EP0490819B1 - Dispersion aqueuse d'absorbant U.V. difficilement solubles - Google Patents

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

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EP0490819B1
EP0490819B1 EP91810944A EP91810944A EP0490819B1 EP 0490819 B1 EP0490819 B1 EP 0490819B1 EP 91810944 A EP91810944 A EP 91810944A EP 91810944 A EP91810944 A EP 91810944A EP 0490819 B1 EP0490819 B1 EP 0490819B1
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acid
component
process according
mol
compound
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EP0490819A1 (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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    • 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.
  • EP-A-0 345 219 describes aqueous stable dispersions of benzotriazole UV absorbers.
  • FR-A-2 546 544 discloses the use of solutions of specific UV absorbers (resorcinol monobenzoates, phenyl salicilates and benzophenone compounds of the formula (I)) and an emulsifier in an organic solvent system as an aid for dyeing hydrophobic fiber materials.
  • 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 in the definition of the radicals of the compounds of the formulas (1) and (2) are those groups or group components which have 1 to 5, in particular 1 to 3, carbon atoms.
  • Examples of such groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, 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.
  • the ring A is preferably substituted in the 5-position by halogen, lower alkyl or lower alkoxy.
  • the ring A can have a further substituent, e.g. Have halogen or methyl in the 6-position.
  • the benzene ring B is also preferably adjacent to the hydroxyl group e.g. further substituted by halogen or lower alkyl.
  • C1-C14alkoxy means e.g. Methoxy, ethoxy, propoxy, n-butoxy, octyloxy, dodecyloxy or tetradecyloxy.
  • benzotriazole compounds are 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.
  • 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 by definition substituted and the adduct with a polybasic oxygen acid or a functional derivative of this acid, such as e.g. Acid anhydrides, acid halides, acid esters or acid amides are converted into the acidic esters.
  • alkylene oxide ethylene oxide or propylene oxide
  • a functional derivative of this acid such as 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 acid 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, 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 in a mixture.
  • 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 has, such as butylphenol, tributylphenol, octylphenol, nonylphenol, dinonylphenol, o-phenylphenol, benzylphenol, dibenzylphenol, ⁇ -tolylethylphenol, dibenzyl- (nonyl) -phenol, ⁇ -methylbenzylphenol, bis- ( ⁇ -methylbenzylphenol) 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 methylene-bis-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.
  • dispersions according to the invention which, as component (a), are a mixture of a UV-absorbing benzotriazole compound of the formula wherein R5 is lower alkyl, R6 is hydrogen or lower alkyl and R7 is hydrogen, chlorine or methyl and a 2-hydroxybenzophenone compound of the formula (2) in which R1 is C1-C14alkoxy and contain 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) is 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 aqueous dispersions according to the invention advantageously contain, in each case based on the entire dispersion 5-50 preferably 10-45 percent by weight of component (a), 2-18 preferably 3-15 percent by weight of component (b), 0-10 preferably 0-8 percent by weight of component (c), 0-5 preferably 0.1 to 4 percent by weight of component (d), 0 to 8 percent by weight of the further anionic component other than component (b), 0 - 8 percent by weight of the further nonionic component other than component (c), 0-2 preferably 0.1 to 0.5 percent by weight of antifoam 0-1 preferably 0.1 to 0.5 weight percent preservative and 0-20 weight percent antifreeze.
  • 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 also be added, and the mixture is stirred until uniform.
  • the dispersions according to the invention are notable for good transport and storage stability. In particular, they are very 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.
  • 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) are acidic modified polyester fibers and especially mention linear polyester fibers.
  • Cellulose ester and polyester fibers are preferably dyed with disperse dyes and acid-modified polyester fibers and aromatic polyamide fibers are preferred 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, as well as copolymers of terephthalic and isophthalic acid and ethylene glycol.
  • the linear polyester used almost exclusively in the textile industry so far 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, ketonimine, 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 generally used for dyeing with disperse dyes are suitable.
  • Preferred dispersants are 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, 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 as well as alkyl sulfonates with 10 to 20 carbon atoms in the alkyl chain, alkylbenzenesulfonates with straight-chain or branched alkyl chain with 8 to 20 carbon atoms in the alkyl chain, such as e.g.
  • Nonyl- or dodecylbenzenesulfonate 1,3,5,7-tetramethyloctylbenzenesulfonate or octadecylbenzenesulfonate, as well as alkylnaphthalenesulfonates or sulfosuccinic acid esters, such as sodium dioctylsulfosuccinate.
  • Lignin sulfonates and polyphosphates have proven to be 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 carried out is at least 70 ° C and as a rule it is not higher than 140 ° C. It is preferably in the range from 80 to 135 ° C.
  • the dyeings can, however, 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 also pressure-resistant apparatus at temperatures above 100 ° C., preferably between 110 and 135 ° C., and optionally under pressure.
  • Circulation devices such as cross-winding or tree dyeing machines, reel runners, nozzle or drum dyeing machines, muff dyeing machines, paddles or jiggers are suitable as closed vessels, for example.
  • Cellulose-2 1/2 acetate fibers are preferably dyed at temperatures of 80-85 ° C.
  • the dyeing 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, if appropriate, other 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. 71.4 parts of the dispersion obtained are homogenized with stirring with 20 parts of a 1% aqueous solution of a biopolymer based on polysaccharide and 8.6 parts of water. A storage-stable dispersion is obtained.
  • Example 2 Be in a sand mill
  • 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.
  • 100 g of a knitted polyester fabric are placed in 1 liter in an HT circulation apparatus at 60 ° C. at a liquor ratio of 1:10 at 60 ° C., which 2g ammonium sulfate, the dye mixture consisting of 0.37% of the dye of the formula 0.067% of the dye of the formula 0.01% of the dye of the formula 0.013% of the dye of the formula (the percentages of the dyes used relate to the weight of the goods) and contains a 25% aqueous formulation of a UV absorber mixture.
  • the pH is adjusted to 5 with 85% formic acid.
  • the dye bath is heated to 130 ° C. in the course of 30 minutes with a constantly circulating liquor and dyeing at this temperature for 1 hour.
  • the dyebath is then cooled and the substrate rinsed and, as usual, with the removal of unfixed dye 5 ml / l caustic soda 36 Bé and 2 g / l hydrosulfite conc.

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Claims (24)

  1. Procédé de préparation d'une dispersion aqueuse de mélanges d'absorbants UV, difficilement solubles, caractérisé par le fait qu'on mélange ensemble :
    (a) de 5 à 50 % en poids d'un mélange de composé benzotriazole de formule :
    Figure imgb0051
     et d'un composé 2-hydroxybenzophénone de formule :
    Figure imgb0052
     dans lesquelles R représente un atome d'halogène, un groupe alkyle en C₁-C₁₂, alcoxy inférieur, (alcoxy inférieur)carbonyle, cycloalkyle, aryle, (alkyl en C₁-C₁₂)aryle ou aralkyle et les noyaux A et B, indépendamment l'un de l'autre, peuvent en outre être substitués par des atomes d'halogène ou par des groupes hydroxy, alkyle inférieur, alcoxy inférieur ou (alcoxy inférieur)carbonyle,
    R₁ représente un atome d'hydrogène, un groupe hydroxy, alcoxy en C₁-C₁₄ ou phénoxy,
    R₂ représente un atome d'hydrogène, un atome d'halogène ou un groupe alkyle inférieur,
    R₃ représente un atome d'hydrogène, un groupe hydroxy ou un groupe alcoxy inférieur, et
    R₄ représente un atome d'hydrogène ou un groupe hydroxy ;
    (b) de 2 à 18 % en poids d'un composé anionique, et
    (c) de 0 à 10 % en poids d'un composé non ionogène.
  2. Procédé selon la revendication 1, caractérisé par le fait qu'on mélange les composés de formules (1) et (2) dans un rapport (1):(2) de 30:1 à 1:30.
  3. Procédé selon la revendication 2, caractérisé par le fait que les composés de formules (1) et (2) sont mélangés dans un rapport de 1:5 à 5:1, le rapport en poids du composé de formule (1) étant inférieur à 20 %.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé par le fait que dans la formule (1) le noyau A est substitué en position 5 par un atome d'halogène, un groupe alkyle inférieur ou alcoxy inférieur.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé par le fait que le noyau benzénique (B) dans la formule (1), est en outre substitué en position voisine du groupe hydroxyle par un groupe alkyle inférieur ou par un atome d'halogène.
  6. Procédé selon la revendication 5, caractérisé par le fait que le composé benzotriazole du constituant (a) correspond à la formule :
    Figure imgb0053
     dans laquelle
    R₅ représente un atome d'halogène, un groupe alkyle inférieur ou un groupe alcoxy inférieur, et
    R₆ et R₇, indépendamment l'un de l'autre, représentent chacun un atome d'hydrogène, un atome d'halogène, un groupe alkyle inférieur ou un groupe alcoxy inférieur.
  7. Procédé selon la revendication 6, caractérisé par le fait que R₅ représente un groupe alkyle inférieur, R₆ représente un atome d'hydrogène ou un groupe alkyle inférieur et R₇ représente un atome d'hydrogène, un atome de chlore ou un groupe méthyle.
  8. Procédé selon l'une des revendications 1 à 3, caractérisé par le fait que dans la formule (2), R₁ représente un groupe hydroxy ou un groupe alcoxy en C₁-C₁₄, et R₂, R₃ et R₄ représentent un atome d'hydrogène.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé par le fait que le constituant (b) est un composé choisi parmi :
    (ba) un ester acide ou un sel de ce dernier avec le produit d'addition oxyalkyléné de formule :
    Figure imgb0054
     dans laquelle X représente le reste acide d'un acide inorganique renfermant de l'oxygène, tel que par exemple l'acide sulfurique ou de préférence l'acide phosphorique, ou bien le reste d'un acide organique, et
    Y représente un groupe alkyle en C₁-C₁₂, un groupe aryle ou un groupe aralkyle, "alkylène" représente le reste éthylène et/ou le reste propylène, et
    m représente un nombre de 1 à 4 et n représente un nombre de 4 à 50,
    (bb) les polystyrènesulfonates,
    (bc) les amides de taurine et d'acide gras,
    (bd) les monosulfonates ou disulfonates de diphényloxydes alkylés,
    (be) les sulfonates d'esters d'acides polycarboxyliques,
    (bf) les produits d'addition d'amines grasses, d'amides gras, d'acides gras ou d'alcools gras (comportant de 8 à 22 atomes de carbone) ou d'alcanols de trivalents à hexavalents (comportant de 3 à 6 atomes de carbone), comprenant de 1 à 60 et de préférence de 2 à 30 moles d'oxyde d'éthylène et/ou d'oxyde de propylène, transformés en esters acides au moyen d'un acide organique dicarboxylique ou au moyen d'un acide inorganique polybasique,
    (bg) les ligninesulfonates, et
    (bh) les produits de condensation du formaldéhyde.
  10. Procédé selon la revendication 9, caractérisé par le fait que le constituant (b) est un ester acide de l'acide phosphorique ou le sel de ce dernier avec le produit oxyalkyléné (comportant de 6 à 30 moles d'oxyde d'éthylène) de 1 mole de 4-nonylphénol, dinonylphénol ou sur 1 mole d'un composé préparé par addition de 1 à 3 moles de styrène, d'α-méthylstyrène ou de vinyltoluène sur 1 mole de phénol, crésol ou xylénol.
  11. Procédé selon la revendication 9, caractérisé par le fait que le constituant (b) est un produit de condensation du formaldéhyde avec un acide sulfonique aromatique.
  12. Procédé selon la revendication 11, caractérisé par le fait que le constituant (b) est un produit de condensation du formaldéhyde avec l'acide naphtalènesulfonique.
  13. Procédé selon la revendication 11, caractérisé par le fait que le constituant (b) est un produit de condensation du formaldéhyde avec le ditolyléthersulfonate.
  14. Procédé selon l'une des revendications 1 à 13, caractérisé par le fait qu'on utilise comme constituant facultatif (c) un composé non ionogène choisi parmi :
    (ca) les produits d'addition d'oxyde d'alkylène de formule :
    Figure imgb0055
     dans laquelle Y₁ représente un groupe alkyle en C₁-C₁₂, un groupe aryle ou un groupe aralkyle, "alkylène" représente le reste éthylène ou propylène, et
    m₁ représente un nombre de 1 à 4 et n₁ représente un nombre de 4 à 50 ;
    (cb) les produits d'addition d'oxyde d'alkylène à :
    (cba) des alcools aliphatiques saturés ou insaturés de monovalents à hexavalents,
    (cbb) des acides gras,
    (cbc) des amines grasses,
    (cbd) des amides gras,
    (cbe) des diamines,
    (cbf) de l'ester de sorbitan ;
    (cc) les produits de condensation d'oxyde d'alkylène (produits de polymérisation séquencés) ;
    (cd) les produits de polymérisation de la vinylpyrrolidone, de l'acétate de vinyle ou de l'alcool vinylique ; et
    (ce) des copolymères ou terpolymères de la vinylpyrrolidone avec l'acétate d'éthyle et/ou l'alcool vinylique.
  15. Procédé selon la revendication 14, caractérisé par le fait que le constituant (c) est un produit d'addition de 6 à 30 moles d'oxyde d'éthylène à 1 mole de 4-nonylphénol, à 1 mole de dinonylphénol ou à 1 mole de composés préparés par addition de 1 à 3 moles de styrène à 1 mole de phénol.
  16. Procédé selon l'une des revendications 1 à 15, caractérisé par le fait qu'on utilise en outre comme constituant (d) un agent de stabilisation ou un agent épaississant.
  17. Procédé selon la revendication 16, caractérisé par le fait que le constituant (d) est un polysaccharide.
  18. Procédé selon l'une des revendications 1 à 17, caractérisé par le fait qu'on utilise en outre un agent de conservation et/ou un agent de protection contre le gel.
  19. Procédé selon la revendication 1, caractérisé par le fait que le constituant (a) est un mélange d'un composé benzotriazole et d'un composé 2-hydroxybenzophénone de formule (1) et (2), absorbant les UV, et le constituant (b) est un produit de condensation du formaldéhyde avec un acide sulfonique aromatique.
  20. Procédé selon la revendication 19, caractérisé par le fait que le constituant (a) est un mélange d'un composé benzotriazole absorbant les UV, de formule
    Figure imgb0056
     dans laquelle R₅ représente un groupe alkyle inférieur, R₆ représente un atome d'hydrogène ou un groupe alkyle inférieur et R₇ représente un atome d'hydrogène, un atome de chlore ou un groupe méthyle, et d'un composé 2-hydroxybenzophénone de formule (2), dans laquelle R₁ représente un groupe alcoxy en C₁-C₁₄ ou un groupe hydroxy, et R₂, R₃ et R₄ représentent un atome d'hydrogène, et le constituant (b) est un produit de condensation du formaldéhyde avec un acide sulfonique aromatique.
  21. Procédé selon la revendication 1, caractérisé par le fait que le constituant (a) est un mélange d'un composé benzotriazole absorbant les UV, de formule :
    Figure imgb0057
     dans laquelle R₅ représente un groupe alkyle inférieur, R₆ représente un atome d'hydrogène ou un groupe alkyle inférieur, et R₇ représente un atome d'hydrogène, un atome de chlore ou un groupe méthyle, et d'un composé 2-hydroxybenzophénone de formule (2), dans laquelle R₁ représente un groupe alcoxy en C₁-C₁₄ ou un groupe hydroxy, et R₂, R₃ et R₄ représentent un atome d'hydrogène, et le constituant (b) est un ester acide de l'acide phosphorique ou le sel de ce dernier avec le produit oxyalkyléné (comportant de 6 à 30 moles d'oxyde d'éthylène) de 1 mole de 4-nonylphénol, de dinonylphénol ou de 1 mole d'un composé préparé par addition de 1 à 3 moles de styrène, d'α-méthylstyrène ou de vinyltoluène sur 1 mole de phénol, crésol ou xylénol.
  22. Procédé selon la revendication 1, caractérisé par le fait qu'on utilise :
    de 5 à 50 % en poids de constituant (a),
    de 2 à 18 % en poids de constituant (b),
    de 0 à 10 % en poids de constituant (c),
    de 0 à 5 % en poids de constituant (d),
    de 0 à 8 % en poids d'autres constituants anioniques différents du constituant (b),
    de 0 à 8 % en poids d'autres constituants non ionogènes différents du constituant (c),
    de 0 à 1 % en poids d'agent anti-mousse,
    de 0 à 1 % en poids d'agent de conservation, et
    de 0 à 20 % en poids d'agent de protection contre le gel,
    les pourcentages étant calculés sur le poids total de la dispersion.
  23. Utilisation de la dispersion aqueuse, selon l'une des revendications 1 à 22, pour la teinture de matériaux à base de fibres synthétiques, en particulier de fibres de polyester ou de fibres de polyester modifié par acide.
  24. Procédé de teinture de matériaux textiles à base de fibres synthétiques, de préférence de fibres de polyester ou de fibres de polyester modifié par acide, avec des colorants de dispersion ou avec des colorants cationiques, caractérisé par le fait qu'on teint ces matériaux en présence d'une dispersion aqueuse constituée d'un mélange d'un composé benzotriazole et d'un composé 2-hydroxybenzophénone, selon l'une des revendications 1 à 20.
EP91810944A 1990-12-13 1991-12-05 Dispersion aqueuse d'absorbant U.V. difficilement solubles Revoked EP0490819B1 (fr)

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DE59106479D1 (de) 1995-10-19
US5498345A (en) 1996-03-12
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JPH04339885A (ja) 1992-11-26
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ATE127870T1 (de) 1995-09-15

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