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EP0584044A1 - Process for photochemical and thermal stabilization of undyert and dyert polyester fibrous materials - Google Patents

Process for photochemical and thermal stabilization of undyert and dyert polyester fibrous materials Download PDF

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Publication number
EP0584044A1
EP0584044A1 EP93810563A EP93810563A EP0584044A1 EP 0584044 A1 EP0584044 A1 EP 0584044A1 EP 93810563 A EP93810563 A EP 93810563A EP 93810563 A EP93810563 A EP 93810563A EP 0584044 A1 EP0584044 A1 EP 0584044A1
Authority
EP
European Patent Office
Prior art keywords
formula
bis
acid
photochemical
printing
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.)
Granted
Application number
EP93810563A
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German (de)
French (fr)
Other versions
EP0584044B1 (en
Inventor
Dieter Dr. Reinehr
Gerhard Dr. Reinert
Manfred Dr. Rembold
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.)
BASF Schweiz AG
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Ciba Geigy AG
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Publication of EP0584044A1 publication Critical patent/EP0584044A1/en
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Classifications

    • 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
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65118—Compounds containing hydroxyl groups
    • 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
    • D06M13/10—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 oxygen
    • D06M13/152—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 oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • 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
    • D06M13/10—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 oxygen
    • D06M13/165—Ethers
    • 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
    • D06M13/244—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 sulfur or phosphorus
    • D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
    • D06M13/252—Mercaptans, thiophenols, sulfides or polysulfides, e.g. mercapto acetic acid; Sulfonium 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
    • 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
    • D06P1/64—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
    • 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
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65131—Compounds containing ether or acetal groups
    • 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
    • D06P1/651—Compounds without nitrogen
    • D06P1/65168—Sulfur-containing compounds
    • D06P1/65187—Compounds containing sulfide or disulfide groups
    • 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
    • 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 the photochemical and thermal stabilization of undyed and dyed polyester fiber materials.
  • Dyed or printed polyester fiber material can be damaged under the influence of light and especially when exposed to heat.
  • effective protection of these undyed and dyed fiber materials from UV radiation is essential.
  • the present invention therefore relates to a process for the photochemical and thermal stabilization of undyed and dyed polyester fiber materials with UV absorbers, which is characterized in that the fiber material is mixed with a compound of the formula treated in what
  • R1 and R2 independently of one another C1-C12alkyl mean.
  • C1-C12alkyl are straight-chain or branched alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, heptyl, octyl, isooctyl, nonyl, undecyl or Dodecyl.
  • R1 and R2 independently of one another are C1-C1alkyl.
  • Those compounds of the formula (1) in which R1 and R2 are methyl and those in which R1 is methyl and R2 are propyl are particularly preferred.
  • the compounds of formula (1) are known, e.g. from CH-A-436,285. They can be prepared analogously to the process described in EP-A-0,395,285 by Friedel-Crafts alkylation of 1 mol of cyanuric chloride with one mol of an alkyl mercaptan and subsequent reaction with 2 mol of the corresponding benzene compound in the presence of a Lewis acid, preferably aluminum chloride.
  • the UV absorbers according to the invention are used in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the weight of the fiber material.
  • the UV absorbers according to the invention are sparingly soluble in water and are therefore applied in dispersed form. To do this, they are treated with an appropriate dispersant using e.g. Quartz balls and a high-speed mixer are ground to a fineness of 1-2 ⁇ m.
  • Dispersions which are only slightly soluble in water are suitable as dyes. They are therefore largely in the form of a fine dispersion in the dyeing liquor. They 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 can also be used according to the invention.
  • Polyester fiber material that can be dyed or printed and treated with the UV absorbers mentioned is, for example, cellulose ester fibers, such as cellulose 21 ⁇ 2-acetate fibers and triacetate fibers and particularly linear polyester fibers, which may also be acid-modified, to be understood, for example, 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 polyester fiber material (PES) used almost exclusively in industry so far consists of terephthalic acid and ethylene glycol.
  • the fiber materials can also be used as a mixed fabric among themselves or with other fibers, e.g. Mixtures of polyacrylonitrile / polyester, polyamide / polyester, polyester / cotton, polyester / viscose and polyester / wool can be used and can be dyed or printed discontinuously or continuously by known methods.
  • the textile material can be presented in various forms.
  • Piece goods such as knitted or woven fabrics, or yarn on cross-wound bobbins, warp beams, etc., are preferably used.
  • Textile fabrics in the outer clothing sector which are translucent are also very suitable for the method according to the invention. If such textiles are treated according to the method according to the invention, they can protect the skin tissue located under the transparent outer clothing fabric from the damaging influence of UV radiation.
  • the dyeings are carried out from an aqueous liquor using a continuous or batch process.
  • the liquor 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 dyeing liquors which in addition to the dyes may optionally contain other auxiliaries, are applied to the piece material by, for example, padding or slapping and developed by means of heat setting or HT steaming processes.
  • Linear polyester fibers and cellulose fibers are preferably dyed by the so-called high-temperature process in closed and pressure-resistant apparatus at temperatures> 100 ° C., preferably between 110 ° and 135 ° C. and, if appropriate, under pressure.
  • Circulation apparatuses such as are suitable as closed vessels Cross-winder or tree dyeing machines, reel runners, nozzle or drum dyeing machines, muff dyeing machines, paddles or jiggers.
  • Cellulose-21 ⁇ 2-acetate fibers are preferably dyed at temperatures of 80-85 ° C.
  • the UV absorbers according to the invention are used in the dyeing application, they are used in such a way that the fiber material is first treated with these compounds and then the dyeing is carried out, or preferably the fiber material is simultaneously treated with the UV absorber and the dye in the dye bath.
  • the application of the UV absorber can also be retrofitted 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 dyeing liquors can also contain other additives such as dyeing aids, dispersants, carriers, wool protection and wetting agents and also defoamers.
  • the dye baths can also contain mineral acids, e.g. Contain 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. Contain 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 primarily serve to adjust the pH of the liquors used according to the invention, which is preferably between 4 and 5.
  • the fiber material is preferably allowed to run for 5 minutes at 40 to 80 ° C. in the bath, which contains the dye, the UV absorber and optionally further additives and is adjusted to a pH of 4.5 to 5.5 the temperature within 10 to 20 minutes to 125 to 130 ° C and treated for 15 to 90 minutes, preferably 30 minutes, further at this temperature.
  • the dyeings are completed by cooling the dye liquor to 50 to 80 ° C., rinsing the dyeings with water and, if appropriate, cleaning in a conventional manner in an alkaline medium under reductive conditions. The dyeings are then rinsed again and dried. If vat dyes are used for the cellulose part, the goods are treated in the usual way first with hydrosulfite at a pH of 6 to 12.5 and then with an oxidizing agent and finally washed out.
  • the UV absorbers according to the invention are added to the printing pastes in the form of their aqueous dispersions.
  • the printing paste contains the corresponding UV absorber in amounts of 0.1 to 10%, preferably 0.1 to 5%, based on the weight of the printing paste.
  • the amount of dyes added to the printing pastes depends on the desired shade; In general, amounts of 0.01 to 15, preferably 0.02 to 10 percent by weight, based on the textile material used, have proven successful.
  • the printing pastes advantageously contain acid-stable thickeners, preferably of natural origin such as seed flour derivatives, in particular sodium alginate, alone or in a 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 hydrogenphosphate, preservatives, sequestering agents, emulsifiers, water-insoluble solvents, oxidizing agents or deaerating agents.
  • Particularly suitable preservatives are formaldehyde-releasing agents, such as Paraformaldehyde or trioxane, especially aqueous, about 30 to 40 percent by weight formaldehyde solutions; as sequestering agents e.g. sodium nitrilotriacetic acid, sodium ethylenediaminetetraacetic acid, especially sodium polymethaphosphate, especially 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 e.g.
  • formaldehyde-releasing agents such as Paraformaldehyde or trioxane, especially aqueous, about 30 to 40 percent by weight formaldehyde solutions
  • 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 venting agent e.g. high-boiling solvents, especially turpentine oils, higher alcohols, preferably C8 to C10 alcohols, terpene alcohols or deaerators 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 a C8 alcohol such as 2-ethyl-n-hexanol.
  • a venting agent e.g. high-boiling solvents, especially turpentine oils, higher alcohols, preferably C8 to C10 alcohols, terpene alcohols or deaerators based on mineral and / or silicone oils, in particular commercial formulations of about 15 to 25 percent by weight of a mineral and silicone
  • the fiber material is dried at temperatures up to 150 ° C., preferably 80 ° to 120 ° C.
  • the material is then fixed by heat treatment at temperatures of preferably 100 ° to 220 ° C.
  • the heat treatment is generally carried out with superheated steam under pressure.
  • the fixation can take place for 20 seconds to 10 minutes, preferably 4 to 8 minutes.
  • the prints are also finished in the usual way by rinsing with water and can, if appropriate, be carried out by additional cleaning in an alkaline medium under reductive conditions, e.g. be made with sodium dithionite. In the latter case, the printing stains are again rinsed, dewatered and dried.
  • the percentages relate to the weight.
  • the amounts relate to pure substance in the case of dyes and UV absorbers.
  • 3 samples of 10 g each of a PES jersey are dyed in an HT dyeing machine, for example a ®Labomat (Mathis, Niederhasli) at a liquor ratio of 1:10.
  • 3 liquors [(I) to (III)] are prepared, the 2 g / l ammonium sulfate, 0.5 g / l of a dyeing aid, for example ®Univadin 3-flex and the dyes of the formulas (1) to (4) in the following Quantities include: 0.210% of the dye of the formula 0.087% of the dye of the formula 0.80% of the dye of the formula and 0.087% of the dye of the formula
  • liquor (I) contains no further additives
  • liquors (II) and (III) are each additionally 0.6% of the compounds of the formulas respectively. admitted.
  • the jersey pieces are dyed in pressure bombs in the dispersed liquors. This is done at 50 ° C and after a treatment time of 5 minutes at 3 ° C / min Heated up to 130 ° C. At this temperature you dye for 45 minutes, cool to 50 ° C and rinse warm and cold with distilled water and dry.
  • Printing pastes with the following composition are used to print PES car upholstery:

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Decoration Of Textiles (AREA)

Abstract

Described is a process for photochemical and thermal stabilisation of dyed and undyed polyester fibre materials. It is characterised in that the fibre material is treated with a compound of the formula <IMAGE> where R1 and R2 are independently of each other C1-C12alkyl. The process makes it possible to obtain highly lightfast and sublimation-resistant polyester and cellulose acetate dyeings and prints.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur photochemischen und thermischen Stabilisierung von ungefärbten und gefärbten Polyesterfasermaterialien.The present invention relates to a method for the photochemical and thermal stabilization of undyed and dyed polyester fiber materials.

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 ungefärbten und gefärbten Fasermaterialien vor UV-Strahlung unerlässlich.Dyed or printed polyester fiber material can be damaged under the influence of light and especially when exposed to heat. For use in the automotive sector, for example, effective protection of these undyed and dyed fiber materials from UV radiation is essential.

Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur photochemischen und thermischen Stabilisierung von ungefärbten und gefärbten Polyesterfasermaterialien mit UV-Absorbern, das dadurch gekennzeichnet ist, dass man das Fasermaterial mit einer Verbindung der Formel

Figure imgb0001

behandelt, worinThe present invention therefore relates to a process for the photochemical and thermal stabilization of undyed and dyed polyester fiber materials with UV absorbers, which is characterized in that the fiber material is mixed with a compound of the formula
Figure imgb0001
treated in what

R₁ und R₂, unabhängig voneinander C₁-C₁₂Alkyl
bedeuten.R₁ and R₂, independently of one another C₁-C₁₂alkyl
mean.

C₁-C₁₂Alkyl sind geradkettige oder verzweigte Alkylreste wie z.B. Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.Butyl, tert.Butyl, Amyl, Isoamyl oder tert.Amyl, Heptyl, Octyl, Isooctyl, Nonyl, Undecyl oder Dodecyl.C₁-C₁₂alkyl are straight-chain or branched alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, heptyl, octyl, isooctyl, nonyl, undecyl or Dodecyl.

Im Vordergrund des Interesses stehen Verbindungen der Formel (1), bei denen R₁ und R₂ unabhängig voneinander C₁-C₅Alkyl bedeuten. Besonders bevorzugt sind solche Verbindungen der Formel (1), bei denen R₁ und R₂ Methyl bedeutet und solche, bei denen R₁ Methyl und R₂ Propyl bedeuten.Of primary interest are compounds of the formula (1) in which R₁ and R₂ independently of one another are C₁-C₁alkyl. Those compounds of the formula (1) in which R₁ and R₂ are methyl and those in which R₁ is methyl and R₂ are propyl are particularly preferred.

Als Beispiele für Verbindungen der Formel (1) seien genannt:

  • 4,6-Bis(2-hydroxy-4-methoxyphenyl)-2-methylthio-1,3,5-triazin
  • 4,6-Bis(2-hydroxy-4-methoxyphenyl)-2-ethylthio-1,3,5-triazin
  • 4,6-Bis(2-hydroxy-4-methoxyphenyl)-2-n-propylthio-1,3,5-triazin
  • 4,6-Bis(2-hydroxy-4-ethoxyphenyl)-2-ethylthio-1,3,5-triazin
  • 4,6-Bis(2-hydroxy-4-ethoxyphenyl)-2-methylthio-1,3,5-triazin
  • 4,6-Bis(2-hydroxy-4-ethoxyphenyl)-2-n-propylthio-1,3,5-triazin
  • 4,6-Bis(2-hydroxy-4-n-propoxyphenyl)-2-methylthio-1,3,5-triazin
  • 4,6-Bis(2-hydroxy-4-n-propoxyphenyl)-2-ethylthio-1,3,5-triazin
  • 4,6-Bis(2-hydroxy-4-n-propoxyphenyl)-2-n-propylthio-1,3,5-triazin
The following may be mentioned as examples of compounds of the formula (1):
  • 4,6-bis (2-hydroxy-4-methoxyphenyl) -2-methylthio-1,3,5-triazine
  • 4,6-bis (2-hydroxy-4-methoxyphenyl) -2-ethylthio-1,3,5-triazine
  • 4,6-bis (2-hydroxy-4-methoxyphenyl) -2-n-propylthio-1,3,5-triazine
  • 4,6-bis (2-hydroxy-4-ethoxyphenyl) -2-ethylthio-1,3,5-triazine
  • 4,6-bis (2-hydroxy-4-ethoxyphenyl) -2-methylthio-1,3,5-triazine
  • 4,6-bis (2-hydroxy-4-ethoxyphenyl) -2-n-propylthio-1,3,5-triazine
  • 4,6-bis (2-hydroxy-4-n-propoxyphenyl) -2-methylthio-1,3,5-triazine
  • 4,6-bis (2-hydroxy-4-n-propoxyphenyl) -2-ethylthio-1,3,5-triazine
  • 4,6-bis (2-hydroxy-4-n-propoxyphenyl) -2-n-propylthio-1,3,5-triazine

Die Verbindungen der Formel (1) sind bekannt, z.B. aus der CH-A-436,285. Sie lassen sich analog dem in der EP-A-0,395,285 beschriebenen Verfahren durch Friedel-Crafts-Alkylierung von 1 Mol Cyanurchlorid mit einem Mol eines Alkylmercaptans und anschliessende Umsetzung mit 2 Mol der entsprechenden Benzolverbindung in Gegenwart einer Lewis-Säure, vorzugsweise Aluminiumchlorid, herstellen.The compounds of formula (1) are known, e.g. from CH-A-436,285. They can be prepared analogously to the process described in EP-A-0,395,285 by Friedel-Crafts alkylation of 1 mol of cyanuric chloride with one mol of an alkyl mercaptan and subsequent reaction with 2 mol of the corresponding benzene compound in the presence of a Lewis acid, preferably aluminum chloride.

Die erfindungsgemässen UV-Absorber werden in einer Menge von 0,01 bis 10 Gew.-%, vorzugsweise 0,1 bis 5 Gew.-%, bezogen auf das Gewicht des Fasermaterials, eingesetzt.The UV absorbers according to the invention are used in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the weight of the fiber material.

Die erfindungsgemässen UV-Absorber sind in Wasser schwerlöslich und werden daher 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 µm gemahlen.The UV absorbers according to the invention are sparingly soluble in water and are therefore applied in dispersed form. To do this, they are treated with an appropriate dispersant using e.g. Quartz balls and a high-speed mixer are ground to a fineness of 1-2 µm.

Als Dispergatoren für die UV-Absorber 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 Verbindungen, 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 sechswertige 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 Naphthylaminsulfonsäuren 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 UV absorbers of the formula (1) are:
  • acidic esters or their salts of alkylene oxide adducts, such as acidic esters or whose 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, in particular, with 1 mole of compounds which are formed by addition of 1 to 3 moles of optionally substituted styrenes are prepared in 1 mole 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 naphthylamine sulfonic acids and formaldehyde sulfonate and phenyl sulfononic acids and formaldehyde sulfonates and phenyl sulfononic acids and formaldehyde sulfonates and phenyl sulfonic acids and formaldehyde sulfonates and phenyl sulfonic acids and formaldehyde sulfonates and phenyl sulfone acids and formaldehyde sulfonic acids / formaldehyde sulfonates and phenyl sulfonates and phenyl sulfonates and phenyl sulfonates and phenyl sulfonates and phenyl sulfonates and phenyl and sulfonated products of 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 Färbstoffe 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. They are therefore largely in the form of a fine dispersion in the dyeing liquor. They 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 can also be used according to the invention.

Als Polyesterfasermaterial, das gefärbt oder bedruckt und mit den genannten UV-Absorbern behandelt werden kann, sind z.B. Celluloseesterfasern, wie z.B. Cellulose-2½-acetatfasern und -triacetatfasern und besonders lineare Polyesterfasern, die eventuell auch sauer modifiziert sind, zu verstehen, die z.B. durch Kondensation von Terephthalsäure mit Ethylenglykol oder von Isophthalsäure oder Terephthalsäure mit 1,4-Bis(hydroxymethyl)-cyclohexan erhalten werden, sowie Fasern aus Mischpolymeren von Terephthal- und Isophthalsäure und Ethylenglykol. Das in der Industrie bisher fast ausschliesslich eingesetzte lineare Polyesterfasermaterial (PES) besteht aus Terephthalsäure und Ethylenglykol.Polyester fiber material that can be dyed or printed and treated with the UV absorbers mentioned is, for example, cellulose ester fibers, such as cellulose 2½-acetate fibers and triacetate fibers and particularly linear polyester fibers, which may also be acid-modified, to be understood, for example, 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 polyester fiber material (PES) used almost exclusively in industry so far consists of terephthalic acid and ethylene glycol.

Die Fasermaterialien können auch als Mischgewebe unter sich oder mit anderen Fasern, 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 used as a mixed fabric among themselves or with other fibers, e.g. Mixtures of polyacrylonitrile / polyester, polyamide / polyester, polyester / cotton, polyester / viscose and polyester / wool can be used and can be dyed or printed discontinuously or continuously by known methods.

Das Textilmaterial kann in verschiedenen Aufmachungsformen vorliegen. Vorzugsweise kommt Stückware, wie Gewirke oder Gewebe, oder auch Garn auf Kreuzspulen, Kettbäumen usw. in Betracht.The textile material can be presented in various forms. Piece goods, such as knitted or woven fabrics, or yarn on cross-wound bobbins, warp beams, etc., are preferably used.

Gut geeignet für das erfindungsgemässe Verfahren sind ferner Textilgewebe im Oberbekleidungssektor, die lichtdurchlässig sind. Werden solche Textilien nach dem erfindungsgmässen Verfahren behandelt, können sie das unter dem transparenten Oberbekleidungsstoff befindliche Hautgewebe vor dem schädigenden Einfluss der UV-Strahlung schützen.Textile fabrics in the outer clothing sector which are translucent are also very suitable for the method according to the invention. If such textiles are treated according to the method according to the invention, they can protect the skin tissue located under the transparent outer clothing fabric from 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 using a continuous or batch process. In the discontinuous process (exhaust process), the liquor 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 Fouladieren oder Pflatschen aufgebracht und mittels Thermofixier- oder HT-Dämpfprozessen entwickelt.In continuous dyeing processes, the dyeing liquors, which in addition to the dyes may optionally contain other auxiliaries, are applied to the piece material by, for example, padding or slapping and developed by means of heat setting or HT steaming processes.

Lineare Polyesterfasern und Cellulosefasern 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 by the so-called high-temperature process in closed and pressure-resistant apparatus at temperatures> 100 ° C., preferably between 110 ° and 135 ° C. and, if appropriate, under pressure. Circulation apparatuses such as are suitable as closed vessels Cross-winder or tree dyeing machines, reel runners, nozzle or drum dyeing machines, muff dyeing machines, paddles or jiggers.

Cellulose-2½-acetatfasern färbt man vorzugsweise bei Temperaturen von 80-85°C.Cellulose-2½-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, they are used in such a way that the fiber material is first treated with these compounds and then the dyeing is carried out, or preferably the fiber material is simultaneously treated with the UV absorber and the dye in the dye bath. However, the application of the UV absorber can also be retrofitted 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 dyeing liquors can also contain other additives such as dyeing aids, dispersants, carriers, wool protection and wetting agents and also defoamers.

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 Einstellung des pH-Wertes der erfindungsgemäss verwendeten Flotten, der zwischen vorzugsweise 4 und 5 liegt.The dye baths can also contain mineral acids, e.g. Contain 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 primarily serve to adjust the pH of the liquors used according to the invention, which 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 allowed to run for 5 minutes at 40 to 80 ° C. in the bath, which contains the dye, the UV absorber and optionally further additives and is adjusted to a pH of 4.5 to 5.5 the temperature within 10 to 20 minutes to 125 to 130 ° C and treated for 15 to 90 minutes,
preferably 30 minutes, further at this temperature.

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., rinsing the dyeings with water and, if appropriate, cleaning in a conventional manner in an alkaline medium under reductive conditions. The dyeings are then rinsed again and dried. If vat dyes are used for the cellulose part, the goods are treated in the usual way first with hydrosulfite at a pH of 6 to 12.5 and then with an oxidizing agent and finally washed out.

Für die Herstellung von Drucken werden die erfindungsgemässen UV-Absorber in Form ihrer wässrigen Dispersionen den Druckpasten beigemischt. Die Druckpaste enthält dabei den entsprechenden UV-Absorber in Mengen von 0,1 bis 10 %, vorzugsweise 0,1 bis 5%, bezogen auf das Gewicht der Druckpaste.For the production of prints, the UV absorbers according to the invention are added to the printing pastes in the form of their aqueous dispersions. The printing paste contains the corresponding UV absorber in amounts of 0.1 to 10%, preferably 0.1 to 5%, based on the weight of the printing paste.

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 shade; In general, amounts of 0.01 to 15, preferably 0.02 to 10 percent by weight, based on the textile material used, have proven successful.

Die Druckpasten enthalten neben den Farbstoffen und der wässrigen UV-Absorber-Dispersion zweckmässigerweise säurestabile Verdickungsmittel, vorzugsweise natürlicher Herkunft wie Kernmehlabkömmlinge, 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 advantageously contain acid-stable thickeners, preferably of natural origin such as seed flour derivatives, in particular sodium alginate, alone or in a 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 hydrogenphosphate, preservatives, sequestering agents, emulsifiers, water-insoluble solvents, oxidizing agents or deaerating agents.

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-Polymethaphosphat, 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 Alkohle, 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.Particularly suitable preservatives are formaldehyde-releasing agents, such as Paraformaldehyde or trioxane, especially aqueous, about 30 to 40 percent by weight formaldehyde solutions; as sequestering agents e.g. sodium nitrilotriacetic acid, sodium ethylenediaminetetraacetic acid, especially sodium polymethaphosphate, especially 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 e.g. 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 venting agent e.g. high-boiling solvents, especially turpentine oils, higher alcohols, preferably C₈ to C₁₀ alcohols, terpene alcohols or deaerators 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 a C₈ 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- und Flachfilmdruckmaschinen eingesetzt werden.When printing on the fiber materials, the printing paste becomes full or in places applied directly to the fiber material, printing machines of conventional design, for example rotogravure, rotary screen printing and flat film printing machines, being expediently used.

Das Fasermaterial wird nach dem Bedrucken bei Temperaturen bis 150°C, vorzugsweise 80° bis 120°C getrocknet.After printing, the fiber material is dried at temperatures up to 150 ° C., preferably 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 of 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 10 Minuten, vorzugsweise 4 bis 8 Minuten erfolgen.Depending on the temperature, the fixation can take place for 20 seconds to 10 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 Druckfärbungen wiederum gespült, entwässert und getrocknet.The prints are also finished in the usual way by rinsing with water and can, if appropriate, be carried out by additional cleaning in an alkaline medium under reductive conditions, e.g. be made with sodium dithionite. In the latter case, the printing stains are again 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 polyester dyeings and prints can be achieved. A targeted pre- or post-treatment of the fiber material is not necessary with the method according to the invention.

In den folgenden Applikationsbeispielen beziehen sich die Prozentsätze auf das Gewicht. Die Mengen beziehen sich bei den Farbstoffen und bei den UV-Absorbern auf Reinsubstanz.In the following application examples, the percentages relate to the weight. The amounts relate to pure substance in the case of dyes and UV absorbers.

Beispiel 1: Anwendung in der FärbereiExample 1: Application in dyeing

Es werden 3 Muster von je 10 g eines PES-Trikots in einem HT-Färbeapparat, z.B. einem ®Labomat (Firma Mathis, Niederhasli) bei einem Flottenverhältnis von 1:10 gefärbt. Es werden 3 Flotten [(I) bis (III)] bereitet, die 2g/l Ammoniumsulfat, 0,5 g/l eines Färbereihilfmittels, z.B. ®Univadin 3-flex und die Farbstoffe der Formeln (1) bis (4) in folgenden Mengen enthalten:
0,210 % des Farbstoffs der Formel

Figure imgb0002

0,087 % des Farbstoffs der Formel
Figure imgb0003
0,80% des Farbstoffes der Formel
Figure imgb0004
und 0,087% des Farbstoffes der Formel
Figure imgb0005
 3 samples of 10 g each of a PES jersey are dyed in an HT dyeing machine, for example a ®Labomat (Mathis, Niederhasli) at a liquor ratio of 1:10. 3 liquors [(I) to (III)] are prepared, the 2 g / l ammonium sulfate, 0.5 g / l of a dyeing aid, for example ®Univadin 3-flex and the dyes of the formulas (1) to (4) in the following Quantities include:
0.210% of the dye of the formula
Figure imgb0002
0.087% of the dye of the formula
Figure imgb0003
0.80% of the dye of the formula
Figure imgb0004
and 0.087% of the dye of the formula
Figure imgb0005

Während die Flotte (I) keine weiteren Zusätze enthält, werden den Flotten (II) und (III) zusätzlich noch jeweils 0,6 % der Verbindungen der Formeln

Figure imgb0006

bzw.
Figure imgb0007
zugegeben.While the liquor (I) contains no further additives, the liquors (II) and (III) are each additionally 0.6% of the compounds of the formulas
Figure imgb0006
respectively.
Figure imgb0007
admitted.

Die UV-Absorber werden vor dem Einsatz in der Färbeflotte oder als Druckpaste formuliert. Dazu werden

  • die jeweiligen Verbindungen,
  • das als Dispergator eingesetzte Kondensationsprodukt aus Naphthalinsulfonsäure und Formaldehyd im Verhätnis 1:1,
  • die 2-4 fache Menge Wasser und
  • die vierfache Menge Quarzkugeln (⌀ 1mm)

mit einem Schnellrührer so lange gemahlen, bis das Produkt eine Feinheit von 1-2 µm aufweist. Die Dispersion wird mit einem feinen Maschensieb abgetrennt, mit 0,5% Carboxymethylcellulose stabilisiert und auf 30% eingestellt.The UV absorbers are formulated before use in the dyeing liquor or as a printing paste. To do this
  • the respective connections,
  • the condensation product of naphthalenesulfonic acid and formaldehyde used as a dispersant in a ratio of 1: 1,
  • 2-4 times the amount of water and
  • four times the amount of quartz balls (⌀ 1mm)

with a high-speed stirrer until the product has a fineness of 1-2 µm. The dispersion is separated with a fine mesh sieve, stabilized with 0.5% carboxymethyl cellulose and adjusted to 30%.

Die Trikotstücke werden in den dispergierten Flotten in Druckbomben gefärbt. Dazu wird bei 50°C eingegangen und nach einer Behandlungszeit von 5 Minuten mit 3°C/min auf 130°C aufgeheizt. Bei dieser Temperatur färbt man 45 Minuten, kühlt auf 50°C ab und spült warm und kalt mit destilliertem Wasser und trocknet.The jersey pieces are dyed in pressure bombs in the dispersed liquors. This is done at 50 ° C and after a treatment time of 5 minutes at 3 ° C / min Heated up to 130 ° C. At this temperature you dye for 45 minutes, cool to 50 ° C and rinse warm and cold with distilled water and dry.

Zur Ermittlung der Lichtechtheiten werden die Färbungen nach DIN 75.202 (FAKRA) und nach SAE J 1885 belichtet. Die Ergebnisse sind in Tabelle 1 aufgeführt. Tabelle 1: Farbabstandsbeiwert ΔE Färbung (Flotte Nr.) FAKRA 260 Stunden 488 KJ SAE J 1885 (I) ohne Zusatz 4,25 7,25 (II) + 0,6 % der Verbindung (101) 1,8 3,5 (III) + 0,6 % der Verbindung (102) 1,7 3,4 To determine the light fastness, the dyeings are exposed according to DIN 75.202 (FAKRA) and according to SAE J 1885. The results are shown in Table 1. Table 1: Color difference coefficient ΔE Coloring (fleet number) FAKRA 260 hours 488 KJ SAE J 1885 (I) without addition 4.25 7.25 (II) + 0.6% of compound (101) 1.8 3.5 (III) + 0.6% of compound (102) 1.7 3.4

Beispiel 2: Anwendung im DruckExample 2: Application in printing

Zur Bedruckung von PES-Autopolsterstoff werden Druckpasten mit folgender Zusammensetzung verwendet:Printing pastes with the following composition are used to print PES car upholstery:

750 Teile einer Stammverdickung, enthaltend

9
Teile Stärkeether als Verdickungsmittel
18
Teile Natriumalginat als Verdickungsmittel
3,75
Teile Natriumdihydrogenphosphat
2,48
Teile Natriumchlorat und
716,77
Teile Wasser.
Containing 750 parts of a trunk thickening
9
Share starch ether as a thickener
18th
Parts of sodium alginate as a thickener
3.75
Parts of sodium dihydrogen phosphate
2.48
Parts of sodium chlorate and
716.77
Parts of water.

Diese Stammverdickung wird vermischt mit

6,4
Teilen des Farbstoffgemisches, bestehend aus
2,0
Teilen des Farbstoffes der Formel (4)
1,4
Teilen des Farbstoffes der Formel
Figure imgb0008
2,0
Teilen des Farbstoffes der Formel (2) und
1,0
Teilen des Farbstoffes der Formel (3)
243,6
Teilen Wasser (=Druckpaste A)
213,6
Teilen Wasser (= Druckpaste B) und
0
Teilen UV Absorber (= Druckpaste A)
30
Teilen der gemäss Beispiel 1 dispergierten 30%igen UV-Absorberformulierung der Formel (101) (= Druckpaste B).
This thickening is mixed with
6.4
Parts of the dye mixture consisting of
2.0
Sharing the dye of formula (4)
1.4
Share the dye of the formula
Figure imgb0008
2.0
Share the dye of formula (2) and
1.0
Sharing the dye of formula (3)
243.6
Parts of water (= printing paste A)
213.6
Divide water (= printing paste B) and
0
Share UV absorber (= printing paste A)
30th
Share the 30% UV absorber formulation of the formula (101) (= printing paste B) dispersed according to Example 1.

Mit den beiden Druckpasten A und B werden zwei vorgereinigte PES-Trikotmuster auf einem Drucktisch nach Zimmer (Hersteller Firma Zimmer, Klagenfurt/Österreich) bedruckt. Diese Muster werden getrocknet und mit überhitztem Dampf bei 180°C während 8 Minuten gedämpft. Danach wird mit kaltem Wasser gespült und bei 70°C 30 Minuten in Bädern mit 2 ml/l Natronlauge 36° Bé und 3 g/l Natriumdithionit reduktiv gereinigt. Abschliessend wird warm und kalt gespült und nach dem Zentrifugieren bei 100°C getrocknet. Die beiden graubraunen Muster werden auf ihre Heisslichtechtheiten nach DIN 75.202 (FAKRA) und SAE J 1885 (SAE) geprüft. Die Ergebnisse sind in Tabelle 2 zusammengestellt. Tabelle 2: Lichtechtheiten nach Drucke FAKRA 288 Stunden SAE 489 KJ SAE 489 KJ ohne UV-Absorber 2 1-2 1-2 + Verbindung (101) 4 4 3-4 With the two printing pastes A and B, two pre-cleaned PES jersey patterns are printed on a printing table according to Zimmer (manufacturer company Zimmer, Klagenfurt / Austria). These samples are dried and steamed with superheated steam at 180 ° C for 8 minutes. It is then rinsed with cold water and reductively cleaned at 70 ° C. for 30 minutes in baths with 2 ml / l sodium hydroxide solution 36 ° Bé and 3 g / l sodium dithionite. Finally, it is rinsed warm and cold and, after centrifugation, dried at 100 ° C. The two gray-brown samples are tested for their hot light fastness according to DIN 75.202 (FAKRA) and SAE J 1885 (SAE). The results are summarized in Table 2. Table 2: Lightfastness after Prints FAKRA 288 hours SAE 489 KJ SAE 489 KJ without UV absorber 2nd 1-2 1-2 + Connection (101) 4th 4th 3-4

Aus den Ergebnissen der Tabelle 2 ist ersichtlich, dass der eingesetzte UV-Absorber der Formel (101) eine deutliche Verbesserung der Heisslichtechtheiten bewirkt.It can be seen from the results in Table 2 that the UV absorber of the formula (101) used brings about a significant improvement in the hot light fastness.

Claims (8)

Verfahren zur photochemischen und thermischen Stabilisierung von ungefärbten und gefärbten Polyesterfasermaterialien, dadurch gekennzeichnet, dass man das Fasermaterial mit einer Verbindung der Formel
Figure imgb0009
 behandelt, worin
R₁ und R₂, unabhängig voneinander C₁-C₁₂Alkyl
bedeuten. Process for the photochemical and thermal stabilization of undyed and dyed polyester fiber materials, characterized in that the fiber material with a compound of the formula
Figure imgb0009
 treated in what
R₁ and R₂, independently of one another C₁-C₁₂alkyl
mean. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass R₁ und R₂ unabhängig voneinander C₁-C₅Alkyl bedeuten.A method according to claim 1, characterized in that R₁ and R₂ independently of one another are C₁-C₅alkyl. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass R₁ und R₂ Methyl bedeuten.A method according to claim 1 or 2, characterized in that R₁ and R₂ are methyl. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass R₁ Methyl und R₂ Propyl bedeuten.A method according to claim 1 or 2, characterized in that R₁ is methyl and R₂ is propyl. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass man die Verbindung der Formel (1) in einer Menge von 0,01 bis 10 Gew.-% des Fasermaterials verwendet.Method according to one of claims 1 to 4, characterized in that the compound of formula (1) is used in an amount of 0.01 to 10 wt .-% of the fiber material. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass man die Verbindung der Formel (1) in der Färbeapplikation direkt der Auszieh- oder der Foulardflotte zusetzt.Method according to one of claims 1 to 5, characterized in that the compound of formula (1) is added directly to the exhaust or padding liquor in the dyeing application. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass man die Verbindung der Formel (1) bei der Druckapplikation der Druckpaste beimischt.Method according to one of claims 1 to 6, characterized in that the compound of formula (1) is added to the printing paste in the printing application. Das nach einem der Ansprüche 1 bis 7 behandelte Fasermaterial.The fiber material treated according to one of claims 1 to 7.
EP93810563A 1992-08-18 1993-08-09 Process for photochemical and thermal stabilization of undyed and dyed polyester fibrous materials Expired - Lifetime EP0584044B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH2568/92 1992-08-18
CH256892 1992-08-18

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EP0584044A1 true EP0584044A1 (en) 1994-02-23
EP0584044B1 EP0584044B1 (en) 1997-07-16

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US (1) US5649980A (en)
EP (1) EP0584044B1 (en)
JP (1) JP3243341B2 (en)
KR (1) KR940004141A (en)
AT (1) ATE155538T1 (en)
BR (1) BR9303391A (en)
DE (1) DE59306916D1 (en)
ES (1) ES2106308T3 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0795640A1 (en) * 1996-03-13 1997-09-17 Ciba SC Holding AG Combination of stabilizers
EP0962586A1 (en) * 1998-06-05 1999-12-08 Ciba SC Holding AG Process for improving the photochemical and thermal stability of dyeings and printings of polyester fibrous materials
WO2001053091A1 (en) * 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh Matt, uv-stable, co-extruded polyester film, a method for the production thereof and the use of the same
WO2001053081A1 (en) * 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh Amorphous, multi-layer, matt, thermoformable polyester film, a method for the production thereof and the use of the same
WO2001053087A1 (en) * 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh Matt, uv-stable, thermoformable, co-extruded polyester film, a method for the production thereof and the use of the same
WO2001053089A1 (en) * 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh Matt, uv-stable, flame-retardant, co-extruded polyester film, a method for the production thereof and the use of the same
US6872461B2 (en) 2000-01-20 2005-03-29 Mitsubishi Polyester Film Gmbh Matt, flame-retardant, co-extruded polyester film, a method for the production thereof and the use of the same
WO2010081625A2 (en) 2009-01-19 2010-07-22 Basf Se Organic black pigments and their preparation

Families Citing this family (3)

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US20020019183A1 (en) * 1997-02-12 2002-02-14 Demott Roy P. Release barrier fabrics
US20050155163A1 (en) * 2004-01-21 2005-07-21 Griffin Bruce O. Dye mixtures
TWI835843B (en) * 2018-10-03 2024-03-21 瑞士商亨斯邁紡織染化（瑞士）有限公司 New pyridine- and pyrimidine-substituted triazine uv absorbers

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EP0395938A2 (en) * 1989-04-21 1990-11-07 Ciba-Geigy Ag Process for the preparation of 2-(2',4'-dihydroxyphenyl)-4,6-diaryl-s-triazines

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US4886518A (en) * 1987-10-01 1989-12-12 Ciba-Geigy Corporation Dyeing cellulose fibres without incurring ending with colorless pyrimidine, triazine, aromatic, furfuryl or quinolinyl compound
US4950304A (en) * 1987-10-02 1990-08-21 Ciba-Geigy Corporation Process for quenching or suppressing the fluorescence of substrates treated with fluorescent whitening agents

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CH436285A (en) * 1963-01-25 1967-05-31 Ciba Geigy Use of new aryl-1,3,5-triazines as protective agents against ultraviolet radiation for non-textile organic materials
EP0280653A1 (en) * 1987-02-27 1988-08-31 Ciba-Geigy Ag Process for improving the photochemical stability of dyeings on fibrous polyester materials
EP0395938A2 (en) * 1989-04-21 1990-11-07 Ciba-Geigy Ag Process for the preparation of 2-(2',4'-dihydroxyphenyl)-4,6-diaryl-s-triazines

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0795640A1 (en) * 1996-03-13 1997-09-17 Ciba SC Holding AG Combination of stabilizers
US5871669A (en) * 1996-03-13 1999-02-16 Ciba Specialty Chemicals Corporation Stabilizer combination
US5997769A (en) * 1996-03-13 1999-12-07 Ciba Specialty Chemicals Corporation Stabilizer combination
CN1091794C (en) * 1996-03-13 2002-10-02 希巴特殊化学控股公司 Stabilizer combination
EP0962586A1 (en) * 1998-06-05 1999-12-08 Ciba SC Holding AG Process for improving the photochemical and thermal stability of dyeings and printings of polyester fibrous materials
WO2001053087A1 (en) * 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh Matt, uv-stable, thermoformable, co-extruded polyester film, a method for the production thereof and the use of the same
WO2001053081A1 (en) * 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh Amorphous, multi-layer, matt, thermoformable polyester film, a method for the production thereof and the use of the same
WO2001053089A1 (en) * 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh Matt, uv-stable, flame-retardant, co-extruded polyester film, a method for the production thereof and the use of the same
WO2001053091A1 (en) * 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh Matt, uv-stable, co-extruded polyester film, a method for the production thereof and the use of the same
US6872460B2 (en) 2000-01-20 2005-03-29 Mitsubishi Polyester Film Gmbh Matt, UV-stable, Thermoformable, co-extruded polyester film, a method for the production thereof and the use of the same
US6872461B2 (en) 2000-01-20 2005-03-29 Mitsubishi Polyester Film Gmbh Matt, flame-retardant, co-extruded polyester film, a method for the production thereof and the use of the same
US7056573B2 (en) 2000-01-20 2006-06-06 Mitsubishi Polyester Film Gmbh Matt, UV-stable, co-extruded polyester film, a method for the production thereof and the use of the same
WO2010081625A2 (en) 2009-01-19 2010-07-22 Basf Se Organic black pigments and their preparation

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BR9303391A (en) 1994-03-15
EP0584044B1 (en) 1997-07-16
JP3243341B2 (en) 2002-01-07
ATE155538T1 (en) 1997-08-15
ES2106308T3 (en) 1997-11-01
DE59306916D1 (en) 1997-08-21
JPH06200477A (en) 1994-07-19
US5649980A (en) 1997-07-22
KR940004141A (en) 1994-03-14

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