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EP0466647B1 - Process for the photochemical and thermal stabilisation of polyamide fiber materials - Google Patents

Process for the photochemical and thermal stabilisation of polyamide fiber materials Download PDF

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Publication number
EP0466647B1
EP0466647B1 EP91810519A EP91810519A EP0466647B1 EP 0466647 B1 EP0466647 B1 EP 0466647B1 EP 91810519 A EP91810519 A EP 91810519A EP 91810519 A EP91810519 A EP 91810519A EP 0466647 B1 EP0466647 B1 EP 0466647B1
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Prior art keywords
formula
lower alkyl
radical
compound
hydrogen
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EP91810519A
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German (de)
French (fr)
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EP0466647A1 (en
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Francesco Dr. Fuso
Gerhard Dr. Reinert
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Novartis AG
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Ciba Geigy AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/487—Aziridinylphosphines; Aziridinylphosphine-oxides or sulfides; Carbonylaziridinyl or carbonylbisaziridinyl compounds; Sulfonylaziridinyl or sulfonylbisaziridinyl compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/241—Polyamides; Polyurethanes using acid dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358—Triazines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
    • D06P1/628—Compounds containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6426—Heterocyclic compounds

Definitions

  • the present invention relates to a method for the photochemical and thermal stabilization of polyamide fiber materials.
  • the new process is characterized in that colored undyed polyamide fiber materials with water-soluble triazine derivatives of the general formula treated, wherein R1 is a radical of the formula where R3 is hydrogen, oxyl, hydroxy, lower alkyl, lower alkenyl, lower alkoxy, acyl or benzyl and Z -O- or - (NR4) -, wherein R4 is hydrogen or lower alkyl, R2 is hydrogen, halogen, lower alkyl, lower alkoxy, acylamino, carboxy, an unsubstituted or substituted by a halogen atom or lower alkyl phenylsulfo, phenoxy, phenylthio or styryl radical or -SO3M, Q - (NR4) -, R halogen, lower alkyl, lower alkoxy, phenyl-lower alkoxy, cycloalkoxy, lower alkylthio, phenyl-lower alkylthio, cycl
  • lower alkyl, lower alkoxy, lower alkylthio, mono-lower alkylamino and di-lower alkylamino represent such groups or group components which have 1 to 5, in particular 1 to 3, carbon atoms.
  • groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert.
  • Cycloalkyloxy and cycloalkylthio groups have 4 to 8, preferably 5 to 7, carbon atoms. Examples of such groups are cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, methylcyclohexyloxy, ethylcyclohexyloxy, cycloheptyloxy or cyclooctyloxy. Cyclohexyloxy is a preferred cycloalkyloxy group.
  • Lower alkenyl means, for example, vinyl, propenyl, butenyl or preferably allyl.
  • Phenyl-lower alkylamino means, for example, phenethyl-, phenylpropyl-, phenylbutyl- or preferably benzylamino.
  • Halogen in the radicals R and R2 is fluorine, bromine or preferably chlorine.
  • R3 acyl means especially formyl, lower alkanoyl, such as eg acetyl, propionyl or benzoyl.
  • Lithium, sodium or potassium may be mentioned as examples of alkali metals. Sodium is preferred. Examples of alkaline earth metals are calcium and magnesium.
  • Trimethylammonium or preferably triethylammonium is suitable as the organic ammonium radical.
  • Lower alkylamino, di-lower alkylamino and cyclo-lower alkylamino can be substituted with halogen, alkoxy, hydroxy, carboxy or carboxyalkyl.
  • Lower alkoxy and cycloalkoxy can be substituted with lower alkoxy.
  • Lower alkylthio and cycloalkylthio can be substituted by alkoxy or hydroxy.
  • Phenyl can be substituted by lower alkyl.
  • 1-Azacycloalkyl can be substituted by C1-C3-alkyl, phenyl, hydroxy, carboxy or acylamido. Phenyl can be substituted by lower alkyl and lower alkoxy or halogen.
  • Morpholino can be substituted by one or more C1 to C3 alkyl radicals.
  • R and R1 correspond to a radical of formula (4).
  • water-soluble triazine derivatives according to formula (1) are of importance in which the radical R is lower alkoxy, cycloalkoxy, phenoxy, lower alkylthio, cycloalkylthio or phenylthio and R1 is a radical of the formula (4).
  • R is a radical of the formula wherein R6 and R7, independently of one another, denote hydrogen, lower alkyl, cycloalkyl or unsubstituted or phenyl which is substituted by lower alkyl, where if one of the radicals R6 and R7 is hydrogen, the other must not be hydrogen or R 1-azacycloalkyl or morpholino and R1 is a radical of formula (4) and R2 has the meaning given in formula (1).
  • the water-soluble triazine derivatives used for the process according to the invention are known in some cases, for example from Zhurnal Prikladnoi Khimii, 59 (5), 1144ff (1986). However, they also represent new compounds.
  • the new water-soluble triazine derivatives form a further subject of the invention in the present application and correspond to the formula wherein R'1 is a radical of the formula wherein R'3 is hydrogen, hydroxy, lower alkyl, lower alkenyl, lower alkoxy, acyl or benzyl and Z '-O- or - (NR'4) -, wherein R'4 is hydrogen or lower alkyl, R'2 is hydrogen, halogen, lower alkyl, lower alkoxy, acylamino, carboxy, an unsubstituted or substituted by a halogen atom or lower alkyl phenylsulfo, phenoxy, phenylthio or styryl radical or -SO3M, Q
  • water-soluble triazine derivatives corresponding to formula (5), in which R 'is a radical of formula (7) and R'1 is a radical of formula (9).
  • R ' is a radical of the formula means what R'6 and R'7, independently of one another, are hydrogen, C1-C4-alkyl, cycloalkyl or phenyl which is unsubstituted or substituted by lower alkyl, where if one of the radicals R'6 or R'7 is hydrogen, the other is not hydrogen may, or R 'signifies 1-azacycloalkyl or morpholino.
  • the preparation of the water-soluble triazine derivatives according to the formula (5) can different ways.
  • the starting compound is generally a 2,4,6-trihalo-s-triazine compound. In cases where R 'is lower alkyl or phenyl, the starting point is always 2,4-dihalo-6-lower alkyl or 6-phenyl-s-triazine.
  • the water-soluble triazine derivatives of the formula (5) according to the invention are prepared, for example, by adding 1 mol of a 2,4,6-trihalogen-s-triazine compound or a 2,4-dihalogen-6-lower alkyl or -phenyl-s- triazine compound successively with one mole of the compound of formula wherein M 'is hydrogen or alkali metal, and Q' and R'2 have the meaning given in formula (5), with one or 2 moles of the piperidine compound of the formula wherein R'3 and Z 'have the meaning given in formula (6), and, if 1 mol of the piperidine compound of the formula (11) is used, with one mol of a lower alkanolate, cycloalkanolate, phenolate, lower alkylthiolate, cycloalkylthiolate or a phenylthiolate compound, a mono-lower alkylamine, di-lower alkylamine, cycloalkylamine
  • the reaction temperature is between 0 and 50, preferably 20 and 40 ° C, the reaction time between 1 and 20, preferably 1 and 4 hours.
  • the corresponding dipiperidyl-substituted triazine compounds according to the formula wherein R'2, R'3, M ', Q' and Z 'have the meaning given in the formulas (5) and (6) are prepared by combining the compound of formula (12) with one mole of the piperidine compound Implements formula (11).
  • Water-soluble triazine derivatives corresponding to formula (13) can also be prepared by reacting 1 mole of a 2,4,6-trihalo-s-triazine compound in succession with one mole of the compound of formula (10) and 2 moles of the piperidine compound of formula (11) .
  • the reaction temperature is between 20 and 100, preferably 30 and 80 ° C.
  • the procedure is such that during a reaction time of 1 to 6, preferably 2 to 4 hours, the reaction temperature is gradually increased within 2 to 5, preferably 3 increased to 4 levels.
  • Compounds of formula (15) can also be obtained by mixing one mole of the compound of formula (12) with one mole of the corresponding lower alkanolate, phenylalkanolate, cycloalkanolate, phenolate, lower alkylthiolate, cycloalkylthiolate, phenylthiolate or a phenylalkylthiolate compound implements.
  • the chronological order the reactions with the piperidine compound of formula (11) and the N-alkyl compound depend on the reactivity of the respective compounds.
  • the procedure is such that the 2,4,6-trihalo-s-triazine compound is reacted with the compound which has the lower reactivity in the first reaction step.
  • the hydrohalic acid formed in the condensation reactions can be trapped by the end product itself or by adding a further base, such as, for example, aqueous ammonia, alkali metal hydroxides, alkali metal carbonates, hydrogen carbonates or an organic base, such as, for example, triethylamine.
  • a further base such as, for example, aqueous ammonia, alkali metal hydroxides, alkali metal carbonates, hydrogen carbonates or an organic base, such as, for example, triethylamine.
  • Alkali metal carbonate e.g. Sodium carbonate.
  • the reactions are expediently carried out in aqueous solution without the addition of organic solvents.
  • the 2,4,6-trihalo-s-triazine compounds used as starting compounds are generally known. They are preferably used as aqueous suspensions.
  • a particularly preferred starting compound is cyanuric chloride.
  • All compounds according to formula (5) are preferably used as sodium salts. For this purpose, they are dissolved, for example, with the equivalent amount of sodium hydroxide solution and formulated as a solution, dispersion or emulsion for an application.
  • the process according to the invention and the new water-soluble triazine derivatives according to formula (5) are suitable for increasing the thermal and photochemical stability of undyed and dyed polyamide fiber materials.
  • the use of the compounds according to the invention for increasing the thermal and photochemical stability of polyamide fibers and dyeings thus represents a further subject of the present invention.
  • novel and known compounds represent representatives of the class of sterically hindered amines ("HALS" stabilizers) and can be applied to the polyamide fiber materials from conventional liquors by customary methods.
  • HALS sterically hindered amines
  • the compounds of the formula (1) are applied from an aqueous bath which contains the compounds in an amount of 0.005 to 10% by weight, preferably 0.05 to 2% by weight.
  • the compounds are preferably added to the dyebath.
  • the application can take place before, during or after dyeing, using an exhaust or continuous process. Application during dyeing is preferred.
  • the liquor ratio can be selected within a wide range, e.g. 1: 5 to 1: 300, preferably 1:10 to 1:50. It is convenient to work at a temperature of 30 to 120 ° C, preferably 50 to 98 ° C.
  • the liquor application is expediently 30-400% by weight, preferably 75-250% by weight.
  • the fiber material is subjected to a heat treatment.
  • the fixing process can also be carried out using the cold dwell method.
  • the heat treatment is preferably carried out by a steaming process with treatment in a steamer with possibly superheated steam at a temperature of 98 to 105 ° C during e.g. 1 to 7, preferably 1 to 5 minutes.
  • the dyes and the compounds of formula (1) can be fixed in accordance with the cold residence process by storing the impregnated and preferably rolled-up goods at room temperature (15 to 30 ° C), e.g. take place for 3 to 24 hours, the cold residence time being known to depend on the type of dye applied.
  • the dyeings produced are rinsed and dried in the customary manner.
  • the process according to the invention gives polyamide dyeings and fibers with good thermal and photochemical stability.
  • dyeings to be stabilized according to the invention there are those which are characterized by acid or metal complex dyes, e.g. 1: 2 chromium, 1: 2 cobalt complex dyes or Cu complex dyes but also dispersion and reactive dyes.
  • acid or metal complex dyes e.g. 1: 2 chromium, 1: 2 cobalt complex dyes or Cu complex dyes but also dispersion and reactive dyes.
  • Polyamide fiber material is understood to mean synthetic polyamide, such as, for example, polyamide 6, polyamide 6,6 or polyamide 12, and modified polyamide, for example polyamide which can be dyed in a basic manner.
  • fiber blends made of polyurethane and polyamide, for example tricot material made of polyamide / polyurethane in a mixing ratio of 70:30.
  • the pure or mixed polyamide fiber material can be in a wide variety of processing forms, such as fiber, yarn, woven, knitted, nonwoven or pile material.
  • the present method is particularly advantageous for the treatment of polyamide fiber material which is exposed to light and heat and e.g. used as car upholstery or carpet.
  • Example 1 An ice-cold suspension of 10.3 g of 4-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 100 ml of dist. 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine are added to water with rapid stirring. The temperature is allowed to rise to room temperature and the mixture is stirred at 35 ° C. for one hour. After cooling to room temperature, the reaction mixture is mixed with 1.6 g of sodium carbonate and stirred for 15 hours. The suspension is filtered off, with distilled water. Washed water and dried at 40 ° C in a vacuum. 12.8 g of a colorless powder of the formula are obtained The compound shows the longest-wavelength absorption maximum at 282 nm (water / DMF (1: 1)).
  • EXAMPLE 2 4.7 g of 4-amino-2,2, to a suspension of 10.3 g of 3-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 100 ml of distilled water at 5 ° C. 6,6-tetramethylpiperidine entered. The internal temperature is allowed to rise to 20 ° C. and the mixture is stirred at this temperature for 2 hours. The mixture is then left stand for 15 hours at room temperature. The resulting precipitate is filtered off, washed free of chloride with distilled water and dried in vacuo at 40 ° C. 11.7 g of a colorless compound of the formula are obtained with the longest wave absorption maximum at 266 nm (water).
  • Example 3 The procedure is as described in Example 1, but instead of 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine, 5.1 g of 4-amino-1,2,2,6,6-pentamethylpiperidine are used a. 13.4 g of a colorless powder of the formula are obtained The compound shows the longest-wavelength absorption maximum at 282 nm (water / DMF (1: 1)).
  • EXAMPLE 4 The procedure is as described in Example 1, but 4.7 g of 4-N-methylamino-2,2,6,6-tetramethylpiperidine are used instead of 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine a. 12.2 g of a colorless compound of the formula are obtained The compound shows the longest wave absorption maximum at 275 nm (water).
  • Example 5 To an ice-cold suspension of 10.3 g of 4-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 80 ml of dist. 4.7 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine are added to water. Then 2.5 g of sodium hydrogen carbonate are introduced. The temperature is allowed to rise to room temperature and then heated to 30-40 ° C for 4 hours. After cooling to room temperature, the reaction mixture is neutralized with conc. Hydrochloric acid and mixed with 8 g of sodium chloride. The suspension is filtered off, washed with 10% sodium chloride solution and dried at 60 ° C. in vacuo. 14.4 g of a colorless powder of the formula are obtained with an active content of 81%. The longest wave absorption maximum is 277 nm (water).
  • Example 6 To a suspension of 10.3 g of 4-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 100 ml of dist. 11.2 g of 4-amino-1,2,2,6,6-pentamethylpiperidine are added to water at 0.degree. The temperature is allowed to rise to 20 ° C. and the mixture is stirred at this temperature for 3 hours. The mixture is then stirred for a further 2 hours at 35 ° C. and 8 hours at 75 ° C. After cooling, the precipitate formed is filtered off with a little dist. Washed water and dried at 40 ° C in a vacuum. 11.8 g of a colorless compound of the formula are obtained The longest wave absorption maximum is 273 nm (water).
  • Example 7 In a suspension of 5.2 g of 4-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 80 ml of dist. 9.4 g of 4-amino-2,2,6,6-tetramethylpiperidine are introduced into the water at 0.degree. The temperature is allowed to rise to room temperature and then heated to 35, 45 and 90 ° C. for 1 hour each. The reaction mixture is cooled to 70 ° C. and 12% sodium chloride is added. The mixture is cooled further to room temperature and stirred for 4 hours at room temperature. The precipitate is filtered off, washed with brine and dried at 50 ° C. in vacuo. 11.7 g of a colorless compound of the formula are obtained with an active content of 68%. The longest wave absorption maximum is 273 nm (water).
  • Example 8 The procedure is as described in Example 7, but instead of 9.4 g of 4-amino-2,2,6,6-tetramethylpiperidine, 10.2 g of 4-N-methylamino-2,2,6,6-tetramethylpiperidine are used , the compound of the formula is obtained with an active content of 94%. The compound shows the longest-wave absorption maximum at 275 nm (water).
  • Example 9 To an ice-cold suspension of 10.3 g of 4-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 350 ml of dist. 2.8 g of aniline are introduced into the water within 5 minutes. At the same time, the pH of the reaction mixture is kept at 6 by dropwise addition of 2 M sodium hydroxide solution. The consumption of sodium hydroxide solution is 15 ml. The internal temperature is allowed to rise to 20 ° C., diluted with 30 ml of distilled water and stirred at 30 to for 1 hour 35 ° C after. 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine are then introduced and the mixture is stirred at 70 ° C.
  • Example 10 The procedure is as described in Example 2 and instead of 4.7 g 4-amino-2,2,6,6-tetramethylpiperidine 5.1 g 4-N-methylamino-2,2,6,6-tetramethylpiperidine, the product obtained is a compound of the formula The compound shows the longest wave absorption maximum at 235 nm (water).
  • Example 11 The procedure is as described in Example 2, but instead of 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine, 5.1 g of 4-amino-1,2,2,6,6-pentamethylpiperidine are used , a compound of the formula is obtained The longest wave absorption maximum is 269 nm (water).
  • Examples 12 to 14 The following compounds (Table I) can be prepared by the method described in Example 2.
  • Example 15 A solution of 4-N- (2-chloro-4-isopropoxy-6-triazinyl) is prepared from 18.4 g of cyanuric chloride, 46.7 g of isopropanol and 17.4 g of sulfanilic acid analogously to DE-A-2,828,030. aminobenzenesulfonic acid sodium salt in 100 ml dist. Water. 15.6 g of 4-amino-2,2,6,6-tetramethylpiperidine are then added to the reaction mixture at room temperature and the mixture is stirred at 70 ° C. for 16 h.
  • Example 16 A suspension of 10.3 g of 4-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid Sodium salt in 50 ml dist. Water is added dropwise at 20 ° C with a neutral solution of 5.2 g of sulfanilic acid in 30 ml of dist. Water is added, the pH of the reaction mixture being kept between 6 and 7 by simultaneous dropwise addition of 2 M sodium hydroxide solution. The mixture is then stirred at 40 ° C. for 2.5 h. 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine are then rapidly introduced and the mixture is stirred at 70 ° C. for 12 hours.
  • the resulting reaction solution is evaporated to dryness at 70 ° C. in vacuo. 25.9 g of a colorless powder of the formula are obtained with an active content of 75%.
  • the compound shows the longest-wavelength absorption maximum at 284 nm (water).
  • Example 17 3.15 g of diethanolamine are added to an ice-cold suspension of 10.3 g of 4-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt. The mixture is slowly warmed to 40 ° C. and the pH of the reaction mixture is kept between 6.5 and 7 by dropwise addition of about 15 ml of 15% sodium carbonate solution. After 3 hours at 40 ° C., 4.7 g of 4-amino are rapidly 2,2,6,6-tetramethylpiperidine entered. The mixture is subsequently stirred at 70 ° C. for 16 hours and the reaction solution is evaporated in vacuo. 11.8 g of a colorless powder of the formula are obtained which has an active content of 73% and the longest-wavelength absorption maximum at 275 nm (water).
  • Example 18 A suspension of 10.3 g of 2-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 100 ml of dist. 2.6 g of morpholine are added to water at 5 ° C. and the mixture is heated to 40 ° C. in the course of 1.5 hours, the pH of the reaction mixture being kept between 6.5 and 7 by dropwise addition of 19 ml of 15% sodium carbonate solution . The mixture is then stirred at 40 ° C for 1 hour. The colorless suspension is mixed with 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine and heated to 70.degree. The mixture is stirred at this temperature for 15 hours, cooled to room temperature and filtered. The residue is washed with water and dried in vacuo at 80 ° C. 11.7 g of a colorless compound of the formula are obtained which has the longest wave absorption maximum at 264 nm (water).
  • Example 19 A suspension of 4.4 g of the compound from Example 1 in 30 ml of dist. Water is concentrated by adding 2 ml. Bring sodium hydroxide solution. Then neutralize the solution with conc. Hydrochloric acid, creating a finely divided suspension. 5 ml of an aqueous solution of 0.94 g of phenol are then added and the mixture is heated at 90 ° C. for 15 hours. After cooling to room temperature, the mixture is filtered, washed with water and dried in vacuo at 80 ° C. 4.7 g of a white powder of the formula are obtained with the longest wave absorption maximum at 275 nm (water).
  • Example 20 A suspension of 10.3 g of 2-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 100 ml of dist. Water is mixed with 3.3 g of thiophenol at 5 ° C. The pH of the reaction mixture is kept between 6.5 and 7 by dropwise addition of 15% sodium carbonate solution and the internal temperature is allowed to rise to room temperature at the same time. The mixture is then stirred at 40 ° C. for one hour, 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine are rapidly introduced and the mixture is heated to 70 ° C. for 16 hours. The mixture is cooled to room temperature, the reaction mixture is ground in a mixer, filtered and washed with water. The residue is suspended in 100 ml of ethanol, filtered off, washed with ethanol and dried in vacuo at 80 ° C. 9.7 g of a colorless compound of the formula are obtained melting point 354 ° C.
  • Example 21 A solution of 5.9 g of 2,4-dichloro-6-methylthio-s-triazine in 30 ml of acetone is stirred into 50 ml of ice water. 100 ml of a neutral aqueous solution of 5.2 g of sulfanilic acid are then added dropwise, and the pH of the reaction mixture is kept between 6.5 and 7 by the dropwise addition of 15% sodium carbonate solution one hour at 40 ° C and the acetone is then distilled off under reduced pressure. The reaction mixture is quickly mixed with 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine and stirred at 70 ° C. for 2 hours. The suspension is cooled to room temperature, filtered off and distilled with dist. Washed water. After drying in vacuo at 80 ° C., 13.1 g of a colorless compound of the formula remain which has the longest-wavelength absorption maximum at 281 nm (water).
  • Example 22 A suspension of 9.95 g of 2-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 100 ml of dist. Water is added at 5 ° C with 5.0 g of 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl and stirred for 16 hours at room temperature. The orange-colored suspension is then brought into solution by adding concentrated sodium hydroxide solution at a pH of 10. 7.8 g of sodium dithionite are added and the mixture is stirred at room temperature until it has completely decolorized. Then the reaction mixture is neutralized with conc. Hydrochloric acid, filtered and washed with dist. Water. The residue is dried in vacuo at 50 ° C. 6.1 g of a colorless powder of the formula are obtained in this way with the longest wave absorption maximum at 279 nm (water).
  • Example 23a (intermediate): A slurry of 22.6 g of 2-phenyl-4,6-dichloro-s-triazine in 150 ml of acetone is poured onto 100 ml of ice water with stirring and then with a neutral solution of 17.3 g of sulfanilic acid in 100 ml dist. Water added. The internal temperature is allowed to rise to 10-15 ° C. and the pH of the Reaction mixture by dropwise addition of 30% sodium hydroxide solution at 6 (consumption 13 ml). The mixture is then stirred at 40 ° C. for 15 hours. The resulting solution is cooled to room temperature. The precipitated product is filtered off, washed with 20% sodium chloride solution and dried in vacuo at 50 ° C. 39.1 g of a white powder of the formula are obtained with an active content of 90.1%.
  • Example 23 A suspension of 12.8 g of the compound of the formula (123a) in 70 ml of dist. 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine are added to water at room temperature with stirring. The mixture is then stirred at 55 ° C. for 30 minutes, with solution entering, and then at 80 ° C. for one hour. Finally, the mixture is stirred at 55 ° C. for 15 hours. The mixture is cooled to room temperature, the precipitate is filtered off and washed with dist. Chloride-free water. After drying in vacuo at 50 ° C., 13.5 g of a colorless compound of the formula are obtained The longest wave absorption maximum is 262 nm (water).
  • Example 24 A suspension of 12.8 g of the compound of formula (123a) in 70 ml of dist.
  • Example 25 A suspension of 12.8 g of the compound of formula (123a) in 70 ml of dist. 6.4 g of 4-N-butylamino-2,2,6,6-tetramethylpiperidine are added to water at room temperature with stirring. The reaction mixture is stirred at 70 ° C. for 4 hours, cooled to room temperature and filtered. After washing with dist. Water and drying in vacuo at 55 ° C remain 15.2 g of a colorless powder of the formula The longest wave absorption maximum is 255 nm (methanol).
  • Example 26 A suspension of 4-N-methyl- (2-chloro-4-phenyl-6-s-triazinyl) -aminobenzenesulfonic acid sodium salt is prepared by reacting 5.65 g of 2-phenyl-4,6-dichloro-s -triazine with 4.7 g of N-methylsulfanilic acid and the reaction conditions of Example 23a. 4.3 g of 4-N-methylamino-2,2,6,6-tetramethylpiperidine are then introduced with stirring at 40 ° C. and the temperature is raised to 75 ° C. The mixture is subsequently stirred at this temperature for 18 hours, cooled to room temperature and the precipitate formed is filtered off with suction. After washing with dist. Water and drying in vacuo at 55 ° C gives 12.6 g of a colorless compound of the formula which has the longest-wavelength absorption maximum at 250 nm (methanol).
  • Example 27 The procedure is as described in Example 23a, but using 2-p-tolyl-4,6-dichloro-s-triazine instead of 2-phenyl-4,6-dichloro-s-triazine and instead of sulfanil-metanilic acid , the corresponding 3-N- (2-chloro-4-p-tolyl-6-s-triazinyl) aminobenzenesulfonic acid is obtained as the sodium salt. This is condensed directly with 4-amino-1,2,2,6,6-pentamethyl-piperidine without isolation under the reaction conditions of Example 24. A colorless powder of the formula is obtained The longest wave absorption maximum is 265 nm (water).
  • Example 28 A solution of 4.9 g of 2,4-dichloro-6-methyl-s-triazine in acetone (50 ml) is discharged onto ice water (50 ml). A neutral solution of 5.2 g of sulfanilic acid is then added with rapid stirring at 10 ° C. and the pH of the reaction mixture is kept at 6 by dropwise addition of a 30% strength sodium hydroxide solution. The consumption of sodium hydroxide solution is 4.1 ml. The mixture is then stirred at room temperature for 1 hour and at 40 ° C. for 3 hours. 5.1 g of 4-N-methylamino-2,2,6,6-tetramethylpiperidine are rapidly introduced and the temperature is raised to 55 ° C. in the course of 30 minutes.
  • Example 29 4 samples of a polyamide 6 knitted fabric of 10 g each are prepared and treated in a dyeing machine, for example an ®AHIBA dyeing machine, at a liquor ratio of 1:30. Two of these samples are "blind-dyed" (ie treated without dye: fleets 1 and 3), two are stained (fleets 2 and 4).
  • a dyeing machine for example an ®AHIBA dyeing machine
  • dyeing liquors are thus prepared, each containing 0.5 g / l monosodium phosphate and 1.5 g / l disodium phosphate ( ⁇ pH 7).
  • the following dyes (calculated on the weight of the goods) are dissolved in fleets 2 and 4: 0.04% of the dye mixture consisting of 81 parts of the compound of the formula and 12 parts of the compound of the formula and 0.002% of the dye of the formula
  • the liquors 3 and 4 additionally contain 1% of the sodium salt of the compound of the formula (101).
  • the blind dyeings are exposed according to DIN 75.202 for 216 hours and tear strength and elongation determined according to SN 198.461.
  • Example 30 Two samples of a polyamide 6 knitted fabric of 10 g each are dyed as described in Example 29, with the difference that the two liquors contain the following dyes: 0.05% of the dye of the formula 0.085% of the dye mixture of the formulas and 0.035% of the dye mixture of the formulas (Ia) and (Ib).
  • the liquor (2) additionally contains 1% of the sodium salt of the compound of the formula (101).
  • Examples 31 and 32 As described in Examples 29 and 30, light gray and olive dyeings are produced in a conventional manner on polyamide 6 woven jersey. These dyeings are impregnated on a foulard (squeezing effect 105%) with solutions which contain 10 g / l of the compounds of the formulas (105) and (107) in solution. The padded dyeings are rolled and then left in a polyethylene film for 2 hours. The mixture is then dried at 80 ° C.
  • the dyeings are tested for their light fastness in accordance with DIN 75.202 ("FAKRA").
  • the two dyeings are exposed on an area of approx. 4 x 12 cm for 216 hours using the same method and then tested for tensile strength and elongation according to SN 198 461.
  • the results are shown in Table IV: Table IV COLORING * FAKRA light fastness
  • Tensile strength / elongation (% of starting material) 144 hours 216 hours 1 1 1 10.7 / 16.2 2nd 2-3 2nd 76.7 / 79.2 * Assessment according to gray scale 1-5
  • Examples 34 and 35 Three samples of 10 g each of a knitted polyamide fabric are prepared, dyed and finished as described in Example 29, using the same dye combination.
  • the liquor for dyeing No. 1 contains no further additives, dye liquor 2 still contains 0.75% of the sodium salt of the compound of formula (111), dye liquor 3 contains 0.75% of the sodium salt of the compound of formula (110).
  • Example 36 10 samples of a PA jersey of 10 g each and 10 fleets are prepared as indicated in Example 29.
  • 0.04% of the dye mixture of the formulas (Ia) and (Ib) and 0.002% of the dye of the formula (II) are dissolved; in the liquors 6 to 10, dyeing is carried out blindly without any additional dye.
  • Fleets 2 and 7 are each added 0.75% of the sodium salt of the compound of the formula (109), fleets 3 and 8 each 0.75% of the compound of the formula (112), fleets 4 and 9 each 0.75% 0.75% of a compound of the formula (114) was added to the compound of the formula (113) and the liquors 5 and 10 in dissolved form.
  • Example 37 The procedure is as described in Example 29, ie blind treatments and light gray colorations are alternately produced and tested.

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Abstract

There are described a process for the photochemical and thermal stabilisation of polyamide fibre materials and novel water-soluble triazine derivatives. <??>Polyamide dyeings and fibres of good thermal and photochemical stability are obtained.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur photochemischen und thermischen Stabilisierung von Polyamid-Fasermaterialien.The present invention relates to a method for the photochemical and thermal stabilization of polyamide fiber materials.

In Journal of Applied polymer Science, Bd. 33, Nr. 5, 1987, Seiten 2087 bis 2095 wird ein Verfahren zum Photostabilisieren von Wolle durch eine Kombination aus sulfonierten UV-Absorbern und Antioxidantien offenbart.Journal of Applied polymer Science, Vol. 33, No. 5, 1987, pages 2087 to 2095 discloses a process for photostabilizing wool by a combination of sulfonated UV absorbers and antioxidants.

Das neue Verfahren ist dadurch gekennzeichnet, dass man gefärbte ungefärbte Polyamid-Fasermaterialien mit wasserlöslichen Triazinderivaten der allgemeinen Formel

Figure imgb0001

behandelt, worin R₁ einen Rest der Formel
Figure imgb0002
wobei R₃ Wasserstoff, Oxyl, Hydroxy, Niederalkyl, Niederalkenyl, Niederalkoxy, Acyl oder Benzyl und
Z -O- oder -(NR₄)-,
worin R₄ Wasserstoff oder Niederalkyl,
R₂ Wasserstoff, Halogen, Niederalkyl, Niederalkoxy, Acylamino, Carboxy, einen nichtsubstituierten oder durch ein Halogenatom oder Niederalkyl substituierten Phenylsulfo-, Phenoxy-, Phenylthio-, oder Styrylrest oder -SO₃M, Q -(NR₄)-,
R Halogen, Niederalkyl, Niederalkoxy, Phenylniederalkoxy, Cycloalkoxy, Niederalkylthio, Phenylniederalkylthio, Cycloalkylthio, Mononiederalkylamino, Diniederalkylamino, Phenylniederalkylamino, Cycloalkylamino, Phenoxy, Phenylamino, Phenylthio, Phenyl, 1-Azacycloalkyl, Morpholino, R₁ oder einen Rest der Formel
Figure imgb0003
bedeutet, worin
M Wasserstoff, Alkalimetall, Erdalkalimetall, Ammonium oder einen organischen Ammoniumrest bedeuten und
Q die in Formel (1) angegebene Bedeutung hat,
und die Verbindungen der Formel (1) maximal 2 -SO₃M-Substituenten aufweisen.The new process is characterized in that colored undyed polyamide fiber materials with water-soluble triazine derivatives of the general formula
Figure imgb0001
treated, wherein R₁ is a radical of the formula
Figure imgb0002
where R₃ is hydrogen, oxyl, hydroxy, lower alkyl, lower alkenyl, lower alkoxy, acyl or benzyl and
Z -O- or - (NR₄) -,
wherein R₄ is hydrogen or lower alkyl,
R₂ is hydrogen, halogen, lower alkyl, lower alkoxy, acylamino, carboxy, an unsubstituted or substituted by a halogen atom or lower alkyl phenylsulfo, phenoxy, phenylthio or styryl radical or -SO₃M, Q - (NR₄) -,
R halogen, lower alkyl, lower alkoxy, phenyl-lower alkoxy, cycloalkoxy, lower alkylthio, phenyl-lower alkylthio, cycloalkylthio, mono-lower alkylamino, di-lower alkylamino, phenyl-lower alkylamino, cycloalkylamino, phenoxy, phenylamino, phenylthio, phenyl, 1-azacycloalkyl, or morpholino, R 1, morpholino, formula
Figure imgb0003
means what
M is hydrogen, alkali metal, alkaline earth metal, ammonium or an organic ammonium radical and
Q has the meaning given in formula (1),
and the compounds of formula (1) have a maximum of 2 -SO₃M substituents.

Bei der Definition der Reste R, R₂, R₃ und R₄ stellen Niederalkyl, Niederalkoxy, Niederalkylthio, Mononiederalkylamino und Diniederalkylamino solche Gruppen oder Gruppenbestandteile dar, die 1 bis 5, insbesondere 1 bis 3 Kohlenstoffatome aufweisen. Beispiele für derartige Gruppen sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.-Butyl, tert. Butyl, Amyl oder Isoamyl bzw. Methoxy, Ethoxy, Isopropoxy, Isobutoxy, tert-Butoxy oder tert.-Amyloxy bzw. Methylthio, Ethylthio, Propylthio oder Butylthio. Cycloalkyloxy- und Cycloalkylthiogruppen weisen 4 bis 8, vorzugsweise 5 bis 7 Kohlenstoffatome auf. Beispiele für solche Gruppen sind Cyclobutyloxy, Cyclopentyloxy, Cyclohexyloxy, Methylcyclohexyloxy, Ethylcyclohexyloxy, Cycloheptyloxy oder Cyclooctyloxy. Als bevorzugte Cycloalkyloxygruppe kommt Cyclohexyloxy in Frage.In the definition of the radicals R, R₂, R₃ and R₄, lower alkyl, lower alkoxy, lower alkylthio, mono-lower alkylamino and di-lower alkylamino represent such groups or group components which have 1 to 5, in particular 1 to 3, carbon atoms. Examples of such groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert. Butyl, amyl or isoamyl or methoxy, ethoxy, isopropoxy, isobutoxy, tert-butoxy or tert-amyloxy or methylthio, ethylthio, propylthio or butylthio. Cycloalkyloxy and cycloalkylthio groups have 4 to 8, preferably 5 to 7, carbon atoms. Examples of such groups are cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, methylcyclohexyloxy, ethylcyclohexyloxy, cycloheptyloxy or cyclooctyloxy. Cyclohexyloxy is a preferred cycloalkyloxy group.

Niederalkenyl bedeutet beispielsweise Vinyl, Propenyl, Butenyl oder vorzugsweise Allyl.Lower alkenyl means, for example, vinyl, propenyl, butenyl or preferably allyl.

Phenylniederalkylamino bedeutet beispielsweise Phenethyl-, Phenylpropyl-, Phenylbutyl- oder vorzugsweise Benzylamino.Phenyl-lower alkylamino means, for example, phenethyl-, phenylpropyl-, phenylbutyl- or preferably benzylamino.

Halogen bei den Resten R und R₂ bedeutet Fluor, Brom oder vorzugsweise Chlor.Halogen in the radicals R and R₂ is fluorine, bromine or preferably chlorine.

Bei der Definition des Restes R₃ bedeutet Acyl besonders Formyl, Niederalkanoyl, wie z.B. Acetyl, Propionyl oder Benzoyl.In the definition of the radical R₃ acyl means especially formyl, lower alkanoyl, such as eg acetyl, propionyl or benzoyl.

Als Beispiele für Alkalimetalle seien Lithium, Natrium oder Kalium genannt. Bevorzugt ist Natrium. Beispiele für Erdalkalimetalle sind Calcium und Magnesium.Lithium, sodium or potassium may be mentioned as examples of alkali metals. Sodium is preferred. Examples of alkaline earth metals are calcium and magnesium.

Als organischer Ammoniumrest kommt Trimethylammonium oder vorzugsweise Triethylammonium in Betracht.Trimethylammonium or preferably triethylammonium is suitable as the organic ammonium radical.

Niederalkylamino, Diniederalkylamino und Cycloniederalkylamino können mit Halogen, Alkoxy, Hydroxy, Carboxy oder Carboxyalkyl substituiert sein. Niederalkoxy und Cycloalkoxy können mit Niederalkoxy substituiert sein. Niederalkylthio und Cycloalkylthio können durch Alkoxy oder Hydroxy substituiert sein. Phenyl kann durch Niederalkyl substituiert sein. 1-Azacycloalkyl kann durch C₁-C₃-Alkyl, Phenyl, Hydroxy, Carboxy oder Acylamido substituiert sein. Phenyl kann durch Niederalkyl und Niederalkoxy bzw. Halogen substituiert sein. Morpholino kann durch einen oder mehrere C₁ bis C₃-Alkylreste substituiert sein.Lower alkylamino, di-lower alkylamino and cyclo-lower alkylamino can be substituted with halogen, alkoxy, hydroxy, carboxy or carboxyalkyl. Lower alkoxy and cycloalkoxy can be substituted with lower alkoxy. Lower alkylthio and cycloalkylthio can be substituted by alkoxy or hydroxy. Phenyl can be substituted by lower alkyl. 1-Azacycloalkyl can be substituted by C₁-C₃-alkyl, phenyl, hydroxy, carboxy or acylamido. Phenyl can be substituted by lower alkyl and lower alkoxy or halogen. Morpholino can be substituted by one or more C₁ to C₃ alkyl radicals.

Von besonderem Interesse sind wasserlösliche Triazinderivate, bei denen in Formel (1) R Halogen und R₁ den Rest der Formel

Figure imgb0004

bedeuten, worin
R₅ Wasserstoff oder Niederalkyl bedeutet und
Z die in Formel (2) angegebene Bedeutung hat.Of particular interest are water-soluble triazine derivatives, in which in formula (1) R halogen and R₁ the rest of the formula
Figure imgb0004
mean what
R₅ is hydrogen or lower alkyl and
Z has the meaning given in formula (2).

Weiterhin bevorzugt sind Verbindungen, bei denen in Formel (1) R und R₁ einem Rest der Formel (4) entsprechen.Also preferred are compounds in which in formula (1) R and R₁ correspond to a radical of formula (4).

Von Interesse sind weiterhin wasserlösliche Triazinderivate gemäss Formel (1), bei denen R einen Rest der Formel (3) und R₁ einen Rest der Formel (4) bedeuten.Of interest are also water-soluble triazine derivatives according to formula (1), in which R is a radical of formula (3) and R₁ is a radical of formula (4).

Weiterhin sind wasserlösliche Triazinderivate gemäss Formel (1) von Bedeutung, bei denen der Rest R Niederalkoxy, Cycloalkoxy, Phenoxy, Niederalkylthio, Cycloalkylthio oder Phenylthio und R₁ einen Rest der Formel (4) bedeuten.Furthermore, water-soluble triazine derivatives according to formula (1) are of importance in which the radical R is lower alkoxy, cycloalkoxy, phenoxy, lower alkylthio, cycloalkylthio or phenylthio and R₁ is a radical of the formula (4).

Von Interesse sind auch wasserlösliche Triazinderivate der Formel (1), bei denen R einen Rest der Formel

Figure imgb0005

worin R₆ und R₇, unabhängig voneinander Wasserstoff, Niederalkyl, Cycloalkyl oder nichtsubstituiertes oder durch Niederalkyl substituiertes Phenyl bedeuten, wobei, wenn einer der Reste R₆ und R₇ Wasserstoff bedeutet, der andere nicht Wassrstoff sein darf oder
R 1-Azacycloalkyl oder Morpholino und
R₁ einen Rest der Formel (4) bedeuten und
R₂ die in Formel (1) angegebene Bedeutung hat.Also of interest are water-soluble triazine derivatives of the formula (1) in which R is a radical of the formula
Figure imgb0005
wherein R₆ and R₇, independently of one another, denote hydrogen, lower alkyl, cycloalkyl or unsubstituted or phenyl which is substituted by lower alkyl, where if one of the radicals R₆ and R₇ is hydrogen, the other must not be hydrogen or
R 1-azacycloalkyl or morpholino and
R₁ is a radical of formula (4) and
R₂ has the meaning given in formula (1).

Die für das erfindungsgemässe Verfahren eingesetzten wasserlösliche Triazinderivate sind z.T. bekannt, beispielsweise aus Zhurnal Prikladnoi Khimii, 59(5), 1144ff (1986). Sie stellen aber auch neue Verbindungen dar. Die neuen wasserlöslichen Triazinderivate bilden einen weiteren Erfindungsgegenstand der vorliegenden Anmeldung und entsprechen der Formel

Figure imgb0006

worin R'₁ einen Rest der Formel
Figure imgb0007
wobei R'₃ Wasserstoff, Hydroxy, Niederalkyl, Niederalkenyl, Niederalkoxy, Acyl oder Benzyl und
Z' -O- oder -(NR'₄)-,
worin R'₄ Wasserstoff oder Niederalkyl bedeutet,
R'₂ Wasserstoff, Halogen, Niederalkyl, Niederalkoxy, Acylamino, Carboxy, einen nichtsubstituierten oder durch ein Halogenatom oder Niederalkyl substituierten Phenylsulfo-, Phenoxy-, Phenylthio- oder Styrylrest oder -SO₃M bedeutet, Q' -(NR'₄)-,
R' Halogen, Niederalkyl, Niederalkoxy, Phenylniederalkoxy, Cycloalkoxy, Niederalkylthio, Phenylniederalkylthio, Cycloalkylthio, Mononiederalkylamino, Diniederalkylamino, Cycloalkylamino, Phenoxy, Phenylamino, Phenylthio, Phenyl, 1-Azacycloalkyl, Morpholino, R'₁ oder einen Rest der Formel
Figure imgb0008
bedeuten, worin
R'₂ und Q' die in Formel (5) angegebene Bedeutung haben,
M' Wasserstoff, Alkalimetall, Erdalkalimetall, Ammonium oder einen organischen Ammoniumrest bedeutet,
wobei, wenn R' Chlor und R'₂ Wasserstoff bedeuten, R'₁ nicht einen Rest der Formel
Figure imgb0009
bedeutet, und wenn R' einen Rest der Formel (7),
R'₂ nicht Wasserstoff bedeutet
und die Verbindungen der Formel (5) maximal 2 SO₃M'-Substituenten aufweisen. Von besonderem Interesse sind wasserlösliche Triazinderivate der Formel (5), bei denen R' Halogen und R'₁ den Rest der Formel
Figure imgb0010
bedeuten, worin
R'₅ Wasserstoff oder Niederalkyl bedeutet und
Z' die in Formel (6) angegebene Bedeutung hat,
wobei, wenn R' Chlor und R'₂ Wasserstoff bedeuten, R'₁ nicht einen Rest der Formel (8) bedeutet.The water-soluble triazine derivatives used for the process according to the invention are known in some cases, for example from Zhurnal Prikladnoi Khimii, 59 (5), 1144ff (1986). However, they also represent new compounds. The new water-soluble triazine derivatives form a further subject of the invention in the present application and correspond to the formula
Figure imgb0006
wherein R'₁ is a radical of the formula
Figure imgb0007
wherein R'₃ is hydrogen, hydroxy, lower alkyl, lower alkenyl, lower alkoxy, acyl or benzyl and
Z '-O- or - (NR'₄) -,
wherein R'₄ is hydrogen or lower alkyl,
R'₂ is hydrogen, halogen, lower alkyl, lower alkoxy, acylamino, carboxy, an unsubstituted or substituted by a halogen atom or lower alkyl phenylsulfo, phenoxy, phenylthio or styryl radical or -SO₃M, Q '- (NR'₄) -,
R 'halogen, lower alkyl, lower alkoxy, phenyl-lower alkoxy, cycloalkoxy, lower alkylthio, phenyl-lower alkylthio, cycloalkylthio, mono-lower alkylamino, di-lower alkylamino, cycloalkylamino, phenoxy, phenylamino, phenylthio, phenyl, 1-azacycloalkyl, morpholino, R'₁ or a radical of the formula R 1
Figure imgb0008
mean what
R'₂ and Q 'have the meaning given in formula (5),
M 'denotes hydrogen, alkali metal, alkaline earth metal, ammonium or an organic ammonium radical,
where, when R 'is chlorine and R'₂ is hydrogen, R'₁ is not a radical of the formula
Figure imgb0009
and when R 'is a radical of formula (7),
R'₂ does not mean hydrogen
and the compounds of formula (5) have a maximum of 2 SO₃M 'substituents. Of particular interest are water-soluble triazine derivatives of the formula (5), in which R 'halogen and R'₁ the rest of the formula
Figure imgb0010
mean what
R'₅ is hydrogen or lower alkyl and
Z 'has the meaning given in formula (6),
where, when R 'is chlorine and R'₂ is hydrogen, R'₁ is not a radical of formula (8).

Weiterhin bevorzugt sind auch wasserlösliche Triazinderivate entsprechend Formel (5), bei denen R' einen Rest der Formel (7) und R'₁ einen Rest der Formel (9) bedeuten.Also preferred are water-soluble triazine derivatives corresponding to formula (5), in which R 'is a radical of formula (7) and R'₁ is a radical of formula (9).

Von besonderem Interesse sind auch wasserlösliche Triazinderivate entsprechend Formel (5), bei denen R' und R'₁ einen Rest der Formel (6) bedeuten.Of particular interest are also water-soluble triazine derivatives corresponding to formula (5), in which R 'and R'₁ represent a radical of formula (6).

Weitere bedeutende wasserlösliche Triazinderivate entsprechen der Formel (5), worin R' Niederalkoxy, Cycloalkoxy, Phenoxy, Phenylalkoxy, Niederalkylthio Phenylthio oder Phenylalkylthio bedeutet und
Q', R'₁ und R'₂ die angegebene Bedeutung haben.Other important water-soluble triazine derivatives correspond to the formula (5), in which R 'denotes lower alkoxy, cycloalkoxy, phenoxy, phenylalkoxy, lower alkylthio, phenylthio or phenylalkylthio and
Q ', R'₁ and R'₂ have the meaning given.

Von Interesse sind auch wasserlösliche Triazinderivate entsprechend Formel (5), bei denen R' einen Rest der Formel

Figure imgb0011

bedeutet, worin
R'₆ und R'₇, unabhängig voneinander, Wasserstoff, C₁-C₄-Alkyl, Cycloalkyl oder nichtsubstituiertes oder durch Niederalkyl substituiertes Phenyl bedeuten, wobei, wenn einer der Reste R'₆ oder R'₇ Wasserstoff bedeutet, der andere nicht Wasserstoff sein darf, oder R' 1-Azacycloalkyl oder Morpholino bedeutet.Also of interest are water-soluble triazine derivatives corresponding to formula (5), in which R 'is a radical of the formula
Figure imgb0011
means what
R'₆ and R'₇, independently of one another, are hydrogen, C₁-C₄-alkyl, cycloalkyl or phenyl which is unsubstituted or substituted by lower alkyl, where if one of the radicals R'₆ or R'₇ is hydrogen, the other is not hydrogen may, or R 'signifies 1-azacycloalkyl or morpholino.

Die Herstellung der wasserlöslichen Triazinderivate entsprechend der Formel (5) kann auf verschiedene Art und Weise erfolgen. Ausgangsverbindung ist im allgemeinen eine 2,4,6-Trihalogen-s-triazinverbindung. In den Fällen, wo R' Niederalkyl oder Phenyl ist, geht man immer vom 2,4-Dihalogen-6-niederalkyl- bzw. 6-phenyl-s-triazin aus.The preparation of the water-soluble triazine derivatives according to the formula (5) can different ways. The starting compound is generally a 2,4,6-trihalo-s-triazine compound. In cases where R 'is lower alkyl or phenyl, the starting point is always 2,4-dihalo-6-lower alkyl or 6-phenyl-s-triazine.

Die Herstellung der erfindungsgemässen wasserlöslichen Triazinderivate entsprechend Formel (5) erfolgt z.B. dadurch, dass man 1 Mol einer 2,4,6-Trihalogen-s-triazinverbindung oder einer 2,4-Dihalogen-6-niederalkyl- bzw. -phenyl-s-triazinverbindung nacheinander mit einem Mol der Verbindung der Formel

Figure imgb0012

worin M' Wasserstoff oder Alkalimetall bedeutet, und Q' und R'₂ die in Formel (5) angegebene Bedeutung haben, mit einem oder 2 Mol der Piperidinverbindung der Formel
Figure imgb0013
worin R'₃ und Z' die in Formel (6) angegebene Bedeutung haben, und, wenn man 1 Mol der Piperidinverbindung der Formel (11) einsetzt, mit einem Mol einer Niederalkanolat-, Cycloalkanolat-, Phenolat-, Niederalkylthiolat-, Cycloalkylthiolat- oder einer Phenylthiolatverbindung, eines Mononiederalkylamins, Diniederalkylamins, Cycloalkylamins, Phenylamins, einer 1-Azacycloalkyl-, einer Morpholinoverbindung oder einer Verbindung der Formel (10) umsetzt, wobei die Reihenfolge der einzelnen Reaktionsschritte beliebig ist.The water-soluble triazine derivatives of the formula (5) according to the invention are prepared, for example, by adding 1 mol of a 2,4,6-trihalogen-s-triazine compound or a 2,4-dihalogen-6-lower alkyl or -phenyl-s- triazine compound successively with one mole of the compound of formula
Figure imgb0012
wherein M 'is hydrogen or alkali metal, and Q' and R'₂ have the meaning given in formula (5), with one or 2 moles of the piperidine compound of the formula
Figure imgb0013
wherein R'₃ and Z 'have the meaning given in formula (6), and, if 1 mol of the piperidine compound of the formula (11) is used, with one mol of a lower alkanolate, cycloalkanolate, phenolate, lower alkylthiolate, cycloalkylthiolate or a phenylthiolate compound, a mono-lower alkylamine, di-lower alkylamine, cycloalkylamine, phenylamine, a 1-azacycloalkyl, a morpholino compound or a compound of the formula (10), the order of the individual reaction steps being arbitrary.

Zur Herstellung von wasserlöslichen Triazinderivaten, bei denen R' Halogen bedeutet, geht man so vor, dass man 1 Mol einer 2,4,6-Trihalogen-s-triazinverbindung mit einem Mol einer Verbindung der Formel (10) und einem Mol der Piperidinverbindung der Formel (11) zu einer Verbindung der Formel

Figure imgb0014

worin R'₂, R'₃, M', Q' und Z' die in den Formeln (5) und (6) angegebene Bedeutung haben, umsetzt. Auf diese Weise entstehen monopiperidyl-substituierte Triazinderivate.For the preparation of water-soluble triazine derivatives in which R 'is halogen, the procedure is such that 1 mol of a 2,4,6-trihalogen-s-triazine compound with one mol of a compound of the formula (10) and one mol of the piperidine compound of Formula (11) to a compound of formula
Figure imgb0014
wherein R'₂, R'₃, M ', Q' and Z 'have the meaning given in the formulas (5) and (6). In this way, monopiperidyl-substituted triazine derivatives are formed.

Bei dieser Reaktionsführung liegt die Reaktionstemperatur zwischen 0 und 50, vorzugsweise 20 und 40°C, die Reaktionszeit zwischen 1 und 20, vorzugsweise 1 und 4 Stunden.In this reaction procedure, the reaction temperature is between 0 and 50, preferably 20 and 40 ° C, the reaction time between 1 and 20, preferably 1 and 4 hours.

Die entsprechenden dipiperidyl-substituierten Triazinverbindungen entsprechend Formel

Figure imgb0015

worin R'₂, R'₃, M', Q' und Z' die in den Formeln (5) und (6) angegebene Bedeutung haben, werden hergestellt, indem man die Verbindung der Formel (12) mit einem Mol der Piperidinverbindung der Formel (11) umsetzt. Wasserlösliche Triazinderivate entsprechend Formel (13) lassen sich auch herstellen, indem man 1 Mol einer 2,4,6-Trihalogen-s-triazinverbindung nacheinander mit einem Mol der Verbindung der Formel (10) und 2 Mol der Piperidinverbindung der Formel (11) umsetzt. Bei dieser Reaktionsführung liegt die Reaktionstemperatur zwischen 20 und 100, vorzugsweise 30 und 80°C. Dabei geht man so vor, dass man während einer Reaktionszeit von 1 bis 6, vorzugsweise 2 bis 4 Stunden, die Reaktionstemperatur stufenweise innerhalb von 2 bis 5, vorzugsweise 3 bis 4 Stufen erhöht.The corresponding dipiperidyl-substituted triazine compounds according to the formula
Figure imgb0015
wherein R'₂, R'₃, M ', Q' and Z 'have the meaning given in the formulas (5) and (6) are prepared by combining the compound of formula (12) with one mole of the piperidine compound Implements formula (11). Water-soluble triazine derivatives corresponding to formula (13) can also be prepared by reacting 1 mole of a 2,4,6-trihalo-s-triazine compound in succession with one mole of the compound of formula (10) and 2 moles of the piperidine compound of formula (11) . In this reaction procedure, the reaction temperature is between 20 and 100, preferably 30 and 80 ° C. The procedure is such that during a reaction time of 1 to 6, preferably 2 to 4 hours, the reaction temperature is gradually increased within 2 to 5, preferably 3 increased to 4 levels.

Die Herstellung von wasserlöslichen Triazinderivaten, bei denen der Rest R' einen Rest der Formel (7) und R'₁ einen Rest der Formel (6) bedeuten, erfolgt dadurch, dass man 1 Mol einer 2,4,6-Trihalogen-s-triazinverbindung mit zwei Mol der Verbindung der Formel (10), worin Q' -(NR'₄)- und R'₂ Halogen, Niederalkyl, Niederalkoxy, Acylamino, Carboxy oder -SO₃M' bedeuten und anschliessend mit einem Mol der Piperidinverbindung der Formel (11) zu Verbindungen der Formel

Figure imgb0016

worin Q' -(NR'₄)- und
R'₂ Halogen, Niederalkyl, Niederalkoxy, Acylamino, Carboxy oder -SO₃H bedeuten und R'₃ und Z' die in der Formel (6) angegebene Bedeutung haben, umsetzt.The preparation of water-soluble triazine derivatives in which the radical R 'is a radical of the formula (7) and R'₁ is a radical of the formula (6) is carried out by adding 1 mol of a 2,4,6-trihalogen-s- triazine compound with two moles of the compound of the formula (10), in which Q '- (NR'₄) - and R'₂ are halogen, lower alkyl, lower alkoxy, acylamino, carboxy or -SO₃M' and then with one mole of the piperidine compound of the formula ( 11) to compounds of the formula
Figure imgb0016
wherein Q '- (NR'₄) - and
R'₂ is halogen, lower alkyl, lower alkoxy, acylamino, carboxy or -SO₃H and R'₃ and Z 'have the meaning given in formula (6).

Die Herstellung von wasserlöslichen Triazinderivaten, bei denen der Rest R Niederalkoxy, Cycloalkoxy, Phenylalkoxy, Phenoxy, Niederalkylthio, Cycloalkylthio, Phenylthio oder Phenylalkylthio bedeutet, erfolgt dadurch, dass man nacheinander 1 Mol einer 2,4,6-Trihalogen-s-triazinverbindung mit einem Mol der entsprechenden Niederalkanolat-, Phenylalkanolat-, Cycloalkanolat, Phenolat-, Niederalkylthiolat-, Cycloalkylthiolat-, Phenylthiolat- oder einer Phenylalkylthiolatverbindung, einem Mol der Verbindung der Formel (10) und einem Mol der Piperidinverbindung der Formel (11) zu Verbindungen der Formel

Figure imgb0017

worin R'₉ Niederalkoxy, Cycloalkoxy, Phenylalkoxy, Phenoxy, Niederalkylthio, Cycloalkylthio, Phenylthio oder Phenylalkylthio bedeuten und R'₂, R'₃, M', Q' und Z' die oben angegebene Bedeutung haben, umsetzt. Zu Verbindungen der Formel (15) gelangt man auch, indem man ein Mol der Verbindung der Formel (12) mit einem Mol der entsprechenden Niederalkanolat-, Phenylalkanolat-, Cycloalkanolat-, Phenolat-, Niederalkylthiolat-, Cycloalkylthiolat-, Phenylthiolat- oder einer Phenylalkylthiolatverbindung umsetzt.The preparation of water-soluble triazine derivatives in which the radical R is lower alkoxy, cycloalkoxy, phenylalkoxy, phenoxy, lower alkylthio, cycloalkylthio, phenylthio or phenylalkylthio is carried out by successively adding 1 mol of a 2,4,6-trihalo-s-triazine compound with a Moles of the corresponding lower alkanolate, phenylalkanolate, cycloalkanolate, phenolate, lower alkylthiolate, cycloalkylthiolate, phenylthiolate or a phenylalkylthiolate compound, one mole of the compound of formula (10) and one mole of the piperidine compound of formula (11) to compounds of the formula
Figure imgb0017
wherein R'₉ lower alkoxy, cycloalkoxy, phenylalkoxy, phenoxy, lower alkylthio, cycloalkylthio, phenylthio or phenylalkylthio and R'₂, R'₃, M ', Q' and Z 'have the meaning given above. Compounds of formula (15) can also be obtained by mixing one mole of the compound of formula (12) with one mole of the corresponding lower alkanolate, phenylalkanolate, cycloalkanolate, phenolate, lower alkylthiolate, cycloalkylthiolate, phenylthiolate or a phenylalkylthiolate compound implements.

Die Herstellung von wasserlöslichen Triazinderivaten, bei denen der Rest R Mononiederalkylamino, Diniederalkylamino, Phenylniederalkylamino, Cycloalkylamino, Phenylamino, 1-Azacycloalkyl oder Morpholino, bedeutet, erfolgt dadurch, dass man eine 2,4,6-Trihalogen-s-triazinverbindung nacheinander mit einer Verbindung der Formel (10), einer Piperidinverbindung der Formel (11) und einer N-Alkylverbindung oder Aminophenylverbindung zu einer Verbindung der Formel

Figure imgb0018

worin R' einen Rest der Formel
Figure imgb0019
bedeutet, worin R'₇ und R'₈, unabhängig voneinander, Wasserstoff, C₁-C₄Alkyl, Cycloalkyl, unsubstituiertes oder durch Niederalkyl substituiertes Phenyl bedeuten oder der Rest R' 1-Azacycloalkyl oder Morpholino bedeutet, wobei, wenn einer der Reste R'₇ oder R'₈ Wasserstoff bedeutet, der andere nicht Wasserstoff sein darf, und R'₂, R'₃, M', Q' und Z' die in den Formeln (5) und (6) angegebene Bedeutung haben, umsetzt. Die Reihenfolge der Umsetzungen mit der Piperidinverbindung der Formel (11) und der N-Alkylverbindung hängt von der Reaktivität der jeweiligen Verbindungen ab. In der Regel geht man so vor, dass man im ersten Reaktionsschritt die 2,4,6-Trihalogen-s-triazinverbindung mit der Verbindung umsetzt, die die geringere Reaktivität aufweist.The preparation of water-soluble triazine derivatives in which the radical R is mono-lower alkylamino, di-lower alkylamino, phenyl-lower alkylamino, cycloalkylamino, phenylamino, 1-azacycloalkyl or morpholino means that a 2,4,6-trihalo-s-triazine compound is used in succession with a compound of the formula (10), a piperidine compound of the formula (11) and an N-alkyl compound or aminophenyl compound to give a compound of the formula
Figure imgb0018
wherein R 'is a radical of the formula
Figure imgb0019
means in which R'₇ and R'₈, independently of one another, are hydrogen, C₁-C₄alkyl, cycloalkyl, unsubstituted or substituted by lower alkyl or the radical R 'is 1-azacycloalkyl or morpholino, where if one of the radicals R'₇ or R'₈ is hydrogen, the other must not be hydrogen, and R'₂, R'₃, M ', Q' and Z 'have the meaning given in the formulas (5) and (6). The chronological order the reactions with the piperidine compound of formula (11) and the N-alkyl compound depend on the reactivity of the respective compounds. As a rule, the procedure is such that the 2,4,6-trihalo-s-triazine compound is reacted with the compound which has the lower reactivity in the first reaction step.

Die bei den Kondensationsreaktionen entstehende Halogenwasserstoffsäure kann durch das Endprodukt selbst oder durch Hinzufügen einer weiteren Base, wie beispielsweise wässrigem Ammoniak, Alkalimetallhydroxiden, Alkalimetallcarbonaten, -hydrogencarbonaten oder einer organischen Base, wie beispielsweise Triethylamin, abgefangen werden. Vorzugsweise wird als Base Alkalimetallcarbonat, wie z.B. Natriumcarbonat, verwendet.The hydrohalic acid formed in the condensation reactions can be trapped by the end product itself or by adding a further base, such as, for example, aqueous ammonia, alkali metal hydroxides, alkali metal carbonates, hydrogen carbonates or an organic base, such as, for example, triethylamine. Alkali metal carbonate, e.g. Sodium carbonate.

Die Umsetzungen erfolgen zweckmässigerweise in wässriger Lösung ohne den Zusatz von organischen Lösungsmitteln. Die als Ausgangsverbindungen verwendeten 2,4,6-Trihalogen-s-triazinverbindungen sind allgemein bekannt. Sie werden dabei vorzugsweise als wässrige Suspensionen eingesetzt. Besonders bevorzugte Ausgangsverbindung ist Cyanurchlorid.The reactions are expediently carried out in aqueous solution without the addition of organic solvents. The 2,4,6-trihalo-s-triazine compounds used as starting compounds are generally known. They are preferably used as aqueous suspensions. A particularly preferred starting compound is cyanuric chloride.

Alle Verbindungen gemäss Formel (5) werden vorzugsweise als Natriumsalze eingesetzt. Dazu werden sie beispielsweise mit der äquivalenten Menge Natronlauge gelöst und als Lösung, Dispersion oder Emulsion für eine Anwendung formuliert..All compounds according to formula (5) are preferably used as sodium salts. For this purpose, they are dissolved, for example, with the equivalent amount of sodium hydroxide solution and formulated as a solution, dispersion or emulsion for an application.

Das erfindungsgemässe Verfahren sowie die neuen wasserlöslichen Triazinderivate gemäss Formel (5) eignen sich dazu, die thermische und photochemische Stabilität von ungefärbten und gefärbten Polyamid-Fasermaterialien zu erhöhen. Die Verwendung der erfindungsgemässen Verbindungen zur Erhöhung der thermischen und photochemischen Stabilität von Polyamidfasern und -färbungen stellt somit einen weiteren Gegenstand der vorliegenden Erfindung dar.The process according to the invention and the new water-soluble triazine derivatives according to formula (5) are suitable for increasing the thermal and photochemical stability of undyed and dyed polyamide fiber materials. The use of the compounds according to the invention for increasing the thermal and photochemical stability of polyamide fibers and dyeings thus represents a further subject of the present invention.

Die neuartigen und bekannten Verbindungen stellen Vertreter der Klasse der sterisch gehinderten Amine ("HALS"-Stabilisatoren) dar und können aus üblichen Flotten nach gängigen Methoden auf die Polyamid-Fasermaterialien aufgebracht werden.The novel and known compounds represent representatives of the class of sterically hindered amines ("HALS" stabilizers) and can be applied to the polyamide fiber materials from conventional liquors by customary methods.

Die Verbindungen der Formel (1 ) werden erfindungsgemäss aus wässrigem Bad appliziert, das die Verbindungen in einer Menge von 0,005 bis 10 Gew.-%, vorzugsweise 0,05 bis 2 Gew.-% enthält. Vorzugsweise werden die Verbindungen dem Färbebad zugefügt.According to the invention, the compounds of the formula (1) are applied from an aqueous bath which contains the compounds in an amount of 0.005 to 10% by weight, preferably 0.05 to 2% by weight. The compounds are preferably added to the dyebath.

Die Applikation kann dabei vor, während oder nach dem Färben, nach einem Auszieh- oder Kontinueverfahren erfolgen. Die Applikation während des Färbens ist bevorzugt.The application can take place before, during or after dyeing, using an exhaust or continuous process. Application during dyeing is preferred.

Beim Ausziehverfahren kann das Flottenverhältnis innerhalb eines weiten Bereiches gewählt werden, z.B. 1:5 bis 1:300, vorzugsweise 1:10 bis 1:50. Man arbeitet zweckmässig bei einer Temperatur von 30 bis 120°C, vorzugsweise 50 bis 98°C.In the exhaust process, the liquor ratio can be selected within a wide range, e.g. 1: 5 to 1: 300, preferably 1:10 to 1:50. It is convenient to work at a temperature of 30 to 120 ° C, preferably 50 to 98 ° C.

Beim Kontinue-Verfahren beträgt der Flottenauftrag zweckmässig 30-400 Gew.-%, vorzugsweise 75-250 Gew.-%. Zur Fixierung der applizierten Farbstoffe und der bekannten und neuen Verbindungen wird das Fasermaterial einer Hitzebehandlung unterworfen. Der Fixierprozess kann auch nach der Kaltverweilmethode erfolgen.In the continuous process, the liquor application is expediently 30-400% by weight, preferably 75-250% by weight. To fix the applied dyes and the known and new compounds, the fiber material is subjected to a heat treatment. The fixing process can also be carried out using the cold dwell method.

Die Hitzebehandlung erfolgt vorzugsweise durch ein Dämpfverfahren unter Behandlung in einem Dämpfer mit gegebenenfalls überhitztem Dampf bei einer Temperatur von 98 bis 105°C während z.B. 1 bis 7, vorzugsweise 1 bis 5 Minuten. Die Fixierung der Farbstoffe und der Verbindungen der Formel (1) gemäss dem Kaltverweilverfahren kann durch Lagerung der imprägnierten und vorzugsweise aufgerollten Ware bei Raumtemperatur (15 bis 30°C), z.B. während 3 bis 24 Stunden erfolgen, wobei die Kaltverweilzeit bekanntlich von der Art des applizierten Farbstoffes abhängig ist.The heat treatment is preferably carried out by a steaming process with treatment in a steamer with possibly superheated steam at a temperature of 98 to 105 ° C during e.g. 1 to 7, preferably 1 to 5 minutes. The dyes and the compounds of formula (1) can be fixed in accordance with the cold residence process by storing the impregnated and preferably rolled-up goods at room temperature (15 to 30 ° C), e.g. take place for 3 to 24 hours, the cold residence time being known to depend on the type of dye applied.

Nach Beendigung des Färbeprozesses bzw. der Fixierung werden die hergestellten Färbungen auf übliche Weise gespült und getrocknet.After the dyeing process or fixation has ended, the dyeings produced are rinsed and dried in the customary manner.

Man erhält mit dem erfindungsgemässen Verfahren Polyamid-Färbungen und -fasern mit guter thermischer und photochemischer Stabilität.The process according to the invention gives polyamide dyeings and fibers with good thermal and photochemical stability.

Als die erfindungsgemäss zu stabilisierenden Färbungen kommen solche in Betracht, die durch Säure- oder Metallkomplexfarbstoffe, z.B. 1:2-Chrom, 1:2-Kobaltkomplexfarbstoffe oder Cu-Komplexfarbstoffe aber auch Dispersions- und Reaktivfarbstoffe erzeugt werden.As the dyeings to be stabilized according to the invention, there are those which are characterized by acid or metal complex dyes, e.g. 1: 2 chromium, 1: 2 cobalt complex dyes or Cu complex dyes but also dispersion and reactive dyes.

Beispiele für solche Farbstoffe sind in Colour Index, 3. Auflage, 1971, Band 4, beschrieben.Examples of such dyes are described in Color Index, 3rd edition, 1971, volume 4.

Unter Polyamidfasermaterial wird synthetisches Polyamid, wie z.B. Polyamid 6, Polyamid 6,6 oder Polyamid 12, sowie modifiziertes Polyamid, z.B. basisch anfärbbares Polyamid verstanden. Neben den reinen Polyamidfasern kommen vor allem auch Fasermischungen aus Polyurethan und Polyamid in Betracht, so z.B. Trikotmaterial aus Polyamid/Polyurethan im Mischungsverhältnis 70:30. Grundsätzlich kann das reine oder gemischte Polyamidfasermaterial in den verschiedensten Verarbeitungsformen vorliegen, wie z.B. als Faser, Garn, Gewebe, Gewirke, Vlies oder Flormaterial.Polyamide fiber material is understood to mean synthetic polyamide, such as, for example, polyamide 6, polyamide 6,6 or polyamide 12, and modified polyamide, for example polyamide which can be dyed in a basic manner. In addition to the pure polyamide fibers, there are also fiber blends made of polyurethane and polyamide, for example tricot material made of polyamide / polyurethane in a mixing ratio of 70:30. In principle, the pure or mixed polyamide fiber material can be in a wide variety of processing forms, such as fiber, yarn, woven, knitted, nonwoven or pile material.

Das vorliegende Verfahren eignet sich besonders vorteilhaft zur Behandlung von Polyamidfasermaterial, das Licht und Hitze ausgesetzt wird und z.B. als Autopolsterstoff oder Teppich Verwendung findet.The present method is particularly advantageous for the treatment of polyamide fiber material which is exposed to light and heat and e.g. used as car upholstery or carpet.

Die folgenden Beispiele veranschaulichen die Erfindung. Teile bedeuten Gewichtsteile und Prozente Gewichtsprozente.The following examples illustrate the invention. Parts mean parts by weight and percentages percentages by weight.

Herstellung der bekannten Verbindungen:Production of the known compounds:

Beispiel 1: Eine eiskalte Suspension von 10,3 g 4-N-(2,4-Dichlor-6-triazinyl)aminobenzolsulfonsäure Natriumsalz in 100 ml dest. Wasser wird unter schnellem Rühren mit 4,7 g 4-Amino-2,2,6,6-tetramethylpiperidin versetzt. Man lässt die Temperatur auf Raumtemperatur steigen und rührt noch während einer Stunde bei 35°C nach. Nach dem Abkühlen auf Raumtemperatur versetzt man das Reaktionsgemisch mit 1,6 g Natriumcarbonat und rührt während 15 Stunden. Die Suspension wird abfiltriert, mit dest. Wasser gewaschen und bei 40°C im Vakuum getrocknet. Man erhält 12,8 g eines farblosen Pulvers der Formel

Figure imgb0020

Die Verbindung zeigt das langwelligste Absorptionsmaximum bei 282 nm (Wasser/DMF (1:1)). Example 1: An ice-cold suspension of 10.3 g of 4-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 100 ml of dist. 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine are added to water with rapid stirring. The temperature is allowed to rise to room temperature and the mixture is stirred at 35 ° C. for one hour. After cooling to room temperature, the reaction mixture is mixed with 1.6 g of sodium carbonate and stirred for 15 hours. The suspension is filtered off, with distilled water. Washed water and dried at 40 ° C in a vacuum. 12.8 g of a colorless powder of the formula are obtained
Figure imgb0020
The compound shows the longest-wavelength absorption maximum at 282 nm (water / DMF (1: 1)).

Beispiel 2: Zu einer Suspension von 10,3 g 3-N-(2,4-Dichlor-6-triazinyl)aminobenzolsulfonsäure Natriumsalz in 100 ml destilliertem Wasser von 5°C werden 4,7 g 4-Amino-2,2,6,6-tetramethylpiperidin eingetragen. Man lässt die Innentemperatur auf 20°C steigen, und rührt während 2 Stunden bei dieser Temperatur. Anschliessend lässt man das Gemisch während 15 Stunden bei Raumtemperatur stehen. Der entstandene Niederschlag wird abgesaugt, mit destilliertem Wasser chloridfrei gewaschen und im Vakuum bei 40°C getrocknet. Man erhält 11,7 g einer farblosen Verbindung der Formel

Figure imgb0021

mit dem langwelligsten Absorptionsmaximum bei 266 nm (Wasser). EXAMPLE 2 4.7 g of 4-amino-2,2, to a suspension of 10.3 g of 3-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 100 ml of distilled water at 5 ° C. 6,6-tetramethylpiperidine entered. The internal temperature is allowed to rise to 20 ° C. and the mixture is stirred at this temperature for 2 hours. The mixture is then left stand for 15 hours at room temperature. The resulting precipitate is filtered off, washed free of chloride with distilled water and dried in vacuo at 40 ° C. 11.7 g of a colorless compound of the formula are obtained
Figure imgb0021
with the longest wave absorption maximum at 266 nm (water).

Herstellung neuer Verbindungen:Establishing new connections:

Beispiel 3: Man verfährt wie in Beispiel 1 beschrieben, setzt jedoch statt 4,7 g 4-Amino-2,2,6,6-tetramethylpiperidin 5,1 g 4-Amino-1,2,2,6,6-pentamethylpiperidin ein. Man erhält 13,4 g eines farblosen Pulvers der Formel

Figure imgb0022

Die Verbindung zeigt das langwelligste Absorptionsmaximum bei 282 nm (Wasser/DMF (1:1)). Example 3: The procedure is as described in Example 1, but instead of 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine, 5.1 g of 4-amino-1,2,2,6,6-pentamethylpiperidine are used a. 13.4 g of a colorless powder of the formula are obtained
Figure imgb0022
The compound shows the longest-wavelength absorption maximum at 282 nm (water / DMF (1: 1)).

Beispiel 4: Man verfährt wie in Beispiel 1 beschrieben, setzt jedoch statt 4,7 g 4-Amino-2,2,6,6-tetramethylpiperidin 4,7 g 4-N-Methylamino-2,2,6,6-tetramethylpiperidin ein. Man erhält 12,2 g einer farblosen Verbindung der Formel

Figure imgb0023

Die Verbindung zeigt das langwelligste Absorptionsmaximum bei 275 nm (Wasser). EXAMPLE 4 The procedure is as described in Example 1, but 4.7 g of 4-N-methylamino-2,2,6,6-tetramethylpiperidine are used instead of 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine a. 12.2 g of a colorless compound of the formula are obtained
Figure imgb0023
The compound shows the longest wave absorption maximum at 275 nm (water).

Beispiel 5: Zu einer eiskalten Suspension von 10,3 g 4-N-(2,4-Dichlor-6-triazinyl)aminobenzolsulfonsäure Natriumsalz in 80 ml dest. Wasser werden 4,7 g 4-Hydroxy-2,2,6,6-tetramethylpiperidin gegeben. Anschliessend trägt man 2,5 g Natriumhydrogencarbonat ein. Man lässt die Temperatur auf Raumtemperatur steigen und erwärmt dann während 4 Stunden auf 30-40°C. Nach dem Abkühlen auf Raumtemperatur neutralisiert man das Reaktionsgemisch mit konz. Salzsäure und versetzt mit 8 g Natriumchlorid. Die Suspension wird abfiltriert, mit 10%iger Natriumchloridlösung gewaschen und bei 60°C im Vakuum getrocknet. Man erhält 14,4 g eines farblosen Pulvers der Formel

Figure imgb0024

mit einem Aktivgehalt von 81 %. Das langwelligste Absorptionsmaximum beträgt 277 nm (Wasser). Example 5: To an ice-cold suspension of 10.3 g of 4-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 80 ml of dist. 4.7 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine are added to water. Then 2.5 g of sodium hydrogen carbonate are introduced. The temperature is allowed to rise to room temperature and then heated to 30-40 ° C for 4 hours. After cooling to room temperature, the reaction mixture is neutralized with conc. Hydrochloric acid and mixed with 8 g of sodium chloride. The suspension is filtered off, washed with 10% sodium chloride solution and dried at 60 ° C. in vacuo. 14.4 g of a colorless powder of the formula are obtained
Figure imgb0024
with an active content of 81%. The longest wave absorption maximum is 277 nm (water).

Beispiel 6: Zu einer Suspension von 10,3 g 4-N-(2,4-Dichlor-6-triazinyl)aminobenzolsulfonsäure Natriumsalz in 100 ml dest. Wasser von 0°C werden 11,2 g 4-Amino-1,2,2,6,6-pentamethylpiperidin hinzugegeben. Man lässt die Temperatur auf 20°C steigen und rührt während 3 Stunden bei dieser Temperatur. Anschliessend wird noch 2 Stunden bei 35°C und 8 Stunden bei 75°C gerührt. Nach dem Erkalten wird der gebildete Niederschlag abfiltriert, mit wenig dest. Wasser gewaschen und bei 40°C im Vakuum getrocknet. Man erhält 11,8 g einer farblosen Verbindung der Formel

Figure imgb0025

Das langwelligste Absorptionsmaximum beträgt 273 nm (Wasser). Example 6: To a suspension of 10.3 g of 4-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 100 ml of dist. 11.2 g of 4-amino-1,2,2,6,6-pentamethylpiperidine are added to water at 0.degree. The temperature is allowed to rise to 20 ° C. and the mixture is stirred at this temperature for 3 hours. The mixture is then stirred for a further 2 hours at 35 ° C. and 8 hours at 75 ° C. After cooling, the precipitate formed is filtered off with a little dist. Washed water and dried at 40 ° C in a vacuum. 11.8 g of a colorless compound of the formula are obtained
Figure imgb0025
The longest wave absorption maximum is 273 nm (water).

Beispiel 7: In eine Suspension von 5,2 g 4-N-(2,4-Dichlor-6-triazinyl)aminobenzolsulfonsäure Natriumsalz in 80 ml dest. Wasser werden bei 0°C 9,4 g 4-Amino-2,2,6,6-tetramethylpiperidin eingetragen. Man lässt die Temperatur auf Raumtemperatur steigen und erhitzt anschliessend je 1 Stunde auf 35, 45 und 90°C. Das Reaktionsgemisch wird auf 70°C gekühlt und mit 12 % Natriumchlorid versetzt. Man kühlt weiter auf Raumtemperatur ab und rührt 4 Stunden bei Raumtemperatur. Der Niederschlag wird abfiltriert, mit Sole gewaschen und bei 50°C im Vakuum getrocknet. Man erhält 11,7 g einer farblosen Verbindung der Formel

Figure imgb0026

mit einem Aktivgehalt von 68 %. Das langwelligste Absorptionsmaximum beträgt 273 nm (Wasser). Example 7: In a suspension of 5.2 g of 4-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 80 ml of dist. 9.4 g of 4-amino-2,2,6,6-tetramethylpiperidine are introduced into the water at 0.degree. The temperature is allowed to rise to room temperature and then heated to 35, 45 and 90 ° C. for 1 hour each. The reaction mixture is cooled to 70 ° C. and 12% sodium chloride is added. The mixture is cooled further to room temperature and stirred for 4 hours at room temperature. The precipitate is filtered off, washed with brine and dried at 50 ° C. in vacuo. 11.7 g of a colorless compound of the formula are obtained
Figure imgb0026
with an active content of 68%. The longest wave absorption maximum is 273 nm (water).

Beispiel 8: Verfährt man wie in Beispiel 7 beschrieben, setzt jedoch statt 9,4 g 4-Amino-2,2,6,6-tetramethylpiperidin 10,2 g 4-N-Methylamino-2,2,6,6-tetramethylpiperidin ein, so erhält man die Verbindung der Formel

Figure imgb0027

mit einem Aktivgehalt von 94 %. Die Verbindung zeigt bei 275 nm (Wasser) das langwelligste Absorptionsmaximum. Example 8: The procedure is as described in Example 7, but instead of 9.4 g of 4-amino-2,2,6,6-tetramethylpiperidine, 10.2 g of 4-N-methylamino-2,2,6,6-tetramethylpiperidine are used , the compound of the formula is obtained
Figure imgb0027
with an active content of 94%. The compound shows the longest-wave absorption maximum at 275 nm (water).

Beispiel 9: Zu einer eiskalten Suspension von 10,3 g 4-N-(2,4-Dichlor-6-triazinyl)aminobenzolsulfonsäure Natriumsalz in 350 ml dest. Wasser werden 2,8 g Anilin innerhalb von 5 Minuten eingetragen. Gleichzeitig hält man den pH-Wert des Reaktionsgemisches durch Zutropfen von 2 M Natronlauge auf 6. Der Verbrauch an Natronlauge beträgt 15 ml. Man lässt die Innentemperatur auf 20°C steigen, verdünnt mit 30 ml destilliertem Wasser und rührt während einer Stunde bei 30 bis 35°C nach. Anschliessend trägt man 4,7 g 4-Amino-2,2,6,6-tetramethylpiperidin ein und rührt während 15 Stunden bei 70°C. Nach dem Erkalten auf Raumtemperatur wird der gebildete Niederschlag abgesaugt, mit destilliertem Wasser chloridfrei gewaschen und bei 50°C im Vakuum getrocknet. Man erhält quantitativ eine farblose Verbindung der Formel

Figure imgb0028

Die Verbindung zeigt in Wasser das langwelligste Absorptionsmaximum bei 277 nm. Example 9: To an ice-cold suspension of 10.3 g of 4-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 350 ml of dist. 2.8 g of aniline are introduced into the water within 5 minutes. At the same time, the pH of the reaction mixture is kept at 6 by dropwise addition of 2 M sodium hydroxide solution. The consumption of sodium hydroxide solution is 15 ml. The internal temperature is allowed to rise to 20 ° C., diluted with 30 ml of distilled water and stirred at 30 to for 1 hour 35 ° C after. 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine are then introduced and the mixture is stirred at 70 ° C. for 15 hours. After cooling to room temperature, the precipitate formed is filtered off with suction, washed free of chloride with distilled water and dried at 50 ° C. in vacuo. A colorless compound of the formula is obtained quantitatively
Figure imgb0028
The compound shows the longest-wavelength absorption maximum at 277 nm in water.

Beispiel 10: Verfährt man wie in Beispiel 2 beschrieben und setzt anstelle von 4,7 g 4-Amino-2,2,6,6-tetramethylpiperidin 5,1 g
4-N-Methylamino-2,2,6,6-tetramethylpiperidin ein, so erhält man als Produkt eine Verbindung der Formel

Figure imgb0029

Die Verbindung zeigt das langwelligste Absorptionsmaximum bei 235 nm (Wasser). Example 10: The procedure is as described in Example 2 and instead of 4.7 g 4-amino-2,2,6,6-tetramethylpiperidine 5.1 g
4-N-methylamino-2,2,6,6-tetramethylpiperidine, the product obtained is a compound of the formula
Figure imgb0029
The compound shows the longest wave absorption maximum at 235 nm (water).

Beispiel 11: Verfährt man wie in Beispiel 2 beschrieben, setzt jedoch statt 4,7 g 4-Amino-2,2,6,6-tetramethylpiperidin 5,1 g 4-Amino-1,2,2,6,6-pentamethylpiperidin ein, so erhält man eine Verbindung der Formel

Figure imgb0030

Die langwelligste Absorptionsmaximum beträgt 269 nm (Wasser). Example 11: The procedure is as described in Example 2, but instead of 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine, 5.1 g of 4-amino-1,2,2,6,6-pentamethylpiperidine are used , a compound of the formula is obtained
Figure imgb0030
The longest wave absorption maximum is 269 nm (water).

Beispiele 12 bis 14: Die folgenden Verbindungen (Tabelle I) können nach dem in Beispiel 2 beschriebenen Verfahren hergestellt werden.

Figure imgb0031

Beispiel 15: Man bereitet aus 18,4 g Cyanurchlorid, 46,7 g Isopropanol und 17,4 g Sulfanilsäure analog der DE-A-2,828,030 eine Lösung von 4-N-(2-Chlor-4-isopropoxy-6-triazinyl)aminobenzolsulfonsäure Natriumsalz in 100 ml dest. Wasser. Anschliessend gibt man bei Raumtemperatur 15,6 g 4-Amino-2,2,6,6-tetramethylpiperidin zum Reaktionsgemisch und rührt während 16 h bei 70°C. Danach werden unter vermindertem Druck ca. 70 ml Isopropanol/Wasser-Gemisch abdestilliert. Man kühlt auf Raumtemperatur, filtriert und wäscht mit dest. Wasser chloridfrei. Nach dem Trocknen im Vakuum bei 60°C erhält man 34,6 g eines farblosen Pulvers der Formel
Figure imgb0032
Das langwelligste Absorptionsmaximum beträgt 274 nm (Wasser). Examples 12 to 14: The following compounds (Table I) can be prepared by the method described in Example 2.
Figure imgb0031
Example 15: A solution of 4-N- (2-chloro-4-isopropoxy-6-triazinyl) is prepared from 18.4 g of cyanuric chloride, 46.7 g of isopropanol and 17.4 g of sulfanilic acid analogously to DE-A-2,828,030. aminobenzenesulfonic acid sodium salt in 100 ml dist. Water. 15.6 g of 4-amino-2,2,6,6-tetramethylpiperidine are then added to the reaction mixture at room temperature and the mixture is stirred at 70 ° C. for 16 h. Then about 70 ml of isopropanol / water mixture are distilled off under reduced pressure. It is cooled to room temperature, filtered and washed with dist. Chloride-free water. After drying in vacuo at 60 ° C., 34.6 g of a colorless powder of the formula are obtained
Figure imgb0032
The long-wave absorption maximum is 274 nm (water).

Beispiel 16: Eine Suspension von 10,3 g 4-N-(2,4-Dichlor-6-triazinyl)aminobenzolsulfonsäure Natriumsalz in 50 ml dest. Wasser wird bei 20°C tropfenweise mit einer neutralen Lösung von 5,2 g Sulfanilsäure in 30 ml dest. Wasser versetzt, wobei durch gleichzeitiges Zutropfen von 2 M Natronlauge der pH-Wert des Reaktionsgemisches zwischen 6 und 7 gehalten wird. Man rührt danach 2,5 h bei 40°C. Anschliessend trägt man rasch 4,7 g 4-Amino-2,2,6,6-tetramethylpiperidin ein und rührt während 12 Stunden bei 70°C aus. Die entstandene Reaktionslösung wird bei 70°C im Vakuum zur Trockne eingedampft. Man erhält 25,9 g eines farblosen Pulvers der Formel

Figure imgb0033

mit einem Aktivgehalt von 75%. Die Verbindung zeigt bei 284 nm (Wasser) das langwelligste Absorptionsmaximum. Example 16: A suspension of 10.3 g of 4-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid Sodium salt in 50 ml dist. Water is added dropwise at 20 ° C with a neutral solution of 5.2 g of sulfanilic acid in 30 ml of dist. Water is added, the pH of the reaction mixture being kept between 6 and 7 by simultaneous dropwise addition of 2 M sodium hydroxide solution. The mixture is then stirred at 40 ° C. for 2.5 h. 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine are then rapidly introduced and the mixture is stirred at 70 ° C. for 12 hours. The resulting reaction solution is evaporated to dryness at 70 ° C. in vacuo. 25.9 g of a colorless powder of the formula are obtained
Figure imgb0033
with an active content of 75%. The compound shows the longest-wavelength absorption maximum at 284 nm (water).

Beispiel 17: Eine eiskalte Suspension von 10,3 g 4-N-(2,4-Dichlor-6-triazinyl)aminobenzolsulfonsäure Natriumsalz wird mit 3,15 g Diethanolamin versetzt. Man erwärmt langsam auf 40°C und hält den pH-Wert des Reaktionsgemisches durch Zutropfen von ca. 15 ml 15%iger Sodalösung zwischen 6,5 und 7. Nach 3 Stunden bei 40°C werden rasch 4,7 g 4-Amino-2,2,6,6-tetramethylpiperidin eingetragen. Man rührt während 16 Stunden bei 70°C nach und dampft die Reaktionslösung im Vakuum ein. Man erhält 11,8 g eines farblosen Pulvers der Formel

Figure imgb0034

das einen Aktivgehalt von 73% und bei 275 nm (Wasser) das langwelligste Absorptionsmaximum aufweist. Example 17: 3.15 g of diethanolamine are added to an ice-cold suspension of 10.3 g of 4-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt. The mixture is slowly warmed to 40 ° C. and the pH of the reaction mixture is kept between 6.5 and 7 by dropwise addition of about 15 ml of 15% sodium carbonate solution. After 3 hours at 40 ° C., 4.7 g of 4-amino are rapidly 2,2,6,6-tetramethylpiperidine entered. The mixture is subsequently stirred at 70 ° C. for 16 hours and the reaction solution is evaporated in vacuo. 11.8 g of a colorless powder of the formula are obtained
Figure imgb0034
which has an active content of 73% and the longest-wavelength absorption maximum at 275 nm (water).

Beispiel 18: Eine Suspension von 10,3 g 2-N-(2,4-Dichlor-6-triazinyl)aminobenzolsulfonsäure Natriumsalz in 100 ml dest. Wasser wird bei 5°C mit 2,6 g Morpholin versetzt und innerhalb von 1,5 Stunden auf 40°C erwärmt, wobei der pH-Wert des Reaktionsgemisches durch Zutropfen von 19 ml 15%iger Sodalösung zwischen 6,5 und 7 gehalten wird. Danach wird 1 Stunde bei 40°C ausgerührt. Die farblose Suspension wird mit 4,7 g 4-Amino-2,2,6,6-tetramethylpiperidin versetzt und auf 70°C erhitzt. Man rührt während 15 Stunden bei dieser Temperatur, kühlt auf Raumtemperatur ab und filtriert. Der Rückstand wird mit Wasser gewaschen und im Vakuum bei 80°C getrocknet. Man erhält 11,7 g einer farblosen Verbindung der Formel

Figure imgb0035

welche bei 264 nm (Wasser) das langwelligste Absorptionsmaximum aufweist. Example 18: A suspension of 10.3 g of 2-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 100 ml of dist. 2.6 g of morpholine are added to water at 5 ° C. and the mixture is heated to 40 ° C. in the course of 1.5 hours, the pH of the reaction mixture being kept between 6.5 and 7 by dropwise addition of 19 ml of 15% sodium carbonate solution . The mixture is then stirred at 40 ° C for 1 hour. The colorless suspension is mixed with 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine and heated to 70.degree. The mixture is stirred at this temperature for 15 hours, cooled to room temperature and filtered. The residue is washed with water and dried in vacuo at 80 ° C. 11.7 g of a colorless compound of the formula are obtained
Figure imgb0035
which has the longest wave absorption maximum at 264 nm (water).

Beispiel 19: Eine Suspension von 4,4 g der Verbindung von Beispiel 1 in 30 ml dest. Wasser wird durch Zugabe von 2 ml konz. Natronlauge in Lösung gebracht. Anschliessend neutralisiert man die Lösung mit konz. Salzsäure, wobei eine fein verteilte Suspension entsteht. Man gibt dann 5 ml einer wässrigen Lösung von 0,94 g Phenol hinzu und erhitzt während 15 Stunden auf 90°C. Nach dem Abkühlen auf Raumtemperatur filtriert man, wäscht mit Wasser und trocknet im Vakuum bei 80°C. Man erhält 4,7 g eines weissen Pulvers der Formel

Figure imgb0036

mit dem langwelligsten Absorptionsmaximum bei 275 nm (Wasser). Example 19: A suspension of 4.4 g of the compound from Example 1 in 30 ml of dist. Water is concentrated by adding 2 ml. Bring sodium hydroxide solution. Then neutralize the solution with conc. Hydrochloric acid, creating a finely divided suspension. 5 ml of an aqueous solution of 0.94 g of phenol are then added and the mixture is heated at 90 ° C. for 15 hours. After cooling to room temperature, the mixture is filtered, washed with water and dried in vacuo at 80 ° C. 4.7 g of a white powder of the formula are obtained
Figure imgb0036
with the longest wave absorption maximum at 275 nm (water).

Beispiel 20: Eine Suspension von 10,3 g 2-N-(2,4-Dichlor-6-triazinyl)aminobenzolsulfonsäure Natriumsalz in 100 ml dest. Wasser wird bei 5°C mit 3,3 g Thiophenol versetzt. Man hält den pH-Wert des Reaktionsgemisches durch Zutropfen von 15%iger Sodalösung zwischen 6,5 und 7 und lässt die Innentemperatur gleichzeitig auf Raumtemperatur steigen. Anschliessend rührt man während einer Stunde bei 40°C aus, trägt rasch 4,7 g 4-Amino-2,2,6,6-tetramethylpiperidin ein und erhitzt während 16 Stunden auf 70°C. Man kühlt auf Raumtemperatur ab, zerkleinert das Reaktionsgemisch in einem Mixer, filtriert und wäscht mit Wasser. Der Rückstand wird in 100 ml Ethanol angeschlämmt, abfiltriert, mit Ethanol gewaschen und im Vakuum bei 80°C getrocknet. Man erhält 9,7 g einer farblosen Verbindung der Formel

Figure imgb0037

vom Schmelzpunkt 354°C. Example 20: A suspension of 10.3 g of 2-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 100 ml of dist. Water is mixed with 3.3 g of thiophenol at 5 ° C. The pH of the reaction mixture is kept between 6.5 and 7 by dropwise addition of 15% sodium carbonate solution and the internal temperature is allowed to rise to room temperature at the same time. The mixture is then stirred at 40 ° C. for one hour, 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine are rapidly introduced and the mixture is heated to 70 ° C. for 16 hours. The mixture is cooled to room temperature, the reaction mixture is ground in a mixer, filtered and washed with water. The residue is suspended in 100 ml of ethanol, filtered off, washed with ethanol and dried in vacuo at 80 ° C. 9.7 g of a colorless compound of the formula are obtained
Figure imgb0037
melting point 354 ° C.

Beispiel 21: Eine Lösung von 5,9 g 2,4-Dichlor-6-methylthio-s-triazin in 30 ml Aceton wird in 50 ml Eiswasser eingerührt. Anschliessend tropft man 100 ml einer neutralen wässrigen Lösung von 5,2 g Sulfanilsäure hinzu und hält den pH-Wert des Reaktionsgemisches durch Zutropfen von 15%iger Sodalösung zwischen 6,5 und 7. Danach erwärmt man eine Stunde auf 40°C und destilliert das Aceton anschliessend unter vermindertem Druck ab. Das Reaktionsgemisch wird rasch mit 4,7 g 4-Amino-2,2,6,6-tetramethylpiperidin versetzt und während 2 Stunden bei 70°C gerührt. Die Suspension wird auf Raumtemperatur gekühlt, abfiltriert und mit dest. Wasser gewaschen. Nach dem Trocknen im Vakuum bei 80°C verbleiben 13,1 g einer farblosen Verbindung der Formel

Figure imgb0038

welche bei 281 nm (Wasser) das langwelligste Absorptionsmaximum aufweist. Example 21: A solution of 5.9 g of 2,4-dichloro-6-methylthio-s-triazine in 30 ml of acetone is stirred into 50 ml of ice water. 100 ml of a neutral aqueous solution of 5.2 g of sulfanilic acid are then added dropwise, and the pH of the reaction mixture is kept between 6.5 and 7 by the dropwise addition of 15% sodium carbonate solution one hour at 40 ° C and the acetone is then distilled off under reduced pressure. The reaction mixture is quickly mixed with 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine and stirred at 70 ° C. for 2 hours. The suspension is cooled to room temperature, filtered off and distilled with dist. Washed water. After drying in vacuo at 80 ° C., 13.1 g of a colorless compound of the formula remain
Figure imgb0038
which has the longest-wavelength absorption maximum at 281 nm (water).

Beispiel 22: Eine Suspension von 9,95 g 2-N-(2,4-Dichlor-6-triazinyl)aminobenzolsulfonsäure Natriumsalz in 100 ml dest. Wasser wird bei 5°C mit 5,0 g 4-Amino-2,2,6,6-tetramethylpiperidin-1-oxyl versetzt und während 16 Stunden bei Raumtemperatur gerührt. Anschliessend wird die orangefarbene Suspension durch Hinzufügen konzentrierter Natronlauge bei einem pH-Wert von 10 in Lösung gebracht. Man versetzt mit 7,8 g Natriumdithionit und rührt bei Raumtemperatur bis zur vollständigen Entfärbung. Danach neutralisiert man das Reaktionsgemisch mit konz. Salzsäure, filtriert und wäscht mit dest. Wasser. Der Rückstand wird im Vakuum bei 50°C getrocknet. Man erhält auf diese Weise 6,1 g eines farblosen Pulvers der Formel

Figure imgb0039

mit dem langwelligsten Absorptionsmaximum bei 279 nm (Wasser). Example 22: A suspension of 9.95 g of 2-N- (2,4-dichloro-6-triazinyl) aminobenzenesulfonic acid sodium salt in 100 ml of dist. Water is added at 5 ° C with 5.0 g of 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl and stirred for 16 hours at room temperature. The orange-colored suspension is then brought into solution by adding concentrated sodium hydroxide solution at a pH of 10. 7.8 g of sodium dithionite are added and the mixture is stirred at room temperature until it has completely decolorized. Then the reaction mixture is neutralized with conc. Hydrochloric acid, filtered and washed with dist. Water. The residue is dried in vacuo at 50 ° C. 6.1 g of a colorless powder of the formula are obtained in this way
Figure imgb0039
with the longest wave absorption maximum at 279 nm (water).

Beispiel 23a(Zwischenprodukt): Eine Anschlämmung von 22,6 g 2-Phenyl-4,6-dichlor-s-triazin in 150 ml Aceton wird unter Rühren auf 100 ml Eiswasser gegossen und anschliessend mit einer neutralen Löstung von 17,3 g Sulfanilsäure in 100 ml dest. Wasser versetzt. Man lässt die Innentemperatur auf 10 - 15°C steigen und hält den pH-Wert des Reaktionsgemisches durch Zutropfen von 30%iger Natronlauge bei 6 (Verbrauch 13 ml). Danach rührt man während 15 Stunden bei 40°C. Die entstandene Lösung wird auf Raumtemperatur gekühlt. Das ausgefallene Produkt wird abgesaugt, mit 20%iger Kochsalzlösung gewaschen und im Vakuum bei 50°C getrocknet. Man erhält 39,1 g eines weissen Pulvers der Formel

Figure imgb0040

mit einem Aktivgehalt von 90,1%. Example 23a (intermediate): A slurry of 22.6 g of 2-phenyl-4,6-dichloro-s-triazine in 150 ml of acetone is poured onto 100 ml of ice water with stirring and then with a neutral solution of 17.3 g of sulfanilic acid in 100 ml dist. Water added. The internal temperature is allowed to rise to 10-15 ° C. and the pH of the Reaction mixture by dropwise addition of 30% sodium hydroxide solution at 6 (consumption 13 ml). The mixture is then stirred at 40 ° C. for 15 hours. The resulting solution is cooled to room temperature. The precipitated product is filtered off, washed with 20% sodium chloride solution and dried in vacuo at 50 ° C. 39.1 g of a white powder of the formula are obtained
Figure imgb0040
with an active content of 90.1%.

Beispiel 23: Eine Suspension von 12,8 g der Verbindung der Formel (123a) in 70 ml dest. Wasser wird bei Raumtemperatur unter Rühren mit 4,7 g 4-Amino-2,2,6,6-tetramethylpiperidin versetzt. Anschliessend rührt man während 30 Minuten bei 55°C, wobei Lösung eintritt, und dann während einer Stunde bei 80°C. Zuletzt rührt man während 15 Stunden bei 55°C nach. Man kühlt auf Raumtemperatur, saugt den Niederschlag ab und wäscht mit dest. Wasser chloridfrei. Nach dem Trocknen im Vakuum bei 50°C erhält man 13,5 g einer farblosen Verbindung der Formel

Figure imgb0041

Das langwelligste Absorptionsmaximum beträgt 262 nm (Wasser). Example 23: A suspension of 12.8 g of the compound of the formula (123a) in 70 ml of dist. 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine are added to water at room temperature with stirring. The mixture is then stirred at 55 ° C. for 30 minutes, with solution entering, and then at 80 ° C. for one hour. Finally, the mixture is stirred at 55 ° C. for 15 hours. The mixture is cooled to room temperature, the precipitate is filtered off and washed with dist. Chloride-free water. After drying in vacuo at 50 ° C., 13.5 g of a colorless compound of the formula are obtained
Figure imgb0041
The longest wave absorption maximum is 262 nm (water).

Beispiel 24: Eine Suspension von 12,8 g der Verbindung der Formel (123a) in 70 ml dest. Example 24: A suspension of 12.8 g of the compound of formula (123a) in 70 ml of dist.

Wasser wird bei Raumtemperatur unter Rühren mit 5,1 g 4-N-Methylamino-2,2,6,6-tetramethylpiperidin versetzt. Man rührt nacheinander während einer Stunde bei 55°C und 18 Stunden bei 70°C. Nach dem Abkühlen auf Raumtemperatur wird der entstandene Niederschlag abgesaugt, mit dest. Wasser chloridfrei gewaschen und im Vakuum bei 55°C getrocknet. Man erhält 14,1 g einer farblosen Verbindung der Formel

Figure imgb0042

mit dem langwelligsten Absorptionsmaximum bei 265 nm (Wasser).5.1 g of 4-N-methylamino-2,2,6,6-tetramethylpiperidine are added to water at room temperature with stirring. The mixture is stirred in succession for one hour at 55 ° C. and 18 hours at 70 ° C. After cooling to room temperature, the precipitate formed is filtered off with distilled water. Washed water free of chloride and dried in vacuo at 55 ° C. 14.1 g of a colorless compound of the formula are obtained
Figure imgb0042
with the longest wave absorption maximum at 265 nm (water).

Beispiel 25: Eine Suspension von 12,8 g der Verbindung der Formel (123a) in 70 ml dest. Wasser wird bei Raumtemperatur unter Rühren mit 6,4 g 4-N-Butylamino-2,2,6,6-tetramethylpiperidin versetzt. Das Reaktionsgemisch wird während 4 Stunden bei 70°C gerührt, auf Raumtemperatur gekühlt und filtriert. Nach dem Waschen mit dest. Wasser und Trocknen im Vakuum bei 55°C verbleiben 15,2 g eines farblosen Pulvers der Formel

Figure imgb0043

Das langwelligste Absorptionsmaximum beträgt 255 nm (Methanol). Example 25: A suspension of 12.8 g of the compound of formula (123a) in 70 ml of dist. 6.4 g of 4-N-butylamino-2,2,6,6-tetramethylpiperidine are added to water at room temperature with stirring. The reaction mixture is stirred at 70 ° C. for 4 hours, cooled to room temperature and filtered. After washing with dist. Water and drying in vacuo at 55 ° C remain 15.2 g of a colorless powder of the formula
Figure imgb0043
The longest wave absorption maximum is 255 nm (methanol).

Beispiel 26: Man bereitet eine Suspension von 4-N-Methyl-(2-chlor-4-phenyl-6-s-triazinyl)-aminobenzolsulfonsäure Natriumsalz durch Umsetzung von 5,65 g 2-Phenyl-4,6-dichlor-s-triazin mit 4,7 g N-Methylsulfanilsäure und den Reaktionsbedingungen von Beispiel 23a. Anschliessend werden unter Rühren bei 40°C 4,3 g 4-N-Methylamino-2,2,6,6-tetramethylpiperidin eingetragen und die Temperatur auf 75°C erhöht. Man rührt während 18 Stunden bei dieser Temperatur nach, kühlt auf Raumtemperatur und saugt den entstandenen Niederschlag ab. Nach dem Waschen mit dest. Wasser und Trocknen im Vakuum bei 55°C erhält man 12,6 g einer farblosen Verbindung der Formel

Figure imgb0044

welche bei 250 nm (Methanol) das langwelligste Absorptionsmaximum aufweist. Example 26: A suspension of 4-N-methyl- (2-chloro-4-phenyl-6-s-triazinyl) -aminobenzenesulfonic acid sodium salt is prepared by reacting 5.65 g of 2-phenyl-4,6-dichloro-s -triazine with 4.7 g of N-methylsulfanilic acid and the reaction conditions of Example 23a. 4.3 g of 4-N-methylamino-2,2,6,6-tetramethylpiperidine are then introduced with stirring at 40 ° C. and the temperature is raised to 75 ° C. The mixture is subsequently stirred at this temperature for 18 hours, cooled to room temperature and the precipitate formed is filtered off with suction. After washing with dist. Water and drying in vacuo at 55 ° C gives 12.6 g of a colorless compound of the formula
Figure imgb0044
which has the longest-wavelength absorption maximum at 250 nm (methanol).

Beispiel 27: Verfährt man wie in Beispiel 23a beschrieben, setzt jedoch anstelle von 2-Phenyl-4,6-dichlor-s-triazin 2-p-Tolyl-4,6-dichlor-s-triazin und anstelle von Sulfanil-Metanilsäure ein, so erhält man die entsprechende 3-N-(2-Chlor-4-p-tolyl-6-s-triazinyl)aminobenzolsulfonsäure als Natriumsalz. Diese wird ohne Isolierung direkt mit 4-Amino-1,2,2,6,6-pentamethyl-piperidin unter den Reaktionsbedungungen von Beispiel 24 kondensiert. Man erhält ein farbloses Pulver der Formel

Figure imgb0045

Das langwelligste Absorptionsmaximum beträgt 265 nm (Wasser). Example 27: The procedure is as described in Example 23a, but using 2-p-tolyl-4,6-dichloro-s-triazine instead of 2-phenyl-4,6-dichloro-s-triazine and instead of sulfanil-metanilic acid , the corresponding 3-N- (2-chloro-4-p-tolyl-6-s-triazinyl) aminobenzenesulfonic acid is obtained as the sodium salt. This is condensed directly with 4-amino-1,2,2,6,6-pentamethyl-piperidine without isolation under the reaction conditions of Example 24. A colorless powder of the formula is obtained
Figure imgb0045
The longest wave absorption maximum is 265 nm (water).

Beispiel 28: Eine Lösung von 4,9 g 2,4-Dichlor-6-methyl-s-triazin in Aceton (50 ml) wird auf Eiswasser (50 ml) ausgetragen. Anschliessend wird unter raschem Rühren bei 10°C eine neutrale Lösung von 5,2 g Sulfanilsäure zugegeben und durch Zutropfen einer 30%igen Natronlauge der pH-Wert des Reaktionsgemisches bei 6 gehalten. Der Verbrauch an Natronlauge beträgt 4,1 ml. Danach rührt man während einer Stunde bei Raumtemperatur und 3 Stunden bei 40°C aus. Man trägt rasch 5,1 g 4-N-Methylamino-2,2,6,6-tetramethylpiperidin ein und erhöht die Temperatur innerhalb von 30 Minuten auf 55°C. Zuletzt rührt man während einer Stunde bei dieser Temperatur. Nach dem Abkühlen auf Raumtemperatur lässt man das Reaktionsgemisch über Nacht stehen. Man saugt vom Niederschlag ab, wäscht mit dest. Wasser nach und trocknet im Vakuum bei 50°C. Es werden 9,9 g einer farblosen Verbindung der Formel

Figure imgb0046

erhalten, welche das langwelligste Absorptionsmaximum bei 276 nm (Wasser) aufweist. Example 28: A solution of 4.9 g of 2,4-dichloro-6-methyl-s-triazine in acetone (50 ml) is discharged onto ice water (50 ml). A neutral solution of 5.2 g of sulfanilic acid is then added with rapid stirring at 10 ° C. and the pH of the reaction mixture is kept at 6 by dropwise addition of a 30% strength sodium hydroxide solution. The consumption of sodium hydroxide solution is 4.1 ml. The mixture is then stirred at room temperature for 1 hour and at 40 ° C. for 3 hours. 5.1 g of 4-N-methylamino-2,2,6,6-tetramethylpiperidine are rapidly introduced and the temperature is raised to 55 ° C. in the course of 30 minutes. Finally, the mixture is stirred for one hour at this temperature. After cooling to room temperature, the reaction mixture is left to stand overnight. It is suctioned off from the precipitate, washed with dist. Water and dries in vacuo at 50 ° C. There are 9.9 g of a colorless compound of the formula
Figure imgb0046
obtained, which has the longest wave absorption maximum at 276 nm (water).

Applikationsbeispiele:Application examples:

Beispiel 29: Es werden 4 Muster einer Polyamid 6-Maschenware von je 10 g vorbereitet und in einem Färbeapparat, z.B. einem ®AHIBA-Färbeapparat, bei einem Flottenverhältnis von 1:30 behandelt. Zwei dieser Muster werden "blindgefärbt" (d.h. ohne Farbstoff behandelt: Flotten 1 und 3), zwei dagegen gefärbt (Flotten 2 und 4). Example 29: 4 samples of a polyamide 6 knitted fabric of 10 g each are prepared and treated in a dyeing machine, for example an ®AHIBA dyeing machine, at a liquor ratio of 1:30. Two of these samples are "blind-dyed" (ie treated without dye: fleets 1 and 3), two are stained (fleets 2 and 4).

Es werden somit 4 Färbeflotten bereitet, die jeweils 0,5 g/l Mononatriumphosphat und 1,5 g/l Dinatriumphosphat (≙ pH-Wert 7) enthalten. In den Flotten 2 und 4 werden folgende Farbstoffe (berechnet auf das Warengewicht) gelöst:
0,04 % des Farbstoffgemisches, bestehend aus 81 Teilen der Verbindung der Formel

Figure imgb0047

und 12 Teilen der Verbindung der Formel
Figure imgb0048
und 0,002 % des Farbstoffes der Formel
Figure imgb0049
Die Flotten 3 und 4 enthalten zusätzlich noch 1 % des Natriumsalzes der Verbindung der Formel (101).4 dyeing liquors are thus prepared, each containing 0.5 g / l monosodium phosphate and 1.5 g / l disodium phosphate (≙ pH 7). The following dyes (calculated on the weight of the goods) are dissolved in fleets 2 and 4:
0.04% of the dye mixture consisting of 81 parts of the compound of the formula
Figure imgb0047
and 12 parts of the compound of the formula
Figure imgb0048
and 0.002% of the dye of the formula
Figure imgb0049
The liquors 3 and 4 additionally contain 1% of the sodium salt of the compound of the formula (101).

Mit dem vorbereiteten Textilmaterial geht man bei 40°C in die Flotten ein, verweilt 10 Minuten bei dieser Temperatur und erhitzt innerhalb von 30 Minuten auf 95°C. Nach einer Behandlungszeit von 20 Minuten gibt man 2 % Essigsäure (80%ig) hinzu und behandelt weitere 20 Minuten. Schliesslich kühlt man auf 60°C ab, spült, zentrifugiert und trocknet die Muster.With the prepared textile material, one enters the liquors at 40 ° C, stays at this temperature for 10 minutes and heats to 95 ° C within 30 minutes. After a treatment time of 20 minutes, add 2% acetic acid (80%) and treat for a further 20 minutes. Finally, cool to 60 ° C, rinse, centrifuge and dry the samples.

Die Färbungen werden auf ihre Lichtechtheiten nach SN-ISO 105-B02 (= XENON) und DIN 75.202 (= FAKRA) geprüft, sodann werden sie einem Hitzetest bei 130°C, 60 Stunden zur Prüfung der Farbtonbeständigkeit unterworfen. Die Blindfärbungen werden nach DIN 75.202 während 216 Stunden belichtet und Reissfestigkeit und Dehnung nach SN 198.461 ermittelt.The dyeings are tested for their light fastness according to SN-ISO 105-B02 (= XENON) and DIN 75.202 (= FAKRA), then they are subjected to a heat test at 130 ° C for 60 hours to check the color stability. The blind dyeings are exposed according to DIN 75.202 for 216 hours and tear strength and elongation determined according to SN 198.461.

Folgende Ergebnisse werden erhalten: Tabelle II Lichtechtheit Reissfestigkeit/Dehnung % Hitzetest 130°; 60 h Xenon Fakra 144h Fakra 216h Flotte 1 - - - 7,5/27,4 - Flotte 2 7 *1H *1H - Farbton: beige Flotte 3 - - - 74,4/85,5 - Flotte 4 7-8 3-4 2-3 - Farbton: grau (kaum verändert) * keine Reissfestigkeit mehr The following results are obtained: Table II Lightfastness Tensile strength / elongation% Heat test 130 °; 60 h xenon Fakra 144h Fakra 216h Fleet 1 - - - 7.5 / 27.4 - Fleet 2 7 * 1H * 1H - Color: beige Fleet 3 - - - 74.4 / 85.5 - Fleet 4 7-8 3-4 2-3 - Color: gray (hardly changed) * no more tear resistance

Es ist ersichtlich, dass durch die Applikation der Verbindung der Formel (101) eine deutliche photochemische und thermische Stabilität des Fasermaterials bzw. der Färbung erzielt wird.It can be seen that the application of the compound of the formula (101) results in a clear photochemical and thermal stability of the fiber material or the dyeing.

Beispiel 30: Zwei Muster einer Polyamid 6 - Maschenware von je 10 g werden wie in Beispiel 29 beschrieben, gefärbt, mit dem Unterschied, dass die beiden Flotten folgende Farbstoffe enthalten: 0,05 % des Farbstoffes der Formel

Figure imgb0050

0,085 % des Farbstoffgemisches der Formeln
Figure imgb0051
sowie 0,035 % des Farbstoffgemisches der Formeln (Ia) und (Ib). Example 30: Two samples of a polyamide 6 knitted fabric of 10 g each are dyed as described in Example 29, with the difference that the two liquors contain the following dyes: 0.05% of the dye of the formula
Figure imgb0050
0.085% of the dye mixture of the formulas
Figure imgb0051
and 0.035% of the dye mixture of the formulas (Ia) and (Ib).

Die Flotte (2) enthält zusätzlich 1 % des Natriumsalzes der Verbindung der Formel (101).The liquor (2) additionally contains 1% of the sodium salt of the compound of the formula (101).

Die Prüfung von Lichtechtheit und Hitzebeständigkeit der Färbungen ergibt folgendes Ergebnis (Tabelle III): Tabelle III Lichtechtheit Hitzetest 130°; 60 h Xenon Fakra 144h Fakra 216 h Flotte 1 7 *1H *1H Farbton: oliv → braun Flotte 2 7-8 2-3 1-2 Farbton: kaum verändert * nicht mehr reissfest Testing the lightfastness and heat resistance of the dyeings gives the following result (Table III): Table III Lightfastness Heat test 130 °; 60 h xenon Fakra 144h Fakra 216 h Fleet 1 7 * 1H * 1H Color: olive → brown Fleet 2 7-8 2-3 1-2 Color: hardly changed * no longer tearproof

Beispiel 31 und 32: Wie in den Beispielen 29 und 30 beschrieben, werden auf Polyamid 6 - Webtrikot Hellgrau- und Olivfärbungen auf herkömmliche Weise hergestellt. Diese Färbungen werden auf einem Foulard (Abquetscheffekt 105 %) mit Lösungen imprägniert, die 10 g/l der Verbindungen der Formeln (105) und (107) gelöst enthalten. Die foulardierten Färbungen werden gerollt, man lässt sie sodann in einer Polyethylenfolie 2 Stunden verweilen. Anschliessend wird bei 80°C getrocknet. Examples 31 and 32: As described in Examples 29 and 30, light gray and olive dyeings are produced in a conventional manner on polyamide 6 woven jersey. These dyeings are impregnated on a foulard (squeezing effect 105%) with solutions which contain 10 g / l of the compounds of the formulas (105) and (107) in solution. The padded dyeings are rolled and then left in a polyethylene film for 2 hours. The mixture is then dried at 80 ° C.

Unterwirft man diese Färbungen der Lichtechtheitsbewertung und dem Hitzetest, so erhält man ebenfalls Ergebnisse, die eine erhöhte photochemische und thermische Stabilität beweisen.If these colors are subjected to the light fastness assessment and the heat test, results are also obtained which demonstrate increased photochemical and thermal stability.

Beispiel 33: Man verfährt wie in Beispiel 30 beschrieben mit dem Unterschied, dass die Flotte 2 anstelle der Verbindung der Formel (101) die Verbindung der Formel (108) enthält. EXAMPLE 33 The procedure is as described in Example 30, with the difference that the liquor 2 contains the compound of the formula (108) instead of the compound of the formula (101).

Die Färbungen werden auf ihre Lichtechtheiten nach DIN 75.202 ("FAKRA") geprüft. Die beiden Färbungen werden dazu auf einer Fläche von ca. 4 x 12 cm während 216 Stunden nach derselben Methode belichtet und danach nach SN 198 461 auf ihre Reissfestigkeit und Dehnung geprüft. Die Ergebnisse sind in Tabelle IV aufgeführt: Tabelle IV FÄRBUNG * Lichtechtheit nach FAKRA Reissfestigkeit/Dehnung (% vom Ausgangsmaterial) 144 Stunden 216 Stunden 1 1 1 10,7/16,2 2 2-3 2 76,7/79,2 * Bewertung nach Graumassstab 1-5 The dyeings are tested for their light fastness in accordance with DIN 75.202 ("FAKRA"). The two dyeings are exposed on an area of approx. 4 x 12 cm for 216 hours using the same method and then tested for tensile strength and elongation according to SN 198 461. The results are shown in Table IV: Table IV COLORING * FAKRA light fastness Tensile strength / elongation (% of starting material) 144 hours 216 hours 1 1 1 10.7 / 16.2 2nd 2-3 2nd 76.7 / 79.2 * Assessment according to gray scale 1-5

Das Ergebnis zeigt, dass die Verbindung der Formel (108) eine deutliche Stabilisierung des Faserpolymers sowie des Farbstoffes selbst bewirkt.The result shows that the compound of the formula (108) brings about a significant stabilization of the fiber polymer and of the dye itself.

Beispieie 34 und 35: Drei Muster von je 10 g einer Polyamid-Maschenware werden, wie in Beispiel 29 beschrieben, vorbereitet, gefärbt und fertiggestellt, wobei dieselbe Farbstoffkombination verwendet wird. Die Flotte für die Färbung Nr. 1 enthält keine weiteren Zusätze, Färbeflotte 2 enthält noch 0,75% des Natriumsalzes der Verbindung der Formel (111), Färbeflotte 3 enthält 0,75 % des Natriumsalzes der Verbindung der Formel (110). Examples 34 and 35: Three samples of 10 g each of a knitted polyamide fabric are prepared, dyed and finished as described in Example 29, using the same dye combination. The liquor for dyeing No. 1 contains no further additives, dye liquor 2 still contains 0.75% of the sodium salt of the compound of formula (111), dye liquor 3 contains 0.75% of the sodium salt of the compound of formula (110).

Die Bestimmungen der Lichtechtheiten der Färbungen nach SN-ISO 105-B02 (Xenon) und DIN 75.202("FAKRA") ergeben folgende Ergebnisse (Tabelle V): Tabelle V GRAUFÄRBUNG LICHTECHTHEITEN nach XENON FAKRA 144 h FAKRA 216 h 1 (ohne Zusatz) 6-7 1(*) 1(*) 2 [+ Verbindung (111)] 7-8 -3 2+ 3 [+ Verbindung (110)] 7 2-3 2 (*) nicht mehr reissfest The determination of the lightfastness of the dyeings according to SN-ISO 105-B02 (xenon) and DIN 75.202 ("FAKRA") gives the following results (Table V): Table V GRAY COLORING LIGHT FASTNESSES after XENON FAKRA 144 h FAKRA 216 h 1 (without addition) 6-7 1(*) 1(*) 2 [+ compound (111)] 7-8 -3 2+ 3 [+ connection (110)] 7 2-3 2nd (*) no longer tearproof

Aus den Resultaten ist ersichtlich, dass die Verbindungen (110) und (111) die photochemische Stabilität der Graufärbungen sehr deutlich verbessern. Die Färbung ohne Stabilisator ist von ihrer mechanischen Stabilität als auch von der Lichtechtheit betrachtet, unbrauchbar.The results show that compounds (110) and (111) very significantly improve the photochemical stability of the gray colorations. The coloring without stabilizer is unusable from its mechanical stability as well as from the light fastness.

Beispiel 36: Es werden 10 Muster eines PA - Trikots von je 10 g und 10 Flotten bereitet wie in Beispiel 29 angegeben. In den Flotten 1 bis 5 werden jeweils 0,04 % des Farbstoffgemisches der Formeln (Ia) und (Ib) und 0,002 % des Farbstoffes der Formel (II) gelöst, in den Flotten 6 bis 10 wird ohne weiteren Farbstoffzusatz blindgefärbt. Den Flotten 2 und 7 werden jeweils 0,75 % des Natriumsalzes der Verbindung der Formel (109) zugesetzt, den Flotten 3 und 8 jeweils 0,75 % der Verbindung der Formel (112), den Flotten 4 und 9 jeweils 0,75 % der Verbindung der Formel (113) und den Flotten 5 und 10 jeweils 0,75 % einer Verbindung der Formel (114) in gelöster Form zugegeben. Alle 10 Muster werden, wie in Beispiel 29 beschrieben, behandelt und fertiggestellt. Die Färbungen 1 bis 5 werden nach DIN 75.202 (FAKRA) auf ihre Lichtechtheiten geprüft. Die Blindfärbungen 6 - 10 werden 216 Stunden nach SN-ISO 105-B02 (=XENON) und DIN 75.202 (FAKRA) belichtet und nach SN 198.451 auf Reissfestigkeit und Dehnung geprüft mit folgenden Ergebnissen (Tabelle VI): Tabelle VI MUSTER VON LICHTECHTHEIT REISSFESTIGKEIT/DEHNUNG (%) XENON FAKRA 144 Stunden 216 Stunden Flotte 1 ● 7 1H* 1H* - Flotte 6 - - - 3,9/22,8 Flotte 2 X 7 - 8 3 - 4 2 - 3 - Flotte 7 - - - 61,7/73,7 Flotte 3 △ 7 - 8 3 - 4 2 - 3 - Flotte 8 - - - 66,2/74,7 Flotte 4 □ 7 - 8 3 - 4 2 - 3 - Flotte 9 - - - 79,3/84,9 Flotte 5 ○ 7 - 8 2 - 3 2 - Flotte 10 - - - 62,4/77,4 * Muster nicht mehr reissfest ● ohne Zusatz
X + Verbindung der Formel (109)
△ + Verbindung der Formel (112)
□ + Verbindung der Formel (113)
○ + Verbindung der Formel (114) Example 36: 10 samples of a PA jersey of 10 g each and 10 fleets are prepared as indicated in Example 29. In each of the liquors 1 to 5, 0.04% of the dye mixture of the formulas (Ia) and (Ib) and 0.002% of the dye of the formula (II) are dissolved; in the liquors 6 to 10, dyeing is carried out blindly without any additional dye. Fleets 2 and 7 are each added 0.75% of the sodium salt of the compound of the formula (109), fleets 3 and 8 each 0.75% of the compound of the formula (112), fleets 4 and 9 each 0.75% 0.75% of a compound of the formula (114) was added to the compound of the formula (113) and the liquors 5 and 10 in dissolved form. All 10 samples are treated and completed as described in Example 29. Colorings 1 to 5 are tested for light fastness according to DIN 75.202 (FAKRA). The blind dyeings 6-10 are exposed 216 hours according to SN-ISO 105-B02 (= XENON) and DIN 75.202 (FAKRA) and tested according to SN 198.451 for tear strength and elongation with the following results (Table VI): Table VI PATTERN OF LIGHT FASTNESS TENSILE STRENGTH / EXPANSION (%) XENON FAKRA 144 hours 216 hours Fleet 1 ● 7 1H * 1H * - Fleet 6 - - - 3.9 / 22.8 Fleet 2 X 7-8 3-4 2-3 - Fleet 7 - - - 61.7 / 73.7 Fleet 3 △ 7-8 3-4 2-3 - Fleet 8 - - - 66.2 / 74.7 Fleet 4 □ 7-8 3-4 2-3 - Fleet 9 - - - 79.3 / 84.9 Fleet 5 ○ 7-8 2-3 2nd - Fleet 10 - - - 62.4 / 77.4 * Pattern no longer tearproof ● without addition
X + compound of the formula (109)
△ + compound of the formula (112)
□ + compound of formula (113)
○ + compound of formula (114)

Die Ergebnisse zeigen, dass dem Polyamidmaterial durch die Verbindungen der Formeln (109), (112), (113) und (114) eine deutliche photochemische Stabilisierung gegeben wird.The results show that the polyamide material is given a clear photochemical stabilization by the compounds of the formulas (109), (112), (113) and (114).

Beispiel 37: Man verfährt wie in Beispiel 29 beschrieben, d.h. es werden abwechselnd Blindbehandlungen und Hellgraufärbungen hergestellt und getestet. Somit enthalten die vorbereiteten Färbeflotten 1, 3, 5, 7, 9 (= Blindfärbung) und 2, 4, 6, 8, 10 (= Färbungen) jeweils 0,25% der Verbindungen der Formeln (122), (123), (127) und (128). Die Ergebnisse sind aus Tabelle VII zu entnehmen, wobei die Blindfärbungen durch die Reissfestigkeit und Dehnung (belichtet nach DIN 75.202 (=FAKRA) und geprüft nach SN 198.451), die Färbungen nach deren Lichtechtheiten (DIN 75.202/FAKRA) charakterisiert wurden. Tabelle VII FLOTTE Nr./ZUSATZ REISSFESTIGKEIT/DEHNUNG (%) nach Belichtung nach 216 h FAKRA LICHTECHTHEITEN FAKRA 144 h FAKRA 216 h Flotte 1: kein Zusatz 7,9/28,6 - - Flotte 2: kein Zusatz 1H 1H Flotte 3: + 0,25% der Verbindung der Formel (123) 75,8/82,1 - - Flotte 4: + 0,25% der Verbindung der Formel (123) - 3 2-3 Flotte 5: + 0,25% der Verbindung der Formel (128) 58,0/71,6 - - Flotte 6: + 0,25% dr Verbindung der Formel (128) - 2-3 1-2 Flotte 7: + 0,25% der Verbindung der Formel (127) 64,3/72,0 - - Flotte 8: + 0,25% der Verbindung der Formel (127) - 3 2-3 Flotte 9: + 0,25% der Verbindung der Formel (122) 87,9/88,5 - - Flotte 10: + 0,25% der Verbindung der Formel (122) - 3-4 3 Example 37: The procedure is as described in Example 29, ie blind treatments and light gray colorations are alternately produced and tested. The prepared dyeing liquors 1, 3, 5, 7, 9 (= blind dyeing) and 2, 4, 6, 8, 10 (= dyeing) each contain 0.25% of the compounds of the formulas (122), (123), ( 127) and (128). The results are shown in Table VII, the blind dyeings due to the tear strength and elongation (exposed according to DIN 75.202 (= FAKRA) and tested according to SN 198.451), the dyeings according to their light fastness (DIN 75.202 / FAKRA) were characterized. Table VII FLEET No./ ADDITIONAL Tear resistance / elongation (%) after exposure after 216 h of FAKRA LIGHT FASTNESSES FAKRA 144 h FAKRA 216 h Fleet 1: no addition 7.9 / 28.6 - - Fleet 2: no addition 1H 1H Fleet 3: + 0.25% of the compound of formula (123) 75.8 / 82.1 - - Fleet 4: + 0.25% of the compound of formula (123) - 3rd 2-3 Fleet 5: + 0.25% of the compound of formula (128) 58.0 / 71.6 - - Fleet 6: + 0.25% of the compound of the formula (128) - 2-3 1-2 Fleet 7: + 0.25% of the compound of formula (127) 64.3 / 72.0 - - Fleet 8: + 0.25% of the compound of formula (127) - 3rd 2-3 Fleet 9: + 0.25% of the compound of formula (122) 87.9 / 88.5 - - Fleet 10: + 0.25% of the compound of formula (122) - 3-4 3rd

Claims (14)

  1. A process for the photochemical and thermal stabilisation of polyamide fibre materials, which comprises treating dyed or undyed polyamide fibre materials with water-soluble triazine derivatives of the general formula
    Figure imgb0067
     where R₁ is a radical of the formula
    Figure imgb0068
     where R₃ is hydrogen, oxygen, hydroxyl, lower alkyl, lower alkenyl, lower alkoxy, acyl or benzyl and Z is -O- or -(NR₄)-, where R₄ is hydrogen or lower alkyl, R₂ is hydrogen, halogen, lower alkyl, lower alkoxy, acylamino, carboxyl, an unsubstituted or halogen- or (lower alkyl)-substituted phenylsulfo, phenoxy, phenylthio or styryl radical or -SO₃M, Q is -(NR₄)-, R is halogen, lower alkyl, lower alkoxy, phenyl(lower alkoxy), cycloalkoxy, (lower alkyl)thio, phenyl(lower alkyl)thio, cycloalkylthio, mono(lower alkyl)amino, di(lower alkyl)amino, phenyl(lower alkyl)amino, cycloalkylamino, phenoxy, phenylamino, phenylthio, phenyl, 1-azacycloalkyl, morpholino, R₁ or a radical of the formula
    Figure imgb0069
     where M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or an organic ammonium radical, and Q is as defined for the formula (1), the compounds of the formula (1) having not more than 2 -SO₃M substituents.
  2. A process according to claim 1, wherein R is halogen and R₁ is the radical of the formula
    Figure imgb0070
     where R₅ is hydrogen or lower alkyl, and Z is as defined for the formula (2).
  3. A process according to claim 1, wherein R and R₁ are each a radical of the formula (4).
  4. A process according to claim 1, wherein R is a radical of the formula (3) and R₁ is a radical of the formula (4).
  5. A process according to claim 1, wherein R is lower alkoxy, cycloalkoxy, phenoxy, (lower alkyl)thio, cycloalkylthio or phenylthio and R₁ is a radical of the formula (4).
  6. A process according to claim 1, wherein R is a radical of the formula
    Figure imgb0071
     where R₆ and R₇ are each independently of the other hydrogen, C₁-C₄alkyl, cycloalkyl or unsubstituted or (lower alkyl)-substituted phenyl where, when one of the radicals R₆ and R₇ is hydrogen, the other is not hydrogen, or R is 1-azacycloalkyl or morpholino and R₁ is a radical of the formula (4), and R₂ is as defined in claim 1.
  7. A water-soluble triazine derivative of the formula
    Figure imgb0072
     where R'₁ is a radical of the formula
    Figure imgb0073
     where R'₃ is hydrogen, oxygen, hydroxyl, lower alkyl, lower alkenyl, lower alkoxy, acyl or benzyl and Z' is -O- or -(NR'₄)-, where R'₄ is hydrogen or lower alkyl, R'₂ is hydrogen, halogen, lower alkyl, lower alkoxy, acylamino, carboxyl, an unsubstituted or halogen- or (lower alkyl)-substituted phenylsulfo, phenoxy, phenylthio or styryl radical or -SO₃M, Q' is -(NR'₄)-, R' is halogen, lower alkyl, lower alkoxy, phenyl(lower alkoxy), cycloalkoxy, (lower alkyl)thio, phenyl(lower alkyl)thio, cycloalkylthio, mono(lower alkyl)amino, di(lower alkyl)amino, cycloalkylamino, phenoxy, phenylamino, phenylthio, phenyl, 1-azacycloalkyl, morpholino, R'₁ or a radical of the formula
    Figure imgb0074
     where R'₂ and Q' are each as defined for the formula (5), M' is hydrogen, an alkali metal, an alkaline earth metal, ammonium or an organic ammonium radical, although if R' is chlorine and R'₂ is hydrogen R'₁ is not a radical of the formula
    Figure imgb0075
     and if R' is a radical of the formula (7), R'₂ is not hydrogen, the compounds of the formula (5) having not more than 2 SO₃M' substituents.
  8. A water-soluble triazine derivative according to claim 7, wherein R' is halogen and R'₁ is the radical of the formula
    Figure imgb0076
     where R'₅ is hydrogen or lower alkyl and Z' is as defined for the formula (6), although when R' is chlorine and R'₂ is hydrogen, R'₁ is not a radical of the formula (8).
  9. A water-soluble triazine derivative according to claim 7, wherein R' is a radical of the formula (7) and R'₁ is a radical of the formula (6).
  10. A water-soluble triazine derivative according to claim 7, wherein R' and R'₁ are each a radical of the formula (6).
  11. A water-soluble triazine derivative according to claim 7, wherein R' is lower alkoxy, cycloalkoxy, phenoxy, phenylalkoxy, (lower alkyl)thio, phenylthio or phenylalkylthio.
  12. A water-soluble triazine derivative according to claim 7, wherein R' is a radical of the formula
    Figure imgb0077
     where R'₆ and R'₇ are each independently of the other hydrogen, C₁-C₄alkyl, cycloalkyl or unsubstituted or (lower alkyl)-substituted phenyl, with the proviso that when one of R'₆ and R'₇ is hydrogen, the other must not be hydrogen, or R' is 1-azacycloalkyl or morpholino.
  13. A process for preparing the triazine derivatives according to claim 7, which comprises reacting 1 mol of a 2,4,6-trihalo-s-triazine compound or, when R' is lower alkyl or phenyl, a 2,4-dihalo-6-lower alkyl or -phenyl-s-triazine compound in succession with one or 2 mol of the compound of the formula
    Figure imgb0078
     and/or with one or 2 mol of the piperidine compound of the formula
    Figure imgb0079
     or reacting a 2,4,6-halo-s-triazine compound with 1 mol of the piperidine compound of the formula (11) and 1 mol of the compound of the formula (10) and one mole of a lower alkanolate, cycloalkanolate, phenolate, (lower alkyl)thiolate, cycloalkylthiolate or phenylthiolate compound, a mono(lower alkyl)amine, a di(lower alkyl)amine, a cycloalkylamine, a phenylamine, a 1-azacycloalkyl or morpholino compound, the order of the individual reaction steps being freely choosable, or, when R' is halogen, reacting a 2,4,6-trihalo-s-triazine compound with one mole of a compound of the formula (10) and one mole of the piperidine compound of the formula (11) to give a compound of the formula
    Figure imgb0080
     or, when R' is 1-azacycloalkyl, morpholino or a radical of the formula
    Figure imgb0081
     reacting a 2,4,6-trihalo-s-triazine compound in succession with a compound of the formula (10), a piperidine compound of the formula (11) and an N-alkyl compound or amino compound where
    R'₂, R'₃, Q', M' and Z' are each as defined for the formulae (5) and (6), R'₇ and R'₈ are each independently of the other hydrogen, C₁-C₄alkyl, cycloalkyl or unsubstituted or (lower alkyl)-substituted phenyl with the proviso that when one of R'₇ and R'₈ is hydrogen, the other must not be hydrogen.
  14. The use of the triazine derivatives according to any one of claims 7 to 12 for the photochemical and thermal stabilisation of polyamide fibre materials and dyeings.
EP91810519A 1990-07-12 1991-07-03 Process for the photochemical and thermal stabilisation of polyamide fiber materials Expired - Lifetime EP0466647B1 (en)

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US5281707A (en) 1994-01-25
BR9102947A (en) 1992-02-11
KR920002875A (en) 1992-02-28
JPH04241170A (en) 1992-08-28
US5160346A (en) 1992-11-03
ATE130882T1 (en) 1995-12-15
DE59106971D1 (en) 1996-01-11

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