EP0074590B1 - Preparations of optical brighteners - Google Patents
Preparations of optical brighteners Download PDFInfo
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- brightener
- denotes
- preparations
- radical
- brighteners
- 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
Links
- 230000003287 optical effect Effects 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- 239000003945 anionic surfactant Substances 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 239000007859 condensation product Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 229920001732 Lignosulfonate Polymers 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- FDLFMPKQBNPIER-UHFFFAOYSA-N 1-methyl-3-(3-methylphenoxy)benzene Chemical compound CC1=CC=CC(OC=2C=C(C)C=CC=2)=C1 FDLFMPKQBNPIER-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 5
- 239000000203 mixture Substances 0.000 claims 5
- 239000004117 Lignosulphonate Substances 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 235000019357 lignosulphonate Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- -1 ditolyl ether sulfonic acids Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- VVPHSMHEYVOVLH-UHFFFAOYSA-N 6-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=CC(O)=CC=C21 VVPHSMHEYVOVLH-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 229960001506 brilliant green Drugs 0.000 description 1
- HXCILVUBKWANLN-UHFFFAOYSA-N brilliant green cation Chemical compound C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 HXCILVUBKWANLN-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- 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.
Landscapes
- 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
- 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
- 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
- Z = Triazolylrest mit quartärem Stickstoffatom, beispielsweise
- X die obige Bedeutung hat,
- Z Imidazolylrest mit quartärem N-Atom, z.B.
- Z = triazolyl radical with a quaternary nitrogen atom, for example
- X has the above meaning
- Z imidazolyl radical with a quaternary N atom, for example
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.
- 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.
3,6 g des optischen Aufhellers der Formel
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.
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.
6 g des optischen Aufhellers der Formel
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)
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 |
Family
ID=6141843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP82108168A Expired EP0074590B1 (en) | 1981-09-16 | 1982-09-04 | Preparations of optical brighteners |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0074590B1 (en) |
| JP (1) | JPS5861196A (en) |
| DE (2) | DE3136809A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0498288U (en) * | 1991-01-22 | 1992-08-25 | ||
| GB9413270D0 (en) * | 1994-07-01 | 1994-08-24 | Ciba Geigy Ag | Textile treatment |
| DE69533417T2 (en) * | 1994-05-12 | 2005-08-18 | Ciba Specialty Chemicals Holding Inc. | textile treatments |
| GB9409465D0 (en) * | 1994-05-12 | 1994-06-29 | Ciba Geigy Ag | Protective use |
| 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)
| 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 |
-
1981
- 1981-09-16 DE DE19813136809 patent/DE3136809A1/en not_active Withdrawn
-
1982
- 1982-09-04 DE DE8282108168T patent/DE3276440D1/en not_active Expired
- 1982-09-04 EP EP82108168A patent/EP0074590B1/en not_active Expired
- 1982-09-13 JP JP57158246A patent/JPS5861196A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE3136809A1 (en) | 1983-03-31 |
| EP0074590A3 (en) | 1984-05-16 |
| EP0074590A2 (en) | 1983-03-23 |
| JPS5861196A (en) | 1983-04-12 |
| DE3276440D1 (en) | 1987-07-02 |
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