EP0665325A2 - Process for the manufacture of aminated cotton fibers - Google Patents
Process for the manufacture of aminated cotton fibers Download PDFInfo
- Publication number
- EP0665325A2 EP0665325A2 EP95100369A EP95100369A EP0665325A2 EP 0665325 A2 EP0665325 A2 EP 0665325A2 EP 95100369 A EP95100369 A EP 95100369A EP 95100369 A EP95100369 A EP 95100369A EP 0665325 A2 EP0665325 A2 EP 0665325A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- amino
- sulfato
- groups
- hydroxy
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229920000742 Cotton Polymers 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000004043 dyeing Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 9
- 238000007639 printing Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 5
- 238000009472 formulation Methods 0.000 claims abstract description 4
- 229920000728 polyester Polymers 0.000 claims abstract description 4
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 125000004122 cyclic group Chemical group 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 44
- -1 amino, sulfo, hydroxy Chemical group 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 230000004048 modification Effects 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 125000004185 ester group Chemical group 0.000 claims description 11
- 125000003277 amino group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002657 fibrous material Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229960001893 piperazine sulfate Drugs 0.000 claims description 6
- NDPBYMFTBWPSNB-UHFFFAOYSA-N piperazine;sulfuric acid;hydrate Chemical compound O.OS(O)(=O)=O.C1CNCCN1 NDPBYMFTBWPSNB-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 229960005141 piperazine Drugs 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 150000007824 aliphatic compounds Chemical class 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 7
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 abstract 1
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 238000009992 mercerising Methods 0.000 abstract 1
- 238000009991 scouring Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 19
- 239000000975 dye Substances 0.000 description 17
- 239000004744 fabric Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- 238000005406 washing Methods 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000004753 textile Substances 0.000 description 7
- 238000004061 bleaching Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000009981 jet dyeing Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000985 reactive dye Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000009990 desizing Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005517 mercerization Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 241001584775 Tunga penetrans Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010016 exhaust dyeing Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000003032 molecular docking Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 239000010981 turquoise Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
- D06M11/40—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table combined with, or in absence of, mechanical tension, e.g. slack mercerising
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/328—Amines the amino group being bound to an acyclic or cycloaliphatic carbon atom
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
-
- 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
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/22—Effecting variation of dye affinity on textile material by chemical means that react with the fibre
- D06P5/225—Aminalization of cellulose; introducing aminogroups into cellulose
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2400/00—Specific information on the treatment or the process itself not provided in D06M23/00-D06M23/18
- D06M2400/01—Creating covalent bondings between the treating agent and the fibre
-
- 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
- Y10S8/916—Natural fiber dyeing
- Y10S8/918—Cellulose textile
-
- 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
- Y10S8/93—Pretreatment before dyeing
Definitions
- the invention relates to a method for producing aminated cotton fibers.
- European laid-open specification EP 0 546 476 A1 describes a "process for producing a modified fiber material and a process for dyeing the modified fiber material with anionic dyes".
- the fiber material is modified in such a way that an aliphatic or cyclic compound containing amino and ester groups is applied to the material and subjected to a thermal treatment. Another possibility is to leave the material in such a solution for a long time at an elevated temperature.
- the materials to be modified are ready-to-dye, ie boiled and bleached cotton and cotton blended fabrics. This procedure, namely to subsequently modify ready-to-use materials in order to then dye them free of salt and alkali, is very uneconomical and unecological in a total cost calculation.
- This object is achieved by a process for the production of aminated cotton fibers, characterized in that raw cotton or raw cotton-polyester mixtures are simultaneously boiled, boiled or dry mercerized by the addition of one, if necessary, by 1 or 2 or more hydroxyl-substituted, saturated aliphatic compound of 3 to 15 carbon atoms with at least one primary, secondary, tertiary or quaternary amino group and at least one hydrolyzable ester group in which the saturated radical (s) branches in a straight chain and / or is (are) and can optionally be interrupted by one or more hetero groups, modified.
- esters groups of the compounds containing amino groups are a sulfato or phosphato group or a C1-C4-alkanoyloxy group, phenylsulfonyloxy or one on the benzene nucleus by substituents from the group carboxy, C1-C4-alkyl, have proven to be favorable C1-C4 alkoxy and nitro substituted phensulfonyloxy group.
- N can also be used advantageously - ( ⁇ -Sulfatoethyl) piperidine, 2-sulfato-3-hydroxy-1-aminopropane, 3-sulfato-2-hydroxy-1-aminopropane, 1-sulfato-3-hydroxy-2-aminopropane , 3-Hydroxy-1-sulfato-2-aminopropane, 2,3-disulfato-1-aminopropane or 1,3-disulfato-2-aminopropane, a derivative of these compounds with another ester group mentioned above instead of that Sulfato group, especially N- (2-sulfatoethyl) piperazine sulfate.
- those amino compounds that have an ⁇ -chloro- ⁇ -hydroxy substitution as a reactive residue on the amine component are also suitable for the modification of raw cotton articles.
- compounds which can react with hydroxyl groups, for example cellulose, or amino and thiol groups, for example wool and silk, and which are capable of forming a covalent chemical bond are also suitable for the modification of raw cotton articles.
- the modification during the brewing or boiling of raw cotton articles can be carried out continuously or discontinuously.
- Soda lye with about 5 to 30 g / l NaOH is used as the baking or decoction liquid in a batch process. It is preferably carried out in closed tanks at temperatures between 80 ° C and 120 ° C, preferably 90 and 102 ° C.
- the pretreatment agent can be added linearly, degressively or directly.
- the concentrations are between 10 and 100 g / l, preferably 15 to 30 g / l.
- the modification according to the invention in discontinuous form can directly follow a bleaching process with hydrogen peroxide by adding the amount of alkali required for the pretreatment to the bleaching solution, thereby destroying excess bleaching agent and then adding the modification agent. It has proven to be advantageous if no peroxide stabilizer is added to the bleaching solution.
- the amounts of NaOH fluctuate between 5 to 20% by weight, based on the weight of the goods, depending on the type of energy supply and the type of fleet order.
- Based on the weight of the goods between 2 and 10% by weight, preferably 3 and 8% by weight, of modification agent are used.
- the modification according to the invention can directly follow a continuous bleaching process by squeezing an alkaline active substance solution which has been strengthened two to three times compared to a conventional liquor onto the pre-bleached, still very moist material and then subjecting the goods to a steaming process.
- No stabilizer should be added to the solution for the pre-bleaching in order to ensure that after squeezing the strongly alkaline modification liquor, the hydrogen peroxide is quickly destroyed and thus no fiber damage occurs.
- the textile fiber material that is used in the pretreatment process according to the invention can be present in all processing states, such as yarn, flake, sliver and piece goods (fabric).
- An essential and surprising advantage of the method according to the invention is that the fiber damage that always occurs in the course of boiling or baking processes is significantly reduced during pretreatment with said modification agents.
- Mercerization processes are also suitable for modification.
- the preferred embodiment is dry mercerization by squeezing a sodium hydroxide solution of 22 to 32 ° Be, preferably 24 ° Be, which contains between 30 and 120 g of modification agent per liter, onto the fabric.
- the goods are then over dried on a stenter with hot air at 120 ° C.
- a wash-out process a material is obtained which has an increased gloss and can be dyed free of salt and alkali according to the invention.
- Another embodiment is the impregnation with hot, modification agent-containing liquor. Following the hot impregnation the goods pass through a roller marking compartment. Contrary to common techniques, the temperature should be kept between 80 and 95 ° C for a longer period during the swelling and in the subsequent stabilization zone.
- the dyeing of the aminated cotton fibers according to the invention is carried out analogously to known dyeing methods and printing processes for dyeing and printing fiber materials with water-soluble textile dyes and using the temperature ranges and customary amounts of dye known to be used for this.
- the particular advantage here is that the dye baths, padding processes, printing pastes and ink-jet formulations do not require the addition of alkaline compounds, as are usually used for fixing fiber-reactive dyes, and furthermore also the usual additions of electrolyte salts can be dispensed with.
- Dyeing processes which can be used according to the invention are, for example, the various exhaust processes, such as dyeing on the jigger and on the reel runner or dyeing from a long and short liquor, dyeing in jet dyeing machines, dyeing by padding-cold dwelling or padding -Hot steam fixing process.
- the dyeing methods which can be used according to the invention also include the printing techniques, including ink-jet printing and transfer printing.
- the dyes used to dye the aminated cotton fiber are generally anionic in nature.
- the fiber-reactive textile dyes which can react with hydroxyl groups, for example of cellulose, or amino and thiol groups, for example of wool and silk, of synthetic polymers, such as polyamides, or also modified polymers, namely the aminated celluloses, and a covalent bond are particularly suitable able to enter.
- the fiber-reactive component on the textile dyes are, in particular, the sulfatoethylsulfonyl, vinylsulfonyl, chlorotriazinyl, fluorotriazinyl, trichloropyrimidyl, difluorochloropyrimidyl, Dichloroquinoxalinyl, chloropropylamidyl, ⁇ -bromoacrylamidyl and combinations of these “anchor systems” are mentioned.
- Cotton twill pre-desized, raw white, weight 200 g / kg is mixed with an aqueous liquor containing 60 parts sulfatoethylpiperazine, 100 parts sodium hydroxide, 5 parts ®Hostapal FA (trade name of a nonionic wetting and detergent) and 6 parts ®Ladit RBO in 1000 parts Contains water, impregnated.
- the liquor intake with this treatment is approx. 150%.
- the tissue is then docked and left at 95 to 103 ° C for 60 minutes.
- the temperature treatment is followed by a three-time washing process, the washing solution optionally being able to contain a commercially available surfactant, at boiling temperature, in order to remove the water-soluble impurities present on the fabric.
- the cotton material After rinsing with warm and cold water, the cotton material is dried. This gives a textile fabric with a degree of desizing of 9 (Tegewa rating) and a suction head of 6.5 cm after 300 minutes, which can be processed directly in a dyeing process using the block process.
- an aqueous dye solution containing 20 parts of the dye of the formula known from European Patent Application 158 233, Example 1, and 3 parts of a commercially available nonionic wetting agent dissolved, applied to the fabric at 25 ° C by means of a pad with a liquor absorption of 80%, based on the weight of the fabric.
- the fabric padded with the dye solution is wound onto a dock, wrapped in a plastic sheet, left for 4 hours at 40 to 50 ° C and then with cold and hot water, which may optionally contain a commercially available surfactant, and then optionally again with cold water Rinsed water and dried.
- cold and hot water which may optionally contain a commercially available surfactant, and then optionally again with cold water Rinsed water and dried.
- a strong, uniformly colored yellow coloration is obtained which has good general fastness properties, in particular good fastness to rubbing and light.
- Polyester-cotton blend 50/50 (pre-desized, raw white, weight 200 g / kg) is mixed with an aqueous liquor containing 30 parts of sulfatoethylpiperazine, 50 parts of sodium hydroxide and 5 parts of ®Leonil EB (trade name of a nonionic wetting and washing agent) Contains 1000 parts of water, impregnated. The liquor intake with this treatment is approx. 150%. The tissue is then docked and left at 95 to 103 ° C for 30 minutes. The temperature treatment is followed directly by a multi-course washing process, the washing solutions optionally being able to contain commercially available surfactant, at the boiling temperature, in order to remove the water-soluble impurities present on the fabric.
- the cotton material After rinsing with warm and cold water, the cotton material is dried. 10 parts of this polyester / cotton blended fabric are in a liquor ratio of 1:10 with a liquor containing 0.1 part of a 50% by weight electrolyte-containing CI Reactive Red 198 by a customary drawing-out process (mainly containing sodium chloride) and 0.1 part of a disperse dye dissolved or dispersed in 100 parts of water contains brought together in an HT apparatus. The mixture is heated to 130 ° C. After 30 minutes at this temperature, the mixture is allowed to cool, the colorless liquor is discarded and the fabric is washed as usual. This gives a strong, level, level red dyeing, the authenticity of which is equivalent to that of the dyeing obtained in the prior art in all respects.
- the temperature treatment is followed by a three-time washing process, the washing solution optionally being able to contain a commercially available surfactant, at boiling temperature, in order to remove the water-soluble impurities present on the fabric.
- the washing solution optionally being able to contain a commercially available surfactant, at boiling temperature, in order to remove the water-soluble impurities present on the fabric.
- the cotton material is dried. This gives a textile fabric with a degree of desizing of 9 (Tegewa rating) and a suction head of 6.5 cm after 300 minutes, which can be further processed directly in an exhaust dyeing process.
- the pretreated but still wet goods are then mixed with 1000 parts of water in a dyeing apparatus. The mixture is heated to 60 ° C.
- a cotton twill fabric (raw white, desized, weight 200 g / kg) is impregnated with a 60 ° C warm sodium hydroxide solution of 30 ° Be, which contains 60 g N- (2-sulfatoethyl) piperazine sulfate per liter and rolled up under pressure and then rolled up on a second roller preheated to 80 ° C. After rewinding, which takes place from roller to roller in constant direct contact and at a temperature of 90 ° C and thus prevents shrinking, closes a span. The process of rolling over takes 15 minutes, the dwell time in the tensioning field is 10 minutes.
- cotton interlock is unbleached as a tube at 100 ° C in a bath containing 1%, based on the amount of liquid, a 50% by weight sodium hydroxide solution and 1%, based on the amount of liquid, a 35% by weight. contains hydrogen peroxide solution, immersed.
- the goods are allowed to linger for 10 minutes and then pulled through a crusher, so that a fleet order of approximately 80% remains.
- the material is then passed through a mesh trough with multiple squeezing mechanism in which there is a solution which contains 210 g / l of N- (2-sulfatoethyl) piperazine sulfate and 210 ml / l of a 50% by weight sodium hydroxide solution.
- the material is impregnated with a fleet order of 110%.
- the strand of goods then goes into a J-box and remains at a temperature between 95 and 98 ° C for 30 minutes. Then you wash out thoroughly, free the goods from loosened dirt particles and excess alkali and adjust to a residual moisture of 100%.
- the still moist material can then be dyed directly in a jet dyeing machine using a pull-out method.
- 1000 parts of the material are mixed with 10000 parts of water.
- 20 parts of a dye of the general formula are metered in known from DE-A-1 179 317, Example 2, over a period of 10 minutes.
- the mixture is heated to 80 ° C. and the material is left at this temperature for 45 minutes.
- the mixture is then cooled to 60 ° C., the remaining liquor is drained off and the material is treated according to customary methods. After drying you get a strong turquoise color with the usual fastness to use.
- Example 5 The procedure of Example 5 is followed.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung aminierter Baumwollfasern.The invention relates to a method for producing aminated cotton fibers.
In der Europäischen Offenlegungsschrift EP 0 546 476 A1 wird ein "Verfahren zur Herstellung eines modifizierten Fasermaterials und ein Verfahren zum Färben des modifizierten Fasermaterials mit anionischen Farbstoffen" beschrieben. Die Modifizierung des Fasermaterials erfolgt in der Weise, daß man eine amino-und estergruppenhaltige aliphatische oder cyclische Verbindung auf das Material aufbringt und einer thermischen Behandlung aussetzt. Eine weitere Möglichkeit ist, das Material in einer solchen Lösung über längere Zeit bei erhöhter Temperatur zu belassen.
Bei dem zu modifizierenden Materialien handelt es sich jeweils um färbefertige, d.h. abgekochte und gebleichte Baumwoll- und Baumwoll-Mischgewebequalitäten.
Diese Verfahrensweise, nämlich färbefertige Materialien nachträglich zu modifizieren, um sie dann salz- und alkalifrei zu färben, stellt sich bei einer Gesamtkostenkalkulation als sehr unökonomisch und unökologisch dar.European laid-open specification EP 0 546 476 A1 describes a "process for producing a modified fiber material and a process for dyeing the modified fiber material with anionic dyes". The fiber material is modified in such a way that an aliphatic or cyclic compound containing amino and ester groups is applied to the material and subjected to a thermal treatment. Another possibility is to leave the material in such a solution for a long time at an elevated temperature.
The materials to be modified are ready-to-dye, ie boiled and bleached cotton and cotton blended fabrics.
This procedure, namely to subsequently modify ready-to-use materials in order to then dye them free of salt and alkali, is very uneconomical and unecological in a total cost calculation.
Es bestand daher ein großer Bedarf nach einem Verfahren, das den Prozeß der Modifikation von Baumwolle in Verfahrensschritte integriert, die ohnehin mit Baumwolle durchgeführt werden müssen, um sie mit Reaktivfarbstoffen einfärben zu können, das also auch mit roher unvorbehandelter Baumwolle durchgeführt werden kann.There was therefore a great need for a process which integrates the process of modifying cotton into process steps which have to be carried out with cotton anyway in order to be able to dye them with reactive dyes, and which can therefore also be carried out with raw, untreated cotton.
Diese Aufgabe wird gelöst durch ein Verfahren zur Herstellung aminierter Baumwollfasern, dadurch gekennzeichnet, daß man Rohbaumwolle oder Rohbaumwolle-Polyester-Gemische gleichzeitig mit dem Abkochen, Beuchen oder Trockenmercerisieren durch Zusatz von einer gegebenenfalls durch 1 oder 2 oder mehrere Hydroxygruppen substituierten, gesättigten aliphatischen Verbindung von 3 bis 15 C-Atomen mit mindestens einer primären, sekundären, tertiären oder quartären Aminogruppe und mindestens einer hydrolysierbaren Estergruppe, in welcher der (die) gesättigte(n) Rest(e) geradkettig, verzweigt und/oder cyclisch ist (sind) und gegebenenfalls durch ein oder mehrere Heterogruppen unterbrochen sein kann (können), modifiziert.This object is achieved by a process for the production of aminated cotton fibers, characterized in that raw cotton or raw cotton-polyester mixtures are simultaneously boiled, boiled or dry mercerized by the addition of one, if necessary, by 1 or 2 or more hydroxyl-substituted, saturated aliphatic compound of 3 to 15 carbon atoms with at least one primary, secondary, tertiary or quaternary amino group and at least one hydrolyzable ester group in which the saturated radical (s) branches in a straight chain and / or is (are) and can optionally be interrupted by one or more hetero groups, modified.
Zur Modifizierung der Rohbaumwollfasern haben sich Verbindungen der allgemeinen Formel (1a), (1b) oder (1c) bewährt:
H₂N-alkylen-Ym (1c)
in welchen bedeuten:
- Y
- ist eine Estergruppe;
- A und N
- bilden zusammen mit 1 oder 2 Alkylengruppen von 1 bis 4 C-Atomen den bivalenten Rest eines heterocyclischen Ringes, worin
- A
- ein Sauerstoffatom oder eine Gruppe der allgemeinen Formel (a), (b) oder (c)
- R
- ein Wasserstoffatom oder eine Aminogruppe ist oder eine Alkylgruppe von 1 bis 6 C-Atomen bedeutet, die durch 1 oder 2 Substituenten aus der Gruppe Amino, Sulfo, Hydroxy, Sulfato, Phosphato und Carboxy substituiert sein kann, oder eine Alkylgruppe von 3 bis 8 C-Atomen ist, die durch 1 oder 2 Gruppen der Formeln -O- und -NH- oder eine Kombination davon unterbrochen ist und durch eine Amino-, Sulfo-, Hydroxy-, Sulfato- oder Carboxygruppe substituiert sein kann,
- R¹
- Wasserstoff, Methyl oder Ethyl ist,
- R²
- Wasserstoff, Methyl oder Ethyl ist und
- Z(-)
- ein Anion bedeutet;
- B
- ist die Aminogruppe der Formel H₂N- oder eine Amino- oder Ammoniumgruppe der allgemeinen Formel (d) oder (e)
- R¹, R² und Z(-)
- eine der obengenannten Bedeutungen besitzen,
- R³
- Methyl oder Ethyl ist und
- R⁴
- Wasserstoff, Methyl oder Ethyl bedeutet;
- p
- ist die Zahl 1 oder 2
- alkylen
- ist ein geradkettiger oder verzweigter Alkylenrest von 2 bis 6 C-Atomen, der durch 1 oder 2 Hydroxygruppen substituiert sein kann, oder ist ein geradkettiger oder verzweigter Alkylenrest von 3 bis 8 C-Atomen, der durch 1 oder 2 Gruppen der Formeln - O- und -NH- oder eine Kombination davon unterbrochen ist;
- alk
- ist ein geradkettiger oder verzweigter Alkylenrest von 2 bis 6 C-Atomen, oder ist ein geradkettiger oder verzweigter Alkylenrest von 3 bis 8 C-Atomen, der durch 1 oder 2 Gruppen der Formeln -O- und -NH- oder eine Kombination davon unterbrochen ist und ist bevorzugt ein geradkettiger oder verzweigter Alkylenrest von 2 bis 6 C-Atomen;
- m
- ist die Zahl 1 oder 2;
- n
- ist eine Zahl von 1 bis 4;
H₂N alkylene Y m (1c)
in which mean:
- Y
- is an ester group;
- A and N
- together with 1 or 2 alkylene groups of 1 to 4 carbon atoms form the divalent radical of a heterocyclic ring, in which
- A
- an oxygen atom or a group of the general formula (a), (b) or (c)
- R
- is a hydrogen atom or an amino group or denotes an alkyl group of 1 to 6 C atoms which can be substituted by 1 or 2 substituents from the group amino, sulfo, hydroxy, sulfato, phosphato and carboxy, or an alkyl group of 3 to 8 C. -Atoms which is interrupted by 1 or 2 groups of the formulas -O- and -NH- or a combination thereof and which can be substituted by an amino, sulfo, hydroxyl, sulfato or carboxy group,
- R¹
- Is hydrogen, methyl or ethyl,
- R²
- Is hydrogen, methyl or ethyl and
- Z (-)
- means an anion;
- B
- is the amino group of the formula H₂N or an amino or ammonium group of the general formula (d) or (e)
- R¹, R² and Z (-)
- have one of the meanings mentioned above,
- R³
- Is methyl or ethyl and
- R⁴
- Represents hydrogen, methyl or ethyl;
- p
- is the number 1 or 2
- alkylene
- is a straight-chain or branched alkylene radical of 2 to 6 C atoms, which can be substituted by 1 or 2 hydroxyl groups, or is a straight-chain or branched alkylene radical of 3 to 8 C atoms, which is represented by 1 or 2 groups of the formulas - O- and -NH- or a combination thereof is interrupted;
- alk
- is a straight-chain or branched alkylene radical of 2 to 6 C atoms, or is a straight-chain or branched alkylene radical of 3 to 8 C atoms which is interrupted by 1 or 2 groups of the formulas -O- and -NH- or a combination thereof and is preferably a straight-chain or branched alkylene radical of 2 to 6 carbon atoms;
- m
- is the number 1 or 2;
- n
- is a number from 1 to 4;
In vielen Fällen als günstig erwiesen haben sich Verbindungen, in denen die Estergruppen der aminogruppenhaltigen Verbindungen eine Sulfato- oder Phosphatogruppe ist oder eine C₁-C₄-Alkanoyloxygruppe, Phenylsulfonyloxy-oder eine am Benzolkern durch Substituenten aus der Gruppe Carboxy, C₁-C₄-Alkyl, C₁-C₄-Alkoxy und Nitro substituierte Phensulfonyloxygruppe ist.In many cases, compounds in which the ester groups of the compounds containing amino groups are a sulfato or phosphato group or a C₁-C₄-alkanoyloxy group, phenylsulfonyloxy or one on the benzene nucleus by substituents from the group carboxy, C₁-C₄-alkyl, have proven to be favorable C₁-C₄ alkoxy and nitro substituted phensulfonyloxy group.
Vorteilhaft verwenden lassen sich auch z.B. die Verbindungen N-(β-Sulfatoethyl)-piperazin, N-[β-(β-Sulfatoethoxy)-ethyl]piperazin, N-(γ-Sulfato-β-hydroxy-propyl)-pyrrolidin, N-(β-Sulfatoethyl)-piperidin, 2-Sulfato-3-hydroxy-1-amino-propan, 3-Sulfato-2-hydroxy-1-amino-propan, 1-Sulfato-3-hydroxy-2-amino-propan, 3-Hydroxy-1-sulfato-2-amino-propan, 2,3-Disulfato-1-amino-propan oder 1,3-Disulfato-2-amino-propan, ein Derivat dieser Verbindungen mit einer anderen vorstehend genannten Estergruppe statt der Sulfatogruppe, insbesondere N-(2-Sulfatoethyl)-piperazinsulfat.The compounds N- (β-sulfatoethyl) piperazine, N- [β- (β-sulfatoethoxy) ethyl] piperazine, N- (γ-sulfato-β-hydroxypropyl) pyrrolidine, N can also be used advantageously - (β-Sulfatoethyl) piperidine, 2-sulfato-3-hydroxy-1-aminopropane, 3-sulfato-2-hydroxy-1-aminopropane, 1-sulfato-3-hydroxy-2-aminopropane , 3-Hydroxy-1-sulfato-2-aminopropane, 2,3-disulfato-1-aminopropane or 1,3-disulfato-2-aminopropane, a derivative of these compounds with another ester group mentioned above instead of that Sulfato group, especially N- (2-sulfatoethyl) piperazine sulfate.
Darüberhinaus sind für die Modifizierung von Rohbaumwollartikeln auch solche Aminoverbindungen geeignet, die als reaktiven Rest an der Aminkomponente eine α-Chlor-β-hydroxy-Substitution aufweisen. Weiterhin können auch solche Verbindungen eingesetzt werden, die mit Hydroxylgruppen, beispielsweise von Cellulose, oder Amino- und Thiolgruppen, beispielsweise von Wolle und Seide, reagieren können und eine kovalente chemische Bindung einzugehen vermögen.In addition, those amino compounds that have an α-chloro-β-hydroxy substitution as a reactive residue on the amine component are also suitable for the modification of raw cotton articles. Furthermore, it is also possible to use compounds which can react with hydroxyl groups, for example cellulose, or amino and thiol groups, for example wool and silk, and which are capable of forming a covalent chemical bond.
Das Modifizieren während des Beuchens oder des Abkochens von Rohbaumwollartikeln kann kontinuierlich oder diskontinuierlich erfolgen. Als Beuch- oder Abkochflüssigkeit verwendet man in diskontinuierlicher Arbeitsweise Natronlauge mit etwa 5 bis 30 g/l NaOH. Man arbeitet vorzugsweise in geschlossenen Kesseln bei Temperaturen zwischen 80°C und 120°C, vorzugsweise 90 und 102°C. Das Vorbehandlungsagens kann linear, degressiv oder direkt zugegeben werden. Die Konzentrationen betragen zwischen 10 und 100 g/l, vorzugsweise 15 bis 30 g/l.The modification during the brewing or boiling of raw cotton articles can be carried out continuously or discontinuously. Soda lye with about 5 to 30 g / l NaOH is used as the baking or decoction liquid in a batch process. It is preferably carried out in closed tanks at temperatures between 80 ° C and 120 ° C, preferably 90 and 102 ° C. The pretreatment agent can be added linearly, degressively or directly. The concentrations are between 10 and 100 g / l, preferably 15 to 30 g / l.
Das erfindungsgemäße Modifizieren in diskontinuierlicher Form kann sich direkt einem Bleichprozeß mit Wasserstoffperoxid anschließen, indem man die zur Vorbehandlung notwendigen Menge Alkali der Bleichlösung zusetzt, dabei überschüssiges Bleichmittel zerstört und dann das Modifizierungsagenz addiert. Dabei hat es sich als vorteilhaft erwiesen, wenn der Bleichlösung kein Peroxidstabilisator zugesetzt wird.The modification according to the invention in discontinuous form can directly follow a bleaching process with hydrogen peroxide by adding the amount of alkali required for the pretreatment to the bleaching solution, thereby destroying excess bleaching agent and then adding the modification agent. It has proven to be advantageous if no peroxide stabilizer is added to the bleaching solution.
Bei einer kontinuierlichen Verfahrensführung schwanken die Mengen an NaOH zwischen 5 bis 20 Gew.-%, bezogen auf das Gewicht der Ware, je nach Art der Energiezufuhr und Art des Flottenauftrages. Als Anlageeinrichtungen dienen der Stiefel, Rollenbetten, Breit- und Blitzdämpfer, Rollendämpfer, HT-Dämpfer, Conveyor, Umdock-Anlagen und Unterflottenverweilanlagen. Gerechnet auf das Warengewicht, werden zwischen 2 und 10 Gew.-%, vorzugsweise 3 und 8 Gew.-%, Modifizierungsagens eingesetzt.In a continuous process, the amounts of NaOH fluctuate between 5 to 20% by weight, based on the weight of the goods, depending on the type of energy supply and the type of fleet order. The boots, roller beds, wide and lightning dampers, roller dampers, HT dampers, Conveyor, docking facilities and sub-fleet dwellings. Based on the weight of the goods, between 2 and 10% by weight, preferably 3 and 8% by weight, of modification agent are used.
Auch hier kann sich das erfindungsgemäße Modifizieren direkt einem kontinuierlichen Bleichprozeß anschließen, indem man auf das vorgebleichte, noch stark feuchte Material eine gegenüber einer üblichen Flotte zwei bis dreifach aufgestärkte, alkalische Wirksubstanzlösung aufquetscht und die Ware anschließend einem Dämpfprozeß unterwirft. Der Lösung für die Vorbleiche sollte kein Stabilisator zugesetzt sein, um zu gewährleisten, daß nach dem Aufquetschen der stark alkalischen Modifizierungsflotte das Wasserstoffperoxid schnell zerstört wird und so keine Faserschädigungen auftreten.Here too, the modification according to the invention can directly follow a continuous bleaching process by squeezing an alkaline active substance solution which has been strengthened two to three times compared to a conventional liquor onto the pre-bleached, still very moist material and then subjecting the goods to a steaming process. No stabilizer should be added to the solution for the pre-bleaching in order to ensure that after squeezing the strongly alkaline modification liquor, the hydrogen peroxide is quickly destroyed and thus no fiber damage occurs.
Das textile Fasermaterial, das in das erfindungsgemäße Vorbehandlungsverfahren eingesetzt wird, kann in allen Verarbeitungszuständen, so als Garn, Flocke, Kammzug und Stückware (Gewebe) vorliegen.The textile fiber material that is used in the pretreatment process according to the invention can be present in all processing states, such as yarn, flake, sliver and piece goods (fabric).
Ein wesentlicher und überraschender Vorteil des erfindungsgemäßen Verfahrens besteht darin, daß die Faserschädigung, die im Verlauf von Abkoch- oder Beuchprozessen immer auftritt, bei einer Vorbehandlung mit besagten Modifizierungsagenzien deutlich vermindert ist.An essential and surprising advantage of the method according to the invention is that the fiber damage that always occurs in the course of boiling or baking processes is significantly reduced during pretreatment with said modification agents.
Zum Modifizieren eignen sich ebenfalls Mercerisierprozesse. Die bevorzugte Ausführungsform ist ein Trockenmercerisieren, indem man auf das Gewebe eine Natronlauge von 22 bis 32° Be, vorzugsweise 24° Be, die im Liter zwischen 30 und 120 g Modifizierungsagens enthält, aufquetscht. Anschließend wird die Ware auf einem Spannrahmen mit Heißluft von 120°C übertrocknet. Nach einem Auswaschprozeß wird ein Material erhalten, das einen erhöhten Glanz zeigt und erfindungsgemäß salz- und alkalifrei gefärbt werden kann.Mercerization processes are also suitable for modification. The preferred embodiment is dry mercerization by squeezing a sodium hydroxide solution of 22 to 32 ° Be, preferably 24 ° Be, which contains between 30 and 120 g of modification agent per liter, onto the fabric. The goods are then over dried on a stenter with hot air at 120 ° C. After a wash-out process, a material is obtained which has an increased gloss and can be dyed free of salt and alkali according to the invention.
Einer andere Ausführungsform stellt die Imprägnierung mit heißer, modifizierungsagenshaltiger Flotte dar. Im Anschluß an die Heißimprägnierung durchläuft die Ware ein Walzenmercerisierabteil. Abweichend von gängigen Techniken sollte die Temperatur während der Quellung und in der anschließenden Stabilisierzone für eine längere Zeit zwischen 80 und 95°C gehalten werden.Another embodiment is the impregnation with hot, modification agent-containing liquor. Following the hot impregnation the goods pass through a roller marking compartment. Contrary to common techniques, the temperature should be kept between 80 and 95 ° C for a longer period during the swelling and in the subsequent stabilization zone.
Das erfindungsgemäße Färben der aminierten Baumwollfasern erfolgt analog bekannten Färbeweisen und Druckverfahren zum Färben und Bedrucken von Fasermaterialien mit wasserlöslichen textilen Farbstoffen und unter Anwendung der hierfür bekanntermaßen eingesetzten Temperaturbereiche und üblichen Farbstoffmengen. Der besondere Vorteil hierbei ist, daß für die Färbebäder, Klotzverfahren, Druckpasten und Ink-Jet-Formulierungen ein Zusatz von alkalisch wirkenden Verbindungen, wie sie üblicherweise zur Fixierung von faserreaktiven Farbstoffen benutzt werden, nicht nötig ist und des weiteren auch auf übliche Zusätze an Elektrolytsalzen verzichtet werden kann.The dyeing of the aminated cotton fibers according to the invention is carried out analogously to known dyeing methods and printing processes for dyeing and printing fiber materials with water-soluble textile dyes and using the temperature ranges and customary amounts of dye known to be used for this. The particular advantage here is that the dye baths, padding processes, printing pastes and ink-jet formulations do not require the addition of alkaline compounds, as are usually used for fixing fiber-reactive dyes, and furthermore also the usual additions of electrolyte salts can be dispensed with.
Färbeverfahren, die erfindungsgemäß eingesetzt werden können, sind beispielsweise die verschiedenen Ausziehverfahren, wie das Färben auf dem Jigger und auf der Haspelkufe oder das Färben aus langer und kurzer Flotte, das Färben in Jet-Färbemaschinen, das Färben nach Klotz-Kaltverweilverfahren oder nach einem Klotz-Heißdampf-Fixierverfahren.
Zu den erfindungsgemäß nutzbaren Färbeverfahren zählen auch die Drucktechniken, einschließlich des Ink-Jet-Printings und des Transferdruckes.Dyeing processes which can be used according to the invention are, for example, the various exhaust processes, such as dyeing on the jigger and on the reel runner or dyeing from a long and short liquor, dyeing in jet dyeing machines, dyeing by padding-cold dwelling or padding -Hot steam fixing process.
The dyeing methods which can be used according to the invention also include the printing techniques, including ink-jet printing and transfer printing.
Die Farbstoffe, die zum Färben der aminierten Baumwollfaser genutzt werden, sind im allgemeinen anionischer Natur. Besonders geeignet sind die faserreaktiven Textilfarbstoffe, die mit Hydroxylgruppen, beispielsweise von Cellulose, oder Amino- und Thiolgruppen, beispielsweise von Wolle und Seide, von synthetischen Polymeren, wie Polyamiden, oder auch modifizierten Polymeren, eben den aminierten Cellulosen, reagieren können und eine kovalente Bindung einzugehen vermögen. Als faserreaktive Komponente an den Textilfarbstoffen seien besonders der Sulfatoethylsulfonyl-, Vinylsulfonyl-, Chlortriazinyl-, Fluortriazinyl-, Trichlorpyrimidyl-, Difluorchlorpyrimidyl-, Dichlorchinoxalinyl-, Chlorpropylamidyl-, α-Bromacrylamidyl sowie Kombinationen dieser "Ankersysteme" genannt.The dyes used to dye the aminated cotton fiber are generally anionic in nature. The fiber-reactive textile dyes, which can react with hydroxyl groups, for example of cellulose, or amino and thiol groups, for example of wool and silk, of synthetic polymers, such as polyamides, or also modified polymers, namely the aminated celluloses, and a covalent bond are particularly suitable able to enter. The fiber-reactive component on the textile dyes are, in particular, the sulfatoethylsulfonyl, vinylsulfonyl, chlorotriazinyl, fluorotriazinyl, trichloropyrimidyl, difluorochloropyrimidyl, Dichloroquinoxalinyl, chloropropylamidyl, α-bromoacrylamidyl and combinations of these “anchor systems” are mentioned.
Die nachfolgenden Beispiele dienen zur Erläuterung des erfindungsgemäßen Verfahrens. Wenn nicht anders angegeben, sind die in den Beispielen angeführten Teile Gewichtsteile.The following examples serve to explain the method according to the invention. Unless otherwise stated, the parts given in the examples are parts by weight.
Baumwollköper (vorentschlichtet, rohweiß, Gewicht 200 g/kg) wird mit einer wäßrigen Flotte, die 60 Teile Sulfatoethylpiperazin, 100 Teile Natriumhydroxid, 5 Teile ®Hostapal FA (Handelsname eines nichtionischen Netz- und Waschmittels) und 6 Teile ®Ladit RBO in 1000 Teilen Wasser enthält, imprägniert. Die Flottenaufnahme bei dieser Behandlung beträgt ca. 150 %. Das Gewebe wird anschließend aufgedockt und 60 Minuten bei 95 bis 103°C belassen. Der Temperaturbehandlung schließt sich ein dreimaliger Waschvorgang, wobei die Waschlösung gegebenenfalls ein handelsübliches Tensid enthalten kann, bei Kochtemperatur an, um die auf dem Gewebe befindlichen wasserlöslichen Verunreinigungen zu entfernen. Nach Spülen mit warmem und kaltem Wasser wird das Baumwollmaterial getrocknet. Man erhält so ein textiles Gewebe mit einem Entschlichtungsgrad von 9 (Bewertung nach Tegewa) und einer Saughöhe von 6,5 cm nach 300 Minuten, das direkt in einem Färbeprozeß nach dem Klotz-Verfahren weiterverarbeitet werden kann. Hierzu wird eine wäßrige Farbstofflösung, die in 1000 Vol.-Teilen 20 Teile des Farbstoffs der Formel,
bekannt aus der Europäischen Patentanmeldung 158 233, Bsp. 1, und 3 Teile eines handelsüblichen nichtionogenen Benetzungsmittels gelöst enthält, mittels eines Foulards mit einer Flottenaufnahme von 80 %, bezogen auf das Gewicht des Gewebes, bei 25°C auf das Gewebe aufgebracht. Das mit der Farbstofflösung geklotzte Gewebe wird auf eine Docke aufgewickelt, in eine Plastikfolie gewickelt, während 4 Stunden bei 40 bis 50°C liegen gelassen und danach mit kaltem und heißem Wasser, das gegebenenfalls ein handelsübliches Tensid enthalten kann, und gegebenenfalls anschließend nochmals mit kaltem Wasser gespült und getrocknet. Es wird eine farbstarke, gleichmäßig gefärbte gelbe Färbung erhalten, die gute Allgemeinechtheiten, insbesondere gute Reib-und Lichtechtheiten, besitzt.Cotton twill (pre-desized, raw white, weight 200 g / kg) is mixed with an aqueous liquor containing 60 parts sulfatoethylpiperazine, 100 parts sodium hydroxide, 5 parts ®Hostapal FA (trade name of a nonionic wetting and detergent) and 6 parts ®Ladit RBO in 1000 parts Contains water, impregnated. The liquor intake with this treatment is approx. 150%. The tissue is then docked and left at 95 to 103 ° C for 60 minutes. The temperature treatment is followed by a three-time washing process, the washing solution optionally being able to contain a commercially available surfactant, at boiling temperature, in order to remove the water-soluble impurities present on the fabric. After rinsing with warm and cold water, the cotton material is dried. This gives a textile fabric with a degree of desizing of 9 (Tegewa rating) and a suction head of 6.5 cm after 300 minutes, which can be processed directly in a dyeing process using the block process. For this purpose, an aqueous dye solution containing 20 parts of the dye of the formula
known from European Patent Application 158 233, Example 1, and 3 parts of a commercially available nonionic wetting agent dissolved, applied to the fabric at 25 ° C by means of a pad with a liquor absorption of 80%, based on the weight of the fabric. The fabric padded with the dye solution is wound onto a dock, wrapped in a plastic sheet, left for 4 hours at 40 to 50 ° C and then with cold and hot water, which may optionally contain a commercially available surfactant, and then optionally again with cold water Rinsed water and dried. A strong, uniformly colored yellow coloration is obtained which has good general fastness properties, in particular good fastness to rubbing and light.
Polyester-Baumwoll-Mischgewebe, 50/50 (vorentschlichtet, rohweiß, Gewicht 200 g/kg) wird mit einer wäßrigen Flotte, die 30 Teile Sulfatoethylpiperazin, 50 Teile Natriumhydroxid und 5 Teile ®Leonil EB (Handelsname eines nichtionischen Netz- und Waschmittels) in 1000 Teilen Wasser enthält, imprägniert. Die Flottenaufnahme bei dieser Behandlung beträgt ca. 150 %. Das Gewebe wird anschließend aufgedockt und 30 Minuten bei 95 bis 103°C belassen. Der Temperaturbehandlung schließt sich direkt ein mehrgängiger Waschvorgang, wobei die Waschlösungen gegebenenfalls handelsübliches Tensid enthalten können, bei Kochtemperatur an, um die auf dem Gewebe befindlichen wasserlöslichen Verunreinigungen zu entfernen. Nach Spülen mit warmem und kaltem Wasser wird das Baumwollmaterial getrocknet. 10 Teile dieses Polyester/Baumwoll-Mischgewebes werden nach einem üblichen Ausziehverfahren in einem Flottenverhältnis von 1:10 mit einer Flotte, die 0,1 Teile eines 50 gew.-%igen elektrolythaltigen C.I. Reactive Red 198
(vorwiegend natriumchloridhaltig) und 0,1 Teile eines Dispersionsfarbstoffes
in 100 Teile Wasser gelöst oder dispergiert enthält in einer HT-Apparatur zusammengebracht. Man erwärmt auf 130°C. Nach 30 Minuten bei dieser Temperatur läßt man abkühlen, verwirft die farblose Flotte und wäscht das Gewebe wie üblich nach. Man erhält eine farbstarke egale rote Färbung, die in ihren Echtheiten der einer nach dem Stand der Technik erzielten Färbung in allen Punkten gleichwertig ist.Polyester-cotton blend, 50/50 (pre-desized, raw white, weight 200 g / kg) is mixed with an aqueous liquor containing 30 parts of sulfatoethylpiperazine, 50 parts of sodium hydroxide and 5 parts of ®Leonil EB (trade name of a nonionic wetting and washing agent) Contains 1000 parts of water, impregnated. The liquor intake with this treatment is approx. 150%. The tissue is then docked and left at 95 to 103 ° C for 30 minutes. The temperature treatment is followed directly by a multi-course washing process, the washing solutions optionally being able to contain commercially available surfactant, at the boiling temperature, in order to remove the water-soluble impurities present on the fabric. After rinsing with warm and cold water, the cotton material is dried. 10 parts of this polyester / cotton blended fabric are in a liquor ratio of 1:10 with a liquor containing 0.1 part of a 50% by weight electrolyte-containing CI Reactive Red 198 by a customary drawing-out process
(mainly containing sodium chloride) and 0.1 part of a disperse dye
dissolved or dispersed in 100 parts of water contains brought together in an HT apparatus. The mixture is heated to 130 ° C. After 30 minutes at this temperature, the mixture is allowed to cool, the colorless liquor is discarded and the fabric is washed as usual. This gives a strong, level, level red dyeing, the authenticity of which is equivalent to that of the dyeing obtained in the prior art in all respects.
In einer HT-Apparatur werden 150 Teile Baumwoll-Köper (rohweiß, Gewicht 200 g/kg) mit einer wäßrigen Flotte, die 15 Teile Natriumhydroxid und 5 Teile Leonil EB (Handelsnahme eines nichtionischen Netz- und Waschmittels) in 750 Teilen Wasser enthält, auf 120°C erwärmt. Bei dieser Temperatur werden dann über einen Zeitraum von 30 Minuten 30 Teile N-(2-Sulfatoethyl)piperazinsulfat, bekannt aus EP-A-0 601 351, gelöst in 30 Teilen Wasser, linear zudosiert. Nach beendeter Zugabe wird die Temperatur noch 10 Minuten bei 120°C belassen und anschließend die Flotte verworfen. Der Temperaturbehandlung schließt sich ein dreimaliger Waschvorgang, wobei die Waschlösung gegebenenfalls ein handelsübliches Tensid enthalten kann, bei Kochtemperatur an, um die auf dem Gewebe befindlichen wasserlöslichen Verunreinigungen zu entfernen. Nach Spülen mit warmem und kaltem Wasser wird das Baumwollmaterial getrocknet. Man erhält so ein textiles Gewebe mit einem Entschlichtungsgrad von 9 (Bewertung nach Tegewa) und einer Saughöhe von 6,5 cm nach 300 Minuten, das direkt in einem Ausziehfärbeprozeß weiterverarbeitet werden kann. Die vorbehandelte, aber noch nasse Ware wird dann in einer Färbeapparatur mit 1000 Teilen Wasser versetzt. Man heizt auf 60°C auf und dosiert insgesamt 2 Teile eines 50 gew.-%igen elektrolythaltigen (vorwiegend natriumchloridhaltigen) Farbstoffpulvers der Formel, bekannt aus der DE-A-1943904,
über eine Zeit von 30 Minuten zu. Nach einer Nachlaufzeit von 5 Minuten wird die farblose Restflotte abgelassen und das Material nach üblichen Methoden ausgewaschen und getrocknet. Man erhält eine farbstarke tiefrote Färbung mit sehr guten Gebrauchsechtheiten.In an HT apparatus, 150 parts of cotton twill (raw white, weight 200 g / kg) are mixed with an aqueous liquor which contains 15 parts of sodium hydroxide and 5 parts of Leonil EB (trade name of a nonionic wetting and washing agent) in 750 parts of water Heated to 120 ° C. At this temperature, 30 parts of N- (2-sulfatoethyl) piperazine sulfate, known from EP-A-0 601 351, dissolved in 30 parts of water, are then metered in linearly over a period of 30 minutes. After the addition is complete, the temperature is at 10 minutes Leave at 120 ° C and then discard the fleet. The temperature treatment is followed by a three-time washing process, the washing solution optionally being able to contain a commercially available surfactant, at boiling temperature, in order to remove the water-soluble impurities present on the fabric. After rinsing with warm and cold water, the cotton material is dried. This gives a textile fabric with a degree of desizing of 9 (Tegewa rating) and a suction head of 6.5 cm after 300 minutes, which can be further processed directly in an exhaust dyeing process. The pretreated but still wet goods are then mixed with 1000 parts of water in a dyeing apparatus. The mixture is heated to 60 ° C. and a total of 2 parts of a 50% by weight electrolyte-containing (predominantly sodium chloride-containing) dye powder of the formula known from DE-A-1943904 are metered in.
over a period of 30 minutes. After a run-on time of 5 minutes, the colorless remaining liquor is drained off and the material is washed out and dried by customary methods. A deep red color with very good fastness properties is obtained.
Ein Baumwoll-Köper-Gewebe (rohweiß, entschlichtet, Gewicht 200 g/kg) wird mit einer 60°C warmen Natronlauge von 30°Be, die im Liter 60 g N-(2-Sulfatoethyl)piperazinsulfat enthält, imprägniert und unter Druck aufgerollt und dann auf eine zweite, auf 80°C vorgeheizte Walze aufgerollt. Nach dem Umrollen, das von Walze zu Walze in dauernder direkter Berührung und bei einer Temperatur von 90°C erfolgt und somit ein Schrumpfen verhindert, schließt sich ein Spannfeld an. Der Prozess des Umrollens dauert 15 Minuten, die Verweilzeit im Spannfeld beträgt 10 Minuten. Es folgt ein Entlaugen durch Aufspritzen von heißem Wasser und ein Waschvorgang, wobei die Waschlösung ein handelsübliches Tensid enthalten kann, bei Kochtemperatur. Nach Ansäurern und einem nochmaligen Spülen mit warmem und kaltem Wasser wird das Baumwollmaterial getrocknet. Man erhält so ein textiles Gewebe, daß unter bekannten Bedingungen anschließend abgekocht, ohne Salz und Alkali gefärbt werden kann. Dazu werden 10 Teile dieses Materials in einen Färbeapparat überführt und in einem Flottenverhältnis von 1:10 mit einer wäßrigen Flotte behandelt, die - bezogen auf das Warengewicht der trockenen Ware - 0,1 Teile eines Reaktivfarbstoffes der Formel,
bekannt aus EP-A-0 028 788 Bsp. 2, gelöst enthält, behandelt. Man färbt die Fasermischung 30 Minuten bei 80°C. Die Weiterbehandlung der so erzeugten Färbung erfolgt durch Spülen und Seifen in der üblichen Weise. Man erhält eine tiefblaue Färbung mit den nach dem Stand der Technik üblichen sehr guten Gebrauchsechtheiten.A cotton twill fabric (raw white, desized, weight 200 g / kg) is impregnated with a 60 ° C warm sodium hydroxide solution of 30 ° Be, which contains 60 g N- (2-sulfatoethyl) piperazine sulfate per liter and rolled up under pressure and then rolled up on a second roller preheated to 80 ° C. After rewinding, which takes place from roller to roller in constant direct contact and at a temperature of 90 ° C and thus prevents shrinking, closes a span. The process of rolling over takes 15 minutes, the dwell time in the tensioning field is 10 minutes. This is followed by a leaching by spraying hot water and a washing process, wherein the washing solution can contain a commercial surfactant, at boiling temperature. After acidification and rinsing again with warm and cold water, the cotton material is dried. A textile fabric is thus obtained which can then be boiled under known conditions and dyed without salt and alkali. For this purpose, 10 parts of this material are transferred to a dyeing apparatus and treated in a liquor ratio of 1:10 with an aqueous liquor which, based on the weight of the dry goods, contains 0.1 part of a reactive dye of the formula
known from EP-A-0 028 788 Ex. 2, contains dissolved, treated. The fiber mixture is dyed at 80 ° C. for 30 minutes. The dyeing thus produced is further treated by rinsing and soaping in the customary manner. A deep blue color is obtained with the very good fastness properties customary according to the prior art.
In einer kontinuierlichen Arbeitsweise wird Baumwoll-Interlock ungebleicht als Schlauch bei 100°C in ein Bad, das 1 %, bezogen auf die Flüssigkeitsmenge, einer 50 gew.-%igen Natronlauge und 1 %, bezogen auf Flüssigkeitsmenge, einer 35 gew.- %igen Wasserstoffperoxidlösung enthält, getaucht. Die Ware läßt man 10 min verweilen und zieht sie dann durch ein Quetschwerk, so daß ein Flottenauftrag von ca. 80 % verbleibt. Anschließend führt man das Material durch einen Netztrog mit Mehrfachquetschwerk, in dem sich eine Lösung befindet, die 210 g/l N-(2-Sulfatoethyl)-piperazinsulfat und 210 ml/l einer 50 gew.- %igen Natronlauge enthält. Bei diesem Vorgang wird das Material mit einem Flottenauftrag von 110 % imprägniert. Zur weiteren Behandlung fährt der Warenstrang dann in eine J-Box und verbleibt hierin über 30 Minuten bei einer Temperatur zwischen 95 und 98°C. Anschließend wäscht man gründlich aus, befreit die Ware dabei von gelösten Schmutzpartikeln und überschüssigem Alkali und stellt auf eine Restfeuchte von 100 % ein. Das noch feuchte Material kann danach direkt nach einer Ausziehmethode in einer Düsenfärbemaschine gefärbt werden. Dazu werden 1000 Teile des Materials mit 10000 Teilen Wasser versetzt.
Anschließend dosiert man 20 Teile eines Farbstoffs der allgemeinen Formel
bekannt aus der DE-A-1 179 317, Beispiel 2, über eine Zeit von 10 Minuten zu. Man heizt auf 80°C auf und beläßt das Material bei dieser Temperatur über 45 Minuten. Anschließend kühlt man auf 60°C, läßt die Restflotte ab und behandelt das Material nach gängigen Methoden nach. Nach dem Trocknen erhält man eine farbstarke Türkisfärbung mit den üblichen Gebrauchsechtheiten.In a continuous process, cotton interlock is unbleached as a tube at 100 ° C in a bath containing 1%, based on the amount of liquid, a 50% by weight sodium hydroxide solution and 1%, based on the amount of liquid, a 35% by weight. contains hydrogen peroxide solution, immersed. The goods are allowed to linger for 10 minutes and then pulled through a crusher, so that a fleet order of approximately 80% remains. The material is then passed through a mesh trough with multiple squeezing mechanism in which there is a solution which contains 210 g / l of N- (2-sulfatoethyl) piperazine sulfate and 210 ml / l of a 50% by weight sodium hydroxide solution. In this process, the material is impregnated with a fleet order of 110%. For further treatment, the strand of goods then goes into a J-box and remains at a temperature between 95 and 98 ° C for 30 minutes. Then you wash out thoroughly, free the goods from loosened dirt particles and excess alkali and adjust to a residual moisture of 100%. The still moist material can then be dyed directly in a jet dyeing machine using a pull-out method. For this purpose, 1000 parts of the material are mixed with 10000 parts of water.
Then 20 parts of a dye of the general formula are metered in
known from DE-A-1 179 317, Example 2, over a period of 10 minutes. The mixture is heated to 80 ° C. and the material is left at this temperature for 45 minutes. The mixture is then cooled to 60 ° C., the remaining liquor is drained off and the material is treated according to customary methods. After drying you get a strong turquoise color with the usual fastness to use.
1000 Teile Baumwoll-Jersey, ungebleicht, werden in einer Düsenfärbemaschine mit 5000 Teilen Wasser, das 50 Teile einer 35 gew.-%igen Wasserstoffperoxidlösung und 75 Teile einer 50 gew.-%igen Natronlauge enthält, versetzt. Man heizt das Gewirke mit 3°C pro Minute auf 98°C auf und beläßt bei dieser Temperatur für 10 min. Nach dieser Zeit werden 360 Teile einer 50 gew.-%igen Natronlauge zugegeben, die Temperatur oberhalb 95°C gehalten und damit überschüssiges Wasserstoffperoxid zerstört. Innerhalb von 10 min läßt man dann 760 Volumenteile einer Lösung zulaufen, die 180 Teile N-(2-Sulfatoethyl)-piperazinsulfat gelöst enthält und stellt die Temperatur für weitere 30 Minuten auf 98°C. Danach kühlt man auf 60°C ab, wäscht alkalifrei und behandelt das Material mit Essigsäure nach. Das auf diese Weise vorgebleichte und modifizierte Gewirke kann im Anschluß daran direkt ohne jede Zusätze gefärbt werden. Dabei verfährt man entsprechend den Angaben des Beispiels 5.1000 parts of cotton jersey, unbleached, are mixed in a jet dyeing machine with 5000 parts of water, which contains 50 parts of a 35% by weight hydrogen peroxide solution and 75 parts of a 50% by weight sodium hydroxide solution. The knitted fabric is heated to 98 ° C. at 3 ° C. per minute and left at this temperature for 10 minutes. After this time, 360 parts of a 50% strength by weight sodium hydroxide solution are added, the temperature is kept above 95 ° C. and thus excess hydrogen peroxide is destroyed. 760 parts by volume of a solution containing 180 parts of N- (2-sulfatoethyl) piperazine sulfate in solution are then run in within 10 minutes and the temperature is set at 98 ° C. for a further 30 minutes. The mixture is then cooled to 60 ° C., washed free of alkali and the material is treated with acetic acid. The knitted fabric which has been pre-bleached and modified in this way can then be dyed directly without any additives. The procedure of Example 5 is followed.
Man verfährt entsprechend den Angaben des Beispiels 1 und färbt mit den nachfolgend aufgeführten Farbstoffen. Dabei erhält man ähnlich gute Ergebnisse.
Claims (9)
H₂N-alkylen-Ym (1c)
ist, in welchen bedeuten:
worin
H₂N alkylene Y m (1c)
is in which mean:
wherein
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4402210 | 1994-01-26 | ||
| DE4402210A DE4402210A1 (en) | 1994-01-26 | 1994-01-26 | Process for the production of aminated cotton fibers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0665325A2 true EP0665325A2 (en) | 1995-08-02 |
| EP0665325A3 EP0665325A3 (en) | 1997-10-22 |
Family
ID=6508713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95100369A Withdrawn EP0665325A3 (en) | 1994-01-26 | 1995-01-12 | Process for the manufacture of aminated cotton fibers. |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5542954A (en) |
| EP (1) | EP0665325A3 (en) |
| JP (1) | JPH07300779A (en) |
| KR (1) | KR950032873A (en) |
| CN (1) | CN1112979A (en) |
| AU (1) | AU1010395A (en) |
| BR (1) | BR9500318A (en) |
| CA (1) | CA2141094A1 (en) |
| DE (1) | DE4402210A1 (en) |
| MA (1) | MA23436A1 (en) |
| PL (1) | PL306950A1 (en) |
| TR (1) | TR28440A (en) |
| ZA (1) | ZA95575B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19547649C2 (en) | 1995-12-20 | 1999-05-06 | Dystar Textilfarben Gmbh & Co | Aqueous solution of N- (2-sulfatoethyl) piperazine sulfate, process for its preparation and its use for modifying cellulosic fiber materials |
| US6240601B1 (en) | 2000-04-24 | 2001-06-05 | Cotton Conditioners, Inc. | Method and apparatus for conditioning textile fibers |
| GB0801346D0 (en) * | 2008-01-25 | 2008-03-05 | Secr Defence | Modified cellulosic materials |
| CN105316929A (en) * | 2014-11-29 | 2016-02-10 | 耿云花 | Preparation method of formaldehyde-removing cotton fabric |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB441448A (en) * | 1934-08-14 | 1936-01-20 | Ig Farbenindustrie Ag | Process for the manufacture of nitrogenous cellulose derivatives |
| GB465200A (en) * | 1935-08-26 | 1937-04-26 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of valuable condensation products containing nitrogen, phosphorus or sulphur |
| GB494766A (en) * | 1936-05-28 | 1938-11-01 | Roehm & Haas Co | Production of ammonia derivatives |
| GB668961A (en) * | 1949-04-21 | 1952-03-26 | Basf Ag | Assistants for the textile and dyeing industries |
| EP0546476A1 (en) * | 1991-12-07 | 1993-06-16 | Hoechst Aktiengesellschaft | Process for making a modified fiber material and process for dyeing the modified fiber material with anionic dyestuffs |
| EP0590397A1 (en) * | 1992-09-26 | 1994-04-06 | Hoechst Aktiengesellschaft | Process for the preparation of dyes following the ink-jet print technique on modified fiber materials with anionic textile dyesstuffs |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0158233B1 (en) * | 1984-04-09 | 1989-12-13 | Hoechst Aktiengesellschaft | Process for the manufacture of liquid, aqueous dyestuff preparations with a low salt content |
| TW360645B (en) * | 1992-11-21 | 1999-06-11 | Hoechst Ag | N-(2-sulfatoethyl) piperazine sulfate and it preparation |
-
1994
- 1994-01-26 DE DE4402210A patent/DE4402210A1/en not_active Withdrawn
-
1995
- 1995-01-09 AU AU10103/95A patent/AU1010395A/en not_active Abandoned
- 1995-01-12 EP EP95100369A patent/EP0665325A3/en not_active Withdrawn
- 1995-01-23 MA MA23763A patent/MA23436A1/en unknown
- 1995-01-24 US US08/377,438 patent/US5542954A/en not_active Expired - Fee Related
- 1995-01-24 CN CN95101352A patent/CN1112979A/en active Pending
- 1995-01-24 TR TR00079/95A patent/TR28440A/en unknown
- 1995-01-25 PL PL95306950A patent/PL306950A1/en unknown
- 1995-01-25 CA CA002141094A patent/CA2141094A1/en not_active Abandoned
- 1995-01-25 BR BR9500318A patent/BR9500318A/en not_active Application Discontinuation
- 1995-01-25 KR KR1019950001290A patent/KR950032873A/en not_active Application Discontinuation
- 1995-01-25 ZA ZA95575A patent/ZA95575B/en unknown
- 1995-01-25 JP JP7010138A patent/JPH07300779A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB441448A (en) * | 1934-08-14 | 1936-01-20 | Ig Farbenindustrie Ag | Process for the manufacture of nitrogenous cellulose derivatives |
| GB465200A (en) * | 1935-08-26 | 1937-04-26 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of valuable condensation products containing nitrogen, phosphorus or sulphur |
| GB494766A (en) * | 1936-05-28 | 1938-11-01 | Roehm & Haas Co | Production of ammonia derivatives |
| GB668961A (en) * | 1949-04-21 | 1952-03-26 | Basf Ag | Assistants for the textile and dyeing industries |
| EP0546476A1 (en) * | 1991-12-07 | 1993-06-16 | Hoechst Aktiengesellschaft | Process for making a modified fiber material and process for dyeing the modified fiber material with anionic dyestuffs |
| EP0590397A1 (en) * | 1992-09-26 | 1994-04-06 | Hoechst Aktiengesellschaft | Process for the preparation of dyes following the ink-jet print technique on modified fiber materials with anionic textile dyesstuffs |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA95575B (en) | 1995-10-04 |
| AU1010395A (en) | 1995-08-03 |
| TR28440A (en) | 1996-06-19 |
| CN1112979A (en) | 1995-12-06 |
| US5542954A (en) | 1996-08-06 |
| CA2141094A1 (en) | 1995-07-27 |
| EP0665325A3 (en) | 1997-10-22 |
| PL306950A1 (en) | 1995-08-07 |
| KR950032873A (en) | 1995-12-22 |
| MA23436A1 (en) | 1995-10-01 |
| JPH07300779A (en) | 1995-11-14 |
| DE4402210A1 (en) | 1995-07-27 |
| BR9500318A (en) | 1995-10-17 |
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