EP0466647A1 - 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 PDFInfo
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- EP0466647A1 EP0466647A1 EP91810519A EP91810519A EP0466647A1 EP 0466647 A1 EP0466647 A1 EP 0466647A1 EP 91810519 A EP91810519 A EP 91810519A EP 91810519 A EP91810519 A EP 91810519A EP 0466647 A1 EP0466647 A1 EP 0466647A1
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- 0 **1C=CC(*c2nc(I)nc(*)n2)=C*(*)C=C1 Chemical compound **1C=CC(*c2nc(I)nc(*)n2)=C*(*)C=C1 0.000 description 2
- BMFATYQLPBBUTC-UHFFFAOYSA-N CC(C)(C1)NC(C)(C)CC1Nc1nc(Cl)nc(Nc2cc(S(O)(=O)=O)ccc2)n1 Chemical compound CC(C)(C1)NC(C)(C)CC1Nc1nc(Cl)nc(Nc2cc(S(O)(=O)=O)ccc2)n1 BMFATYQLPBBUTC-UHFFFAOYSA-N 0.000 description 2
- NSNVYXZUMHAIRN-UHFFFAOYSA-N CC(C)(C1)NC(C)(C)CC1Nc1nc(Nc(cccc2)c2S(O)(=O)=O)nc(Sc2ccccc2)n1 Chemical compound CC(C)(C1)NC(C)(C)CC1Nc1nc(Nc(cccc2)c2S(O)(=O)=O)nc(Sc2ccccc2)n1 NSNVYXZUMHAIRN-UHFFFAOYSA-N 0.000 description 1
Classifications
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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 dyed or 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 -O- or - (NR4) -, R halogen, lower alkyl, lower alkoxy, phenyl-lower alkoxy, cycloalkoxy, lower alkylthio, phenyl-lower al
- 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.
- 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 means 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 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 important 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 in which R6 and R7, independently of one another, denote hydrogen, lower alkyl, cycloalkyl or unsubstituted or substituted by lower alkyl or phenyl, 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 present application and correspond to the formula wherein R'1 is a radical of the formula where 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′-O- or
- 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'1-azacycloalkyl or morpholino means.
- 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.
- R ' is lower alkyl or phenyl, one always starts from 2,4-dihalo-6-lower alkyl or 6-phenyl-s-triazine.
- the water-soluble triazine derivatives according to 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 phenyl thiolate compound, a mono-lower alkylamine, di-lower alkylamine, cycloalkyl
- 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 in the first reaction step the 2,4,6-trihalo-s-triazine compound is reacted with the compound which has the lower reactivity.
- 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 conventional 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 fixation 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 fixation of the dyes and the compounds of formula (1) according to the cold residence process can be carried out 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.
- a solution of 4-N- (2-chloro-4-isopropoxy-6-triazinyl) aminobenzenesulfonic acid sodium salt in is prepared analogously to DE-A-2,828,030 from 18.4 g of cyanuric chloride, 46.7 g of isopropanol and 17.4 g of sulfanilic acid 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 The longest wave absorption maximum is 274 nm (water).
- 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 wave absorption maximum at 281 nm (water).
- a slurry of 22.6 g of 2-phenyl-4,6-dichloros-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 of 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%.
- a suspension of 4-N-methyl- (2-chloro-4-phenyl-6-striazinyl) 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-methylamino2,2,6,6-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. give 12.6 g of a colorless compound of the formula which has the longest-wavelength absorption maximum at 250 nm (methanol).
- Example 23a If the procedure is as described in Example 23a, but instead of 2-phenyl-4,6-dichloro-s-triazine, 2-p-tolyl 4,6-dichloro-s-triazine and instead of sulfanil-metanilic acid, the result is the corresponding 3-N- (2-chloro-4-p-tolyl-6-s-triazinyl) -aminobenzenesulfonic acid 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 long-wave absorption maximum is 265 nm (water).
- a solution of 4.9 g of 2,4-dichloro-6-methyl-s-triazine in acetone (50 ml) is poured 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 30% 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.
- dyeing liquors are thus prepared, each containing 0.5 g / l monosodium phosphate and 1.5 g / l disodium phosphate ( pH 7) included.
- 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 DM 75.202 for 216 hours and tear strength and elongation determined according to SN 198.461.
- the liquor (2) additionally contains 1% of the sodium salt of the compound of the formula (101).
- light gray and olive dyeings are produced in a conventional manner on polyamide 6 woven jersey. These dyeings are impregnated on a pad (105% squeezing effect) with solutions which contain 10 g / l of the compounds of the formulas (105) and (107) in solution. The padded dyeings are rolled, then left to stand 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: The result shows that the compound of the formula (108) brings about a clear stabilization of the fiber polymer and of the dye itself.
- Example 29 All 10 samples are treated and completed as described in Example 29.
- the colors 1 to 5 are tested for light fastness according to DIN 75.202 (FAKRA).
- the procedure is as described in Example 29, ie blind treatments and light gray colorations are produced and tested alternately.
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Abstract
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.
Das neue Verfahren ist dadurch gekennzeichnet, dass man gefärbte oder ungefärbte Polyamid-Fasermaterialien mit wasserlöslichen Triazinderivaten der allgemeinen Formel
behandelt, worin R₁ einen Rest der Formel
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 -O- oder -(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
bedeutet, worinThe new process is characterized in that dyed or 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 -O- or - (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
means what
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.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 means 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 Carboxyalkylsein. 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 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
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
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 gemass 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 important 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
worin R₆ und R₇, unabhangig 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
in which R₆ and R₇, independently of one another, denote hydrogen, lower alkyl, cycloalkyl or unsubstituted or substituted by lower alkyl or phenyl, 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
worin R′₁ einen Rest der Formel
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′-O- oder -(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
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
bedeutet, und wenn R'einen Rest der Formel (7) und
Q′-O- bedeuten, 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
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 present application and correspond to the formula
wherein R'₁ is a radical of the formula
where 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′-O- or - (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 of the formula R'₁ or a radical
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
means and when R 'is a radical of formula (7) and
Q'-O- mean 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
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
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.Of interest are also water-soluble triazine derivatives according to formula (5), in which 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'1-azacycloalkyl or morpholino means.
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, one always starts from 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
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
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 according to 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 phenyl thiolate 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
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 mole of a 2,4,6-trihalogen-s-triazine compound with one mole of a compound of the formula (10) and one mole of the piperidine compound Formula (11) to a compound of formula
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
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
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
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 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
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
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 denotes 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
wherein R'₉ lower alkoxy, cycloalkoxy, phenylalkoxy, phenoxy, lower alkylthio, cycloalkylthio, phenylthio or phenylalkylthio mean and R'₂, R'₃, M ', Q' and Z 'have the meaning given above, is implemented. 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
worin R′ einen Rest der Formel
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 Wassrstoff sein darf, und R′₂, R′₃, M′, Q′und Z′ die in den Formeln (5) und (6) angegeben 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 formula (10), a piperidine compound of formula (11) and an N-alkyl compound or aminophenyl compound to a compound of formula
wherein R 'is a radical of the formula
means
wherein 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 means 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 in the first reaction step the 2,4,6-trihalo-s-triazine compound is reacted with the compound which has the lower reactivity.
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 conventional 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 Ausziehoder 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 fixation 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 fixation of the dyes and the compounds of formula (1) according to the cold residence process can be carried out 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-Kobaltkcomplexfarbstoffe 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 percent by weight.
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
Die Verbindung zeigt das langwelligste Absorptionsmaximum bei 282 nm (Wasser/DMF (1:1)).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)).
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
mit dem langwelligsten Absorptionsmaximum bei 266 nm (Wasser).4.7 g of 4-amino-2,2,6,6 are added 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. -tetramethylpiperidine entered. The internal temperature is allowed to rise to 20 ° C. and the mixture is stirred for 2 hours at this temperature. 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).
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
Die Verbindung zeigt das langwelligste Absorptionsmaximum bei 282 nm (Wasser/DMF (1:1)).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. 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)).
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
Die Verbindung zeigt das langwelligste Absorptionsmaximum bei 275 nm (Wasser).The procedure is as described in Example 1, but instead of 4.7 g of 4-amino-2,2,6,6-tetramethylpiperidine, 4.7 g of 4-N-methylamino-2,2,6,6-tetramethylpiperidine are used. 12.2 g of a colorless compound of the formula are obtained
The compound shows the longest wave absorption maximum at 275 nm (water).
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
mit einem Aktivgehalt von 81 %. Das langwelligste Absorptionsmaximum beträgt 277 nm (Wasser).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).
Zu einer Suspension von 10,3 g 4-N-(2,4-Dichlor-6-triazinyl)aminobenzolsulfonsäure Natriumsalz in 100 ml dest. Wasser von O°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
Das langwelligste Absorptionsmaximum beträgt 273 nm (Wasser).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).
In eine Suspension von 5,2 g 4-N-(2,4-Dichlor-6-triazinyl)aminobenzolsulfonsäure Natriumsalz in 80 ml dest. Wasser werden bei O°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
mit einem Aktivgehalt von 68 %. Das lanbwelligste Absorptionsmaximum beträgt 273 nm (Wasser).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. It 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).
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
mit einem Aktivgehalt von 94 %. Die Verbindung zeigt bei 275 nm (Wasser) das langwelligste Absorptionsmaximum .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 you get the compound of formula
with an active content of 94%. The compound shows the longest-wavelength absorption maximum at 275 nm (water).
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
Die Verbindung zeigt in Wasser das langwelligste Absorptionsmaximum bei 277 nmTo 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 for 15 hours at 70 ° C. After cooling to room temperature, the precipitate formed is filtered off with suction, washed with distilled water until free of chloride and at 50 ° C dried in vacuo. A colorless compound of the formula is obtained quantitatively
The compound shows the longest-wavelength absorption maximum at 277 nm in water
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
Die Verbindung zeigt das langwelligste Absorptionsmaximum bei 235 nm (Wasser).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).
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
Die langwelligste Absorptionsmaximum beträgt 269 nm (Wasser).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 is used you get a compound of the formula
The longest wave absorption maximum is 269 nm (water).
Die folgenden Verbindungen (Tabelle I) können nach dem in Beispiel 2 beschriebenen Verfahren hergestellt werden.
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
Das langwelligste Absorptionsmaximum beträgt 274 nm (Wasser).A solution of 4-N- (2-chloro-4-isopropoxy-6-triazinyl) aminobenzenesulfonic acid sodium salt in is prepared analogously to DE-A-2,828,030 from 18.4 g of cyanuric chloride, 46.7 g of isopropanol and 17.4 g of sulfanilic acid 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
The longest wave absorption maximum is 274 nm (water).
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
mit einem Aktivgehalt von 75%. Die Verbindung zeigt bei 284 nm (Wasser) das langwelligste Absorptionsmaximum.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).
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
das einen Aktivgehalt von 73% und bei 275 nm (Wasser) das langwelligste Absorptionsmaximum aufweist.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).
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
welche bei 264 nm (Wasser) das langwelligste Absorptionsmaximum aufweist.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 the 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-wavelength absorption maximum at 264 nm (water).
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 filiert man, wäscht mit Wasser und trocknet im Vakuum bei 80°C. Man erhält 4,7 g eines weissen Pulvers der Formel
mit dem langwelligsten Absorptionsmaximum bei 275 nm (Wasser).A suspension of 4.4 g of the compound of 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, it is fileted, 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).
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
vom Schmelzpunkt 354°C.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.
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
welche bei 281 nm (Wasser) das langwelligste Absorptionsmaximum aufweist.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 wave absorption maximum at 281 nm (water).
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 versetz 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
mit dem langwelligsten Absorptionsmaximum bei 279 nm (Wasser).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 mixed with 5.0 g of 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl at 5 ° C. and stirred at room temperature for 16 hours. 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).
Eine Anschlämmung von 22,6 g 2-Phenyl-4,6-dichlors-triazin in 150 ml Aceton wird unter Rühren auf 100 ml Eiswasser gegossen und anschliessend mit einer neutralen Lösung 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
mit einem Aktivgehalt von 90, 1 %.A slurry of 22.6 g of 2-phenyl-4,6-dichloros-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 of 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%.
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
Das langwelligste Absorptionsmaximum beträgt 262 nm (Wasser).A suspension of 12.8 g of the compound of 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).
Eine Suspension von 12,8 g der Verbindung der Formel ( 123a) in 70 ml dest. 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
mit dem langwelligsten Absorptionsmaximum bei 265 nm (Wasser).A suspension of 12.8 g of the compound of formula (123a) in 70 ml of dist. 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
with the longest wave absorption maximum at 265 nm (water).
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
Das langwelligste Absorptionsmaximum beträgt 255 nm (Methanol).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).
Man bereitet eine Suspension von 4-N-Methyl-(2-chlor-4-phenyl-6-striazinyl)-aminöbenzolsulfonsäure 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-Methylamino2,2,6,6-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
welche bei 250 nm (Methanol) das langwelligste Absorptionsmaximum aufweist.A suspension of 4-N-methyl- (2-chloro-4-phenyl-6-striazinyl) 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-methylamino2,2,6,6-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. give 12.6 g of a colorless compound of the formula
which has the longest-wavelength absorption maximum at 250 nm (methanol).
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
Das langwelligste Absorptionsmaximum beträgt 265 nm (Wasser).If the procedure is as described in Example 23a, but instead of 2-phenyl-4,6-dichloro-s-triazine, 2-p-tolyl 4,6-dichloro-s-triazine and instead of sulfanil-metanilic acid, the result is the corresponding 3-N- (2-chloro-4-p-tolyl-6-s-triazinyl) -aminobenzenesulfonic acid 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 long-wave absorption maximum is 265 nm (water).
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-2,2,6,6tetramethylpiperidin 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
erhalten, welche das langwelligste Absorptionsmaximum bei 276 nm (Wasser) aufweist.A solution of 4.9 g of 2,4-dichloro-6-methyl-s-triazine in acetone (50 ml) is poured 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 30% 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, stir at this temperature for one hour. 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
obtained, which has the longest wavelength absorption maximum at 276 nm (water).
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).4 samples of a polyamide 6 knitted fabric of 10 g each are prepared and placed in a dyeing machine, e.g. an ®AHIBA dyeing machine, treated at a liquor ratio of 1:30. Two of these samples are "blind-dyed" (i.e. 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 (
0,04 % des Farbstoffgemisches, bestehend aus 81 Teilen der Verbindung der Formel
und 12 Teilen der Verbindung der Formel
und 0,002 % des Farbstoffes der Formel
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 (
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).
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 DM 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 DM 75.202 for 216 hours and tear strength and elongation determined according to SN 198.461.
Folgende Ergebnisse werden erhalten:
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.The following results are obtained:
It can be seen that the application of the compound of the formula (101) results in clear photochemical and thermal stability of the fiber material or the dyeing.
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
0,085 % des Farbstoffgemisches der Formeln
sowie 0,035 % des Farbstoffgemisches der Formeln (Ia) und (Ib).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).
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):
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.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 pad (105% squeezing effect) with solutions which contain 10 g / l of the compounds of the formulas (105) and (107) in solution. The padded dyeings are rolled, then left to stand 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 that demonstrate increased photochemical and thermal stability.
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.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:
Das Ergebnis zeigt, dass die Verbindung der Formel (108) eine deutliche Stabilisierung des Faserpolymers sowie des Farbstoffes selbst bewirkt.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:
The result shows that the compound of the formula (108) brings about a clear stabilization of the fiber polymer and of the dye itself.
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).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):
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 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):
From the results it can be seen that the compounds (110) and (111) very significantly improve the photochemical stability of the gray colorations. The coloration without stabilizer is useless from its mechanical stability as well as from the light fastness.
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):
Die Ergebnisse zeigen, dass dem Polyamidmaterial durch die Verbindungen der Formeln (109), (112), (113) und (114) eine deutliche photochemische Stabilisierung gegeben wird.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. The liquors 2 and 7 are each added 0.75% of the sodium salt of the compound of the formula (109), the liquors 3 and 8 each 0.75% of the compound of the formula (112), the liquors 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. The colors 1 to 5 are tested for light fastness according to DIN 75.202 (FAKRA). The blind dyeings 6-10 are exposed for 216 hours according to SN-ISO 105-B02 (= XENON) and DIN 75.202 (FAKRA) and tested for tensile strength and elongation according to SN 198.451 with the following results (Table VI):
The results show that the compounds of the formulas (109), (112), (113) and (114) give the polyamide material a clear photochemical stabilization.
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.
Claims (22)
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 -O- oder -(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
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 Process for the photochemical and thermal stabilization of polyamide fiber materials, characterized in that colored or uncolored polyamide fiber materials with water-soluble triazine derivatives of the general formula
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 -O- or - (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, morpholino or R₁
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
R Halogen und R₁ den Rest der Formel
R₅ Wasserstoff oder Niederalkyl bedeutet, und
Z die in Formel (2) angegebene Bedeutung hat.A method according to claim 1, characterized in that
R halogen and R₁ the rest of the formula
R₅ is hydrogen or lower alkyl, and
Z has the meaning given in formula (2).
R 1-Azacycloalkyl oder Morpholino und
R₁ einen Rest der Formel (4) bedeuten und
R₂ die in Anspruch 1 angegebene Bedeutung hat.A method according to claim 1, characterized in that R is a radical of the formula
R 1-azacycloalkyl or morpholino and
R₁ is a radical of formula (4) and
R₂ has the meaning given in claim 1.
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′-O- oder -(NR′₄)-,
R′Halogen, Niederalkyl, Niederalkoxy, Phenylniederalkoxy, Cycloalkoxy, Niederalkylthio, Phenylniederalkylthio, Cycloalkylthio, Mononiederalkylamino, Diniederalkylamino, Cycloalkylamino, Phenoxy, Phenylamino, Phenylthio, Phenyl,
1-Azacycloakyl, Morpholino, R′₁ oder einen Rest der Formel
R′₂ und Q′ die in Formel (5) angegebene Bedeutung hat,
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
Q′-O- bedeuten, R′₂ nicht Wasserstoff bedeutet
und die Verbindungen der Formel (5) maximal 2 SO₃M′-Substituenten aufweisen.Water-soluble triazine derivatives of the formula
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′-O- or - (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-azacycloakyl, morpholino, R'₁ or a radical of the formula
R'₂ and Q 'has 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
Q'-O- mean R'₂ does not mean hydrogen
and the compounds of formula (5) have a maximum of 2 SO₃M'-substituents.
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.Water-soluble triazine derivatives according to claim 7, characterized in that R 'halogen and R'₁ the rest of the formula
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).
R′₆ und R′₇, unabhängig voneinander, Wasserstoff, C₁ - C₄-Alkyl, Cycloalkyl oder nichtsubstituiertes oder durch Niederarlkyl substituiertes Phenyl bedeuten, wobei, wenn einer der Reste R′₆ und R′₇ Wasserstoff bedeutet, der andere nicht Wasserstoff sein darf oder
R′ 1-Azacycloalkyl oder Morpholino bedeutet.Water-soluble triazine derivatives according to claim 7, characterized in that R 'is a radical of the formula
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 and R′₇ is hydrogen, the other is not hydrogen may or
R 'means 1-azacycloalkyl or morpholino.
Q′ und R′₂ die in Formel (5) angegebene Bedeutung haben,
mit einem oder 2 Mol der Piperidinverbindung der Formel
und, wenn man 1 Mol der Piperidinverbindung der Formel (11) einsetzt, mit einem Mol einer Niederalkanolat-, Cycloalkanolat-, Phenolat-, Niederalkylthiolat-, Cycloalkylthiolatoder einer Phenylthiolatverbindunb, 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.A process for the preparation of the triazine derivatives according to claim 7, characterized in that 1 mole of a 2,4,6-halogeno-s-triazine compound or a 2,4-dihalo-6-lower alkyl or -phenyl-s-triazine compound is added in succession one mole of the compound of the formula
Q ′ and R′₂ have the meaning given in formula (5),
with one or 2 moles of the piperidine compound of the formula
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.
worin R′₂, R′₃, M′, Q′ und Z′ die in den Formeln (5) und (6) angegebene Bedeutung haben, dadurch gekennzeichnet, 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) umsetzt.Process for the preparation of the triazine derivatives of the formula
wherein R′₂, R′₃, M ′, Q ′ and Z ′ have the meaning given in the formulas (5) and (6), characterized in that 1 mol of a 2,4,6-trihalogen-s- triazine compound with one mole of a compound of formula (10) and one mole of the piperidine compound of formula (11).
R′₂ Halogen, Niederalkyl, Niederalkoxy, Acylamino,Carboxy oder -SO₃H bedeuten und R′₃, M′ und Z′ die in der Formel (6) angegebene Bedeutung haben, dadurch gekennzeichnet, dass man 1 Mol einer 2,4,6-Trihalogen-s-triazinverbindung mit zwei Mol der Verbindung der Formel (10), worin Q′-(NR′₄)- und und R′₂ Halogen, Niederalkyl, Niederalkoxy, Acylamino, Carboxy oder -SO₃H bedeuten und anschliessend mit einem Mol der Piperidinverbindung der Formel (11) umsetzt.Process for the preparation of the triazine derivatives of the formula
R'₂ is halogen, lower alkyl, lower alkoxy, acylamino, carboxy or -SO₃H and R′₃, M 'and Z' have the meaning given in the formula (6), characterized in that 1 mol of a 2,4,6 -Trihalogen-s-triazine compound with two moles of Compound of formula (10) in which Q '- (NR'₄) - and and R'₂ are halogen, lower alkyl, lower alkoxy, acylamino, carboxy or -SO₃H and then reacted with one mole of the piperidine compound of formula (11).
R′₂, R′₃, M′, Q′ und Z′ die in den Formeln (5) und (6) angegebene Bedeutung haben, dadurch gekennzeichnet, dass man nacheinander 1 Mol einer 2,4,6-Trihalogen-s-triazinverbindung mit einem Mol der entsprechenden Niederalkanolat-, Cycloalkanolat-, Phenylalkanolat-, Phenolat-, Niederalkylthiolat-, Cycloalkylthiolat-, Phenylthiolat- oder einer Phenylalkylthiolatverbindung, einem Mol der Verbindung der Formel (10) und einem Mol der Piperidinverbindung der Formel (11) umsetzt.Process for the preparation of the triazine derivatives of the formula
R′₂, R′₃, M ′, Q ′ and Z ′ have the meaning given in the formulas (5) and (6), characterized in that 1 mol of a 2,4,6-trihalogen-s- triazine compound with one mole of the corresponding lower alkanolate, cycloalkanolate, phenylalkanolate, 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) .
R′₇ und R′₈, unabhängig voneinander, Wasserstoff, C₁ - C₄-Alkyl, Cycloalkyl unsubstituiertes oder durch Niederalkyl substituiertes Phenyl bedeuten, wobei, wenn einer der Reste R′₇ und R′₈ Wasserstoff bedeutet, der andere nicht Wasserstoff sein darf oder R′₁-Azacycloalkyl oder Morpholino bedeutet und
R′₂, R′₃, Q′ und Z′ die in den Formeln (5) und (6) angegebene Bedeutung haben, dadurch gekennzeichnet, 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 umsetzt.Process for the preparation of the triazine derivatives of the formula
R′₇ and R′₈, 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′₇ and R′₈ is hydrogen, the other must not be hydrogen or R'₁-azacycloalkyl or morpholino means and
R'₂, R′₃, Q 'and Z' have the meaning given in the formulas (5) and (6), characterized in that one in succession a 2,4,6-trihalogen-s-triazine compound with a compound of Formula (10), a piperidine compound of formula (11) and an N-alkyl compound or aminophenyl compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2324/90 | 1990-07-12 | ||
| CH232490 | 1990-07-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0466647A1 true EP0466647A1 (en) | 1992-01-15 |
| EP0466647B1 EP0466647B1 (en) | 1995-11-29 |
Family
ID=4231151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91810519A Expired - Lifetime EP0466647B1 (en) | 1990-07-12 | 1991-07-03 | Process for the photochemical and thermal stabilisation of polyamide fiber materials |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US5160346A (en) |
| EP (1) | EP0466647B1 (en) |
| JP (1) | JPH04241170A (en) |
| KR (1) | KR920002875A (en) |
| AT (1) | ATE130882T1 (en) |
| BR (1) | BR9102947A (en) |
| DE (1) | DE59106971D1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0481300A2 (en) * | 1990-10-16 | 1992-04-22 | BASF Aktiengesellschaft | Polyalkylpiperidine-derivatives and their use as light stabilizers |
| EP0702011A1 (en) | 1994-08-25 | 1996-03-20 | Ciba-Geigy Ag | Water soluble piperidine-triazine compounds for use as stabilizers for polyamide fibers |
| EP0703227A1 (en) | 1994-09-19 | 1996-03-27 | Ciba-Geigy Ag | Watersoluble antioxidants, process of their preparation, and their use for the photochemical and thermical stabilisation of polyamide fibers |
| US5814107A (en) * | 1996-07-31 | 1998-09-29 | Basf Corporation | Photochemically stabilized polyamide compositions |
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| WO2004076419A1 (en) * | 2003-02-26 | 2004-09-10 | Ciba Specialty Chemicals Holding Inc. | Water compatible sterically hindered alkoxyamines and hydroxy substituted alkoxyamines |
| EP1787989A1 (en) * | 2005-11-17 | 2007-05-23 | Degussa GmbH | Triazine derivatives containing amino and carboxylic acic group |
| EP2128198A1 (en) | 2008-05-30 | 2009-12-02 | Lurgi Zimmer GmbH | Process for the preparation of polyamides using carboxylic acids and amides |
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| KR20140113712A (en) * | 2012-01-06 | 2014-09-24 | 아지오스 파마슈티컬스 아이엔씨. | Therapeutically active compounds and their methods of use |
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| KR19980701718A (en) | 1995-11-28 | 1998-06-25 | 바바라 에이취. 폴 | Improved Color Stabilizer |
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| US6326368B1 (en) | 1996-03-27 | 2001-12-04 | Dupont Pharmaceuticals Company | Aryloxy- and arylthiosubstituted pyrimidines and triazines and derivatives thereof |
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| US6524379B2 (en) | 1997-08-15 | 2003-02-25 | Kimberly-Clark Worldwide, Inc. | Colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
| KR100591999B1 (en) | 1998-06-03 | 2006-06-22 | 킴벌리-클라크 월드와이드, 인크. | Neo-nanoplasm and inkjet printing inks manufactured by microemulsion technology |
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| WO2000004104A1 (en) | 1998-07-20 | 2000-01-27 | Kimberly-Clark Worldwide, Inc. | Improved ink jet ink compositions |
| EP1117698B1 (en) | 1998-09-28 | 2006-04-19 | Kimberly-Clark Worldwide, Inc. | Chelates comprising chinoid groups as photoinitiators |
| EP1144512B1 (en) | 1999-01-19 | 2003-04-23 | Kimberly-Clark Worldwide, Inc. | Novel colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
| US6331056B1 (en) | 1999-02-25 | 2001-12-18 | Kimberly-Clark Worldwide, Inc. | Printing apparatus and applications therefor |
| US6294698B1 (en) | 1999-04-16 | 2001-09-25 | Kimberly-Clark Worldwide, Inc. | Photoinitiators and applications therefor |
| US6297296B1 (en) | 1999-05-19 | 2001-10-02 | Kodak Polychrome Graphics Llc | Latex complexes as stabilized colorant |
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| US7550599B2 (en) * | 2003-02-26 | 2009-06-23 | Ciba Specialty Chemicals Corporation | Water compatible sterically hindered alkoxyamines and hydroxy substituted alkoxyamines |
| DE102005039580A1 (en) * | 2005-08-19 | 2007-02-22 | Henkel Kgaa | Color protecting detergent |
| CN111875584A (en) * | 2020-08-07 | 2020-11-03 | 宿迁市振兴化工有限公司 | Preparation method of multifunctional light stabilizer |
| CN114058079A (en) * | 2021-12-23 | 2022-02-18 | 中交第一公路勘察设计研究院有限公司 | Asphalt light stabilizer with strong ultraviolet absorption function and preparation method thereof |
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| DE4000551A1 (en) * | 1989-01-13 | 1990-07-19 | Ciba Geigy Ag | Photochemical stabilisation of dyed wool - by treatment in an aq. bath contg. sterically hindered amine light protection agent |
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| ATE102666T1 (en) * | 1988-06-14 | 1994-03-15 | Ciba Geigy Ag | PROCESS FOR THE PHOTOCHEMICAL STABILIZATION OF DYED AND DYED POLYPROPYLENE FIBERS. |
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-
1991
- 1991-07-03 AT AT91810519T patent/ATE130882T1/en active
- 1991-07-03 DE DE59106971T patent/DE59106971D1/en not_active Expired - Fee Related
- 1991-07-03 EP EP91810519A patent/EP0466647B1/en not_active Expired - Lifetime
- 1991-07-09 US US07/727,514 patent/US5160346A/en not_active Expired - Fee Related
- 1991-07-11 BR BR919102947A patent/BR9102947A/en active Search and Examination
- 1991-07-11 KR KR1019910011750A patent/KR920002875A/en not_active Application Discontinuation
- 1991-07-12 JP JP3172218A patent/JPH04241170A/en active Pending
-
1992
- 1992-08-10 US US07/928,253 patent/US5281707A/en not_active Expired - Fee Related
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| EP0378054A2 (en) * | 1989-01-05 | 1990-07-18 | Ciba-Geigy Ag | Process for the photochemical stabilization of undyed and ready to be dyed artificial leather |
| DE4000551A1 (en) * | 1989-01-13 | 1990-07-19 | Ciba Geigy Ag | Photochemical stabilisation of dyed wool - by treatment in an aq. bath contg. sterically hindered amine light protection agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0481300A2 (en) * | 1990-10-16 | 1992-04-22 | BASF Aktiengesellschaft | Polyalkylpiperidine-derivatives and their use as light stabilizers |
| EP0481300A3 (en) * | 1990-10-16 | 1993-03-10 | Basf Aktiengesellschaft | Polyalkylpiperidine-derivatives and their use as light stabilizers |
| EP0702011A1 (en) | 1994-08-25 | 1996-03-20 | Ciba-Geigy Ag | Water soluble piperidine-triazine compounds for use as stabilizers for polyamide fibers |
| EP0703227A1 (en) | 1994-09-19 | 1996-03-27 | Ciba-Geigy Ag | Watersoluble antioxidants, process of their preparation, and their use for the photochemical and thermical stabilisation of polyamide fibers |
| US5814107A (en) * | 1996-07-31 | 1998-09-29 | Basf Corporation | Photochemically stabilized polyamide compositions |
| US5851238A (en) * | 1996-07-31 | 1998-12-22 | Basf Corporation | Photochemically stabilized polyamide compositions |
| US6136433A (en) * | 1997-05-01 | 2000-10-24 | Basf Corporation | Spinning and stability of solution-dyed nylon fibers |
| US6358458B1 (en) | 1997-05-01 | 2002-03-19 | Basf Corporation | Spinning and stability of solution-dyed nylon fibers |
| WO2004076419A1 (en) * | 2003-02-26 | 2004-09-10 | Ciba Specialty Chemicals Holding Inc. | Water compatible sterically hindered alkoxyamines and hydroxy substituted alkoxyamines |
| EP1787989A1 (en) * | 2005-11-17 | 2007-05-23 | Degussa GmbH | Triazine derivatives containing amino and carboxylic acic group |
| WO2007057265A2 (en) * | 2005-11-17 | 2007-05-24 | Evonik Degussa Gmbh | Triazine compounds comprising substituents containing amino groups and carboxyl groups |
| WO2007057265A3 (en) * | 2005-11-17 | 2008-12-24 | Evonik Degussa Gmbh | Triazine compounds comprising substituents containing amino groups and carboxyl groups |
| EP2128198A1 (en) | 2008-05-30 | 2009-12-02 | Lurgi Zimmer GmbH | Process for the preparation of polyamides using carboxylic acids and amides |
| DE102008026075A1 (en) | 2008-05-30 | 2009-12-03 | Lurgi Zimmer Gmbh | Process for the preparation of polyamides using carboxylic acids and amides |
| WO2010081625A2 (en) | 2009-01-19 | 2010-07-22 | Basf Se | Organic black pigments and their preparation |
| KR20140113712A (en) * | 2012-01-06 | 2014-09-24 | 아지오스 파마슈티컬스 아이엔씨. | Therapeutically active compounds and their methods of use |
| EP2800743A1 (en) * | 2012-01-06 | 2014-11-12 | Agios Pharmaceuticals, Inc. | Therapeutically active compounds and their methods of use |
| EP2800743A4 (en) * | 2012-01-06 | 2015-08-26 | Agios Pharmaceuticals Inc | Therapeutically active compounds and their methods of use |
| EP3406608A1 (en) * | 2012-01-06 | 2018-11-28 | Agios Pharmaceuticals, Inc. | Therapeutically active compounds and their methods of use |
| AU2017265096B2 (en) * | 2012-01-06 | 2019-08-08 | Les Laboratoires Servier | Therapeutically active compounds and their methods of use |
| AU2017265096B9 (en) * | 2012-01-06 | 2019-09-05 | Les Laboratoires Servier | Therapeutically active compounds and their methods of use |
| US9738625B2 (en) | 2013-08-02 | 2017-08-22 | Agios Pharmaceuticals, Inc. | Therapeutically active compounds and their methods of use |
| US10093654B2 (en) | 2013-08-02 | 2018-10-09 | Agios Pharmaceuticals, Inc. | Therapeutically active compounds and their methods of use |
| US10730854B2 (en) | 2013-08-02 | 2020-08-04 | Agios Pharmaceuticals, Inc. | Therapeutically active compounds and their methods of use |
| US9751863B2 (en) | 2015-08-05 | 2017-09-05 | Agios Pharmaceuticals, Inc. | Therapeutically active compounds and their methods of use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04241170A (en) | 1992-08-28 |
| US5281707A (en) | 1994-01-25 |
| EP0466647B1 (en) | 1995-11-29 |
| ATE130882T1 (en) | 1995-12-15 |
| US5160346A (en) | 1992-11-03 |
| DE59106971D1 (en) | 1996-01-11 |
| KR920002875A (en) | 1992-02-28 |
| BR9102947A (en) | 1992-02-11 |
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