EP0124086B1 - Procédé pour réaliser des impressions d'une réserve - Google Patents

Procédé pour réaliser des impressions d'une réserve Download PDF

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Publication number
EP0124086B1
EP0124086B1 EP84104688A EP84104688A EP0124086B1 EP 0124086 B1 EP0124086 B1 EP 0124086B1 EP 84104688 A EP84104688 A EP 84104688A EP 84104688 A EP84104688 A EP 84104688A EP 0124086 B1 EP0124086 B1 EP 0124086B1
Authority
EP
European Patent Office
Prior art keywords
reactive
paste
aqueous
sulfite
printing
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.)
Expired
Application number
EP84104688A
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German (de)
English (en)
Other versions
EP0124086A2 (fr
EP0124086A3 (en
Inventor
Sienling Dr. Ong
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0124086A2 publication Critical patent/EP0124086A2/fr
Publication of EP0124086A3 publication Critical patent/EP0124086A3/de
Application granted granted Critical
Publication of EP0124086B1 publication Critical patent/EP0124086B1/fr
Expired legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/12—Reserving parts of the material before dyeing or printing ; Locally decreasing dye affinity by chemical means

Definitions

  • the method according to DE-C-2 046 410 had to be used to produce colored reserves with reactive dyes among developing dyes, which may also be produced and fixed on cellulose fibers in a mixture with phthalocyanine precondensates (Ingrain types).
  • phthalocyanine precondensates Ingrain types.
  • phenol-formaldehyde condensation products containing sulfo groups were primarily considered.
  • the present invention thus relates to the production of reserve effects on a differently colored background; of textile fabrics containing or consisting of cellulosic fiber materials with reactive dyes under azo-developing dyes, the textile material printed or grafted with a phonolic or enolic coupling component or an alkali salt thereof with an aqueous form paste which contains one or more reactive dyes and the formation of an insoluble axo dye contains preventive reservation agent, printed in the desired pattern and then this wet-on-wet form with one or more aqueous, acidified, pastes containing one or more stabilized diazonium salts, overprinted with overlap, or overlaid with aqueous, acidified diazonium salt solutions or blanketed is, after which the applied reactive dyes are then fixed in an alkaline medium after drying the thus treated goods without long-term thermal action and the text patterned in this way tilgut freed by washing out soluble components and residues of non-fixed dyes, characterized in that the form paste as a reservation
  • Hydrogen sulfite-toning substances and is set to acidic conditions that an excess of acid is present in the diazonium salt-containing preparations so that the acidity at the attack sites is retained even during the drying process, and that to fix the reactive dyes, the printed product with an alkaline, concentrated electrolyte - or with a glass of water solution at room temperature, or gassed over and then left to stand for a period of at least 10 minutes at room temperature.
  • the basic concept for realizing the claimed process is based on the fact that the resistance of the reactive dyes to sulfite or hydrogen sulfite ions at acidic pH values is made useful in practical use, during which such sulfur compounds which provide ions react with the diazonium salts under the same conditions and thus preventing the formation of azo dyes.
  • the formation of a diazosulfonate which cannot be coupled under the fixing conditions according to the invention is characteristic of the sulfite reserves.
  • the reactive dyes required to illuminate the reserved areas would react with the sulfite ions within a very short time and would be inactivated as a result, i.e. henceforth, as a result of blocking the reactive group, they would no longer be available for a further reaction with the cellulose, even in the presence of alkalis.
  • the sulfite ions react fastest in the alkaline medium with the highly reactive dyes of the sulfatoethyl sulfone type. Reactive dyes with a different chemistry are hardly or only very slowly affected by these sulfur compounds in their reactivity.
  • the color reserve process with reactive dyes among reactive dyes according to DE-C-2 326 522 is also based on this principle of different sensitivity of different reactive dye systems in view of sulfite compounds. Bearing in mind this behavior of reactive dyes towards sulfurous acid, their anhydrides and salts, it was surprising that, according to the present invention, the same sulfatoethyl sulfone dyes can be used to illuminate the reserved sites under acidic conditions.
  • the reserve printing pastes containing sulfite or hydrogensulfite ion according to the invention have pH values which are between 2.5 and below 7, preferably between 4 and 6.5. Within this pH range, the reactive dyes hardly react with sulfite or hydrogen sulfite ions at room temperature.
  • the textile fabrics consist, in particular, of fabrics or effect.
  • cellulose-containing fiber materials are in particular those which contain small amounts of synthetic fibers, mostly polyester fibers, in a mixture with cotton.
  • Fabrics made from pure cotton are very particularly preferably suitable for the patterning method according to the invention.
  • phenolic coupling components are to be understood in particular as naphthols and hydroxycarbazoles.
  • enolic coupling components recognized as being useful include N-acetoacetyl, N-benzoylacetyl and N, N'-terephthaloyl-bisacctyl-aminobenzene derivatives.
  • Hydrogen sulfite ion-releasing reservation agents which prevent the formation of insoluble azo dyes are alkali hydrogen sulfites, in particular sodium hydrogen sulfite (sodium bisulfite), or their condensation products such as e.g. Sodium disulfite (sodium pyrosulfite), or such compounds which can be converted into hydrogen sulfite by the action of acids or alkalis, such as alkali hydrogen sulfites in combination clay with an aldehyde, advantageously in the form of a prefabricated aldehyde-alkali hydrogen sulfite adduct.
  • alkali hydrogen sulfites in particular sodium hydrogen sulfite (sodium bisulfite), or their condensation products such as e.g. Sodium disulfite (sodium pyrosulfite), or such compounds which can be converted into hydrogen sulfite by the action of acids or alkalis, such as alkali hydrogen sulfites in combination
  • the amounts of sulfite or. Hydrogen sulfite-toning substances depend on the color depth of the development dyes to be reserved and are between 5 and 50 g per 1000 g of printing paste. Since the chemicals found here are usually marketed in the form of their alkali salts, the weight proportions of the cations and the water of crystallization must also be taken into account when calculating the amount by weight.
  • alkali hydrogen sulfites must also be taken into account, if acid is added to disintegrate under the development of sulfur dioxide, and in this connection the tendency of sulfur dioxide to escape as gas from the aqueous alkali hydrogen sulfite solutions at lower pH values and somewhat higher temperatures. It is therefore recommended that the pH of these solutions be raised to pH 5.5 to 6.5 with alkaline substances such as sodium acetate or sodium sulfite. Reserve printing pastes, which contain such solutions with corrected pH value, are stable at room temperature and hardly release sulfur dioxide.
  • reactive dyes for the claimed process those are considered which have one or more reactive groups or removable substituents which, when the dyes are applied to cellulose fiber materials in the presence of acid-binding agents, are able to react with the hydroxyl groups of cellulose to form covalent bonds.
  • Such fiber-reactive groups are from the Literature known in large numbers.
  • cyclic carbonamides such as e-caprolactam
  • hydrotropic aids may also be present in the printing pastes.
  • no alginate can be used as the thickening agent of the reactive dye-containing reserve printing pastes, but only guar or kernel meal derivatives.
  • the so-called true-color salts are listed in particular as stabilized diazonium salts in the overprint pastes or padding liquors.
  • stabilized diazonium salts are either used directly as aqueous pastes or, before the coupling reaction, are converted into aqueous diazonium salt solutions in which the diazo component is already present in a form ready for reaction.
  • the overpressure pastes also contain acids or acid salts in excess.
  • the amount of acid in the preparations containing diazonium salt must not be too short, so that the acidity at the attack sites is retained even when drying.
  • volatile acids such as formic or acetic acid
  • the greatest danger is that they volatilize in the attic too quickly than being able to keep the attack sites acidic for a certain period of time.
  • the preservation of a sufficiently acidic medium at the attack sites for a certain period of time in the course of the drying phase in the garret is an essential feature of the present invention, because sulfur dioxide is to be released and expelled from the reservation agent at the attack sites.
  • this goal can also be achieved with fixed organic or inorganic acids of a different type of behavior, if care is taken to ensure that the fiber is not damaged as a result of the drying treatment.
  • Kernel meal ethers are preferably used as thickeners for the printing pastes containing diazonium salt.
  • cellulose fabric which has been prepared in a completely braid manner in the naphtholate or enolate form or which has been pattern-printed by printing an appropriate paste and which has been dried following this impregnation, is prepared in a known manner with the phenolic or enolic coupling component, afterwards in textile printing Conventional technology and in the desired patterns applied aqueous printing pastes which contain the reservation agent and a reactive dye or the reservation agent and a mixture of several reactive dyes. Thereupon, the diazonium salt preparations for the rear are overprinted overlapping on this form with the reserve printing paste, or are splashed or padded over them to cover the surface.
  • the printed matter with an electrolyte-containing alkaline liquor according to DE-C-1 469 722 and DE-C 1 619 492, which contains sodium hydroxide solution, soda, potash and table salt or Glauber's salt, or with Blended mixtures of water glass and sodium hydroxide liquors and then exposed to air for 10 to 60 minutes.
  • DE-C-1 469 722 and DE-C 1 619 492 which contains sodium hydroxide solution, soda, potash and table salt or Glauber's salt, or with Blended mixtures of water glass and sodium hydroxide liquors and then exposed to air for 10 to 60 minutes.
  • the reactive dyes used as color dye must be fixed in the alkaline medium without long-term thermal action, so that pure full color reserves result under all possible combinations of commercially available enolic or phenolic coupling components and stabilized diazonium salts.
  • the method according to the present invention writes for reserves under the blue combinations of Developmental dyes only fix the dyes at room temperature before.
  • reactive dyes which are suitable according to the method for coloring the colored reserves, only those are suitable which can react with the cellulose at room temperature between 10 ° and 40 ° C, preferably between 15 ° and 30 ° C under the action of aecalytes.
  • reactive dyes include, for example, the sulfatoethyl sulfone dyes and the vinyl sulfone derivatives resulting from this as a result of acid release.
  • the patterns produced by the claimed process are subjected to a washing process in order to remove excess, uncoupled coupling component, rinsed and finished as usual.
  • the printing method according to the invention is particularly suitable for Rouleaux printing, rotary film printing and flat film printing.
  • the product treated in this way is then rinsed in cold water and aftertreated in an aqueous bath containing 1 to 3 g of soda or 1 to 2 g of sodium hydroxide solution at 38 ° C. to remove the excess coupling component from the base primer at 60 ° C.
  • the process product is then rinsed cold with water and dried.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)

Claims (6)

1. Procédé pour la réalisation d'effets de réserve sur un fond, d'une autre couleur, d'étoffes textiles contenant des matières fibreuses cellulosiques ou constituées de matières fibreuses cellulosiques, à l'aide de colorants réactifs sous des colorants de développement azoïques, l'article textile, imprimé ou plaqué à l'aide d'un composant de copulation phénolique ou énolique ou l'un de ses sels de métaux alcalins, étant imprimé selon le dessin voulu à l'aide d'une pâte de préimpression aqueuse contenant un ou plusieurs colorants réactifs et un agent de réserve empêchant la formation d'un colorant azoïque insoluble, puis en surimprimant ce préimprimé, mouillé sur mouillé, et par chevauchement, à l'aide d'une ou plusieurs pâtes d'impression aqueuses, ajustées à un pH acide, contenant un ou plusieurs sels de diazonium, ou en le surplaquant ou le surfoulardant, par recouvrement en surface, à l'aide de solutions aqueuses de sels de diazonium ajustés à un pH acide, ce après quoi on fixe immédiatement, en milieu alcalin, et après le séchage de l'article ainsi traité, et sans un traitement thermique trop long. les colorants réactifs appliqués, et par lavage on débarrasse l'article textile ayant ainsi reçu un dessin des constituants solubles et des résidus des colorants non-fixés, caractérisé en ce que la pâte de préimpression, en tant qu'agent de réserve, contient des substances qui, en milieu aqueux, cèdent des ions sulfite ou hydrogénosulfite, et est ajustée à des conditions acides; que l'on a dans les préparations contenant des sels de diazonium un exc]s d'acide de façon à maintenir l'acidité aux points de déversement même lors de l'opération de séchage; et que, pour fixer les colorants réactifs, on foularde ou surplaque à la température ambiante le produit imprimé à l'aide d'une solution ajustée à un pH alcalin d'un électrolyte concentré ou d'une solution silicatée, avant de laisser reposer pendant au moins 10 minutes à la température ambiante.
2. Procédé selon la revendication 1, caractérisé en ce qu'il s'agit, pour ce qui est du composant de copulation phénolique, d'un dérivé du naphtol ou d'un dérivé de l'hydroxycarbazole.
3. Procédé selon la revendication 1, caractérisé en ce qu'il s'agit, pour ce qui est du composant de copulation énolique, d'un dérivé N-acétoacétylique, N-benzoylacétylique ou N,N'- téréphtaloyl-bis-acétylique de l'aminobenzène.
4. Procédé selon les revendications 1 à 3, caractérisé en ce qu'il s'agit, pour ce qui est de l'agent de réserve cédant des ions sulfite ou hydrogénosulfite, d'un hydrogénosulfite de métal alcalin ou de ses produits de condensation, ou de composés qui, sous l'effet d'acides ou d'alcalis, peuvent être convertis en un hydrogénosulfite.
5. Procédé selon les revendications 1 à 4, caractérisé en ce que l'acidité et la quantité d'acide dans les préparations contenant des sels de diazonium sont suffisantes pour libérer de l'anhydride sulfureux des points de déversement.
6. Procédé selon les revendications 1 à 5, caractérisé en ce que l'expulsion de l'anhydride sulfureux des points de déversement s'effectue pendant le séchage.
EP84104688A 1983-04-28 1984-04-26 Procédé pour réaliser des impressions d'une réserve Expired EP0124086B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3315370 1983-04-28
DE19833315370 DE3315370A1 (de) 1983-04-28 1983-04-28 Verfahren zur herstellung von reservedrucken

Publications (3)

Publication Number Publication Date
EP0124086A2 EP0124086A2 (fr) 1984-11-07
EP0124086A3 EP0124086A3 (en) 1985-05-02
EP0124086B1 true EP0124086B1 (fr) 1986-12-17

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP84104688A Expired EP0124086B1 (fr) 1983-04-28 1984-04-26 Procédé pour réaliser des impressions d'une réserve

Country Status (4)

Country Link
EP (1) EP0124086B1 (fr)
JP (1) JPS59204988A (fr)
DE (2) DE3315370A1 (fr)
TR (1) TR21998A (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB843369A (en) * 1957-11-01 1960-08-04 Ici Ltd New textile printing process
DE2104065A1 (de) * 1970-12-31 1972-07-06 Ciba-Geigy Ag, Basel (Schweiz) Verfahren zur Herstellung von farbstarken Drucken bzw. Buntreserven unter Diazoechtsalzen
DE2916673C2 (de) * 1979-04-25 1981-11-12 Basf Ag, 6700 Ludwigshafen Reservedruckverfahren
DE3118193A1 (de) * 1981-05-08 1982-11-25 Basf Ag, 6700 Ludwigshafen Verfahren zum bedrucken von textilien

Also Published As

Publication number Publication date
EP0124086A2 (fr) 1984-11-07
JPS59204988A (ja) 1984-11-20
DE3461725D1 (en) 1987-01-29
DE3315370A1 (de) 1984-10-31
TR21998A (tr) 1988-03-25
EP0124086A3 (en) 1985-05-02

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