EP0489422A1 - Water-containing organophilic lamellar silicates - Google Patents
Water-containing organophilic lamellar silicates Download PDFInfo
- Publication number
- EP0489422A1 EP0489422A1 EP91120840A EP91120840A EP0489422A1 EP 0489422 A1 EP0489422 A1 EP 0489422A1 EP 91120840 A EP91120840 A EP 91120840A EP 91120840 A EP91120840 A EP 91120840A EP 0489422 A1 EP0489422 A1 EP 0489422A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- organic
- onium salt
- layered silicate
- drying
- 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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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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/46—Non-macromolecular organic compounds
Definitions
- organophilically modified layered silicates as rheological additives in organic media.
- examples of this are the commercial products sold under the names ®Tixogel (manufacturer: Südchemie AG) and ®Bentone.
- ®Tixogel manufactured by Südchemie AG
- ®Bentone a commercial product sold under the names ®Tixogel (manufacturer: Südchemie AG) and ®Bentone.
- These rheological additives create a thixotropic structure in organic media, for example in paints and varnishes.
- the organophilically modified layered silicates are obtained by treating layered silicates in aqueous suspension with an aqueous solution of an onium compound, preferably a quaternary organic ammonium salt, this organic ammonium salt being incorporated between the layers of the layered silicate.
- the layered silicate modified in this way in an organophilic manner is then separated from the water by filtration and dried under the action of heat, for example in a drum dryer at approximately 100.degree.
- the modified organophilic layered silicates obtained in this way are water-insoluble.
- the invention thus relates to the use of water-containing organophilic layered silicates, obtained by the reaction of a layered silicate which is completely delaminated in water and is cation-exchangeable an organic onium salt in aqueous suspension and subsequent mechanical separation of the water without drying by heating, as a rheological additive in organic media and for coating paper.
- organophilic layered silicates are obtained by methods known per se, which therefore need not be explained in more detail.
- All synthetic or natural smectic layer silicates preferably bentonite or montmorillonite, which can contain 25-30% by weight of impurities in the form of other minerals in addition to a smectic layer silicate, are suitable as cation-exchangeable layer silicates which are completely delaminated in water.
- the minerals are treated with an aqueous solution of onium compounds, such as phosphonium compounds, but preferably quaternary organic ammonium salts, these compounds being embedded between the layers of these minerals.
- Suitable quaternary organic ammonium salts are, in particular, compounds of formula where R1 is C8-C22-alkyl or C8-C22-alkenyl, R2 is C1-C4-alkyl and A is an anion, preferably chloride or methosulfate.
- the compound di-stearyl-dimethyl-ammonium chloride is particularly preferred.
- Organic media in the sense of this invention are, for example, paints, lacquers, Paints, putties, greases, cosmetics, paint strippers, fillers and similar preparations containing organic solvents.
- the water-containing organophilically modified layered silicates according to the invention have a thixotropic effect. This effect makes the preparations mentioned easier to process.
- these layered silicates also prevent the insoluble components from settling, e.g. of the pigments within these media.
- it was found in these water-containing organophilic layered silicates that the thickening effect is significantly higher in comparison to the analog commercial products with the same solids content, but from which the water was removed by drying with heating.
- the water-containing organophilic sheet silicates according to the invention are particularly suitable for coating paper.
- improvements are being made to use thin printing paper for printed matter with a large circulation, for example for magazines or mail-order catalogs.
- problems with the opacity ie there is an annoying shine through of the print on the other side of the paper during printing.
- it is already known (EP 192 252) to coat paper with an organophilic complex of a smectic layered silicate and a quaternary organic ammonium compound from a suspension in organic solvents.
- the starting material is in a form that the water has been extracted as much as possible by heating.
- solvent coating suspensions can also contain white pigments (TiO2).
- TiO2 white pigments
- these white pigments are well bonded to the paper by the layered silicates; an additional binder is therefore not required. In this way, a good hold-out effect is obtained, ie prevention of strikethrough on the printed paper.
- the water-containing organophilic phyllosilicates according to the present invention give a very good hold-out effect.
- the examples in the table show that conventional white pigments can also be applied to the paper and firmly anchored there by means of the dispersion of the organophil-modified layered silicate in toluene; an additional binder is not required.
Abstract
Description
Es ist weitgehend bekannt, organophil modifizierte Schichtsilikate als rheologische Additive in organischen Medien einzusetzen. Beispiele hierfür sind die Handelsprodukte, die unter den Bezeichnungen ®Tixogel (Hersteller: Südchemie AG) und ®Bentone vertrieben werden. Diese rheologischen Additive bewirken in organischen Medien, beispielsweise in Farben und Lacken, den Aufbau einer thixotropen Struktur. Infolge dieser thixotropen Struktur lassen sich solche organischen Medien besser verarbeiten. Erhalten werden die organophil modifizierten Schichtsilikate, indem man Schichtsilikate in wäßriger Suspersion mit einer wäßrigen Lösung einer Oniumverbindung, vorzugsweise eines quartären organischen Ammoniumsalzes behandelt, wobei dieses organische Ammoniumsalz zwischen die Schichten des Schichtsilikats eingelagert wird. Anschließend wird das auf diese Weise organophil modifizierte Schichtsilikat durch Filtration vom Wasser abgetrennt und unter Einwirkung von Hitze getrocknet, beispielsweise im Trommeltrockner bei ca. 100 °C. Die auf diese Weise erhaltenen modifizierten organophilen Schichtsilikate sind wasserunlöslich.It is widely known to use organophilically modified layered silicates as rheological additives in organic media. Examples of this are the commercial products sold under the names ®Tixogel (manufacturer: Südchemie AG) and ®Bentone. These rheological additives create a thixotropic structure in organic media, for example in paints and varnishes. As a result of this thixotropic structure, such organic media can be processed better. The organophilically modified layered silicates are obtained by treating layered silicates in aqueous suspension with an aqueous solution of an onium compound, preferably a quaternary organic ammonium salt, this organic ammonium salt being incorporated between the layers of the layered silicate. The layered silicate modified in this way in an organophilic manner is then separated from the water by filtration and dried under the action of heat, for example in a drum dryer at approximately 100.degree. The modified organophilic layered silicates obtained in this way are water-insoluble.
Ein solcher Trocknungsvorgang wurde bisher für notwendig erachtet, da der Filterkuchen, der beim Abfiltrieren des Wassers anfällt, beträchtliche Mengen an Wasser enthält und dieser Wassergehalt beim Einsatz der organophilen Schichtsilikate in den organischen Medien stören sollte. Es wurde nun überraschend gefunden, daß dies nicht der Fall ist und daß man den Filterkuchen solcher organophilen Schichtsilikate auch ohne Trocknung als rheologisches Additiv in organischen Medien einsetzen kann.Such a drying process has hitherto been considered necessary since the filter cake which is obtained when the water is filtered off contains considerable amounts of water and this water content should interfere with the use of the organophilic phyllosilicates in the organic media. It has now surprisingly been found that this is not the case and that the filter cake of such organophilic phyllosilicates can be used as a rheological additive in organic media even without drying.
Gegenstand der Erfindung ist somit die Verwendung von wasserhaltigen organophilen Schichtsilikaten, erhalten durch die Umsetzung eines in Wasser kolloidal vollständig delaminierten, kationenaustauschfähigen Schichtsilikates mit einem organischen Oniumsalz in wäßriger Suspension und anschließender mechanischer Abtrennung des Wassers ohne Trocknung durch Erwärmung, als rheologisches Additiv in organischen Medien und zum Beschichten von Papier.The invention thus relates to the use of water-containing organophilic layered silicates, obtained by the reaction of a layered silicate which is completely delaminated in water and is cation-exchangeable an organic onium salt in aqueous suspension and subsequent mechanical separation of the water without drying by heating, as a rheological additive in organic media and for coating paper.
Diese organophilen Schichtsilikate werden erhalten nach an sich bekannten Methoden, die deshalb nicht näher erläutert werden müssen. Als kationenaustauschfähige, in Wasser kolloidal vollständig delaminierte Schichtsilikate kommen alle synthetischen oder natürlichen smektitischen Schichtsilikate in Frage, vorzugsweise Bentonit oder Montmorillonit, der neben einem smektischen Schichtsilikat noch 25 - 30 Gew.-% Verunreinigungen in Form anderer Minerale enthalten kann. Die Minerale werden mit einer wäßrigen Lösung von Oniumverbindungen, wie beispielsweise Phosphoniumverbindungen, vorzugsweise jedoch quartären organischen Ammoniumsalzen behandelt, wobei diese Verbindungen zwischen die Schichten dieser Minerale eingelagert werden. Als quartäre organische Ammoniumsalze kommen insbesondere in Frage Verbindungen der
Formel
wobei R¹ C₈-C₂₂-Alkyl oder C₈-C₂₂-Alkenyl, R² C₁-C₄-Alkyl und A ein Anion, bevorzugt Chlorid oder Methosulfat bedeuten. Besonders bevorzugt ist die Verbindung Di-stearyl- di-methyl-ammonium-chlorid. Wenn das Schichtsilikat mit dem quartären organischen Ammoniumsalz beladen ist, wird vom Wasser abfilitriert bzw. abgepreßt. Dies geschieht nach den üblichen Verfahren der Trenntechnik. Der dabei anfallende Filterkuchen besteht, in Abhängigkeit von der Reinheit der Schichtsilikate zu ca. 65 bis 83 % aus Wasser und wird erfindungsgemäß in dieser Form unmittelbar als rheologisches Additiv in organischen Medien eingesetzt.These organophilic layered silicates are obtained by methods known per se, which therefore need not be explained in more detail. All synthetic or natural smectic layer silicates, preferably bentonite or montmorillonite, which can contain 25-30% by weight of impurities in the form of other minerals in addition to a smectic layer silicate, are suitable as cation-exchangeable layer silicates which are completely delaminated in water. The minerals are treated with an aqueous solution of onium compounds, such as phosphonium compounds, but preferably quaternary organic ammonium salts, these compounds being embedded between the layers of these minerals. Suitable quaternary organic ammonium salts are, in particular, compounds of
formula
where R¹ is C₈-C₂₂-alkyl or C₈-C₂₂-alkenyl, R² is C₁-C₄-alkyl and A is an anion, preferably chloride or methosulfate. The compound di-stearyl-dimethyl-ammonium chloride is particularly preferred. When the layered silicate is loaded with the quaternary organic ammonium salt, the water is filtered off or pressed off. This is done according to the usual methods of separation technology. The filter cake obtained consists, depending on the purity of the layered silicates, of approximately 65 to 83% water and is used according to the invention in this form as a rheological additive in organic media.
Organische Medien im Sinne dieser Erfindung sind beispielsweise Farben, Lacke, Anstriche, Kitte, Schmierfette, Kosmetika, Abbeizmittel, Spachtelmassen und ähnliche Zubereitungen mit einem Gehalt an organischen Lösemitteln. In all diesen Systemen bewirken die wasserhaltigen organophil modifizierten Schichtsilikate gemäß der Erfindung einen thixotropierenden Effekt. Durch diesen Effekt lassen sich die genannten Zubereitungen leichter verarbeiten. Daneben verhindern diese Schichtsilikate auch ein Absetzen der unlöslichen Komponenten, z.Bsp. der Pigmente innerhalb dieser Medien. Als weiterer überraschender Effekt wurde bei diesen wasserhaltigen organophilen Schichtsilikaten gefunden, daß hier die verdickende Wirkung deutlich höher ist im Vergleich zu den analogen handelsüblichen Produkten mit gleichem Feststoffgehalt, denen aber das Wasser durch Trocknung unter Erhitzen entzogen wurde.Organic media in the sense of this invention are, for example, paints, lacquers, Paints, putties, greases, cosmetics, paint strippers, fillers and similar preparations containing organic solvents. In all of these systems, the water-containing organophilically modified layered silicates according to the invention have a thixotropic effect. This effect makes the preparations mentioned easier to process. In addition, these layered silicates also prevent the insoluble components from settling, e.g. of the pigments within these media. As a further surprising effect, it was found in these water-containing organophilic layered silicates that the thickening effect is significantly higher in comparison to the analog commercial products with the same solids content, but from which the water was removed by drying with heating.
Die Art und Weise der Zugabe dieser wasserhaltigen organophil modifizierten Schichtsilikate zu der organischen Medien erfolgt nach an sich bekannten Methoden. Auch die Menge dieser rheologischen Additive liegt im Bereich dessen, was dem Fachmann auf diesem Gebiet bekannt ist (ca. 0,5 bis 3 Gew.-%).The manner in which these water-containing organophilically modified layered silicates are added to the organic media is carried out according to methods known per se. The amount of these rheological additives is also in the range of what is known to the person skilled in the art (approx. 0.5 to 3% by weight).
Besonders eignen sich die erfindungsgemäßen wasserhaltigen organophilen Schichtsilikate zum Beschichten von Papier. Aus wirtschaftlichen Überlegungen heraus ist man bestrebt, bei Druckerzeugnissen mit hoher Auflage, beispielsweise bei Zeitschriften oder Versandkatalogen, Dünndruckpapiere zu nehmen. Hierbei ergeben sich aber Probleme hinsichtlich der Opazität, d.h. es kommt beim Drucken zu einem störenden Durchscheinen des Druckes auf die andere Seite des Papiers. Zur Verhinderung dieses Effekts ist es bereits bekannt (EP 192 252), Papier mit einem organophilen Komplex aus einem smektischen Schichtsilikat und einer quartären organischen Ammoniumverbindung aus einer Suspersion in organischen Lösemitteln zu beschichten. Das Ausgangsmaterial liegt hier in einer Form vor, der durch Erwärmen das Wassers möglichst weitgehend entzogen wurde. Im Rahmen der vorliegenden Erfindung wurde nun gefunden, daß man bei diesem Verfahren (solvent coating) auf die Trocknung des organophil modifizierten Schichtsilikats verzichten und direkt den wasserhaltigen Preßkuchen dieses organophil modifizierten Schichtsilikats einsetzen kann. Überraschend dabei ist, daß das Wasser in dem Preßkuchen die Homogenität des organischen Gesamtsystems nicht stört. Das Wasser verbleibt in der inneren Phase und es tritt keine Quellung der Papierfasern auf, wie es bei einem wäßrigen Strich der Fall wäre. Dieser Befund ist deshalb von größerer Bedeutung, da in Zukunft solche "solvent coating" Verfahren auf der Basis von Toluol oder Testbenzin zunehmend an Bedeutung gewinnen. Der Feststoffgehalt (d.h. ohne den Gehalt an Wasser aus dem Preßkuchen) beträgt bei solchen Suspensionen ca. 3 bis 9 Gew.-%. Diese "solvent coating" Suspensionen können außerdem noch Weißpigmente (TiO₂) enthalten. Infolge der Fähigkeit der organophil modifizierten Schichtsilikate zur Filmbildung werden diese Weißpigmente von den Schichtsilikaten gut auf dem Papier gebunden; eines zusätzlichen Bindemittels bedarf es daher nicht. Man erhält auf diese Weise einen guten Hold-out-Effekt, d.h. eine Verhinderung des Durchschlagens auf dem bedruckten Papier.The water-containing organophilic sheet silicates according to the invention are particularly suitable for coating paper. For economic reasons, efforts are being made to use thin printing paper for printed matter with a large circulation, for example for magazines or mail-order catalogs. However, there are problems with the opacity here, ie there is an annoying shine through of the print on the other side of the paper during printing. To prevent this effect, it is already known (EP 192 252) to coat paper with an organophilic complex of a smectic layered silicate and a quaternary organic ammonium compound from a suspension in organic solvents. The starting material is in a form that the water has been extracted as much as possible by heating. In the context of the present invention, it has now been found that in this process (solvent coating) drying of the organophilically modified layered silicate can be dispensed with and the water-containing presscake of this organophilically modified layered silicate can be used directly. The surprising thing is that the Water in the press cake does not interfere with the homogeneity of the overall organic system. The water remains in the inner phase and there is no swelling of the paper fibers, as would be the case with an aqueous coating. This finding is of greater importance because in the future such "solvent coating" processes based on toluene or white spirit will become increasingly important. The solids content (ie without the water content from the press cake) is about 3 to 9% by weight in such suspensions. These "solvent coating" suspensions can also contain white pigments (TiO₂). As a result of the ability of the organophilically modified layered silicates to form films, these white pigments are well bonded to the paper by the layered silicates; an additional binder is therefore not required. In this way, a good hold-out effect is obtained, ie prevention of strikethrough on the printed paper.
Ein handelsüblicher, nicht gereinigter Na-Bentonit (Austauschkapazität 80 mVal/100 g) wurde in einer heißen Lösung von Di-stearyl-di-methyl-ammonium-chlorid verrührt bei einem Verhältnis der beiden Produkte von 69 Gew.-% Na- Bentonit und 31 Gew.-% quartäres organisches Ammoniumsalz. Nach Beeendigung der Reaktion wurde abfiltriert und der nunmehr organophil modifizierte Bentonit wurde auf einen Feststoffgehalt von ca. 31 Gew.-% abgepreßt. Dieser Filterkuchen wurde in Toluol dispergiert und in dünner Schicht auf ein Papierblatt aufgebracht und getrocknet. Die Einzelheiten der Beispiele und die jeweilige Bewertung des Hold-out-Effekts ergeben sich aus den folgenden Tabellen 1 und 2.A commercially available, unpurified Na bentonite (exchange capacity 80 mVal / 100 g) was stirred in a hot solution of di-stearyl-dimethyl-ammonium chloride at a ratio of the two products of 69% by weight Na bentonite and 31% by weight of quaternary organic ammonium salt. After the reaction had ended, the mixture was filtered off and the now organophilically modified bentonite was pressed to a solids content of approximately 31% by weight. This filter cake was dispersed in toluene and applied in a thin layer to a paper sheet and dried. The details of the examples and the respective evaluation of the hold-out effect can be found in Tables 1 and 2 below.
Wie die Beispiele zeigen, erhält man mit den wasserhaltigen organophilen Schichtsilikaten gemäß der vorliegenden Erfindung einen sehr guten Hold-out-Effekt. Die Beispiele in der Tabelle zeigen, daß man mittels der Dispersion des organophil modifizierten Schichtsilikats in Toluol auch übliche Weißpigmente auf das Papier aufbringen und dort fest verankern kann; eines zusätzlichen Bindemittels bedarf es dabei nicht.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4038886 | 1990-12-06 | ||
| DE4038886A DE4038886C2 (en) | 1990-12-06 | 1990-12-06 | Use of water-containing organophilic layered silicates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0489422A1 true EP0489422A1 (en) | 1992-06-10 |
| EP0489422B1 EP0489422B1 (en) | 1997-04-09 |
Family
ID=6419699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91120840A Expired - Lifetime EP0489422B1 (en) | 1990-12-06 | 1991-12-04 | Use of water-containing organophilic lamellar silicates as rheological additiv and for coating paper |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0489422B1 (en) |
| JP (1) | JPH04359082A (en) |
| AT (1) | ATE151480T1 (en) |
| BR (1) | BR9105274A (en) |
| CA (1) | CA2057110C (en) |
| DE (2) | DE4038886C2 (en) |
| FI (1) | FI915720A (en) |
| NO (1) | NO914793L (en) |
| ZA (1) | ZA919603B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0572037A1 (en) * | 1992-05-29 | 1993-12-01 | Süd-Chemie Ag | Coating pigment |
| DE4438306A1 (en) * | 1994-10-26 | 1996-05-02 | Sued Chemie Ag | Pigments for print media using the inkjet printing process |
| DE19541945C1 (en) * | 1995-11-10 | 1997-04-10 | Hoechst Ag | Thickener system for building material mixtures, process for its preparation and use |
| US5876922A (en) * | 1985-07-31 | 1999-03-02 | Institute Pasteur | Papillomavirus probe and a process for in vitro diagnosis of papillomavirus infections |
| WO2011120876A1 (en) * | 2010-03-29 | 2011-10-06 | Akzo Nobel Chemicals International B.V. | Process of producing a cellulosic fibre web |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5851289B2 (en) * | 2012-03-07 | 2016-02-03 | 株式会社ヤマグチマイカ | Thixotropic agent and method for producing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0279313A1 (en) * | 1987-02-10 | 1988-08-24 | Institut für Papier-,Zellstoff-und Fasertechnik der Technischen Universität Graz | Process for preparing a pigmentary agent suited for use in the paper-making industry, said agent improving the printability of paper or board, the agent and its use |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4208218A (en) * | 1978-03-27 | 1980-06-17 | Nl Industries, Inc. | Viscosity increasing additive for non-aqueous fluid systems |
| ATE13041T1 (en) * | 1981-11-19 | 1985-05-15 | Spiess C F & Sohn | PROCESS FOR THE PREPARATION OF TERTIARY SULFONIUM MONTMORILLONITES AND THEIR USE. |
-
1990
- 1990-12-06 DE DE4038886A patent/DE4038886C2/en not_active Expired - Fee Related
-
1991
- 1991-12-04 AT AT91120840T patent/ATE151480T1/en active
- 1991-12-04 EP EP91120840A patent/EP0489422B1/en not_active Expired - Lifetime
- 1991-12-04 DE DE59108654T patent/DE59108654D1/en not_active Expired - Fee Related
- 1991-12-04 FI FI915720A patent/FI915720A/en not_active Application Discontinuation
- 1991-12-05 ZA ZA919603A patent/ZA919603B/en unknown
- 1991-12-05 JP JP3322135A patent/JPH04359082A/en not_active Withdrawn
- 1991-12-05 NO NO91914793A patent/NO914793L/en unknown
- 1991-12-05 CA CA002057110A patent/CA2057110C/en not_active Expired - Fee Related
- 1991-12-06 BR BR919105274A patent/BR9105274A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0279313A1 (en) * | 1987-02-10 | 1988-08-24 | Institut für Papier-,Zellstoff-und Fasertechnik der Technischen Universität Graz | Process for preparing a pigmentary agent suited for use in the paper-making industry, said agent improving the printability of paper or board, the agent and its use |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5876922A (en) * | 1985-07-31 | 1999-03-02 | Institute Pasteur | Papillomavirus probe and a process for in vitro diagnosis of papillomavirus infections |
| EP0572037A1 (en) * | 1992-05-29 | 1993-12-01 | Süd-Chemie Ag | Coating pigment |
| US5423911A (en) * | 1992-05-29 | 1995-06-13 | Sud-Chemie A.G. Aktiengesellschaft | Coating pigment for cellulose - based printing media |
| DE4438306A1 (en) * | 1994-10-26 | 1996-05-02 | Sued Chemie Ag | Pigments for print media using the inkjet printing process |
| EP0710742A2 (en) * | 1994-10-26 | 1996-05-08 | Süd-Chemie Ag | Pigments for printing supports according to the ink jet printing process |
| EP0710742A3 (en) * | 1994-10-26 | 1997-04-02 | Sued Chemie Ag | Pigments for printing supports according to the ink jet printing process |
| DE19541945C1 (en) * | 1995-11-10 | 1997-04-10 | Hoechst Ag | Thickener system for building material mixtures, process for its preparation and use |
| WO2011120876A1 (en) * | 2010-03-29 | 2011-10-06 | Akzo Nobel Chemicals International B.V. | Process of producing a cellulosic fibre web |
| CN102803609A (en) * | 2010-03-29 | 2012-11-28 | 阿克佐诺贝尔化学国际公司 | Process of producing a cellulosic fibre web |
Also Published As
| Publication number | Publication date |
|---|---|
| NO914793L (en) | 1992-06-09 |
| NO914793D0 (en) | 1991-12-05 |
| FI915720A (en) | 1992-06-07 |
| CA2057110A1 (en) | 1992-06-07 |
| DE4038886A1 (en) | 1992-06-11 |
| DE59108654D1 (en) | 1997-05-15 |
| ATE151480T1 (en) | 1997-04-15 |
| BR9105274A (en) | 1992-08-18 |
| CA2057110C (en) | 2001-04-10 |
| JPH04359082A (en) | 1992-12-11 |
| EP0489422B1 (en) | 1997-04-09 |
| FI915720A0 (en) | 1991-12-04 |
| DE4038886C2 (en) | 2000-08-03 |
| ZA919603B (en) | 1992-08-26 |
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