EP0274666B1 - Paper-coating compositions comprising whitening agents - Google Patents
Paper-coating compositions comprising whitening agents Download PDFInfo
- Publication number
- EP0274666B1 EP0274666B1 EP87118124A EP87118124A EP0274666B1 EP 0274666 B1 EP0274666 B1 EP 0274666B1 EP 87118124 A EP87118124 A EP 87118124A EP 87118124 A EP87118124 A EP 87118124A EP 0274666 B1 EP0274666 B1 EP 0274666B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- formula
- fluorescent brightener
- salt
- paper
- 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.)
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- YXFVVABEGXRONW-UHFFFAOYSA-N Cc1ccccc1 Chemical compound Cc1ccccc1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
Definitions
- aqueous coating slips are used to a very large extent, which in addition to the usual white pigments - especially china clay and calcium carbonate - contain plastic dispersions as binders.
- whiteners of the alkali salt type of bistriazonylaminostilbene-disulfonic acids are generally used.
- these whiteners only have very unsatisfactory brightening effects and a very low graying limit (whitener concentration, at which further addition of the whitener does not result in an increase or even a decrease in the whiteness).
- the white toner types mentioned have a very low light fastness in those coating slips.
- this brightener salt for the stated purpose must be regarded as extremely surprising, since it is known that water-soluble brighteners based on bistriazonyl-aminostilbene-disulfonic acids, when used with conventional poly-cationic products according to GB-A-721 238 and GB-A -1 058 918 can be precipitated, in cobinder-free paper coating slips none or only very much unsatisfactory effect and the brightener salts mentioned in JP-A-57 123 262 have a significantly lower degree of whiteness (CIE).
- CIE degree of whiteness
- the brightener salt according to the invention shows a more or less pronounced fluorescence in finely divided or dissolved additive, even if the cationic component is used in excess.
- the reaction takes place in water and / or organic solvents, such as methanol, ethanol, propanol, isopropanol, butanol, glycol, glycol methyl ether, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide at temperatures from 20 ° C. to the reflux temperature of the corresponding solvent.
- organic solvents such as methanol, ethanol, propanol, isopropanol, butanol, glycol, glycol methyl ether, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide
- the poorly soluble whitening salt obtained in this way can be used as a whitening agent directly or after prior fine grinding or liquid formation.
- the dispersions according to the invention can be prepared as follows: The press cakes and / or powders are homogenized with vigorous stirring after the addition of a surface-active substance and optionally water. The amount of the surface-active substance can then be increased, if necessary to the total amount required for the stability of the dispersion.
- the suspension obtained is then comminuted and wet-ground.
- Pre-shredding can be carried out using stone or tooth colloid mills.
- the subsequent wet comminution can take place in colloid, vibratory, cone and vibromills as well as in dissolvers or in sub-micron dispersers.
- continuous agitator mills with grinding media preferably those made of SiO2 of 0.2 to 5 mm in diameter, are preferably used.
- surface-active substances or hydrotropic substances such as e.g. Ethylene glycol or glycerin, preservatives, wetting agents, defoamers and / or water are added, unless this has been done at an earlier point in time e.g. before grinding.
- a further possibility of producing the brightening agent according to the invention, which is sparingly or insoluble in water, and its dispersions, is the combination of the reaction and grinding process:
- the alkali salt of the brightener according to formula (II) is wet-comminuted together with the basic nitrogen compound of formula (III) and water and surface-active substances after homogenization and pre-comminution, the amounts used being able to be varied, as indicated above.
- the complete reaction of the whitening salt II with the basic nitrogen compound III takes place in the grinder, preferably in a continuous agitator mill with SiO 2 grinding media.
- Suitable surface-active substances are all customary, cationic and nonionic surface-active substances, as are described, for example, in DE-A 2 334 769, pages 8 to 10 (corresponds to GB-A 1 417 071).
- Nonionic surfactants are preferably used.
- the paper coating slips into which the brightener salts to be used according to the invention are incorporated are structured as follows: plastic dispersions based on styrene-butadiene, carboxylated styrene-butadiene or polyvinyl acetate copolymers or of acrylic acid esters in combination with white pigments, both with and without low levels of hydrophilic co-binders.
- the amount of compound I used depends on the desired lightening effect. In general, 0.01 to 0.5% by weight of pure active substance (based on the solids of the paper coating slip to be lightened) is sufficient.
- a particular advantage is that, depending on the composition of the coating slip, the graying limit that can be achieved (up to which a further brightener additive brings additional effects) is extremely high.
- 200 g of the water-insoluble brightener salt prepared according to Example 1 are homogenized together with 200 g of emulsifier W and 600 g of water and comminuted using a toothed colloid mill. The suspension is then wet crushed in a bead mill at room temperature with 4 passes. The resulting stable dispersion is easy to incorporate into paper coating slips and shows excellent white effects, even when large amounts are added (cf. Example 4).
- the suspension is wet-crushed at room temperature with 4 passes in a bead mill and shows excellent white effects after incorporation into paper coating slips.
- coated papers After spreading the lightened coating slip onto paper with the help of a hand-held squeegee or a test coater and after drying at 20-130 ° C, coated papers are obtained which, depending on the brightener additive, have a clear to excellent brightening effect. An increase in the degree of whiteness can usually still be achieved even with brightener additives higher than 50 g / kg of coating slip.
Description
Zur Herstellung gestrichener Papiere und Kartons werden in sehr großem Umfang wäßrige Streichmassen verwendet, welche neben den üblichen Weißpigmenten - vor allem China Clay und Calciumcarbonat - Kunststoff-Dispersionen als Bindemittel enthalten.For the production of coated papers and cardboard, aqueous coating slips are used to a very large extent, which in addition to the usual white pigments - especially china clay and calcium carbonate - contain plastic dispersions as binders.
Zur optischen Aufhellung dieser Streichmassen werden in der Regel Weißtöner vom Typ der Alkalisalze von Bistriazonylaminostilben-disulfonsäuren eingesetzt. Diese Weißtöner bringen jedoch nur sehr unbefriedigende Aufhell-Effekte und eine sehr niedrige Vergrauungsgrenze (Weißtöner-Konzentration, bei welcher eine weitere Zugabe des Weißtöners keine Steigerung oder sogar einen Abfall des Weißgrades ergibt). Darüber hinaus besitzen die genannten Weißtönertypen in jenen Streichmassen eine sehr niedrige Lichtechtheit.For the optical brightening of these coating slips, whiteners of the alkali salt type of bistriazonylaminostilbene-disulfonic acids are generally used. However, these whiteners only have very unsatisfactory brightening effects and a very low graying limit (whitener concentration, at which further addition of the whitener does not result in an increase or even a decrease in the whiteness). In addition, the white toner types mentioned have a very low light fastness in those coating slips.
Es ist allgemein bekannt, die genannten Schwierigkeiten auf zweierlei Wegen teilweise zu lösen:
- 1. Durch Zusatz von geringen Anteilen an hydrophilen Cobindern zur Streichmasse, auf welche die Weißtöner aufziehen können. Solche Cobinder sind z.B.:
Stärke, Kasein, Carboxymethylcellulose, Alginate, Polyvinylalkohol, Polyacrylate, Melamin- oder Harnstoff-Formaldehydharze (vgl. "Das Papier" 36 (1982), 66). - 2. Verwendung von speziellen wasserlöslichen Weißtönern, welche hydrophile Carrier enthalten. Solche Carrier können z.B. Polyglykole sein (vgl. DE-A-35 02 038 und EP-A-43 790).
- 1. By adding small proportions of hydrophilic co-binders to the coating slip, onto which the whiteners can apply. Examples of such cobinders are:
Starch, casein, carboxymethyl cellulose, alginates, polyvinyl alcohol, polyacrylates, melamine or urea-formaldehyde resins (see "Das Papier" 36 (1982), 66). - 2. Use of special water-soluble whiteners which contain hydrophilic carriers. Such carriers can be, for example, polyglycols (cf. DE-A-35 02 038 and EP-A-43 790).
Beide Möglichkeiten können nur eine Teillösung darstellen, da dem Zusatz der genannten Produkte zu den Streichmassen deutliche Grenzen gesetzt sind:
Sie erhöhen die Wasser-Empfindlichkeit der gestrichenen Papiere, was bei bestimmten Druckverfahren und beim Gebrauch der gestrichenen Papiere zu Schwierigkeiten führt. Außerdem entstehen mit diesen Zusätzen zur Streichmasse häufig auf modernen schnell-laufenden Streichanlagen rheologische Probleme.Both options can only be a partial solution, since there are clear limits to adding the products mentioned to the coating slips:
They increase the water sensitivity of the coated papers, which leads to difficulties with certain printing processes and when using the coated papers. In addition, these additives to the coating slip often cause rheological problems on modern, high-speed coating systems.
Die Herstellung von gestrichenen Papieren mit höherem und hohem Weißgrad ist daher in den meisten Fällen eine schwierige bzw. vielfach nicht befriedigend lösbare Aufgabe.The production of coated papers with higher and high whiteness is therefore in most cases a difficult or often unsatisfactory task.
Es ist deshalb bereits vorgeschlagen worden (vgl. DE-A 3 112 435), wasserlösliche Weißtöner auf bestimmte Kunststoffe wie z.B. Harnstoff- oder Methylol-Harze aufziehen zu lassen und diese aufgehellten Kunststoffe als Dispersion der Papierstreichmasse zuzusetzen. Diese Vorschläge haben sich jedoch bisher wegen ihrer viel zu hohen Kosten oder wegen rheologischer Schwierigkeiten nicht durchsetzen können,It has therefore already been proposed (cf. DE-A 3 112 435) to use water-soluble whiteners on certain plastics, e.g. Allow urea or methylol resins to be drawn in and add these lightened plastics as a dispersion of the paper coating slip. However, these proposals have so far not been able to prevail because of their high costs or rheological difficulties,
Es wurde nun gefunden, daß man Streichmassen für den Papierstrich ohne die genannten Nachteile aufhellen kann, wenn man ein in Wasser praktisch unlösliches niedermolekulares (d.h. keine polymeren Gruppen enthaltendes) Aufhellersalz der Formel (I)
einsetzt.It has now been found that coating slips for the paper coating can be lightened without the disadvantages mentioned if a low molecular weight (ie containing no polymeric groups) brightener salt of the formula (I) is practically insoluble in water.
starts.
Die Eignung dieses Aufhellersalzes für den genannten Zweck muß als ausgesprochen überraschend angesehen werden, da bekannt ist, daß wasserlösliche Aufheller auf Basis der Bistriazonyl-aminostilben-disulfonsäuren, wenn sie mit üblichen poly-kationischen Produkten gemäß GB-A-721 238 und GB-A-1 058 918 ausgefällt werden, in Cobinderfreien Papierstreichmassen keinen oder nur einen sehr unbefriedigenden Effekt ergeben und die in JP-A-57 123 262 genannten Aufhellersalze einen wesentlich niedrigeren Weißheitsgrad (CIE) aufweisen.The suitability of this brightener salt for the stated purpose must be regarded as extremely surprising, since it is known that water-soluble brighteners based on bistriazonyl-aminostilbene-disulfonic acids, when used with conventional poly-cationic products according to GB-A-721 238 and GB-A -1 058 918 can be precipitated, in cobinder-free paper coating slips none or only very much unsatisfactory effect and the brightener salts mentioned in JP-A-57 123 262 have a significantly lower degree of whiteness (CIE).
Im Gegensatz dazu zeigt das erfindungsgemäße Aufhellersalz in fein verteiltem oder gelöstem Zusatz eine mehr oder weniger ausgeprägte Fluoreszenz, selbst wenn die kationische Komponente im Überschuß verwendet wird.In contrast, the brightener salt according to the invention shows a more or less pronounced fluorescence in finely divided or dissolved additive, even if the cationic component is used in excess.
Bei der Herstellung der Verbindung der Formel I geht man zweckmäßigerweise so vor, daß man den optischen Aufheller gemäß der Formel (II)
als Sulfonsäure bzw. deren wasserlösliche Salze, insbesondere deren Alkalisalze, mit den niedermolekularen basischen Stickstoffverbindungen der Formel (III)
worin
- Y
- ein farbloses, nichtfluoreszierendes Anion oder OH bedeutet,
as sulfonic acid or its water-soluble salts, especially its alkali salts, with the low molecular weight basic nitrogen compounds of the formula (III)
wherein
- Y
- is a colorless, non-fluorescent anion or OH,
Die Umsetzung erfolgt in Wasser und/oder organischen Lösungsmitteln, wie Methanol, Ethanol, Propanol, Isopropanol, Butanol, Glykol, Glykolmethylether, Dimethylformamid, Dimethylacetamid, Dimethylsulfoxid, Sulfolan, Hexamethylphosphorsäuretriamid bei Temperaturen von 20°C bis zur Rückflußtemperatur des entsprechenden Lösungsmittels.The reaction takes place in water and / or organic solvents, such as methanol, ethanol, propanol, isopropanol, butanol, glycol, glycol methyl ether, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide at temperatures from 20 ° C. to the reflux temperature of the corresponding solvent.
Das so erhaltene schwerlösliche Aufhellersalz kann direkt oder nach vorheriger Feinmahlung oder Flüssigformierung als Aufhellungsmittel eingesetzt werden.The poorly soluble whitening salt obtained in this way can be used as a whitening agent directly or after prior fine grinding or liquid formation.
Die erfindungsgemäßen Dispersionen können wie folgt hergestellt werden:
Die Preßkuchen und/oder Pulver werden nach Zugabe eines oberflächenaktiven Stoffes und gegebenenfalls Wasser unter starkem Rühren homogenisiert. Danach kann eine Erhöhung der Menge des oberflächenaktiven Stoffes, gegebenenfalls auf die gesamte, für die Stabilität der Dispersion benötigte Menge, erfolgen.The dispersions according to the invention can be prepared as follows:
The press cakes and / or powders are homogenized with vigorous stirring after the addition of a surface-active substance and optionally water. The amount of the surface-active substance can then be increased, if necessary to the total amount required for the stability of the dispersion.
Die erhaltene Suspension wird dann vorzerkleinert und naßgemahlen.The suspension obtained is then comminuted and wet-ground.
Die Vorzerkleinerung kann über Stein- oder Zahnkolloidmühlen erfolgen.Pre-shredding can be carried out using stone or tooth colloid mills.
Die anschließende Naßzerkleinerung kann in Kolloid-, Schwing-, Kegel- und Vibromühlen sowie in Dissolvern oder in Sub-Mikron-Dispersern erfolgen. Vorzugsweise werden jedoch kontinuierliche Rührwerksmühlen mit Mahlkörpern, vorzugsweise solche aus SiO₂ von 0,2 bis 5 mm Durchmesser verwendet.The subsequent wet comminution can take place in colloid, vibratory, cone and vibromills as well as in dissolvers or in sub-micron dispersers. However, continuous agitator mills with grinding media, preferably those made of SiO₂ of 0.2 to 5 mm in diameter, are preferably used.
Nach der Mahlbehandlung können gegebenenfalls noch weitere Mengen oberflächenaktiver Stoffe oder auch hydrotrope Substanzen wie z.B. Ethylenglykol oder Glycerin, Konservierungsmittel, Netzmittel, Entschäumer und/oder Wasser zugegeben werden, soweit dies nicht schon zu einem früheren Zeitpunkt z.B. vor der Mahlung erfolgte.After the grinding treatment, further amounts of surface-active substances or hydrotropic substances such as e.g. Ethylene glycol or glycerin, preservatives, wetting agents, defoamers and / or water are added, unless this has been done at an earlier point in time e.g. before grinding.
Eine weitere Möglichkeit, das erfindungsgemäße, in Wasser schwer- bzw. unlöslichen Aufhellungsmittel und seine Dispersionen herzustellen, stellt die Kombination des Reaktions- und Mahlvorgangs dar:
Dazu wird das Alkalisalz des Aufhellers gemäß Formel (II) zusammen mit der basischen Stickstoffverbindung der Formel (III) sowie Wasser und oberflächenaktive Stoffe nach Homogenisierung und Vorzerkleinerung naßzerkleinert, wobei die Einsatzmengen, wie weiter oben angegeben, varriert werden können.A further possibility of producing the brightening agent according to the invention, which is sparingly or insoluble in water, and its dispersions, is the combination of the reaction and grinding process:
For this purpose, the alkali salt of the brightener according to formula (II) is wet-comminuted together with the basic nitrogen compound of formula (III) and water and surface-active substances after homogenization and pre-comminution, the amounts used being able to be varied, as indicated above.
Die vollständige Reaktion des Aufhellersalzes II mit der basischen Stickstoffverbindung III findet dabei im Mahlapparat, vorzugsweise in einer kontinuierlichen Rührwerksmühle mit SiO₂-Mahlkörpern statt.The complete reaction of the whitening salt II with the basic nitrogen compound III takes place in the grinder, preferably in a continuous agitator mill with SiO 2 grinding media.
Die nach den beiden Verfahren hergestellten, erfindungsgemäßen Dispersionen enthalten 1 bis 25 %, vorzugsweise 5 bis 20 % des erfindungsgemäßen, in Wasser schwer- bzw. unlöslichen Aufhellersalzes, 1 bis 50 %, vorzugsweise 5 bis 20 % oberflächenaktive Stoffe, 0 bis 15 % Konservierungsmittel und Wasser, wobei ein Teil des Wassers durch hydrotrope Substanzen ersetzt werden kann (% = Gewichtsprozent).The dispersions according to the invention prepared by the two processes contain 1 to 25%, preferably 5 to 20% of the brightener salt according to the invention which is sparingly or insoluble in water, 1 to 50%, preferably 5 to 20% of surface-active substances, 0 to 15% of preservative and water, whereby part of the water can be replaced by hydrotropic substances (% = weight percent).
Als oberflächenaktive Stoffe kommen alle üblichen, kationischen und nichtionogenen oberflächenaktiven Stoffe in Betracht, wie sie beispielsweise in der DE-A 2 334 769, Seiten 8 bis 10 (entspricht GB-A 1 417 071) beschrieben sind.Suitable surface-active substances are all customary, cationic and nonionic surface-active substances, as are described, for example, in DE-A 2 334 769, pages 8 to 10 (corresponds to GB-A 1 417 071).
Bevorzugt werden nichtionogene Tenside eingesetzt.Nonionic surfactants are preferably used.
Die Papierstreichmassen, in welche die erfindungsgemäß zu verwendenden Aufhellersalze eingearbeitet werden, sind folgendermaßen aufgebaut: Kunststoff-Dispersionen auf Basis von Styrol-Butadien-, carboxylierten Styrol-Butadien- oder Polyvinylacetat-Copolymeren oder von Acrylsäureestern in Kombination mit Weißpigmenten, sowohl ohne als auch mit geringen Anteilen an hydrophilen Cobindern.The paper coating slips into which the brightener salts to be used according to the invention are incorporated are structured as follows: plastic dispersions based on styrene-butadiene, carboxylated styrene-butadiene or polyvinyl acetate copolymers or of acrylic acid esters in combination with white pigments, both with and without low levels of hydrophilic co-binders.
Die Einsatzmenge der Verbindung I richtet sich nach dem angestrebten Aufhelleffekt. Im allgemeinen genügt 0,01 bis 0,5 Gew.-% reiner Wirksubstanz (bezogen auf den Feststoff der aufzuhellenden Papierstreichmasse). Ein besonderer Vorteil ist, daß je nach Streichmassen-Zusammensetzung die erreichbare Vergrauungsgrenze (bis zu welche ein weiterer Aufheller-Zusatz noch zusätzliche Effekte bringt) außerordentlich hoch liegt.The amount of compound I used depends on the desired lightening effect. In general, 0.01 to 0.5% by weight of pure active substance (based on the solids of the paper coating slip to be lightened) is sufficient. A particular advantage is that, depending on the composition of the coating slip, the graying limit that can be achieved (up to which a further brightener additive brings additional effects) is extremely high.
10 g des optischen Aufhellers der Formel
und 10 g Benzyl-n-dodecyldimethylammoniumchlorid werden in 100 ml Wasser 30 Min. am Rückfluß erhitzt. Danach wird bei ca, 60°C abfiltriert und mit 60°C warmen Wasser gewaschen. Nach Trocknen i. Vak. erhält man 14,5 g des quartären Ammoniumsalzes des optischen Aufhellers der obigen Formel vom Schmelzpunkt: 258-259°C, das in n-Butanol umkristallisiert werden kann, Die Substanz ist im Wasser unlöslich und läßt sich gemäß Beispielen 2 und 3 in eine wäßrige Dispersion überführen,10 g of the optical brightener of the formula
and 10 g of benzyl-n-dodecyldimethylammonium chloride are refluxed in 100 ml of water for 30 minutes. Then it is filtered off at about 60 ° C and washed with 60 ° C warm water. After drying i. Vac. 14.5 g of the quaternary ammonium salt of the optical brightener of the above formula of melting point: 258-259 ° C., which can be recrystallized in n-butanol, are obtained. The substance is insoluble in water and can be dissolved in an aqueous solution according to Examples 2 and 3 Transfer dispersion,
Die Dispersion, gemäß Beispiel 4 in eine Papierstreichmasse eingearbeitet, ergibt hervorragende Weißeffekte.The dispersion, incorporated into a paper coating slip in accordance with Example 4, gives excellent white effects.
200 g des nach Beispiel 1 hergestellten, in Wasser unlöslichen Aufhellersalzes werden zusammen mit 200 g Emulgator W und 600 g Wasser homogenisiert und mit einer Zahnkolloidmühle vorzerkleinert. Die Suspension wird dann bei Raumtemperatur mit 4 Durchgängen in einer Perlmühle naßzerkleinert. Die resultierende stabile Dispersion ist leicht in Papierstreichmassen einzuarbeiten und zeigt ausgezeichnete Weißeffekte, auch noch bei hohen Zusatzmengen (vgl. Beispiel 4).200 g of the water-insoluble brightener salt prepared according to Example 1 are homogenized together with 200 g of emulsifier W and 600 g of water and comminuted using a toothed colloid mill. The suspension is then wet crushed in a bead mill at room temperature with 4 passes. The resulting stable dispersion is easy to incorporate into paper coating slips and shows excellent white effects, even when large amounts are added (cf. Example 4).
160 g des optischen Aufhellers der Formel 1 aus Beispiel 1 werden mit 128 g Benzyl-dodecyl-dimethyl-ammoniumchlorid (= 110 % der stöchiometrischen Menge), 16 g Emulgator W und 520 g Wasser unter Rühren homogenisiert und mit einer Zahnkolloidmühle vorzerkleinert. Die Suspension wird bei Raumtemperatur mit 4 Durchgängen in einer Perlmühle naßzerkleinert und zeigt nach der Einarbeitung in Papierstreichmassen hervorragende Weißeffekte.160 g of the optical brightener of formula 1 from Example 1 are homogenized with 128 g of benzyl-dodecyl-dimethyl-ammonium chloride (= 110% of the stoichiometric amount), 16 g of emulsifier W and 520 g of water and comminuted with a toothed colloid mill. The suspension is wet-crushed at room temperature with 4 passes in a bead mill and shows excellent white effects after incorporation into paper coating slips.
Durch Zusammenrühren von
- 31 Gew.-Teilen
- China Clay SPS,
- 13 Gew.-Teilen
- Calciumcarbonat,
- 26 Gew.-Teilen
- einer 50 %igen Dispersion aus einem Butadien-Styrol-Copolymeren,
- 30 Gew.-Teilen
- Wasser,
- 31 parts by weight
- China Clay SPS,
- 13 parts by weight
- Calcium carbonate,
- 26 parts by weight
- a 50% dispersion of a butadiene-styrene copolymer,
- 30 parts by weight
- Water,
Auf 1 kg dieser Streichmasse werden
5 bzw. 10 bzw. 30 bzw. 50 g
der nach Beispielen 2 und 3 hergestellten Aufheller-Dispersionen zugesetzt und eingerührt.Be on 1 kg of this coating slip
5 or 10 or 30 or 50 g
the brightener dispersions prepared according to Examples 2 and 3 are added and stirred in.
Nach dem Aufstreichen der aufgehellten Streichmasse auf Papier mit Hilfe eines Handrakels oder einer Versuchsstreichanlage und nach Trocknen bei 20-130°C erhält man gestrichene Papiere, welche je nach Aufheller-Zusatz einen deutlichen bis hervorragenden Aufhellungseffekt zeigen. Auch bei höheren Aufheller-Zusätzen als 50 g/kg Streichmasse ist meistens noch eine Steigerung des Weißgrades erzielbar.After spreading the lightened coating slip onto paper with the help of a hand-held squeegee or a test coater and after drying at 20-130 ° C, coated papers are obtained which, depending on the brightener additive, have a clear to excellent brightening effect. An increase in the degree of whiteness can usually still be achieved even with brightener additives higher than 50 g / kg of coating slip.
Claims (4)
- Aqueous paper-coating slips based on polymer dispersions, containing a fluorescent brightener salt of the formula (I)
- Process for the preparation of coating slips according to Claim 1, characterised in that a fluorescent brightener of the formula (II)
- Process according to Claim 2, characterised in that the sparingly soluble fluorescent brightener salt is subjected to wet-comminution in the presence of surfactants.
- Process according to Claim 2, characterised in that the fluorescent brightener is subjected to wet-comminution together with the basic nitrogen compound and the surfactants.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863643215 DE3643215A1 (en) | 1986-12-18 | 1986-12-18 | WHITE-TONED PAPER COATINGS |
| DE3643215 | 1986-12-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0274666A1 EP0274666A1 (en) | 1988-07-20 |
| EP0274666B1 true EP0274666B1 (en) | 1992-03-25 |
Family
ID=6316456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87118124A Expired - Lifetime EP0274666B1 (en) | 1986-12-18 | 1987-12-08 | Paper-coating compositions comprising whitening agents |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4888128A (en) |
| EP (1) | EP0274666B1 (en) |
| JP (1) | JPS63165596A (en) |
| DE (2) | DE3643215A1 (en) |
| FI (1) | FI87378C (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9000850A (en) * | 1989-02-28 | 1991-02-05 | Ciba Geigy Ag | STABLE ACLARATING FORMULATION FOR STORAGE, PROCESS FOR ITS PREPARATION AND APPLICATION |
| NO903004L (en) * | 1989-07-21 | 1991-01-22 | Bayer Ag | PROCEDURE FOR WHITENING OF PAPER COATING MATERIALS AND WHITENING PREPARATIONS FOR THE PROCEDURE. |
| IT1246376B (en) * | 1990-04-11 | 1994-11-18 | Sigma Prodotti Chimici Srl | PATINA FOR PAPER |
| GB2277749B (en) * | 1993-05-08 | 1996-12-04 | Ciba Geigy Ag | Fluorescent whitening of paper |
| 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 |
| EP0905317B1 (en) * | 1997-09-16 | 2009-12-23 | Basf Se | A method for optically brightening paper |
| NZ331438A (en) | 1997-09-16 | 2000-01-28 | Ciba Sc Holding Ag | A method of increasing the whiteness of paper by using a formulation containing a swellale layered silicate and an optical brightener 4,4-bis-(triazinylamino)-stilbene-2,2-disulphonic acid |
| JPH11130975A (en) * | 1997-10-29 | 1999-05-18 | Hakkooru Chemical Kk | Fluorescent organic white pigment composition excellent in opacifying properties |
| US5948153A (en) * | 1998-04-24 | 1999-09-07 | Milliken & Company | Water-soluble complexes of optical brighteners and quaternary ammonium compounds which are substantially free from unwanted salts |
| US6046330A (en) * | 1998-04-24 | 2000-04-04 | Qinghong; Jessica Ann | Complexes of ultraviolet absorbers and quaternary ammonium compounds which are substantially free from unwanted salts |
| GB9813248D0 (en) | 1998-06-22 | 1998-08-19 | Clariant Int Ltd | Improvements in or relating to organic compounds |
| GB9930247D0 (en) * | 1999-12-22 | 2000-02-09 | Clariant Int Ltd | Improvements in or relating to organic compounds |
| GB9930177D0 (en) * | 1999-12-22 | 2000-02-09 | Clariant Int Ltd | Improvements in or relating to organic compounds |
| US20040149410A1 (en) * | 2001-05-29 | 2004-08-05 | Peter Rohringer | Composition for the fluorescent whitening of paper |
| ES2365391T3 (en) * | 2003-05-02 | 2011-10-03 | Canon Kabushiki Kaisha | FLUORESCENT WATER INK, PRINTED IMAGE USING THE SAME AND EVALUATION METHOD. |
| CN1882626A (en) * | 2003-11-18 | 2006-12-20 | 西巴特殊化学品控股有限公司 | Fluorescent whiteninig pigments |
| EP1712677A1 (en) * | 2005-04-08 | 2006-10-18 | Clariant International Ltd. | Aqueous solutions of optical brighteners |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1441109A (en) * | 1973-01-23 | 1976-06-30 | Ici Ltd | Coating compositions |
| CH582275A5 (en) * | 1973-02-02 | 1976-11-30 | Ciba Geigy Ag | |
| JPS5725364A (en) * | 1980-07-22 | 1982-02-10 | Showa Kagaku Kogyo Kk | Dyestuff salt |
| JPS5725365A (en) * | 1980-07-22 | 1982-02-10 | Showa Kagaku Kogyo Kk | Dyestuff salt-containing fluorescent brightener composition |
| JPS57123262A (en) * | 1981-01-26 | 1982-07-31 | Showa Kagaku Kogyo Kk | Fluorescent brightener composition |
| CH647021A5 (en) * | 1981-09-22 | 1984-12-28 | Ciba Geigy Ag | METHOD FOR PRODUCING STORAGE-STABLE BRIGHTENER FORMULATIONS. |
| DE3502038A1 (en) * | 1985-01-23 | 1986-07-24 | Sandoz-Patent-GmbH, 7850 Lörrach | AQUEOUS BRIGHTENING DEVICES AND THEIR USE IN THE PAPER LINE |
-
1986
- 1986-12-18 DE DE19863643215 patent/DE3643215A1/en not_active Withdrawn
-
1987
- 1987-12-08 DE DE8787118124T patent/DE3777789D1/en not_active Expired - Lifetime
- 1987-12-08 EP EP87118124A patent/EP0274666B1/en not_active Expired - Lifetime
- 1987-12-10 JP JP62311145A patent/JPS63165596A/en active Pending
- 1987-12-11 US US07/131,780 patent/US4888128A/en not_active Expired - Fee Related
- 1987-12-16 FI FI875517A patent/FI87378C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FI875517A0 (en) | 1987-12-16 |
| DE3777789D1 (en) | 1992-04-30 |
| FI87378B (en) | 1992-09-15 |
| US4888128A (en) | 1989-12-19 |
| EP0274666A1 (en) | 1988-07-20 |
| FI875517A (en) | 1988-06-19 |
| DE3643215A1 (en) | 1988-06-30 |
| JPS63165596A (en) | 1988-07-08 |
| FI87378C (en) | 1992-12-28 |
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