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EP0466647B1 - Procédé pour la stabilisation photochimique et thermique de matériaux fibreux en polyamides - Google Patents

Procédé pour la stabilisation photochimique et thermique de matériaux fibreux en polyamides 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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EP0466647A1 (fr
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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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Claims (14)

  1. Procédé de stabilisation thermique et photochimique de matières en fibres de polyamides, caractérisé en ce que l'on traite des matières en fibres de polyamides, teintes ou non, avec des dérivés hydrosolubles de triazine, de formule générale
    Figure imgb0082
     dans laquelle R₁ représente un reste de formule
    Figure imgb0083
     où R₃ représente un atome d'hydrogène ou d'oxygène ou un groupe hydroxy, alkyle inférieur, alcényle inférieur, alcoxy inférieur, acyle ou benzyle, et
    Z représente -O- ou -(NR₄)-,
    où R₄ représente un atome d'hydrogène ou un groupe alkyle inférieur, R₂ représente un atome d'hydrogène ou d'halogène, un groupe alkyle inférieur, alcoxy inférieur, acylamino ou carboxy, ou un reste phénylsulfo, phénoxy, phénylthio ou styryle, portant ou non des substituants halogéno ou alkyle inférieur, ou encore -SO₃M,
    Q représente -(NR₄)-,
    R représente un atome d'halogène ou un groupe alkyle inférieur, alcoxy inférieur, phényl-(alcoxy inférieur), cycloalcoxy, alkylthio inférieur, phényl-(alkylthio inférieur), cycloalkylthio, mono(alkyle inférieur)-amino, di(alkyle inférieur)-amino, phényl-(alkyle inférieur)-amino, cycloalkylamino, phénoxy, phénylamino, phénylthio, phényle, 1-aza-cycloalkyle ou morpholino, ou R₁, ou encore un reste de formule
    Figure imgb0084
     où M représente un atome d'hydrogène, de métal alcalin ou de métal alcalino-terreux, un ion ammonium ou un reste ammonium organique, et Q a la signification indiquée à propos de la formule (1), étant entendu que les composés de formule (1) comportent au maximum deux substituants -SO₃M.
  2. Procédé conforme à la revendication 1, caractérisé en ce que R représente un atome d'halogène et R₁ représente un reste de formule
    Figure imgb0085
     où R₅ représente un atome d'hydrogène ou un groupe alkyle inférieur, et Z a la signification indiquée à propos de la formule (2).
  3. Procédé conforme à la revendication 1, caractérisé en ce que R et R₁ représentent chacun un reste de formule (4).
  4. Procédé conforme à la revendication 1, caractérisé en ce que R représente un reste de formule (3) et R₁ représente un reste de formule (4).
  5. Procédé conforme à la revendication 1, caractérisé en ce que R représente un groupe alcoxy inférieur, cycloalcoxy, phénoxy, alkylthio inférieur, cycloalkylthio ou phénylthio, et R₁ représente un reste de formule (4).
  6. Procédé conforme à la revendication 1, caractérisé en ce que R représente un reste de formule
    Figure imgb0086
     où R₆ et R₇ représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène ou un groupe alkyle en C₁₋₄ ou cycloalkyle, ou phényle portant ou non des substituants alkyle inférieur, étant entendu que, si l'un des symboles R₆ et R₇ représente un atome d'hydrogène, l'autre ne représente pas un atome d'hydrogène,
    ou bien R représente un groupe 1-aza-cycloalkyle ou morpholino, R₁ représente un reste de formule (4), et
    R₂ a la signification indiquée dans la revendication 1.
  7. Dérivés hydrosolubles de triazine, de formule
    Figure imgb0087
     dans laquelle R'₁ représente un reste de formule
    Figure imgb0088
     où R'₃ représente un atome d'hydrogène ou d'oxygène ou un groupe hydroxy, alkyle inférieur, alcényle inférieur, alcoxy inférieur, acyle ou benzyle, et
    Z' représente -O- ou -(NR'₄)-,
    où R'₄ représente un atome d'hydrogène ou un groupe alkyle inférieur, R'₂ représente un atome d'hydrogène ou d'halogène, un groupe alkyle inférieur, alcoxy inférieur, acylamino ou carboxy, ou un reste phénylsulfo, phénoxy, phénylthio ou styryle, portant ou non des substituants halogéno ou alkyle inférieur, ou encore -SO₃M',
    Q' représente -(NR'₄)-,
    R' représente un atome d'halogène ou un groupe alkyle inférieur, alcoxy inférieur, phényl-(alcoxy inférieur), cycloalcoxy, alkylthio inférieur, phényl-(alkylthio inférieur), cycloalkylthio, mono(alkyle inférieur)-amino, di(alkyle inférieur)-amino, phényl-(alkyle inférieur)-amino, cycloalkylamino, phénoxy, phénylamino, phénylthio, phényle, 1-aza-cycloalkyle ou morpholino, ou R'₁, ou encore un reste de formule
    Figure imgb0089
     où R'₂ et Q' ont les significations indiquées à propos de la formule (5), M' représente un atome d'hydrogène, de métal alcalin ou de métal alcalino-terreux, un ion ammonium ou un reste ammonium organique, étant entendu que, si R' représente un atome de chlore et R'₂ un atome d'hydrogène, R'₁ ne représente pas un reste de formule
    Figure imgb0090
     et que, si R' représente un reste de formule (7), R'₂ ne représente pas un atome d'hydrogène,
    et que les composés de formule (5) comportent au maximum deux substituants -SO₃M'.
  8. Dérivés hydrosolubles de triazine, conformes à la revendication (7), caractérisés en ce que R' représente un atome d'halogène et R'₁ représente un reste de formule
    Figure imgb0091
     où R'₅ représente un atome d'hydrogène ou un groupe alkyle inférieur, et Z' a la signification indiquée à propos de la formule (6),
    étant entendu que, si R' représente un atome de chlore et R'₂ un atome d'hydrogène, R'₁ ne représente pas un reste de formule (8).
  9. Dérivés hydrosolubles de triazine, conformes à la revendication (7), caractérisés en ce que R' représente un reste de formule (7) et R'₁ représente un reste de formule (6).
  10. Dérivés hydrosolubles de triazine, conformes à la revendication (7), caractérisés en ce que R' et R₁ représentent chacun un reste de formule (6).
  11. Dérivés hydrosolubles de triazine, conformes à la revendication (7), caractérisés en ce que R' représente un groupe alcoxy inférieur, cycloalcoxy, phénoxy, phénylalcoxy, alkylthio inférieur, phénylthio ou phénylalkylthio.
  12. Dérivés hydrosolubles de triazine, conformes à la revendication (7), caractérisés en ce que R' représente un reste de formule
    Figure imgb0092
     où R'₆ et R'₇ représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène ou un groupe alkyle en C₁₋₄ ou cycloalkyle, ou phényle portant ou non des substituants alkyle inférieur, étant entendu que, si l'un des symboles R'₆ et R'₇ représente un atome d'hydrogène, l'autre ne représente pas un atome d'hydrogène, ou bien R' représente un groupe 1-aza-cycloalkyle ou morpholino.
  13. Procédé de préparation de dérivés de triazine conformes à la revendication 7, caractérisé en ce que l'on fait réagir 1 mole d'un composé de type 2,4,6-halogéno-s-triazine ou bien, si R' représente un groupe alkyle inférieur ou phényle, d'un composé de type 2,4-dihalogéno-6-(alkyle inférieur ou phényle)-s-triazine, successivement, avec 1 ou 2 moles d'un composé de formule
    Figure imgb0093
     et/ou avec 1 ou 2 moles d'un dérivé de pipéridine de formule
    Figure imgb0094
     ou bien l'on fait réagir un composé de type 2,4,6-halogéno-s-triazine avec 1 mole d'un dérivé de pipéridine de formule (11), 1 mole d'un composé de formule (10) et 1 mole d'un alkylate inférieur, cycloalkylate, phénolate, alkylthiolate inférieur, cycloalkylthiolate ou phénylthiolate, d'une mono(alkyle inférieur)amine, di(alkyle inférieur)amine, cycloalkylamine ou phénylamine, ou d'un composé à groupe 1-aza-cycloalkyle ou morpholino, l'ordre dans lequel sont effectuées les réactions individuelles étant quelconque,
    ou bien, si R' représente un atome d'halogène, on fait réagir un composé de type 2,4,6-trihalogéno-s-triazine avec 1 mole d'un composé de formule (10) et 1 mole d'un dérivé de pipéridine de formule (11), pour obtenir un composé de formule
    Figure imgb0095
     ou bien, si R' représente un groupe 1-aza-cycloalkyle ou morpholino ou un reste de formule
    Figure imgb0096
     on fait réagir un composé de type 2,4,6-trihalogéno-s-triazine, successivement, avec un composé de formule (10), un dérivé de pipéridine de formule (11) et un composé N-alkylé ou aminé,
    R'₂, R'₃, Q', M' et Z' ayant les significations indiquées à propos des formules (5) et (6),
    et R'₇ et R'₈ représentant chacun, indépendamment l'un de l'autre, un atome d'hydrogène ou un groupe alkyle en C₁₋₄, cycloalkyle ou phényle portant ou non des substituants alkyle inférieur, étant entendu que, si l'un des symboles R'₇ et R'₈ représente un atome d'hydrogène, l'autre ne peut représenter un atome d'hydrogène.
  14. Utilisation de dérivés de triazine conformes à l'une des revendications 7 à 12, pour la stabilisation thermique et photochimique de matières en fibres de polyamides et de teintures sur fibres de polyamides.
EP91810519A 1990-07-12 1991-07-03 Procédé pour la stabilisation photochimique et thermique de matériaux fibreux en polyamides Expired - Lifetime EP0466647B1 (fr)

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EP0466647A1 (fr) 1992-01-15
JPH04241170A (ja) 1992-08-28
DE59106971D1 (de) 1996-01-11
US5160346A (en) 1992-11-03
KR920002875A (ko) 1992-02-28
ATE130882T1 (de) 1995-12-15
US5281707A (en) 1994-01-25
BR9102947A (pt) 1992-02-11

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