deeper dye, as almost all disperse dye baths are consumed.

Example 6

A range of commercially available disperse dyes was selected and applied at 60% fiber / polyester fabrics at 2% fiber by weight in the presence of 5% fiber and 10% fiber by weight FAA100. The dye bath was buffered to pH 7 using sodium acetate / acetic acid buffer (3 g / L). As in Example 5, also hydrogen peroxide (2 mL / 1.27 weight / vol%) and Briquest 422-33N (2 mL / L, manufactured by All-Blive and Wilson, Inc.) were added to the dye bath. As the dye was completed, the fabric was washed thoroughly with hot (50 ° C.) soapy water to remove other surface dyes. In order to make a sample range for comparison with the parent mixed dyes, the dyes in this range are also applied to 100% polyester fabrics with a light weight of 2% by weight under normal dispersion dyeing conditions (45 minutes at 130 ° C., pH 6). It was. The lightness of the obtained dye was evaluated by measuring f _k , which is a K / S function, for each sample.

Method for fiber arylation / disperse dyeing of wool / polyester mixtures

The dyeings thus made were subjected to a wash resistance and dry friction test. The following table shows the trade names of the dyes used.

Dye number Trade name C.I.Number One Serene Disperse Red 202 Disperse Red 202 2 Serene Disperse Orange 30 Disperse Orange 30 3 Serene Disperse Yellow 114 Disperse Yellow 114 4 Serene Disperse Yellow ERF - 5 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 Dispersol Yellos B-6G (Zeneca) Disperse Yellow 218 10 Dispersol Navy D-3G (Zeneca) Disperse Blue 79: 1 11 Dispersol Navy ZF (Zeneca) - 12 Dispersol Black ZF (Zeneca) - 13 Dispersol Red C-BN (Zeneca) Disperse Red 356 14 Dispersol Scarlet D-SF (Zeneca) Disperse Red 367 15 Dispersol Red 4G PC (Zeneca) - 16 Dispersol Yellow 7G PC (Zeneca) - 17 Dispersol Blue R PC (Zeneca) - 18 Dispersol Brown 3G PC (Zeneca) - 19 Dispersol Black R PC (Zeneca) - 20 Dispersol Navy G PC (Zeneca) - 21 Dispersol Navy 5R PC (Zeneca) - 22 Dispersol Orange G PC (Zeneca) - 23 Dispersol Rubine 3B PC (Zeneca) - 24 Polycron Yellow 10GF (Hollidays) Disperse Yellow 82 25 Polycron Blue GLP (Hollidays) Disperse Blue 60 26 Polycron Brill. Red D (Hollidays) Disperse Red 277

Wool / polyester dyeing dyes PESStd. 0% FAA 100 5% FAA 100 10% FAA 100 One 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 93.8 20 110.1 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 25 39.6 19.2 23.2 25.8 26 33.4 25.1 31.3 37.9

F _k value of wool / polyester dispersion dyeing

These figures demonstrate that FAA treated fabrics are significantly improved in lightness over untreated fabrics. A 72% average increase in K / S (f _k ) was observed for fabrics treated with 5% fiber by weight over untreated fabrics, with some dyes showing an increase in lightness of 100% excess (dye 7, 16, 20, 21 , 23). An increase in FAA concentration, applied at 10% fiber weight, results in an average% increase, up 96% from lightness (ie doubling the amount of FAA applied only increases the lightness to 33%), Some dyes (5, 8, 9, 10, 19, 20, 21, 22, 23) yielded better color yields at the 5% level. In general, staining was also brighter at lower FAA concentrations. Thus, it can be seen that the application concentration of about 5% by weight of fiber is the ideal FAA concentration for disperse dyeing the wool / polyester blend fabric.

Fastness test

The results of the test for washing (ISO2) in the dyed fabrics (5% fiber and 10% fiber by weight FAA100) are shown below. SDC multifiber test fabrics were used for this test and the color and change of color was assessed using the ISO gray scale. Coloring in adjacent nylon was cited as the most critical. As can be seen from the figures, the coloration for nylon is generally about 3-4 at both 5% and 10% fiber by weight of FAA100. The color change is again on average 4-5 for all FAA applied concentrations. A dry friction test was performed on the dyed fabric, yielding extremely good results (4-5 in all cases) on FAA 5 fiber wt% treated test samples. The friction test results for FAA 10 fiber wt% treated fabrics were generally about 1 point lower (bad) on the gray scale compared to the FAA 5% sample. This suggests that surface deposition of dyes at higher application concentrations becomes a problem. This could also explain the reduction in the sharpness of staining at higher FAA concentrations already noted.

dyes Colorable in nylon 5% FAA 100 Color change 5% FAA 100 Coloring in nylon 10% FAA 100 Color change 10% FAA 100 One 2/3 4 2/3 4 2 4 4/5 4 4/5 3 3 4/5 3 4/5 4 3/4 4 3 4/5 5 4 4/5 4 5 6 3 4/5 2/3 4/5 7 2/3 4 2/3 4 8 2/3 4 3 4/5 9 2/3 5 2/3 4/5 10 3 4/5 3 4/5 11 3 4/5 3 4/5 12 4 4/5 4 4/5 13 4/5 4/5 4/5 4/5 14 4 4/5 4 4 15 3 4 3 4 16 4/5 4/5 4/5 5 17 4 4 3/4 4/5 18 4/5 4/5 4/5 5 19 2/3 4/5 2/3 4/5 20 4 4 4 4/5 21 3 4 3 4 22 4 4/5 4 4/5 23 3 4 3 4/5 24 3 3/4 3/4 4 25 4 4/5 4 4/5 26 3 4/5 2/3 4/5

Wash resistance test for FAA-treated, disperse dyed wool / polyester fabrics (dye described above)

Example 7

100% wool was treated to pH 7 in a dye bath containing 10% by weight FAA100 fiber. The temperature of the dye bath was raised to boiling and maintained at this temperature for 1 hour. The fabric was then removed from the dye bath and rinsed thoroughly in cold water. As a control, the same wool samples were treated similarly except without the FAA100. After drying, FAA treated wool samples showed better handling properties than untreated samples. That is, the control fabric was coarse, significantly yellowed, and there was evidence of shrinkage during the treatment. In contrast, the FAA treated wool showed no roughness, no yellowing, and no shrinkage.

Example 8

The method of Example 5 was followed except that FAA200 (see Example 2) was used as the arylating agent. Again, a good dark and clear dye was made, which showed excellent adhesion for both wet and dry treatments.

Example 9

The method of Example 6 was followed except that FAA200 (see Example 2) was used as the arylating agent. Again, a good dark and clear dye was made, which showed excellent adhesion for both wet and dry treatments.

Example 10

The method of Example 6 was followed except that FAA300 (see Example 3) was used as the arylating agent. Again, a good dark and clear dye was made, which showed excellent adhesion for both wet and dry treatments.

Example 11

The method of Example 6 was followed except that FAA400 (see Example 4) was used as the arylating agent. Again, a good dark and clear dye was made, which showed excellent adhesion for both wet and dry treatments.

Example 12

In this case, the method of Example 6 was followed except that the initial dye bath was set at pH 5 and the temperature of this dye bath was maintained at 80 ° C. for 10 minutes. At the end of this period, the pH of the dye bath was adjusted back to 6.5-7 and the temperature was raised to 120 ° C. for 40 minutes as before. The dyeing thus produced was at an extreme level, excellently thick and clear.

Example 13

In this case the method of Example 6 was followed, except that disperse dyes (2% fiber) and FAA200 (5% fiber) were applied to the 60/40 wool / polyester yarn package. In addition, 5 g / l Matexil DA-AC (I.C.I) dispersant was added at the beginning of the dyeing. The dyeing levels obtained were exceptionally dark and clear, with little evidence of surface deposition of dye / FAA on the package surface as it consumed almost all of the disperse dye baths.

Example 14

A range of commercially available disperse dyes were selected and applied at 100% wool to 2% fiber by weight in the presence of 5% fiber dispersion by weight of the activated vinylsulfone form of FAA200. It was activated as follows. The calculated amount of water-soluble arylating agent was dissolved in water at 20% w / w of anionic dispersant (Matexil DA-AC (ICI), the pH of the solution was adjusted to pH 8, the temperature raised to boiling and at that temperature The fine FAA dispersant obtained was used for the disperse dyeing of the wool according to the method of Example 5. The obtained dyeing had excellent darkness and clarity and showed excellent adhesion to both wet and dry treatments.

Example 15

A range of commercially available disperse dyes was selected and applied at 2 fiber% by weight for wool / polyester fiber 60/40 in the presence of 3 fiber% by weight dispersant in activated vinylsulfone form FAA 200. Activated FAA 200 dispersants were prepared as shown in the overview of Example 13 and wool / polyester fabrics were dispersed and dyed according to the method of Example 6. The dyeings obtained had excellent darkness and vividness, and showed excellent adhesion to both wet and dry treatments.

Example 16

Following the method of Example 15, in this case, disperse dyes (2% fiber) and activated FAA 200 dispersant (3% fiber) were applied for the parent / polyester yarn eye package. The dyeing method was controlled as follows: the temperature was reached at 80 ° C. and the dye bath was kept at this temperature for 20 minutes. The temperature was then raised to 120 ° C. and maintained for 40 minutes as before. The dyeing levels obtained were of good darkness and clarity depending on the overall consumption of the disperse dye baths. In addition, the dyeing showed good adhesion in both the wet and dry treatments.

Example 17

100% wool at pH 6 in a bath containing either 5% fiber, 10% fiber or 15% fiber FAA 200 hydrogen peroxide (2ml / l) and Briquest 422-33N (2ml / l) Treated. The bath temperature was raised to boiling and held at this temperature for 1 hour. The fabric was then removed from the bath and thoroughly washed in hot (50 ° C.) running water. Samples of each treated fabric were then immersed in a bath at pH 3 and 80 ° C. containing 5 g / l Uvinul MS-40 (BASF), a water soluble benzophenone-based UV adsorbent. The sample was then processed for 20 minutes, then removed from the bath and washed with warm water. After staining, all wool samples (with or without Uvinul MS-40 post-treatment) were tested for light resistance with Standard 5 using the SDC Blue Wool Standard from Microscal Light Fastness Tester.

Upon removal from the lightfastness tester, all samples not post-treated with Uvinul MS-40 showed yellowing for very severe light, whereas very little yellowing for light even if post-treated with Uvinul MS-40. .

Example 18

A range of commercially available disperse dyes (Teratop from CIBA) was selected and applied at 2 fiber wt% for wool / polyester fiber 60/40 in the presence of 5 fiber wt% of FAA 200. The dye bath was buffered to pH 8 (sodium acetate / acetic acid buffer) and hydrogen peroxide / Briquest 422-33N ws was added to the dye bath as in Example 5. Dyeing was initiated at 40 ° C., raised to 80 ° C. at 2 ° C./min, held at this temperature for 20 minutes, and then raised to 120 ° C. at 2 ° C./min. The dye bath was kept at this temperature for 40 minutes. Upon completion of the dyeing, the dyed fabric was removed from the dye bath and thoroughly washed with hot (50 ° C.) running water. Samples of each dyed fabric were then immersed in a bath at pH 3 and 80 ° C. containing 5 g / l Uvinul MS-40 (BASF). The sample was treated for 20 minutes, then removed from the bath and washed with warm water. After staining, all samples (with or without Uvinul MS-40 post-treatment) were tested for light resistance with Standard 5 using the SDC Blue Wool Standard from Microscal Light Fastness Tester.

The following table lists the disperse dyes used in this example.

Dye number Trade name C.I.Number One Teratop Yellow GWL - 2 Teratop Violet BL Disperse Violet 57 3 Teratop Pink 2GLA Disperse Red 86 4 Teratop Blue HLB - 5 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 10 Teratop Yellow NFG - 11 Teratop Red HLR - 12 Teratop Blue GLF - 13 Teratop Pink 3G -

The following light resistance values were obtained.

Dye number 5 fiber weight% FAA200 ONLY 5% by weight FAA200 + Uninul MS-40 One 4-5 5 2 4 5 3 5 5 4 4 5 5 3-4 4-5 6 4 5 7 3-4 4-5 8 4 5 9 3-4 5 10 4-5 5 11 4 5 12 3-4 5 13 3-4 4-5

Light Resistance Values of Hair / Polyester Disperse Dyes

These figures show the importance of UV adsorbents in systems where good light resistance of the resulting dyed fabric is required. Inclusion of the UV adsorbent resulted in a dyed fabric having an average light resistance (measured against the Blue Wool Standard) 5, whereas the absence of the UV adsorbent had an average light resistance value of 4.

Example 19

100% wool was treated in a bath containing 5% fiber, 10% fiber or 15% fiber FAA 200 with hydrogen peroxide / Briquest 422-33N (2 mL / L) at pH 6. The fabric was placed in a 40 ° C. bath and raised to a bath temperature of 2 ° C./min. The bath was kept at this temperature for 1 hour, after which the fabric was removed from the bath and thoroughly washed in hot (50 ° C.) running water. The treated fabric was subjected to three consecutive Wascator Woolmark washes (IWS test method 31), corresponding to 25 to 30 home Woolmark washes, to measure fabric area shrinkage. These results were compared to the untreated fabric washed side by side with the treated fabric. The results are shown in tables and graphs.

1 wash-% area shrinkage 2 washes-% area shrinkage 3 washes-% area shrinkage Untreated 8.4 16.2 23.2 5% FAA200 5.0 10.8 14.9 10% FAA200 3.6 7.1 9.7 15% FAA200 2.3 5.0 7.1 20% FAA200 2.0 4.1 6.3

Area shrinkage of FAA200-treated wool

Area shrinkage of FAA200-treated wool (after 3 washes)

After three washes, the untreated fiber contracted at least 23%, whereas the fiber treated with 20% FAA 200 contracted 6.3%. This is equivalent to a 73% reduction in fiber area shrinkage and clearly showed the effect of arylating agents.

Claims (21)

The compound of formula (I) Equation I Here, R ¹ and R ² each represent an arylamino, diphenylamino, benzylamino or dibenzylamino group, and Z is a leaving group. The compound of claim 1, wherein the group —SO ₂ —CH ₂ —CH ₂ —Z is blocked vinylsulfone or free vinylsulfone. The method of claim 2, wherein the leaving group Z is sulfatoethylsulfonyl (-OSO ₃ ^-), S- thio sulfatoethylsulfonyl (-SSO ₃ ^-), Sako new (Sarcosine), N- methyl taurine, N, N- dialkyl acetate _{(-O-CO-CH 3)} , acyloxy (-O-CO-R, where R is alkyl, e.g., C ₁ -C _5), phosphine sulfatoethylsulfonyl (-OPO ₃ ^-), or a halogen Compound consisting of. A compound according to any one of claims 1 to 3, wherein the compounds R ¹ and R ² and the aromatic rings represented by formula I are substituted by substituents which do not interfere with the reactive moiety, for example alkyl or alkoxy groups or chlorine atoms. Compound. The compound of claim 1, wherein the arylating agent is covalently bound to the fiber by nucleophilic addition of one or more benzene moieties and vinylsulfone groups. A compound according to claim 5 having the formula II below. Equation II 6. The compound of claim 5, wherein the sulfato group is replaced with an S-thiosulfato group, a phosphate group, a sacosinate group or an N-methyl-taurine residue. A product having a halogenoheterocyclic compound of formula IA and an amine of formula H ₂ N-Ar-SO ₂ -CH ₂ CH ₂ Z (where Ar is an aromatic ring) and having an aromatic amine of formula IB A process for preparing a fibrous reactive arylating agent of formula (I), comprising reacting with another amine of formula IB. Formula IA Here, Hal represents a chlorine, bromine or fluorine atom, two of Y represents a nitrogen atom, and the other Y represents a nitrogen or carbon atom having a hydrogen atom or a chlorine atom or a cyano group. Formula IB D-Ar-NH ₂ Wherein Ar is an aromatic ring and D is hydrogen, halogen, cyano, substituted amino, alkyl, alkoxy, aryl or alkylaryl. According to claim 8, wherein the halogenoheterocyclic compound is cyanuric chloride, cyanuric bromide, cyanuric fluoride, trifluoro pyrimidine, trichloropyrimidine, tetrachloropyrimidine, 5-chloro-2,4 , 6-trifluoropyrimidine and 5-cyano-2,4-6-trichloropyrimidine. The amine of formula IB according to claim 8 or 9, wherein the amine of formula IB is aniline, p-chloroaniline, 2,5-dichloroaniline, p-anisidine, p-phenetidine, p-toluidine, 2,4- Dimethylaniline, 2,4,5-trimethylaniline, p-butylaniline, p-dodecylaniline, p-acetanilide, N-methylaniline, N-butylaniline, p-aminobenzonitrile, p-benzylaniline, 4 -Aminobiphenyl, α-naphthylamine, 2-ethoxy-1-aminonaphthalene. To increase the affinity for natural (protein, polyamide and cellulose) textile fibers and synthetic polyamide fibers to their disperse dyes, the fibers are treated with an aqueous solution or an aqueous dispersion of a fiber reactive arylating agent of formula (I), or And a dispersant in the form of a preformed reactive vinylsulfone of the arylating agent. The method of claim 11, wherein the fiber reactive arylating agent is reacted with the textile material under pH and temperature conditions similar to those used when applying reactive dyes to textile materials. The method according to claim 10 or 11, wherein the treatment is carried out before or simultaneously with the application of the dye. 14. The method of any one of claims 10 to 13, wherein a fiber tangible sulfonated benzophenone UV adsorbent is provided to increase the light stability of the treated article. The method of claim 14, wherein the UV adsorbents are applied simultaneously or as a post treatment. 16. The method of any one of claims 11-15, wherein the amount of arylating agent provided is 2-20% by weight of the fiber. 17. The method of any one of claims 11-16, wherein the amino-triazinyl reactive arylating agent is applied from the long liquor by wasting or by padding. 18. The arylating agent according to claim 17, wherein the arylating agent is applied from the elongate solution and dissolved or dispersed in the presence of water, optionally anionic dispersant and buffer, the textile material is raised to the required processing temperature and at this temperature for 10 minutes to 2 hours How to be dipped in a set bathtub. 18. The method of claim 17, wherein the arylating agent is applied by padding and the formulation is dispersed or dissolved with water, optionally a swelling agent for textiles such as urea and thickening agents. 18. The method of claim 17, wherein the formulation is applied by a pad-drying process and fixed for a sublimation transfer printing process (30 seconds to 60 seconds at 180 to 210 ° C). A composition consisting of a disperse dye, an anionic dispersant and an arylating agent according to claim 1.