EP0385374B2 - Storage-stable brightener composition - Google Patents
Storage-stable brightener composition Download PDFInfo
- Publication number
- EP0385374B2 EP0385374B2 EP90103750A EP90103750A EP0385374B2 EP 0385374 B2 EP0385374 B2 EP 0385374B2 EP 90103750 A EP90103750 A EP 90103750A EP 90103750 A EP90103750 A EP 90103750A EP 0385374 B2 EP0385374 B2 EP 0385374B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- whitener
- storage
- suspension
- stable aqueous
- weight
- 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 - Lifetime
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- 239000000203 mixture Substances 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000000129 anionic group Chemical group 0.000 claims abstract description 10
- 239000003599 detergent Substances 0.000 claims abstract description 10
- 229920001586 anionic polysaccharide Polymers 0.000 claims abstract description 6
- 150000004836 anionic polysaccharides Chemical class 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 229920001285 xanthan gum Polymers 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 14
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- -1 sulfonic acid radical Chemical class 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 7
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000006081 fluorescent whitening agent Substances 0.000 claims 11
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 6
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims 6
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 230000002087 whitening effect Effects 0.000 claims 2
- 238000009472 formulation Methods 0.000 description 14
- 230000003287 optical effect Effects 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000230 xanthan gum Substances 0.000 description 4
- 229940082509 xanthan gum Drugs 0.000 description 4
- 235000010493 xanthan gum Nutrition 0.000 description 4
- 0 CCc1nc(Nc2cc(*)c(C=C[C@]3C(*)=CC(Nc4nc(*)nc(*)n4)=CC3)cc2)nc(*)n1 Chemical compound CCc1nc(Nc2cc(*)c(C=C[C@]3C(*)=CC(Nc4nc(*)nc(*)n4)=CC3)cc2)nc(*)n1 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- ZMLPKJYZRQZLDA-UHFFFAOYSA-N 1-(2-phenylethenyl)-4-[4-(2-phenylethenyl)phenyl]benzene Chemical group C=1C=CC=CC=1C=CC(C=C1)=CC=C1C(C=C1)=CC=C1C=CC1=CC=CC=C1 ZMLPKJYZRQZLDA-UHFFFAOYSA-N 0.000 description 1
- ULOIAOPTGWSNHU-UHFFFAOYSA-N 2-butyl radical Chemical compound C[CH]CC ULOIAOPTGWSNHU-UHFFFAOYSA-N 0.000 description 1
- IIVWHGMLFGNMOW-UHFFFAOYSA-N 2-methylpropane Chemical compound C[C](C)C IIVWHGMLFGNMOW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- 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
- D06L4/614—Optical bleaching or brightening in aqueous solvents
- D06L4/621—Optical bleaching or brightening in aqueous solvents with anionic brighteners
-
- 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 present invention relates to storage-stable, aqueous, concentrated Whitener suspensions and a process for their preparation and their Use.
- optical brighteners are preferred in the form of aqueous solutions in brought the trade.
- the wet filter cake or the dry Powder slurried with water This suspension is mixed with dispersants and Thickeners to increase homogeneity, wettability and stability added.
- an electrolyte is added to these auxiliaries.
- the adjuvants used so far could sediment the brightener Do not prevent for a long period of time.
- such formulations contain anionic optical brighteners which contain at least one sulfonic acid residue.
- X and Y which may be the same or different and denote a secondary or tertiary amine group or a mono- or di-substituted alkoxy group
- M represents a hydrogen atom or a salt-forming cation
- X 1 and Y 1 which may be the same or different, have a phenylamino group which is optionally mono- or di-substituted by alkyl groups having 1 or 2 carbon atoms, the morpholino group, an alkylamino group having 1 to 4 carbon atoms substituted by hydroxyl groups may represent an alkoxy group having 1 to 4 carbon atoms, and M represents hydrogen or a salt-forming cation.
- X 2 and Y 2 which may be the same or different, are the phenylamino, the morpholino, an alkylamino group having 1 to 4 carbon atoms which may be substituted by hydroxyl groups and M is hydrogen or a salt-forming cation.
- X 3 and Y 3 which may be the same or different, represent a phenylamino, morpholino, N-methyl-N-ethanolamine group and M represents hydrogen or a salt-forming cation.
- X 4 and Y 4 which may be the same or different, mean the morpholino or the N-methyl-N-ethanolamine group and M is hydrogen or a salt-forming cation.
- M ' represents an alkali metal ion, wherein in the case of this optical brightener, a content of 4 to 25 wt.%, based on the total weight of the slurry, of a strong electrolyte is suitably present.
- Particularly preferred compounds are compounds of the formula where A, B and n have the above meaning and M is a salt-forming cation.
- halogens are especially fluorine, chlorine and bromine in question, in particular but chlorine.
- C 1 -C 4 -alkyl radicals are unbranched and branched alkyl radicals such as the methyl, ethyl, n- and iso-propyl, n-, sec- and tert-butyl radical into consideration. These C 1 -C 4 -alkyl radicals may in turn be substituted with, for example, aryl (phenyl, naphthyl), C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, OH or CN groups.
- Salt-forming cations M are, for example, alkali metal, ammonium or amine salt ions.
- amine salt ions those of the formula H + NR 8 R 9 R 10 are preferred in which R 8 , R 9 and R 10 independently of one another are hydrogen, alkyl, alkenyl, hydroxyalkyl, cyanoalkyl, haloalkyl or phenylalkyl or R 8 and R 9 together represent the complement to a 5-7-membered saturated nitrogen heterocycle, which may additionally contain a nitrogen or oxygen atom as a ring member, for example a piperidine, piperazine, pyrrolidine, imidazoline or morpholine ring, while R 10 is hydrogen.
- Preferred distyrylbiphenyl compounds of the formula (X) are those in which Cation M is an alkali metal, ammonium, or amine ion, with practical Considerations of potassium and sodium are of particular importance.
- the amount of xanthan is 0.01-0.5 wt%, with a range of 0.05-0.5 Wt.%, Particularly preferred, based on the total weight of Formulation.
- the formulation may contain adjuvants; be exemplary called electrolytes, preservatives like chloroacetamide or aqueous Formaldehyde solution and odor improver.
- the electrolyte can be sodium chloride, sodium sulfate, sodium carbonate or one of the corresponding potassium salts or mixtures of the aforementioned substances.
- the amount of electrolyte can be from 0.1 to 25% by weight, based on the total weight the formulation, preferably 0.1 to 20 wt.%, Be.
- Formulations according to the invention are obtained by mixing the moist Filter cake or even the dry powder of an anionic optical Brightener, which preferably contains at least one sulfonic acid residue, in one Amount of 10-60 wt.% Based on the total weight of the formulation with 0.01 - 0.5 wt.% Xanthan and water mixed and homogenized.
- the desired content of anionic optical brightener in the suspension can either by adding water, aqueous electrolyte, suspension or further dry powder to the moist filter cake. This setting may be before, during or after the addition of xanthan be made.
- the proportion of the anionic optical brightener is Suitably 10 to 60%, preferably 15 to 40 wt.%, Based on the Weight of the suspension.
- the suspension is then mixed with the xanthan until homogeneous.
- the formulation can be incorporated into a detergent, e.g. by Injecting the required amount of the suspension from a container in a mixing device comprising a suspension of the detergent or the detergent contains.
- the present invention accordingly also relates to a process for the preparation of detergents, as well as the detergent obtained thereafter, thereby characterized in that a suspension for detergents of conventional detergents with a suspension of brightener according to the invention, mixed and dried.
- the resulting suspensions are advantageously dried by placing them in a Subject spray drying method.
- inventive brightener formulation for the preparation of liquid detergents are used.
- Example 1 As in Example 1 will be 0,075 Parts of xanthan gum 0.2 Parts of chloroacetamide 1.3 Parts of sodium sulfate 5 Parts of sodium chloride in 72 Dissolve water, with 21.5 Divide the dry presscake containing 1.5 parts of water and 20 parts of the optical brightener mixed and homogenized with stirring.
- the brightener formulation corresponds in its properties to those of Example 1.
- Example 1 0.1 Parts of chloroacetamide 3.0 Parts of sodium chloride 1.0 Part of tallow fatty alcohol with 11 moles of ethylene oxide 0.3 Parts xanthan in 37.5 Dissolve water, with 58.1 Parts of the water-moist filter cake, containing 56 parts of water and 44 parts of the optical brightener mixed and homogenized with stirring.
- the brightener formulation forms after standing for several months Room temperature and 40 ° C no deposits.
- the brightener formulation is storage stable at room temperature and 40 ° C.
- the brightener formulation is storage stable at room temperature and 40 ° C.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicinal Preparation (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft lagerstabile, wässrige, konzentrierte Aufhellersuspensionen und ein Verfahren zu deren Herstellung sowie deren Verwendung.The present invention relates to storage-stable, aqueous, concentrated Whitener suspensions and a process for their preparation and their Use.
Heutzutage werden optische Aufheller bevorzugt in Form wässriger Lösungen in den Handel gebracht. Hierzu wird der feuchte Filterkuchen oder auch das trockene Pulver mit Wasser aufgeschlämmt. Diese Suspension wird mit Dispergatoren und Verdickungsmitteln zur Erhöhung von Homogenität, Benetzbarkeit und Stabilität versetzt. Zu diesen Hilfsstoffen setzt man häufig noch einen Elektrolyten hinzu. Die bisher verwendeten Hilfsstoffe konnten jedoch ein Sedimentieren der Aufheller nicht über einen längeren Zeitraum verhindern.Nowadays, optical brighteners are preferred in the form of aqueous solutions in brought the trade. For this purpose, the wet filter cake or the dry Powder slurried with water. This suspension is mixed with dispersants and Thickeners to increase homogeneity, wettability and stability added. Often, an electrolyte is added to these auxiliaries. However, the adjuvants used so far could sediment the brightener Do not prevent for a long period of time.
Es wurde nun überraschenderweise gefunden, dass man lagerstabile, konzentrierte, wässrige Aufhellersuspensionen erhält, wenn man zu der wässrigen Suspension derartiger Aufheller Xanthan in geringen Mengen zugibt. Derartige Suspensionen setzen sich während der Lagerung kaum ab. Zusätzlich zu dem guten Sedimentationsverhalten bleiben die Suspensionen während der Lagerung homogen.It has now surprisingly been found that storage-stable, concentrated, aqueous brightener suspensions, when added to the aqueous Suspension of such brightener xanthan gum in small amounts admits. such Suspensions hardly settle during storage. In addition to that good sedimentation behavior, the suspensions remain during storage homogeneous.
Die Suspensionen gemäss der Erfindung sind demnach gekennzeichnet durch
einen Gehalt an:
Diese Formulierungen stellen Suspensionen dar.These formulations are suspensions.
Vorzugsweise enthalten solche Formulierungen anionische optische Aufheller, die mindestens einen Sulfonsäurerest enthalten. Preferably, such formulations contain anionic optical brighteners which contain at least one sulfonic acid residue.
Beispielsweise handelt es sich um Aufheller der Triazinreihe der Formel: worin X und Y, die gleichartig oder verschieden sein können und einen sekundären oder tertiären Aminrest oder eine mono- oder di-substituierte Alkoxygruppe bedeuten, und M ein Wasserstoffatom oder ein salzbildendes Kation bedeutet.For example, it is brighteners of the triazine series of the formula: wherein X and Y, which may be the same or different and denote a secondary or tertiary amine group or a mono- or di-substituted alkoxy group, and M represents a hydrogen atom or a salt-forming cation.
Von besonderem Interesse sind: worin X1 und Y1, die gleichartig oder verschieden sein können, eine Phenylaminogruppe, welche gegebenenfalls durch Alkylreste mit 1 oder 2 Kohlenstoffatomen mono- oder di-substituiert ist, die Morpholinogruppe, eine Alkylaminogruppe mit 1 bis 4 Kohlenstoffatomen, die durch Hydroxylreste substituiert sein kann, eine Alkoxygruppe mit 1 bis 4 Kohlenstoffatomen bedeuten, und M Wasserstoff oder ein salzbildendes Kation darstellt. worin X2 und Y2, die gleichartig oder verschieden sein können, die Phenylamino-, die Morpholino-, eine Alkylaminogruppe mit 1 bis 4 Kohlenstoffatomen, die durch Hydroxylreste substituiert sein kann und M Wasserstoff oder ein salzbildendes Kation bedeuten. worin X3 und Y3, die gleichartig oder verschieden sein können, eine Phenylamino-, Morpholino-, die N-Methyl-N-äthanolaminogruppe und M Wasserstoff oder ein salzbildendes Kation bedeuten. worin X4 und Y4, die gleichartig oder verschieden sein können, die Morpholinooder die N-Methyl-N-äthanolaminogruppe und M Wasserstoff oder ein salzbildendes Kation bedeuten. worin M' ein Alkalimetallion bedeutet, wobei im Falle dieses optischen Aufhellers zweckmässig ein Gehalt von 4 bis 25 Gew.%, bezogen auf das Gesamtgewicht der Aufschlämmung an einem starken Elektrolyten vorhanden ist.Of particular interest are: wherein X 1 and Y 1 , which may be the same or different, have a phenylamino group which is optionally mono- or di-substituted by alkyl groups having 1 or 2 carbon atoms, the morpholino group, an alkylamino group having 1 to 4 carbon atoms substituted by hydroxyl groups may represent an alkoxy group having 1 to 4 carbon atoms, and M represents hydrogen or a salt-forming cation. wherein X 2 and Y 2 , which may be the same or different, are the phenylamino, the morpholino, an alkylamino group having 1 to 4 carbon atoms which may be substituted by hydroxyl groups and M is hydrogen or a salt-forming cation. wherein X 3 and Y 3 , which may be the same or different, represent a phenylamino, morpholino, N-methyl-N-ethanolamine group and M represents hydrogen or a salt-forming cation. wherein X 4 and Y 4 , which may be the same or different, mean the morpholino or the N-methyl-N-ethanolamine group and M is hydrogen or a salt-forming cation. wherein M 'represents an alkali metal ion, wherein in the case of this optical brightener, a content of 4 to 25 wt.%, based on the total weight of the slurry, of a strong electrolyte is suitably present.
Weiterhin kann man optische Aufheller der Distilbenreihe einsetzen. So zum Beispiel Verbindungen der Formel wobei A = Sulfonsäurerest, Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy oder Halogen und B = Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy oder Halogen bedeuten, mit der Bedingung, dass mindestens ein Substituent A = Sulfonsäurerest ist und m, n, o, p unabhängig voneinander eine Zahl 1 oder 2 bedeuten.Furthermore, you can use optical brighteners of the distillate series. So for example compounds of the formula where A = sulfonic acid radical, hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or halogen and B = hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or halogen, with the Condition that at least one substituent A = sulfonic acid radical and m, n, o, p independently of one another denote a number 1 or 2.
Bevorzugt sind solche Verbindungen in denen o = 2 ist.Preference is given to those compounds in which o = 2.
Besonders bevorzugte Verbindungen sind Verbindungen der Formel wobei A, B und n obige Bedeutung haben und M ein salzbildendes Kation ist.Particularly preferred compounds are compounds of the formula where A, B and n have the above meaning and M is a salt-forming cation.
Von praktischem Interesse sind dabei die Verbindungen wobei M' ein Alkalimetallion bedeutet.Of practical interest are the compounds wherein M 'represents an alkali metal ion.
Als Halogene kommen vor allem Fluor, Chlor und Brom in Frage, insbesondere jedoch Chlor.As halogens are especially fluorine, chlorine and bromine in question, in particular but chlorine.
Als C1-C4-Alkylreste kommen unverzweigte und verzweigte Alkylreste wie der Methyl-, Ethyl-, n- und iso-Propyl, n-, sec- und tert.-Butylrest in Betracht. Diese C1-C4-Alkylreste können ihrerseits substituiert sein mit z.B. Aryl-(Phenyl-, Naphthyl-), C1-C4-Alkyl-, C1-C4-Alkoxy-, OH- oder CN-Gruppen.As C 1 -C 4 -alkyl radicals are unbranched and branched alkyl radicals such as the methyl, ethyl, n- and iso-propyl, n-, sec- and tert-butyl radical into consideration. These C 1 -C 4 -alkyl radicals may in turn be substituted with, for example, aryl (phenyl, naphthyl), C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, OH or CN groups.
Salzbildende Kationen M sind z.B. Alkalimetall-, Ammonium- oder Aminsalzionen. Unter Aminsalzionen sind solche der Formel H+NR8R9R10 bevorzugt, in denen R8, R9 und R10 unabhängig voneinander Wasserstoff, Alkyl, Alkenyl, Hydroxyalkyl, Cyanoalkyl, Halogenalkyl oder Phenylalkyl bedeuten oder worin R8 und R9 zusammen die Ergänzung zu einem 5-7-gliedrigen gesättigten Stickstoffheterocyclus darstellen, der noch zusätzlich ein Stickstoff- oder Sauerstoffatom als Ringglied enthalten kann, beispielsweise einen Piperidin-, Piperazin-, Pyrrolidin-, Imidazolin- oder Morpholinring, während R10 für Wasserstoff steht.Salt-forming cations M are, for example, alkali metal, ammonium or amine salt ions. Among amine salt ions, those of the formula H + NR 8 R 9 R 10 are preferred in which R 8 , R 9 and R 10 independently of one another are hydrogen, alkyl, alkenyl, hydroxyalkyl, cyanoalkyl, haloalkyl or phenylalkyl or R 8 and R 9 together represent the complement to a 5-7-membered saturated nitrogen heterocycle, which may additionally contain a nitrogen or oxygen atom as a ring member, for example a piperidine, piperazine, pyrrolidine, imidazoline or morpholine ring, while R 10 is hydrogen.
Bevorzugte Distyrylbiphenylverbindungen der Formel (X) sind solche in denen das Kation M ein Alkalimetall-, Ammonium-, oder Aminion ist, wobei aus praktischen Erwägungen Kalium und Natrium eine besondere Bedeutung haben.Preferred distyrylbiphenyl compounds of the formula (X) are those in which Cation M is an alkali metal, ammonium, or amine ion, with practical Considerations of potassium and sodium are of particular importance.
Die Menge an Xanthan beträgt 0,01-0,5 Gew.%, wobei ein Bereich von 0.05 - 0.5 Gew.%, besonders bevorzugt ist, bezogen auf das Gesamtgewicht der Formulierung.The amount of xanthan is 0.01-0.5 wt%, with a range of 0.05-0.5 Wt.%, Particularly preferred, based on the total weight of Formulation.
Gegebenenfalls kann die Formulierung Hilfsstoffe enthalten; exemplarisch seien genannt Elektrolyte, Konservierungsmittel wie Chloracetamid oder wässrige Formaldehydlösung und Geruchsverbesserer.Optionally, the formulation may contain adjuvants; be exemplary called electrolytes, preservatives like chloroacetamide or aqueous Formaldehyde solution and odor improver.
Der Elektrolyt kann Natriumchlorid, Natriumsulfat, Natriumcarbonat oder eines der entsprechenden Kaliumsalze sein oder auch Mischungen der vorgenannten Stoffe. Die Menge an Elektrolyt kann 0,1 bis 25 Gew.%, bezogen auf das Gesamtgewicht der Formulierung, vorzugsweise 0,1 bis 20 Gew.%, betragen.The electrolyte can be sodium chloride, sodium sulfate, sodium carbonate or one of the corresponding potassium salts or mixtures of the aforementioned substances. The amount of electrolyte can be from 0.1 to 25% by weight, based on the total weight the formulation, preferably 0.1 to 20 wt.%, Be.
Erfindungsgemässe Formulierungen erhält man, indem man den feuchten Filterkuchen oder auch das trockene Pulver eines anionischen optischen Aufhellers, der vorzugsweise mindestens einen Sulfonsäurerest enthält, in einer Menge von 10-60 Gew.% bezogen auf das Gesamtgewicht der Formulierung mit 0,01 - 0.5 Gew.% Xanthan und Wasser vermischt und homogenisiert.Formulations according to the invention are obtained by mixing the moist Filter cake or even the dry powder of an anionic optical Brightener, which preferably contains at least one sulfonic acid residue, in one Amount of 10-60 wt.% Based on the total weight of the formulation with 0.01 - 0.5 wt.% Xanthan and water mixed and homogenized.
Der gewünschte Gehalt an anionischem optischen Aufheller in der Suspension kann entweder durch Zugabe von Wasser, wässrigem Elektrolyt, Suspension oder weiterem trockenen Pulver zu dem feuchten Filterkuchen eingestellt werden. Diese Einstellung kann vor, während oder nach Zusatz des Xanthans vorgenommen werden. Der Anteil des anionischen optischen Aufhellers beträgt zweckmässig 10 bis 60 %, vorzugsweise 15 bis 40 Gew.%, bezogen auf das Gewicht der Suspension.The desired content of anionic optical brightener in the suspension can either by adding water, aqueous electrolyte, suspension or further dry powder to the moist filter cake. This setting may be before, during or after the addition of xanthan be made. The proportion of the anionic optical brightener is Suitably 10 to 60%, preferably 15 to 40 wt.%, Based on the Weight of the suspension.
Die Suspension wird dann mit dem Xanthan vermischt, bis sie homogen ist.The suspension is then mixed with the xanthan until homogeneous.
Die Formulierung kann in ein Waschmittel eingearbeitet werden, z.B. durch Einfliessenlassen der erforderlichen Menge der Suspension aus einem Behälter in eine Mischvorrichtung, die eine Suspension des Waschmittels bzw. des Detergenz enthält.The formulation can be incorporated into a detergent, e.g. by Injecting the required amount of the suspension from a container in a mixing device comprising a suspension of the detergent or the detergent contains.
Die vorliegende Erfindung betrifft demzufolge auch ein Verfahren zur Herstellung von Waschmitteln, sowie die danach erhaltenen Waschmittel, dadurch gekennzeichnet, dass man eine Suspension für Waschmittel üblicher Detergentien mit einer erfindungsgemässen Suspension von Aufhellem, vermischt und trocknet. Die erhaltenen Suspensionen werden vorteilhaft getrocknet, indem man sie einem Sprühtrocknungsverfahren unterwirft.The present invention accordingly also relates to a process for the preparation of detergents, as well as the detergent obtained thereafter, thereby characterized in that a suspension for detergents of conventional detergents with a suspension of brightener according to the invention, mixed and dried. The resulting suspensions are advantageously dried by placing them in a Subject spray drying method.
Weiterhin kann die erfindungsgemässe Aufhellerformulierung zur Herstellung von flüssigen Waschmitteln verwendet werden.Furthermore, the inventive brightener formulation for the preparation of liquid detergents are used.
Die folgenden Beispiele erläutern die Erfindung, ohne sie darauf zu beschränken. Teile sind auf das Gewicht bezogen.The following examples illustrate the invention without being limited thereto. Parts are by weight.
Unter Rühren werden in diese Lösung
32,5 Teile feuchter Presskuchen, enthaltend 12 Teile Wasser, 0,5 Teile
Natriumchlorid und 20 Teile des optischen Aufhellers
eingetragen und homogenisiert.While stirring in this solution
32.5 parts wet presscake containing 12 parts water, 0.5 parts
Sodium chloride and 20 parts of the optical brightener registered and homogenized.
Die weisse Aufhellerformulierung hat eine Viskosität von 108 cP (Haake VT 18, MVII, 22°C, D = 42 sec-1) und bildet nach zweimonatigem Stehen bei -5°C, RT und 40°C keine Ablagerungen. The white brightener formulation has a viscosity of 108 cP (Haake VT 18, MVII, 22 ° C, D = 42 sec -1 ) and forms no deposits after standing for two months at -5 ° C, RT and 40 ° C.
Wie im Beispiel 1 werden
Die Aufhellerformulierung entspricht in ihren Eigenschaften derjenigen aus Beispiel 1.The brightener formulation corresponds in its properties to those of Example 1.
Wie in Beispiel 1 werden
Die Aufhellerformulierung bildet nach mehrmonatigem Stehen bei Raumtemperatur und 40°C keine Ablagerungen.The brightener formulation forms after standing for several months Room temperature and 40 ° C no deposits.
Wie in Beispiel 3 werden
Die Aufhellerformulierung ist bei Raumtemperatur und 40°C lagerstabil.The brightener formulation is storage stable at room temperature and 40 ° C.
Wie in Beispiel 3 werden
Die Aufhellerformulierung ist bei Raumtemperatur und 40°C lagerstabil.The brightener formulation is storage stable at room temperature and 40 ° C.
Claims (18)
- A storage-stable aqueous whitener suspension which comprisesa) 10 to 60 % by weight, based on the total weight of the whitener suspension, of an anionic fluorescent whitening agent,b) 0.01 to 0.5 % by weight of an anionic polysaccharide which is xanthan, based on the total weight of the whitener suspension, andc) water.
- A storage-stable aqueous whitener suspension according to claim 1, 14, 15 or 16, which contains 15-40 % by weight of whitening agent.
- A storage-stable aqueous whitener suspension according to claim 1, which comprises an electrolyte.
- A storage-stable aqueous whitener suspension according to claim 1, which contains 2-25 % of electrolyte.
- A storage-stable aqueous whitener suspension according to claim 1, 14, 15 or 16, wherein the fluorescent whitening agent is of the formula in which X and Y may be identical or different and are a secondary or tertiary amine radical or a mono- or disubstituted alkoxy group, and M is a hydrogen atom or a salt-forming cation.
- A storage-stable aqueous whitener suspension according to claim 5, wherein the fluorescent whitening agent is of the formula in which X2 and Y2 may be identical or different and are the phenylamino group, the morpholino group, an alkylamino group of 1 to 4 carbon atoms which may be substituted by hydroxyl radicals, and M is hydrogen or a salt-forming cation.
- A storage-stable aqueous whitener suspension according to claim 1, 14, 15 or 16, wherein the fluorescent whitening agent is of the formula where A is a sulfonic acid radical, hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen, and B is hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen, with the proviso that at least one substituent A is a sulfonic acid radical and m, n, o and p are each independently of one another 1 or 2.
- A storage-stable aqueous whitener suspension according to claim 7, wherein the fluorescent whitening agent is of the formula where A is a sulfonic acid radical, hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen, and B is a sulfonic acid radical, hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen, and each n independently of the other is 1 or 2, and M is a salt-forming cation.
- A storage-stable aqueous whitener suspension according to claim 7, wherein the fluorescent whitening agent is of the formula where A is a sulfonic acid radical, hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen, and B is hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen, and each n independently of the other is 1 or 2, and M is a salt-forming cation.
- A process for the preparation of a storage-stable aqueous whitener suspension according to claim 1 or claim 14, which comprises admixing the moist filter cake or the dry powder of the whitening agent according to claim 1 or claim 14 with xanthan, mixing with water, and homogenizing the suspension.
- The use of a storage-stable aqueous whitener suspension according to claim 1 or claim 14 for the preparation of a detergent composition.
- A storage-stable aqueous whitener suspension which comprisesa) 10 to 60 % by weight, based on the total weight of the whitener suspension, of an anionic fluorescent whitening agent,b) 0.01 to 0.5 % by weight of an anionic polysaccharide which is xanthan, based on the total weight of the whitener suspension, andc) water, and optionallyd) auxiliaries.
- A storage-stable aqueous whitener suspension according to claim 14, wherein the auxiliary is an electrolyte or a mixture of electrolytes.
- A storage-stable aqueous whitener suspension according to claim 15, which contains 0.1-25 % by weight of electrolyte.
- A storage-stable aqueous whitener suspension according to claim 14, which comprisesa) 10 to 60 % by weight, based on the total weight of the whitener suspension, of an anionic fluorescent whitening agent of the formula or where M' is an alkali metal ion,b) 0.01 to 0.5 % by weight, based on the total weight of the whitener suspension, of an anionic polysaccharide which is xanthane,c) water, and optionallyd) an electrolyte or a mixture of electrolytes.
- A storage-stable aqueous whitener suspension according to claim 14, which comprisesa) 10 to 60 % by weight, based on the total weight of the whitener suspension, of an anionic fluorescent whitening agent of the formula or or where M' is an alkali metal ion,b) 0.01 to 0.5 % by weight, based on the total weight of the whitener suspension, of an anionic polysaccharide which is xanthane,c) water, and optionallyd) an electrolyte or a mixture of electrolytes.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT90103750T ATE100484T1 (en) | 1989-02-28 | 1990-02-26 | SHELF-STABLE BRIGHTENER FORMULATION. |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH73389 | 1989-02-28 | ||
CH73389 | 1989-02-28 | ||
CH733/89 | 1989-02-28 |
Publications (3)
Publication Number | Publication Date |
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EP0385374A1 EP0385374A1 (en) | 1990-09-05 |
EP0385374B1 EP0385374B1 (en) | 1994-01-19 |
EP0385374B2 true EP0385374B2 (en) | 2005-01-12 |
Family
ID=4193929
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90103750A Expired - Lifetime EP0385374B2 (en) | 1989-02-28 | 1990-02-26 | Storage-stable brightener composition |
Country Status (9)
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US (1) | US5076968A (en) |
EP (1) | EP0385374B2 (en) |
JP (1) | JP2688378B2 (en) |
AT (1) | ATE100484T1 (en) |
BR (1) | BR9000850A (en) |
CA (1) | CA2010909C (en) |
DE (1) | DE59004269D1 (en) |
ES (1) | ES2048343T5 (en) |
MX (1) | MX170189B (en) |
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US8865294B2 (en) | 2012-10-25 | 2014-10-21 | The Glad Products Company | Thermoplastic multi-ply film with metallic appearance |
CH682748A5 (en) * | 1991-11-07 | 1993-11-15 | Ciba Geigy Ag | A storage-stable formulation of optical brightener. |
MY109837A (en) * | 1992-06-30 | 1997-08-30 | Ciba Specialty Chemicals Holding Inc | Hydrates of the disodium salt or dipotassium salt of 4, 4''-bis (2-sulfostyryl)bipheny] |
CH686959A5 (en) * | 1992-12-22 | 1996-08-15 | Ciba Geigy Ag | A storage-stable formulation of optical brighteners. |
US5697985A (en) * | 1995-06-07 | 1997-12-16 | Bayer Corporation | Process for the preparation storage-stable dye dispersions |
PT835906E (en) * | 1996-10-10 | 2004-03-31 | Ciba Sc Holding Ag | OPTICAL APRILHANTATOR SCATTERS |
US20070185032A1 (en) * | 1996-12-11 | 2007-08-09 | Praecis Pharmaceuticals, Inc. | Pharmaceutical formulations for sustained drug delivery |
GB9710569D0 (en) * | 1997-05-23 | 1997-07-16 | Ciba Geigy Ag | Compounds |
US5980904A (en) * | 1998-11-18 | 1999-11-09 | Amway Corporation | Skin whitening composition containing bearberry extract and a reducing agent |
US6030443A (en) * | 1999-04-29 | 2000-02-29 | Hercules Incorporated | Paper coating composition with improved optical brightener carriers |
EP1335001A1 (en) * | 2001-10-05 | 2003-08-13 | Bayer Aktiengesellschaft | Solid whitener preparations |
DE10149313A1 (en) * | 2001-10-05 | 2003-04-17 | Bayer Ag | Use of aqueous brightener preparations to lighten natural and synthetic materials |
DE10149314A1 (en) * | 2001-10-05 | 2003-04-17 | Bayer Ag | Use solid brightener preparations to lighten paper |
MXPA05013012A (en) * | 2003-06-11 | 2006-03-02 | Ciba Sc Holding Ag | Storage-stable fluorescent whitener formulations. |
WO2005065185A2 (en) * | 2003-12-24 | 2005-07-21 | Collegium Pharmaceuticals, Inc. | Temperature-stable formulations, and methods of development thereof |
JP2008523185A (en) * | 2004-12-09 | 2008-07-03 | クラリアント インターナショナル リミティド | Aqueous dispersion of optical brightener |
US8674021B2 (en) | 2006-07-21 | 2014-03-18 | Akzo Nobel N.V. | Sulfonated graft copolymers |
KR100876368B1 (en) | 2006-09-23 | 2008-12-29 | 연세대학교 산학협력단 | Low Voltage Driven Electro-Fluorescent Devices and Their Uses |
DE102009027812A1 (en) | 2009-07-17 | 2011-01-20 | Henkel Ag & Co. Kgaa | Liquid washing or cleaning agent with graying-inhibiting polymer |
MX341475B (en) | 2009-07-31 | 2016-08-19 | Akzo Nobel N V * | Hybrid copolymer compositions for personal care applications. |
US10780669B2 (en) | 2009-11-16 | 2020-09-22 | The Glad Products Company | Films and bags with visually distinct regions and methods of making the same |
MY162539A (en) * | 2011-01-20 | 2017-06-15 | Huntsman Advanced Mat (Switzerland) Gmbh | Formulations of fluorescent whitening agents in dispersed form |
US8636918B2 (en) | 2011-08-05 | 2014-01-28 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale |
US8853144B2 (en) | 2011-08-05 | 2014-10-07 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage |
US8679366B2 (en) | 2011-08-05 | 2014-03-25 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale |
US8841246B2 (en) | 2011-08-05 | 2014-09-23 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage |
CN103945828A (en) | 2011-11-04 | 2014-07-23 | 阿克佐诺贝尔化学国际公司 | Hybrid dendrite copolymers, compositions thereof and methods for producing the same |
JP2014532792A (en) | 2011-11-04 | 2014-12-08 | アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップAkzo Nobel Chemicals International B.V. | Grafted dendritic copolymer and method for producing the same |
US8945314B2 (en) | 2012-07-30 | 2015-02-03 | Ecolab Usa Inc. | Biodegradable stability binding agent for a solid detergent |
US9365805B2 (en) | 2014-05-15 | 2016-06-14 | Ecolab Usa Inc. | Bio-based pot and pan pre-soak |
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US3962115A (en) * | 1970-07-09 | 1976-06-08 | Ciba-Geigy Ag | Treatment of optical brightening agents |
CH582275A5 (en) * | 1973-02-02 | 1976-11-30 | Ciba Geigy Ag | |
CH632631B (en) * | 1977-11-23 | Ciba Geigy Ag | AQUATIC PREPARATIONS OF COLORS, INSOLUBLE TO PORTIONAL, AND OPTICAL BRIGHTENERS | |
DE2850382A1 (en) * | 1978-11-21 | 1980-06-04 | Hoechst Ag | COLOR-STABLE DETERGENT WHITENER |
US4298490A (en) * | 1978-12-22 | 1981-11-03 | Ciba-Geigy Corporation | Process for the production of washing powders of stabilized or enhanced appearance which contain fluorescent whitening agents |
GB2076011A (en) * | 1980-05-19 | 1981-11-25 | Procter & Gamble | Coated white diphenyl and stilbene fabric brighteners |
ATE7898T1 (en) * | 1981-02-26 | 1984-06-15 | Ciba-Geigy Ag | AMPHOTERE STYRENE DERIVATIVES. |
DE3643215A1 (en) * | 1986-12-18 | 1988-06-30 | Bayer Ag | WHITE-TONED PAPER COATINGS |
DE3726266A1 (en) * | 1987-08-07 | 1989-02-23 | Bayer Ag | FLUESSIGWASCHMITTEL |
-
1990
- 1990-02-22 BR BR909000850A patent/BR9000850A/en unknown
- 1990-02-26 DE DE90103750T patent/DE59004269D1/en not_active Expired - Lifetime
- 1990-02-26 EP EP90103750A patent/EP0385374B2/en not_active Expired - Lifetime
- 1990-02-26 AT AT90103750T patent/ATE100484T1/en not_active IP Right Cessation
- 1990-02-26 CA CA002010909A patent/CA2010909C/en not_active Expired - Fee Related
- 1990-02-26 ES ES90103750T patent/ES2048343T5/en not_active Expired - Lifetime
- 1990-02-27 US US07/485,695 patent/US5076968A/en not_active Expired - Lifetime
- 1990-02-27 MX MX019682A patent/MX170189B/en unknown
- 1990-02-28 JP JP2046003A patent/JP2688378B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
ATE100484T1 (en) | 1994-02-15 |
EP0385374B1 (en) | 1994-01-19 |
US5076968A (en) | 1991-12-31 |
BR9000850A (en) | 1991-02-05 |
JPH02266000A (en) | 1990-10-30 |
ES2048343T5 (en) | 2005-07-01 |
CA2010909C (en) | 2002-01-22 |
ES2048343T3 (en) | 1994-03-16 |
JP2688378B2 (en) | 1997-12-10 |
CA2010909A1 (en) | 1990-08-31 |
EP0385374A1 (en) | 1990-09-05 |
DE59004269D1 (en) | 1994-03-03 |
MX170189B (en) | 1993-08-10 |
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