CA2057110C - Water-containing organophilic phyllosilicates - Google Patents
Water-containing organophilic phyllosilicates Download PDFInfo
- Publication number
- CA2057110C CA2057110C CA002057110A CA2057110A CA2057110C CA 2057110 C CA2057110 C CA 2057110C CA 002057110 A CA002057110 A CA 002057110A CA 2057110 A CA2057110 A CA 2057110A CA 2057110 C CA2057110 C CA 2057110C
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- CA
- Canada
- Prior art keywords
- water
- organic
- phyllosilicate
- onium salt
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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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
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Paper (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Silicon Polymers (AREA)
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to the use of water-containing organophilic phyllosilicates obtained by the reaction of a phyllosilicate, which is completely delaminated colloidally in water and is capable of cation exchange, with an organic onium salt in aqueous suspension and subsequent mechanical removal of the water, without drying by heating, as a rheological additive in organic media.
The water-containing organophilic phyllosilicates are particularly suitable for coating paper.
The water-containing organophilic phyllosilicates are particularly suitable for coating paper.
Description
20~'~l.~.r HOECHST ARTIEPIGESELLSCHAFT HOE 90/F 364 Dr.ICI/1 Description Water-containing organophilic phyllosilicates It is widely known that organophilically modified phyllosilicates can be employed as Theological additives in organic media. Examples of these are the commercial products marketed under the names ~Tixogel (manufacturer:
Sudchemie AG) and ~Bentone. These theological additives have the effect of the build-up of a thixotropic struc- ' tuts in organic media, for example in paints and var-nishes. As a result of this thixotropic structure, such organic media are easier to process . The organophilically modified phyllosilicates are obtained by treating phyllo-silicates in aqueous suspension with an aqueous solution of an onium compound, preferably a quaternary organic ammonium salt, this organic ammonium salt being embedded between the layers of the phyllosilicate. The phyllo-silicate organophilically modified in this manner is then separated from the water by filtration and dried under the action of heat, for example in a drum drier at about 100°C. The modified organophilic phyllosilicates obtained in this manner are water-insoluble.
Such a drying operation has previously been considered necessary, since the filtercake obtained when the water is filtered off contains considerable amounts of water, and this water content has been said to interfere in the use of the organophilic phyllosilicates in the organic media. It has now been found, surprisingly, that this is not the case and that the filtercake of such organophilic phyllosilicates can be employed as a Theological additive in organic media even without being dried.
The invention thus relates to the use of water-containing organophilic phyllosilicates which are obtained by the reaction of a phyllosilicate, which is completely delaminated colloidally in water and is capable of ration exchange, with an organic onium salt in aqueous suspension and subsequent mechanical removal of the water, without drying by heating, as a rheological additive in organic media and for coating paper.
These organophilic phyllosilicates are obtained by methods which are known per se, which therefore do not have to be explained in more detail. Possible phyllo-silicates which are capable of cation exchange and are completely delaminated colloidally in water are all the synthetic or naturally occurring smectic phyllosilicates, preferably bentonite or montmorillonite, which, in addition to a smectic phyllosilicate, can also contain 25-30~ by weight of impurities in the form of other minerals. The minerals are treated with an aqueous solution of onium compounds, such as, for example, phosphonium compounds, but preferably quaternary organic ammonium salts, these compounds being embedded between the layers of these minerals. Possible quaternary organic ammonium salts are, in particular, compounds of the formula R, Rz 2 0 ~ N ~ A°' R,/ ~Rz in which Rl is C8-CZZ-alkyl or C8-CZZ-alkenyl, RZ is Cl-Cd-alkyl and A is an anion, preferably chloride or metho-sulfate. The compound distearyl-dimethyl-ammonium chloride is particularly preferred. When the phyllo-silicate is charged with the quaternary organic ammonium salt, the water is filtered off or pressed off. This is done by the customary processes of separation. The filtercake obtained consists, depending on the purity of the phyllosilicates, to the extent of about 65 to 83$ of water and is employed according to the invention in this form directly as a rheological additive in organic media.
Examples of organic media in the sense of this invention are paints, varnishes, coatings, putties, lubricating greases, cosmetics, paint removers, filler compositions and similar formulations containing organic solvents. The water-containing organophilically modified phyllo-silicates according to the invention have a thixotroping effect in all these systems. As a result of this effect, .
the formulations mentioned are easier to process. In addition, these phyllosilicates also prevent settling of the insoluble components, for example the pigments within these media. As another surprising effect of these water containing organophilic phyllosilicates it has been found that the thickening action here is significantly higher in comparison with the analogous commercially available products having the same solids content, but from which the water has been removed by drying by heating.
These water-containing organophilically modified phyllo-silicates are added to the organic media by methods which are known per se. The amount of these rheological addi-tives also lies within the range known to the expert in this field (about 0.5 to 3% by weight).
The water-containing organophilic phyllosilicates accord-ing to the invention are particularly suitable for coating paper. From economic considerations, efforts are made to use thin printing papers for printed products with a high circulation, for example newspapers or mail-order catalogs. However, problems arise here in respect of opacity, i.e. in the case of printing the print shows through in an interfering manner on the other side of the paper. To prevent this effect, it is already known (EP 192 252) that paper can be coated with an organo-philic complex of a smectic phyllosilicate and a quaternary organic ammonium compound from a suspension in organic solvents. The starting material is present here in a form from which as much of the water as possible has been removed by heating. In the context of the present invention, it has now been found that drying of the organophilically modified phyllosilicate can be dispensed with in this process (solvent coating) and the water-containing presscake of this organophilically modified phyllosilicate can be employed directly. It is surprising here that the water in the presscake does not interfere with the homogeneity of the overall organic system. The water remains in the inner phase, and no swelling of the paper fibers occurs, as would be the case with an aqueous coating. This finding is therefore of relatively great importance, since in future such "solvent coating"
processes based on toluene or white spirit will gain increasing importance. The solids content (i.e. without the content of water from the presscake) of such suspen-sions is about 3 to 9% by weight. These "solvent coating"
suspensions can furthermore also contain white pigments (TiOz). As a result of the ability of the organo-philically modified phyllosilicates to form films, these white pigments are bonded firmly to the paper by the phyllosilicates; no additional binder is therefore needed. A good hold-out effect is obtained in this manner, i.e. print-through on the printed paper is prevented.
Examples A commercially available, non-purified Na bentonite (exchange capacity 80 milliequivalents/100 g) was stirred in a hot solution of distearyl-dimethyl-ammonium chloride at a ratio of the two products of 69% by weight of Na bentonite and 31% by weight of quaternary organic ammonium salt. When the reaction had ended, the mixture was filtered and the now organophilically modified bentonite was pressed off to a solids content of about 31% by weight. This filtercake was dispersed in toluene and the dispersion was applied in a thin layer to a sheet of paper and dried. The details of the examples and the particular evaluation of the hold-out effect can be seen from the following Tables 1 and 2.
As the examples show, a very good hold-out effect is obtained with the water-containing organophilic phyllosilicates according to the present invention. The examples in the table show that customary white pigments can also be applied to the paper and firmly anchored there by means of the dispersion of the organophilically modified phyllosilicate in toluene; no additional binder is required here.
Table 1 Toluene 87.5 g 85 g 82.5 g Filtercake 12.5 g 15 g 17.5 g Brookfield viscosity in mPas at 100 rpm after 2 days 308 528 720 Weight applied 1.5-1.8 1.6-1.7 1.4-1.6 (g/m2) Hold-out good good good Weight applied (g/mz) 2.3-2.5 2.8-3.0 2.5-2.7 Hold-out very goo best very good Table 2 Toluene to 100 to 100 to 100 Filtercake 15 g 15 g 15 g Titanium dioxide 0.4 g China clay 0.4 g Optical 0.1 g brightener Brookfield viscosity in mPas at 100 rpm after 2 days 29g 324 216 Weight applied g/mz~ 1.3 1.4 1.5 Hold-out good good good
Sudchemie AG) and ~Bentone. These theological additives have the effect of the build-up of a thixotropic struc- ' tuts in organic media, for example in paints and var-nishes. As a result of this thixotropic structure, such organic media are easier to process . The organophilically modified phyllosilicates are obtained by treating phyllo-silicates in aqueous suspension with an aqueous solution of an onium compound, preferably a quaternary organic ammonium salt, this organic ammonium salt being embedded between the layers of the phyllosilicate. The phyllo-silicate organophilically modified in this manner is then separated from the water by filtration and dried under the action of heat, for example in a drum drier at about 100°C. The modified organophilic phyllosilicates obtained in this manner are water-insoluble.
Such a drying operation has previously been considered necessary, since the filtercake obtained when the water is filtered off contains considerable amounts of water, and this water content has been said to interfere in the use of the organophilic phyllosilicates in the organic media. It has now been found, surprisingly, that this is not the case and that the filtercake of such organophilic phyllosilicates can be employed as a Theological additive in organic media even without being dried.
The invention thus relates to the use of water-containing organophilic phyllosilicates which are obtained by the reaction of a phyllosilicate, which is completely delaminated colloidally in water and is capable of ration exchange, with an organic onium salt in aqueous suspension and subsequent mechanical removal of the water, without drying by heating, as a rheological additive in organic media and for coating paper.
These organophilic phyllosilicates are obtained by methods which are known per se, which therefore do not have to be explained in more detail. Possible phyllo-silicates which are capable of cation exchange and are completely delaminated colloidally in water are all the synthetic or naturally occurring smectic phyllosilicates, preferably bentonite or montmorillonite, which, in addition to a smectic phyllosilicate, can also contain 25-30~ by weight of impurities in the form of other minerals. The minerals are treated with an aqueous solution of onium compounds, such as, for example, phosphonium compounds, but preferably quaternary organic ammonium salts, these compounds being embedded between the layers of these minerals. Possible quaternary organic ammonium salts are, in particular, compounds of the formula R, Rz 2 0 ~ N ~ A°' R,/ ~Rz in which Rl is C8-CZZ-alkyl or C8-CZZ-alkenyl, RZ is Cl-Cd-alkyl and A is an anion, preferably chloride or metho-sulfate. The compound distearyl-dimethyl-ammonium chloride is particularly preferred. When the phyllo-silicate is charged with the quaternary organic ammonium salt, the water is filtered off or pressed off. This is done by the customary processes of separation. The filtercake obtained consists, depending on the purity of the phyllosilicates, to the extent of about 65 to 83$ of water and is employed according to the invention in this form directly as a rheological additive in organic media.
Examples of organic media in the sense of this invention are paints, varnishes, coatings, putties, lubricating greases, cosmetics, paint removers, filler compositions and similar formulations containing organic solvents. The water-containing organophilically modified phyllo-silicates according to the invention have a thixotroping effect in all these systems. As a result of this effect, .
the formulations mentioned are easier to process. In addition, these phyllosilicates also prevent settling of the insoluble components, for example the pigments within these media. As another surprising effect of these water containing organophilic phyllosilicates it has been found that the thickening action here is significantly higher in comparison with the analogous commercially available products having the same solids content, but from which the water has been removed by drying by heating.
These water-containing organophilically modified phyllo-silicates are added to the organic media by methods which are known per se. The amount of these rheological addi-tives also lies within the range known to the expert in this field (about 0.5 to 3% by weight).
The water-containing organophilic phyllosilicates accord-ing to the invention are particularly suitable for coating paper. From economic considerations, efforts are made to use thin printing papers for printed products with a high circulation, for example newspapers or mail-order catalogs. However, problems arise here in respect of opacity, i.e. in the case of printing the print shows through in an interfering manner on the other side of the paper. To prevent this effect, it is already known (EP 192 252) that paper can be coated with an organo-philic complex of a smectic phyllosilicate and a quaternary organic ammonium compound from a suspension in organic solvents. The starting material is present here in a form from which as much of the water as possible has been removed by heating. In the context of the present invention, it has now been found that drying of the organophilically modified phyllosilicate can be dispensed with in this process (solvent coating) and the water-containing presscake of this organophilically modified phyllosilicate can be employed directly. It is surprising here that the water in the presscake does not interfere with the homogeneity of the overall organic system. The water remains in the inner phase, and no swelling of the paper fibers occurs, as would be the case with an aqueous coating. This finding is therefore of relatively great importance, since in future such "solvent coating"
processes based on toluene or white spirit will gain increasing importance. The solids content (i.e. without the content of water from the presscake) of such suspen-sions is about 3 to 9% by weight. These "solvent coating"
suspensions can furthermore also contain white pigments (TiOz). As a result of the ability of the organo-philically modified phyllosilicates to form films, these white pigments are bonded firmly to the paper by the phyllosilicates; no additional binder is therefore needed. A good hold-out effect is obtained in this manner, i.e. print-through on the printed paper is prevented.
Examples A commercially available, non-purified Na bentonite (exchange capacity 80 milliequivalents/100 g) was stirred in a hot solution of distearyl-dimethyl-ammonium chloride at a ratio of the two products of 69% by weight of Na bentonite and 31% by weight of quaternary organic ammonium salt. When the reaction had ended, the mixture was filtered and the now organophilically modified bentonite was pressed off to a solids content of about 31% by weight. This filtercake was dispersed in toluene and the dispersion was applied in a thin layer to a sheet of paper and dried. The details of the examples and the particular evaluation of the hold-out effect can be seen from the following Tables 1 and 2.
As the examples show, a very good hold-out effect is obtained with the water-containing organophilic phyllosilicates according to the present invention. The examples in the table show that customary white pigments can also be applied to the paper and firmly anchored there by means of the dispersion of the organophilically modified phyllosilicate in toluene; no additional binder is required here.
Table 1 Toluene 87.5 g 85 g 82.5 g Filtercake 12.5 g 15 g 17.5 g Brookfield viscosity in mPas at 100 rpm after 2 days 308 528 720 Weight applied 1.5-1.8 1.6-1.7 1.4-1.6 (g/m2) Hold-out good good good Weight applied (g/mz) 2.3-2.5 2.8-3.0 2.5-2.7 Hold-out very goo best very good Table 2 Toluene to 100 to 100 to 100 Filtercake 15 g 15 g 15 g Titanium dioxide 0.4 g China clay 0.4 g Optical 0.1 g brightener Brookfield viscosity in mPas at 100 rpm after 2 days 29g 324 216 Weight applied g/mz~ 1.3 1.4 1.5 Hold-out good good good
Claims (11)
1. The use of a water-containing organophilic phyllosilicate obtained by the reaction of a phyllosilicate, which is completely delaminated colloidally in water and is capable of cation exchange, with an organic onium salt in aqueous suspension and subsequent mechanical removal of the water, without drying by heating, as a rheological additive in organic media.
2. The use of a water-containing organophilic phyllosilicate obtained as claimed in claim 1 for coating paper from a suspension in an organic solvent.
3. The use as claimed in claim 1 or 2, wherein the phyllosilicate used for the reaction with the onium salt is a Na bentonite.
4. The use as claimed in claim 1, wherein the organic onium salt is an organic quaternary ammonium salt.
5. The use as claimed in claim 1 or 2, wherein the onium salt is distearyl-dimethyl-ammonium chloride.
6. An organic medium containing a water-containing organophilic phyllosilicate obtained by the reaction of a phyllosilicate, which is completely delaminated coloidally in water and is capable of canon exchange, with an organic onium salt in aqueous suspension and subsequent mechanical removal of the water without drying by heating.
7. The organic medium of claim 6 for use in coating paper from a suspension in an organic solvent.
8. The organic medium of claim 6 or 7 wherein the phyllosilicate used for the reaction with the onium salt is a Na bentonite.
9. The organic medium of claim 6, 7 or 8 wherein the organic onium salt is an organic quaternary ammonium salt.
10. The organic medium of any one of claims 6 to 9 wherein the onium salt is distearyl-dimethyl-ammonium chloride.
11. A method of preparing an organic medium containing a water-containing organophilic phyllosilicate comprising the steps of:
a) preparing a water-containing organophilic phyllosilicate obtained by the reaction of a phyllosilicate which is completely delaminated colloidally in water and is capable of cation exchange, with an organic onium salt in aqueous suspension and subsequent mechanical removal of the water without drying by heating; and b) adding the water-containing organophilic phyllosilicate of step a) to an organic medium.
a) preparing a water-containing organophilic phyllosilicate obtained by the reaction of a phyllosilicate which is completely delaminated colloidally in water and is capable of cation exchange, with an organic onium salt in aqueous suspension and subsequent mechanical removal of the water without drying by heating; and b) adding the water-containing organophilic phyllosilicate of step a) to an organic medium.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4038886A DE4038886C2 (en) | 1990-12-06 | 1990-12-06 | Use of water-containing organophilic layered silicates |
| DEP4038886.7 | 1990-12-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2057110A1 CA2057110A1 (en) | 1992-06-07 |
| CA2057110C true CA2057110C (en) | 2001-04-10 |
Family
ID=6419699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002057110A Expired - Fee Related CA2057110C (en) | 1990-12-06 | 1991-12-05 | Water-containing organophilic phyllosilicates |
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) | FI915720L (en) |
| NO (1) | NO914793L (en) |
| ZA (1) | ZA919603B (en) |
Families Citing this family (6)
| 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 |
| DE4217779A1 (en) * | 1992-05-29 | 1993-12-02 | Sued 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 |
| SG183831A1 (en) * | 2010-03-29 | 2012-10-30 | Akzo Nobel Chemicals Int Bv | Process of producing a cellulosic fibre web |
| 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 |
Family Cites Families (3)
| 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 |
| EP0079972B1 (en) * | 1981-11-19 | 1985-05-02 | C.F. Spiess & Sohn GmbH & Co. Chemische Fabrik | Process for producing tertiary sulfonium montmorrillonites, and their use |
| DE3703957A1 (en) * | 1987-02-10 | 1988-08-18 | Inst Zellstoff & Papier | METHOD FOR PRODUCING A PIGMENT-BASED AGENT, THE AGENT AND ITS USE FOR THE PAPER AND CARDBOARD INDUSTRY, IMPROVING THE PRINTABILITY OF PAPER AND CARDBOARD |
-
1990
- 1990-12-06 DE DE4038886A patent/DE4038886C2/en not_active Expired - Fee Related
-
1991
- 1991-12-04 DE DE59108654T patent/DE59108654D1/en not_active Expired - Fee Related
- 1991-12-04 AT AT91120840T patent/ATE151480T1/en active
- 1991-12-04 EP EP91120840A patent/EP0489422B1/en not_active Expired - Lifetime
- 1991-12-04 FI FI915720A patent/FI915720L/en not_active Application Discontinuation
- 1991-12-05 CA CA002057110A patent/CA2057110C/en not_active Expired - Fee Related
- 1991-12-05 JP JP3322135A patent/JPH04359082A/en not_active Withdrawn
- 1991-12-05 NO NO91914793A patent/NO914793L/en unknown
- 1991-12-05 ZA ZA919603A patent/ZA919603B/en unknown
- 1991-12-06 BR BR919105274A patent/BR9105274A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR9105274A (en) | 1992-08-18 |
| DE59108654D1 (en) | 1997-05-15 |
| FI915720A7 (en) | 1992-06-07 |
| EP0489422A1 (en) | 1992-06-10 |
| EP0489422B1 (en) | 1997-04-09 |
| JPH04359082A (en) | 1992-12-11 |
| ZA919603B (en) | 1992-08-26 |
| NO914793L (en) | 1992-06-09 |
| ATE151480T1 (en) | 1997-04-15 |
| DE4038886C2 (en) | 2000-08-03 |
| NO914793D0 (en) | 1991-12-05 |
| FI915720A0 (en) | 1991-12-04 |
| FI915720L (en) | 1992-06-07 |
| CA2057110A1 (en) | 1992-06-07 |
| DE4038886A1 (en) | 1992-06-11 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |