CH689479GA3 - Compounds of the s-triazine series. - Google Patents

Description

The invention relates to compounds of the s-triazine series, which are excellently suitable as UV absorbers for application in the textile field and also give the textile material treated therewith dirt-repellent properties (stain blocking). In addition, the areas of the textile material treated with the new compounds show a reservation for anionic dyes.

The compounds of general formula I

wherein R1 is the radical of an aromatic diamine which optionally bears 1 or 2 substituents or is the radical of a C1-22 aliphatic diamine, which optionally bears 1 or 2 substituents and / or is interrupted by heteroatoms, each R2, independently of one another, denotes a phenyl radical which optionally bears 1 or 2 sulphonic acid groups, each X independently of one another is fluorine, chlorine or bromine, with the condition that each compound contains at least a sulphonic acid group, with the further condition that R1 is not a stilbene radical.

The aromatic radicals mentioned are to be understood as meaning phenyl or naphthyl, in particular phenyl, radicals. As aromatic diamines (R1) e.g. o-, m- or p-phenylenediamine, preferably p-phenylenediamine, but also 2,5-diaminothiophene are possible.

Particularly suitable substituents on the radicals of aromatic character are halogen atoms, preferably chlorine or bromine, methyl, hydroxyl, C1-2-alkoxy, carboxy, alkoxycarbonyl or sulfonic acid groups.

Preferred compounds of the formula I have substituents on the aromatic diamine radical which, independently of one another, are halogen atoms, methyl, hydroxyl, C1-4-alkoxy, carboxy, alkoxycarbonyl or sulphonic acid groups.

Preferred compounds of the formula I have substituents on the aliphatic diamine radical which, independently of one another, are hydroxyl, C1-4-alkoxy, carboxy, C1-3-alkoxycarbonyl or C1-3-alkylcarbonyloxy groups.

The new compounds of the formula I are prepared by condensation of 2 moles of a compound or a mixture of compounds of the formula II

with 1 mole of a compound of formula III

R1H2 (III)

and 2 moles of a compound or a mixture of compounds of the formula IV

R2NH2 (IV).

The condensation reactions of compounds of the formulas III and IV with trihalo-s-triazines are familiar to the person skilled in the art and need not be described in more detail here.

These new compounds are reactive towards textile materials containing hydroxyl or amino groups (native or regenerated cellulosic materials, natural and synthetic polyamides), which means that the materials containing hydroxyl or amino groups treated with them according to the invention are permanently UV-absorbent and dirt-repellent and towards anionic dyes are equipped to reserve. When textiles finished in this way are worn, the skin underneath these textiles is also very effectively protected against aggressive UV radiation.

The new compounds of the formula I mainly absorb UVB and UVC radiation, but hardly any UVA radiation, so that they have practically no effect on the action of optical brighteners.

In general, the new compounds, like the known reactive dyes, if appropriate together with such dyes, are applied to the substrates mentioned and fixed there, preferably with the application of heat. This can be done according to the known exhaust process or according to a pad / padding process or a known printing process.

In general, 0.05 to 5%, preferably 0.1 to 3%, in particular 0.5 to 2.5%, of one or more compounds of the formula I, based on the weight of the substrate, are used. These new compounds are very well absorbed by the substrates mentioned. The surfaces of the textiles that are dyed or printed with them can later only be dyed poorly or not at all with anionic dyes. If one wishes to reduce the later dyeability to a large extent, preferably more than 2.5%, e.g. 3 to 8% of the new compounds of the formula I, based on the weight of the substrate treated in this way, are used. This reserved application is carried out in analogy to the method described in GB Patent Specification 2,011,883.

In the following examples, the parts are parts by weight and the percentages are percentages by weight. 1 part by volume corresponds to 1 part by weight of water (at +4 ° C). The temperatures are given in degrees Celsius.

example 1

50 parts of trichlorotriazine are stirred in 400 parts of water at 0-5 °, 48 parts of sulfanilic acid are added after about 15 minutes and the mixture is stirred for a further 90 minutes. The hydrochloric acid formed is neutralized by gradually adding 54 parts by volume of 30% sodium hydroxide solution. 15.4 parts of m-phenylenediamine are then introduced with stirring, the mixture is heated to 50 °, the pH of the reaction mixture is kept at 7 by adding about 20 percent sodium carbonate solution, the resulting suspension is filtered (eg through a suction filter) and the suspension is dried Filter cake at 50 °. The di-Na salt of the compound of the formula is obtained in this way

The table below shows further compounds of the formula according to the invention which can be prepared analogously to the instructions in Example 1

listed. <TABLE> Columns = 3 Table Head Col 1: Example No. Head Col 2: Binding on the ring A Head Col 3: Position of -SO3H 2 para 4 min 3 ortho 4 min <CEL AL = L> 4 para 2 min and 5 min 5 para 3 min 6 ortho <CEL AL = L> 2 min and 5 min </TABLE>

Examples 7 and 8

The procedure described in Example 1 is followed, but instead of the 15.4 parts of m-phenylenediamine, 8.55 parts of ethylenediamine (Example 7) or 10.5 parts of 1,3-diaminopropane (Example 8) are used and thus obtains the compounds of the formula I in which R1 is the divalent radical of 1,2-ethylenediamine or 1,3-propylenediamine, the two R2-NH-, the two R3 p-phenylene-para-sulfonic acid, X = chlorine, and n = 0.

Use as UV absorber, application examples 1-6

Application example 1

100 parts of cotton fabric are introduced into 1000 parts of an aqueous liquor heated to 60 ° and containing 80 parts of Glauber's salt. 1 part of the compound obtained according to Example 1 is then added, the substrate is agitated for 15 minutes in the bath, 10 parts of soda are added, the mixture is heated to 80 ° in 20 minutes and the substrate is treated at this temperature for a further 30 minutes. The cotton fabric is then taken out of the bath, first rinsed hot, then cold and dried.

The compounds prepared according to Examples 2 to 8 can also be applied to cotton fabric in the same way. The fixation yields, determined by spectrophotometric measurement of the content of UV absorber in the bath (before and after treatment of the substrate), are as follows: <TABLE> Columns = 2 Head Col 1: Compound according to example Head Col 2: Fixation yield 1,86 % 2 73% 3 46% <CEL AL = L> 4 <CEL AL = L> 75% 5 77% 6 30% 7 42% 8 42% </TABLE>

The textile materials obtained in this way are very effectively protected against damage from light, they are also more dirt-repellent than material not treated according to the invention and their ability to be dyed with anionic dyes is reduced. Their permeability for UVB and UVC rays is so low that these textiles offer the wearer effective protection against UVB and UVC rays.

Application examples 2-5

100 parts of cotton tricot (200 g / m 2) and X parts of the compound from Example 1 are introduced into 1000 parts of an aqueous liquor containing 80 parts of Glauber's salt. The mixture is heated to 95 ° C. within 30 minutes 10 parts of soda and treated the substrate at this temperature for 30 minutes. The cotton fabric is then taken out of the bath, first rinsed hot, then cold and dried.

Transmission measurements are carried out and the sun protection factor (UPF, ultraviolet protection factor, according to the Australian Radiation Laboratory) is calculated. <TABLE> Columns = 3 Head Col 1: Application example Head Col 2: Parts connection 1 Head Col 3: UPF 2 0 5 3 0.16 20 4 <CEL AL = L> 0.48 <CEL AL = L> 25 5 0 , 8 30 </TABLE>

Application example 6

100 parts of polyamide 66 (nylon fabric, 130 g / m 2) and 0.24 part of compound 1 are added to 1000 parts of an aqueous liquor containing 80 parts of Glauber's salt. This liquor is brought to 95 ° C. over 30 minutes brought, and held at this temperature for 45 minutes. After cooling, the fabric is taken out of the bath, rinsed hot and cold, and dried. The sun protection factor (UPF) is increased from 10 to 20 by such a treatment.

Use as "stain blocker", application examples 7 and 8

Application example 7

100 parts of woolen fabric are treated with 5 parts of the compound obtained in Example 1 at pH 4 (liquor ratio 1:19) at 95 ° C. for 60 minutes. After cooling to 70 ° C., 5 parts of a formaldehyde condensate composed of naphthalenesulfonic acid and dihydroxydiphenylsulfone are added and treatment is continued for 20 minutes. The fabric treated in this way shows an excellent protective effect in the soiling test with C.I. Food Red 17 (IWS Draft Test Method No. 282).

Application example 8

100 parts of polyamide (PA 6.6) are treated like the 100 parts of woolen fabric in Application Example 7. The fabric treated in this way shows excellent protection against soiling with C.I. Food Red 17.

Application example 9 (as a means of reservation).

A pattern is printed on 100 parts of polyamide (PA 6.6) with a paste containing 2.5 parts of the compound obtained in Example 1, 2.0 parts of common salt and a thickener based on alginate, at pH 6.5 (pick up 100%). It is then fixed in saturated steam at 102 ° C. for 20 minutes. After thorough rinsing, the goods are placed in a bath containing 0.55 parts of C.I. Acid Red 57 and 0.45 parts C.I. Acid Red 266 contains, overdyed for one hour at 98 ° C. at a liquor ratio of 1:10. After dyeing and rinsing, a pattern is obtained in which the preprinted areas are lighter than the colored ground.

Claims (7)

1. Compounds of the general formula I wherein R1 is the radical of an aromatic diamine which optionally bears 1 or 2 substituents or is the radical of a C1-22 aliphatic diamine, which optionally bears 1 or 2 substituents and / or is interrupted by heteroatoms, each R2, independently of one another, denotes a phenyl radical which optionally bears 1 or 2 sulphonic acid groups, each X independently of one another is fluorine, chlorine or bromine, with the proviso that each compound contains at least one sulphonic acid group, with the further condition that R1 is not a stilbene residue. 2. Compounds according to claim 1, characterized in that the substituents on the aromatic diamine radical are independently halogen atoms, methyl, hydroxyl, C1-4-alkoxy, carboxy, alkoxycarbonyl or sulphonic acid groups. 3. Compounds according to claim 1, characterized in that the substituents of the aliphatic diamine radical are independently of one another hydroxyl, C1-4-alkoxy, carboxy, C1-3-alkoxycarbonyl or C1-3-alkylcarbonyloxy groups. 4. Process for the preparation of compounds of the formula I according to claim 1, characterized in that 2 mol of a compound or a mixture of compounds of the formula II with 1 mole of a compound of formula III R1H2 (III) and 2 moles of a compound or a mixture of compounds of the formula IV R2NH2 (IV) condensed. 5. Use of the compounds of formula I according to claim 1 for the treatment of textile materials containing hydroxyl or amino groups. 6. Use of the compound of the formula I according to claim 5 as a UV absorber. 7. Use of the compound of formula I according to claim 5 for a dirt-repellent finish. 8. Use of the compound of the formula I according to claim 5 for reservation against anionic dyes. 7. Use of the compounds of formula I according to claim 1 for the production of UVB and UVC rays absorbing textiles which protect their wearer from skin damage.