EP0499090A1 - Process for dyeing polyester and polyester-contaning textile materials - Google Patents
Process for dyeing polyester and polyester-contaning textile materials Download PDFInfo
- Publication number
- EP0499090A1 EP0499090A1 EP92101415A EP92101415A EP0499090A1 EP 0499090 A1 EP0499090 A1 EP 0499090A1 EP 92101415 A EP92101415 A EP 92101415A EP 92101415 A EP92101415 A EP 92101415A EP 0499090 A1 EP0499090 A1 EP 0499090A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrogen
- carbon atoms
- chlorine
- bromine
- nitro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000004043 dyeing Methods 0.000 title claims abstract description 31
- 229920000728 polyester Polymers 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title claims abstract description 7
- 239000004753 textile Substances 0.000 title claims abstract description 7
- 239000000975 dye Substances 0.000 claims abstract description 47
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 67
- 239000001257 hydrogen Substances 0.000 claims description 67
- 125000004432 carbon atom Chemical group C* 0.000 claims description 56
- 150000002431 hydrogen Chemical group 0.000 claims description 48
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 46
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 44
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 43
- 239000000460 chlorine Chemical group 0.000 claims description 40
- 229910052801 chlorine Inorganic materials 0.000 claims description 40
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 39
- 229910052794 bromium Inorganic materials 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 38
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 11
- 239000000872 buffer Substances 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 238000004040 coloring Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 7
- -1 alkali metal salt Chemical class 0.000 description 7
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000986 disperse dye Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000985 reactive dye Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000012928 buffer substance Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- KSQXVLVXUFHGJQ-UHFFFAOYSA-M Sodium ortho-phenylphenate Chemical compound [Na+].[O-]C1=CC=CC=C1C1=CC=CC=C1 KSQXVLVXUFHGJQ-UHFFFAOYSA-M 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- ZSAMVMZLILOYMO-UHFFFAOYSA-N [O-][N+](=O)BrCl Chemical compound [O-][N+](=O)BrCl ZSAMVMZLILOYMO-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940093740 amino acid and derivative Drugs 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- HVZWVEKIQMJYIK-UHFFFAOYSA-N nitryl chloride Chemical compound [O-][N+](Cl)=O HVZWVEKIQMJYIK-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- HCJLVWUMMKIQIM-UHFFFAOYSA-M sodium;2,3,4,5,6-pentachlorophenolate Chemical compound [Na+].[O-]C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl HCJLVWUMMKIQIM-UHFFFAOYSA-M 0.000 description 1
- LJRGBERXYNQPJI-UHFFFAOYSA-M sodium;3-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 LJRGBERXYNQPJI-UHFFFAOYSA-M 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
-
- 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
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8214—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester and amide groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- 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
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8223—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups
- D06P3/8228—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using one kind of dye
- D06P3/8233—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using one kind of dye using dispersed dyes
-
- 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 present invention relates to a process for HT dyeing polyester or polyester-containing textile materials.
- polyester or polyester-containing textile materials are dyed with disperse dyes from an aqueous dyebath under HT conditions in a temperature range from 120 to 140 o C at pH values from 4 to 6, since the disperse dyes are partially or completely destroyed at higher pH values. At higher pH values, there is a loss of color strength and color deviations during dyeing and the dyeings are not reproducible.
- the polyester fiber is normally subjected to an alkaline rinse treatment in a separate step before dyeing, in order to remove auxiliaries which have been used in the weaving or spinning of the fibers. These aids are, for example, oiling or sizing agents, which, if present, would make leveling of the polyester fiber difficult or impossible.
- the alkaline treatment is also carried out in order to destroy oligomers of the polyester fiber which have emerged from the interior of the fiber during the dyeing process and make the dyeing appear uneven, and to keep it in the aqueous dyeing liquor.
- This alkaline rinsing treatment is advantageously carried out at an elevated temperature.
- alkaline pretreatment and dyeing it has always been the goal to combine both processes into a one-bath rinsing and dyeing process.
- processes must be developed which give reproducible dyeings in the aqueous dye bath at pH 8 to pH 11.
- Polyester-cellulose or polyester-polyamide blended fabrics are usually dyed with dispersing or reactive dyes from an aqueous dyebath in two dyeing steps.
- the disperse dyes are applied to the polyester portion at pH 4 to 6, the reactive dyes to the cellulose or polyamide portion in the pH range between pH 11 and 13.
- the goal in the past was a to develop a single-bath application process for both dye classes.
- a search has been made for reactive dyes which can already be dyed at pH values between 8 and 11, and processes were also required here which ensure that under these conditions the polyester content can be dyed reproducibly with disperse dyes.
- DOS 39 38 631 describes a method in which disperse dyes in the pH range between pH 8 and 10 in the presence of at least one amino acid which is optionally substituted on nitrogen and / or an alkali metal salt of one which is optionally substituted on nitrogen Amino acid can be colored.
- a preferred radical X2 in the dyes of the general formula I is hydrogen.
- Preferred radicals X3 are nitro and alkylsulfonyl with 1 to 4 C atoms or chlorine and bromine if X1 simultaneously denotes nitro or methylsulfonyl, where, if X1 is methylsulfonyl, X3 cannot simultaneously be X3 alkylsulfonyl and vice versa .
- Preferred radicals R are hydrogen, allyl or alkyl having 1 to 4 carbon atoms.
- Particularly preferred dyes of the general formula Ia are those in which X1 is nitro or methylsulfonyl, X3 nitro or alkylsulfonyl having 1 to 4 carbon atoms and Y4 is hydrogen, methyl, ethyl, methoxy or ethoxy, where either X1 or X3 is nitro.
- Very particularly preferred dyes of the general formula Ia are those in which X1 is nitro, X3 nitro, X4 is hydrogen, chlorine or bromine and Y4 is hydrogen.
- Particularly preferred dyes of the general formula Ib are those in which X1 is chlorine, bromine, nitro or methylsulfonyl, X2 is hydrogen, X3 is nitro or alkylsulfonyl having 1 to 4 C atoms, X4 is hydrogen and R is alkyl having 1 to 4 C atoms, where, when X1 is methylsulfonyl, X3 cannot simultaneously be alkylsulfonyl with 1 to 4 carbon atoms and vice versa.
- a very particularly preferred dye of the general formula Ib is that in which X1 is chlorine, X3 nitro and X2, X3 and R are hydrogen.
- Particularly preferred dyes of the general formula Ic are those in which X1 chlorine, bromine, nitro or methylsulfonyl, X2 hydrogen, X3 nitro or alkylsulfonyl having 1 to 4 carbon atoms, X4 hydrogen, chlorine or bromine, Y1 hydrogen or methyl and R allyl or mean alkyl with 1 to 4 carbon atoms and in particular hydrogen, where if X 1 is methylsulfonyl, X 3 cannot simultaneously be alkyl sulfonyl with 1 to 4 carbon atoms and vice versa.
- the dyes of general formula I are known and e.g. described in DE-22 12 755 and in DE-31 63 272.
- the HT process according to the invention is preferably carried out in a dyeing autoclave.
- polyesters to be colored by the process according to the invention are in particular those based on polyethylene glycol terephthalates.
- Textile materials containing polyester are mixtures of polyester and polyamides and in particular polyester / cellulose blended fabrics.
- the dyes or dye mixtures are used in a fine distribution.
- the fine distribution of the dyes is carried out in a manner known per se by adding the dye obtained in production together with dispersants a liquid medium, preferably in water, and the mixture is exposed to the action of shear forces, the originally present dye particles being mechanically comminuted to such an extent that an optimal specific surface is achieved and the sedimentation of the dye is as low as possible.
- the particle sizes of the dyes are generally between 0.5 and 5 ⁇ m, preferably around 1 ⁇ m.
- the dispersants used in the grinding process can be nonionic or anionic.
- Nonionic dispersants are e.g. Reaction products of alkylene oxides, e.g. Ethylene or propylene oxide with alkylatable compounds such as e.g. Fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxamides.
- Anionic dispersants are, for example, lignin sulfonates, alkyl or alkylaryl sulfonates or alkyl aryl polyglycol ether sulfonates.
- the dye preparations thus obtained are said to be pourable for most applications.
- the dye and dispersant content is therefore limited in these cases.
- the dispersions are adjusted to a dye content of up to 50% by weight and a dispersant content of up to about 25%.
- the dye content is usually not below 15% by weight.
- the dispersions can also contain other auxiliaries, e.g. those that act as oxidizing agents, e.g. Sodium m-nitrobenzenesulfonate or fungicidal agents such as e.g. Sodium o-phenyl phenolate and sodium pentachlorophenolate.
- auxiliaries e.g. those that act as oxidizing agents, e.g. Sodium m-nitrobenzenesulfonate or fungicidal agents such as e.g. Sodium o-phenyl phenolate and sodium pentachlorophenolate.
- Powder settings are preferred for certain areas of application. These powders contain the dye or dye mixture, dispersants and other auxiliaries, such as wetting, oxidizing, preserving and dedusting agents.
- a preferred method of manufacturing powdered dye formulations is to withdraw the liquid from the liquid dye dispersions described above, e.g. by vacuum drying, freeze drying, by drying on drum dryers, but preferably also by spray drying.
- the required amounts of the dye settings which have been prepared in accordance with the above information are diluted with the dyeing medium, preferably with water, to such an extent that a liquor ratio of 1: 5 to 150 is obtained for the dyeing.
- further dyeing aids such as dispersing, wetting and fixing aids, are generally added to the liquors.
- the required pH of the dye liquor is determined before or during the dyeing by adding bases such as alkali metal hydroxides, e.g. aqueous sodium hydroxide solution, alkali hydrogen carbonates, e.g. Sodium bicarbonate or alkali carbonates e.g. Soda, discontinued.
- bases such as alkali metal hydroxides, e.g. aqueous sodium hydroxide solution, alkali hydrogen carbonates, e.g. Sodium bicarbonate or alkali carbonates e.g. Soda, discontinued.
- a preferred pH is 9 to 10.
- buffer substances are preferably added, as described, for example, in JSDC, 77 (1979) p. 47 or JSDC 79 (1981), p. 115.
- Particularly suitable buffer substances are those which have the greatest buffer effect in the pH range between 9 and 11.
- Suitable buffer systems are, for example, acetic acid / sodium pyrophosphate, boric acid / borax, sodium dihydrogen phosphate / disodium hydrogen phosphate, phosphoric acid / succinic acid / boric acid or combinations of organic phosphorus compounds with polycarboxylic acids.
- the amounts of buffer system used are preferably between 0.5 and 10 g / l. The idea of the invention will be explained in more detail in the examples below.
- 1.5 g of a 20% liquid preparation of the dye of the formula II are in a dyeing autoclave in a dyeing liquor consisting of 2 l of water, 2 g of a dyeing aid based on formaldehyde condensation product and 5 g of a buffer substance, which is a mixture of an organic phosphorus compound and a polycarboxylic acid, at 130 o C for 100 g of a fabric dyed from polyethylene terephthalate after the pH of the dye liquor had previously been set to 9 with aqueous sodium hydroxide solution. The dyeing is then reductively cleaned, rinsed and dried. This gives an orange color.
- the dyeing is repeated, 4 g of sodium acetate now being added as the buffer substance and the pH of the dyeing liquor being adjusted to 4.5 with acetic acid.
- the resulting orange coloration serves as a reference in a colorimetric comparison with the pH 9 coloration.
- the colorimetric values of the pH9 staining are: color strength: 101.6%, ⁇ H 0.02, ⁇ C - 0.33, ie both colors are practically identical in color.
- the dye has practically not decomposed at pH 9.
- the dye of the formula II in Example 1 is replaced by 4 g of a 10% strength liquid preparation of the dye of the formula III
- the dye liquor is buffered with a mixture of 3.6 ml phosphoric acid, 4 g succinic acid and 4 g boric acid and the pH of the dye liquor is adjusted to 10 with aqueous sodium hydroxide solution, a dark brown color is obtained.
- This coloration shows the following colorimetric values in comparison to a coloration carried out at pH 4.5: color strength: 101.9%, ⁇ H-0.59, ⁇ C 0.02.
- the dye has practically not decomposed at an elevated pH.
- the dye of the formula II in Example 1 is replaced by 3 g of a 10% liquid setting of the dye of the formula IV and dyeing at pH 9.5, the resulting yellow-brown coloration shows the following colorimetric values compared to that obtained at pH 4.5: color strength: 102%, ⁇ H - 0.16, ⁇ C 0.1 and is therefore also almost identical in color .
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Coloring (AREA)
Abstract
Die vorliegende Erfindung betrifft ein Verfahren zum HT-Färben von Polyester oder polyesterhaltigen Textilmaterialien bei pH 8 bis pH 11, dadurch gekennzeichnet, daß man einen oder mehrere Monoazofarbstoffe der allgemeinen Formel I <IMAGE> einsetzt, worin X¹ bis X<4>, Y¹ bis Y<4> sowie R wie in Anspruch 1 angegeben definiert sind.The present invention relates to a process for HT dyeing polyester or polyester-containing textile materials at pH 8 to pH 11, characterized in that one or more monoazo dyes of the general formula I <IMAGE> are used, wherein X¹ to X <4>, Y¹ bis Y <4> and R are defined as indicated in claim 1.
Description
Die vorliegende Erfindung betrifft ein Verfahren zum HT-Färben von Polyester oder polyesterhaltigen Textilmaterialien.The present invention relates to a process for HT dyeing polyester or polyester-containing textile materials.
In der Regel werden Polyester oder polyesterhaltige Textilmaterialien mit Dispersionsfarbstoffen aus wäßrigem Färbebad bei HT-Bedingungen in einem Temperaturbereich von 120 bis 140oC bei pH-Werten von 4 bis 6 gefärbt, da bei höheren pH-Werten die Dispersionsfarbstoffe teilweise oder ganz zerstört werden. Bei höheren pH-Werten kommt es zu Farbstärkeverlusten und Farbtonabweichungen beim Färben und die Färbungen sind nicht reproduzierbar. Nun wird normalerweise die Polyesterfaser in einem separaten Schritt vor dem Färben einer alkalischen Spülbehandlung unterworfen, um Hilfsmittel, die beim Weben oder Spinnen der Fasern eingesetzt worden sind, zu entfernen. Diese Hilfsmittel sind z.B. Ölungs- oder Schlichtemittel, die bei ihrem Vorhandensein ein egales Anfärben der Polyesterfaser erschweren oder unmöglich machen würden. Die alkalische Behandlung wird auch durchgeführt, um Oligomere der Polyesterfaser, die beim Färbevorgang aus dem Faserinnern herausgetreten sind und die Färbung unegal erscheinen lassen, zu zerstören und in der wäßrigen Färbeflotte zu halten.As a rule, polyester or polyester-containing textile materials are dyed with disperse dyes from an aqueous dyebath under HT conditions in a temperature range from 120 to 140 o C at pH values from 4 to 6, since the disperse dyes are partially or completely destroyed at higher pH values. At higher pH values, there is a loss of color strength and color deviations during dyeing and the dyeings are not reproducible. Now the polyester fiber is normally subjected to an alkaline rinse treatment in a separate step before dyeing, in order to remove auxiliaries which have been used in the weaving or spinning of the fibers. These aids are, for example, oiling or sizing agents, which, if present, would make leveling of the polyester fiber difficult or impossible. The alkaline treatment is also carried out in order to destroy oligomers of the polyester fiber which have emerged from the interior of the fiber during the dyeing process and make the dyeing appear uneven, and to keep it in the aqueous dyeing liquor.
Diese alkalische Spülbehandlung wird zweckmäßigerweise bei erhöhter Temperatur durchgeführt. Um Zeit und Energie zu sparen und um die Anzahl der für beide Prozesse, alkalische Vorbehandlung und Färben, benötigen Apparate zu reduzieren, war es schon immer das Ziel, beide Prozesse zu einem Ein-Bad-Spül- und Färbeverfahren zu vereinigen. Zur Realisierung dieses Zieles müssen allerdings Verfahren entwickelt werden, die im wäßrigen Färbebad bei pH 8 bis pH 11 reproduzierbare Färbungen ergeben.This alkaline rinsing treatment is advantageously carried out at an elevated temperature. In order to save time and energy and to reduce the number of apparatuses required for both processes, alkaline pretreatment and dyeing, it has always been the goal to combine both processes into a one-bath rinsing and dyeing process. To achieve this goal, however, processes must be developed which give reproducible dyeings in the aqueous dye bath at pH 8 to pH 11.
Polyester-Zellulose- bzw. Polyester-Polyamid-Mischgewebe werden mit Dispergier- bzw. Reaktivfarbstoffen aus wäßrigem Färbebad in der Regel in zwei Färbeschritten gefärbt. Wie oben erwähnt, werden dabei die Dispersionsfarbstoffe auf dem Polyesteranteil bei pH 4 bis 6 appliziert, der Reaktivfarbstoffe auf den Zellulose- bzw. Polyamid-Anteil im pH-Bereich zwischen pH 11 und 13. Auch hier war es in der Vergangenheit das Ziel, ein einbadiges Applikationsverfahren für beide Farbstoffklassen zu entwickeln. Hierfür hat man nach Reaktivfarbstoffen gesucht, die bereits bei pH-Werten zwischen 8 und 11 gefärbt werden können, und es waren auch hier Verfahren erforderlich, die sicherstellen, daß unter diesen Bedingungen der Polyesteranteil mit Dispersionsfarbstoffen reproduzierbar gefärbt werden kann.Polyester-cellulose or polyester-polyamide blended fabrics are usually dyed with dispersing or reactive dyes from an aqueous dyebath in two dyeing steps. As mentioned above, the disperse dyes are applied to the polyester portion at pH 4 to 6, the reactive dyes to the cellulose or polyamide portion in the pH range between pH 11 and 13. Here, too, the goal in the past was a to develop a single-bath application process for both dye classes. For this purpose, a search has been made for reactive dyes which can already be dyed at pH values between 8 and 11, and processes were also required here which ensure that under these conditions the polyester content can be dyed reproducibly with disperse dyes.
Zur Behebung der Mängel bisheriger Verfahren wird in der DOS-39 38 631 eine Methode beschrieben, bei der Dispersionsfarbstoffe in pH-Bereich zwischen pH 8 und 10 in Gegenwart mindestens einer, gegebenenfalls am Stickstoff substituierter Aminosäure und/oder eines Alkalimetallsalzes einer gegebenenfalls am Stickstoff substituierten Aminosäure gefärbt werden.To remedy the shortcomings of previous methods, DOS 39 38 631 describes a method in which disperse dyes in the pH range between pH 8 and 10 in the presence of at least one amino acid which is optionally substituted on nitrogen and / or an alkali metal salt of one which is optionally substituted on nitrogen Amino acid can be colored.
Es wurde nun überraschenderweise gefunden, daß sich bei pH-Werten zwischen 8 und 11 auch ohne die in der DOS-39 38 631 als Färbereihilfsmittel beschriebene Aminosäuren und -derivate reproduzierbare Färbungen erzielen lassen, wenn man Farbstoffe der allgemeinen Formel I einsetzt.It has now surprisingly been found that at pH values between 8 and 11, reproducible colorations can be achieved even without the amino acids and derivatives described in DOS-39 38 631 as dyeing aids if dyes of the general formula I are used.
Die Erfindung betrifft somit ein Verfahren zum HT-Färben von Polyester oder polyesterhaltigen Textilmaterialien bei pH 8 bis pH 11, dadurch gekennzeichnet, daß man einen oder mehrere Monoazofarbstoffe der allgemeinen Formel I
einsetzt,
in der
- X¹
- Wasserstoff, Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen,
- X²
- Wasserstoff, Chlor oder Brom,
- X³
- Wasserstoff, Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen,
- X⁴
- Wasserstoff, Chlor oder Brom,
- Y¹
- Wasserstoff oder Methyl,
- Y²
- Wasserstoff,
- Y³
- Wasserstoff,
- Y⁴
- Wasserstoff, Alkyl mit 1 bis 4 C-Atomen oder Alkoxy mit 1 bis 4 C-Atomen und
- R
- Wasserstoff, Allyl oder Alkyl mit 1 bis 6 C-Atomen, das gegebenenfalls durch Alkoxy mit 1 bis 4 C-Atomen substituiert sein kann,
begins,
in the
- X¹
- Hydrogen, chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms,
- X²
- Hydrogen, chlorine or bromine,
- X³
- Hydrogen, chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms,
- X⁴
- Hydrogen, chlorine or bromine,
- Y¹
- Hydrogen or methyl,
- Y²
- Hydrogen,
- Y³
- Hydrogen,
- Y⁴
- Hydrogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms and
- R
- Hydrogen, allyl or alkyl having 1 to 6 C atoms, which may optionally be substituted by alkoxy having 1 to 4 C atoms,
Ein bevorzugtes erfindungsgemäßes Verfahren ist dadurch gekennzeichnet, daß ein oder mehrere Monoazofarbstoffe der allgemeinen Formel Ia,
eingesetzt werden,
in der
- X¹
- Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen,
- X³
- Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen,
- X⁴
- Wasserstoff, Chlor oder Brom und
- Y⁴
- Wasserstoff, Alkyl mit 1 bis 4 C-Atomen oder Alkoxy mit 1 bis 4 C-Atomen
be used
in the
- X¹
- Chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms,
- X³
- Chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms,
- X⁴
- Hydrogen, chlorine or bromine and
- Y⁴
- Hydrogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms
Ein bevorzugtes erfindungsgemäßes Verfahren ist auch ein Verfahren, bei dem ein oder mehrere Monoazofarbstoffe der allgemeinen Formel Ib
eingesetzt werden,
in der
- X¹
- Wasserstoff, Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen,
- X²
- Wasserstoff, Chlor oder Brom,
- X³
- Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen,
- X⁴
- Wasserstoff, Chlor oder Brom und
- R
- Wasserstoff, Allyl oder Alkyl mit 1 bis 6 C-Atomen, das gegebenenfalls durch Alkoxy mit 1 bis 4 C-Atomen substituiert sein kann,
be used
in the
- X¹
- Hydrogen, chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms,
- X²
- Hydrogen, chlorine or bromine,
- X³
- Chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms,
- X⁴
- Hydrogen, chlorine or bromine and
- R
- Hydrogen, allyl or alkyl having 1 to 6 C atoms, which may optionally be substituted by alkoxy having 1 to 4 C atoms,
Schließlich ist auch ein Färbeverfahren bevorzugt, bei dem ein oder mehrere Monoazofarbstoffe der allgemeinen Formel Ic
eingesetzt werden, in der
- X¹
- Wasserstoff, Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen,
- X²
- Wasserstoff, Chlor oder Brom,
- X³
- Nitro, Chlor, Brom oder Alkylsulfonyl mit 1 bis 4 C-Atomen
- X⁴
- Wasserstoff, Chlor oder Brom,
- Y¹
- Wasserstoff oder Methyl und
- R
- Wasserstoff, Allyl oder Alkyl mit 1 bis 6 C-Atomen, das gegebenenfalls durch Alkoxy mit 1 bis 4 C-Atomen, substituiert sein kann,
be used in the
- X¹
- Hydrogen, chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms,
- X²
- Hydrogen, chlorine or bromine,
- X³
- Nitro, chlorine, bromine or alkylsulfonyl with 1 to 4 carbon atoms
- X⁴
- Hydrogen, chlorine or bromine,
- Y¹
- Hydrogen or methyl and
- R
- Hydrogen, allyl or alkyl having 1 to 6 C atoms, which may optionally be substituted by alkoxy having 1 to 4 C atoms,
Ein bevorzugter Rest X² in den Farbstoffen der allgemeinen Formel I ist Wasserstoff. Bevorzugte Reste X³ sind Nitro und Alkylsulfonyl mit 1 bis 4 C-Atomen oder aber Chlor und Brom, wenn gleichzeitig X¹ Nitro oder Methylsulfonyl bedeutet, wobei, wenn X¹ Methylsulfonyl ist, nicht gleichzeitig X³ Alkylsulfonyl mit 1 bis 4 C-Atomen sein kann und umgekehrt. Bevorzugte Reste R sind Wasserstoff, Allyl oder Alkyl mit 1 bis 4 C-Atomen.A preferred radical X² in the dyes of the general formula I is hydrogen. Preferred radicals X³ are nitro and alkylsulfonyl with 1 to 4 C atoms or chlorine and bromine if X¹ simultaneously denotes nitro or methylsulfonyl, where, if X¹ is methylsulfonyl, X³ cannot simultaneously be X³ alkylsulfonyl and vice versa . Preferred radicals R are hydrogen, allyl or alkyl having 1 to 4 carbon atoms.
Besonders bevorzugte Farbstoffe der allgemeinen Formel Ia sind solche, in denen X¹ Nitro oder Methylsulfonyl, X³ Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen und Y⁴ Wasserstoff, Methyl, Ethyl, Methoxy oder Ethoxy bedeuten, wobei entweder X¹ oder X³ Nitro bedeutet. Ganz besonders bevorzugte Farbstoffe der allgemeinen Formel Ia sind solche, in den X¹ Nitro, X³ Nitro, X⁴ Wasserstoff, Chlor oder Brom und Y⁴ Wasserstoff bedeuten.Particularly preferred dyes of the general formula Ia are those in which X¹ is nitro or methylsulfonyl, X³ nitro or alkylsulfonyl having 1 to 4 carbon atoms and Y⁴ is hydrogen, methyl, ethyl, methoxy or ethoxy, where either X¹ or X³ is nitro. Very particularly preferred dyes of the general formula Ia are those in which X¹ is nitro, X³ nitro, X⁴ is hydrogen, chlorine or bromine and Y⁴ is hydrogen.
Besonders bevorzugte Farbstoffe der allgemeinen Formel Ib sind solche, in denen X¹ Chlor, Brom, Nitro oder Methylsulfonyl, X² Wasserstoff, X³ Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen, X⁴ Wasserstoff und R Alkyl mit 1 bis 4 C-Atomen bedeuten, wobei, wenn X¹ Methylsulfonyl ist, nicht gleichzeitig X³ Alkylsulfonyl mit 1 bis 4 C-Atomen sein kann und umgekehrt. Ein ganz besonders bevorzugter Farbstoff der allgemeinen Formel Ib ist der, in dem X¹ Chlor, X³ Nitro und X², X³ und R Wasserstoff bedeuten.Particularly preferred dyes of the general formula Ib are those in which X¹ is chlorine, bromine, nitro or methylsulfonyl, X² is hydrogen, X³ is nitro or alkylsulfonyl having 1 to 4 C atoms, X⁴ is hydrogen and R is alkyl having 1 to 4 C atoms, where, when X¹ is methylsulfonyl, X³ cannot simultaneously be alkylsulfonyl with 1 to 4 carbon atoms and vice versa. A very particularly preferred dye of the general formula Ib is that in which X¹ is chlorine, X³ nitro and X², X³ and R are hydrogen.
Besonders bevorzugte Farbstoffe der allgemeinen Formel Ic sind solche, in denen X¹ Chlor, Brom, Nitro oder Methylsulfonyl, X² Wasserstoff, X³ Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen, X⁴ Wasserstoff, Chlor oder Brom, Y¹ Wasserstoff oder Methyl und R Allyl oder Alkyl mit 1 bis 4 C-Atomen und insbesondere Wasserstoff bedeuten, wobei, wenn X¹ Methylsulfonyl ist, nicht gleichzeitig X³ Alkylsulfonyl mit 1 bis 4 C-Atomen sein kann und umgekehrt.Particularly preferred dyes of the general formula Ic are those in which X¹ chlorine, bromine, nitro or methylsulfonyl, X² hydrogen, X³ nitro or alkylsulfonyl having 1 to 4 carbon atoms, X⁴ hydrogen, chlorine or bromine, Y¹ hydrogen or methyl and R allyl or mean alkyl with 1 to 4 carbon atoms and in particular hydrogen, where if X 1 is methylsulfonyl, X 3 cannot simultaneously be alkyl sulfonyl with 1 to 4 carbon atoms and vice versa.
Die Farbstoffe der allgemeinen Formel I sind bekannt und z.B. in der DE-22 12 755 und in der DE-31 63 272 beschrieben.The dyes of general formula I are known and e.g. described in DE-22 12 755 and in DE-31 63 272.
Das erfindungsgemäße HT-Verfahren wird bevorzugt im Färbeautoklaven durchgeführt.The HT process according to the invention is preferably carried out in a dyeing autoclave.
Die nach dem erfindungsgemäßen Verfahren zu färbenden Polyester sind insbesondere solche auf Basis von Polyethylenglykolterephthalaten. Polyesterhaltige Textilmaterialien sind Mischungen aus Polyester und Polyamiden und insbesondere Polyester/Cellulose-Mischgewebe.The polyesters to be colored by the process according to the invention are in particular those based on polyethylene glycol terephthalates. Textile materials containing polyester are mixtures of polyester and polyamides and in particular polyester / cellulose blended fabrics.
Bei dem erfindinngsgemäßen Verfahren werden die Farbstoffe oder Farbstoffmischungen in feiner Verteilung eingesetzt. Die Feinverteilung der Farbstoffe erfolgt in an sich bekannter Weise dadurch, daß man den in der Fabrikation anfallenden Farbstoff zusammen mit Dispergiermitteln in einem flüssigen Medium, vorzugsweise in Wasser, aufschlämmt und die Mischung der Einwirkung von Scherkräften aussetzt, wobei die ursprünglich vorhandenen Farbstoffteilchen mechanisch so weit zerkleinert werden, daß eine optimale spezifische Oberfläche erreicht wird und die Sedimentation des Farbstoffs möglichst gering ist. Die Teilchengrößen der Farbstoffe liegt im allgemeinen zwischen 0,5 und 5 µm, vorzugsweise bei etwa 1 µm.In the process according to the invention, the dyes or dye mixtures are used in a fine distribution. The fine distribution of the dyes is carried out in a manner known per se by adding the dye obtained in production together with dispersants a liquid medium, preferably in water, and the mixture is exposed to the action of shear forces, the originally present dye particles being mechanically comminuted to such an extent that an optimal specific surface is achieved and the sedimentation of the dye is as low as possible. The particle sizes of the dyes are generally between 0.5 and 5 μm, preferably around 1 μm.
Die bei dem Mahlvorgang mitverwendeten Dispergiermittel können nichtionogen oder anionaktiv sein. Nichtionogene Dispergiermittel sind z.B. Umsetzungsprodukte von Alkylenoxiden, wie z.B. Ethylen- oder Propylenoxid mit alkylierbaren Verbindungen, wie z.B. Fettalkoholen, Fettaminen, Fettsäuren, Phenolen, Alkylphenolen und Carbonsäureamiden. Anionaktive Dispergiermittel sind beispielsweise Ligninsulfonate, Alkyl- oder Alkylarylsulfonate oder Alkyl-aryl-polyglykolethersulfonate.The dispersants used in the grinding process can be nonionic or anionic. Nonionic dispersants are e.g. Reaction products of alkylene oxides, e.g. Ethylene or propylene oxide with alkylatable compounds such as e.g. Fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxamides. Anionic dispersants are, for example, lignin sulfonates, alkyl or alkylaryl sulfonates or alkyl aryl polyglycol ether sulfonates.
Die so erhaltenen Farbstoffzubereitungen sollen für die meisten Anwendungsweisen gießbar sein. Der Farbstoff- und Dispergiermittelgehalt ist daher in diesen Fällen limitiert. Im allgemeinen werden die Dispersionen auf einen Farbstoffgehalt bis zu 50 Gew.% und einen Dispergiermittelgehalt bis zu etwa 25% eingestellt. Aus ökonomischen Gründen werden Farbstoffgehalte von 15 Gew.% meist nicht unterschritten.The dye preparations thus obtained are said to be pourable for most applications. The dye and dispersant content is therefore limited in these cases. In general, the dispersions are adjusted to a dye content of up to 50% by weight and a dispersant content of up to about 25%. For economic reasons, the dye content is usually not below 15% by weight.
Die Dispersionen können noch weitere Hilfsmittel enthalten, z.B. solche, die als Oxidationsmittel wirken, wie z.B. Natrium-m-nitrobenzolsulfonat oder fungicide Mittel, wie z.B. Natrium-o-phenyl-phenolat und Natriumpentachlorphenolat.The dispersions can also contain other auxiliaries, e.g. those that act as oxidizing agents, e.g. Sodium m-nitrobenzenesulfonate or fungicidal agents such as e.g. Sodium o-phenyl phenolate and sodium pentachlorophenolate.
Für gewisse Anwendungsbereiche werden Pulvereinstellungen bevorzugt. Diese Pulver enthalten den Farbstoff oder das Farbstoffgemisch, Dispergiermittel und andere Hilfsmittel, wie z.B. Netz-, Oxydations-, Konservierungs- und Entstaubungsmittel.Powder settings are preferred for certain areas of application. These powders contain the dye or dye mixture, dispersants and other auxiliaries, such as wetting, oxidizing, preserving and dedusting agents.
Ein bevorzugtes Herstellungsverfahren für pulverförmige Farbstoffzubereitungen besteht darin, daß den oben beschriebenen flüssigen Farbstoffdispersionen die Flüssigkeit entzogen wird, z.B. durch Vakuumtrocknung, Gefriertrocknung, durch Trocknung auf Walzentrocknern, vorzugsweise aber auch durch Sprühtrocknung.A preferred method of manufacturing powdered dye formulations is to withdraw the liquid from the liquid dye dispersions described above, e.g. by vacuum drying, freeze drying, by drying on drum dryers, but preferably also by spray drying.
Zur Herstellung der Färbeflotten werden die erforderlichen Mengen der Farbstoffeinstellungen, die gemäß den obigen Angaben hergestellt wurden, mit dem Färbemedium, vorzugsweise mit Wasser, so weit verdünnt, daß sich für die Färbung ein Flottenverhältnis von 1:5 bis 1 50 ergibt. Zusätzlich werden den Flotten im allgemeinen weitere Färbereihilfsmittel, wie Dispergier-, Netz- und Fixierhilfsmittel zugesetzt.To prepare the dyeing liquors, the required amounts of the dye settings which have been prepared in accordance with the above information are diluted with the dyeing medium, preferably with water, to such an extent that a liquor ratio of 1: 5 to 150 is obtained for the dyeing. In addition, further dyeing aids, such as dispersing, wetting and fixing aids, are generally added to the liquors.
Der erforderliche pH-Wert der Färbeflotte wird vor bzw. auch während des Färbens durch Zugabe von Basen wie Alkalihydroxiden, z.B. wäßriger Natronlauge, Alkalihydrogencarbonaten, z.B. Natriumhydrogencarbonat oder Alkalicarbonaten z.B. Soda, eingestellt. Ein bevorzugter pH-Wert ist pH 9 bis 10.The required pH of the dye liquor is determined before or during the dyeing by adding bases such as alkali metal hydroxides, e.g. aqueous sodium hydroxide solution, alkali hydrogen carbonates, e.g. Sodium bicarbonate or alkali carbonates e.g. Soda, discontinued. A preferred pH is 9 to 10.
Um pH-Schwankungen zu minimieren, werden vorzugsweise Puffersubstanzen zugesetzt, wie sie z.B. in JSDC, 77 (1979) S. 47 oder JSDC 79 (1981), S. 115 beschrieben sind. Besonders geeignete Puffersubstanzen sind solche, die im pH-Bereich zwischen 9 und 11 die größte Pufferwirkung besitzen. Geeignete Puffersysteme sind z.B. Essigsäure/ Natriumpyrophosphat, Borsäure/Borax, Natriumdihydrogenphosphat/Dinatriumhydrogenphosphat, Phosphorsäure/Bernsteinsäure/Borsäure oder Kombinationen organischer Phosphorverbindungen mit Polycarbonsäuren. Die Einsatzmengen an Puffersystem liegen vorzugsweise zwischen 0,5 und 10 g/l. An den nachfolgenden Beispielen soll der Erfindungsgedanke näher erläutert werden.In order to minimize pH fluctuations, buffer substances are preferably added, as described, for example, in JSDC, 77 (1979) p. 47 or JSDC 79 (1981), p. 115. Particularly suitable buffer substances are those which have the greatest buffer effect in the pH range between 9 and 11. Suitable buffer systems are, for example, acetic acid / sodium pyrophosphate, boric acid / borax, sodium dihydrogen phosphate / disodium hydrogen phosphate, phosphoric acid / succinic acid / boric acid or combinations of organic phosphorus compounds with polycarboxylic acids. The amounts of buffer system used are preferably between 0.5 and 10 g / l. The idea of the invention will be explained in more detail in the examples below.
1,5 g einer 20%igen Flüssigpräparation des Farbstoffs der Formel II
werden in einem Färbeautoklav in einer Färbeflotte bestehend aus 2 l Wasser, 2 g eines Färbereihilfsmittels auf Basis Formaldehydkondensationsprodukt und 5 g einer Puffersubstanz, die eine Mischung aus einer organischen Phosphorverbindung und einer Polycarbonsäure darstellt, 45 Min. bei 130oC auf 100 g eines Gewebes aus Polyethylenterephthalat gefärbt, nachdem vorher der pH-Wert der Färbeflotte mit wäßriger Natronlauge auf 9 gestellt wurde. Danach wird die Färbung reduktiv nachgereinigt, gespült und getrocknet. Man erhält so eine orangefarbene Färbung.1.5 g of a 20% liquid preparation of the dye of the formula II
are in a dyeing autoclave in a dyeing liquor consisting of 2 l of water, 2 g of a dyeing aid based on formaldehyde condensation product and 5 g of a buffer substance, which is a mixture of an organic phosphorus compound and a polycarboxylic acid, at 130 o C for 100 g of a fabric dyed from polyethylene terephthalate after the pH of the dye liquor had previously been set to 9 with aqueous sodium hydroxide solution. The dyeing is then reductively cleaned, rinsed and dried. This gives an orange color.
Die Färbung wird wiederholt, wobei als Puffersubstanz jetzt 4 g Natriumacetat zugesetzt und der pH-Wert der Färbeflotte mit Essigsäure auf 4,5 eingestellt wird. Die resultierende orangefarbene Färbung dient bei einem farbmetrischen Vergleich mit der pH 9-Färbung als Bezug. Die farbmetrischen Werte der pH9-Färbung sind demgegenüber: Farbstärke: 101,6 %, ΔH 0,02, ΔC - 0,33, d.h. beide Färbungensind praktisch farbtongleich. DerFarbstoff hat sich bei pH 9 praktisch nicht zersetzt.The dyeing is repeated, 4 g of sodium acetate now being added as the buffer substance and the pH of the dyeing liquor being adjusted to 4.5 with acetic acid. The resulting orange coloration serves as a reference in a colorimetric comparison with the pH 9 coloration. In contrast, the colorimetric values of the pH9 staining are: color strength: 101.6%, ΔH 0.02, ΔC - 0.33, ie both colors are practically identical in color. The dye has practically not decomposed at pH 9.
Ersetzt man den Farbstoff der Formel II im Beispiel 1 durch 4 g einer 10%igen Flüssigpräparation des Farbstoffs der Formel III
puffert die Färbeflotte mit einer Mischung 3,6 ml Phosphorsäure, 4 g Bernsteinsäure und 4 g Borsäure und stellt den pH-Wert der Färbeflotte mit wäßriger Natronlauge auf 10, so erhält man eine dunkelbraune Färbung. Diese Färbung zeigt im Vergleich zu einer bei pH 4,5 durchgeführten Färbung die folgenden farbmetrischen Werte: Farbstärke: 101,9 %, ΔH - 0,59, ΔC 0,02. Auch hier hat sich bei erhöhtem pH-Wert der Farbstoff praktisch nicht zersetzt.If the dye of the formula II in Example 1 is replaced by 4 g of a 10% strength liquid preparation of the dye of the formula III
If the dye liquor is buffered with a mixture of 3.6 ml phosphoric acid, 4 g succinic acid and 4 g boric acid and the pH of the dye liquor is adjusted to 10 with aqueous sodium hydroxide solution, a dark brown color is obtained. This coloration shows the following colorimetric values in comparison to a coloration carried out at pH 4.5: color strength: 101.9%, ΔH-0.59, ΔC 0.02. Here too, the dye has practically not decomposed at an elevated pH.
Ersetzt man den Farbstoff der Formel II in Beispiel 1 durch 3 g einer 10%igen Flüssigeinstellung des Farbstoffs der Formel IV
und färbt bei pH 9,5, so zeigt die resultierende gelbbraune Färbung im Vergleich zu der bei pH 4,5 erhaltenen die folgenden farbmetrischen Werte: Farbstärke: 102 %, ΔH - 0,16, ΔC 0,1 und ist somit ebenfalls nahezu farbtongleich.The dye of the formula II in Example 1 is replaced by 3 g of a 10% liquid setting of the dye of the formula IV
and dyeing at pH 9.5, the resulting yellow-brown coloration shows the following colorimetric values compared to that obtained at pH 4.5: color strength: 102%, ΔH - 0.16, ΔC 0.1 and is therefore also almost identical in color .
In den nachfolgenden Tabellen sind weitere Farbstoffe aufgeführt, die nach dem erfindungsgemäßen verfahren eingesetzt werden können.
Claims (10)
in der
wobei Y¹ statt Wasserstoff oder Methyl und Y² statt Wasserstoff auch zusammen mit dem sie tragenden Benzolkern einen Naphthylrest und Y² und Y³ statt Wasserstoff zusammen eine direkte Bindung bilden können.Process for HT dyeing polyester or polyester-containing textile materials at pH 8 to pH 11, characterized in that one or more monoazo dyes of the general formula I
in the
where Y¹ instead of hydrogen or methyl and Y² instead of hydrogen together with the benzene nucleus carrying them can form a naphthyl radical and Y² and Y³ together can form a direct bond instead of hydrogen.
X¹ Nitro, X³ Nitro, X⁴ Wasserstoff, Chlor oder Brom und Y⁴ Wasserstoff bedeuten.A method according to claim 3, characterized in that in the general formula Ia
X¹ is nitro, X³ is nitro, X⁴ is hydrogen, chlorine or bromine and Y⁴ is hydrogen.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE4104655 | 1991-02-15 | ||
DE4104655A DE4104655A1 (en) | 1991-02-15 | 1991-02-15 | METHOD FOR DYING POLYESTERS AND TEXTILE MATERIALS CONTAINING POLYESTERS |
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Publication Number | Publication Date |
---|---|
EP0499090A1 true EP0499090A1 (en) | 1992-08-19 |
EP0499090B1 EP0499090B1 (en) | 1995-04-05 |
Family
ID=6425108
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92101415A Expired - Lifetime EP0499090B1 (en) | 1991-02-15 | 1992-01-29 | Process for dyeing polyester and polyester-contaning textile materials |
Country Status (5)
Country | Link |
---|---|
US (1) | US5244471A (en) |
EP (1) | EP0499090B1 (en) |
JP (1) | JPH04333677A (en) |
DE (2) | DE4104655A1 (en) |
ES (1) | ES2070533T3 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5248314A (en) * | 1991-11-07 | 1993-09-28 | Hoechst Mitsubishi Kasei Co. | High temperature dyeing of polyester and polyester-containing textile materials with cyano group containing azo dye |
US5279621A (en) * | 1991-02-28 | 1994-01-18 | Cassella Ag | High temperature dyeing of polyester and polyester-containing textile materials under alkaline conditions |
EP0661351A1 (en) * | 1994-01-03 | 1995-07-05 | Hoechst Mitsubishi Kasei Co., Ltd. | Monoazocarbazol dyestuffs |
EP0694587A1 (en) | 1994-06-25 | 1996-01-31 | Hoechst Mitsubishi Kasei Co., Ltd. | Monoazoindole dyestuffs |
EP0719888A2 (en) * | 1994-12-28 | 1996-07-03 | DyStar Japan Ltd. | Process for dyeing polyester or polyester containing textile materials |
DE4303359C2 (en) * | 1992-05-26 | 2002-06-20 | Inst Chemii Przemyslowej Warsc | Reactive carbazole dyes and process for their preparation |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996018767A1 (en) * | 1994-12-13 | 1996-06-20 | Hoechst Celanese Corporation | A process for dyeing polyester/cotton blends |
WO2011052007A1 (en) | 2009-10-28 | 2011-05-05 | トヨタ自動車株式会社 | Brake control device |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1185413A (en) * | 1956-02-16 | 1959-07-31 | Hoechst Ag | Textile printing process |
DE2212755A1 (en) * | 1972-03-16 | 1973-09-20 | Cassella Farbwerke Mainkur Ag | HYDRO-INSOLUBLE MONOAZO DYES AND PROCESS FOR THEIR MANUFACTURING |
EP0034716A1 (en) * | 1980-02-08 | 1981-09-02 | BASF Aktiengesellschaft | Navy blue dyestuff mixtures and their use in dyeing polyesters |
EP0035671A1 (en) * | 1980-02-28 | 1981-09-16 | CASSELLA Aktiengesellschaft | Water-insoluble azo dyestuffs, methods for their preparation and their use in dyeing and printing synthetic hydrophobic fibre materials |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3984199A (en) * | 1972-03-16 | 1976-10-05 | Cassella Farbwerke Mainkur Aktiengesellschaft | Water-insoluble monoazo dyestuffs |
JPS58160356A (en) * | 1982-03-18 | 1983-09-22 | Sumitomo Chem Co Ltd | Production of monoazo dye |
US5019133A (en) * | 1988-11-25 | 1991-05-28 | Mitsubishi Kasei Corporation | Method for dyeing polyester-containing fibers in an alkaline dyeing bath and dyeing assistant, an amino-acid compound |
DE4106323A1 (en) * | 1991-02-28 | 1992-09-03 | Cassella Ag | METHOD FOR ADVERTISING POLYESTER AND POLYESTER-BASED TEXTILE MATERIALS |
-
1991
- 1991-02-15 DE DE4104655A patent/DE4104655A1/en not_active Withdrawn
-
1992
- 1992-01-29 EP EP92101415A patent/EP0499090B1/en not_active Expired - Lifetime
- 1992-01-29 DE DE59201801T patent/DE59201801D1/en not_active Expired - Fee Related
- 1992-01-29 US US07/827,624 patent/US5244471A/en not_active Expired - Fee Related
- 1992-01-29 ES ES92101415T patent/ES2070533T3/en not_active Expired - Lifetime
- 1992-02-13 JP JP4026797A patent/JPH04333677A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1185413A (en) * | 1956-02-16 | 1959-07-31 | Hoechst Ag | Textile printing process |
DE2212755A1 (en) * | 1972-03-16 | 1973-09-20 | Cassella Farbwerke Mainkur Ag | HYDRO-INSOLUBLE MONOAZO DYES AND PROCESS FOR THEIR MANUFACTURING |
EP0034716A1 (en) * | 1980-02-08 | 1981-09-02 | BASF Aktiengesellschaft | Navy blue dyestuff mixtures and their use in dyeing polyesters |
EP0035671A1 (en) * | 1980-02-28 | 1981-09-16 | CASSELLA Aktiengesellschaft | Water-insoluble azo dyestuffs, methods for their preparation and their use in dyeing and printing synthetic hydrophobic fibre materials |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS, vol. 100, no. 14, 2. April 1984, Columbus, Ohio, US; abstract no. 105089, 'Monoazo disperse dye.' Seite 86 ; * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5279621A (en) * | 1991-02-28 | 1994-01-18 | Cassella Ag | High temperature dyeing of polyester and polyester-containing textile materials under alkaline conditions |
US5248314A (en) * | 1991-11-07 | 1993-09-28 | Hoechst Mitsubishi Kasei Co. | High temperature dyeing of polyester and polyester-containing textile materials with cyano group containing azo dye |
DE4303359C2 (en) * | 1992-05-26 | 2002-06-20 | Inst Chemii Przemyslowej Warsc | Reactive carbazole dyes and process for their preparation |
EP0661351A1 (en) * | 1994-01-03 | 1995-07-05 | Hoechst Mitsubishi Kasei Co., Ltd. | Monoazocarbazol dyestuffs |
EP0694587A1 (en) | 1994-06-25 | 1996-01-31 | Hoechst Mitsubishi Kasei Co., Ltd. | Monoazoindole dyestuffs |
EP0719888A2 (en) * | 1994-12-28 | 1996-07-03 | DyStar Japan Ltd. | Process for dyeing polyester or polyester containing textile materials |
EP0719888A3 (en) * | 1994-12-28 | 1997-01-22 | Dystar Japan Ltd | Process for dyeing polyester or polyester containing textile materials |
Also Published As
Publication number | Publication date |
---|---|
DE59201801D1 (en) | 1995-05-11 |
JPH04333677A (en) | 1992-11-20 |
EP0499090B1 (en) | 1995-04-05 |
DE4104655A1 (en) | 1992-08-20 |
ES2070533T3 (en) | 1995-06-01 |
US5244471A (en) | 1993-09-14 |
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