EP0864687A2 - Process for improving the photochemical stability of coloration and prints on polyester fibers - Google Patents

Process for improving the photochemical stability of coloration and prints on polyester fibers Download PDF

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Publication number
EP0864687A2
EP0864687A2 EP98810183A EP98810183A EP0864687A2 EP 0864687 A2 EP0864687 A2 EP 0864687A2 EP 98810183 A EP98810183 A EP 98810183A EP 98810183 A EP98810183 A EP 98810183A EP 0864687 A2 EP0864687 A2 EP 0864687A2
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EP
European Patent Office
Prior art keywords
formula
fiber material
compound
polyester fiber
treated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98810183A
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German (de)
French (fr)
Other versions
EP0864687A3 (en
Inventor
Francesco Fuso
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
BASF Schweiz AG
Original Assignee
Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
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Publication of EP0864687A2 publication Critical patent/EP0864687A2/en
Publication of EP0864687A3 publication Critical patent/EP0864687A3/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
    • 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
    • D06P3/34—Material containing ester groups
    • D06P3/40—Cellulose acetate
    • D06P3/42—Cellulose acetate using dispersed dyestuffs
    • 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
    • D06P3/34—Material containing ester groups
    • D06P3/40—Cellulose acetate
    • D06P3/46—Cellulose triacetate
    • D06P3/48—Cellulose triacetate using dispersed dyestuffs
    • 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
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D06P3/54—Polyesters using dispersed dyestuffs
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/922—Polyester fiber

Definitions

  • the present invention relates to a method for photochemical and thermal stabilization of dyeing and printing on polyester fiber materials and those containing polyester Mixed fibers.
  • Dyed or printed polyester fiber material can be under the influence of light and in particular be damaged while being exposed to heat.
  • R 1 , R 2 , R 3 and R 4 as C 1 -C 4 alkyl are methyl, ethyl, propyl, i-propyl, n-butyl, sec-butyl, i-butyl or tert. Butyl.
  • R 1 , R 2 and R 3 as C 1 -C 4 alkoxy are, for example, methoxy, ethoxy, propoxy, i-propoxy or butoxy.
  • Phenyl as a substituent in R 4 and the phenyl radicals in benzyloxy as a substituent in R 1 and R 2 can be further substituted one or more times by C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen.
  • Also preferred for the process according to the invention are compounds of the formula (1) in which R 3 is methyl, ethyl or n-butyl.
  • the compounds of formula (1) are e.g. known from US-A-3,896,125 or can according to known methods are produced.
  • the compounds used according to the invention are used in an amount of 0.01 to 5 % By weight, preferably 0.1 to 3% by weight, based on the weight of the fiber material, used.
  • the compounds used according to the invention are sparingly soluble in water and become therefore advantageously applied in dispersed form. To do this, they will use a appropriate dispersant using e.g. Quartz balls and a rapid mixer a fineness of 1-2 mm is ground.
  • Dispersions which are only slightly soluble in water are suitable as dyes. she are therefore mostly present in the dye liquor in the form of a fine dispersion. she can belong to different classes of dyes, for example the acridone, azo, Anthraquinone, coumarin, methine, perinone, naphthoquinone imine, quinophthalone, styryl, or nitro dyes. Mixtures of disperse dyes according to the invention can also be used be used.
  • polyester fiber material that is dyed or printed and with the compounds of the formula (1) can be treated are e.g. Cellulose ester fibers, e.g. Cellulose 24 acetate fiber and triacetate fibers and especially linear polyester fibers, which may also be acidic are modified to understand, e.g. by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane are obtained, as well as fibers from copolymers of terephthalic and isophthalic acid and ethylene glycol.
  • the linear that has been used almost exclusively in industry up to now Polyester fiber material (PES) consists of terephthalic acid and ethylene glycol.
  • the fiber materials can also be mixed with each other or with other fibers, e.g. Mixtures of polyacrylonitrile / polyester, polyamide / polyester, polyester / cotton, Polyester / viscose and polyester / wool, are used and by known methods discontinuously or continuously colored or printed.
  • the polyester fiber material can be presented in various forms. Preferably comes in piece goods, such as knitted fabrics, fiber composite or fabric, or also gam Cross-wound bobbins, warp beams, etc. into consideration.
  • Polyester textile fabrics and are also very suitable for the method according to the invention Textile blended fabrics containing polyester fibers in the outerwear sector that are translucent are. If such textiles are treated by the process according to the invention, you can see the skin tissue under the transparent outer clothing fabric protect against the damaging influence of UV radiation.
  • the dyeings are carried out from an aqueous liquor after a continuous or discontinuous one Method.
  • this can Fleet ratio can be selected in a wide range, e.g. 1: 4 to 1: 100, preferably 1: 6 to 1:50.
  • the temperature at which dyeing is carried out is at least 50 ° C and usually it is not higher than 140 ° C. It is preferably in the range from 80 to 135 ° C.
  • the dye liquors which in addition to the dyes, may be used may contain further aids, for example on the piece material Padding or padding applied and by means of heat setting or HT steaming processes developed.
  • Linear polyester fibers and cellulose fibers are preferably dyed according to the so-called High temperature processes in closed and pressure-resistant equipment Temperatures> 100 ° C, preferably between 110 ° and 135 ° C and optionally below Pressure.
  • Circulation apparatuses such as are suitable as closed vessels Cross-winder or tree dyeing machines, reel runners, jet or drum dyeing machines, Muff dyeing machines, paddles or jiggers.
  • Cellulose-24-acetate fibers are preferably dyed at temperatures of 80-85 ° C.
  • the UV absorbers according to the invention are used in the dyeing application, this is done the application so that the fiber material is first with these compounds treated and then carries out the coloring or preferably simultaneously Fiber material treated with the UV absorber and the dye in the dye bath.
  • the UV absorber can also be added to the finished coloring by means of heat setting, e.g. at 190 to 230 ° C in a period of 30 seconds to 5 Minutes.
  • the dye liquors can also contain other additives such as dyeing aids, dispersants, Carrier, wool protection and wetting agents as well as defoamers included.
  • the dye baths can also contain mineral acids, e.g. Sulfuric acid or phosphoric acid, or expediently organic acids, for example aliphatic carboxylic acids such as formic acid, acetic acid, oxalic acid or citric acid and / or salts such as ammonium acetate, ammonium sulfate or sodium acetate.
  • mineral acids e.g. Sulfuric acid or phosphoric acid
  • organic acids for example aliphatic carboxylic acids such as formic acid, acetic acid, oxalic acid or citric acid and / or salts such as ammonium acetate, ammonium sulfate or sodium acetate.
  • the acids serve especially the adjustment of the pH of the liquors used according to the invention, the is preferably between 4 and 5.
  • the fiber material is preferably left in the bath at 40 to 80 ° C. for 5 minutes contains the dye, the UV absorber and optionally other additives and on one pH is set to 4.5 to 5.5, the temperature increases within 10 to 20 minutes at 125 to 130 ° C and treated for 15 to 90 minutes, preferably 30 minutes, at this temperature further.
  • the dyeings are completed by cooling the dye liquor to 50 to 80 ° C. Rinse the dyeings with water and, if necessary, by cleaning in the usual way in an alkaline medium under reductive conditions. The stains then turn again rinsed and dried.
  • vat dyes for the cellulose content
  • the goods are first treated with hydrosulfite at a pH of 6 to 12.5 and then treated with an oxidizing agent and finally washed out.
  • UV absorbers used according to the invention are used for the production of prints expediently mixed with the printing pastes in the form of their aqueous dispersions.
  • the printing paste contains the corresponding UV absorber in quantities from 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the weight of the printing paste.
  • the UV absorbers can already be used in the preparation of the pressure floor, e.g. after this Heat-setting processes can be applied.
  • the amount of dyes added to the printing pastes depends on the desired one Color shade; in general, amounts of 0.01 to 15, preferably 0.02 to 10 weight percent, based on the textile material used, proven.
  • the printing pastes contain expediently acid-stable thickeners, preferably more natural Origin such as corn flour derivatives, especially sodium alginate on its own or in Mixture with modified cellulose, in particular with preferably 20 to 25 percent by weight Carboxymethyl cellulose.
  • the printing pastes can also contain acid donors, such as butyrolactone or sodium hydrogen phosphate, preservatives, sequestering agents, Emulsifiers, water-insoluble solvents, oxidizing agents or deaerating agents contain.
  • Suitable preservatives are, above all, formaldehyde-releasing agents, such as, for example, paraformaldehyde or trioxane, especially aqueous, about 30 to 40 percent by weight formaldehyde solutions; as sequestering agents, for example sodium nitrilotriacetic acid, sodium ethylenediaminetetraacetic acid, especially sodium polymetaphosphate, in particular sodium hexamethaphosphate; as emulsifiers, especially adducts of an alkylene oxide and a fatty alcohol, in particular an adduct of oleyl alcohol and ethylene oxide; as water-insoluble solvents, high-boiling, saturated hydrocarbons, especially paraffins with a boiling range of about 160 to 210 ° C (so-called mineral spirits); as an oxidizing agent, for example an aromatic nitro compound, especially an aromatic mono- or dinitrocarboxylic acid or sulfonic acid, which is optionally present as an alkylene oxide ad
  • the printing paste becomes direct over the entire surface or in places applied to the fiber material, expediently printing machines more commonly Type, e.g. Gravure, rotary screen, flat film or inkjet machines be used.
  • the fiber material is preferably at temperatures up to 150 ° C. Dried 80 ° to 120 ° C.
  • the material is then fixed by heat treatment at temperatures from preferably 100 ° to 220 ° C.
  • the heat treatment is generally carried out with superheated steam under pressure.
  • the fixation can last 20 seconds to 12 minutes, preferably 4 to 8 Minutes.
  • the prints are also finished in the usual way by rinsing with water and can, if necessary, by additional cleaning in an alkaline medium under reductive Conditions, e.g. be made with sodium dithionite. In the latter case the prints are rinsed, dewatered and dried.
  • Draw the polyester fiber materials treated with the method according to the invention is also characterized by a very high sun protection factor.
  • the determination of the sun protection factor can e.g. after that of B.L. Diffey and J. Robson in J. Soc. Cosmet. Chem. 40, 127-133 (March / June 1989).
  • the dyeing liquor is adjusted to a pH of 5 with acetic acid, homogenized and added to the polyester tricot in the high-temperature dyeing apparatus and heated to 70 ° C. and then to 130 ° C. within 30 minutes.
  • the polyester jersey is dyed at this temperature for 60 minutes.
  • the liquor is then cooled to 75 ° C., the dyed polyester tricot is rinsed with hot and cold water and a reductive cleaning by treatment with a liquor containing 3 ml / l of a 30% aqueous solution of NaOH and 2 g / l sodium dithionite during Subjected for 20 minutes at 70 ° C.
  • the piece of polyester tricot is then rinsed with warm and cold water, centrifuged and dried at 80 ° C.
  • Example 1 The procedure is as described in Example 1 (a), but instead of 5 parts by weight of the compound of the formula (10), the same amount of the compound of the formula is used (f)
  • the procedure is as described in Example 1 (b), but instead of 0.5 g of the formulation comprising the compound of the formula (10), the same amount of a formulation of the compound of the formula (12) described under (e) is obtained also a gray-colored polyester jersey with good general fastness properties, especially very good hot light fastness.

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  • Textile Engineering (AREA)
  • Coloring (AREA)

Abstract

Photochemical stabilisation of dyes and printing on polyester fibre material, comprises treating the material with a substituted 2-alkyl-4,6-bis(o-hydroxyphenyl)-1,3,5-triazine of formula (I); (where: R1, R2 = hydrogen (H), 1-4 carbon (C) alkyl, 1-4 C alkoxy, halogen, allyloxy or benzyloxy; R3 = 1-4 C alkyl, optionally substituted by 1-4 C alkoxy; R4 = H, 1-4 C alkyl, optionally substituted by phenyl, or allyl; n, m = 1, 2 or 3.)

Description

Die vorliegende Erfindung betrifft ein Verfahren zur photochemischen und thermischen Stabilisierung von Färbungen und Drucken auf Polyesterfasermaterialien und polyesterenthaltenden Mischfasern.The present invention relates to a method for photochemical and thermal stabilization of dyeing and printing on polyester fiber materials and those containing polyester Mixed fibers.

Gefärbtes oder bedrucktes Polyesterfasermaterial kann unter Lichteinfluss und insbesondere bei gleichzeitiger Wärmeeinwirkung geschädigt werden. Für den Einsatz im Automotive--Sektor ist beispielsweise ein wirkungsvoller Schutz dieser gefärbten Fasermaterialien vor UV-Strahlung unerlässlich.Dyed or printed polyester fiber material can be under the influence of light and in particular be damaged while being exposed to heat. For use in the automotive sector is, for example, an effective protection against these dyed fiber materials UV radiation essential.

Lichtschutzmittel für Polyesterfasermaterialien auf Triazinbasis sind bekannt. Die Schutzwirkung dieser Verbindungen genügt aber den heutigen Anforderungen, insbesondere im Automotive-Sektor, nicht vollumfänglich.
Es besteht daher weiterhin ein Bedarf nach einem besseren Schutz dieser Färbungen und Drucke.Light stabilizers for triazine-based polyester fiber materials are known. However, the protective effect of these connections does not fully meet today's requirements, particularly in the automotive sector.
There is therefore still a need for better protection of these dyeings and prints.

Es wurde nun gefunden, dass man mit bestimmten Derivaten des 2-(2'-Hydroxyphenyl)-s-triazines einen sehr guten Schutz von Färbungen und Drucken auf Polyestermaterialien erreichen kann.It has now been found that certain derivatives of 2- (2'-hydroxyphenyl) -s-triazines achieve very good protection of dyeings and prints on polyester materials can.

Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur photochemischen Stabilisierung von Färbungen und Drucken auf Polyesterfasermaterial, welches dadurch gekennzeichnet ist, dass man das Polyesterfasermaterial mit einer Verbindung der Formel

Figure 00010001
worin

  • R1 und R2, unabhängig voneinander, Wasserstoff; C1-C4-Alkyl; C1-C4-Alkoxy, Halogen, Allyloxy oder Benzyloxy bedeuten,
  • R3 ein unsubstituiertes oder durch C1-C4-Alkoxy substituiertes C1-C4-Alkyl ist,
  • R4 Wasserstoff, ein unsubstituiertes oder durch Phenyl substituiertes C1-C4-Alkyl oder Allyl ist, und
  • n und m unabhängig voneinander 1, 2 oder 3 sind, behandelt.
    • The present invention therefore relates to a process for the photochemical stabilization of dyeings and prints on polyester fiber material, which is characterized in that the polyester fiber material is mixed with a compound of the formula
    Figure 00010001
    wherein
  • R 1 and R 2 , independently of one another, are hydrogen; C 1 -C 4 alkyl; C 1 -C 4 alkoxy, halogen, allyloxy or benzyloxy,
  • R 3 is an unsubstituted or 4 -alkoxy-substituted by C 1 -C C 1 -C 4 alkyl,
  • R 4 is hydrogen, an unsubstituted or substituted by phenyl C 1 -C 4 alkyl or allyl, and
  • n and m are independently 1, 2 or 3 treated.

    • R1, R2, R3 und R4 als C1-C4-Alkyl sind Methyl, Ethyl, Propyl,i-Propyl, n-Butyl, sec.-Butyl, i-Butyl oder tert. Butyl.R 1 , R 2 , R 3 and R 4 as C 1 -C 4 alkyl are methyl, ethyl, propyl, i-propyl, n-butyl, sec-butyl, i-butyl or tert. Butyl.

    R1, R2 und R3 als C1-C4-Alkoxy sind z.B. Methoxy, Ethoxy, Propoxy, i-Propoxy oder Butoxy.R 1 , R 2 and R 3 as C 1 -C 4 alkoxy are, for example, methoxy, ethoxy, propoxy, i-propoxy or butoxy.

    Phenyl als Substituent in R4 und die Phenylreste in Benzyloxy als Substituenten in R1 und R2 können weiter ein- oder mehrmals substituiert sein durch C1-C4-Alkyl, C1-C4-Alkoxy oder Halogen.Phenyl as a substituent in R 4 and the phenyl radicals in benzyloxy as a substituent in R 1 and R 2 can be further substituted one or more times by C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen.

    Bevorzugt für das erfindungsgemässe Verfahren sind Verbindungen der Formel (1), worin R1 und R2 voneinander unabhängig Wasserstoff oder C1-C4-Alkoxy sind.Compounds of the formula (1) in which R 1 and R 2 are independently hydrogen or C 1 -C 4 alkoxy are preferred for the process according to the invention.

    Ebenfalls bevorzugt für das erfindungsgemässe Verfahren sind Verbindungen der Formel (1), wonn R3 Methyl, Ethyl oder n-Butyl ist.Also preferred for the process according to the invention are compounds of the formula (1) in which R 3 is methyl, ethyl or n-butyl.

    Ebenfalls bevorzugt für das erfindungsgemässe Verfahren sind Verbindungen der Formel (1), wonn n 2 und insbesondere 1 ist.Compounds of the formula are also preferred for the process according to the invention (1), when n is 2 and in particular 1.

    Ebenfalls bevorzugt für das erfindungsgemässe Verfahren sind Verbindungen der Formel (1), worin m 1 ist.Compounds of the formula are also preferred for the process according to the invention (1) where m is 1.

    Besonders bevorzugt für das erfindungsgemässe Verfahren sind Verbindungen der Formel (1), worin R1 und R2 voneinander unabhängig C1-C4-Alkoxy in Position 4 auf dem Phenylring sind. Compounds of the formula (1) in which R 1 and R 2 are independently of one another C 1 -C 4 alkoxy in position 4 on the phenyl ring are particularly preferred for the process according to the invention.

    Ebenfalls besonders bevorzugt für das erfindungsgemässe Verfahren sind Verbindungen der Formel (1), wonn R3 Methyl oder n-Butyl ist.Likewise particularly preferred for the process according to the invention are compounds of the formula (1) in which R 3 is methyl or n-butyl.

    Ebenfalls besonders bevorzugt für das erfindungsgemässe Verfahren sind Verbindungen der Formel (1), worin R4 Wasserstoff ist.Likewise particularly preferred for the process according to the invention are compounds of the formula (1) in which R 4 is hydrogen.

    Ganz besonders bevorzugt für das erfindungsgemässe Verfahren sind Verbindungen der Formel (1), worin R1 4-Methoxy und R2 4-Methoxy sind.Compounds of the formula (1) in which R 1 is 4-methoxy and R 2 are 4-methoxy are very particularly preferred for the process according to the invention.

    Die Verbindungen der Formel (1) sind z.B. aus US-A-3,896,125 bekannt oder können nach bekannten Methoden hergestellt werden.The compounds of formula (1) are e.g. known from US-A-3,896,125 or can according to known methods are produced.

    Die erfindungsgemäss verwendeten Verbindungen werden in einer Menge von 0,01 bis 5 Gew.-%, vorzugsweise 0,1 bis 3 Gew.-%, bezogen auf das Gewicht des Fasermaterials, eingesetzt.The compounds used according to the invention are used in an amount of 0.01 to 5 % By weight, preferably 0.1 to 3% by weight, based on the weight of the fiber material, used.

    Die erfindungsgemäss verwendeten Verbindungen sind in Wasser schwerlöslich und werden daher vorteilhafterweise in dispergierter Form appliziert. Dazu werden sie mit einem entsprechenden Dispergator mit Hilfe von z.B. Quarzkugeln und einem Schnellrührgerät auf eine Feinheit von 1-2 mm gemahlen.The compounds used according to the invention are sparingly soluble in water and become therefore advantageously applied in dispersed form. To do this, they will use a appropriate dispersant using e.g. Quartz balls and a rapid mixer a fineness of 1-2 mm is ground.

    Als Dispergatoren für die Verbindungen der Formel (1) kommen z.B. in Betracht:

    • saure Ester oder deren Salze von Alkylenoxidaddukten, wie z.B. saure Ester oder deren Salze eines Polyadduktes von 4 bis 40 Mol Ethylenoxid an 1 Mol eines Phenols, oder Phosphorsäureester der Addukte von 6 bis 30 Mol Ethylenoxid an 1 Mol 4-Nonylphenol, 1 Mol Dinonylphenol oder besonders an 1 Mol von Verbin dungen, die durch Anlagerung von 1 bis 3 Mol von gegebenenfalls substituierten Styrolen an 1 Mol Phenol hergestellt werden,
    • Polystyrolsulfonate,
    • Fettsäuretauride,
    • alkylierte Diphenyloxid-mono- oder -di-sulfonate,
    • Sulfonate von Polycarbonsäureestern,
    • mit einer organischen Dicarbonsäure, oder einer anorganischen mehrbasischen Säure in einen sauren Ester übergeführte Anlagerungsprodukte von 1 bis 60, vorzugsweise 2 bis 30 Mol Ethylenoxid und/oder Propylenoxid an Fettamine, Fettamide, Fettsäuren oder Fettalkohole mit je 8 bis 22 Kohlenstoffatomen oder an drei- bis sechs-wertige Alkanole mit 3 bis 6 Kohlenstoffatomen,
    • Ligninsulfonate, und ganz besonders
    • Formaldehyd-Kondensationsprodukte wie z.B. Kondensationsprodukte von Ligninsulfonaten und/oder Phenol und Formaldehyd, Kondensationsprodukte von Formaldehyd mit aromatischen Sulfonsäuren, wie Kondensationsprodukte von Ditolylethersulfonaten und Formaldehyd, Kondensationsprodukte von Naphthalinsulfonsäure und/oder Naphthol- oder Naphthylaminosulfonsäuren mit Formaldehyd, Kondensationsprodukte von Phenolsulfonsäuren und/oder sulfoniertem Dihydroxydiphenylsulfon und Phenolen bzw. Kresolen mit Formaldehyd und/oder Harnstoff sowie Kondensationsprodukte von Diphenyloxid-disulfonsäure- Derivaten mit Formaldehyd.
    Examples of suitable dispersants for the compounds of the formula (1) are:
    • acidic esters or their salts of alkylene oxide adducts, such as acidic esters or their salts of a polyadduct of 4 to 40 moles of ethylene oxide with 1 mole of a phenol, or phosphoric acid ester of the adducts of 6 to 30 moles of ethylene oxide with 1 mole of 4-nonylphenol, 1 mole of dinonylphenol or especially to 1 mol of compounds which are prepared by adding 1 to 3 mol of optionally substituted styrenes to 1 mol of phenol,
    • Polystyrene sulfonates,
    • Fatty acid aurides,
    • alkylated diphenyl oxide mono- or di-sulfonates,
    • Sulfonates of polycarboxylic acid esters,
    • with an organic dicarboxylic acid, or an inorganic polybasic acid, adducts of 1 to 60, preferably 2 to 30, mol of ethylene oxide and / or propylene oxide converted to fatty amines, fatty amides, fatty acids or fatty alcohols each having 8 to 22 carbon atoms or to three to hexavalent alkanols with 3 to 6 carbon atoms,
    • Lignin sulfonates, and especially
    • Formaldehyde condensation products such as, for example, condensation products of lignin sulfonates and / or phenol and formaldehyde, condensation products of formaldehyde with aromatic sulfonic acids, such as condensation products of ditolyl ether sulfonates and formaldehyde, condensation products of naphthalenesulfonic acid and / or naphthol or naphthylaminosulfonic acids and phenaldehyde sulfonate and formaldehyde sulfonic acids and formaldehyde sulfonic acids and formaldehyde sulfonic acids and formaldehyde sulfonic acids and formaldehyde sulfonic acids and formaldehyde sulfonic acids and formaldehyde sulfonate and condensation products and phenols or cresols with formaldehyde and / or urea as well as condensation products of diphenyl oxide disulfonic acid derivatives with formaldehyde.

    Als Farbstoffe kommen in Wasser nur gering lösliche Dispersionsfarbstoffe in Betracht. Sie liegen deshalb in der Färbeflotte zum grössten Teil in Form einer feinen Dispersion vor. Sie können verschiedenen Farbstoffklassen angehören, beispielsweise den Acridon-, Azo-, Anthrachinon-, Cumarin-, Methin-, Perinon-, Naphthochinonimin-, Chinophthalon-, Styryl-, oder Nitrofarbstoffen. Es können auch Mischungen von Dispersionsfarbstoffen erfindungsgemäss eingesetzt werden.Dispersions which are only slightly soluble in water are suitable as dyes. she are therefore mostly present in the dye liquor in the form of a fine dispersion. she can belong to different classes of dyes, for example the acridone, azo, Anthraquinone, coumarin, methine, perinone, naphthoquinone imine, quinophthalone, styryl, or nitro dyes. Mixtures of disperse dyes according to the invention can also be used be used.

    Als Polyesterfasermaterial, das gefärbt oder bedruckt und mit den Verbindungen der Formel (1) behandelt werden kann, sind z.B. Celluloseesterfasern, wie z.B. Cellulose-24-acetatfasem und -triacetatfasem und besonders lineare Polyesterfasern, die eventuell auch sauer modifiziert sind, zu verstehen, die z.B. durch Kondensation von Terephthalsäure mit Ethylenglykol oder von lsophthalsäure oder Terephthalsäure mit 1 ,4-Bis(hydroxymethyl)-cyclohexan erhalten werden, sowie Fasem aus Mischpolymeren von Terephthal- und Isophthalsäure und Ethylenglykol. Das in der Industrie bisher fast ausschliesslich eingesetzte lineare Polyesterfasermaterial (PES) besteht aus Terephthalsäure und Ethylenglykol.As a polyester fiber material that is dyed or printed and with the compounds of the formula (1) can be treated are e.g. Cellulose ester fibers, e.g. Cellulose 24 acetate fiber and triacetate fibers and especially linear polyester fibers, which may also be acidic are modified to understand, e.g. by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane are obtained, as well as fibers from copolymers of terephthalic and isophthalic acid and ethylene glycol. The linear that has been used almost exclusively in industry up to now Polyester fiber material (PES) consists of terephthalic acid and ethylene glycol.

    Die Fasermaterialien können aucn als Mischgewebe unter sich oder mit anderen Fasem, z.B. Mischungen aus Polyacrylnitril/Polyester, Polyamid/Polyester, Polyester/Baumwolle, Polyester/Viskose und Polyester/Wolle, verwendet werden und nach bekannten Verfahren diskontinuierlich oder kontinuierlich gefärbt oder auch bedruckt werden.The fiber materials can also be mixed with each other or with other fibers, e.g. Mixtures of polyacrylonitrile / polyester, polyamide / polyester, polyester / cotton, Polyester / viscose and polyester / wool, are used and by known methods discontinuously or continuously colored or printed.

    Das Polyesterfasermaterial kann in verschiedenen Aufmachungsformen vorliegen. Vorzugsweise kommt Stückware, wie Gewirke, Faserverbund oder Gewebe, oder auch Gam auf Kreuzspulen, Kettbäumen usw. in Betracht.The polyester fiber material can be presented in various forms. Preferably comes in piece goods, such as knitted fabrics, fiber composite or fabric, or also gam Cross-wound bobbins, warp beams, etc. into consideration.

    Gut geeignet für das erfindungsgemässe Verfahren sind ferner Polyester-Textilgewebe und Textilmischgewebe enthaltend Polyesterfasern im Oberbekleidungssektor, die lichtdurchlässig sind. Werden solche Textilien nach dem erfindungsgemässen Verfahren behandelt, können sie das unter dem transparenten Oberbekleidungsstoff befindliche Hautgewebe vor dem schädigenden Einfluss der UV-Strahlung schützen.Polyester textile fabrics and are also very suitable for the method according to the invention Textile blended fabrics containing polyester fibers in the outerwear sector that are translucent are. If such textiles are treated by the process according to the invention, you can see the skin tissue under the transparent outer clothing fabric protect against the damaging influence of UV radiation.

    Die Färbungen erfolgen aus wässriger Flotte nach einem kontinuierlichen oder diskontinuierlichen Verfahren. Beim diskontinuierlichen Verfahren (Ausziehverfahren) kann das Flottenverhältnis in einem weiten Bereich gewählt werden, z.B. 1:4 bis 1:100, vorzugsweise 1:6 bis 1:50. Die Temperatur, bei der gefärbt wird, beträgt mindestens 50°C und in der Regel ist sie nicht höher als 140°C. Vorzugsweise liegt sie im Bereich von 80 bis 135°C.The dyeings are carried out from an aqueous liquor after a continuous or discontinuous one Method. With the discontinuous process (pull-out process) this can Fleet ratio can be selected in a wide range, e.g. 1: 4 to 1: 100, preferably 1: 6 to 1:50. The temperature at which dyeing is carried out is at least 50 ° C and usually it is not higher than 140 ° C. It is preferably in the range from 80 to 135 ° C.

    Bei kontinuierlichen Färbeverfahren werden die Färbeflotten, die neben den Farbstoffen gegebenenfalls weitere Hilfsmittel enthalten können, auf das Stückmaterial durch beispielsweise Foulardieren oder Pflatschen aufgebracht und mittels Thermofixier- oder HT-Dämpfprozessen entwickelt.In the case of continuous dyeing processes, the dye liquors, which in addition to the dyes, may be used may contain further aids, for example on the piece material Padding or padding applied and by means of heat setting or HT steaming processes developed.

    Lineare Polyesterfasern und Cellulosefasem färbt man vorzugsweise nach dem sogenannten Hochtemperaturverfahren in geschlossenen und druckbeständigen Apparaten bei Temperaturen >100°C, bevorzugt zwischen 110° und 135°C und gegebenenfalls unter Druck. Als geschlossene Gefässe eignen sich beispielsweise Zirkulationsapparaturen, wie Kreuzspul- oder Baumfärbeapparate, Haspelkufen, Düsen- oder Trommelfärbemaschinen, Muff-Färbeapparate, Paddeln oder Jigger.Linear polyester fibers and cellulose fibers are preferably dyed according to the so-called High temperature processes in closed and pressure-resistant equipment Temperatures> 100 ° C, preferably between 110 ° and 135 ° C and optionally below Pressure. Circulation apparatuses such as are suitable as closed vessels Cross-winder or tree dyeing machines, reel runners, jet or drum dyeing machines, Muff dyeing machines, paddles or jiggers.

    Cellulose-24-acetatfasern färbt man vorzugsweise bei Temperaturen von 80-85°C. Cellulose-24-acetate fibers are preferably dyed at temperatures of 80-85 ° C.

    Werden die erfindungsgemässen UV-Absorber in der Färbeapplikation eingesetzt, so erfolgt die Anwendung so, dass man das Fasermaterial zunächst mit diesen Verbindungen behandelt und anschliessend die Färbung durchführt oder vorzugsweise gleichzeitig das Fasermaterial mit dem UV-Absorber und dem Farbstoff im Färbebad behandelt. Die Applikation des UV-Absorbers kann jedoch auch nachträglich auf die fertig hergestellte Färbung mittels Thermofixierung, z.B. bei 190 bis 230°C in einem Zeitraum von 30 Sekunden bis 5 Minuten erfolgen.If the UV absorbers according to the invention are used in the dyeing application, this is done the application so that the fiber material is first with these compounds treated and then carries out the coloring or preferably simultaneously Fiber material treated with the UV absorber and the dye in the dye bath. The application However, the UV absorber can also be added to the finished coloring by means of heat setting, e.g. at 190 to 230 ° C in a period of 30 seconds to 5 Minutes.

    Die Färbeflotten können auch weitere Zusätze, wie z.B.Färbereihilfsmittel, Dispergiermittel, Carrier, Wollschutz- und Netzmittel sowie auch Entschäumer enthalten.The dye liquors can also contain other additives such as dyeing aids, dispersants, Carrier, wool protection and wetting agents as well as defoamers included.

    Die Färbebäder können desweiteren Mineralsäuren, wie z.B. Schwefelsäure oder Phosphorsäure, oder zweckmässigerweise organische Säuren, zum Beispiel aliphatische Carbonsäuren wie Ameisensäure, Essigsäure, Oxalsäure oder Zitronensäure und/oder Salze wie Ammoniumacetat, Ammoniumsulfat oder Natriumacetat enthalten. Die Säuren dienen vor allem der Ein stellung des pH-Wertes der erfindungsgemäss verwendeten Flotten, der zwischen vorzugsweise 4 und 5 liegt.The dye baths can also contain mineral acids, e.g. Sulfuric acid or phosphoric acid, or expediently organic acids, for example aliphatic carboxylic acids such as formic acid, acetic acid, oxalic acid or citric acid and / or salts such as ammonium acetate, ammonium sulfate or sodium acetate. The acids serve especially the adjustment of the pH of the liquors used according to the invention, the is preferably between 4 and 5.

    Vorzugsweise lässt man das Fasermaterial während 5 Minuten bei 40 bis 80°C im Bad, das den Farbstoff, den UV-Absorber und gegebenenfalls weitere Zusätze enthält und auf einen pH-Wert von 4,5 bis 5,5 eingestellt ist, vorlaufen, erhöht die Temperatur innerhalb von 10 bis 20 Minuten auf 125 bis 130°C und behandelt für 15 bis 90 Minuten, vorzugsweise 30 Minuten, bei dieser Temperatur weiter.The fiber material is preferably left in the bath at 40 to 80 ° C. for 5 minutes contains the dye, the UV absorber and optionally other additives and on one pH is set to 4.5 to 5.5, the temperature increases within 10 to 20 minutes at 125 to 130 ° C and treated for 15 to 90 minutes, preferably 30 minutes, at this temperature further.

    Die Fertigstellung der Färbungen erfolgt durch Abkühlen der Färbeflotte auf 50 bis 80°C, Spülen der Färbungen mit Wasser und gegebenenfalls durch Reinigung auf übliche Weise im alkalischen Medium unter reduktiven Bedingungen. Die Färbungen werden dann wiederum gespült und getrocknet. Bei Verwendung von Küpenfarbstoffen für den Celluloseanteil wird die Ware auf übliche Weise zuerst mit Hydrosulfit bei einem pH-Wert von 6 bis 12,5 und dann mit einem Oxidationsmittel behandelt und schliesslich ausgewaschen.The dyeings are completed by cooling the dye liquor to 50 to 80 ° C. Rinse the dyeings with water and, if necessary, by cleaning in the usual way in an alkaline medium under reductive conditions. The stains then turn again rinsed and dried. When using vat dyes for the cellulose content In the usual way, the goods are first treated with hydrosulfite at a pH of 6 to 12.5 and then treated with an oxidizing agent and finally washed out.

    Für die Herstellung von Drucken werden die erfindungsgemäss verwendeten UV-Absorber in Form ihrer wässrigen Dispersionen zweckmässigerweise den Druckpasten beigemischt. The UV absorbers used according to the invention are used for the production of prints expediently mixed with the printing pastes in the form of their aqueous dispersions.

    Die Druckpaste enthält dabei den entsprechenden UV-Absorber in Mengen von 0,01 bis 5 Gew.%, vorzugsweise 0,1 bis 3 Gew.%, bezogen auf das Gewicht der Druckpaste. Die UV-Absorber können aber bereits bei der Druckbodenvorbereitung, z.B. nach dem Thermofixierverfahren, appliziert werden.The printing paste contains the corresponding UV absorber in quantities from 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the weight of the printing paste. However, the UV absorbers can already be used in the preparation of the pressure floor, e.g. after this Heat-setting processes can be applied.

    Die Menge der Farbstoffe, die den Druckpasten zugesetzt werden, richtet sich nach der gewünschten Farbnuance; im allgemeinen haben sich Mengen von 0,01 bis 15, vorzugsweise 0,02 bis 10 Gewichtsprozent, bezogen auf das eingesetzte Textilmaterial, bewährt.The amount of dyes added to the printing pastes depends on the desired one Color shade; in general, amounts of 0.01 to 15, preferably 0.02 to 10 weight percent, based on the textile material used, proven.

    Die Druckpasten enthalten neben den Farbstoffen und der wässrigen UV-Absorber-Dispersion zweckmässigerweise säurestabile Verdickungsmittel, vorzugsweise natürlicher Herkunft wie Kemmehlabkömmlinge, insbesondere Natriumalginat für sich allein oder im Gemisch mit modifizierter Cellulose, insbesondere mit vorzugsweise 20 bis 25 Gewichtsprozent Carboxymethylcellulose. Daneben können die Druckpasten noch Säurespender, wie Butyrolacton oder Natriumhydrogenphosphat, Konservierungsmittel, Sequestriermittel, Emulgatoren, wasserunlösliche Lösungsmittel, Oxidationsmittel oder Entlüftungsmittel enthalten.In addition to the dyes and the aqueous UV absorber dispersion, the printing pastes contain expediently acid-stable thickeners, preferably more natural Origin such as corn flour derivatives, especially sodium alginate on its own or in Mixture with modified cellulose, in particular with preferably 20 to 25 percent by weight Carboxymethyl cellulose. In addition, the printing pastes can also contain acid donors, such as butyrolactone or sodium hydrogen phosphate, preservatives, sequestering agents, Emulsifiers, water-insoluble solvents, oxidizing agents or deaerating agents contain.

    In Betracht kommen als Konservierungsmittel vor allem formaldehydabgebende Mittel, wie z.B. Paraformaldehyd oder Trioxan, vor allem wässrige, etwa 30 bis 40-gewichtsprozentige Formaldehydlösungen; als Sequestriermittel z.B. nitrilotriessigsaures Natrium, ethylendiamintetraessigsaures Natrium, vor allem Natrium-Polymetaphosphat, insbesondere Natrium-Hexamethaphosphat; als Emulgatoren vor allem Addukte aus einem Alkylenoxid und einem Fettalkohol, insbesondere einem Addukt aus Oleylalkohol und Ethylenoxid; als wasserunlösliche Lösungsmittel hochsiedende, gesättigte Kohlenwasserstoffe, vor allem Paraffine mit einem Siedebereich von etwa 160 bis 210°C (sogenannte Lackbenzine); als Oxidationsmittel z.B. eine aromatische Nitroverbindung, vor allem eine aromatische Mono- oder Dinitrocarbonsäure oder -sulfonsäure, die gegebenenfalls als Alkylenoxidaddukt vorliegt, insbesondere eine Nitrobenzolsulfonsäure; und als Entlüftungsmittel z.B. hochsiedende Lösungsmittel, vor allem Terpentinöle, höhere Alkohole, vorzugsweise C8- bis C10-Alkohole, Terpenalkohole oder Entlüftungsmittel auf Basis von Mineral- und/oder Silikonölen, insbesondere Handelsformulierungen aus etwa 15 bis 25 Gewichtsprozent eines Mineral- und Silikonölgemisches und etwa 75 bis 85 Gewichtsprozent eines C8-Alkohols wie z.B. 2-Ethyl-n-hexanol.Suitable preservatives are, above all, formaldehyde-releasing agents, such as, for example, paraformaldehyde or trioxane, especially aqueous, about 30 to 40 percent by weight formaldehyde solutions; as sequestering agents, for example sodium nitrilotriacetic acid, sodium ethylenediaminetetraacetic acid, especially sodium polymetaphosphate, in particular sodium hexamethaphosphate; as emulsifiers, especially adducts of an alkylene oxide and a fatty alcohol, in particular an adduct of oleyl alcohol and ethylene oxide; as water-insoluble solvents, high-boiling, saturated hydrocarbons, especially paraffins with a boiling range of about 160 to 210 ° C (so-called mineral spirits); as an oxidizing agent, for example an aromatic nitro compound, especially an aromatic mono- or dinitrocarboxylic acid or sulfonic acid, which is optionally present as an alkylene oxide adduct, in particular a nitrobenzenesulfonic acid; and as a deaerating agent, for example high-boiling solvents, especially turpentine oils, higher alcohols, preferably C 8 to C 10 alcohols, terpene alcohols or deaerating agents based on mineral and / or silicone oils, in particular commercial formulations of about 15 to 25 percent by weight of a mineral and silicone oil mixture and about 75 to 85 percent by weight of a C 8 alcohol such as 2-ethyl-n-hexanol.

    Beim Bedrucken der Fasermaterialien wird die Druckpaste ganzflächig oder stellenweise direkt auf das Fasermaterial aufgebracht, wobei zweckmässigerweise Druckmaschinen üblicher Bauart, z.B. Tiefdruck-, Rotationssiebdruck-, Flachfilmdruck- oder Inkjetmaschinen eingesetzt werden.When printing on the fiber materials, the printing paste becomes direct over the entire surface or in places applied to the fiber material, expediently printing machines more commonly Type, e.g. Gravure, rotary screen, flat film or inkjet machines be used.

    Das Fasermaterial wird nach dem Bedrucken bei Temperaturen bis 150°C, vorzugsweise 80° bis 120°C getrocknet.After printing, the fiber material is preferably at temperatures up to 150 ° C. Dried 80 ° to 120 ° C.

    Anschliessend erfolgt die Fixierung des Materials durch eine Wärmebehandlung bei Temperaturen von vorzugsweise 100° bis 220°C. Die Wärmebehandlung erfolgt im allgemeinen mit überhitztem Wasserdampf unter Druck.The material is then fixed by heat treatment at temperatures from preferably 100 ° to 220 ° C. The heat treatment is generally carried out with superheated steam under pressure.

    Je nach Temperatur kann die Fixierung 20 Sekunden bis 12 Minuten, vorzugsweise 4 bis 8 Minuten erfolgen.Depending on the temperature, the fixation can last 20 seconds to 12 minutes, preferably 4 to 8 Minutes.

    Die Fertigstellung der Drucke erfolgt ebenfalls auf übliche Weise durch Spülen mit Wasser und kann gegebenenfalls durch zusätzliche Reinigung im alkalischen Medium unter reduktiven Bedingungen, z.B. mittels Natriumdithionit vorgenommen werden. Im letzteren Fall werden die Drucke wiederum gespült, entwässert und getrok-knet.The prints are also finished in the usual way by rinsing with water and can, if necessary, by additional cleaning in an alkaline medium under reductive Conditions, e.g. be made with sodium dithionite. In the latter case the prints are rinsed, dewatered and dried.

    Mit dem erfindungsgemässen Verfahren lassen sich hochlichtechte und sublimationsbeständige Polyester-Färbungen und Drucke erzielen. Eine gezielte Vor- oder Nachbehandlung des Fasermaterials ist mit dem erfindungsgemässen Verfahren nicht erforderlich.With the method according to the invention, highly lightfast and sublimation-resistant Achieve polyester dyeings and prints. A targeted pre- or post-treatment of the fiber material is not necessary with the method according to the invention.

    Die mit dem erfindungsgemässen Verfahren behandelten Polyesterfasermaterialien zeichnen sich auch durch einen sehr hohen Sonnenschutzfaktor aus.Draw the polyester fiber materials treated with the method according to the invention is also characterized by a very high sun protection factor.

    Die Verwendung der Verbindungen der Formel (1) als Mittel zur Erhöhung des Sonnenschutzfaktores von gefärbten oder bedruckten Polyesterfasermaterialien stellt somit einen weiteren Gegenstand der vorliegenden Erfindung dar. The use of the compounds of formula (1) as an agent for increasing the sun protection factor of dyed or printed polyester fiber materials further subject of the present invention.

    Die Bestimmung des Sonnenschutzfaktors kann z.B. nach der von B. L. Diffey und J. Robson in J. Soc. Cosmet. Chem. 40, 127-133 (May/June 1989) beschriebenen Methode erfolgen.The determination of the sun protection factor can e.g. after that of B.L. Diffey and J. Robson in J. Soc. Cosmet. Chem. 40, 127-133 (May / June 1989).

    Die nachfolgenden Beispiele dienen der Veranschaulichung der Erfindung. Darin sind die Teile Gewichtsteile und die Prozente Gewichtsprozente. Die Temperaturen sind in Celsiusgraden angegeben. Die Beziehung zwischen Gewichtsteilen und Volumenteilen ist dieselbe wie diejenige zwischen Gramm und Kubikzentimeter.The following examples serve to illustrate the invention. That's where they are Parts by weight and the percentages by weight. The temperatures are in degrees Celsius specified. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimeters.

    Beispiel 1:Example 1:

    (a) 5 Gewichtsteile der Verbindung der Formel

    Figure 00090001
    werden in einer mit einem Rührer versehenen Laborapparatur mit 2,5 Gewichtsteilen eines Kondensationsproduktes aus Naphthalinsulfonsäure und Formaldehyd als Dispergator, welches in 15 ml Wasser gelöst ist, mit 25 Gewichtsteilen Quarzkügelchen versetzt bei ca. 1600 Umdrehungen/Minute so lange gemahlen, bis eine Teilchengrösse unter 2 µm resultiert. Die Dispersion wird anschliessend von den Quarzkügelchen abgetrennt. Durch Zugabe von Wasser wird der Gehalt von der Verbindung der Formel (10) auf 10 Gewichtsprozent, bezogen auf die Formulierung, eingestellt.(a) 5 parts by weight of the compound of the formula
    Figure 00090001
    are mixed in a laboratory apparatus equipped with a stirrer with 2.5 parts by weight of a condensation product of naphthalenesulfonic acid and formaldehyde as a dispersant, which is dissolved in 15 ml of water, with 25 parts by weight of quartz beads at about 1600 revolutions / minute until a particle size is below 2 µm results. The dispersion is then separated from the quartz beads. The content of the compound of the formula (10) is adjusted to 10% by weight, based on the formulation, by adding water.

    (b) Ein Stück von 10 g Polyestertrikot, wird in einer Hochtemperaturfärbeapparatur (Turbomat® der Firma Mathis, Niederhasli, CH) mit einem Flottenverhältnis von 1:10 gefärbt. Die wässrige Färbeflotte enthält pro 1 l der Flotte

  • 2 g Ammoniumsulfat,
  • 0,5 g eines handelsüblichen Egalisierhilfsmittels,
  • 0,5 g der unter (a) hergestellten Formulierung der Verbindung der Formel (10),
  • 0,83 g einer Farbstoffmischung enthaltend
  • 0,28 g des Farbstoffes der Formel
    Figure 00100001
  • 0,26 g des Farbstoffes der Formel
    Figure 00100002
  • 0,16 g des Farbstoffes der Formel
    Figure 00100003
    und
  • 0,13 g des Farbstoffes der Formel
    Figure 00100004
    • (b) A piece of 10 g polyester jersey is dyed in a high temperature dyeing machine (Turbomat® from Mathis, Niederhasli, CH) with a liquor ratio of 1:10. The aqueous dye liquor contains 1 l of the liquor
  • 2 g ammonium sulfate,
  • 0.5 g of a commercial leveling aid,
  • 0.5 g of the formulation of the compound of the formula (10) prepared under (a),
  • Containing 0.83 g of a dye mixture
  • 0.28 g of the dye of the formula
    Figure 00100001
  • 0.26 g of the dye of the formula
    Figure 00100002
  • 0.16 g of the dye of the formula
    Figure 00100003
    and
  • 0.13 g of the dye of the formula
    Figure 00100004
    •

    Die Färbeflotte wird mit Essigsäure auf einen pH-Wert von 5 eingestellt, homogenisiert und mit dem Polyestertrikot in die Hochtemperaturfärbeapparatur gegeben und auf 70° C und anschliessend innerhalb von 30 Minuten auf 130° C aufgeheizt. Bei dieser Temperatur wird das Polyestertrikot 60 Minuten gefärbt.
    Anschliessend wird die Flotte auf 75°C abkekühlt, das gefärbte Polyestertrikot mit heissem und kaltem Wasser gespüllt und einer reduktiven Reinigung durch Behandlung mit einer Flotte enthaltend 3 ml/l einer 30%-igen wässrigen Lösung von NaOH und 2 g/l Natriumdithionit, während 20 Minuten bei 70° C unterzogen.
    Danach wird das Polyestertrikotstück mit warmem und kaltem Wasser gespüllt, zentrifugiert und bei 80° C getrocknet.
    Man erhält ein grau gefärbtes Polyestertrikot mit guten Allgemeinechtheiten, insbesondere einer sehr guten Heisslichtechtheit.    The dyeing liquor is adjusted to a pH of 5 with acetic acid, homogenized and added to the polyester tricot in the high-temperature dyeing apparatus and heated to 70 ° C. and then to 130 ° C. within 30 minutes. The polyester jersey is dyed at this temperature for 60 minutes.
    The liquor is then cooled to 75 ° C., the dyed polyester tricot is rinsed with hot and cold water and a reductive cleaning by treatment with a liquor containing 3 ml / l of a 30% aqueous solution of NaOH and 2 g / l sodium dithionite during Subjected for 20 minutes at 70 ° C.
    The piece of polyester tricot is then rinsed with warm and cold water, centrifuged and dried at 80 ° C.
    A gray-colored polyester jersey with good general fastness properties, in particular a very good hot light fastness, is obtained.

    Beispiel 2:Example 2:

    (c) Man verfährt wie im Beispiel 1 (a) angegeben, verwendet aber anstatt 5 Gewichtsteile der Verbindung der Formel (10) die gleiche Menge der Verbindung der Formel

    Figure 00110001
    (c) The procedure is as described in Example 1 (a), but instead of 5 parts by weight of the compound of the formula (10), the same amount of the compound of the formula is used
    Figure 00110001

    (d) Verfährt man wie im Beispiel 1 (b) angegeben, verwendet aber anstatt 0,5 g der Formulierung enthaltend die Verbindung der Formel (10) die gleiche Menge einer unter (c) beschriebenen Formulierung der Verbindung der Formel (11) erhält man ebenfalls ein grau gefärbtes Polyestertrikot mit guten Allgemeinechtheiten, insbesondere einer sehr guten Heisslichtechtheit.(d) The procedure is as described in Example 1 (b), but instead of 0.5 g of the formulation containing the compound of formula (10) the same amount of one described in (c) Formulation of the compound of formula (11) also gives a gray dyed polyester jersey with good general fastness properties, especially a very good one Hot light fastness.

    Beispiel 3: Example 3 :

    (e) Man verfährt wie im Beispiel 1 (a) angegeben, verwendet aber anstatt 5 Gewichtsteile der Verbindung der Formel (10) die gleiche Menge der Verbindung der Formel

    Figure 00110002
    (f) Verfährt man wie im Beispiel 1 (b) angegeben, verwendet aber anstatt 0,5 g der Formulierung enthaltend die Verbindung der Formel (10) die gleiche Menge einer unter (e) beschriebenen Formulierung der Verbindung der Formel (12) erhält man ebenfalls ein grau gefärbtes Polyestertrikot mit guten Allgemeinechtheiten, insbesondere einer sehr guten Heisslichtechtheit.(e) The procedure is as described in Example 1 (a), but instead of 5 parts by weight of the compound of the formula (10), the same amount of the compound of the formula is used
    Figure 00110002
    (f) The procedure is as described in Example 1 (b), but instead of 0.5 g of the formulation comprising the compound of the formula (10), the same amount of a formulation of the compound of the formula (12) described under (e) is obtained also a gray-colored polyester jersey with good general fastness properties, especially very good hot light fastness.

    Beispiel 4:Example 4:

    Grau gefärbte Polyestertrikots mit guten Allgemeinechtheiten, insbesondere einer sehr guten Heisslichtechtheit resultieren ebenfalls aus Färbeverfahren gemäss Beispiel 1, wenn man anstatt 0,5 g der Verbindung der Formel (10) jeweils 0,5 g der folgenden in der Tabelle 1 aufgeführten Verbindungen verwendet.

    Figure 00120001
    Gray-colored polyester jerseys with good general fastness properties, in particular very good hot light fastness, also result from the dyeing process according to Example 1 if, instead of 0.5 g of the compound of the formula (10), 0.5 g of the following compounds listed in Table 1 is used.
    Figure 00120001

    Claims (13)

    Verfahren zur photochemischen Stabilisierung von Färbungen und Drucken auf Polyesterfasermaterial, dadurch gekennzeichnet, dass man das Polyesterfasermaterial mit einer Verbindung der Formel
    Figure 00130001
    worin R1 und R2, unabhängig voneinander, Wasserstoff; C1-C4-Alkyl; C1-C4-Alkoxy, Halogen, Allyloxy oder Benzyloxy bedeuten, R3 ein unsubstituiertes oder durch C1-C4-Alkoxy substituiertes C1-C4-Alkyl ist, R4 Wasserstoff, ein unsubstituiertes oder durch Phenyl substituiertes C1-C4-Alkyl oder Allyl ist, und n und m unabhängig voneinander 1, 2 oder 3 sind, behandelt.    Process for the photochemical stabilization of dyeings and prints on polyester fiber material, characterized in that the polyester fiber material with a compound of the formula
    Figure 00130001
    wherein R 1 and R 2 , independently of one another, are hydrogen; C 1 -C 4 alkyl; C 1 -C 4 alkoxy, halogen, allyloxy or benzyloxy, R 3 is an unsubstituted or 4 -alkoxy-substituted by C 1 -C C 1 -C 4 alkyl, R 4 is hydrogen, an unsubstituted or substituted by phenyl C 1 -C 4 alkyl or allyl, and n and m are independently 1, 2 or 3, treated.         Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man das Polyesterfasermaterial mit einer Verbindung der Formel (1), worin R1 und R2 voneinander unabhängig Wasserstoff oder C1-C4-Alkoxy sind, behandelt.A method according to claim 1, characterized in that the polyester fiber material is treated with a compound of formula (1), wherein R 1 and R 2 are independently hydrogen or C 1 -C 4 alkoxy. Verfahren gemäss Anspruch 2, dadurch gekennzeichnet, dass man das Polyesterfasermaterial mit einer Verbindung der Formel (1), worin R1 und R2 voneinander unabhängig C1-C4-Alkoxy in Position 4 auf dem Phenylring sind, behandelt. Process according to Claim 2, characterized in that the polyester fiber material is treated with a compound of the formula (1) in which R 1 and R 2 are, independently of one another, C 1 -C 4 alkoxy in position 4 on the phenyl ring. Verfahren gemäss Anspruch 3, dadurch gekennzeichnet, dass man das Polyesterfasermaterial mit einer Verbindung der Formel (1), worin R1 4-Methoxy und R2 4-Methoxy sind, behandelt.Process according to Claim 3, characterized in that the polyester fiber material is treated with a compound of the formula (1) in which R 1 is 4-methoxy and R 2 is 4-methoxy. Verfahren gemäss einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass man das Polyesterfasermaterial mit einer Verbindung der Formel (1), worin R3 Methyl, Ethyl oder n-Butyl ist, behandelt.Process according to one of Claims 1 to 4, characterized in that the polyester fiber material is treated with a compound of the formula (1) in which R 3 is methyl, ethyl or n-butyl. Verfahren gemäss Anspruch 5, dadurch gekennzeichnet, dass man das Polyesterfasermaterial mit einer Verbindung der Formel (1), worin R3 Methyl oder n-Butyl ist, behandelt.Process according to Claim 5, characterized in that the polyester fiber material is treated with a compound of the formula (1) in which R 3 is methyl or n-butyl. Verfahren gemäss einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass man das Polyesterfasermaterial mit einer Verbindung der Formel (1), worin R4 Wasserstoff ist, behandelt.Process according to one of Claims 1 to 6, characterized in that the polyester fiber material is treated with a compound of the formula (1) in which R 4 is hydrogen. Verfahren gemäss einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass man das Polyesterfasermaterial mit einer Verbindung der Formel (1), worin n 2 und insbesondere 1 ist, behandelt.Method according to one of claims 1 to 7, characterized in that the Polyester fiber material with a compound of the formula (1), in which n is 2 and in particular 1 is treated. Verfahren gemäss einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass man das Polyesterfasermaterial mit einer Verbindung der Formel (1), worin m 1 ist, behandelt.Method according to one of claims 1 to 8, characterized in that the Polyester fiber material treated with a compound of formula (1), wherein m is 1. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man das Polyesterfasermaterial mit einer Verbindung der Formel (1), worin R1 Wasserstoff, Methyl, Methoxy, Allyloxy oder Benzyloxy, R2 Wasserstoff, Chlor, Methoxy, Allyloxy oder Benzyloxy, R3 Methyl, Ethyl, i-Propyl oder n-Butyl, und R4 Wasserstoff oder Methyl sind, behandelt.A method according to claim 1, characterized in that the polyester fiber material with a compound of formula (1), wherein R 1 is hydrogen, methyl, methoxy, allyloxy or benzyloxy, R 2 is hydrogen, chlorine, methoxy, allyloxy or benzyloxy, R3 is methyl, ethyl , i-propyl or n-butyl, and R 4 are hydrogen or methyl, treated. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man 0,01 bis 5 Gew.-%, bezogen auf das Gewicht des Fasermaterials, der Verbindung der Formel (1) verwendet.A method according to claim 1, characterized in that 0.01 to 5 wt .-%, based on the weight of the fiber material, the compound of formula (1) used. Verwendung von Verbindungen der Formel (1) gemäss Anspruch 1 als Stabilisatoren für Färbungen und Drucken auf Polyesterfasermaterial gegen Schädigung durch Licht, Sauerstoff und/oder Wärme. Use of compounds of formula (1) according to claim 1 as stabilizers for dyeing and printing on polyester fiber material against damage by light, Oxygen and / or heat. Verwendung von Verbindungen der Formel (1) gemäss Anspruch 1 zur Erhöhung des Sonnenschutzfaktores von gefärbtem oder bedrucktem Polyesterfasermaterial.Use of compounds of formula (1) according to claim 1 to increase the Sun protection factors from dyed or printed polyester fiber material.
    EP98810183A 1997-03-11 1998-03-04 Process for improving the photochemical stability of coloration and prints on polyester fibers Withdrawn EP0864687A3 (en)

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    US3896125A (en) * 1963-01-24 1975-07-22 Ciba Geigy Ag O-hydroxyphenyl-s-triazines
    US4831068A (en) * 1987-02-27 1989-05-16 Ciba-Geigy Corporation Process for improving the photochemical stability of dyeings on polyester fibre materials
    US4895981A (en) * 1987-02-27 1990-01-23 Ciba-Geigy Corporation Process for improving the photochemical stability of dyeings on polyester fibre materials
    EP0468921A1 (en) * 1990-07-23 1992-01-29 Ciba-Geigy Ag Aqueous dispersions of slightly soluble UV absorbing agents
    EP0523006A1 (en) * 1991-07-12 1993-01-13 Ciba-Geigy Ag Process for printing and photochemically stabilizing polyester fibre materials
    US5298030A (en) * 1992-02-21 1994-03-29 Ciba-Geigy Corporation Process for the photochemical and thermal stabilization of undyed and dyed or printed polyester fiber materials

    Patent Citations (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3896125A (en) * 1963-01-24 1975-07-22 Ciba Geigy Ag O-hydroxyphenyl-s-triazines
    US4831068A (en) * 1987-02-27 1989-05-16 Ciba-Geigy Corporation Process for improving the photochemical stability of dyeings on polyester fibre materials
    US4895981A (en) * 1987-02-27 1990-01-23 Ciba-Geigy Corporation Process for improving the photochemical stability of dyeings on polyester fibre materials
    EP0468921A1 (en) * 1990-07-23 1992-01-29 Ciba-Geigy Ag Aqueous dispersions of slightly soluble UV absorbing agents
    EP0523006A1 (en) * 1991-07-12 1993-01-13 Ciba-Geigy Ag Process for printing and photochemically stabilizing polyester fibre materials
    US5298030A (en) * 1992-02-21 1994-03-29 Ciba-Geigy Corporation Process for the photochemical and thermal stabilization of undyed and dyed or printed polyester fiber materials

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