EP0309909B1 - Process for improvement of colour fastness of polyester dyeings by using benzophenone ether esters and the new benzophenone ether esters - Google Patents
Process for improvement of colour fastness of polyester dyeings by using benzophenone ether esters and the new benzophenone ether esters Download PDFInfo
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- EP0309909B1 EP0309909B1 EP88115564A EP88115564A EP0309909B1 EP 0309909 B1 EP0309909 B1 EP 0309909B1 EP 88115564 A EP88115564 A EP 88115564A EP 88115564 A EP88115564 A EP 88115564A EP 0309909 B1 EP0309909 B1 EP 0309909B1
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- Prior art keywords
- acid
- formula
- benzophenone
- polybasic
- organic radical
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- 0 **(C(CC1O)CC=C1C(C1=CC=CCC1)=O)=O Chemical compound **(C(CC1O)CC=C1C(C1=CC=CCC1)=O)=O 0.000 description 3
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/54—Polyesters using dispersed dyestuffs
-
- 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
-
- 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 invention relates to a process for dyeing textile polyester material with disperse dyes using benzophenone ether esters to improve lightfastness, the use of these benzonophenone ether esters in dyeing textile polyester material and new benzophenone ether esters as such.
- DE-B-1 156 760 discloses a process for improving the lightfastness of polyester dyeings, in which the fibers are placed in a boiling aqueous dyebath which contains, in addition to the dye, alkyl ether of 2,2 ', 4,4'-tetrahydroxybenzophenone contains, treated.
- the benzophenone derivative is drawn onto the fiber together with the dye.
- the fiber dyed in this way has better lightfastness when exposed in an exposure device (for example a Xenotest or fadeometer) compared to a fiber dyed without the addition of the tetrahydroxybenzophenone derivative.
- the compounds described in DE-B-1 156 760 have a number of disadvantages: due to their intrinsic color, they shift the hue in particular in the case of brilliant dyeings and tarnish the coloring to a greater or lesser extent.
- the absorption capacity on the textile structures is not exhaustive enough, so that the wastewater from the dyeing plants is contaminated with organic compounds.
- the compounds mentioned tend to sublimation in a thermal aftertreatment usually carried out after the dyeing process.
- benzophenone ether esters are proposed to improve the light fastness when dyeing textile polyester material. These are optionally substituted 2-hydroxy-4- (2-hydroxyethyl) benzophenone esters, in which the ester residue is derived from a monobasic organic acid.
- JP-A-60-126 246 discloses 2-hydroxybenzophenone ether esters, in which the acid component of the esters is derived from dicarboxylic acids containing methylidene groups, such as itaconic acid. These connections are expressly excluded from the scope of protection of claims 5 and 6.
- the 2-hydroxybenzophenone ether esters described are used as comonomers in the copolymerization with other ethylenically unsaturated monomers and as UV absorbers.
- the object of the invention is to provide materials for the improvement of the light fastness of dyeings with disperse dyes on polyester, which are good for polyester, show a low tendency to sublimation and which do not or only slightly impair the dyeings, in particular with regard to their brilliance.
- the invention therefore also relates to the new benzophenone derivatives of the formulas III to V in which Y represents a polyvalent organic radical derived from a polybasic heterocyclic acid and R1, R2, m, n and p have the meanings given for formula I, the new benzophenone derivatives of the formula IV in which g is the number 3 or 4 and R1, R2, m and X have the meanings given for formula I, and the new benzophenone derivatives of formula V in which R1, R2, m, n, p and X have the meanings given for formula I, with the proviso that at least one of the radicals R1 and R2 must be different from hydrogen.
- alkyl radicals for R 1 and R 2 are methyl, ethyl, propyl, n- and tert-butyl.
- Preferred radicals for R1 are hydrogen, chlorine and methyl, for R2 hydrogen and methyl.
- polybasic aliphatic, cycloaliphatic or aromatic acids on which the radical X is based are: carbonic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, 3,3-dimethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, fumaric acid , Itaconic acid (applies exclusively to formulas I and II), citric acid, tricarballyl acid, butane-1,2,3,4-tetracarboxylic acid, ethylenediaminetetraacetic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 3- and 4-phthalic acid, 3- and 4-phthalic acid, m-phenylene diacetic acid, p-phenylene diacetic acid, p
- Thiophene-2,5-dicarboxylic acid, pyridine-2,6-, pyridine-2,5- and pyridine-3,5-dicarboxylic acid are mentioned as polyvalent organic radicals derived from a polybasic heterocyclic acid or the acids on which these are based. These acid residues correspond in particular to the radical Y in the formula III.
- the polybasic acids can be expressed as X (COOH) p or Y (COOH) p , where X, Y and p have the meanings given for the formulas I to V.
- Preferred polybasic acids are succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, p-phenylenedioxyacetic acid and diphenylene ether dicarboxylic acid.
- the new compounds of the formula III to V are prepared in a manner known per se by reacting an alcohol of the formula VI in which R1, R2, m and n or g have the meanings given for the formulas III to V, with a polybasic acid X (COOH) p in the case of the preparation of compounds in formulas IV and V or with a polybasic acid Y ( COOH) p in the case of the preparation of compounds of the formula III, where X, Y and p have the meanings given above, in an inert solvent, in particular benzene, toluene or xylene, in the presence of an acidic catalyst, in particular sulfuric acid, p-toluenesulfonic acid or a strongly acidic ion exchanger, at reflux temperatures and working up in a conventional manner.
- the starting compounds of the formula VI are known or, as in the case of the compounds substituted by radicals R 1 and / or R 2, can be obtained by reacting a corresponding substituted 2,4-dihydroxybenzophenone.
- the 2-hydroxy-4- (ß-hydroxyethoxy) -4'-chloro and 2-hydroxy-4- (ß-hydroxyethoxyl) -4'-methylbenzophenone by conventional reaction with ethylene oxide or ethylene carbonate from the corresponding 2,4 -Dihydroxy-4'-chloro and 2,4-dihydroxy-4'-methylbenzophenone obtained.
- textile materials made from polyesters are dyed in a conventional manner.
- structures such as fibers, threads, flakes, foils, fabrics and knitted fabrics come into consideration as such.
- the known dye classes such as Azo, anthraquinone, methine, quinophthalone and coumarin dyes belong, according to methods known per se, such as e.g. the high temperature process, the thermosol process or the carrier dyeing process are colored, e.g. can be found in the "Advice, dyeing and finishing of polyester fibers and polyester fiber mixtures", published by BASF Aktiengesellschaft 1974.
- the benzophenone derivatives are added to the dyebaths in finely divided form, optionally as a powder or liquid preparation. They are used in amounts of 0.1 to 10, preferably 0.3 to 5% by weight, based on the textile material.
- Benzophenone ether esters to be used particularly preferably in the process according to the invention are the diesters of succinic acid, glutaric acid, adipic acid, phthalic acid, p-phenylenedioxyacetic acid with the 2-hydroxy-4- (2-hydroxyethoxy) benzophenone.
- 100 parts of a polyester yarn are in a dye bath containing 1500 parts of water, 0.6 parts of a mixture of the finely divided dyes 1.8 parts of a product obtained by adding 50 moles of ethylene oxide to 1 mole of sperm oil alcohol and subsequent sulfonation as a dyeing aid and 1.5 parts of the finely divided benzophenone compound of the formula contains, treats.
- the process is started at 60 ° C., the temperature is raised to 130 ° C. in 20 minutes and dyeing is carried out for a further 90 minutes at this temperature in an HT dyeing machine.
- a brown coloration is obtained which, when exposed to xenotest under hot and humid conditions (e.g. temperature 75 ° C, relative air humidity 80%), is significantly more lightfast than the same coloration without the addition of the benzophenone compound.
- 100 parts of a knitted fabric made of polyester are in a dyebath, the 2500 parts of water, 1.2 parts of a mixture of the finely divided dyes 5 parts of a carrier based on salicylic acid methyl ester and 2 parts of the finely divided benzophenone compound of the formula contains, treats.
- the dyeing is carried out for 90 minutes at the boiling point and a reddish-brown coloration is obtained which, in an exposure test in a fadeometer, gives significantly better results than a similar coloration without the addition of the benzophenone compound.
- a polyester fabric is impregnated on a three-roll pad with a dye liquor containing 25 parts of a mixture of the finely divided dyes in 1000 parts
- the fabric After impregnation with 60% liquor absorption, the fabric is dried at 120 ° C and thermosolated at 200 ° C for 60 seconds.
- a gray coloration is obtained which is significantly better in light fastness than a same coloration without the addition of the benzophenone compound.
- a dyeing is carried out analogously to Example 2 using the benzophenone compound of the formula by.
Description
Die Erfindung betrifft ein Verfahren zum Färben von textilem Polyestermaterial mit Dispersionsfarbstoffen unter Verwendung von Benzophenonether-estern zur Verbesserung der Lichtechtheit, die Verwendung dieser Benzonphenonether-ester beim Färben von textilem Polyestermaterial und neue Benzophenonether-ester als solche.The invention relates to a process for dyeing textile polyester material with disperse dyes using benzophenone ether esters to improve lightfastness, the use of these benzonophenone ether esters in dyeing textile polyester material and new benzophenone ether esters as such.
Aus der DE-B-1 156 760 ist beispielsweise ein Verfahren zur Verbesserung der Lichtechtheit von Polyesterfärbungen bekannt, bei dem man die Fasern in einem siedenden wäßrigen Färbebad, das neben dem Farbstoff noch Alkylether des 2,2',4,4'-Tetrahydroxybenzophenons enthält, behandelt. Bei diesem Verfahren zieht das Benzophenon-Derivat zusammen mit dem Farbstoff auf die Faser auf. Die so gefärbte Faser weist bei der Belichtung in einem Belichtungsgerät (beispielsweise Xenotest oder Fadeometer) eine im Vergleich zu einer ohne Zusatz des Tetrahydroxybenzophenon-Derivats gefärbten Faser bessere Lichtechtheit auf.DE-B-1 156 760, for example, discloses a process for improving the lightfastness of polyester dyeings, in which the fibers are placed in a boiling aqueous dyebath which contains, in addition to the dye, alkyl ether of 2,2 ', 4,4'-tetrahydroxybenzophenone contains, treated. In this process, the benzophenone derivative is drawn onto the fiber together with the dye. The fiber dyed in this way has better lightfastness when exposed in an exposure device (for example a Xenotest or fadeometer) compared to a fiber dyed without the addition of the tetrahydroxybenzophenone derivative.
Die in der DE-B-1 156 760 beschriebenen Verbindungen weisen jedoch eine Reihe von Nachteilen auf: aufgrund ihrer Eigenfarbe verschieben sie insbesondere bei brillanten Färbungen den Farbton und trüben die Färbung mehr oder weniger stark ab. Das Aufziehvermögen auf die textilen Gebilde ist nicht erschöpfend genug, so daß das Abwasser der Färbereien mit organischen Verbindungen belastet wird. Außerdem neigen die genannten Verbindungen bei einer im Anschluß an den Färbeprozess üblicherweise durchgeführten thermischen Nachbehandlung zur Sublimation.The compounds described in DE-B-1 156 760, however, have a number of disadvantages: due to their intrinsic color, they shift the hue in particular in the case of brilliant dyeings and tarnish the coloring to a greater or lesser extent. The absorption capacity on the textile structures is not exhaustive enough, so that the wastewater from the dyeing plants is contaminated with organic compounds. In addition, the compounds mentioned tend to sublimation in a thermal aftertreatment usually carried out after the dyeing process.
Aus der DE-A-2 017 825 ist bekannt, daß 2-Hydroxy-4-(2-hydroxyethoxy)-benzophenon-ester als Lichtstabilisatoren von Kunststoffen, Polymeren wie z.B. Polypropylen, Polyvinylchlorid, Polyester oder Polyamide, verwendet werden können, wobei diese Verbindungen in die Polymermassen eingebracht oder Lösungen und Emulsionen von Oberflächenüberzügen, allgemein Lacke (Firnisse), zugesetzt werden. Aus diesem Stand der Technik hat es nicht nahegelegen, diese Verbindungen in einem System aus Farbstoffen und textilem Polyestermaterial zur Stabilisierung der Farbstoffe einzusetzen.From DE-A-2 017 825 it is known that 2-hydroxy-4- (2-hydroxyethoxy) benzophenone esters as light stabilizers for plastics, polymers such as e.g. Polypropylene, polyvinyl chloride, polyester or polyamides can be used, these compounds being introduced into the polymer compositions or solutions and emulsions of surface coatings, in general lacquers (varnishes) being added. From this prior art it was not obvious to use these compounds in a system of dyes and textile polyester material to stabilize the dyes.
In der vorgängigen aber nicht vorveröffentlichten EP-A-0 254 987 (Stand der Technik nach Art. 54 (3) EPÜ) werden Benzophenonether-ester zur Verbesserung der Lichtechtheit beim Färben von textilem Polyestermaterial vorgeschlagen. Es handelt sich dabei um gegebenenfalls substituierte 2-Hydroxy-4-(2-hydroxyethyl)-benzophenon-ester, bei denen sich der Esterrest von einer einbasischen organischen Säure ableitet.In the previous but not prepublished EP-A-0 254 987 (prior art according to Art. 54 (3) EPC), benzophenone ether esters are proposed to improve the light fastness when dyeing textile polyester material. These are optionally substituted 2-hydroxy-4- (2-hydroxyethyl) benzophenone esters, in which the ester residue is derived from a monobasic organic acid.
Aus der JP-A-60-126 246 sind 2-Hydroxybenzophenonether-ester bekannt, bei denen sich die Säurekomponente der Ester von Methylidengruppen enthaltenden Dicarbonsäuren, wie beispielsweise Itaconsäure, ableitet. Diese Verbindungen sind vom Schutzumfang der Ansprüche 5 und 6 ausdrücklich ausgeschlossen. Die beschriebenen 2-Hydroxybenzophenonether-ester werden als Comonomer bei der Copolymerisation mit anderen ethylenisch ungesättigten Monomeren und als UV-Absorber verwendet.JP-A-60-126 246 discloses 2-hydroxybenzophenone ether esters, in which the acid component of the esters is derived from dicarboxylic acids containing methylidene groups, such as itaconic acid. These connections are expressly excluded from the scope of protection of claims 5 and 6. The 2-hydroxybenzophenone ether esters described are used as comonomers in the copolymerization with other ethylenically unsaturated monomers and as UV absorbers.
Aufgabe der Erfindung ist es, für die Verbesserung der Lichtechtheit von Färbungen mit Dispersionsfarbstoffen auf Polyester Stoffe zur Verfügung zu stellen, die gut auf Polyester aufziehen, eine geringe Sublimationstendenz zeigen und die die Färbungen insbesondere hinsichtlich ihrer Brillanz nicht oder nur geringfügig beeinträchtigen.The object of the invention is to provide materials for the improvement of the light fastness of dyeings with disperse dyes on polyester, which are good for polyester, show a low tendency to sublimation and which do not or only slightly impair the dyeings, in particular with regard to their brilliance.
Die Aufgabe wird erfindungsgemäß gelöst mit einem Verfahren zum Färben von textilem Polyestermaterial mit Dispersionsfarbstoffen unter gleichzeitiger Verwendung von Benzophenonderivaten zur Verbesserung der Lichtechtheit, das dadurch gekennzeichnet ist, daß man den Färbebädern wenigstens ein Benzophenonderivat der Formel I
in der für
- R¹
- ein Wasserstoffatom, ein Alkylrest mit 1 bis 4 C-Atomen, Cyan, Fluor, Chlor, Brom oder Trifluormethyl, für
- R²
- ein Wasserstoffatom oder ein Alkylrest mit 1 bis 6 C-Atomen und für
- m
- die Zahlen 1 oder 2, für
- n
- die Zahlen 2, 3 oder 4, für
- p
- die Zahlen 2, 3 oder 4 stehen und
- X
- einen von einer polybasischen aliphatischen, cycloaliphatischen, aromatischen oder heterocyclischen Säure abgeleiteten polyvalenten organischen Rest bedeutet, zusetzt, sowie in der Verwendung der Benzophenonderivate der Formel (I) zur Verbesserung der Lichtechtheit von gefärbtem textilem Polyestermaterial.
in the for
- R¹
- a hydrogen atom, an alkyl radical having 1 to 4 carbon atoms, cyan, fluorine, chlorine, bromine or trifluoromethyl, for
- R²
- is a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms and for
- m
- the numbers 1 or 2, for
- n
- the numbers 2, 3 or 4, for
- p
- the numbers 2, 3 or 4 stand and
- X
- means a polyvalent organic radical derived from a polybasic aliphatic, cycloaliphatic, aromatic or heterocyclic acid, and in the use of the benzophenone derivatives of the formula (I) to improve the light fastness of dyed textile polyester material.
In dem erfindungsgemäßen Verfahren werden unsubstituierte Benzophenonderivate der Formel II
in der
- p
- die Zahlen 2, 3 oder 4 und
- X
- einen von einer polybasischen aliphatischen, cycloaliphatischen, aromatischen oder heterocyclischen Säure abgeleiteten polyvalenten organischen Rest bedeuten, besonders bevorzugt.
in the
- p
- the numbers 2, 3 or 4 and
- X
- is a polyvalent organic radical derived from a polybasic aliphatic, cycloaliphatic, aromatic or heterocyclic acid, particularly preferably.
Die Verbindungen der Formeln I und II sind, soweit ihnen ein 2-Hydroxy-4-(2-hydroxyethoxy)-benzophenonrest zugrundeliegt, teilweise aus der DE-A-2 017 825 bekannt und teilweise noch nicht beschrieben.Insofar as they are based on a 2-hydroxy-4- (2-hydroxyethoxy) benzophenone radical, the compounds of the formulas I and II are known in part from DE-A-2 017 825 and some have not yet been described.
Gegenstand der Erfindung sind daher auch die neuen Benzophenonderivate der Formeln III bis V
in der Y für einen von einer polybasischen heterocyclischen Säure abgeleiteten polyvalenten organischen Rest steht und R¹, R², m, n und p die für Formel I genannten Bedeutungen haben,
die neuen Benzophenonderivate der Formel IV
in der für g die Zahl 3 oder 4 steht und R¹, R², m und X die für Formel I genannten Bedeutungen haben,
und die neuen Benzophenonderivate der Formel V
in der R¹, R², m, n, p und X die für Formel I angegebenen Bedeutungen aufweisen, mit der Maßgabe, daß wenigstens einer von den Resten R¹ und R² von Wasserstoff verschieden sein muß.The invention therefore also relates to the new benzophenone derivatives of the formulas III to V
in which Y represents a polyvalent organic radical derived from a polybasic heterocyclic acid and R¹, R², m, n and p have the meanings given for formula I,
the new benzophenone derivatives of the formula IV
in which g is the number 3 or 4 and R¹, R², m and X have the meanings given for formula I,
and the new benzophenone derivatives of formula V
in which R¹, R², m, n, p and X have the meanings given for formula I, with the proviso that at least one of the radicals R¹ and R² must be different from hydrogen.
Zu den obengenannten Formeln I bis V wird ausgeführt:
Als Alkylreste für R¹ und R² seien beispielsweise Methyl, Ethyl, Propyl, n- und tert.-Butyl genannt. Bevorzugte Reste für R¹ sind Wasserstoff, Chlor und Methyl, für R² Wasserstoff und Methyl.Regarding the above formulas I to V:
Examples of alkyl radicals for R 1 and R 2 are methyl, ethyl, propyl, n- and tert-butyl. Preferred radicals for R¹ are hydrogen, chlorine and methyl, for R² hydrogen and methyl.
Als polybasische aliphatische, cycloaliphatische oder aromatische Säuren, die dem Rest X zugrundeliegen, seien beispielsweise genannt: Kohlensäure, Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, 3,3-Dimethylglutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Sebacinsäure, Maleinsäure, Fumarsäure, Glutaconsäure, Itaconsäure (betrifft ausschließlich Formeln I und II), Citronensäure, Tricarballysäure, Butan-1,2,3,4-tetracarbonsäure, Ethylendiamintetraessigsäure, Phthalsäure, Isophthalsäure, Terephthalsäure, Hexahydrophthalsäure, Hexahydroisophthalsäure, Hexahydroterephthalsäure, 3- und 4-Chlorphthalsäure, Tetrachlorphthalsäure, m-Phenylendiessigsäure, p-Phenylendiessigsäure, m-Phenylendioxiessigsäure, p-Phenylendioxiessigsäure, Diphenylether-4,4′-dicarbonsäure, Diphensäure, Diphenyl-4,4′-dicarbonsäure, Diphenylsulfon-4,4′-dicarbonsäure, Benzophenon-4,4′-dicarbonsäure, Naphthalin-2,6-dicarbonsäure, Trimellitsäure, Trimesinsäure, Pyrromellitsäure, Hemimellitsäure.Examples of polybasic aliphatic, cycloaliphatic or aromatic acids on which the radical X is based are: carbonic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, 3,3-dimethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, fumaric acid , Itaconic acid (applies exclusively to formulas I and II), citric acid, tricarballyl acid, butane-1,2,3,4-tetracarboxylic acid, ethylenediaminetetraacetic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 3- and 4-phthalic acid, 3- and 4-phthalic acid, m-phenylene diacetic acid, p-phenylene diacetic acid, m-phenylene diacetic acid, p-phenylene diacetic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenic acid, diphenyl-4,4'-dicarboxylic acid, diphenyl sulfone-4,4'-dicarboxylic acid, benzophenone-4,4 '-Dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, trimellitic acid, trimesins acid, pyromellitic acid, hemimellitic.
Als von einer polybasischen heterocyclischen Säure abgeleitete polyvalente organische Reste bzw. diesen zugrundeliegenden Säuren werden Thiophen-2,5-dicarbonsäure, Pyridin-2,6-, Pyridin-2,5- und Pyridin-3,5-dicarbonsäure genannt. Diese Säurereste entsprechen insbesondere dem Rest Y in der Formel III.Thiophene-2,5-dicarboxylic acid, pyridine-2,6-, pyridine-2,5- and pyridine-3,5-dicarboxylic acid are mentioned as polyvalent organic radicals derived from a polybasic heterocyclic acid or the acids on which these are based. These acid residues correspond in particular to the radical Y in the formula III.
In allgemeiner Form können die polybasischen Säuren als X(COOH)p oder Y(COOH)p, wobei X, Y und p die für die Formeln I bis V angegebenen Bedeutungen aufweisen, ausgedrückt werden.In general form, the polybasic acids can be expressed as X (COOH) p or Y (COOH) p , where X, Y and p have the meanings given for the formulas I to V.
Bevorzugte polybasische Säuren sind Bernsteinsäure, Glutarsäure, Adipinsäure, Sebacinsäure, Phthalsäure, Isophthalsäure, Terephthalsäure, p-Phenylendioxiessigsäure sowie Diphenylenetherdicarbonsäure.Preferred polybasic acids are succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, p-phenylenedioxyacetic acid and diphenylene ether dicarboxylic acid.
Die Herstellung der neuen Verbindungen der Formel III bis V erfolgt in an sich bekannter Weise durch Umsetzung eines Alkohols der Formel VI
in der R¹, R², m und n bzw. g die für die Formeln III bis V angegebenen Bedeutungen aufweisen, mit einer polybasischen Säure X(COOH)p im Falle der Herstellung von Verbindungen bei Formeln IV und V oder mit einer polybasischen Säure Y(COOH)p im Falle der Herstellung von Verbindungen der Formel III, wobei X, Y und p die oben angegebenen Bedeutungen aufweisen, in einem inerten Lösungsmittel, insbesondere Benzol, Toluol oder Xylol, in Gegenwart eines sauren Katalysators, insbesondere von Schwefelsäure, p-Toluolsulfonsäure oder eines stark sauren Ionenaustauschers, bei Rückflußtemperaturen und Aufarbeitung in an sich üblicher Weise.The new compounds of the formula III to V are prepared in a manner known per se by reacting an alcohol of the formula VI
in which R¹, R², m and n or g have the meanings given for the formulas III to V, with a polybasic acid X (COOH) p in the case of the preparation of compounds in formulas IV and V or with a polybasic acid Y ( COOH) p in the case of the preparation of compounds of the formula III, where X, Y and p have the meanings given above, in an inert solvent, in particular benzene, toluene or xylene, in the presence of an acidic catalyst, in particular sulfuric acid, p-toluenesulfonic acid or a strongly acidic ion exchanger, at reflux temperatures and working up in a conventional manner.
Es handelt sich um eine an sich übliche Veresterung eines Alkohols der Formel VI mit einer mehrbasischen organischen Säure, die gegebenenfalls in Form ihres Anhydrids vorliegen kann.It is a conventional esterification of an alcohol of the formula VI with a polybasic organic acid, which may optionally be in the form of its anhydride.
Die Ausgangsverbindungen der Formel VI sind bekannt oder, wie bei den durch Reste R¹ und/oder R² substituierten Verbindungen durch Umsetzung eines entsprechenden substituierten 2,4-Dihydroxybenzophenons erhältlich.The starting compounds of the formula VI are known or, as in the case of the compounds substituted by radicals R 1 and / or R 2, can be obtained by reacting a corresponding substituted 2,4-dihydroxybenzophenone.
Beispielsweise wird das 2-Hydroxy-4-(ß-hydroxyethoxy)-4′-chlor- und 2-Hydroxy-4-(ß-hydroxyethoxyl)-4′-methylbenzophenon durch übliche Umsetzung mit Ethylenoxid oder Ethylencarbonat aus dem entsprechenden 2,4-Dihydroxy-4′-chlor- und 2,4-Dihydroxy-4′-methylbenzophenon erhalten.
Beispielhaft können folgende Verbindungen der Formeln III bis V genannt werden:
Nach dem erfindungsgemäßen Verfahren werden in an sich üblicher Weise textile Materialien aus Polyestern, insbesondere aus Polyethylenterephthalaten, wie Polyethylenglykolterephthalat, gefärbt. Als solche kommen insbesondere Gebilde wie Fasern, Fäden, Flocken, Folien, Gewebe und Gewirke in Betracht. Sie können mit den üblichen Dispersionsfarbstoffen, die den bekannten Farbstoffklassen, wie z.B. Azo-, Anthrachinon-, Methin-, Chinophthalon- und Cumarin-Farbstoffen, angehören, nach an sich bekannten Methoden, wie z.B. das Hochtemperaturverfahren, das Thermosolverfahren oder das Carrierfärbeverfahren, gefärbt werden, wie z.B. dem "Ratgeber, Färben und Ausrüsten von Polyesterfasern und Polyesterfasermischungen", herausgegeben von der BASF Aktiengesellschaft 1974, entnommen werden kann.According to the method according to the invention, textile materials made from polyesters, in particular from polyethylene terephthalates, such as polyethylene glycol terephthalate, are dyed in a conventional manner. In particular, structures such as fibers, threads, flakes, foils, fabrics and knitted fabrics come into consideration as such. You can with the usual disperse dyes, the known dye classes, such as Azo, anthraquinone, methine, quinophthalone and coumarin dyes belong, according to methods known per se, such as e.g. the high temperature process, the thermosol process or the carrier dyeing process are colored, e.g. can be found in the "Advice, dyeing and finishing of polyester fibers and polyester fiber mixtures", published by BASF Aktiengesellschaft 1974.
Bei dem erfindungsgemäßen Verfahren werden die Benzophenon-Derivate den Färbebädern in feinverteilter Form gegebenenfalls als Pulver- oder Flüssigzubereitung zugesetzt. Sie werden in Mengen von 0,1 bis 10, vorzugsweise 0,3 bis 5 Gew.%, bezogen auf das Textilgut, eingesetzt.In the process according to the invention, the benzophenone derivatives are added to the dyebaths in finely divided form, optionally as a powder or liquid preparation. They are used in amounts of 0.1 to 10, preferably 0.3 to 5% by weight, based on the textile material.
Man erhält dabei Färbungen, die im Vergleich zu solchen ohne Zusatz der Benzophenon-Derivate sich im Farbton nicht oder kaum unterscheiden, aber eine deutlich verbesserte Lichtechtheit aufweisen, die auch höheren Anforderungen, wie sie z.B. im Automobilsektor für Sitzbezüge und dergleichen gestellt werden, gerecht werden können.This gives dyeings which, in comparison to those without the addition of the benzophenone derivatives, have little or no difference in color, but have a significantly improved light fastness which also meets higher requirements, such as be provided in the automotive sector for seat covers and the like.
Als in dem erfindungsgemäßen Verfahren besonders bevorzugt zu verwendende Benzophenonether-ester sind zu nennen die Diester von Bernsteinsäure, Glutarsäure, Adipinsäure, Phthalsäure, p-Phenylendioxyessigsäure mit dem 2-Hydroxy-4-(2-hydroxyethoxy)-benzophenon.Benzophenone ether esters to be used particularly preferably in the process according to the invention are the diesters of succinic acid, glutaric acid, adipic acid, phthalic acid, p-phenylenedioxyacetic acid with the 2-hydroxy-4- (2-hydroxyethoxy) benzophenone.
Als besondere Vorteile gegenüber bekannten Benzophenonderivaten gemäß der DE-B-11 56 760 seien hervorgehoben, daß die erfindungsgemäß zu verwendenden Verbindungen eine deutlich geringere Eigenfarbe aufweisen und damit den Farbton von Färbungen praktisch nicht beeinflussen. Während z.B. das 2,2′-Dihydroxy-4,4′-dimethoxyphenon im Färbebad zu etwa 75 % auszieht, erreichen die erfindungsgemäß zu verwendenden Verbindungen Aufziehgrade in der Größenordnung von 85 bis 100 %. Bei den bekannten Verbindungen liegen die Sublimationsverluste (30 sec., 190°C) bei 20 bis 25 %, bezogen auf die aufgezogene Substanz, bei den erfindungsgemäß zu verwendenden Verbindungen unterhalb 10 %.It should be emphasized as a particular advantage over known benzophenone derivatives according to DE-B-11 56 760 that the compounds to be used according to the invention have a significantly lower intrinsic color and thus have practically no influence on the color tone of dyeings. For example, while 2,2'-dihydroxy-4,4'-dimethoxyphenone in the dyebath drains to about 75%, the compounds to be used according to the invention reach degrees of absorption in the order of 85 to 100%. In the known compounds, the sublimation losses (30 sec., 190 ° C.) are 20 to 25%, based on the absorbed substance, in the compounds to be used according to the invention below 10%.
Die in den Anwendungsbeispielen angegebenen Teile sind Gewichtsteile.The parts given in the application examples are parts by weight.
100 Teile eines Polyestergarns werden in einem Färbebad, das 1500 Teile Wasser, 0,6 Teile einer Mischung der feinverteilten Farbstoffe
1,8 Teile eines durch Anlagerung von 50 Mol Ethylenoxid an 1 Mol Spermölalkohol und anschließendes Sulfonieren erhaltenen Produktes als Färbehilfsmittel und 1,5 Teile der feinverteilten Benzophenonverbindung der Formel
enthält, behandelt.100 parts of a polyester yarn are in a dye bath containing 1500 parts of water, 0.6 parts of a mixture of the finely divided dyes
1.8 parts of a product obtained by adding 50 moles of ethylene oxide to 1 mole of sperm oil alcohol and subsequent sulfonation as a dyeing aid and 1.5 parts of the finely divided benzophenone compound of the formula
contains, treats.
Man beginnt bei 60°C, erhöht die Temperatur in 20 Minuten auf 130°C und färbt noch weitere 90 Minuten bei dieser Temperatur in einem HT-Färbeapparat.The process is started at 60 ° C., the temperature is raised to 130 ° C. in 20 minutes and dyeing is carried out for a further 90 minutes at this temperature in an HT dyeing machine.
Es wird eine Braunfärbung erhalten, die bei einer Belichtung im Xenotest unter feucht-heißen Bedingungen (z.B. Temperatur 75°C, relative Luftfeuchtigkeit 80 %) deutlich lichtechter ist als eine gleiche Färbung ohne den Zusatz der Benzophenonverbindung.A brown coloration is obtained which, when exposed to xenotest under hot and humid conditions (e.g. temperature 75 ° C, relative air humidity 80%), is significantly more lightfast than the same coloration without the addition of the benzophenone compound.
100 Teile eines Gewirkes aus Polyester werden in einem Färbebad, das 2500 Teile Wasser, 1,2 Teile einer Mischung der feinverteilten Farbstoffe
5 Teile eines Carriers auf Basis Salicylsäuremethylester und 2 Teile der feinverteilten Benzophenonverbindung der Formel
enthält, behandelt.100 parts of a knitted fabric made of polyester are in a dyebath, the 2500 parts of water, 1.2 parts of a mixture of the finely divided dyes
5 parts of a carrier based on salicylic acid methyl ester and 2 parts of the finely divided benzophenone compound of the formula
contains, treats.
Man färbt während 90 Minuten bei Siedetemperatur und erhält eine rotbraune Färbung, die bei einem Belichtungstest im Fadeometer deutlich bessere Ergebnisse liefert als eine gleiche Färbung ohne den Zusatz der Benzophenonverbindung.The dyeing is carried out for 90 minutes at the boiling point and a reddish-brown coloration is obtained which, in an exposure test in a fadeometer, gives significantly better results than a similar coloration without the addition of the benzophenone compound.
Ein Polyestergewebe wird auf einem Dreiwalzenfoulard mit einer Färbeflotte getränkt, die in 1000 Teilen 25 Teile einer Mischung der feinverteilten Farbstoffe
20 Teile einer 20 %igen wäßrigen Lösung eines Copolymeren aus Acrylsäure und Acrylamid, 25 Teile der feinverteilten Benzophenonverbindung
und 930 Teile Wasser enthält.20 parts of a 20% aqueous solution of a copolymer of acrylic acid and acrylamide, 25 parts of the finely divided benzophenone compound
and contains 930 parts of water.
Nach dem Imprägnieren unter 60 % Flottenaufnahme wird das Gewebe bei 120°C zwischengetrocknet und während 60 Sekunden bei 200°C thermosoliert.After impregnation with 60% liquor absorption, the fabric is dried at 120 ° C and thermosolated at 200 ° C for 60 seconds.
Man erhält eine Graufärbung, die in der Lichtechtheit deutlich besser ist als eine gleiche Färbung ohne den Zusatz der Benzophenonverbindung.A gray coloration is obtained which is significantly better in light fastness than a same coloration without the addition of the benzophenone compound.
Man führt eine Färbung aus analog Beispiel 2 under Verwendung der Benzophenonverbindung der Formel
durch.A dyeing is carried out analogously to Example 2 using the benzophenone compound of the formula
by.
Man erhält eine rotbraune Färbung, die bei einem Belichtungstest im Fadeometer deutlich bessere Ergebnisse liefert als eine gleiche Färbung ohne den Zusatz der Benzophenonverbindung.A reddish-brown coloration is obtained which, in an exposure test in the fadeometer, gives significantly better results than a same coloration without the addition of the benzophenone compound.
Claims (6)
- A process for dyeing textile polyester material with disperse dyes in the presence of benzophenone derivatives to improve the light fastness, which comprises adding to the dyebath one or more benzophenone derivatives of the formula I
R¹ is hydrogen, alkyl of from 1 to 4 carbon atoms, cyano, fluorine, chlorine, bromine or trifluoromethyl,R² is hydrogen or alkyl of from 1 to 6 carbon atoms,m is 1 or 2,n is 2, 3 or 4,p is 2, 3 or 4 andX is a polyvalent organic radical derived from a polybasic aliphatic, cycloaliphatic, aromatic or heterocyclic acid. - A process for dyeing textile polyester material as claimed in claim 1, wherein the benzophenone derivative added to the dyebath has the formula II
p is 2, 3 or 4 andX is a polyvalent organic radical derived from a polybasic aliphatic, cycloaliphatic, aromatic or heterocyclic acid. - The use of benzophenone derivatives of the formula I defined in claim 1 in the dyeing of textile polyester material with disperse dyes for improving the light fastness in an amount of from 0.1 to 10% on weight of fiber.
- The use of benzophenone derivatives of the formula II defined in claim 2 for dyeing textile material with disperse dyes as claimed in claim 3.
- A benzophenone derivative of the formulae III to V
a benzophenone derivative of the formula IV
or a benzophenone derivative of the formula V
- A process for preparing a compound of the formula III or IV or V as claimed in claim 5, which comprises reacting an alcohol of the formula VI
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3732980 | 1987-09-30 | ||
| DE19873732980 DE3732980A1 (en) | 1987-09-30 | 1987-09-30 | METHOD FOR IMPROVING THE LIGHT-FASTNESS OF POLYESTER TESTS USING BENZOPHENONETHER ESTERS AND NEW BENZOPHENONETHER ESTERS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0309909A1 EP0309909A1 (en) | 1989-04-05 |
| EP0309909B1 true EP0309909B1 (en) | 1992-11-25 |
Family
ID=6337251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88115564A Expired - Lifetime EP0309909B1 (en) | 1987-09-30 | 1988-09-22 | Process for improvement of colour fastness of polyester dyeings by using benzophenone ether esters and the new benzophenone ether esters |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4911732A (en) |
| EP (1) | EP0309909B1 (en) |
| JP (1) | JPH01128956A (en) |
| DE (2) | DE3732980A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3930516A1 (en) * | 1989-09-13 | 1991-03-21 | Riedel De Haen Ag | BENZOPHENONETHER ESTER, METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE FOR IMPROVING THE LIGHT STABILITY OF POLYESTER TESTS |
| DE4007765A1 (en) * | 1990-03-12 | 1991-09-19 | Basf Ag | USE OF BENZOPHENONE DERIVATIVES AS LIGHT PROTECTION AGENTS FOR AROMATIC POLYCARBONATES AND AROMATIC POLYESTER CARBONATES |
| US5773182A (en) | 1993-08-05 | 1998-06-30 | Kimberly-Clark Worldwide, Inc. | Method of light stabilizing a colorant |
| US6017471A (en) | 1993-08-05 | 2000-01-25 | Kimberly-Clark Worldwide, Inc. | Colorants and colorant modifiers |
| 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 |
| US5645964A (en) | 1993-08-05 | 1997-07-08 | Kimberly-Clark Corporation | Digital information recording media and method of using same |
| US5721287A (en) | 1993-08-05 | 1998-02-24 | Kimberly-Clark Worldwide, Inc. | Method of mutating a colorant by irradiation |
| US5865471A (en) | 1993-08-05 | 1999-02-02 | Kimberly-Clark Worldwide, Inc. | Photo-erasable data processing forms |
| US6017661A (en) | 1994-11-09 | 2000-01-25 | Kimberly-Clark Corporation | Temporary marking using photoerasable colorants |
| 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 |
| US6576797B1 (en) * | 1994-03-31 | 2003-06-10 | Ciba Specialty Chemicals Corporation | Thioether substituted hydroxybenzophenones and stabilized compositions |
| 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 |
| CA2219450A1 (en) | 1995-06-05 | 1996-12-12 | Ronald Sinclair Nohr | Novel pre-dyes |
| US5786132A (en) | 1995-06-05 | 1998-07-28 | Kimberly-Clark Corporation | Pre-dyes, mutable dye compositions, and methods of developing a color |
| ES2161357T3 (en) | 1995-06-28 | 2001-12-01 | Kimberly Clark Co | STABILIZING COLORING COMPOSITION. |
| SK102397A3 (en) | 1995-11-28 | 1998-02-04 | Kimberly Clark Co | Colorant stabilizers |
| US6099628A (en) | 1996-03-29 | 2000-08-08 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US5782963A (en) | 1996-03-29 | 1998-07-21 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US5855655A (en) | 1996-03-29 | 1999-01-05 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US5891229A (en) | 1996-03-29 | 1999-04-06 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US5763674A (en) * | 1996-12-09 | 1998-06-09 | General Electric Company | High molecular weight dibenzoylresorcinol UV absorbers |
| 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 |
| KR20010022593A (en) | 1998-06-03 | 2001-03-26 | 로날드 디. 맥크레이 | Novel Photoinitiators and Applications Therefor |
| US6228157B1 (en) | 1998-07-20 | 2001-05-08 | Ronald S. Nohr | Ink jet ink compositions |
| JP2003533548A (en) | 1998-09-28 | 2003-11-11 | 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 | Chelates containing quinoid groups as photopolymerization initiators |
| DE60002294T2 (en) | 1999-01-19 | 2003-10-30 | Kimberly Clark Co | DYES, COLOR STABILIZERS, INK COMPOSITIONS AND METHOD FOR THE PRODUCTION THEREOF |
| 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 |
| US6537670B1 (en) | 2000-11-03 | 2003-03-25 | Cytec Technology Corp. | Bis(alkyleneoxybenzophenone) ultraviolet light absorbers |
| KR100517501B1 (en) * | 2003-03-21 | 2005-09-28 | 삼성전자주식회사 | Lightfast colorant and lightfast ink composition comprising the same |
| KR100532102B1 (en) * | 2003-05-27 | 2005-11-29 | 삼성전자주식회사 | Benzophenone compounds and ink composition containing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60126246A (en) * | 1983-12-13 | 1985-07-05 | Mitsubishi Petrochem Co Ltd | Methylene-dibasic acid derivative |
| EP0254987A2 (en) * | 1986-07-26 | 1988-02-03 | BASF Aktiengesellschaft | Benzophenone ether-esters and process for improving the light fastness of polyester colourings by the use of benzophenone ether-esters |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2920978A (en) * | 1958-05-26 | 1960-01-12 | Gen Aniline & Film Corp | Stabilized polyester fibres |
| US3676471A (en) * | 1967-12-21 | 1972-07-11 | Advance Prod Gmbh | 4-(betahydroxyethoxy-2-hydroxy-benzophenones) and esters thereof |
| DE1643307C3 (en) * | 1967-12-21 | 1974-01-17 | Ciba-Geigy Marienberg Gmbh, 6141 Lautern | 2-Hydroxy-4- (acyloxyethoxy) benzophenones and process for their preparation |
| US3644485A (en) * | 1969-04-14 | 1972-02-22 | Eastman Kodak Co | 2-hydroxy-4-(2 - hydroxyethoxy) benzophenone esters and their use as stabilizers |
| GB1553781A (en) * | 1976-08-05 | 1979-10-10 | Exxon Research Engineering Co | Bisphenol derivatives and their use as stabilizers |
| DE3438190A1 (en) * | 1984-10-18 | 1986-04-24 | Riedel-De Haen Ag, 3016 Seelze | UV LIGHT STABILIZER BASED ON BENZOPHENONE |
-
1987
- 1987-09-30 DE DE19873732980 patent/DE3732980A1/en not_active Withdrawn
-
1988
- 1988-09-22 DE DE8888115564T patent/DE3876204D1/en not_active Expired - Lifetime
- 1988-09-22 EP EP88115564A patent/EP0309909B1/en not_active Expired - Lifetime
- 1988-09-27 JP JP63239876A patent/JPH01128956A/en active Pending
- 1988-09-28 US US07/250,118 patent/US4911732A/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60126246A (en) * | 1983-12-13 | 1985-07-05 | Mitsubishi Petrochem Co Ltd | Methylene-dibasic acid derivative |
| EP0254987A2 (en) * | 1986-07-26 | 1988-02-03 | BASF Aktiengesellschaft | Benzophenone ether-esters and process for improving the light fastness of polyester colourings by the use of benzophenone ether-esters |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0309909A1 (en) | 1989-04-05 |
| DE3732980A1 (en) | 1989-04-13 |
| JPH01128956A (en) | 1989-05-22 |
| US4911732A (en) | 1990-03-27 |
| DE3876204D1 (en) | 1993-01-07 |
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