EP0074590B1 - Preparations of optical brighteners - Google Patents

Preparations of optical brighteners Download PDF

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Publication number
EP0074590B1
EP0074590B1 EP82108168A EP82108168A EP0074590B1 EP 0074590 B1 EP0074590 B1 EP 0074590B1 EP 82108168 A EP82108168 A EP 82108168A EP 82108168 A EP82108168 A EP 82108168A EP 0074590 B1 EP0074590 B1 EP 0074590B1
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EP
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Prior art keywords
brightener
denotes
preparations
radical
brighteners
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EP82108168A
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German (de)
French (fr)
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EP0074590A3 (en
EP0074590A2 (en
Inventor
Jochen Ing. Grad. Koll
Hans Dr. Theidel
Hans-Heinz Dr. Mölls
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Bayer AG
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Bayer AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/664—Preparations of optical brighteners; Optical brighteners in aerosol form; Physical treatment of optical brighteners

Definitions

  • the invention relates to brightener preparations in solid or liquid form which contain a cationic optical brightener, an anionic surfactant and optionally other additives, with the exception of those preparations which are obtained by melt formation.
  • the anionic surfactants can be used in the form of the free acid or in the form of their water-soluble salts.
  • inorganic salts such as NaCl, Na 2 S0 4
  • Salts of organic acids for example CH 3 COONa
  • readily water-soluble organic compounds such as, for example, s-caprolactam, sugar, etc.
  • the concentration of the cationic optical brightener in the preferably liquid aqueous preparation is in the range from 1-10%, that of the anionic surfactants from 3 ⁇ 40% and that of the further additives likewise from 3-40%.
  • the brightener preparations according to the invention are produced by homogenizing the cationic optical brighteners together with the anionic surfactants and possibly the other additives in an aqueous medium and, if necessary, dissolving them with heating.
  • the solution can be filtered in order to separate undissolved constituents or impurities.
  • the homogenization is carried out according to known methods with e.g. Rapid stirring, rotor-stator mills, dissolvers or similar devices.
  • liquid preparations can be dried using known drying processes.
  • the brightener preparations according to the invention are outstandingly suitable for the production of dyeing liquors for whitening polyacrylonitrile fibers by the exhaust process, preferably with a bleaching of the fiber material carried out in the same bath, for example with sodium chlorite.
  • this preparation produces brilliant green tints.
  • this preparation can achieve a 60-fold higher concentration.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Description

Gegenstand der Erfindung sind Aufhellerpräparationen in fester oder flüssiger Form, die einen kationischen optischen Aufheller, ein anionisches Tensid und gegebenenfalls weitere Zusätze enthalten mit Ausnahme solcher Präparationen, die durch Schmelzformierung gewonnen werden.The invention relates to brightener preparations in solid or liquid form which contain a cationic optical brightener, an anionic surfactant and optionally other additives, with the exception of those preparations which are obtained by melt formation.

Aus FR-A-2 243 994 (entspricht DE-A 2 442 423) sind nämlich bereits staubfreie, gut rieselfähige Präparationen von optischen Aufhellern bekannt, die man durch eben diese Schmelzformierung von an sich beliebigen Aufhellern in Gegenwart von Trägermaterialien und gegebenenfalls einem Tensid erhält. Obwohl dor neben anionischen und nichtionischen Aufhellern auch kationische Typen beschrieben werden und als Tenside auch anionische Verbindungen genannt werden, fehlt jeglicher konkrete Hinweis, gerade die erfindungsgemäße Kombination von Aufhellerwirkstoff und Tensidart zu wählen.From FR-A-2 243 994 (corresponds to DE-A 2 442 423), dust-free, free-flowing preparations of optical brighteners are already known, which are obtained by this melt formation of brighteners of any kind in the presence of carrier materials and optionally a surfactant . Although cationic types are also described in addition to anionic and nonionic brighteners and anionic compounds are also mentioned as surfactants, there is no concrete indication that it is precisely the combination of brightener active ingredient and type of surfactant according to the invention that is to be selected.

Im übrigen sind für das Gelingen der Schemelzformierung naturgemäß die Anwendung relativ hoher Temperaturen und der Einsatz großer Mengen Trägermaterial (bezogen auf die Wirkstoffmenge) erforderlich, so daß mit Zersetzungserscheinungen an Träger und Aufheller sowie mit starken Umweltbelastungen gerechnet werden muß.In addition, the use of relatively high temperatures and the use of large amounts of carrier material (based on the amount of active ingredient) are naturally necessary for the successful formation of the stool, so that decomposition phenomena on the carrier and brightener as well as severe environmental pollution must be expected.

Erfindungsgemäß einsetzbare kationische optische Aufheller sind in der Literatur in großer Zahl beschrieben. Bevorzugt sind solche der allgemeinen Formel

Figure imgb0001
worin

  • X = Triazolyl-Rest
  • Y = Cumarinyl- oder Benzofuranyl-Rest
  • Z = am N-Atom quaternierter heteroaromatischer Rest
  • An° = Anion

bedeutetCationic optical brighteners which can be used according to the invention are described in large numbers in the literature. Those of the general formula are preferred
Figure imgb0001
 wherein
  • X = triazolyl residue
  • Y = coumarinyl or benzofuranyl residue
  • Z = heteroaromatic residue quaternized on the N atom
  • An ° = anion

means

Innerhalb dieser Gruppe sind solche bevorzugt bei denen

Figure imgb0002
(R , R2 = H, Alkyl, Aryl)
Figure imgb0003

  • Z = Triazolylrest mit quartärem Stickstoffatom, beispielsweise
    Figure imgb0004
    sowie solche bei denen
  • X die obige Bedeutung hat,
    Figure imgb0005
  • Z Imidazolylrest mit quartärem N-Atom, z.B.
    Figure imgb0006
    Besonders bevorzugte Aufheller sind die in den folgenden Literaturstellen beschriebenen DE-A-2 821 116, DE-A-2 040 189 und DE-A-1 670 999.
Within this group, preference is given to those
Figure imgb0002
 (R, R 2 = H, alkyl, aryl)
Figure imgb0003
  • Z = triazolyl radical with a quaternary nitrogen atom, for example
    Figure imgb0004
     as well as those of them
  • X has the above meaning
    Figure imgb0005
  • Z imidazolyl radical with a quaternary N atom, for example
    Figure imgb0006
     Particularly preferred brighteners are DE-A-2 821 116, DE-A-2 040 189 and DE-A-1 670 999 described in the following references.

Als anionische Tenside kommen u.a. solche in Betracht, wie sie in der DE-A-2 257 945 beschrieben sind. Beispielhaft seien genannt:

  • Sulfatierte Alkylenoxidaddukte, sulfatierte partiell veresterte mehrwertige Alkohole, Alkylsulfonat, Natriumdialkylsulfosuccinate, Alkylbenzolsulfonate, Kondensationsprodukte aus Naphthalinsulfonsäuren oder Ditolylethersulfonäuren mit Formaldehyd, Ligninsulfonate und Oxyligninsulfonate, oder Kondensationsprodukte aus Kresol, 2-Napthol-6-sulfonsäure, Formaldehyd und Schwefelsäure: Bevorzugt sind Tenside mit Dispergiermitteleigenschaften, wie die vorstehend genannten Ligninderivate und Formaldehydkondensationsprodukte.
Suitable anionic surfactants include those described in DE-A-2 257 945. Examples include:
  • Sulfated alkylene oxide adducts, sulfated partially esterified polyhydric alcohols, alkyl sulfonate, sodium dialkyl sulfosuccinates, alkyl benzene sulfonates, condensation products from naphthalenesulfonic acids or ditolyl ether sulfonic acids with formaldehyde, ligninsulfonates and oxyligninsulfonates, or condensation products from cresol, 2-naphthol-6-sulfonic acid, formaldehyde and sulfuric acid: surfactants with dispersant properties, such as the above-mentioned lignin derivatives and formaldehyde condensation products, are preferred.

Die anionischen Tenside können in Form de freien Säure oder in Form ihrer wasserlöslichen Salze eingesetzt werden.The anionic surfactants can be used in the form of the free acid or in the form of their water-soluble salts.

Weitere übliche Zusätze sind beispielsweise: anorganische Salze, wie NaCI, Na2S04; Salze organischer Säuren, z.B. CH3COONa, oder gut wasserlösliche organische Verbindungen, wie z.B. s-Caprolactam, Zucker, u.a.Other common additives are, for example: inorganic salts, such as NaCl, Na 2 S0 4 ; Salts of organic acids, for example CH 3 COONa, or readily water-soluble organic compounds, such as, for example, s-caprolactam, sugar, etc.

Die Konzentration des kationischen optischen Aufhellers in der vorzugsweise flüssigen wässrigen Präparation liegt im Bereich von 1-10%, die der anionischen Tenside von 3―40% und die der weiteren Zusätze ebenfalls von 3-40%.The concentration of the cationic optical brightener in the preferably liquid aqueous preparation is in the range from 1-10%, that of the anionic surfactants from 3―40% and that of the further additives likewise from 3-40%.

Die Herstellung der erfindungsgemäßen Aufhellerpräparationen erfolgt dadurch, daß die kationischen optischen Aufheller zusammen mit den anionischen Tensiden und ggf. den weiteren Zusätzen in wäßrigem Medium homogenisiert und ggf. unter Erwärmung in Lösung gebracht werden.The brightener preparations according to the invention are produced by homogenizing the cationic optical brighteners together with the anionic surfactants and possibly the other additives in an aqueous medium and, if necessary, dissolving them with heating.

Die Lösung kann ggf. filtriert werden, um noch ungelöste Bestandteile oder Verunreinigungen abzutrennen. Die Homogenisierung erfolgt nach bekannten Verfahren mit z.B. Schnellrühren, Rotor-Stator-Mühlen, Dissolvern oder ähnlichen Geräten.If necessary, the solution can be filtered in order to separate undissolved constituents or impurities. The homogenization is carried out according to known methods with e.g. Rapid stirring, rotor-stator mills, dissolvers or similar devices.

Wird eine fest Präparation gewünscht, so können die flüssigen Präparationen mit bekannten Trocknungsverfahren getrocknet werden.If a solid preparation is desired, the liquid preparations can be dried using known drying processes.

Die erfindungsgemäßen Aufhellerpräparate eignen sich hervorragend zur Herstellung von Färbeflotten zum Weißtönen von Polyacrylnitrilfasern nach dem Ausziehverfahren, vorzugsweise mit einer im selben Bad durchgeführten Bleiche des Fasermaterials, beispielsweise mit Natriumchlorit.The brightener preparations according to the invention are outstandingly suitable for the production of dyeing liquors for whitening polyacrylonitrile fibers by the exhaust process, preferably with a bleaching of the fiber material carried out in the same bath, for example with sodium chlorite.

Beispiel 1example 1

3,6 g des optischen Aufhellers der Formel

Figure imgb0007
werden in einer Lösung von 40 g eines Kondensationsproduktes aus Ditolylether, Formaldehyd und Schwefelsäure in 66,5 g Wasser bei 70°C unter Rühren gelöst. Die Lösung bleibt auch nach dem Abkühlen auf Raumtemperatur erhalten.3.6 g of the optical brightener of the formula
Figure imgb0007
 are dissolved in a solution of 40 g of a condensation product of ditolyl ether, formaldehyde and sulfuric acid in 66.5 g of water at 70 ° C. with stirring. The solution is retained even after cooling to room temperature.

Gegenüber der geringen Wasserlöslichkeit des Aufheller wirkstoffs von nur 0,07% kann mit der o.g. Zubereitung eine 50-fach höhere Konzentration erzielt werden.Compared to the low water solubility of the brightener active ingredient of only 0.07%, the above Preparation a concentration 50 times higher can be achieved.

Beispiel 2Example 2

7 g des Aufhellers aus Beispiel 1 werden mit 88 g des anionischen Tensids aus Beispiel 1 und 1 g CH3COONa in 250 g Wasser gelöst und anschließend zu einem Pulver mit 4 % Restfeuchte sprühgetrocknet.7 g of the brightener from example 1 are dissolved in 250 g of water with 88 g of the anionic surfactant from example 1 and 1 g of CH 3 COONa and then spray-dried to a powder with 4% residual moisture.

Diese Präparation ergibt auf Polyacrylnitrilfasern im Konzentrationsbereich von 0,2-2% und in Flottenverhältnissen von 1:10 bis 1:40 angewendet, brillante grünstichige Aufhellungen.Applied to polyacrylonitrile fibers in the concentration range of 0.2-2% and in liquor ratios of 1:10 to 1:40, this preparation produces brilliant green tints.

Beispeil 3Example 3

6 g des optischen Aufhellers der Formel

Figure imgb0008
werden zusammen mit 88g des anionischen Tensids aus Beispiel 1 und 1 g CH3COONa in 250 g Wasser unter Rühren homogenisiert und zu einem Pulver mit 5% Restfeuchte sprühgetrocknet.6 g of the optical brightener of the formula
Figure imgb0008
 are homogenized together with 88 g of the anionic surfactant from Example 1 and 1 g of CH 3 COONa in 250 g of water with stirring and spray dried to a powder with 5% residual moisture.

30 g dieses Pulvers werden in 70 g kockendem Wasser von pH 4 (essigsauer) gelöst. Diese Lösung bleibt auch nach dem Abkühlen auf Raumtemperatur erhalten.30 g of this powder are dissolved in 70 g of boiling water of pH 4 (acetic acid). This solution is retained even after cooling to room temperature.

Gegenüber der geringen Wasserlöslichkeit des Aufhellerwirkstoffs von nur 0,030% in Wasser kann mit dieser Präparation eine 60-fach höhere Konzentrtion erreicht werden.Compared to the low water solubility of the brightening agent of only 0.030% in water, this preparation can achieve a 60-fold higher concentration.

Die o.g. Präparation ergibt Polyacrynitrilfasern im Konzentrationsbereich von 0,2-2% und in Flottenverhältnissen von 1:10 bis 1:40 angewendet, brillante blaustichige Färbungen.The above Preparation results in polyacrynitrile fibers in the concentration range of 0.2-2% and in liquor ratios of 1:10 to 1:40, brilliant bluish tints.

Ähnliche Effekte erhält man, wenn man den in der vorstehend beschriebenen Präparation enthaltenen Aufheller durch den Aufheller gemäß Beispiel 1 ersetzt.Similar effects are obtained if the brightener contained in the preparation described above is replaced by the brightener according to Example 1.

Claims (3)

1. Brightener formulations, characterised in that they consist of a cationic optical brightener, an anionic surfactant and, optionally, other customary additives, with the exception of those formulations which are obtained by melt formulation.
2. Brightener formulations according to Claim 1, characterised in that they contain, as surfactants, lignosulphonates, oxylignosulphonates or condensation products of naphthalenesulphonic acids or ditolyl ether sulphonic acids with formaldehyde.
3. Brightener formulations according to Claim 1, characterised in that they contain, as brighteners, compounds of the formula
Figure imgb0010
wherein
X denotes a triazolyl radical,
Y denotes a cumarinyl or benzofuranyl radical,
Z denotes a heteroaromatic radical quaternised at the N atom and
An° denotes an anion.
EP82108168A 1981-09-16 1982-09-04 Preparations of optical brighteners Expired EP0074590B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3136809 1981-09-16
DE19813136809 DE3136809A1 (en) 1981-09-16 1981-09-16 OPTICAL BRIGHTNING PREPARATIONS

Publications (3)

Publication Number Publication Date
EP0074590A2 EP0074590A2 (en) 1983-03-23
EP0074590A3 EP0074590A3 (en) 1984-05-16
EP0074590B1 true EP0074590B1 (en) 1987-05-27

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JP (1) JPS5861196A (en)
DE (2) DE3136809A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0498288U (en) * 1991-01-22 1992-08-25
GB9409465D0 (en) * 1994-05-12 1994-06-29 Ciba Geigy Ag Protective use
DE69533417T2 (en) * 1994-05-12 2005-08-18 Ciba Specialty Chemicals Holding Inc. textile treatments
GB9413270D0 (en) * 1994-07-01 1994-08-24 Ciba Geigy Ag Textile treatment
DE19500195A1 (en) * 1995-01-05 1996-07-11 Bayer Ag Use of white-tinted plastics for tinting paper coating slips and such white-tinted paper coating slips

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1248652A (en) * 1968-04-25 1971-10-06 Du Pont Water-insoluble dye salts
DE2257945A1 (en) * 1972-11-25 1974-05-30 Basf Ag Liquid and powdered cationic dyestuff prepns. - contg. excess anionic dispersants for dyeing/printing polyacrylonitrile, acid-modified polyesters and polyamides
CH597335A5 (en) * 1973-09-14 1978-03-31 Ciba Geigy Ag

Also Published As

Publication number Publication date
EP0074590A3 (en) 1984-05-16
DE3136809A1 (en) 1983-03-31
EP0074590A2 (en) 1983-03-23
JPS5861196A (en) 1983-04-12
DE3276440D1 (en) 1987-07-02

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