EP0385374A1 - Storage-stable brightener composition - Google Patents
Storage-stable brightener composition Download PDFInfo
- Publication number
- EP0385374A1 EP0385374A1 EP90103750A EP90103750A EP0385374A1 EP 0385374 A1 EP0385374 A1 EP 0385374A1 EP 90103750 A EP90103750 A EP 90103750A EP 90103750 A EP90103750 A EP 90103750A EP 0385374 A1 EP0385374 A1 EP 0385374A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- brightener
- storage
- stable
- formulation according
- 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.)
- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920001586 anionic polysaccharide Polymers 0.000 claims abstract description 13
- 150000004836 anionic polysaccharides Chemical class 0.000 claims abstract description 13
- 125000000129 anionic group Chemical group 0.000 claims abstract description 10
- 239000003599 detergent Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 238000009472 formulation Methods 0.000 claims description 49
- 230000003287 optical effect Effects 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 12
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 9
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 9
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical group C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 9
- 229920001285 xanthan gum Polymers 0.000 claims description 9
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 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
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 150000004804 polysaccharides Chemical class 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
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000000725 suspension Substances 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- -1 tertiary amine radical Chemical class 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 7
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 0 C*=**=*(*(C)=C)N=O Chemical compound C*=**=*(*(C)=C)N=O 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 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
- 229920002134 Carboxymethyl cellulose Polymers 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
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-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
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-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
- 239000000654 additive Substances 0.000 description 1
- IAJILQKETJEXLJ-QTBDOELSSA-N aldehydo-D-glucuronic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-QTBDOELSSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl 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
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- RGLYKWWBQGJZGM-ISLYRVAYSA-N diethylstilbestrol Chemical class C=1C=C(O)C=CC=1C(/CC)=C(\CC)C1=CC=C(O)C=C1 RGLYKWWBQGJZGM-ISLYRVAYSA-N 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
- 229940097043 glucuronic acid Drugs 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
- 150000002772 monosaccharides Chemical class 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
- 125000004430 oxygen atom Chemical group O* 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
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- 239000003760 tallow Substances 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 brightener formulations and a process for their preparation and their use.
- optical brighteners are preferably marketed in the form of aqueous solutions.
- the moist filter cake or the dry powder is slurried with water.
- This suspension is mixed with dispersants and thickeners to increase homogeneity, wettability and stability.
- An electrolyte is often added to these auxiliaries.
- the additives used up to now could not prevent sedimentation of the brighteners over a longer period of time.
- Such formulations preferably contain anionic optical brighteners which contain at least one sulfonic acid residue.
- they are brighteners of the triazine series of the formula: wherein X and Y, which may be the same or different and represent a secondary or tertiary amine radical or a mono- or di-substituted alkoxy group, and H represents a hydrogen atom or a salt-forming cation.
- X1 and Y1 which may be the same or different, a phenylamino group which is optionally mono- or di-substituted by alkyl radicals with 1 or 2 carbon atoms, the morpholino group, an alkylamino group with 1 to 4 carbon atoms which may be substituted by hydroxyl radicals, represents an alkoxy group having 1 to 4 carbon atoms, and M represents hydrogen or a salt-forming cation.
- X2 and Y2 which may be the same or different, the phenylamino, the morpholino, an alkylamino group having 1 to 4 carbon atoms, which may be substituted by hydroxyl radicals and M is hydrogen or a salt-forming cation.
- X3 and Y3, which may be the same or different, represent a phenylamino, morpholino, the N-methyl-N-ethanolamine group and M is hydrogen or a salt-forming cation.
- X4 and Y4 which may be the same or different, represent the morpholino or the N-methyl-N-ethanolamine group and M is hydrogen or a salt-forming cation.
- M ' is an alkali metal ion, in the case of this optical brightener a content of 4 to 25% by weight, based on the total weight of the slurry, of a strong electrolyte is expediently present.
- Optical brighteners from the distilbene series can also be used.
- A sulfonic acid residue, hydrogen, C1-C4-alkyl, C1-C4-alkoxy or halogen
- 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 fluorine, chlorine and bromine, but especially chlorine.
- C1-C4 alkyl radicals are unbranched and branched alkyl radicals such as the methyl, ethyl, n- and iso-propyl, n-, sec- and tert-butyl radical. These C1-C4 alkyl radicals can in turn be substituted with e.g. Aryl (phenyl, naphthyl), C1-C4 alkyl, C1-C4 alkoxy, OH or CN groups.
- Salt-forming cations M are e.g. Alkali metal, ammonium or amine salt ions.
- Amine salt ions are preferred those of the formula H+NR8R9R10 in which R8, R9 and R10 independently of one another are hydrogen, alkyl, alkenyl, hydroxyalkyl, cyanoalkyl, haloalkyl or phenylalkyl or in which R8 and R9 together are the addition to a 5-7-membered saturated Represent 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 R10 represents hydrogen.
- Preferred distyrylbiphenyl compounds of the formula (X) are those in which the cation M is an alkali metal, ammonium or amine ion, potassium and sodium being of particular importance for practical reasons.
- the anionic polysaccharides which can be used according to the invention belong to the group of modified polysaccharides which can be derived from cellulose. It can be etherified cellulose, but also heteropolysaccharides that contain other monosaccharides in the side chains, e.g. Mannose and glucuronic acid included.
- the anionic polysaccharide is, for example, Na carboxymethyl cellulose and particularly preferably xanthan.
- the amount of polysaccharide is preferably 0.01 to 1% by weight, with a range of 0.05-0.5% by weight being particularly preferred, based on the total weight of the formulation. However, these ranges can be exceeded in the case of very highly concentrated or very low concentrated formulations.
- the formulation can contain auxiliaries; electrolytes, preservatives such as chloroacetamide or aqueous formaldehyde solution and odor improvers may be mentioned as examples.
- the electrolyte can be sodium chloride, sodium sulfate, sodium carbonate or one of the corresponding potassium salts or also mixtures of the aforementioned substances.
- the amount of electrolyte can be 0.1 to 25% by weight, based on the total weight of the formulation, preferably 0.1 to 20% by weight.
- Formulations according to the invention are obtained by mixing the moist filter cake or the dry powder of an anionic optical brightener, which preferably contains at least one sulfonic acid residue, in an amount of 10-60% by weight, based on the total weight of the formulation, with 0.01-1% by weight % anionic polysaccharide and water mixed and homogenized.
- an anionic optical brightener which preferably contains at least one sulfonic acid residue
- the desired content of anionic optical brightener in the suspension can be adjusted either by adding water, aqueous electrolyte, suspension or further dry powder to the moist filter cake. This setting can be made before, during or after the addition of the anionic polysaccharide.
- the proportion of the anionic optical brightener is expediently 10 to 60%, preferably 15 to 40% by weight, based on the weight of the suspension.
- the suspension is then mixed with the anionic polysaccharide until it is homogeneous.
- the formulation can be incorporated into a detergent, e.g. by flowing the required amount of the suspension from a container into a mixing device which contains a suspension of the detergent or detergent.
- the present invention accordingly also relates to a process for the production of detergents and the detergents obtained thereafter, characterized in that a suspension for detergents of conventional detergents is mixed and dried with a suspension of brighteners according to the invention.
- the suspensions obtained are advantageously dried by subjecting them to a spray drying process.
- the brightener formulation according to the invention can be used for the production of liquid detergents.
- the properties of the brightener formulation correspond to those from Example 1.
- the brightener formulation does not form any deposits after standing for several months at room temperature and 40 ° C.
- the brightener formulation is stable on storage at room temperature and 40 ° C.
- the suspension shows no deposits after standing for 3 months at room temperature.
- the brightener formulation is stable on storage at room temperature and 40 ° C.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (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)
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft lagerstabile, wässrige, konzentrierte Aufhellerformulierungen und ein Verfahren zu deren Herstellung sowie deren Verwendung.The present invention relates to storage-stable, aqueous, concentrated brightener formulations 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 preferably marketed in the form of aqueous solutions. For this purpose, the moist filter cake or the dry powder is slurried with water. This suspension is mixed with dispersants and thickeners to increase homogeneity, wettability and stability. An electrolyte is often added to these auxiliaries. However, the additives used up to now could not prevent sedimentation of the brighteners over a longer period of time.
Es wurde nun überraschenderweise gefunden, dass man lagerstabile, konzentrierte, wässrige Aufhellerformulierungen erhält, wenn man zu der wässrigen Suspension derartiger Aufheller ein anionisches Polysaccharid 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 formulations are obtained by adding an anionic polysaccharide in small amounts to the aqueous suspension of such brighteners. Such suspensions hardly settle out during storage. In addition to the good sedimentation behavior, the suspensions remain homogeneous during storage.
Die Formulierungen gemäss der Erfindung sind demnach gekennzeichnet durch einen Gehalt an:
- a) 10 bis 60 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung eines anionischen optischen Aufhellers,
- b) 0,01 bis 1 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung eines anionischen Polysaccharids und
- c) Wasser; sowie gegebenenfalls
- d) Hilfsstoffe.
- a) 10 to 60% by weight, based on the total weight of the brightener formulation of an anionic optical brightener,
- b) 0.01 to 1% by weight, based on the total weight of the brightener formulation of an anionic polysaccharide and
- c) water; and if necessary
- d) auxiliary substances.
Diese Formulierungen stellen Suspensionen dar.These formulations represent suspensions.
Vorzugsweise enthalten solche Formulierungen anionische optische Aufheller, die mindestens einen Sulfonsäurerest enthalten.Such formulations preferably contain anionic optical brighteners which contain at least one sulfonic acid residue.
Beispielsweise handelt es sich um Aufheller der Triazinreihe der Formel:
Von besonderem Interesse sind:
Weiterhin kann man optische Aufheller der Distilbenreihe einsetzen. So zum Beispiel Verbindungen der Formel
Bevorzugt sind solche Verbindungen in denen o = 2 ist.Compounds in which o = 2 are preferred.
Besonders bevorzugte Verbindungen sind Verbindungen der Formel
Von praktischem Interesse sind dabei die Verbindungen
Als Halogene kommen vor allem Fluor, Chlor und Brom in Frage, insbesondere jedoch Chlor.The most suitable halogens are fluorine, chlorine and bromine, but especially 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 C₁-C₄ alkyl radicals are unbranched and branched alkyl radicals such as the methyl, ethyl, n- and iso-propyl, n-, sec- and tert-butyl radical. These C₁-C₄ alkyl radicals can in turn be substituted with e.g. Aryl (phenyl, naphthyl), C₁-C₄ alkyl, C₁-C₄ 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 e.g. Alkali metal, ammonium or amine salt ions. Amine salt ions are preferred those of the formula H⁺NR₈R₉R₁₀ in which R₈, R₉ and R₁₀ independently of one another are hydrogen, alkyl, alkenyl, hydroxyalkyl, cyanoalkyl, haloalkyl or phenylalkyl or in which R₈ and R₉ together are the addition to a 5-7-membered saturated Represent 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 R₁₀ represents 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 the cation M is an alkali metal, ammonium or amine ion, potassium and sodium being of particular importance for practical reasons.
Die erfindungsgemäss verwendbaren anionischen Polysaccharide gehören zur Gruppe der modifizierten Polysaccharide, die sich von der Zellulose ableiten lassen. Es kann sich um veretherte Zellulose handeln, aber auch um Heteropolysaccharide, die in den Seitenketten weitere Monosaccharide wie z.B. Mannose und Glucuronsäure enthalten.The anionic polysaccharides which can be used according to the invention belong to the group of modified polysaccharides which can be derived from cellulose. It can be etherified cellulose, but also heteropolysaccharides that contain other monosaccharides in the side chains, e.g. Mannose and glucuronic acid included.
Das anionische Polysaccharid ist zum Beispiel Na-Carboxymethylcellulose und besonders bevorzugt Xanthan.The anionic polysaccharide is, for example, Na carboxymethyl cellulose and particularly preferably xanthan.
Die Menge an Polysaccharid beträgt vorzugsweise 0,01 bis 1 Gew.%, wobei ein Bereich von 0,05-0,5 Gew.% besonders bevorzugt ist, bezogen auf das Gesamtgewicht der Formulierung. Es können jedoch bei sehr hoch konzentrierten oder sehr niedrig konzentrierten Formulierungen diese Bereiche überschritten werden.The amount of polysaccharide is preferably 0.01 to 1% by weight, with a range of 0.05-0.5% by weight being particularly preferred, based on the total weight of the formulation. However, these ranges can be exceeded in the case of very highly concentrated or very low concentrated formulations.
Gegebenenfalls kann die Formulierung Hilfsstoffe enthalten; exemplarisch seien genannt Elektrolyte, Konservierungsmittel wie Chloracetamid oder wässrige Formaldehydlösung und Geruchsverbesserer.If appropriate, the formulation can contain auxiliaries; electrolytes, preservatives such as chloroacetamide or aqueous formaldehyde solution and odor improvers may be mentioned as examples.
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 also mixtures of the aforementioned substances. The amount of electrolyte can be 0.1 to 25% by weight, based on the total weight of the formulation, preferably 0.1 to 20% by weight.
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 - 1 Gew.% anionischem Polysaccharid und Wasser vermischt und homogenisiert.Formulations according to the invention are obtained by mixing the moist filter cake or the dry powder of an anionic optical brightener, which preferably contains at least one sulfonic acid residue, in an amount of 10-60% by weight, based on the total weight of the formulation, with 0.01-1% by weight % anionic polysaccharide 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 anionischen Polysaccharids 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 be adjusted either by adding water, aqueous electrolyte, suspension or further dry powder to the moist filter cake. This setting can be made before, during or after the addition of the anionic polysaccharide. The proportion of the anionic optical brightener is expediently 10 to 60%, preferably 15 to 40% by weight, based on the weight of the suspension.
Die Suspension wird dann mit dem anionischen Polysaccharid vermischt, bis sie homogen ist.The suspension is then mixed with the anionic polysaccharide until it is 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 flowing the required amount of the suspension from a container into a mixing device which contains a suspension of the detergent or detergent.
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 Aufhellern, 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 production of detergents and the detergents obtained thereafter, characterized in that a suspension for detergents of conventional detergents is mixed and dried with a suspension of brighteners according to the invention. The suspensions obtained are advantageously dried by subjecting them to a spray drying process.
Weiterhin kann die erfindungsgemässe Aufhellerformulierung zur Herstellung von flüssigen Waschmitteln verwendet werden.Furthermore, the brightener formulation according to the invention can be used for the production of liquid detergents.
Die folgenden Beispiele erläutern die Erfindung, ohne sie darauf zu beschränken. Teile sind auf das Gewicht bezogen.The following examples illustrate the invention without restricting it. Parts are by weight.
0,075 Teile Xanthan
0,2 Teile Chloracetamid
1,3 Teile Natriumsulfat und
5 Teile Natriumchlorid werden in
61 Teilen Wasser gelöst.
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
0.2 parts chloroacetamide
1.3 parts of sodium sulfate and
5 parts of sodium chloride are in
61 parts of water dissolved.
Stir into this solution
32.5 parts of moist press cake, containing 12 parts of water, 0.5 parts of sodium chloride and 20 parts of the optical brightener
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
0,075 Teile Xanthan
0,2 Teile Chloracetamid
1,3 Teile Natriumsulfat
5 Teile Natriumchlorid in
72 Teilen Wasser gelöst, mit
21,5 Teilen des trockenen Presskuchens, enthaltend 1,5 Teile Wasser und 20 Teile des optischen Aufhellers
0.075 parts of xanthan
0.2 parts chloroacetamide
1.3 parts sodium sulfate
5 parts of sodium chloride in
72 parts of water dissolved, with
21.5 parts of the dry press cake, containing 1.5 parts of water and 20 parts of the optical brightener
Die Aufhellerformulierung entspricht in ihren Eigenschaften derjenigen aus Beispiel 1.The properties of the brightener formulation correspond to those from Example 1.
Wie in Beispiel 1 werden
0,1 Teile Chloracetamid
3,0 Teile Natriumchlorid
1,0 Teil Talgfettalkohol mit 11 Mol Ethylenoxid
0,3 Teile Xanthan in
37,5 Teilen Wasser gelöst, mit
58,1 Teilen des wasserfeuchten Filterkuchens, enthaltend 56 Teile Wasser und 44 Teile des optischen Aufhellers
0.1 parts chloroacetamide
3.0 parts sodium chloride
1.0 part of tallow fatty alcohol with 11 moles of ethylene oxide
0.3 parts xanthan in
37.5 parts of water dissolved with
58.1 parts of the water-moist filter cake, containing 56 parts of water and 44 parts of the optical brightener
Die Aufhellerformulierung bildet nach mehrmonatigem Stehen bei Raumtemperatur und 40°C keine Ablagerungen.The brightener formulation does not form any deposits after standing for several months at room temperature and 40 ° C.
Wie in Beispiel 3 werden
0,1 Teile Chloracetamid
0,1 Teile Xanthan
3,0 Teile Natriumchlorid in
5,9 Teilen Wasser gelöst, mit
90,9 Teilen des wasserfeuchten Filterkuchens, enthaltend 56 Teile Wasser und 44 Teile des optischen Aufhellers der Formel (300), versetzt und unter Rühren homogenisiert.As in example 3
0.1 parts chloroacetamide
0.1 part xanthan
3.0 parts sodium chloride in
5.9 parts of water dissolved, with
90.9 parts of the water-moist filter cake, containing 56 parts of water and 44 parts of the optical brightener of the formula (300), were added and the mixture was homogenized with stirring.
Die Aufhellerformulierung ist bei Raumtemperatur und 40°C lagerstabil.The brightener formulation is stable on storage at room temperature and 40 ° C.
Wie in Beispiel 1 werden
0,5 Teile Formaldehyd (37 %) wässrig
2,0 Teile Na-Carboxymethylcellulose in
33,5 Teilen Wasser gelöst, mit
64,5 Teilen des wasserfeuchten Filterkuchens, enthaltend 53,5 Teile Wasser und 46,5 Teile des optischen Aufhellers der Formel
0.5 parts of formaldehyde (37%) aqueous
2.0 parts Na carboxymethyl cellulose in
33.5 parts of water dissolved with
64.5 parts of the water-moist filter cake, containing 53.5 parts of water and 46.5 parts of the optical brightener of the formula
Die Suspension zeigt nach 3-monatigem Stehen bei Raumtemperatur keine Ablagerungen.The suspension shows no deposits after standing for 3 months at room temperature.
Wie in Beispiel 3 werden
0,1 Teile Chloracetamid
0,1 Teile Xanthan in
8,9 Teilen Wasser gelöst, mit
90,9 Teilen des wasserfeuchten Filterkuchens, enthaltend 56 Teile Wasser und 44 Teile des optischen Aufhellers der Formel (300), versetzt und unter Rühren homogenisiert.As in example 3
0.1 parts chloroacetamide
0.1 parts xanthan in
8.9 parts of water dissolved, with
90.9 parts of the water-moist filter cake, containing 56 parts of water and 44 parts of the optical brightener of the formula (300), were added and the mixture was homogenized with stirring.
Die Aufhellerformulierung ist bei Raumtemperatur und 40°C lagerstabil.The brightener formulation is stable on storage at room temperature and 40 ° C.
Claims (21)
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 |
---|---|---|---|
CH733/89 | 1989-02-28 | ||
CH73389 | 1989-02-28 | ||
CH73389 | 1989-02-28 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0385374A1 true EP0385374A1 (en) | 1990-09-05 |
EP0385374B1 EP0385374B1 (en) | 1994-01-19 |
EP0385374B2 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)
Country | Link |
---|---|
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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EP0577557A1 (en) * | 1992-06-30 | 1994-01-05 | Ciba-Geigy Ag | Hydrates of 4,4'-Bis-(2-sulfostyryl)-biphenyl-disodium or -dipotassium salts |
EP0884312A1 (en) * | 1997-05-23 | 1998-12-16 | Ciba SC Holding AG | Triazinylaminostilbene compounds |
US5980904A (en) * | 1998-11-18 | 1999-11-09 | Amway Corporation | Skin whitening composition containing bearberry extract and a reducing agent |
EP1300513A2 (en) * | 2001-10-05 | 2003-04-09 | Bayer Aktiengesellschaft | Use of solid preparations of optical brighteners for optically brightening paper |
EP1335001A1 (en) * | 2001-10-05 | 2003-08-13 | Bayer Aktiengesellschaft | Solid whitener preparations |
WO2004111330A1 (en) * | 2003-06-11 | 2004-12-23 | Ciba Specialty Chemicals Holding Inc. | Storage-stable fluorescent whitener formulations |
EP2454356B1 (en) | 2009-07-17 | 2017-03-01 | Henkel AG & Co. KGaA | Liquid detergent compositon comprising a polymer preventing graying |
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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. |
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 |
ES2208855T3 (en) * | 1996-10-10 | 2004-06-16 | Ciba Specialty Chemicals Holding Inc. | DISPERSIONS OF OPTICAL WHITENERS. |
US20070185032A1 (en) * | 1996-12-11 | 2007-08-09 | Praecis Pharmaceuticals, Inc. | Pharmaceutical formulations for sustained drug delivery |
US6030443A (en) * | 1999-04-29 | 2000-02-29 | Hercules Incorporated | Paper coating composition with improved optical brightener carriers |
DE10149313A1 (en) * | 2001-10-05 | 2003-04-17 | Bayer Ag | Use of aqueous brightener preparations to lighten natural and synthetic materials |
WO2005065185A2 (en) * | 2003-12-24 | 2005-07-21 | Collegium Pharmaceuticals, Inc. | Temperature-stable formulations, and methods of development thereof |
ES2347057T3 (en) * | 2004-12-09 | 2010-10-25 | Clariant Finance (Bvi) Limited | WATERPROOF DISPERSIONS OF OPTICAL GRINDING AGENTS. |
WO2011017223A1 (en) | 2009-07-31 | 2011-02-10 | Akzo Nobel N.V. | Hybrid copolymer compositions for personal care applications |
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 |
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CN103314154B (en) * | 2011-01-20 | 2016-09-14 | 亨斯迈先进材料(瑞士)有限公司 | The fluorescent whitening agent formulation of discrete form |
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WO2013064648A1 (en) | 2011-11-04 | 2013-05-10 | Akzo Nobel Chemicals International B.V. | Graft dendrite copolymers, and methods for producing the same |
US9988526B2 (en) | 2011-11-04 | 2018-06-05 | Akzo Nobel Chemicals International B.V. | Hybrid dendrite copolymers, compositions thereof and methods 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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- 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
- 1990-02-26 DE DE90103750T patent/DE59004269D1/en not_active Expired - Lifetime
- 1990-02-27 US US07/485,695 patent/US5076968A/en not_active Expired - Lifetime
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EP0577557A1 (en) * | 1992-06-30 | 1994-01-05 | Ciba-Geigy Ag | Hydrates of 4,4'-Bis-(2-sulfostyryl)-biphenyl-disodium or -dipotassium salts |
EP0884312A1 (en) * | 1997-05-23 | 1998-12-16 | Ciba SC Holding AG | Triazinylaminostilbene compounds |
US5980904A (en) * | 1998-11-18 | 1999-11-09 | Amway Corporation | Skin whitening composition containing bearberry extract and a reducing agent |
EP1300513A2 (en) * | 2001-10-05 | 2003-04-09 | Bayer Aktiengesellschaft | Use of solid preparations of optical brighteners for optically brightening paper |
EP1335001A1 (en) * | 2001-10-05 | 2003-08-13 | Bayer Aktiengesellschaft | Solid whitener preparations |
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EP2454356B1 (en) | 2009-07-17 | 2017-03-01 | Henkel AG & Co. KGaA | Liquid detergent compositon comprising a polymer preventing graying |
Also Published As
Publication number | Publication date |
---|---|
DE59004269D1 (en) | 1994-03-03 |
EP0385374B1 (en) | 1994-01-19 |
CA2010909A1 (en) | 1990-08-31 |
JPH02266000A (en) | 1990-10-30 |
JP2688378B2 (en) | 1997-12-10 |
ATE100484T1 (en) | 1994-02-15 |
CA2010909C (en) | 2002-01-22 |
MX170189B (en) | 1993-08-10 |
EP0385374B2 (en) | 2005-01-12 |
ES2048343T3 (en) | 1994-03-16 |
US5076968A (en) | 1991-12-31 |
BR9000850A (en) | 1991-02-05 |
ES2048343T5 (en) | 2005-07-01 |
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