EP0185611A1 - Procédé de stabilisation photochimique de matières fibreuses synthétiques contenant des fibres en polyamide - Google Patents

Procédé de stabilisation photochimique de matières fibreuses synthétiques contenant des fibres en polyamide Download PDF

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Publication number
EP0185611A1
EP0185611A1 EP85810513A EP85810513A EP0185611A1 EP 0185611 A1 EP0185611 A1 EP 0185611A1 EP 85810513 A EP85810513 A EP 85810513A EP 85810513 A EP85810513 A EP 85810513A EP 0185611 A1 EP0185611 A1 EP 0185611A1
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EP
European Patent Office
Prior art keywords
dye
copper complex
water
copper
dyes
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Granted
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EP85810513A
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German (de)
English (en)
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EP0185611B1 (fr
Inventor
Gerhard Dr. Reinert
Hans Ulrich Schütz
Gerhard Dr. Back
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Novartis AG
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Ciba Geigy AG
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Publication of EP0185611A1 publication Critical patent/EP0185611A1/fr
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • 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
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/241—Polyamides; Polyurethanes using acid dyes
    • 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
    • D06P1/6423—Compounds containing azide or oxime groups
    • 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
    • Y10S8/924—Polyamide fiber

Definitions

  • the present invention relates to a method for the photochemical stabilization of synthetic polyamide fiber materials with water-soluble copper complex dyes.
  • Dyed synthetic polyamide fiber material is damaged when exposed to light, especially when exposed to heat; therefore synthetic polyamide fibers are used in some areas of application, e.g. viewed as car upholstery or sail fabrics, as problem fibers.
  • the aim is to improve the photochemical stability of synthetic polyamide fiber materials.
  • copper salts e.g. Copper sulfate
  • inorganic or organic copper salts often have the disadvantage that they are insufficiently and unevenly applied to the polyamide fiber and are therefore used in high concentrations and are often used only in an aftertreatment process can be.
  • the object underlying the present invention was to find a process for the photochemical stabilization of synthetic polyamide fiber materials which does not have the disadvantages described above and which meets today's requirements.
  • the present invention thus relates to a process for the photochemical stabilization of fiber materials made of synthetic polyamides, which is characterized in that the fiber material is treated with at least one water-soluble copper complex dye or with a mixture of copper complex compounds, at least one component being a water-soluble copper complex dye.
  • photochemical stabilization here refers to both the light fastness and the maintenance of the mechanical properties of the undyed or dyed polyamide fiber, i.e. Photochemical stabilization against visible and UV light.
  • a particularly preferred embodiment of the process according to the invention is characterized in that copper complexes of azo or azomethine dyes of the formula which contain water-solubilizing groups where D is a residue of the benzene or naphthalene series, X is a nitrogen atom or the CH group, Y is the HO, GH 3 O or HOOC group and Y 'is the HO or an amino group, and wherein K, is for in the case that X is a nitrogen atom, the residue of a coupling component of the benzene, naphthalene or heterocyclic series or the residue of a ketomethylene compound, or, in the case that X is the CH group, K is the residue of an o-hydroxyaldehyde means.
  • water-solubilizing groups include e.g. Sulfone, sulfonamide, N-mono- or N, N-dialkylsulfonamide groups, carboxyl groups or in particular sulfonic acid groups.
  • Suitable sulfone groups are alkyl sulfone and in particular C 1-4 alkyl sulfone groups.
  • N-mono- or N, N-dialkylsulfonamide group is one having one or two C 1-4 -alkyl radicals.
  • copper complex dyes with one to two water-solubilizing groups are used in the process according to the invention.
  • An interesting embodiment of the method according to the invention is characterized in that a copper complex dye of the formula is used in which A is an optionally substituted carboxyphenyl or sulfophenyl radical, R is hydrogen or C l-4 alkyl, X is a nitrogen atom or the CH group and K, in the event that X is a nitrogen atom, the radical of a coupling component of the benzene , Naphthalene, pyrazolone, aminopyrazole, acetoacetanilide, 2,4-dioxy- 'quinoline, pyridone or pyridine series, or, if X is the CH group, is the residue of an o-hydroxybenzaldehyde, and the ring B may optionally be further substituted, for example by chlorine or nitro.
  • azo dyes of the formula (1) have been described in the literature.
  • the azo dyes of the formula (1) are prepared in a manner known per se by using an amine of the formula diazotized and on a coupling component of the formula couples.
  • the diazotization of the diazo component of formula (3) is generally carried out by the action of nitrous acid in aqueous-mineral acid solution at low temperature, and the coupling to the coupling component of formula (4) at acid, neutral or alkaline p H values.
  • Suitable amines of the formula (3) are: 2-amino-l-hydroxybenzene, 2-amino-l-methoxybenzene, anthranilic acid, 4- or 5-sulfonamido-anthranilic acid, 3- or 5-chloroanthranilic acid, 4-chloro and 4,6-dichloro-2-amino-1-hydroxybenzene, 4- or 5- or 6-nitro-2-amino-1-hydroxybenzene, 4-chloro and 4-methyl and 4-acetylamino-6-nitro -2-amino-l-hydroxybenzene, 6-acetylamino and 6-chloro-4-nitro-2-amino-l-hydroxybenzene, 4-cyano-2-amino-1-hydroxybenzene, 4-methoxy-2-amino- 1-hydroxybenzene, 2-amino-l-hydroxybenzene-5-methyl- and -5-benzylsulfone, 2-amino-l-hydroxybenzene-4-methyl-, -e
  • the above-mentioned aromatic amines of the formula (3) are condensed with o-hydroxybenzaldehydes or o-hydroxynaphthaldehydes in a known manner.
  • a process variant for the preparation of the copper complex of an azomethine dye of the formula (1) is characterized in that the copper complex can also be prepared with a mixture of the amine of the formula (3) and an o-hydroxyaldehyde instead of with the azomethine of the formula (1).
  • the metal complexes are prepared by methods known per se in an aqueous or organic medium. Copper salts, such as e.g. Copper sulfate and copper nitrate. The freshly precipitated hydroxides can also be used. The reaction is carried out in the weakly acidic to alkaline range. One works, for example, with copper sulfate in an aqueous medium in the presence of sodium acetate or ammonia or with copper nitrate in the presence of soda in an organic medium such as methyl cellosolve.
  • reaction is carried out with heating, e.g. slightly below the boiling point of the solvent used.
  • a further embodiment of the method according to the invention is characterized in that a mixture containing at least one water-soluble copper complex dye and a fiber-affine, water-soluble copper complex of an organic compound which is not a dye, i.e. which has no chromophoric groups, is used.
  • the copper complex dyes mentioned in the above mixture are suitable as copper complex dyes.
  • Copper complexes of bisazomethines, acylhydrazones, semicarbazones and thiosemicarbazones of aromatic aldehydes or ketones which are preferably used as the non-coloring component are preferably sulfonic acid groups. Such compounds are readily water-soluble and also have an excellent affinity for polyamide fiber. Such complexes are therefore effective even in small amounts. In addition, it has been shown that they not only increase the light fastness of the dyed polyamide material, but also generally protect the polyamide fiber against photochemical degradation and thus largely maintain its mechanical properties, such as tear resistance and elasticity.
  • Bisazomethines of aromatic aldehydes and ketones are 1 "er Schiff bases of aliphatic, .cycloaliphatic or aro understood diamines, wherein the aldehydes and ketones have an OH group in the o-position to the formyl or acyl radical.
  • the bond with the copper atom takes place via these two OH groups and the two nitrogen atoms in the bisazomethine part. Accordingly, these are tidentate ligands.
  • the ligands contain one or more sulfo groups which are located in the aldehyde or ketone part and / or in the bisazomethine bridge.
  • R 2 , R 3 or R 5 denotes an optionally substituted alkyl radical
  • the cyclohexyl radical can also be used, which can also be substituted, for example by C 1 to C 4 alkyl or C 1 to C 4 alkoxy.
  • R 2 , R 3 or R 5 is an optionally substituted aryl radical
  • a phenyl or naphthyl radical is particularly suitable, which can be substituted by C 1 -C 4 alkyl, such as methyl, ethyl, propyl, iso-isopropyl, butyl , Isobutyl, sec.
  • C 1 -C 4 alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and ter-butoxy, halogen, such as fluorine, chlorine and bromine, C 2 -C S alkanoylamino, such as acetylamino, propionylamino and butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.
  • C 1 -C 4 alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and ter-butoxy
  • halogen such as fluorine, chlorine and bromine
  • C 2 -C S alkanoylamino such as acetylamino, propionylamino and butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.
  • Z is an alkylene radical, it is primarily a C 2 to C 4 alkylene radical, in particular a —CH 2 —CH 2 bridge.
  • a C2 to C 8 alkylene chain which is interrupted by oxygen or, in particular, nitrogen is also suitable, in particular the - (CH 2 ) 3 -NH- (CH 2 ) 3 bridge.
  • Z is a cycloalkylene radical, this is preferably cyclohexylene and can have one or two methyl groups.
  • Z is an arylene radical, it is primarily a phenylene radical, in particular an o-phenylene radical. This can also be substituted by C 1 to C 4 alkyl or C 1 to C 4 alkoxy.
  • Suitable substituents for the benzene rings M and N are: C 1 to C 4 alkyl, C 1 to C 4 alkoxy, halogen, such as fluorine, chlorine or bromine, and also the cyano or nitro groups.
  • the sulfo groups which are located in the benzene rings M and / or N and / or in the bridging member Z, if this denotes an arylene radical, are preferably in the form of an alkali metal salt, in particular a sodium salt or also an amine salt.
  • the copper complexes of the formula (5) are used in the present process, in which R 2 is hydrogen, Z is the ethylene or cyclohexylene bridge and n is 2, the two sulfo groups being in the benzene rings M and N, and especially here the complexes in which the sulfo groups are each arranged in p-position to the oxygen.
  • the Z is preferably -CH 2 -CH 2 -.
  • R 4 is an alkyl radical, this can be branched or unbranched and has a chain length of preferably 1 to 8, in particular 1 to 4, carbon atoms.
  • Suitable substituents are halogen, such as fluorine, chlorine or bromine, C 1 to C 4 alkoxy, such as methoxy or ethoxy, further phenyl or carboxyl, C 1 to C 4 alkylcarbonyl, such as acetyl or hydroxy, mono- or dialkylamino.
  • R 4 is an optionally substituted aryl radical, a phenyl or naphthyl radical, which can be substituted by C 1-4 alkyl, such as methyl, ethyl ', propyl, isopropyl, butyl, isobutyl, sec-butyl, is particularly suitable and tert-butyl, C 1-4 alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy, halogen, such as fluorine, chlorine and bromine, C 2- 5 -alkanoylamino, such as acetylamino, propionylamino and butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.
  • C 1-4 alkyl such as methyl, ethyl ', propyl, isopropyl, butyl, isobutyl
  • the complexes of formula (6) are also preferred in neutral form, i.e. used as alkali salt, in particular sodium salt or amine salt.
  • Complexes of the formula (6) are preferably used in which R 3 is hydrogen and R 4 is hydrogen, methyl or in particular the phenyl radical, especially the complexes in which the sulfo group is in turn in the p-position to the oxygen.
  • the ligands of which are derived from sulfosalicylaldehyde or the corresponding phenyl ketones, e.g. also those in which instead of mononuclear, multinuclear aromatic aldehydes and ketones, such as the 2-hydroxy-1-naphthaldehyde sulfonic acid can be used to build up the ligand. It is also pointed out that the fourth coordination point of the metal atom in the complexes of formulas (6) and (7) is occupied by water as the neutral ligand.
  • the copper complexes of the formulas (5) and (6) are preferably used in the present process for photochemical stabilization.
  • the ratio of copper complex dye: fiber-affine, water-soluble copper complex is one organic compound which itself has no dye character, preferably 99: 1 to 10:90
  • the mixing ratio depends on the number of copper complex dyes used and the desired color depth of the dyeings.
  • the copper complexes of the formulas (5), (6) and (7) given and their alkali metal salts, such as potassium and lithium salts, and in particular their sodium salts, are obtained by known methods.
  • the metal complexes of the formula (5) are accessible, for example, in two different ways. So you can first metallize the aldehyde or the ketone and then react with the corresponding diamine to the finished complex of formula (5). However, one can also first synthesize the ligand from aldehyde or ketone and diamine and then carry out the metallization.
  • the acylhydrazones, the ligands of the complexes (6) are obtained, for example, by reacting the aldehyde or ketone with the corresponding monoacylhydrazine and subsequent metallization.
  • the complexes of the formula (7) can also be prepared quite analogously. At least one of the starting products for the preparation of the compounds of the formula (5), (6) and (7) must contain a sulfonic acid group.
  • the copper complexes of the formulas (5) to (7) are preferably used, in particular the copper complexes of the formulas (5) and (6).
  • the copper complexes of the formulas are very particularly preferred within the group of metal complexes with bisazomethine ligand and within the group of metal complexes with acylhydrazone ligand, the copper complexes of the formulas
  • Another preferred embodiment of the process according to the invention is characterized in that at least one copper complex dye is used together with acid dyes, in particular in the same dye bath.
  • acid dyes come e.g. metal-free mono- or polyazo dyes, 1: 2-chromium or 1: 2-cobalt complex azo dyes, anthraquinone, dioxazine, phthalocyanine, nitroaryl or stilbene dyes which contain at least one acid group, such as e.g. Carboxyl or preferably have a sulfonic acid group.
  • An interesting embodiment of the method according to the invention is characterized in that a mixture of at least one red-dyeing dye, at least one yellow- or orange-dyeing dye and at least one blue-dyeing dye is used for trichromatic dyeing, the mixture containing at least one copper complex dye.
  • the polyamide fiber material used in the process according to the invention is that of synthetic polyamides, such as Polyamide-6, polyamide-66 or polyamide-12 used.
  • the polyamide fiber material can be in a wide variety of processing forms, e.g. Fiber, yarn, woven or knitted fabric, in particular textile fiber material.
  • the dyes containing sulfo groups used in the process according to the invention are present either in the form of their free sulfonic acid or preferably as their salts.
  • suitable salts are the alkali metal, alkaline earth metal or ammonium salts or the salts of an organic amine.
  • suitable salts include the sodium, lithium, potassium or ammonium salts or the salt of triethanolamine.
  • the dyes used in the process according to the invention generally contain further additives such as Cooking salt or dextrin.
  • the process according to the invention for dyeing synthetic polyamide fiber materials can be applied to the customary dyeing processes.
  • the dyeing liquors can contain further additives, for example wetting agents, anti-foaming agents, leveling agents, salts, acids or buffer substances.
  • synthetic polyamide fiber materials are stabilized photochemically, i.e. protected against exposure, especially hot exposure, with visible and UV light
  • a particularly noteworthy advantage of the method according to the invention is that, in comparison to previously known methods for the photochemical stabilization of synthetic polyamide fiber materials, no pretreatment or tiling treatment of the fiber material is required.
  • mixtures of copper complex dyes used with the process according to the invention with the copper complex compounds which have no dye character show the advantage that independently. the desired color depth of the dyeings contained with the copper complex dyes, a constant copper content of the fiber can be set, i.e. the protective effect is not subject to nuance-related fluctuations.
  • parts represent parts by weight.
  • the temperatures are degrees Celsius.
  • the relationship between parts by weight and parts by volume is the same as that between grams and cubic centimeters.
  • the tensile strength and elongation values of untreated and unexposed polyamide fiber material are set equal to 100%.
  • the yarn is treated at 50 ° for 5 minutes in the prepared liquors, then the baths at 2 ° / minute heated to 95 ° C.
  • 2% acetic acid (80%) is added after 15 minutes at 95 ° C. and treated for a further 30 minutes and then cooled to 70 °.
  • the treated yarn is rinsed warm and cold, centrifuged and dried at 80 ° in a drying cabinet.
  • a portion of the yarn of the individual treatments is wound up on cardboard and exposed in a fade-ometer (manufacturer: Atlas Electric Devices Co., Chicago) for 250 hours and a "black panel temperature" of 83 °.
  • the dyed yarn is dyed and tested as described in Example 1, but only 200 hours were exposed in the fadeometer at a black panel temperature of 83 °.
  • the treatment bath (4) with a dye combination of the dyes of the formulas (103), (104) and (105) has practically no protective effect on the fiber structure; as soon as on the other hand, one or more Cu complex dyes are on the fiber [treatment baths (2) and (3)], very good fiber protection occurs.
  • Example 3 As described in Example 1, 4 skeins of 10 g each are dyed from polyamide 66 fiber material and finished.
  • Example 2 As described in Example 1, the 4 dyed polyamide yarns are exposed hot for 200 hours and then tested for tear strength and elongation. The results can be found in the table below.
  • Example 4 As described in Example 1, six combinations of two are dyed with the three dyes noted there, as indicated below.
  • the dyed polyamide yarn is exposed to heat for 200 hours (see Example 1) and then tested for tensile strength and elongation in accordance with SNV 97.461.
  • Example 5 The experiments described in Example 1, which lead to bright yellow, red and blue colors (treatment baths 2, 4 and 6), as well as the blind treatment (treatment bath 1), with the addition of 0.075% (based on the Product weight) of the compound of the formula repeated and then subjected to the hot exposure test in the fade-ometer and the exposure test in the Xenotest apparatus as described in Example 1.
  • the dyeings obtained with the addition of the compound of the formula (108) are identified in the following table as treatment bath 1A, 2A, 4A and 6A and are compared with the results of Example 1.
  • Table 4 shows that the photochemical stability of light dyeings with copper complex dyes on synthetic polyamide materials [treatment baths (2), (4) and (6)] can be further improved by adding colorless fiber-affine copper complex compounds [treatment baths (2A), (4A ) and (6A).
  • Example 6 Dyings on nylon filament yarn are carried out using 0.05% dye of the formula (100) as described in Example 1, but at 95 ° C. and in each case using 0.05% of each of the copper complex compounds of the formulas (108) (109) and (110). And with the addition of 2% acetic acid 80%.
  • the material is exposed according to DIN 75202 (Fakra) and xenon (SN-ISO 105 B 0 2) and tested for its tensile strength and elongation. The following results are obtained, the tensile strength values and elongation values of unexposed and untreated polyamide fiber material being set equal to 100%.
  • Example 7 10 g of nylon filament yarn (glossy) are dyed in a laboratory dyeing machine with open dye baths at a liquor ratio of 1:30 in liquors which contain 2% (by weight of the product) ammonium sulfate and 0.1% of the following dyes of the formulas (111) - (118) included.
  • the yarn is passed into the dyebath at 40 ° C., treated for 5 minutes and the temperature is increased to 95 ° C. At this temperature you dye for 45 minutes. Then it is cooled to about 60 ° C. and the dyeings are rinsed with cold water and dried at 105 ° C. in a drying cabinet.
  • the yarn is then wound on cardboard and exposed in a fade ometer at a temperature of 83 ° C.
  • the unexposed and exposed yarn is finally tested for tensile strength and elongation in accordance with SNV 97.461.
  • the yarn dyeings are wrapped on cardboard, exposed for 150 hours in accordance with DIN 75.202 (draft) and checked for tensile strength and elongation in accordance with SNV 97.461. The results are shown in Table 7.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
EP85810513A 1984-12-21 1985-11-04 Procédé de stabilisation photochimique de matières fibreuses synthétiques contenant des fibres en polyamide Expired EP0185611B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH6099/84 1984-12-21
CH609984 1984-12-21

Publications (2)

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EP0185611A1 true EP0185611A1 (fr) 1986-06-25
EP0185611B1 EP0185611B1 (fr) 1988-09-21

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US (1) US4704133A (fr)
EP (1) EP0185611B1 (fr)
JP (1) JPS61152881A (fr)
BR (1) BR8505622A (fr)
DE (1) DE3565136D1 (fr)

Cited By (1)

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EP0255481A1 (fr) * 1986-07-29 1988-02-03 Ciba-Geigy Ag Procédé de stabilisation photochimique de matière fibreuse en polyamide et ses mélanges avec d'autres fibres

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DE3565136D1 (en) 1988-10-27
JPS61152881A (ja) 1986-07-11
BR8505622A (pt) 1986-08-12
EP0185611B1 (fr) 1988-09-21
US4704133A (en) 1987-11-03

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