EP0490819A1 - Dispersion aqueuse d'absorbant U.V. difficilement solubles - Google Patents

Dispersion aqueuse d'absorbant U.V. difficilement solubles Download PDF

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Publication number
EP0490819A1
EP0490819A1 EP91810944A EP91810944A EP0490819A1 EP 0490819 A1 EP0490819 A1 EP 0490819A1 EP 91810944 A EP91810944 A EP 91810944A EP 91810944 A EP91810944 A EP 91810944A EP 0490819 A1 EP0490819 A1 EP 0490819A1
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Prior art keywords
component
acid
dispersion according
formula
compound
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German (de)
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EP0490819B1 (fr
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Martin Dr. Jöllenbeck
Alfred Jonathan Neukom
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Novartis AG
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Ciba Geigy AG
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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
    • 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
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65112—Compounds containing aldehyde or ketone 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
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6426—Heterocyclic compounds

Definitions

  • the present invention relates to an aqueous dispersion of a mixture of sparingly soluble UV absorbers and their use in dyeing synthetic fibers, in particular polyester fibers or acid-modified polyester fibers.
  • the aqueous dispersion according to the invention advantageously contains 10 to 45 percent by weight of component (a), 3 to 15 percent by weight of component (b) and 0-8 percent by weight of component (c).
  • the compounds of component (a) expediently have a particle size below 5 ⁇ m.
  • Both component (a) and components (b) and (c) can be present as a single compound or in the form of a mixture.
  • Lower alkyl and lower alkoxy are, when defining the radicals of the compounds of the formulas (1) and (2), those groups or group components which have 1 to 5, in particular 1 to 3, carbon atoms.
  • groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl or methoxy, ethoxy, isopropoxy, isobutoxy or tert-butoxy.
  • C1-C12alkyl are e.g. Ethyl, amyl, tert-octyl, n-dodecyl and preferably methyl, sec-butyl or tert-butyl.
  • Halogen means for example fluorine, bromine or preferably chlorine.
  • substituent in the formulas (1) and (2) represents an alkyl group
  • this can be straight-chain or branched.
  • alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, n-hexyl, 2-ethylhexyl, n-heptyl, n- Octyl, isooctyl, n-nonyl, isononyl or n-dodecyl.
  • cycloalkyl with the meaning of R are cyclopentyl, cycloheptyl or preferably cyclohexyl.
  • the cycloalkyl radicals can contain one or more C1-C4alkyl radicals, preferably methyl groups, and have a total of 5 to 10 carbon atoms.
  • aryl suitably means phenyl.
  • the aryl, in particular phenyl radical can be mono- or disubstituted by halogen, lower alkyl such as methyl or lower alkoxy, for example methoxy.
  • R as alkylaryl advantageously means alkylphenyl and the alkyl radical is preferably in the para position.
  • the alkyl radicals in the alkylphenyl can be methyl, ethyl, isopropyl, butyl, hexyl, n-octyl, tert-octyl, n-nonyl, iso-nonyl, decyl or dodecyl.
  • R in the meaning of aralkyl advantageously has a total of 7 to 9 carbon atoms and generally represents benzyl, ⁇ -methylbenzyl, ⁇ - ⁇ -dimethylbenzyl, ⁇ -phenethyl, ⁇ -tolylethyl or phenisopropenyl.
  • Ring A is preferably substituted in the 5-position by halogen, lower alkyl or lower alkoxy.
  • ring A can have another substituent, e.g. Have halogen or methyl in the 6-position.
  • the benzene ring B is also preferably further substituted in the vicinity of the hydroxyl group, for example by halogen or lower alkyl.
  • C1-C14alkoxy means e.g. Methoxy, ethoxy, propoxy, n-butoxy, octyloxy, dodecyloxy or tetradecyloxy.
  • benzotriazole compounds those in which R5 is lower alkyl such as methyl or tert-butyl, R6 is hydrogen or lower alkyl and R7 is hydrogen, chlorine or methyl, are preferred.
  • 2-hydroxybenzophenone compounds of the formula (2) are the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy and 5-chloro derivatives.
  • the dispersion according to the invention contains the compounds of the formulas (1) and (2) in a ratio (1) :( 2) of 30: 1 to 1:30, preferably 10: 1 to 1:10. Mixing ratios of 1: 5 to 5: 1 are particularly preferred, the proportion by weight of the compound of the formula (1) being less than 20%.
  • the acid residue X in formula (4) is derived, for example, from low molecular weight dicarboxylic acids, e.g. of maleic acid, succinic acid or sulfosuccinic acid and is connected to the alkylene oxide part of the molecule via an ester bridge.
  • X is derived from inorganic polybasic acids, such as sulfuric acid or, in particular, orthophosphoric acid.
  • substituent Y in formula (4) represents an alkyl group, it can be straight-chain or branched.
  • alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, n-hexyl, 2-ethylhexyl, n-heptyl, n- Octyl, isooctyl, n-nonyl, isononyl or n-dodecyl.
  • Y in the meaning of aralkyl advantageously has a total of 7 to 9 carbon atoms and usually stands for benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, ⁇ -phenethyl, ⁇ -tolylethyl or phenisopropyl.
  • the substituent Y in formula (4) is advantageously C4-C12alkyl, benzyl, preferably C4-C10alkyl or especially ⁇ -methylbenzyl.
  • the substituent Y can also assume various of the meanings given.
  • n is preferably 6 to 30, while m is preferably 1 to 3.
  • Chains are preferably of the ethylene glycol, propylene ethylene glycol or ethylene propylene glycol type; the former is particularly preferred.
  • the acidic esters of the formula (4) which are suitable as component (ba) are prepared by adding alkylene oxide (ethylene oxide or propylene oxide) to a phenol compound which is substituted by definition and the adduct with a polybasic oxygen acid or a functional derivative of this acid, e.g. Acid anhydrides, acid halides, acid esters or acid amides are converted into the acidic esters.
  • these functional derivatives are phosphorus pentoxide, phosphorus oxytrichloride, chlorosulfonic acid or sulfamic acid. Both the alkylene oxide addition and the esterification can be carried out by known methods.
  • Well-suited components (ba) are acidic esters or their salts of a polyadduct of 4 to 40 moles of ethylene oxide with 1 mole of a phenol which has at least one C4-C12alkyl group, a phenyl group, a tolyl group, an ⁇ -tolylethyl group, a benzyl group, an ⁇ - Has methylbenzyl group or an ⁇ , ⁇ -dimethylbenzyl group, such as Butylphenol, Tributylphenol, Octylphenol, Nonylphenol, Dinonylphenol, o-Phenylphenol, Benzylphenol, Dibenzylphenol, ⁇ -Tolylethylphenol, Dibenzyl- (nonyl) -phenol, ⁇ -Methylbenzylphenol, Bis- ( ⁇ -Methylbenzyl) -phenol or Tris- ( ⁇ -methylbenzyl) ) -phenol, whereby these acidic esters can be used individually or
  • the acid residue of the anionic compounds is usually in salt form, i.e. as an alkali metal, ammonium or amine salt.
  • salts are lithium, sodium, potassium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts.
  • Well-suited components are polyadducts of 4 to 40 moles of ethylene oxide with 1 mole of a phenol which has at least one C4-C12alkyl group, a phenyl group, a tolyl group, an ⁇ -tolylethyl group, a benzyl group, an ⁇ -methylbenzyl group or an ⁇ , ⁇ -Dimethylbenzyl distr, such as butylphenol, tributylphenol, octylphenol, nonylphenol, dinonylphenol, o-phenylphenol, benzylphenol, dibenzylphenol, ⁇ -tolylethylphenol, dibenzyl- (nonyl) -phenol, ⁇ -methylbenzylphenol, bis- ( ⁇ -methylbenzylphenol or bis) Tris- ( ⁇ -methylbenzyl) phenol, these adducts can be used individually or in a mixture.
  • Ethylene oxide adducts of the formula are preferred wherein Y2 is C4-C12alkyl, phenyl, tolyl, tolyl-C1-C3alkyl or phenyl-C1-C3alkyl, such as ⁇ -methyl or ⁇ , ⁇ -dimethylbenzyl, and m2 is 1 to 3 and n2 is 4 to 40.
  • Preferred components (cc) are ethylene oxide adducts with polypropylene oxide (so-called EO-PO block polymers) and propylene oxide adducts with polyethylene oxide (so-called reverse EO-PO block polymers).
  • the anionic and nonionic compounds can be used alone or in combination.
  • Ethylene oxide-propylene oxide block polymers with molecular weights of the polypropylene oxide base of 1700 to 4000 and an ethylene oxide content in the total molecule of 30-80%, in particular 60-80%, are particularly preferred.
  • the dispersion according to the invention can expediently additionally contain a stabilizing or thickening agent as component (d).
  • Polymers containing carboxyl groups are particularly suitable as component (d). These are used in the form of 0.5 to 10%, preferably 0.5 to 5%, aqueous solutions or dispersions, based on the solution or dispersion.
  • polymers are advantageously polymerized ethylenically unsaturated mono- or dicarboxylic acids of 3 to 5 carbon atoms, such as polyacrylic acid or polymers of methacrylic acid, crotonic acid, itaconic acid, teraconic acid, maleic acid or their anhydride, fumaric acid, citraconic acid or mesaconic acid, copolymers of olefins, for example ethylene or propylene, diketenes, acrylic acid esters, methacrylic acid esters or acrylamides and the abovementioned monomers including acrylic acid or copolymers of acrylic acid with methacrylic acid, methacrylonitrile or vinyl monomers, such as, for example, vinylphosphonic acid, copolymers from maleic acid and styrene, maleic acid and a vinyl ether or maleic acid and a vinyl ester, for example vinyl acetate or copolymers of vinylpyrrolidone with vinyl acetate or vinyl propi
  • the carboxyl-containing polymers which form thickeners can have a molecular weight of 0.5 to 6 million.
  • solutions of polyacrylic acid or copolymers of acrylic acid and acrylamide have been shown to be particularly useful components (d), the corresponding molecular weight being able to vary from 0.5 to 6 million.
  • the copolymers advantageously have a molar ratio of acrylic acid: acrylamide of 1: 0.8 to 1: 1.2.
  • a partially hydrolyzed polymaleic anhydride can also be used as component (d). This is usually partly in the form of a water-soluble salt and has a molecular weight that is preferably between 300 and 5000.
  • thickeners that can be used as component (d) are polysaccharides such as e.g. Carboxymethyl cellulose, methyl cellulose, methyl or ethyl hydroxyethyl cellulose, locust bean gum ether or starch ether as well as alginates, polyethylene glycols, polyvinyl pyrrolidones, polyvinyl alcohols or finely divided silica, preferably with a specific surface area of 50 to 380 m2 / g and layered silicates, such as e.g. Bentonite, Bentone, Smectite, Montmorillonite.
  • Anionic heteropolysaccharides which are formed from the monosaccharides glucose and mannose and glucuronic acid are also very suitable.
  • the amounts of these additional ingredients (d) are generally between 0.05 and 8 percent by weight, preferably 0.1 and 4 percent by weight, based on the total aqueous dispersion.
  • the dispersion according to the invention can additionally contain antifoams, preservatives or antifreezes.
  • Preferred anti-foaming agents are alkylenediamides, typical representatives being methylenebis-stearic acid amide, ethylene-bis-stearic acid amide or ethylene-bis-behenic acid amide.
  • the alkylene diamide is preferably present in the dispersion in an amount of 0.2 to 0.5 percent by weight.
  • a preferred antifreeze is propylene glycol.
  • Preferred aqueous dispersions according to the invention contain as component (a) a mixture of a UV-absorbing benzotriazole and 2-hydroxybenzophenone compound of the formulas (1) and (2), and as component (b) a condensation product of formaldehyde with an aromatic sulfonic acid.
  • aqueous dispersions which, as component (a), are a mixture of a UV-absorbing benzotriazole compound of the formula and a 2-hydroxybenzophenone compound of the formula (2), and as component (b) an acidic phosphoric acid ester or its salt of the oxyalkylation product of 6 to 30 moles of ethylene oxide with 1 mole of 4-nonylphenol, dinonylphenol or with 1 mole of a compound which is formed by addition of 1 to 3 moles of styrene, ⁇ -methylstyrene or vinyl toluene has been prepared in 1 mole of phenol, cresol or xylenol.
  • the dispersion according to the invention is expediently prepared by the benzotriazole compound of the formula (1) is pasted together with the 2-hydroxybenzophenone compound of the formula (2) with a dispersant, for example the condensation product of formaldehyde with ditolyl ether sulfonate or naphthalenesulfonic acid and water in a mixer and after any addition of the desired additional ingredients such as nonionic surfactants (c ), other anionic and / or non-ionic compounds including the antifoam, preservative and antifreezing agent dispersed for 1 to 30, preferably 1 to 10 hours.
  • the dispersion is advantageously carried out by the action of high shear forces, for example by grinding in a ball, sand or pearl mill. After grinding, an aqueous solution of the stabilizing or thickening agent [component (d)] and, if desired, water can be added, followed by stirring until uniform.
  • the dispersions according to the invention are notable for good transport and storage stability. They are particularly stable at higher temperatures up to 130 ° C when used in dye baths.
  • the dispersion according to the invention is used in the dyeing of synthetic fibers, in particular polyester fibers or also textile material containing acid-modified polyester fibers.
  • the dyeing process is carried out in the usual way.
  • the dispersion according to the invention is slowly introduced into an aqueous bath with stirring, after which the liquor is made available for dyeing after the addition of the dye.
  • the present invention accordingly also relates to a process for dyeing synthetic fiber material with cationic and disperse dyes.
  • the process is characterized in that this material is colored in the presence of the aqueous dispersion of UV absorber mixtures according to the invention.
  • the amounts used in which the dispersion according to the invention is added to the dye baths range from 0.5 to 10%, preferably 1 to 5%, of the weight of the goods.
  • fiber material in particular textile material, which can be dyed in the presence of the new aqueous dispersion
  • fiber material in particular textile material, which can be dyed in the presence of the new aqueous dispersion
  • cellulose ester fibers such as cellulose 2 1/2 acetate fibers and triacetate fibers
  • aromatic polyamide fibers which are derived, for example, from poly (metaphenylene isophthalamide).
  • acid modified polyester fibers and especially to mention linear polyester fibers.
  • Cellulose ester and polyester fibers are preferably colored with disperse dyes and acid-modified polyester fibers and aromatic polyamide fibers preferably with cationic dyes.
  • Linear polyester fibers are to be understood as synthetic fibers which e.g. can be obtained by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane, and also copolymers of terephthalic and isophthalic acid and ethylene glycol.
  • the linear polyester used so far almost exclusively in the textile industry consists of terephthalic acid and ethylene glycol.
  • Acid-modified polyester fibers are, for example, polycondensation products of terephthalic acid or isophthalic acid, ethylene glycol and 1,2-dihydroxy-3- or 1,3-dihydroxy-2- (3-sodium sulfopropoxy) propane, 2,3-dimethylol-1- (sodium sulfopropoxy) -butane, 2,2-bis- (3-sodium sulfopropoxyphenyl) propane or 3,5-dicarboxy-benzenesulfonic acid or sulfonated terephthalic acid, sulfonated 4-methoxybenzenecarboxylic acid or sulfonated diphenyl-4,4'-dicarboxylic acid.
  • 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, polyester / wool and polyester / polyacrylonitrile / polyamide can be used.
  • the textile material to be dyed can be processed in various forms. Examples include: loose material, piece goods, such as knitted or woven fabrics, yarn in the form of a wrap or muff.
  • the latter can have winding densities of 200 to 600 g / dm3, in particular 400 to 450 g / dm3.
  • the cationic dyes suitable for the process according to the invention can belong to different classes of dyes.
  • these are the customary salts, for example chlorides, sulfates or metal halides, such as, for example, zinc chloride double salts of cationic dyes, the cationic character of which derives, for example, from a carbonium, oxonium, sulfonium or, above all, ammonium group.
  • chromophoric systems examples include azo dyes, especially monoazo or hydrazone dyes, diphenylmethane, triphenylmethane, methine or azomethine dyes, coumarin, ketone imine, cyanine, azine, xanthene, oxazine or thiazine dyes.
  • color salts of the phthalocyanine or anthraquinone series with an external onium group for example an alkylammonium or cycloammonium group, can also be used and benzo-1,2-pyran dye salts containing cycloammonium groups can be used.
  • the disperse dyes used which are only sparingly soluble in water and are largely present in the dye liquor in the form of a fine dispersion, can belong to different classes of dyes, for example the acridone, azo, anthraquinone, coumarin, methine, Perinone, naphthoquinoneimine, quinophthalone, styryl or nitro dyes.
  • Mixtures of cationic or disperse dyes can also be used according to the invention.
  • the amount of dyes to be added to the liquor depends on the desired color strength; In general, amounts of 0.01 to 10, preferably 0.02 to 5 percent by weight, based on the textile material used, have proven successful.
  • the dye baths can contain, in addition to the dyes and the aqueous dispersion according to the invention, oligomer inhibitors, wrinkle-free agents, retarders and preferably dispersants and leveling agents.
  • the dispersants are used primarily to achieve a good fine distribution of the disperse dyes.
  • the dispersants which are generally used for dyeing with disperse dyes are suitable.
  • the dispersants used are preferably sulfated or phosphated adducts of 15 to 100 moles of ethylene oxide or preferably propylene oxide with polyhydric aliphatic alcohols containing 2 to 6 carbon atoms, such as e.g. Ethylene glycol, glycerol or pentaerythritol or amines having 2 to 9 carbon atoms and having at least two amino groups or an amino group and a hydroxyl group and alkylsulfonates having 10 to 20 carbon atoms in the alkyl chain, alkylbenzenesulfonates having a straight-chain or branched alkyl chain having 8 to 20 carbon atoms in the alkyl chain, such as e.g.
  • Lignin sulfonates, polyphosphates have proven particularly favorable as anionic dispersants and preferably formaldehyde condensation products from aromatic sulfonic acids, formaldehyde and optionally mono- or bifunctional phenols, such as, for example, from cresol, ⁇ -naphtholsulfonic acid and formaldehyde, from benzenesulfonic acid, formaldehyde and naphthalenesulfonic acid, from naphthalenesulfonic acid and formaldehyde or from naphthalenesulfonic acid, dihydroxydiphenyl sulfone and sulfonate.
  • the disodium salt of di- or tri- (6-sulfonaphthyl-2-) methane is preferred.
  • anionic dispersants can also be used.
  • the anionic dispersants are normally in the form of their alkali metal salts, ammonium salts or amine salts. These dispersants are preferably used in an amount of 0.5 to 8 g / l of liquor.
  • the dye baths can also contain conventional additives, suitably electrolytes such as salts, e.g. Sodium sulfate, ammonium sulfate, sodium or ammonium phosphates or polyphosphates, metal chlorides or nitrates such as calcium chloride, magnesium chloride or calcium nitrates, ammonium acetate or sodium acetate and / or acids, e.g. Mineral acids, such as sulfuric acid or phosphoric acid, or organic acids, suitably contain lower aliphatic carboxylic acids, such as formic, acetic or oxalic acid. The acids serve primarily to adjust the pH of the liquors used according to the invention, which is generally 4 to 6.5, preferably 4.5 to 6.
  • electrolytes such as salts, e.g. Sodium sulfate, ammonium sulfate, sodium or ammonium phosphates or polyphosphates, metal chlorides or nitrates such as calcium chloride, magnesium chloride or calcium
  • the dyeings are advantageously carried out from an aqueous liquor using the exhaust process.
  • the liquor ratio can accordingly be chosen within a wide range, e.g. 1: 3 to 1: 100, preferably 1: 7 to 1:50.
  • the temperature at which dyeing or lightening is at least 70 ° C and is usually not higher than 140 ° C. It is preferably in the range from 80 to 135 ° C.
  • the dyeings can also be carried out continuously using low application systems or hot application systems.
  • Linear polyester fibers and cellulose triacetate fibers are preferably dyed by the so-called high-temperature process in closed and expediently pressure-resistant apparatuses at temperatures above 100 ° C., preferably between 110 and 135 ° C., and optionally under pressure.
  • Circulation devices such as cross-wound or tree dyeing machines, reel runners, nozzle or drum dyeing machines, muff dyeing machines, paddles or jiggers are suitable as closed vessels.
  • Cellulose-2 1/2 acetate fibers are preferably dyed at temperatures of 80-85 ° C.
  • the coloring of the aromatic polyamide fibers or acid-modified polyester fibers is preferably carried out at a temperature of 80 to 130 ° C.
  • the dyeing process can be carried out by either briefly treating the material to be dyed first with the aqueous dispersion according to the invention and then dyeing it, or preferably treating it simultaneously with the dispersion and the dye.
  • the material to be dyed is preferably allowed to run for 5 minutes at 60-80 ° C. in a bath which contains the dye, the aqueous dispersion and optionally further additives and is adjusted to a pH of 4.5 to 5.5, which increases Temperature within 15 to 35 minutes to 110 to 135 ° C, preferably 125-130 ° C and leaves the dye liquor at this temperature for 15 to 90 minutes, preferably 30 to 60 minutes.
  • the dyeings are completed by cooling the dye liquor to 60 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.
  • the parts are parts by weight and the percentages are percentages by weight.
  • Example 1 Be in a sand mill
  • the mixture is then ground with quartz sand until the particle size is ⁇ 5 ⁇ m, and then the dispersion is separated from the quartz sand.
  • Example 2 Be in a sand mill
  • the mixture is ground with quartz sand until the particle size is ⁇ 5 ⁇ m, and then the dispersion is separated from the quartz sand.
  • Example 3 Be in a sand mill
  • the mixture is milled until the particle size is ⁇ 5 ⁇ m and then the dispersion is separated from the quartz sand.
  • Example 4 Be in a sand mill
  • the mixture is ground with quartz sand until the particle size is less than 5 ⁇ m, and then the dispersion is separated from the quartz sand.
  • Example 5 Be in a sand mill
  • the mixture is ground with quartz sand until the particle size is less than 5 ⁇ m, and then the dispersion is separated from the quartz sand.
  • Example 6 Be in a sand mill
  • the mixture is ground with quartz sand until the particle size is less than 5 ⁇ m, and then the dispersion is separated from the quartz sand.
  • a storage-stable dispersion is obtained.
  • Example 7 Be in a sand mill
  • the mixture is ground with quartz sand until the particle size is ⁇ 5 ⁇ m, and then the dispersion is separated from the quartz sand.
  • a storage-stable dispersion is obtained.
  • Example 8 Be in a sand mill
  • the mixture is ground with quartz sand until the particle size is less than 5 ⁇ m, and then the dispersion is separated from the quartz sand.
  • a storage-stable dispersion is obtained.
  • Example 9 Be in a sand mill
  • the mixture is ground with quartz sand until the particle size is less than 5 ⁇ m, and then the dispersion is separated from the quartz sand.
  • a storage-stable dispersion is obtained.
  • Example 10 Be in a sand mill
  • the mixture is ground with quartz sand until the particle size is ⁇ 5 ⁇ m, and then the dispersion is separated from the quartz sand.
  • a storage-stable dispersion is obtained.
  • Example 11 Be in a sand mill
  • the mixture is ground with quartz sand until the particle size is ⁇ 5 ⁇ m, and then the dispersion is separated from the quartz sand.
  • a storage-stable dispersion is obtained.
  • Example 12 Be in a sand mill
  • the mixture is ground with quartz sand until the particle size is ⁇ 5 ⁇ m, and then the dispersion is separated from the quartz sand.
  • a storage-stable dispersion is obtained.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cosmetics (AREA)
  • Colloid Chemistry (AREA)
  • Coloring (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP91810944A 1990-12-13 1991-12-05 Dispersion aqueuse d'absorbant U.V. difficilement solubles Revoked EP0490819B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH3945/90 1990-12-13
CH394590 1990-12-13

Publications (2)

Publication Number Publication Date
EP0490819A1 true EP0490819A1 (fr) 1992-06-17
EP0490819B1 EP0490819B1 (fr) 1995-09-13

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EP91810944A Revoked EP0490819B1 (fr) 1990-12-13 1991-12-05 Dispersion aqueuse d'absorbant U.V. difficilement solubles

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US (1) US5498345A (fr)
EP (1) EP0490819B1 (fr)
JP (1) JPH04339885A (fr)
KR (1) KR920012636A (fr)
AT (1) ATE127870T1 (fr)
BR (1) BR9105355A (fr)
DE (1) DE59106479D1 (fr)
ZA (1) ZA919795B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0674038A1 (fr) * 1994-03-26 1995-09-27 Sandoz Ag Utilisation de composés de 4-H-3,1-benzoxazine-4-one pour améliorer la solidité à la lumière de matériaux textiles
EP0774539A3 (fr) * 1995-11-03 1997-08-27 Boehme Filatex Inc Composition absorbant les rayons UV et procédé pour améliorer le solidités lumière des textiles teints
EP0820978A1 (fr) * 1996-07-22 1998-01-28 Clariant Finance (BVI) Limited Dispersions aqueuses et leur utilisation pour le traitement du textile
WO2000011257A1 (fr) * 1998-08-25 2000-03-02 Clariant Finance (Bvi) Limited Compositions aqueuses d'agents agissant sur les uv, leur production et leur utilisation
FR2807048A1 (fr) * 2000-04-04 2001-10-05 Ciba Sc Holding Ag Melanges synergiques d'absorbants d'uv dans les polyolefines

Families Citing this family (59)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5721287A (en) 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US5645964A (en) 1993-08-05 1997-07-08 Kimberly-Clark Corporation Digital information recording media and method of using same
US6017661A (en) 1994-11-09 2000-01-25 Kimberly-Clark Corporation Temporary marking using photoerasable colorants
US5733693A (en) 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
US5700850A (en) 1993-08-05 1997-12-23 Kimberly-Clark Worldwide Colorant compositions and colorant stabilizers
US6017471A (en) 1993-08-05 2000-01-25 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6211383B1 (en) 1993-08-05 2001-04-03 Kimberly-Clark Worldwide, Inc. Nohr-McDonald elimination reaction
US5681380A (en) 1995-06-05 1997-10-28 Kimberly-Clark Worldwide, Inc. Ink for ink jet printers
US5865471A (en) 1993-08-05 1999-02-02 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms
US5773182A (en) 1993-08-05 1998-06-30 Kimberly-Clark Worldwide, Inc. Method of light stabilizing a colorant
US5690668A (en) * 1994-06-29 1997-11-25 General Surgical Innovations, Inc. Extraluminal balloon dissection
US6242057B1 (en) 1994-06-30 2001-06-05 Kimberly-Clark Worldwide, Inc. Photoreactor composition and applications therefor
US6071979A (en) 1994-06-30 2000-06-06 Kimberly-Clark Worldwide, Inc. Photoreactor composition method of generating a reactive species and applications therefor
US5685754A (en) 1994-06-30 1997-11-11 Kimberly-Clark Corporation Method of generating a reactive species and polymer coating applications therefor
US6008268A (en) 1994-10-21 1999-12-28 Kimberly-Clark Worldwide, Inc. Photoreactor composition, method of generating a reactive species, and applications therefor
US5786132A (en) 1995-06-05 1998-07-28 Kimberly-Clark Corporation Pre-dyes, mutable dye compositions, and methods of developing a color
BR9608367A (pt) 1995-06-05 1998-08-18 Kimberly Clark Co Pré-corantes novos
JP2000506550A (ja) 1995-06-28 2000-05-30 キンバリー クラーク ワールドワイド インコーポレイテッド 新規な着色剤および着色剤用改質剤
US5601756A (en) * 1995-08-23 1997-02-11 Swearengin; John V. Liquid ultraviolet stabilizer and method
US6099628A (en) 1996-03-29 2000-08-08 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5855655A (en) 1996-03-29 1999-01-05 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
ES2175168T3 (es) 1995-11-28 2002-11-16 Kimberly Clark Co Compuestos de colorantes estabilizados por la luz.
US5782963A (en) 1996-03-29 1998-07-21 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5891229A (en) 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6524379B2 (en) 1997-08-15 2003-02-25 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
SK1542000A3 (en) 1998-06-03 2001-11-06 Kimberly Clark Co Neonanoplasts produced by microemulsion technology and inks for ink jet printing
SK1552000A3 (en) 1998-06-03 2000-08-14 Kimberly Clark Co Novel photoinitiators and applications therefor
JP2002520470A (ja) 1998-07-20 2002-07-09 キンバリー クラーク ワールドワイド インコーポレイテッド 改良されたインクジェットインク組成物
BR9914123B1 (pt) 1998-09-28 2010-11-30 fotoiniciadores e aplicações para os mesmos.
EP1144512B1 (fr) 1999-01-19 2003-04-23 Kimberly-Clark Worldwide, Inc. Nouveaux colorants,stabilisateurs de colorants, compositions d'encre, et leur procedes de preparation ameliores
US6331056B1 (en) 1999-02-25 2001-12-18 Kimberly-Clark Worldwide, Inc. Printing apparatus and applications therefor
US6294698B1 (en) 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
US6307671B1 (en) * 1999-05-31 2001-10-23 Fuji Photo Film Co., Ltd. Optical filter comprising transparent support and filter layer containing dye and binder polymer
US6824879B2 (en) 1999-06-10 2004-11-30 Honeywell International Inc. Spin-on-glass anti-reflective coatings for photolithography
EP1190277B1 (fr) * 1999-06-10 2009-10-07 AlliedSignal Inc. Semiconducteur ayant un enduit antireflet spin-on-glass pour photolithographie
EP1068866A3 (fr) * 1999-07-12 2004-03-17 Ciba SC Holding AG Utilisation de mélanges de pigments pour empêcher le bronzage et pour éclaircir la peau et les cheveux
US6586057B1 (en) * 1999-09-29 2003-07-01 Fuji Photo Film Co., Ltd. Optical filter comprising transparent support and filter layer containing dye and binder polymer
US6251173B1 (en) 1999-10-29 2001-06-26 Lexmark International, Inc. Ink compositions containing ultraviolet absorbers
DE50115609D1 (de) * 2000-02-17 2010-10-14 Basf Se Wässrige Dispersion wasserunlöslicher organischer UV-Filtersubstanzen
JP2002122731A (ja) * 2000-10-17 2002-04-26 Fuji Photo Film Co Ltd 光学フィルター
WO2002066548A1 (fr) * 2001-02-21 2002-08-29 Toray Industries, Inc. Article en sulfure de polyphenylene
AU2001279116A1 (en) * 2001-08-01 2003-02-17 Lexmark International, Inc. Ink compositions containing ultraviolet absorbers
KR20040075866A (ko) * 2001-11-15 2004-08-30 허니웰 인터내셔날 인코포레이티드 포토리소그래피용 스핀-온 무반사 코팅
US20050173803A1 (en) * 2002-09-20 2005-08-11 Victor Lu Interlayer adhesion promoter for low k materials
EP1466956A1 (fr) * 2003-04-07 2004-10-13 Clariant International Ltd. Dispersion aqueuse hautement concentrée et stable au stockage pour la stabilisation des glacis et des vernis
US8053159B2 (en) 2003-11-18 2011-11-08 Honeywell International Inc. Antireflective coatings for via fill and photolithography applications and methods of preparation thereof
WO2005059239A2 (fr) * 2003-12-11 2005-06-30 Ciba Specialty Chemicals Holding Inc. Melange d'agents de dispersion
GB0409570D0 (en) * 2004-04-29 2004-06-02 Ciba Spec Chem Water Treat Ltd Particulate compositions and their manufacture
JP4937748B2 (ja) * 2004-08-04 2012-05-23 株式会社Ａｄｅｋａ 光安定剤乳化組成物、及びそれを含有する水系コーティング剤組成物
US20060255315A1 (en) * 2004-11-19 2006-11-16 Yellowaga Deborah L Selective removal chemistries for semiconductor applications, methods of production and uses thereof
CA2669239A1 (fr) * 2006-11-17 2008-05-22 Ciba Holding Inc. Microcapsules, leur utilisation et leurs procedes de fabrication
GB0623110D0 (en) * 2006-11-21 2006-12-27 Ciba Sc Holding Ag Microcapules, their use and processes for their manufacture
GB0623748D0 (en) * 2006-11-28 2007-01-10 Ciba Sc Holding Ag Microcapsules, their use and processes for their manufacture
US8642246B2 (en) * 2007-02-26 2014-02-04 Honeywell International Inc. Compositions, coatings and films for tri-layer patterning applications and methods of preparation thereof
JP2009030214A (ja) * 2007-07-27 2009-02-12 Senka Kk 繊維製品の耐光堅牢度向上剤及び耐光堅牢度向上方法
US8557877B2 (en) 2009-06-10 2013-10-15 Honeywell International Inc. Anti-reflective coatings for optically transparent substrates
US8864898B2 (en) 2011-05-31 2014-10-21 Honeywell International Inc. Coating formulations for optical elements
JP6803842B2 (ja) 2015-04-13 2020-12-23 ハネウェル・インターナショナル・インコーポレーテッドＨｏｎｅｙｗｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｉｎｃ． オプトエレクトロニクス用途のためのポリシロキサン製剤及びコーティング

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2546544A1 (fr) * 1983-05-23 1984-11-30 Sandoz Sa Nouvelles compositions utilisables comme auxiliaires de teinture
EP0345219A1 (fr) * 1988-05-31 1989-12-06 Ciba-Geigy Ag Dispersions aqueuses de 2-(2'-hydroxyphényle) benzotriazoles

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3004896A (en) * 1956-12-14 1961-10-17 Geigy Ag J R Ultra-violet light-absorbing composition of matter
BE563210A (fr) * 1956-12-14 1958-06-13
US3931072A (en) * 1972-08-24 1976-01-06 Champion International Corporation Particleboard, hardboard, and plywood produced in combination with a lignin sulfonate-phenol formaldehyde glue system
US4202838A (en) * 1972-11-03 1980-05-13 Ciba-Geigy Corporation Sulphonated condensation products
CH660828GA3 (fr) * 1980-03-28 1987-05-29
ES2032594T3 (es) * 1987-02-27 1993-02-16 Ciba-Geigy Ag Procedimiento para mejorar la estabilidad fotoquimica de los colorantes sobre materiales de fibra de poliester. (reserva del art. 167.2 cpe).

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2546544A1 (fr) * 1983-05-23 1984-11-30 Sandoz Sa Nouvelles compositions utilisables comme auxiliaires de teinture
EP0345219A1 (fr) * 1988-05-31 1989-12-06 Ciba-Geigy Ag Dispersions aqueuses de 2-(2'-hydroxyphényle) benzotriazoles

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0674038A1 (fr) * 1994-03-26 1995-09-27 Sandoz Ag Utilisation de composés de 4-H-3,1-benzoxazine-4-one pour améliorer la solidité à la lumière de matériaux textiles
US5560852A (en) * 1994-03-26 1996-10-01 Sandoz Ltd. Use of 4H-3,1-benzoxazin-4-one compounds to improve the light fastness of textile materials
EP0774539A3 (fr) * 1995-11-03 1997-08-27 Boehme Filatex Inc Composition absorbant les rayons UV et procédé pour améliorer le solidités lumière des textiles teints
US6391065B1 (en) 1995-11-03 2002-05-21 Boehme Filatex, Inc. UV light absorber composition and method of improving the lightfastness of dyed textiles
EP0820978A1 (fr) * 1996-07-22 1998-01-28 Clariant Finance (BVI) Limited Dispersions aqueuses et leur utilisation pour le traitement du textile
US5955005A (en) * 1996-07-22 1999-09-21 Clariant Finance (Bvi) Limited Aqueous dispersions and their use for treating textiles
WO2000011257A1 (fr) * 1998-08-25 2000-03-02 Clariant Finance (Bvi) Limited Compositions aqueuses d'agents agissant sur les uv, leur production et leur utilisation
US6723256B1 (en) 1998-08-25 2004-04-20 Clariant Finance (Bvi) Limited Aqueous compositions of a UV-active agents, their production and use
FR2807048A1 (fr) * 2000-04-04 2001-10-05 Ciba Sc Holding Ag Melanges synergiques d'absorbants d'uv dans les polyolefines
BE1014092A5 (fr) * 2000-04-04 2003-04-01 Ciba Sc Holding Ag Melanges synergiques d'absorbants d'uv dans les polyolefines.
ES2192928A1 (es) * 2000-04-04 2003-10-16 Ciba Sc Holding Ag Mexclas sinergeticas de absorbedores de uv en poliolefinas.

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JPH04339885A (ja) 1992-11-26
KR920012636A (ko) 1992-07-27
BR9105355A (pt) 1992-08-25
EP0490819B1 (fr) 1995-09-13
ZA919795B (en) 1992-08-26
US5498345A (en) 1996-03-12
ATE127870T1 (de) 1995-09-15
DE59106479D1 (de) 1995-10-19

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