CN101389794B - Method of producing a dyed formed cellulosic article - Google Patents
Method of producing a dyed formed cellulosic article Download PDFInfo
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- CN101389794B CN101389794B CN2006800478248A CN200680047824A CN101389794B CN 101389794 B CN101389794 B CN 101389794B CN 2006800478248 A CN2006800478248 A CN 2006800478248A CN 200680047824 A CN200680047824 A CN 200680047824A CN 101389794 B CN101389794 B CN 101389794B
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- 238000000034 method Methods 0.000 title claims abstract description 82
- 229920002678 cellulose Polymers 0.000 claims abstract description 53
- 239000001913 cellulose Substances 0.000 claims abstract description 52
- 239000000835 fiber Substances 0.000 claims abstract description 28
- 239000007858 starting material Substances 0.000 claims abstract description 5
- 239000000975 dye Substances 0.000 claims description 101
- 238000004043 dyeing Methods 0.000 claims description 84
- 239000000463 material Substances 0.000 claims description 64
- 238000009987 spinning Methods 0.000 claims description 43
- 238000004519 manufacturing process Methods 0.000 claims description 41
- 229920000297 Rayon Polymers 0.000 claims description 33
- 239000004627 regenerated cellulose Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 17
- 238000000465 moulding Methods 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 12
- 229920003043 Cellulose fiber Polymers 0.000 claims description 10
- 239000004753 textile Substances 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 3
- 238000010014 continuous dyeing Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 abstract description 5
- 239000000984 vat dye Substances 0.000 abstract description 3
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 239000000049 pigment Substances 0.000 description 33
- 238000005516 engineering process Methods 0.000 description 15
- 230000009467 reduction Effects 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 11
- 239000002964 rayon Substances 0.000 description 10
- 238000004040 coloring Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 210000002615 epidermis Anatomy 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
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- 238000012545 processing Methods 0.000 description 4
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000009973 dope dyeing Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- CRTGSPPMTACQBL-UHFFFAOYSA-N 2,3-dihydroxycyclopent-2-en-1-one Chemical compound OC1=C(O)C(=O)CC1 CRTGSPPMTACQBL-UHFFFAOYSA-N 0.000 description 2
- 229920000433 Lyocell Polymers 0.000 description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
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- 239000003086 colorant Substances 0.000 description 2
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- 238000005034 decoration Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
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- 239000002699 waste material Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 241000380131 Ammophila arenaria Species 0.000 description 1
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- 206010027626 Milia Diseases 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
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- 238000007380 fibre production Methods 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 238000004045 reactive dyeing Methods 0.000 description 1
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- 230000011218 segmentation Effects 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- JXUKQCUPTNLTCS-UHFFFAOYSA-N vat green 1 Chemical compound C1=CC=C[C]2C(=O)C(C3=C45)=CC=C4C(C4=C67)=CC=C7C(=O)[C]7C=CC=CC7=C6C=C(OC)C4=C5C(OC)=CC3=C21 JXUKQCUPTNLTCS-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/06—Dyes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
- D01F2/16—Addition of dyes to the spinning solution
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a method of producing a formed cellulosic article dyed using a vat dye, in particular a fibre or a film, comprising the following steps: providing a cellulosic starting material which comprises the vat dye in molecularly disperse form; preparing a formable solution from the cellulosic starting material; forming the solution through a suitable forming tool; precipitating or regenerating the cellulose from the formed solution.
Description
The present invention relates to the production by the cellulose cellulose matrix that process, dyed that dyes with reducing dye, this dyeing cellulosic matrix is used to produce the cellulose moulded bodies of dyeing.Molding can be fiber, film or other shape.
The preparation of the molding that in the spinning material, dyes itself is well-known.Proposed different commercial runs for this reason, wherein had some also using up to today:
When the production of cellulose molding; The most important form of spinning material dyeing is the basis with interpolation fine dispersion, insoluble pigment (Pigment) in the spinning material; These pigment are fixed in the cellulose matrix when forming fiber afterwards, and depend on that employed pigment has good COLOR FASTNESS.The instance of this respect is explained as follows:
For the organic or inorganic pigment fine dispersion adds in the spinning material; Enumerate out following instance: Novacel S; A. " Colored regenerated cellulose sponges (regenerated cellulosic sponge of dyeing) "-FR10252961953 April 13 is referring to ChemicalAbstractNo.52:3968; " Coloringviscose fibers (viscose fiber staining) "-FR1114803 of Manusfactures de produits chimiques du Nord (Kuhlmann research institute); On April 17th, 1956 is referring to ChemicalAbstract No.53:102818; Jones, F.B " Glossy, spun-dyed threads from aqueouscellulose solutions (line of the glossiness dope dyeing of processing by moisture cellulose solution "-DE1067173, October 15 nineteen fifty-nine; Keil, A., Popp, P, and Krause, " Process for theproduction of pigmented regenerated cellulosic fibers (production technology of the regenerated celulose fibre of dyeing) "-GB872207 of E, on July 5th, 1961; Eskridge, " Manufacture ofpigmented viscose rayon (manufacturing of the viscose silk of dyeing) "-US3033697 of B.E., on May 8th, 1962; Gomm; A.S., Morgan, L.B. and Wood; L. " Process of incorporating aqueouspigment composition in viscose (adding moisture color compositions in the viscose technology) "-US3156574, on November 10th, 1964; Heinrich; E. " Spin-dyed regenerated celluloseproducts and process for their manufacture (the regenerated cellulose product and the manufacturing technique thereof of dyeing when process is spun) "-GB1046299, on October 19th, 1966; Schoenbach, V., Weissert, J., and Teige, " Pigment dispersions for coloring viscose spinning masses (pigment dispersion that is used for the dyeing of rayon spinning material) "-US3337360 of W., on August 22nd, 1967; Hama; H. and Sakurai; H. " Dope dyeing viscose rayon having a good blackluster (the dip dyeing viscose silk with good black glossy) "-JP47051968, on December 27th, 1972 is referring to Chemical AbstractNo.80:28345.
Adding a shortcoming of not dissolving pigment is will meet the requirements of relatively difficulty of degree in small, broken bits through grinding pigment on the one hand, and this on the other hand degree in small, broken bits will keep also relatively difficulty in the spinning material.Correspondingly also the interpolation of auxiliary agent and additive has been carried out narrating (Keil; A.; Popp.P. and Krause; E. " Processfor the production ofpigmented regenerated cellulosic fibers (production technology of the regenerated celulose fibre of dyeing) "-GB872207, on July 5th, 1961; Eskridge.B.E. " Manufacture ofpigmented viscose rayon (manufacturing of the viscose silk of dyeing) "-US3033697, on May 8th, 1962; Gomm; A.S., Morgan, L.B. and Wood; L. " Process of incorporating aqueouspigment composition in viscose (being attached to the technology in the viscose glue to moisture color compositions) "-US3156574, on November 10th, 1964; Ono, S. and Igase, " Dope dyeing of rayon (the spinning solution dyeing of artificial fibre) "-JP54038919 of T., on March 24th, 1979 is referring to ChemicalAbstract No.91:40853).
When the fiber that dyes according to known technological production material; Also can observe the recrystallization and the transformation (Whitehead of dye granule or dyestuff; W. " Colored organic derivatives ofcellulose and method of making same (the cellulose organic derivative and the manufacturing approach thereof of dyeing) "-US2128338, on August 30th, 1938).
Said technology has some shortcomings: pigment causes producing difficulty because agglomerate deposition (for example at the spinneret place) makes when cellulose regenerated in the stable deficiency on degree in small, broken bits and the chemical constitution, perhaps in the molding of dyeing, causes colour fluctuation.Unfavorable especially also have in regeneration is bathed or in the precipitating bath break down; For example, produce in foam or the deposition bath enrichment (Schoenbach, V. for the required auxiliary agent of stably dispersing; Weissert; J. and Teige, " Pigment dispersions for coloring viscose spinning masses (dispersing of pigments that is used for the dyeing of rayon spinning material) "-US3337360 of W., on August 22nd, 1967).Pollutant in the precipitating bath causes difficulty or stops its enforcement fully also can for the solvent reclamation that carries out in the NMMO-method for example.Use insoluble pigment also can cause effect of frosting and dull colors in the finished product molding.Also possibly observe dichroism and loss of strength (Festigkeitsverlust) (Batt; " Process forproducing colored pellicular gel structures of regenerated cellulose (production method of the dyeing epidermis gel structure of regenerated cellulose) "-US3005723 of I.P, on October 24th, 1961; Ruesch, R. and Schmidt, " Preparation of dyed filaments and films (long filament of dyeing and the preparation of film) "-US2043069 of H, on June 2nd, 1936; Eskridge, " Manufacture of pigmentedviscose rayon (manufacturing of the viscose silk of dyeing) "-US3033697 of B.E., on May 8th, 1962; " Process for the preparation of transparent colored shaped articles ofregenerated cellulose with the aid of organic dyestuffs of low solubility in water (technology for preparing transparent regenerated cellulose dyeing molding by means of the organic dyestuff that in water, has low-solubility) "-GB1128158 of Ciba Co., Ltd, September 25 nineteen sixty-eight).
As dimness, the reason of lacklustre tone should be listed the pigment that exists with finely divided form especially, because the particulate fineness that limits, it will inevitably cause the effect of frosting.
Adding finely divided pigment can evade through being applied to the dye system of solubility in the spinning material with consequent problem in spinning solution.Wherein, Dyestuff can be dissolved in advance polarity, can with solvent that water mixes in or directly add to (Soc.pour lind.chim.a Bale. " Pigment-containing spinning masses (the spinning material that contains pigment) "-CH212386, March 3 nineteen forty-one in the spinning material; Phrix-Werke A.-G. " Spun-dyed regenerated cellulose (being spun into the regenerated cellulose of dyeing) "-NL6407087, January 18 nineteen sixty-five is referring to Chemical AbstractNo.63:63815; " Dyeing of regenerated cellulosic fibers andfilms (dyeing of the cellulose fiber peacekeeping film of regeneration) "-FR1417575 of Ciba Co., Ltd, November 12 nineteen sixty-five is referring to Chemical Abstract No.65:57365; " Transparent coloredregenerated cellulose (transparent painted regenerated cellulose) " NL6514672 of Ciba Co., Ltd, on May 13rd, 1966 is referring to Chemical Abstract No.65:82924; Wegmann, J., and Booker, C. " Coloredviscose dope (coloured viscose glue lacquer) " DE1220964, on July 14th, 1966; " Process for the preparation of transparent colored shaped articles of regeneratedcellulose with the aid of organic dyestuffs of low solubilityin water (by the organic dyestuff of low-solubility in water; prepare the technology of transparent regenerated cellulose dyeing molding) "-GB1128158 of Ciba Co., Ltd, September 25 nineteen sixty-eight; Riehen; W.M. and Reinach; F.S. " Difficultly soluble organic dyecompositions for dyeing transparent; shaped, regenerated cellulose bodies (the organic colouring compositions of indissoluble that is used for the cellulosic molded body dyeing of transparent regeneration) "-DE1806199, on April 29th, 1971; Riehen, W.M. and Reinach, " Sparingly soluble organic dyestuffs indissoluble organic dyestuff "-US3620788 of F.S., on November 16th, 1971).
But; Above-mentioned these technology need limit when selecting dyestuff widely; These dyestuffs for example must withstand the reducibility alkali condition of making viscose intactly, perhaps must under the situation of not carrying out chemical change, withstand the strong oxidation environment of NMMO-cellulose solution.
In addition, when producing viscose, the highly acid treatment step in bathing of should considering to regenerate.The other shortcoming of soluble dye system is to pollute precipitating bath and only can make to have limited wet COLOR FASTNESS in the product; Even move back (Batt because washing of solvable system also taken place herein; I.P. " Process for producing coloredpellicular gel structures of regenerated cellulose (production method of regenerated cellulose dyeing epidermis gel structure) "-US3005723, on October 24th, 1961).
Special scheme suggestion when producing coloured fibre is added SULPHUR DYES in the rayon spinning material.SULPHUR DYES dissolves under said reducibility alkali condition; This SULPHUR DYES and must return its oxidised form (Cassella Farbwerke Mainkur A.-G. " Dyeing of regenerated cellulose in thespinning paste (regenerated cellulose dyes) ")-BE611323 in spinning cream; On December 29th, 1961 is referring to Chemical Abstract No.57:17664).
Another scheme recommends to reuse the cellulosic fabric of reactive dyeing; Be used for producing coloured fibre according to the rayon spinning method; Wherein mention as important shortcoming: the painted of gained can not be formed qualification and can not be reappeared by raw material, because a part of being reduced property of dyestuff destruction, and another part remains (from Eltz as dyestuff; A. " Recycling of dyed cellulosic wastes (recovery of the cellulose wastes of dyeing) "-EP0717131, on June 19th, 1996).
The outstanding COLOR FASTNESS of reducing dye makes its pigment as the production of cellulose molding attractive especially.An important advantage still simultaneously also is that the shortcoming of a processing technology aspect is its indissolubility in various media.From synthetic method, obtain the reducing dye as the diffusing pigment of rough segmentation, its preparation comprises process for purification widely, for example: grind and process with demarcation agent, dispersant.But, even finished product pigment also can not show the typical tone of reducing dye separately, because average particle size particle size is still too big and for colour developing, need be fixed on the molecule discrete form in the cellulose matrix.
Therefore, traditional reduction dyeing requires in dyeing course, to change into the soluble colorless form of alkali (Leukoform) to pigment, and colorless form is absorbed into cellulose fibre and is fixed through reoxidizing with the molecule discrete form at there.
In document, mentioned the distinct methods of using reducing dye production of cellulose molding, wherein can viscose glue technical scope and so-called amine oxide technical scope-or Lyocell-technical scope technology between distinguish.
When producing viscose; Regnant in the spinning material is the reducibility alkali condition; Therefore suggestion is added the reducing dye solution that has reduced in the spinning material to here; Add reducible reducing dye in the spinning material to or dyestuff and reductant add in the spinning material (" The manufacture of dyed artificial masses from regenerated cellulose (manufacturing of the artificial material of the dyeing of processing with regenerated cellulose) "-GB465606 of I.G.FarbenindustrieA.-G., May 10 nineteen thirty-seven to; Kline, H.B., and Helm, " Manufacture of artificial silk (manufacturing of artificial silk) "-US2143883 of E.B., January 17 nineteen thirty-nine; Lockhart, " Manufacture of rayon (manufacturing of artificial silk) "-US1865701 of G.R., on July 5th, 1932; Batt; I.P. " Process forproducing colored pellicular gel structures of regenerated cellulose (production method of regenerated cellulose dyeing epidermis gel structure) "-US3005723, on October 24th, 1961).The shortcoming of this production technology is the enrichment at precipitating bath of the reductant that washes out; Expensive interpolation and sneak into dye formulations with the condition that guarantees homogeneous and the tone that the reaches dependence to spinning condition is the excellent mode of oxidizing of selecting because in acidic precipitation is bathed, reoxidize for reducing dye anything but.
Other technology, through the reducing dye dispersion is handled with reduce subsequently and after the tone colour developing in the vatting step that becomes silk that connects, evaded the difficulty of in the spinning material, carrying out reducing dyes.Ruesch, R. and Schmidt, " Preparation of dyed filaments and films (fiber of dyeing and the preparation of film) "-US2043069 of H., on June 2nd, 1936; " Process for the manufacture of dyed filaments and films (long filament of dyeing and the manufacturing technique of film) "-GB448447 of I.G.Farbenindustrie A.-G., on June 8th, 1936; Maloney, " Mass coloring ofregenerated cellulose with vat dyes (carrying out material dyeing to regenerated cellulose) "-DE1253864 of M.A., on November 9th, 1967 with reducing dye).Therefore, in method summary, this method and technology and the traditional reduction stain that in textile finishing, carries out are as broad as long.
In order to reach the final tone of reducing dye, all these technological something in commons are that reducing dyes is essential.But; These methods also have important disadvantages; These drawbacks limit its application: add the stabilisation that the reducing dye reduced causes the spinning material, the slaking that has changed and the performance of condensing are to production have a negative impact (Ruesch, R. and Schmidt; H. " Preparation of dyed filaments and films (long filament of dyeing and the preparation of film) "-US2043069, on June 2nd, 1936).
Because the negative reduction potential that these dyestuffs are very high; Needed the reoxidizing that be used to develop the color is difficult to control; This can cause tone fluctuation (Dosne, " Colored cellulose material (cellulosic material of dyeing) "-US2041907 of H., on May 26th, 1936).Numerous reducing dyes because their reduction-oxidation current potential can not reduce fully, has received obstruction so that use widely under the rayon spinning condition.Add reductant and then cause that undesirable gel forms in the spinning material (Lutgerhorst, " Spundyed rayon (artificial fibre of dyeing when spinning) "-US2738252 of A.G., on March 13rd, 1956; Batt; I.P. " Process for producing colored pellicular gelstructures of regenerated cellulose (production method of regenerated cellulose dyeing epidermis gel structure) "-US3005723, on October 24th, 1961).
To adding reductic acid or adding colourless ester dyestuff and also narrate, still, shortcoming is the solution instability and observes the tendency that forms the dyestuff agglomerate.(Dosne, " Colored cellulosematerial (cellulosic material of dyeing) "-US2041907 of H., on May 26th, 1936; Lutgerhorst, " Spundyed rayon (artificial fibre of dyeing when spinning) "-US2738252 of A.G., on March 13rd, 1956; I.G.Farbenindustrie A.-G. " The manufacture ofdyed artificialmasses from regenerated cellulose (the artificial material of the dyeing of producing by regenerated cellulose) "-GB465606, May 10 nineteen thirty-seven).
According to amine oxide-or during Lyocell-method production of cellulose molding, equally also can add pigment in the spinning material to.Its prerequisite is to select suitable pigment under the situation of strong oxidizing condition accordingly considering, this strong oxidizing condition is by solvent (N-methyl-N-morpholine-N-oxide-NMMO) cause.Can enumerate WO01/11121 (" Colored cellulosic shapedbodies (cellulosic molded body of dyeing) " of R ü f H. as the example of this respect; Lenzing AG; On August 8th, 2000;) and WO99/46434 (Bartsch P., " the Method for producing cellulosic molded bodies (method of production of cellulose molding) " of R ü f H., Lenzing AG; On March 10th, 1999), they have been described and have added suitable pigment in the NMMO spinning material to.According to WO99/46434; These reducing dyes also are known as colouring agent; They are to add in the spinning material as insoluble pigment, and particularly by the desired colour developing that has stoped desired reducing dye-tone greater than 95% not solubility of WO99/46434.Also having put down in writing to use has color masterbatch, and wherein the color masterbatch that has according to known systems is interpreted as through the cellulose of mixing acquisition and the colorant preparations of NMMO optionally.
Secondly, according to prior art, operational colouring agent for example is pigment or is blended in the reducing dye in the cellulose.Therefore, cellulose can only have the degree in small, broken bits of limited pigment or reducing dye.Therefore, under the reducing dye situation, dyeing never conforms to the result of the reduction stain of textile chemistry during resulting spinning.
Task of the present invention is to provide a kind of method with the cellulose moulded bodies of reducing dye dyeing that is used to make, and this method has overcome the shortcoming of prior art level and used the method can obtain having the product of level dyeing.
This task will solve through the method for claim 1.The preferred implementing form of method of the present invention provides in the dependent claims.
Be attached to the reducing dye molecule in the cellulose matrix dispersedly and produce the possible method of coloured fibre thus through a kind of dyeing course, do not have open in the prior art as yet.
The present invention is based on following beat all cognition: cellulosic material, cellulose (Zellstoff) for example can be as the solid matrix of the reducing dye of molecule dispersed and distributed.The molecule dispersed and distributed of dyestuff can be according to the conventional method that is used to apply reducing dye; For example exhaust the method for dying, continuity method is carried out through dyeing cellulosic; Wherein after accomplishing dyeing; Dyestuff no longer exists as the original pigment of the particle size with micrometer range, but is embedded in the cellulose with the molecule discrete form.Beat all is that this cellulose through dyeing is particularly suitable for a dyestuff and is attached in the spinning material with the molecule discrete form.The manufacturing of real spinning material can according to viscose process or amine oxide-or the Lyocell-method carry out through dissolving cellulos.
Through being incorporated into the dyestuff of molecule discrete form, with avoiding pigment to add problem and the difficulty of unsafty tone colour developing in comparable known method.Different with WO99/46434, with obtaining so painted result, this result no longer is equivalent in the spinning material, add reduction pigments, but is equal to the result of the reduction stain that reaches according to the prior art level.
Can avoid the development step of step reduction stain (reducing/oxidizing) afterwards in the method according to the invention.Exist with the molecule discrete form through dyestuff, will reach high dyestuff Dry Sack rate with high glaze.Different with pigment dyeing, no longer can see pigment at microscopically.Therefore; The result of dyeing is being equivalent to reduction stain aspect tone, color depth and the COLOR FASTNESS; But but can remove from the alkaline bath that sharply expands fiber is handled; And this is very general in the process that dyes with reducing dye, has also avoided dyeing always to be difficult to dye even decoration dyeing, for example: the dyeing of packing.
Particularly; If very high dye strength is used in cellulosic dyeing; For example: the dyestuff based on cellulose 20 weight % carries out, and this cellulosic material that comprises reducing dye can be processed into mouldable solution together with at least a other the raw material that optionally contains dyestuff equally.
Therefore, through being mixed into a part cellulose, carry out dyeing when spinning with reducing dye dyeing.Thus with obtaining the particularly advantageous discharging balance (Emissionsbilanz) relevant with staining procedure.Through the cellulose as coloured fibre matrix is provided, do not add other refining auxiliary agent to this spinning technique interpolation dyestuff, avoided the enrichment and the expensive removal thereof of additive like this.
One especially preferred embodiment in, contain the cellulosic material of reducing dye, do not carrying out under the further dry situation, be supplied to the further processing in the spinning technique.
The working method of the dyeing of cellulosic material in can be according to the present invention; Carry out with reducing dye; Dye level from 0.1 to 25% ratio of cellulosic material quality (the dyestuff quality with), preferred 1 to 20%, preferred especially 5 to 10% (being the ratio of dyestuff quality and cellulosic material quality).
Dye under the method situation exhausting; bath raio
ratio of dye bath volume (the dyeing quality with) for 1:0.8 to 1:50, preferred 1:5 is to 1:10.Decoration method can be carried out 20 ℃ of-80 ℃ of temperature, and uses common reduction vatting.Even can use continuous dyeing technology, for example using under the situation of the band screen equipment of modification.
The preferred especially colouring method that uses the staining technique with dye bath retracting device, for example: the perpendicular bath dyeed.Through dyeing being embodied as the dyeing course of relative high concentration, the discharging relevant with technology (waste water, energy, chemicals) significantly is less than general reduction vatting.
Owing to avoid usually the alkaline reduction dyeing under harsh conditions relatively, carried out, can be with the responsive base material of reducing dye dyeing, and do not influence fibre property.
When cellulosic material dyeed, the equalization difference definitely was acceptable, absorbed because only need realize dyestuff.According to the dissolving of following cellulosic material and the production of fiber, also " automatically " obtains excellent equalization promptly on the whole.
Therefore, when cellulosic material dyes, can use very short process time operation.In addition, can remove interpolation dispersant and levelling auxiliary agent in dye bath from.Also further produced economic aspect thus, also had the benefit of ecological aspect, because the discharging that from this dyeing, produces reduces.
The cellulosic material that contains reducing dye can be according to desirable color depth and the cellulosic material mixing of no dyeing optionally; Wherein containing the raw material of reducing dye and the mixing ratio of one or more other raw materials is 0.1:10 to 10:0.1, preferred 1:10 to 10:1.This moment mixing ratio according to the dyestuff content of the cellulosic material of above-mentioned dyeing with remain to be made spin the time coloring material color depth adjust.
Cellulosic material and/or the optional especially free-fiber of at least a other raw material are plain, the group that the spinning start material (Anspinnmaterial) of the method for natural and artificial cellulose fibre and produce cellulose fibers is formed.
So just can not use the cellulose of dyeing, and give undyed cellulose dyeing and be used as cellulose matrix with reducing dye.For this reason, a kind of so-called spinning start material that especially preferred embodiment used, it forms and unmet quality of fiber requirement still when fiber production apparatus start shooting, still is suitable for as cellulose matrix.
A kind of characteristic of preferred implementation according to the method for the invention is that one or more raw material are continued to be processed into molding by means of viscose process or amine oxide method.
Viscose process and amine oxide method or Lyocell method are familiar with for the professional.Amine oxide method or Lyocel l method such as in EP0356419A or WO93/19230, carried out explanation in more detail.
The present invention relates to the cellulosic material of the reducing dye that contains the molecule discrete form is moulded the raw material of molding as producd fibers purposes subsequently.
In addition, the invention still further relates to cellulose moulded bodies, particularly cellulose fibre, they can obtain through method of the present invention.
Cellulose moulded bodies of the present invention is according to the method for the invention with the complete imbue of reducing dye.
In addition, based on according to the method for the invention, in cellulose matrix, can be less than the average particle size particle size of 0.1 micron reducing dye.Therefore, under the light microscope of for example 400 times of amplifications commonly used, do not observe said dyestuff.
Here it is with can be through soluble pigment being added to the difference of the cellulose moulded article that obtains in the spinning material, wherein, the particle size of the pigment in fiber is a micrometer range.
What the present invention related at last is textiles, for example: line, fabric or clothes, it contains the cellulose moulded bodies of the present invention of fibers form.
Show that the textiles that contains cellulose fibre of the present invention has outstanding microcosmic and macroscopical equalization.They are ability and common definitely, compares to the equalization that textile dyeing reaches with reduction vatting.
Particularly usually be proved to be difficulty for yarn dyeing, and when using cellulose fibre of the present invention, just can produce the yarn of dyeing uniformity with excellence with reducing dye.
In addition, textiles of the present invention, owing to used cellulose fibre of the present invention, by complete imbue.In the common reduction stain of textiles, be difficult to reach complete imbue.
The present invention then will be elaborated through embodiment:
Embodiment 1:
About 350 gram fiberoptic fibers plain (Lenzing AG); In exhausting the method for dying with C.I. vat green 5 (indanthrene brilliant green FFB, Dystar, Frankfurt; Germany) in dye bath with the dyeing 45 minutes 50 ℃ time of the bath raio of 1:15; This dye bath has following composition: 10g/L dyestuff, 6.17g/LNaOH, and 5g/LNa
2S
2O
4
During preparatory vatting, with the dyestuff urn with contain cellulosic residue dye bath and be adjusted to dyeing temperature.After reaching dyeing temperature, the solution that contains the dyestuff that has been reduced mixes with the cellulosic bath that contains preliminary wetting and begins dyeing course.After 45 minutes, finish dyeing course at dyeing temperature.Cellulose is by flushing up hill and dale, and oxidation step is implemented through air oxidation.Then, dry dyed cellulose.The dyed cellulose matrix and the cellulose of no dyeing mix with the ratio of 1:4 and are processed into coloured fibre according to amine oxide method or Lyocell method.Obtain 2.5% dyeing, this dyeing is suitable with the dyeing that produces according to conventional method with COLOR FASTNESS (washable fastness, light resistance) aspect aspect tone.
Claims (21)
1. be used to prepare method, may further comprise the steps with the cellulose moulded bodies of reducing dye dyeing:
-prepare cellulosic material, it comprises the reducing dye of molecule discrete form
Mouldable solution that-production is processed by cellulosic material
-through the molded solution of suitable mold
-by through molded solution precipitation or regenerated cellulose.
2. the process of claim 1 wherein that said cellulose moulded bodies is fiber or film.
3. claim 1 or 2 method, it is characterized in that: cellulosic material comprises reducing dye, and the ratio of dyestuff quality and cellulosic material quality is 0.1% to 25%.
4. the method for claim 3, it is characterized in that: the ratio of dyestuff quality and cellulosic material quality is 1% to 20%.
5. the method for claim 3, it is characterized in that: the ratio of dyestuff quality and cellulosic material quality is 5% to 10%.
6. claim 1 or 2 method is characterized in that: the cellulosic material and at least a other the raw material that contain reducing dye are processed to mouldable solution together.
7. the method for claim 6 is characterized in that: said other raw material comprises dyestuff too.
8. the method for claim 6 is characterized in that: at least a other raw material is a cellulosic material.
9. the method for claim 6 is characterized in that: other the mixing ratio of raw material of cellulosic material and one or more that comprises reducing dye is 0.1: 10 to 10: 0.1.
10. the method for claim 9 is characterized in that: other the mixing ratio of raw material of cellulosic material and one or more that comprises reducing dye is 1: 10 to 10: 1.
11. the method for claim 1 or 2 is characterized in that: cellulosic material and/or at least a other raw material are selected from cellulose.
12. the method for claim 1 or 2 is characterized in that: cellulosic material and/or at least a other raw material are selected from natural and artificial cellulose fibre.
13. the method for claim 1 or 2 is characterized in that: cellulosic material and/or at least a other raw material are selected from the spinning start material of the method that is used for produce cellulose fibers.
14. the method for claim 1 or 2 is characterized in that: one or more raw materials are by means of viscose process or continued to be processed into molding by means of the amine oxide method.
15. the method for claim 1 or 2 is characterized in that: the cellulosic material that comprises reducing dye did not experience drying steps before making mouldable solution.
16. the method for claim 1 or 2, wherein said cellulosic material is through dyeing prepares to cellulosic material with reducing dye according to exhausting the method for dying or continuous dyeing method.
17. cellulosic material is as the purposes that is used for the raw material of production of cellulose molding, said cellulosic material comprises the reducing dye that is the molecule discrete form.
18. the cellulose moulded bodies that the method through one of claim 1 to 16 obtains, it is characterized in that: the average particle size particle size of the reducing dye in cellulose matrix is less than 0.1 micron.
19. textiles, it comprises the cellulose moulded bodies according to claim 18 of fibers form.
20. the textiles of claim 19, it is yarn or fabric.
21. the textiles of claim 20, it is a clothes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ATA2029/2005 | 2005-12-19 | ||
| AT0202905A AT502993B1 (en) | 2005-12-19 | 2005-12-19 | METHOD FOR PRODUCING A DYED CELLULOSIC FORM BODY |
| PCT/AT2006/000521 WO2007070904A1 (en) | 2005-12-19 | 2006-12-18 | Method of producing a dyed formed cellulosic article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101389794A CN101389794A (en) | 2009-03-18 |
| CN101389794B true CN101389794B (en) | 2012-06-06 |
Family
ID=37864525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800478248A Expired - Fee Related CN101389794B (en) | 2005-12-19 | 2006-12-18 | Method of producing a dyed formed cellulosic article |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1963552B1 (en) |
| CN (1) | CN101389794B (en) |
| AT (2) | AT502993B1 (en) |
| DE (1) | DE502006006611D1 (en) |
| EG (1) | EG26561A (en) |
| WO (1) | WO2007070904A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT515152B1 (en) | 2013-11-26 | 2015-12-15 | Chemiefaser Lenzing Ag | A process for pretreating recovered cotton fibers for use in the manufacture of regenerated cellulose moldings |
| AT517020B1 (en) | 2015-02-06 | 2020-02-15 | Chemiefaser Lenzing Ag | Recycling of cellulosic synthetic fibers |
| CN109181360A (en) * | 2018-07-03 | 2019-01-11 | 张华娟 | A kind of reducing dye |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1253864B (en) * | 1962-02-26 | 1967-11-09 | British Cellophane Ltd | Process for dyeing threads or films produced by wet spinning or casting methods |
| DE4444245C1 (en) * | 1994-12-13 | 1996-07-04 | Hoechst Ag | Process for recycling colored, cellulosic waste products into fibers |
| AT2207U1 (en) * | 1998-03-12 | 1998-06-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES |
-
2005
- 2005-12-19 AT AT0202905A patent/AT502993B1/en not_active IP Right Cessation
-
2006
- 2006-12-18 CN CN2006800478248A patent/CN101389794B/en not_active Expired - Fee Related
- 2006-12-18 EP EP06817492A patent/EP1963552B1/en not_active Not-in-force
- 2006-12-18 WO PCT/AT2006/000521 patent/WO2007070904A1/en active Application Filing
- 2006-12-18 AT AT06817492T patent/ATE462809T1/en active
- 2006-12-18 DE DE502006006611T patent/DE502006006611D1/en active Active
-
2008
- 2008-06-18 EG EG2008061038A patent/EG26561A/en active
Non-Patent Citations (1)
| Title |
|---|
| 赵维绳等.还原染料的染色过程.《还原染料》.化学工业出版社,1993,442，452. * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007070904A1 (en) | 2007-06-28 |
| EP1963552B1 (en) | 2010-03-31 |
| EG26561A (en) | 2014-02-18 |
| ATE462809T1 (en) | 2010-04-15 |
| EP1963552A1 (en) | 2008-09-03 |
| AT502993A1 (en) | 2007-07-15 |
| DE502006006611D1 (en) | 2010-05-12 |
| AT502993B1 (en) | 2008-07-15 |
| CN101389794A (en) | 2009-03-18 |
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