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    • 专利摘要:
    DISPERSED DYE MIXTURES, THEIR PREPARATION AND USE The present invention relates to dye mixtures containing at least one dye of formula (I) at least one dye of formula (II) and / or at least one dye of formula (III) in which RAIA -RA 15A, n, o, X, and DAIA-DA 3A are as defined in claim 1. These dye mixtures are useful for coloring or printing of particular hydrophobic materials.
    公开号:BR112013017510B1
    申请号:R112013017510-9
    申请日:2012-01-07
    公开日:2020-10-20
    发明作者:Markus Arnold；Adrian Murgatroyd；Clemens Grund；Gunter Görlitz；Timo Liebig
    申请人:Dystar Colours Distribution Gmbh；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the field of dispersed dyes for coloring hydrophobic textile materials.
    [0002] Azo dispersed dyes in which chromophore is attached to the 2-oxo alkyl keto groups are known and described, for example, in WO 2009/037215 A2, WO 2008/090042 A1, WO 2008/049758 A2, W02005 / 056690 A1, as well as GB 909843 A and DE 26 12 742 A1. None of these documents describe dye mixtures. WO 95/20014 A1 shows a coloring process in which coloring mixtures can be used. Azo dyes with an -SO2F group are related, and they can be used as dye mixtures or in dye mixtures without an -SO2F group. Possible candidates mentioned include azo dyes in which the chromophore is attached to 2-oxo alkyl keto groups.
    [0003] It has now been found that the mixtures defined below of dispersed azo dyes containing 2-oxo alkyl keto- with still selected dispersed azo dyes are distinctly superior to individual dyes in relation to contact and wash fixations and dye sublimation fixation on polyester materials - elastane and polyester.
    [0004] The present invention provides dye mixtures containing at least one dye of Formula (I)
    where R1 is hydrogen, (C1-Cθ) alkyl, (C1-C4) alkoxy, hydroxyl, halogen, -NHCHO, -NHCO (CI-C6) alkyl, -NHCO-aryl, -NHSO2 (CI-C6) alkyl or -NHSθ2-aryl, R2is hydrogen, halogen, (C1-C4) alkoxy, (C1-C4) alkyl or aryloxy, R3 is hydrogen, (Ci-Cβ) alkyl, (Ci-Ce) substituted alkyl, (C3- C4) alkenyl or (C3-C4) substituted alkenyl, especially benzyl, butyl, 2-cyano ethyl or a portion of Formula -CHR4-CnH2n-CHR6-COO-CHR7-CO-R5, OR R2 and R3 combine to form the - C * H (CH3) CH2C (CH3) 2- moiety, where 0 marked carbon atom * is attached to the phenyl nucleus, R4 is hydrogen, (Ci-Ce) alkyl or phenyl, R5 is (Ci-C6) alkyl or (Ci-C6) substituted alkyl, R6 is hydrogen or (Ci-Ce) alkyl, R7 is hydrogen, (Ci-Ce) alkyl or phenyl, and n is 0, 1,2 or 3, and at least one dye of Formula (II)
    where R8 is hydrogen, (C1-C6) alkyl, (C1-C4) -alkoxy, hydroxyl, halogen, -NHCHO, -NHCO (Ci-Cθ) -alkyl, -NHCO-aryl, -NHSO2 (CI-C6) alkyl or -NHSO2-aryl, R9 is hydrogen, halogen, (C1-C4) alkoxy, (C1-C4) alkyl or aryloxy, R10 is hydrogen, (C1-C6) alkyl, (C1-C6) substituted alkyl, (C3 -C4) alkenyl or (C3-C4) substituted alkenyl, especially a portion of Formula -CHR ,, - CmH2m- (X), - R, 21 or R9 and R10 combine to form the -C * H (CH3) CH2C ( CH3) 2-, in which the marked carbon atom * is attached to the phenyl nucleus, R11 is hydrogen, (Ci-Ce) alkyl or phenyl, R12 is hydrogen, (Ci-Ce) alkyl, (Ci-Cδ) substituted alkyl , (C3-C4) alkenyl or (C3-C4) substituted alkenyl, X is -CO-O-, -O-CO-, -O-, -NH- or -S-, 0 is 0 or 1, m is 0, 1,2 or 3, and D1 and D2 are identical or different and they each represent the residue of a diazo component, and / or at least one dye of Formula (III)
    where R13 is hydrogen, cyano, or carboxamido, R14 is methyl, ethyl or phenyl, R15 is optionally substituted (C1-C6) alkyl or optionally substituted oxygen (C2-C6) alkyl, and D3 represents the residue of a component diazo.
    [0005] Residues D1, D2 and D3 of a diazo component are more particularly the usual portions in the field of dispersed dyes and known to those skilled in the art.
    [0006] Preferably, D1, D2 and D3 each independently represent a group of Formula (IVa)
    wherein T1 and T2 are each independently hydrogen, C1-4 alkyl, C1-4 alkoxy, -SO2 (Ci-e) alkyl, -SO2-aryl, cyano, halogen, or nitro, or T1 and T2 combine to form the moiety -CONT14CO ', T14 is hydrogen or C1-6 alkyl, and T3 and T4 are each independently hydrogen, halogen, methyl, cyan, -SCN, -SO2CH3 or nitro, as long as at least one of T1, T2, T3 and T4 are not hydrogen; or represents a group of Formula (IVb):
    where T5 and T5 'are each independently hydrogen or halogen, and T6 is hydrogen, -SO2CH3, -SCN, C1-4 alkoxy, halogen or nitro, contact that at least one of T5 T5' and T6 is not hydrogen ; or represents a compound of Formula (IVc)
    where T12 is hydrogen or halogen; or represents a group of Formula (IVd)
    where T7 is nitro, -CHO, cyano, -COCH3 or a group of Formula (IVda)
    where T10 is hydrogen, halogen, nitro or cyano, or a group of Formula (IVdb)
    where T15 is (C1-6) alkyl, T8 is hydrogen, (C1-6 alkyl) or halogen, and T9 is nitro, cyano, -COCH3 or COOT11, where T11 is (C1-4) alkyl; or represents a group of Formula (IVe)
    where T7 and T8 are each as defined above; or represents a group of Formula (IVf)
    wherein T13 is phenyl or -S- (C1-4 alkyl).
    [0007] Alkyl groups can be straight or branched in the context of the present invention. C1-6 alkyl is, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, or n-hexyl. Similar considerations are applied to alkoxy groups that are methoxy or ethoxy, for example.
    [0008] Substituents on (Ci-e) alkyl groups can be monovalent hydrocarbyl radicals, or cyano, thiocyanate, nitro, hydroxyl, alkoxy, carboxyl, sulfonic acid, carboxylic ester, carboxamide or amino groups as well as halogen atoms. Monovalent hydrocarbyl radicals include alkyl, cycloalkyl, aryl or hetero cyclyl radicals.
    [0009] (C3-4) alkenyl groups are in particular allyl.
    [00010] Substituents for (C3-4) alkenyl are, for example, halogen and phenyl.
    [00011] Arila is in particular phenyl or naphthyl. Aryloxy is in particular naphthyloxy or phenyloxy. Substitutes for aryl or aryloxy are, for example, halogen, methyl, ethyl, hydroxy ethyl, methoxy, ethoxy, hydroxyl, nitro and cyano.
    [00012] -NHSO2-aryl is in particular phenyl sulfonyl amino.
    [00013] Halogen is fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.
    [00014] 0, R1 is preferably hydrogen, methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl, methoxy, ethoxy, hydroxyl, chlorine, bromine, - NHCHO, -NHCO-methyl, -NHCO -phenyl, -NHSO2-methyl or -NHSO2- phenyl. Very particularly preferred R1 radicals are hydrogen, - NHCO-methyl, methyl, and hydroxyl.
    [00015] R2 is preferably hydrogen, chlorine, bromine, methoxy, ethoxy, methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl, or phenoxy. Very particularly preferred R2 radicals are hydrogen and methoxy.
    [00016] R3 is preferably hydrogen, methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl, 2-cyano ethyl, vinyl, allyl, benzyl or a radical of Formula -CHR4-CnH2n-CHR6- COO-CHR7-CO-R5. Very particularly preferred R3 radicals are hydrogen, benzyl, 2-cyano ethyl, methyl, ethyl, n-propyl, n-butyl, and -C2H4-COO-CH2-CO-CH3.
    [00017] R4 is preferably hydrogen, methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl or phenyl. Very particularly preferred R4 radicals are hydrogen and methyl.
    [00018] R5 is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, or substituted C1-6 alkyl (C1-e), such as 2-cyano ethyl or cyano methyl. Methyl is a very particularly preferred R5 radical.
    [00019] R6 is preferably hydrogen, methyl or ethyl. Hydrogen is a very particularly preferred R6 radical.
    [00020] R7 is preferably hydrogen, methyl, ethyl or phenyl. Very particularly preferred R7 radicals are hydrogen and methyl.
    [00021] R8 is preferably hydrogen, methyl, ethyl, n-propyl, s-propyl, n-butyl, s-butyl, methoxy, ethoxy, hydroxyl, chlorine, bromine, - NHCHO, -NHCO-methyl, -NHCO-phenyl , -NHSO2-methyl or -NHSO2- phenyl. Very particularly preferred R8 radicals are hydrogen, methyl, -NHCO-methyl and hydroxyl.
    [00022] R9 is preferably hydrogen, chlorine, bromine, methoxy, ethoxy, methyl, ethyl, n-propyl, s-propyl, n-butyl, s-butyl, or phenoxy. Very particularly preferred R9 radicals are hydrogen, chlorine, methoxy and methyl.
    [00023] R10 is preferably hydrogen, methyl, ethyl, n-propyl, s-propyl, n-butyl, s-butyl, vinyl, allyl, benzyl or a radical of Formula -CHR11-CmH2m- (X) o-R12, where R11, R12, X, m and 0 are each as defined above. Very particularly preferred R10 radicals are hydrogen, methyl, ethyl, benzyl, -CxH2x-O-CH3 where x = 1 or 2, - CXH2X-COO-C2H5 where x = 1 or 2, -CxH2x-OCO-CH3 where x = 1 or 2.
    [00024] R11 is preferably hydrogen, methyl, ethyl, n-propyl, s-propyl, n-butyl, s-butyl, or phenyl. Very particularly preferred R11 radicals are hydrogen or methyl.
    [00025] R12 is preferably hydrogen, methyl, ethyl, n-propyl, s-propyl, n-butyl, s-butyl, benzyl, vinyl, allyl, 2- (N-phthalimidoyl) ethyl, cyano methyl, 2-cyano ethyl or radicals of Formula -CqH2q-Y-CrH2r- (Z) o-R13, where q is 1, 2, 3 or 4, r is 1, 2, 3 or 4, o is 0 or 1, Y is -CO -, -COO- or -OCO-, Z is -COO- or -OCO- and R13 is C1-6 alkyl, phenyl, halogen, cyano, or hetero-cyclyl, especially N-phthalimidoyl. Very particularly preferred R12 radicals are methyl, ethyl, 2- (N-phthalimidoyl) ethyl, cyano methyl, 2-cyano ethyl, -CXH2X-OCO-CH3 where x = 1 or 2, -CXH2X-OCO-C2H5 where x = 1 or 2, -CXH2X- COO-CH3 where x = 1 or 2, -CXH2X-COO-C2H5 where x = 1 or 2, CxH2x-OCO-CyH2y- (N-phthalimidoyl) where x and y are each independently = 1 or 2, more preferably x = 1 and y = 2, -CxH2x-COO-CyH2y- (N-phthalimidoyl) where x and y are each independently = 1 or 2, more preferably x = 1 and y = 2, -CxH2x-COO = CyH2y-OCO-CzH2z -C6H5 where x, y and z are ca one independently = 1 or 2, more preferably x, y and z are each 1.
    [00026] X is preferably -CO-O-, -O-CO- or -O-.
    [00027] R13 is preferably cyan.
    [00028] R14 is preferably ethyl or more particularly methyl.
    [00029] R15 is preferably methyl, ethyl, n-propyl, s-propyl, n-butyl, s-butyl, 1-ethyl pentyl, methoxy methyl, methoxy ethyl, ethoxy methyl, ethoxy ethyl, -CyH2y-COO-CH2- CO-C6H5 where y = 1, 2, 3 or 4 or - CyH2y-O- (C1-4 alkyl) where y = 1,2, 3 or 4.
    [00030] The index m is preferably 0 or 1.
    [00031] The index n is preferably 0 or 1.
    [00032] The index 0 is preferably 1.
    [00033] It is particularly preferable for the dye mixtures according to the present invention to use compounds of Formula I in which R1 is hydrogen, -NHCO-methyl, methyl or hydroxyl, R2 is hydrogen or methoxy, R3 is hydrogen, benzyl, 2- cyano ethyl, methyl, ethyl, n-propyl, n-butyl or -C2H4-COO-CH2-CO-CH3, R4 is hydrogen or methyl, R5 is methyl, R6 is hydrogen, R7 is hydrogen or methyl, and n is 0 or 1.
    [00034] It is particularly preferable for the dye mixtures of the present invention to use Formula II compounds in which R8 is hydrogen, methyl, -NHCO methyl or hydroxyl, R9 is hydrogen, chlorine, methoxy or methyl, R10 is hydrogen, methyl, ethyl, benzyl, -CxH2x-O-CH3 where x = 1 or 2, R11 is hydrogen or methyl, R12 is methyl, ethyl, 2- (N-phthalimidoyl) ethyl, cyano methyl, 2- cyano ethyl, -CxH2x-OCO- CH3 where x = 1 or 2, -CxH2x-OCO-C2H5 where x = 1 or 2, -CxH2x-COO-CH3 where x = 1 or 2, -CxH2x-COO-C2H5 where x = 1 or 2 , -CxH2x-OCO-CyH2y- (N-phthalimidoyl) where x and y are each independently = 1 or 2, more preferably x = 1 and y = 2, -CxH2x-COO-CyH2y-OCO-CzH2z-C6H5 where x, y and z are each independently = 1 or 2, more preferably x, y and z are 1, X is -CO-O -.- O-CO- or -O-, and m is 0 or 1.
    [00035] It is particularly preferable for the dye mixtures according to the present invention to use compounds of Formula III in which R13 is cyano, R14 is ethyl or methyl, and R15 is methyl, ethyl, n-propyl, s-propyl, a, n- butyl, s-butyl, 1-ethyl pentyl, methoxy methyl, methoxy ethyl, ethoxy methyl, ethoxy ethyl, - CyH2yCOO-CH2CO-C6H5 where y = 1, 2, 3 or 4 or -CyH2y-O- (Ci-4 alkyl) where y = 1,2, 3 or 4.
    [00036] Preferred dye mixtures according to the present invention contain at least one dye of Formula (I) in which D1 is a group of Formula (IVa) in which T1 is nitro, T2 is hydrogen or chlorine, T3 is hydrogen, chlorine , bromo, trifluoro methyl, cyano or nitro, T4 is hydrogen, chloro, bromo, trifluoro methyl, cyano or nitro, R1 is hydrogen, chloro, methyl, acetyl amino, propionyl amino, benzoyl amine; methyl sulfonyl amino, ethyl sulfonyl amino or phenyl sulfonyl amino, R2 is hydrogen or chlorine, R3 is hydrogen, methyl, ethyl, propyl, butyl, benzyl, phenyl ethyl, phenoxy ethyl, methoxy ethyl, cyano ethyl or ally, R4, R6 and R7 is hydrogen, R5 is methyl, and n is 0 or 1.
    [00037] Particularly preferred dye mixtures according to the present invention contain at least one dye of Formula (I) in which Di is a group of Formula (IVa) in which Ti is nitro T2 is hydrogen or chlorine, T3 is hydrogen, chlorine, bromine , methyl, cyano or nitro T4 is hydrogen, chlorine, bromine, methyl trifluor, cyano or nitro, R1 is hydrogen, methyl or acetylamino, p2is hydrogen or chlorine, R3 is hydrogen, methyl, ethyl, n-butyl, benzyl, phenyl ethyl, ethyl phenoxy, ethyl cyano or allyl, R4, Re and R7 are hydrogen, R5is methyl, and n is 0.
    [00038] Many particularly preferred dye mixtures according to the present invention contain at least one dye of Formula (la)
    where T2 is hydrogen or chlorine, T3 is hydrogen, chlorine, bromine, or cyan, T4 is hydrogen, chlorine, bromine, cyan, nitro or trifluoromethyl, R1 is hydrogen, -NHCOCH3 or -NHSO2CH3, and R2 is hydrogen or -OCH3.
    [00039] Dye mixtures still preferred according to the present invention contain at least one dye of Formula (Ila)
    where R8 is hydrogen, (C1-4) alkyl, (C1-4) alkoxy, hydroxyl, halogen, -NHCHO, -NHCO (CI-6) alkyl, -NHCO-aryl, -NHSO2 (CI-6) alkyl- la or -NHSθ2-aryl, R9is hydrogen, halogen, (C1-4) alkoxy, (C1-4) alkyl or phoxy, R10 is hydrogen, (Ci-θ) alkyl, (Ci-β) substituted alkyl, ( C3-4) alkenyl, or (C3-4) substituted alkenyl, or R9 and R10 combine to form the C * H (CH3) CH2C (CH3) 2- moiety, where the carbon atom marked with * is attached to the nucleus phenyl, R11 is hydrogen, (Ci-e) alkyl or phenyl, R12 is hydrogen, (Ci-β) alkyl, (Ci-e) substituted alkyl, (C3-4) alkenyl or (C3-4) substituted alkenyl, m is 0, 1,2 or 3, and where D4 is a Formula (IVa) group and / or a Formula (IIla) dye
    where R13 is hydrogen, cyano or carboxamido, R14 is methyl, ethyl or phenyl, R15 is optionally substituted with (C1-e) alkyl or (C2-6) alkyl interrupted with optionally substituted oxygen, and D5 is a group of Formula (IVa) .
    [00040] Dye mixtures still very preferable according to the present invention contain at least one dye of Formula (llb)
    where R8 is hydrogen, (C1-4) alkyl, (C1-4) alkoxy, hydroxyl, halogen, -NHCHO, -NHCO (CI-6) alkyl, -NHCO-aryl, -NHSO2 (CI-6) alkyl, or -NHSO2-aryl, R9 is hydrogen, halogen, (C1-4) alkoxy, (C1-4) alkyl or phoxy, R10 is hydrogen, (C1-6) alkyl, (Ci-e) substituted alkyl, (C3 - 4) alkenyl, or (C3-4) substituted alkenyl, or R9 and R10 combine to form the -C * H (CH3) CH2C (CH3) 2- moiety, where the carbon atom marked with * is attached to the nucleus phenyl, R11 is hydrogen, (Ci-β) alkyl or phenyl.
    [00041] R12is hydrogen, (Ci-β) alkyl, (C1-6) substituted alkyl, (C3-4) alkenyl or (C3-4) substituted alkenyl, m is 0, 1,2 or 3, and D6 is a group Formula (IVa), where T1 is nitro; and / or a Formula dye (lllb)
    where R13 is hydrogen, cyano or carboxamido, R14 is methyl, etla or phenyl, R15 is optionally substituted alkyl (C1-6) or (C2-6) optionally substituted oxygen interrupted alkyl, and D7 is a group of Formula (IVa), where T1 is nitro or - OCH3.
    [00042] Still particularly preferred dye mixtures according to the present invention contain at least one dye of Formula lie
    where R8 is hydrogen, methyl, methoxy, ethoxy, hydroxyl, chlorine, bromine, -NHCOCH3 or -NHCOCH2CH3, R9 is hydrogen, methyl, -OCH3, -OCH2CH3, chlorine or bromine, R10 is hydrogen, (Ci-β) alkyl or (Ci-β) substituted alkyl, R11 is hydrogen, methyl or phenyl, R12 is hydrogen, (C1-6) alkyl or (Ci-β) substituted alkyl, m is 0, 1,2 or 3, and D8 is a group of Formula (IVa), where T1 is nitro, T2 is hydrogen, T3 is hydrogen, chlorine, bromine, nitro, cyan or hydroxyl, and T4 is hydrogen, chlorine, bromine, nitro or cyan; and / or a Formula dye (lllc)
    where R13 is hydrogen, cyano or carboxamido, R14is methyl, ethyl or phenyl, R15is (C1-6) alkyl optionally substituted, and D9is a group of Formula (IVa), where T1 is nitro or -OCH3, T2is hydrogen, T3é hydrogen, chlorine, bromine, nitro or cyan or hydroxyl, and T4 is hydrogen, chlorine, bromine, nitro or cyan.
    [00043] Particularly preferred dye mixtures according to the present invention contain at least one dye of Formula (lb)
    where T3 is hydrogen, chlorine, bromine, or cyan, T4 is cyan or nitro, R1 is hydrogen or -NHCOCH3, and R2 is hydrogen or -OCH3; and also at least one Formula Ild dye
    where R8 is hydrogen, -NHCOCH3 or -NHCOCH2CH3, R9is hydrogen, -OCH3 or -OCH2CH5, R10is hydrogen, (C1-6) alkyl or (C1-6) substituted alkyl R12is hydrogen, (C1-6) alkyl or (C1 -6) substituted alkyl, and where T3 is hydrogen, chlorine, bromine, nitro, cyan or hydroxyl, and T4 is hydrogen, chlorine, bromine, nitro or cyan.
    [00044] The dye mixtures according to the present invention contain the dyes of Formula (I) in mixture with (II) or (III) more particularly in amounts of each from 1% to 99% by weight, more preferably in amounts in each case of 20% to 80% by weight. Particularly highly preferred dye mixtures according to the present invention contain dyes of Formula (I) in amounts of 30% to 60% by weight and dyes of Formula (II) or (III) in amounts of 40% to 70% by weight. This also applies mutatis mutandis to mixtures containing dyes of Formulas la, lb or lc or Formulas Ila, lib, llc or lld or Formulas llla, lllb, or lllc, respectively.
    [00045] Appropriate mixing ratios for Formula (I) dye: Formula (II) or Formula (III) dye are in the range of 90:10 to 10:90, more particularly 90:10, 80:20, 75 : 25, 70:30, 60:40, 55:45, 50:50, 45:55, 40:60, 30:70, 25:75, 20:80 and 10:90. This again applies mutatis mutandis to mixtures containing dyes of Formulas la, lb or lc or Formulas lia, llb, llc or lld or Formulas llla, lllb or lllc, respectively.
    [00046] The dye mixtures according to the present invention are obtainable by mechanically mixing dyes of Formula (I) with dyes of Formulas (II) or (III). The amounts are more particularly chosen to produce mixtures having the desired compositions.
    [00047] The dyes of Formula (I) are known and are described, for example, in W02008 / 049758.
    [00048] The dye mixtures according to the present invention are remarkably useful for coloring and printing hydrophobic materials in which the colorings and the impressions obtained are notable for leveling tones and for high fixation in service. Worthy of particular mention are notable contact and washing fixations and also good sublimation fixation, especially on polyester and polyester - elastane materials.
    [00049] The present invention thus also provides for the use of the coloring mixtures of the present invention for coloring and printing hydrophobic materials, that is, processes for coloring or printing such materials in a conventional manner in which the coloring mixture according to the present invention is used as a dye.
    [00050] The hydrophobic materials mentioned can be of synthetic or semi-synthetic origin. Examples include secondary cellulose acetate, cellulose triacetate, polyamides, polylactides, and more particularly high molecular weight polyesters. High molecular weight polyester composite materials are more particularly those based on polyethylene terephthalates or polytrimethylene terephthalates. Combined fabrics and combined fibers such as, for example, polyester - cotton or polyester - elastane are also possible. Hydrophobic synthetic materials may be present in the form of bodies formed with thread or fabric or self-supporting sheet / film and may, for example, have been processed into yarns or fabrics or textile fabrics. Preference is given to fibrous textile materials, which can also be present in the form of microfibers, for example.
    [00051] The coloring according to the use provided by the present invention can be carried out in a conventional manner, preferably from an aqueous dispersion, if appropriate in the presence of carriers, at between 80 to about 110 ° C through the process of exhaustion or in a coloring autoclave at 110 to 140 ° C through the HT process, and also through the so-called thermal fixation process, in which the fabric is cushioned with dye liquor and subsequently fixed at about 180 to 230 ° Ç.
    [00052] The printing of the mentioned materials can be carried out in a manner known per se by incorporating dye mixtures of the present invention into a printing paste and treating the printed fabric with the same at temperatures between 180 to 230 ° C with HT steam , high pressure steam, or dry heat, if appropriate in the presence of a carrier, to fix the dye.
    [00053] The coloring mixtures of the present invention must be in a very fine subdivision state when they are used in coloring liquors, filled liquors or printing pastes.
    [00054] The dyes are converted into the fine state of subdivision in a conventional manner by obtaining paste from them with dispersants in a liquid medium, preferably water, and subjecting the mixture to the action of shear forces to mechanically crush the dye particles originally present to such an extent that a great specific surface area is obtained and sedimentation of the dye is minimized. This is done in suitable mills, such as ball and sand mills. The particle size of the dyes is generally between 0.5 and 5 micrometers, and preferably equal to about 1 micrometer.
    [00055] The dispersants used in the grinding operation can be non-ionic or anionic. Nonionic dispersants are, for example, reaction products of alkylene oxides, for example, ethylene oxide or propylene oxide, with alkylatable compounds, for example, fatty alcohols, fatty amines, fatty acids, phenols, alkyl phenols and carboxamides. Anionic dispersants are, for example, alkyl lignosulfonates or alkyl aryl, or alkyl aryl polyglycol ether sulfates.
    [00056] The dye preparations thus obtained must be pourable for most applications. In the same way, the dispersant and dye content is limited in these cases. In general, the dispersions are adjusted to a dye content of up to 50 weight percent and a dispersant content of up to about 25 weight percent. For economic reasons, dye contents in most cases are not below 15 percent by weight.
    [00057] The dispersions may also contain auxiliaries, for example, those that act as an oxidizing agent, for example, sodium m-nitro benzene sulfonate, or fungicidal agents, for example, sodium o-phenyl phenpoxide and penta chloro phenoxide sodium, and particularly so-called "acid donors", examples being, buty lactone, mono chloro acetamide, chloro acetate sodium, sodium dichloro acetate, the sodium salt of 3-chloro propionic acid, mono sulphate esters such as sulphate of lauryl, for example, and also sulfuric esters of ethoxylated and propoxylated alcohols, for example, butyl glycol sulfate.
    [00058] The coloring dispersions thus obtained are very advantageous for the manufacture of coloring liquors and printing pastes.
    [00059] There are certain fields of use in which powdered formulations are preferred. These sprays contain the dye, dispersants, and other auxiliaries, for example, humectants, oxidants, preservatives and dustproof agents and the "acid donors" mentioned above.
    [00060] A preferred process for the manufacture of powdery dye preparations consists of separating the liquid dye dispersions described above from their liquid, for example, by vacuum drying, freeze drying, by drying on drying drums, but preferably by drying spread.
    [00061] Coloring liquors are manufactured by diluting required quantities of the coloring formulations described above as a coloring medium, preferably water, so that an appropriate liquor ratio of, for example, 1: 5 to 1:50 is obtained for coloring . In addition, it is usually customary to add coloring aids, such as dispersants, humectants and fixation aids, to liquors. Organic and inorganic acids such as acetic acid, succinic acid, boric acid or phosphoric acid are added to fix a pH in the range of 4 to 5, preferably 4.5. It is advantageous to buffer the pH setting and add a sufficient amount of a buffer system. The acetic acid / sodium acetate system is an example of an advantageous buffer system.
    [00062] For use of dye mixture in textile printing, the required quantities of the dye formulations mentioned above are kneaded in a conventional manner together with thickeners, for example, alkali metal alginates or the like, and optionally still additives, for example, fixing agents, wetting agents and oxidizing agents, to render print pastes.
    [00063] The present invention also provides inks for digital textile printing through an inkjet process, said inks containing a dye mixture according to the present invention.
    [00064] The inks of the present invention are preferably aqueous and contain dye mixtures of the present invention in amounts ranging, for example, from 0.1% to 50% by weight, preferably in amounts ranging from 1% to 30% by weight and more preferably in amounts ranging from 1% to 15% by weight based on the total weight of the paint.
    [00065] They can still contain more particularly from 0.1% to 20% by weight of a dispersant. Suitable dispersants are known to those skilled in the art, are commercially available and include, for example, sulphonated or sulfo methylated lignins, aromatic sulfonic acid and formaldehyde condensation products, optionally substituted phenol and formaldehyde condensation products, polyacrylates and corresponding copolymers, modified polyurethanes and reaction products of alkylene oxides with alkylatable compounds, for example, fatty alcohols, fatty amines, fatty acids, carboxamides and optionally substituted phenols.
    [00066] The paints according to the present invention can still comprise the usual additives, for example, viscosity moderators, for fixing viscosity in the range of 1.5 to 40.0 mPas in the temperature range of 20 to 50 ° C . Preferred inks have a viscosity in the range of 1.5 to 20 mPas and particularly preferred inks have a viscosity in the range of 1.5 to 15 mPas.
    [00067] Suitable viscosity moderators are biological additives, for example, polyvinyl capro lactam, polyvinyl pyrrolidone, and also their copolymers, polyether polyol, associative thickeners, polyurea, sodium alginates, galactomannans, polyether urea, polyurethane, and cellulose anionic ethers.
    [00068] Through further additions, the paints according to the present invention can still contain surfactants to fix surface tensions in the range of 20 to 65 mN / m, which are adapted when appropriate depending on the process used (piezo or thermal technology) ).
    [00069] Suitable surfactant substances are, for example, surfactants of any kind, preferably non-ionic surfactants, butyl diglycol, and 1,2-hexanediol. Inks can still contain usual additions, for example, substances to inhibit the growth of bacteria and fungi in amounts of 0.01% to 1% by weight based on the total weight of the paint.
    [00070] The paints according to the present invention are obtainable in a conventional manner by mixing components in water.
    [00071] The following examples serve to elucidate the invention without being restricted to these examples. Parts and percentages are by weight, unless otherwise stated. Parts by weight refer to parts by volume as kilogram per liter. Example 1 a) 50 parts of the dye (1-1)
    are mechanically mixed with 50 parts of the dye (11-1)
    Then, the mixture is ground as a 40% aqueous suspension with 100 parts of a high temperature stable dispersant until the particle size (diameter) has reached the size magnitude of 0.1-5 micrometers.
    [00072] This dispersion is standardized for a solid product containing 25% of the coloring mixture and 70% dispersant, by adding 99.7 parts of a "cutting agent" and by drying in a spray dryer in spray form. b) 2 g of the dry mixture obtained as per a) are dispensed in 100 ml of water at 40-50 ° C. A dye bath is prepared from 11.5 ml of this aqueous dispersion, 57.5 ml of deionized water and 1.2 ml of buffering solution (pH 4.5) and filled with a piece of 5 g of polyester. The dye bath is heated to 130 ° C for 45 minutes in a high temperature Werner Mathis staining machine. After water rinsing and reduction cleaning, the polyester material has a ruby red hue with excellent washing fixations. A particularly interesting property of this mixture is the remarkable contact and washing fixation and the good sublimation fixation on polyester and polyester microfiber.
    [00073] Example 1 is repeated in a similar manner to obtain the dye mixtures of examples 2 to 20 according to the invention and their use for coloring polyester. The following table indicates the fraction of the respective dye in% by weight based on the total dye content. The indicated mixtures produce red colorations with remarkable washing and contact fixations and also good sublimation fixation.


    [00074] Still dye mixtures according to the present invention can contain the dyes of examples 21 to 29 and also be used for dyeing polyester. The following table indicates the fraction of the respective dye in% by weight based on the total dye content. The indicated mixtures produce red colorations with remarkable contact and washing fixations and also good sublimation fixation.

    [00075] Additional dye mixtures according to the present invention can contain the dyes of examples 30 to 49 and also be used for dyeing polyester. The following table indicates the fraction of the respective dye in% by weight based on the total dye content. The indicated mixtures produce red tints with remarkable contact and washing fixations and also good sublimation fixation.



    [00076] In addition to those already mentioned, the dye mixtures according to the present invention can contain the dyes of examples 50 to 69 and can also be used for coloring polyester. The following table indicates the fraction of the respective dye in% by weight based on the total dye content. The indicated mixtures produce blue tints with remarkable contact and washing fixations and also good sublimation fixation.


    [00077] Still dye mixtures according to the present invention can contain the dyes of examples 70 to 89 and also be used for dyeing polyester. The following table indicates the fraction of the respective dye in% by weight based on the total dye content. The indicated mixtures produce colorations with remarkable contact and washing fixations and also good sublimation fixation.


    Example 90
    [00078] A textile fabric consisting of padded polyester - calendered with a liquor consisting of 50 g / L of an 8% solution of sodium alginate, 100 g / L of an 8-12% solution of caroba flour ether and 5 g / L of mono sodium phosphate in water and then dried. The wet absorption is 70%.
    [00079] The textile thus pretreated is printed with an aqueous ink prepared according to the procedure described above and containing 3.5% of the dye of example 1, 2.5% of dispersant Disperbyk 190, 30% of 1.5 -pentanediol, 5% diethylene glycol mono methyl ether, 0.01% Mergal K9N biocide and 58.99% water using a drop-on-demand (piezo) inkjet printhead. The impression is entirely dried. The fixation is carried out by means of superheated steam at 175 ° C for 7 minutes. The impression is subsequently subjected to alkaline reduction cleaning, hot rinsed and then dried.
    权利要求:
    Claims (16)
    [0001]
    1. Dye mixture, characterized by the fact that it contains at least one dye of Formula (I)
    [0002]
    2. Dye mixture, according to claim 1, characterized by the fact that it contains compounds of Formula I, in which: R1 is hydrogen, -NHCO-methyl, methyl or hydroxyl, R2 is hydrogen or methoxy, R3 is hydrogen , benzyl, 2-cyano ethyl, methyl, ethyl, n-propyl, n-butyl or -C2H4-COO-CH2-CO-CH3, R4 is hydrogen or methyl, R5 is methyl, R6 is hydrogen, R7 is hydrogen or methyl , and n is 0 or 1.
    [0003]
    3. Dye mixture according to claim 1 or 2, characterized by the fact that it contains compounds of Formula II, in which: R8 is hydrogen, methyl, -NHCO-methyl or hydroxyl, R9 is hydrogen, chlorine, methoxy or methyl , R10 is hydrogen, methyl, ethyl, benzyl, -CxH2x-O-CH3, where x = 1 or 2, - CXH2X-COO-C2H5 where x = 1 or 2, -CxH2x-COO-CH3, where x = 1 or 2, - CXH2X-OCO-C2H5 where x = 1 or 2 and -CxH2x-OCO-CH3, where x = 1 or 2, R11 is hydrogen or methyl, R12 is methyl, ethyl, 2- (N -phthalimidoyl) ethyl, cyano methyl, 2-cyano ethyl, - CXH2X-OCO-CH3 where x = 1 or 2, -CXHΣX-OCO-CΣHS, where x = 1 or 2, - CXH2X-COO-CH3 where x = 1 or 2, -CXH2X-COO-C2H5, where x = 1 or 2, - CxH2x-OCO-CyH2y- (N-phthalimidoyl) where x and y are each independently = 1 or 2, and more preferably x = 1 ey = 2, - CxH2x-COO-CyH2y- (N-phthalimidoyl) where x and y are each independently = 1 or 2, more preferably x = 1 and y = 2, - CxH2x-COO-CyH2y-OCO-CzH2z-C6H5 where x, ye z are each independently = 1 or 2, more preferably x, y and z are each 1, X is -CO-O-, -O-CO- or -O-, and m is 0 or 1.
    [0004]
    4. Dye mixture, according to any one of claims 1 to 3, characterized by the fact that it contains compounds of Formula III, in which: R13 is cyan, R14 is ethyl or methyl, and R15 is methyl, ethyl, n -propyl, s-propyl, n-butyl, s-butyl, 1-ethyl pentyl, methyl methoxy, methyl methoxy, methyl ethoxy, ethyl ethoxy, -CyH2y- COO-CH2-CO-C6H5, in which y = 1, 2 , 3 or 4 or -CyH2y-O- (C1-4 alkyl), where y = 1,2, 3 or 4.
    [0005]
    5. Dye mixture, according to claim 1, characterized by the fact that it contains at least one dye of Formula (I), in which D1 is a group of Formula (IVa), in which: T1 is nitro; T2 is hydrogen or chlorine; T3is hydrogen, chlorine, bromine, trifluorine methyl, cyan, or nitro; T4 is hydrogen, chlorine, bromine, trifluoromethyl, cyan or nitro; R1 is hydrogen, chlorine, methyl, acetyl amino, propionyl amino, benzoyl amino; methyl sulfonyl amino, ethyl sulfonyl amino or phenyl sulfonyl amino; R2is hydrogen or chlorine; R3is hydrogen, methyl, ethyl, propyl, butyl, benzyl, phenyl ethyl, phenoxy ethyl, methoxy ethyl, cyano ethyl or allyl; R4, R6 and R7 are each hydrogen; R5 is methyl; and n is 0 or 1.
    [0006]
    6. Dye mixture, according to claim 1, characterized by the fact that it contains at least one dye of Formula (I), in which D1 is a group of Formula (IVa), in which: T1 is nitro; T2 is hydrogen or chlorine; T3is hydrogen, chlorine, bromine, trifluoromethyl, cyan or nitro; T4 is hydrogen, chlorine, bromine, trifluoromethyl, cyan or nitro; R1 is hydrogen, methyl or acetyl amino; R2is hydrogen or chlorine; R3 is hydrogen, methyl, ethyl, n-butyl, benzyl, phenyl ethyl, phenoxy ethyl, cyano ethyl or allyl; R4, R6 and R7 are each hydrogen; R5 is methyl; and n is 0.
    [0007]
    7. Dye mixture according to claim 6, characterized by the fact that it contains at least one dye of Formula (la)
    [0008]
    8. Dye mixture, according to any one of claims 1 to 7, characterized by the fact that it contains at least one dye of Formula (I la)
    [0009]
    9. Dye mixture, according to any of claims 1a 8, characterized by the fact that it contains at least one dye of Formula (llla)
    [0010]
    10. Dye mixture, according to any of the vindications 1 to 9, characterized by the fact that it contains at least one dye of Formula (llb)
    [0011]
    11. Dye mixture, according to any of the vindications 1 to 10, characterized by the fact that it contains at least one dye of Formula (lllb)
    [0012]
    12. Dye mixture, according to any of the vindications 1 to 11, characterized by the fact that it contains at least one dye of Formula (llc)
    [0013]
    13. Dye mixture, according to any of the vindications 1 to 12, characterized by the fact that it contains at least one dye of Formula (lllc)
    [0014]
    14. Dye mixture, according to any of the claims 1 to 13, characterized by the fact that it contains at least one Formula (lb) dye
    [0015]
    15. Use of a dye mixture, as defined in any of claims 1 to 14, characterized by the fact that it is for coloring and for printing hydrophobic materials.
    [0016]
    16. Ink for digital textile printing using an inkjet process, characterized by the fact that it comprises a dye mixture, as defined in any one of claims 1 to 14.
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    同族专利:
    公开号 | 公开日
    DE102011008683A1|2012-07-19|
    WO2012095284A1|2012-07-19|
    JP5876508B2|2016-03-02|
    JP2014505768A|2014-03-06|
    US20140123407A1|2014-05-08|
    CN103890103B|2018-03-06|
    EP2663600A1|2013-11-20|
    TW201229144A|2012-07-16|
    US9096972B2|2015-08-04|
    KR20140030114A|2014-03-11|
    PT2663600T|2017-12-22|
    EP2663600B1|2017-09-20|
    WO2012095284A9|2012-09-07|
    BR112013017510A2|2016-09-27|
    TWI661009B|2019-06-01|
    CN103890103A|2014-06-25|
    CA2806856A1|2012-07-19|
    MX2013005776A|2013-06-28|
    TW201825606A|2018-07-16|
    CA2806856C|2018-09-11|
    KR101782194B1|2017-09-26|
    TWI633158B|2018-08-21|
    ES2652518T3|2018-02-02|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-09| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-06-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-10-20| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/01/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    2021-11-03| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 10A ANUIDADE. |
    2022-02-22| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2652 DE 03-11-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102011008683A|DE102011008683A1|2011-01-15|2011-01-15|Disperse dye mixtures, their preparation and use|
    DE102011008683.8|2011-01-15|
    PCT/EP2012/000049|WO2012095284A1|2011-01-15|2012-01-07|Disperse dye mixtures, their preparation and use|
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