EP0803373A1 - Use of a polymer on the basis of basic vinyl heterocyclic compounds for the coating of printable material - Google Patents

Use of a polymer on the basis of basic vinyl heterocyclic compounds for the coating of printable material Download PDF

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Publication number
EP0803373A1
EP0803373A1 EP19970106530 EP97106530A EP0803373A1 EP 0803373 A1 EP0803373 A1 EP 0803373A1 EP 19970106530 EP19970106530 EP 19970106530 EP 97106530 A EP97106530 A EP 97106530A EP 0803373 A1 EP0803373 A1 EP 0803373A1
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Prior art keywords
polymer
coating
use according
vinylimidazole
weight
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EP19970106530
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German (de)
French (fr)
Inventor
Bernhard Dr. Fussnegger
Manfred Dr. Baumeister
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BASF SE
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BASF SE
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood

Definitions

  • the invention relates to the use of a polymer based on a basic vinyl heterocycle with a pK a of at least 3.8 for coating printable materials, in particular for coating paper and plastic film intended for inkjet printing.
  • Ink-jet inks are solutions of anionic dyes in water or aqueous organic mixtures. When producing a printed product, these inks are sprayed onto a printable surface in a dot-like manner. In order to prevent the size and shape of the applied ink dots from changing due to melting and the edges becoming blurred, the inks must be fixed immediately during application. This is done by fixing the anionic dyes to polymers with which the printable materials have previously been coated. The ink is bound to the polymers either via an ionic mechanism (cationic polymers) or via ⁇ - ⁇ interactions (neutral polymers).
  • soluble cationic polymers predominantly of the quaternary ammonium compound type, have been used as dye-fixing components. These are formulated with absorbent pigments and applied to them.
  • JP 06143800 describes a silica gel in combination with a quaternary polyethyleneimine, a two-layer structure of the components being provided.
  • JP 06092007 it is proposed to use a calcium carbonate as filler directly in papermaking, which is treated with a formulation which contains a copolymer of trimethylammonium methacrylate and vinyl alcohol.
  • EP 487 349 describes silica gel particles which have been treated with a cationic polyamine (Cypro 514®).
  • JP 01009776 proposes the cationic copolymer of diallyldimethylammonium chloride and acrylamide for this purpose.
  • JP 63307979 proposes coating paper for ink-jet printing with a hydrophilic, soluble copolymer of vinylimidazole, vinylpyrrolidone and vinylbenzylsulfonic acid (60:30:10).
  • JP 63307979 the porous system is produced by crosslinking gelatin with 1,4-butanediol diglycidyl ether.
  • the main disadvantage is the reactivity of this component. After the addition of water and the beginning of the crosslinking reaction, the formulation can only be processed in the coating systems for a short time.
  • the invention was therefore based on the object to provide polymers for coating printable materials which meet the above. Do not have disadvantages.
  • EP-A-4 38 713 such polymers are used to remove heavy metals from wine and wine-like beverages. Reference is expressly made to this document with regard to the production of the polymers.
  • Basic vinyl heterocycles (a) are to be understood here as meaning saturated and aromatically unsaturated heterocycles with a vinyl group and at least one basic tertiary ring nitrogen atom with a pK a of at least 3.8.
  • the ring can also contain alkyl groups with 1 to 4 carbon atoms, phenyl or benzyl groups or a fused second one Wear ring.
  • N-vinylimidazole and derivatives thereof such as 2-methyl-1-vinylimidazole, 4-methyl-1-vinylimidazole, 5-methyl-1-vinylimidazole, 2-ethyl-1-vinylimidazole, 2-propyl -1-vinylimidazole, 2-isopropyl-1-vinylimidazole, 2-phenyl-1-vinylimidazole, 1-vinyl-4,5-benzimidazole.
  • the following can also be used, for example: 2-vinylpyridine, 4-vinylpyridine and 2-methyl-5-vinylpyridine. Mixtures of basic vinyl heterocycles with one another can of course also be used.
  • Preferred monomers (a) are N-vinylimidazole and 2-methyl-N-vinylimidazole.
  • the monomers (a) are used in an amount of 50-99.5, preferably 60-96% by weight, based on the total polymer.
  • Suitable crosslinkers (c) are those which contain two or more radically copolymerizable vinyl groups in the molecule.
  • Alkylenebisacrylamides such as methylenebisacrylamide and N, N'-bisacryloylethylenediamine, in addition N, N'-divinylethylene urea, N, N'-divinylpropylene urea, ethylidene-bis-3- (N-vinylpyrrolidone) and N, N'-divinyldiimidazolyl- (2 , 2 ') - and 1,1'-bis (3,3'-vinylbenzimidazolid-2-one) -1,4-butane.
  • crosslinking agents are, for example, alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and tetramethylene glycol di (meth) acrylate, aromatic divinyl compounds such as divinylbenzene and divinyltoluene, and allyl acrylate, divinyldioxane, pentaerythritol triallyl ether and mixtures thereof.
  • alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and tetramethylene glycol di (meth) acrylate
  • aromatic divinyl compounds such as divinylbenzene and divinyltoluene
  • allyl acrylate divinyldioxane
  • pentaerythritol triallyl ether pentaerythritol triallyl ether and mixtures thereof.
  • the crosslinkers (c) are used in an amount of 0.5-10, preferably 1-4% by weight, based on all the monomers of the polymer.
  • the comonomers (b) are polymerized in amounts of up to 49.5%, preferably up to 30% by weight, particularly preferably up to 20% by weight, based on the total monomer mixture.
  • suitable comonomers (b) are styrene, acrylic esters, vinyl esters, acrylamides and N-vinyl-dihydropyridines.
  • Preferred comonomers (b) are N-vinyl lactams such as 3-methyl-N-vinyl pyrrolidone, in particular N-vinyl caprolactam and N-vinyl pyrrolidone (VP).
  • Polymers which are particularly suitable for the use according to the invention are those made from N-vinylimidazole (VI), N-vinylpyrrolidone (VP) and N, N'-divinylethyleneurea (DVEH), in particular from 80-90% by weight VI, 5-15 % By weight of VP and 2-5% by weight of DVEH.
  • VI N-vinylimidazole
  • VP N-vinylpyrrolidone
  • DVEH N, N'-divinylethyleneurea
  • the monomer mixture consisting of basic vinyl heterocycle, the crosslinking agent and optionally N-vinyllactam or another comonomer, is rendered inert by introducing nitrogen and then heated to 100 to 200, preferably 150 to 180 ° C. It is advantageous if a weak stream of nitrogen is further introduced into the mixture. It is particularly advantageous if the batch is brought to the boil by applying a vacuum. Depending on the type of monomers used and the temperature selected, the mixture then polymerizes within 1 to 20 hours.
  • a preferred method of preparation is precipitation polymerization in water.
  • the concentration of the monomers in the reaction mixture is expediently chosen so that the mixture remains readily stirrable over the entire duration of the reaction. If the water is too little, the polymer grains become sticky, so that stirring becomes more difficult than without water.
  • the appropriate monomer concentration based on the aqueous mixture, is about 5 to 30, preferably 8 to 15,% by weight. They can be increased to 50% by weight if powerful stirrers are available. It may also be appropriate to start the polymerization with a relatively concentrated solution and then to dilute it with water in the course of the reaction.
  • the polymerization is expediently carried out at pH values above 6 in order to avoid possible saponification of the comonomers and / or crosslinking agents.
  • the pH can be adjusted by adding small amounts of bases such as sodium hydroxide or ammonia or the usual buffer salts such as soda, sodium bicarbonate or sodium phosphate.
  • the exclusion of oxygen can be achieved by keeping the polymerization batch at the boil and / or, as mentioned, using an inert gas such as nitrogen.
  • the polymerization temperature can be 30 to 150 ° C here. Is preferably carried out at 40 to 100 ° C.
  • a reducing agent such as sodium sulfite, sodium pyrosulfite, sodium dithionite, ascorbic acid and the like in order to completely remove dissolved oxygen before or at the start of the polymerization to add.
  • the water-soluble comonomer preferably NVP or an N-vinyllactam
  • the crosslinking agent water and, if appropriate, a buffer and a reducing agent are heated in a gentle stream of nitrogen until the first polymer particles show up. Then a mixture of the vinyl heterocycle and the remaining crosslinking agent and optionally water, which had been rendered inert by blowing in nitrogen, is added as a diluent within 0.2 to 6 hours.
  • the start of the polymerization can often be started by adding from 0.01 to 5% by weight, based on the monomer mixture, of a crosslinked, less swellable polymer based on basic vinyl heterocycles with a pK a value of at least 3.8 or vinyl lactams, in particular N-vinylimidazole and N-vinylpyrrolidone, are accelerated.
  • the polymer obtained from the aqueous suspension can be isolated by filtration or centrifugation, followed by washing with water and drying in conventional dryers such as a circulating air or vacuum drying cabinet, paddle dryer or current dryer.
  • the polymer is generally used in amounts of 0.5-90, preferably 2-20,% by weight, based on the total dry weight of the coating formulation.
  • the particle size distribution of the polymer particles is usually in the range from 0.01-100 ⁇ m, preferably in the range from 0.3-20 ⁇ m.
  • Another component of the coating formulation is a binder.
  • a binder for example, polyvinyl alcohols or polyvinylpyrrolidones with K values between 60 and 90 are well suited as binders.
  • Fillers known from paper production such as barium sulfate, calcium carbonate, kaolin, talc, titanium dioxide or silicates, can be added as further constituents of the coating formulation.
  • the ingredients are in a liquid medium, preferably in water. suspended, the solids content usually being between 30 and 80% and a viscosity (Brookfield) between 100 and 3000 mPas being achieved.
  • the solids content usually being between 30 and 80% and a viscosity (Brookfield) between 100 and 3000 mPas being achieved.
  • This suspension is used directly to coat the materials to be printed.
  • Papers and cardboards as well as plastic films are particularly suitable as materials for the use according to the invention.
  • the printable materials generally do not need to be pretreated before the coating composition containing the polymer is applied.
  • a mixture of 4 parts of N-vinylpyrrolidone, 0.1 part of N, N'-divinylethylene urea (DVEH), 50 parts of water and 0.5 part of sodium hydroxide solution (5% strength) was placed in a stirred vessel and heated to 60 ° C. in a stream of nitrogen . After addition of 0.01 part of sodium dithionite, the mixture was stirred at 70 ° C. for 60 min.
  • a solution of 37 parts of N-vinylimidazole and 1.2 parts of DVEH in 50 parts of water was metered into the suspension thus obtained within 3 hours.
  • the mixture was then polymerized at 70 ° C for 2 hours.
  • the preparation was carried out by washing on a suction filter, washing with water and drying in a circulating air cabinet 60 ° C. A white fine-grained product was obtained in a yield of 95%.
  • a solution of a mixture of 15 parts of N-vinyl-1,4-dihydropyridine and 15 parts of N-vinylpyrrolidone was in a stirrer equipped with a reflux condenser in 200 parts of water with the addition of 0.6 part of N, N'-divinylethylene urea, first in a Temperature of 60 ° C with nitrogen gassing and then mixed with 1 part of sodium dithionite. After one hour, a solution of 70 parts of N-vinylimidazole and 1.4 parts of N, N'-divinylethylene urea in 200 parts of water was added to the primary suspension thus obtained. The mixture was heated to 80 ° C. with stirring and polymerized for 8 hours. After the precipitation polymer obtained had been separated off on a suction filter, it was carefully washed with water and dried in a vacuum drying cabinet at 50.degree. The yield of white fine-grained and odorless powder was 94.7%.
  • 10 parts of the comminuted polymer according to Example 2 were incorporated with 75 parts of calcium carbonate (95%) with a particle diameter of less than 2 ⁇ m and 10 parts of poly (trimethylammonium methyl methacrylate) and 5 parts of Kurraray R1130® polyvinyl alcohol in 100 parts of water and homogenized.
  • the dispersion obtained in this way was leveled out on the paper using a doctor blade, a doctor blade, a film press, an air brush or a coating press.
  • the application quantity was between 2 and 15 g per m 2 of paper.

Abstract

The use of a polymer (I) based on basic heterocyclic vinyl compounds (II) for coating printable materials is claimed. (I) is a polymer derived from (a) 50-99.5 wt% basic vinyl- heterocycle(s) (II) with a pKa value of at least 3.8, (b) 0-49.5 wt% other comonomer and (c) 0.5-10 wt% crosslinker. Also claimed are materials suitable for ink jet printing, which are coated with (I) before printing.

Description

Die Erfindung betrifft die Verwendung eines Polymerisates auf Basis eines basischen Vinylheterocyclus mit einem pKa-Wert von mindestens 3,8 zur Beschichtung von bedruckbaren Materialien, insbesondere zur Beschichtung von für den Tintenstrahldruck (ink-jet Druck) vorgesehenem Papier und Kunststoffolie.The invention relates to the use of a polymer based on a basic vinyl heterocycle with a pK a of at least 3.8 for coating printable materials, in particular for coating paper and plastic film intended for inkjet printing.

Ink-jet Tinten sind Lösungen anionischer Farbstoffe in Wasser oder wäßrig organischen Mischungen. Bei der Herstellung eines Druckerzeugnisses werden diese Tinten punktförmig auf eine bedruckbare Oberfläche aufgesprüht. Um zu verhindern, daß sich Größe und Form der applizierten Tintenpunkte durch Zerfließen ändert und die Ränder unscharf werden, müssen die Tinten unmittelbar beim Aufbringen fixiert werden. Dies geschieht durch Fixierung der anionischen Farbstoffe an Polymeren, mit denen die bedruckbaren Materialien zuvor beschichtet worden wurden. Die Bindung der Tinte an die Polymeren erfolgt entweder über einen ionischen Mechanismus (kationische Polymere) oder über π-π-Wechselwirkungen (neutrale Polymere).Ink-jet inks are solutions of anionic dyes in water or aqueous organic mixtures. When producing a printed product, these inks are sprayed onto a printable surface in a dot-like manner. In order to prevent the size and shape of the applied ink dots from changing due to melting and the edges becoming blurred, the inks must be fixed immediately during application. This is done by fixing the anionic dyes to polymers with which the printable materials have previously been coated. The ink is bound to the polymers either via an ionic mechanism (cationic polymers) or via π-π interactions (neutral polymers).

Bisher werden als farbstoffixierende Komponenten lösliche kationische Polymere, überwiegend vom Typ der quartären Ammoniumverbindungen eingesetzt. Diese werden mit saugfähigen Pigmenten formuliert und darauf aufgezogen.So far, soluble cationic polymers, predominantly of the quaternary ammonium compound type, have been used as dye-fixing components. These are formulated with absorbent pigments and applied to them.

JP 06143800 beschreibt ein Kieselgel in Kombination mit einem quaternären Polyethylenimin, wobei ein zweilagiger Aufbau der Komponenten vorgesehen ist.JP 06143800 describes a silica gel in combination with a quaternary polyethyleneimine, a two-layer structure of the components being provided.

In JP 06092007 wird vorgeschlagen, direkt bei der Papierherstellung als Füllstoff ein Kalziumkarbonat zu verwenden, das mit einer Formulierung behandelt ist, die ein Copolymer aus Trimethylammoniummethacrylat und Vinylalkohol enthält.In JP 06092007 it is proposed to use a calcium carbonate as filler directly in papermaking, which is treated with a formulation which contains a copolymer of trimethylammonium methacrylate and vinyl alcohol.

In EP 487 349 werden Kieselgelpartikel beschrieben, die mit einem kationischen Polyamin (Cypro 514®) behandelt wurden.EP 487 349 describes silica gel particles which have been treated with a cationic polyamine (Cypro 514®).

JP 01009776 schlägt das kationische Copolymer aus Diallyldimethylammoniumchlorid und Acrylamid für diesen Zweck vor.JP 01009776 proposes the cationic copolymer of diallyldimethylammonium chloride and acrylamide for this purpose.

In JP 63307979 wird vorgeschlagen, Papier für den ink-jet Druck mit einem hydrophilen löslichen Copolymer aus Vinylimidazol, Vinylpyrrolidon und Vinyl-benzylsulfonsäure (60:30:10) zu beschichten.JP 63307979 proposes coating paper for ink-jet printing with a hydrophilic, soluble copolymer of vinylimidazole, vinylpyrrolidone and vinylbenzylsulfonic acid (60:30:10).

Bei den oben beschriebenen Arten der Beschichtung besteht der Nachteil, daß stets zwei Komponenten benötigt werden, die die Farbstoffbindung und die Lösemittelfixierung entweder durch Aufnahme in ein poröses dreidimensionales Hohlraumsystem oder durch Viskositätserhöhung übernehmen. Bei JP 63307979 wird das poröse System erzeugt durch die Vernetzung von Gelatine mit 1,4-Butandioldiglycidylether. Der entscheidende Nachteil liegt in der Reaktivität dieses Bestandteils. Nach Wasserzusatz und der beginnenden Vernetzungsreaktion ist die Formulierung nur kurze Zeit in den Beschichtungsanlagen verarbeitbar.With the types of coating described above, there is the disadvantage that two components are always required, which take over the dye binding and the solvent fixation either by incorporation into a porous three-dimensional cavity system or by increasing the viscosity. In JP 63307979, the porous system is produced by crosslinking gelatin with 1,4-butanediol diglycidyl ether. The main disadvantage is the reactivity of this component. After the addition of water and the beginning of the crosslinking reaction, the formulation can only be processed in the coating systems for a short time.

Der Erfindung lag daher die Aufgabe zugrunde, Polymere zur Beschichtung von bedruckbaren Materialien bereitzustellen, die die o.g. Nachteile nicht besitzen.The invention was therefore based on the object to provide polymers for coating printable materials which meet the above. Do not have disadvantages.

Gegenstand der Erfindung ist die Verwendung eines Polymerisats aus

  • (a) 50 bis 99,5 Gew.-% mindestens eines basischen Vinylheterocyclus mit einem pka-Wert von mindestens 3,8,
  • (b) 0 bis 49,5 Gew.-% eines weiteren copolymerisierbaren Monomeren und
  • (c) 0,5 bis 10 Gew.-%, eines Vernetzers
The invention relates to the use of a polymer
  • (a) 50 to 99.5% by weight of at least one basic vinyl heterocycle with a pk a value of at least 3.8,
  • (b) 0 to 49.5% by weight of a further copolymerizable monomer and
  • (c) 0.5 to 10% by weight of a crosslinker

zur Beschichtung von bedruckbaren Materialien,
sowie die in den Unteransprüchen weiter dargelegten Ausführungsformen.for coating printable materials,
as well as the embodiments further set forth in the subclaims.

In EP-A-4 38 713 werden solche Polymeren zur Entfernung von Schwermetallen aus Wein und weinähnlichen Getränken eingesetzt. Auf diese Schrift wird hinsichtlich der Herstellung der Polymere ausdrücklich Bezug genommen.In EP-A-4 38 713 such polymers are used to remove heavy metals from wine and wine-like beverages. Reference is expressly made to this document with regard to the production of the polymers.

Unter basischen Vinylheterocyclen (a) sind hier gesättigte und aromatisch ungesättigte Heterocyclen mit einer Vinylgruppe und mindestens einem basischen tertiären Ring-Stickstoffatom mit einem pKa von mindestens 3,8 zu verstehen. Außer der Vinylgruppe kann der Ring auch Alkylgruppen mit 1 bis 4 Kohlenstoffatomen, Phenyl- oder Benzyl-Gruppen oder auch einen anellierten zweiten Ring tragen. Als Beispiele seien genannt: N-Vinylimidazol (VI) sowie Derivate davon wie 2-Methyl-1-vinylimidazol, 4-Methyl-1-vinylimidazol, 5-Methyl-1-vinylimidazol, 2-Ethyl-1-vinylimidazol, 2-Propyl-1-vinylimidazol, 2-Isopropyl-1-vinylimidazol, 2-Phenyl-1-vinylimidazol, 1-Vinyl-4,5-benzimidazol. Weiterhin können beispielsweise eingesetzt werden: 2-Vinylpyridin, 4-Vinylpyridin sowie 2-Methyl-5-vinylpyridin. Selbstverständlich können auch Gemische von basischen Vinylheterocyclen untereinander eingesetzt werden.Basic vinyl heterocycles (a) are to be understood here as meaning saturated and aromatically unsaturated heterocycles with a vinyl group and at least one basic tertiary ring nitrogen atom with a pK a of at least 3.8. In addition to the vinyl group, the ring can also contain alkyl groups with 1 to 4 carbon atoms, phenyl or benzyl groups or a fused second one Wear ring. Examples include: N-vinylimidazole (VI) and derivatives thereof such as 2-methyl-1-vinylimidazole, 4-methyl-1-vinylimidazole, 5-methyl-1-vinylimidazole, 2-ethyl-1-vinylimidazole, 2-propyl -1-vinylimidazole, 2-isopropyl-1-vinylimidazole, 2-phenyl-1-vinylimidazole, 1-vinyl-4,5-benzimidazole. The following can also be used, for example: 2-vinylpyridine, 4-vinylpyridine and 2-methyl-5-vinylpyridine. Mixtures of basic vinyl heterocycles with one another can of course also be used.

Bevorzugte Monomere (a) sind N-Vinylimidazol und 2-Methyl-N-vinylimidazol.Preferred monomers (a) are N-vinylimidazole and 2-methyl-N-vinylimidazole.

Die Monomere (a) werden in einer Menge von 50-99,5, bevorzugt von 60-96 Gew.-% bezogen auf das Gesamtpolymer eingesetzt.The monomers (a) are used in an amount of 50-99.5, preferably 60-96% by weight, based on the total polymer.

Geeignete Vernetzer (c) sind solche, die zwei oder mehr radikalisch copolymerisierbare Vinylgruppen im Molekül enthalten. Besonders geeignet sind Alkylenbisacrylamide wie Methylenbisacrylamid und N,N'-Bisacryloylethylendiamin, außerdem N,N'-Divinylethylenharnstoff, N,N'-Divinylpropylenharnstoff, Ethyliden-bis-3-(N-vinylpyrrolidon) sowie N,N'-Divinyldiimidazolyl-(2,2')-und 1,1'-Bis(3,3'-vinylbenzimidazolid-2-on)-1,4-butan. Andere brauchbare Vernetzungsmittel sind beispielsweise Alkylenglykoldi(meth)acrylate wie Ethylenglykoldi(meth)acrylat und Tetramethylenglykoldi(meth)acrylat, aromatische Divinylverbindungen wie Divinylbenzol und Divinyltoluol sowie Allylacrylat, Divinyldioxan, Pentaerythrittriallylether und deren Gemische. Bei Polymerisation in Gegenwart von Wasser sind sie natürlich nur geeignet, soweit sie in der wäßrigen Monomermischung löslich sind.Suitable crosslinkers (c) are those which contain two or more radically copolymerizable vinyl groups in the molecule. Alkylenebisacrylamides such as methylenebisacrylamide and N, N'-bisacryloylethylenediamine, in addition N, N'-divinylethylene urea, N, N'-divinylpropylene urea, ethylidene-bis-3- (N-vinylpyrrolidone) and N, N'-divinyldiimidazolyl- (2 , 2 ') - and 1,1'-bis (3,3'-vinylbenzimidazolid-2-one) -1,4-butane. Other useful crosslinking agents are, for example, alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and tetramethylene glycol di (meth) acrylate, aromatic divinyl compounds such as divinylbenzene and divinyltoluene, and allyl acrylate, divinyldioxane, pentaerythritol triallyl ether and mixtures thereof. In the case of polymerization in the presence of water, they are of course only suitable if they are soluble in the aqueous monomer mixture.

Die Vernetzer (c) werden für in einer Menge von 0,5-10, bevorzugt von 1-4 Gew. %, bezogen auf alle Monomere des Polymerisats, eingesetzt.The crosslinkers (c) are used in an amount of 0.5-10, preferably 1-4% by weight, based on all the monomers of the polymer.

Die Comonomeren (b), werden in Mengen bis zu 49,5, vorzugsweise bis zu 30 Gew.-%, besonders bevorzugt bis zu 20 Gew.-%, bezogen auf die gesamte Monomermischung, einpolymerisiert. Als Comonomere (b) kommen beispielsweise Styrol, Acrylester, Vinylester, Acrylamide, N-Vinyl-dihydropyridine in Betracht. Bevorzugt werden als Comonomere (b) N-Vinyllactame wie 3-Methyl-N-vinylpyrrolidon, insbesondere N-Vinylcaprolactam und N-Vinylpyrrolidon (VP) verwendet.The comonomers (b) are polymerized in amounts of up to 49.5%, preferably up to 30% by weight, particularly preferably up to 20% by weight, based on the total monomer mixture. Examples of suitable comonomers (b) are styrene, acrylic esters, vinyl esters, acrylamides and N-vinyl-dihydropyridines. Preferred comonomers (b) are N-vinyl lactams such as 3-methyl-N-vinyl pyrrolidone, in particular N-vinyl caprolactam and N-vinyl pyrrolidone (VP).

Für die erfindungsgemäße Verwendung besonders gut geeignete Polymere sind solche aus N-Vinylimidazol (VI), N-Vinylpyrrolidon (VP) und N,N'-Divinylethylenharnstoff (DVEH), insbesondere solche aus 80-90 Gew.-% VI, 5-15 Gew.-% VP und 2-5 Gew.-% DVEH.Polymers which are particularly suitable for the use according to the invention are those made from N-vinylimidazole (VI), N-vinylpyrrolidone (VP) and N, N'-divinylethyleneurea (DVEH), in particular from 80-90% by weight VI, 5-15 % By weight of VP and 2-5% by weight of DVEH.

Zur Durchführung der Polymerisation ohne Lösungsmittel wird das Monomerengemisch, bestehend aus basischem Vinylheterocyclus, dem vernetzenden Agens und gegebenenfalls N-Vinyllactam oder einem anderen Comonomeren, durch Einleiten von Stickstoff inertisiert und anschließend auf 100 bis 200, vorzugsweise 150 bis 180°C erhitzt. Vorteilhaft ist es, wenn in die Mischung weiter ein schwacher Stickstoffstrom eingeleitet wird. Besonders vorteilhaft ist es, wenn der Ansatz durch Anlegen von Vakuum zum Sieden gebracht wird. Je nach Art der eingesetzten Monomeren und der gewählten Temperatur polymerisiert dann die Mischung innerhalb 1 bis 20 Stunden. Beispielsweise bilden sich bei der Polymerisation von 2Methyl-vinylimidazol mit 2 % N,N'-Divinylethylenharnstoff bei 150°C unter Rühren mit einem kräftigen Rührwerk und einem Druck von 310 mbar nach 2,5 h die ersten Polymerisatteilchen, die langsam zunehmen, bis nach 10 h der Ansatz aus einem bräunlichen Pulver besteht. Nach Auswaschen mit Wasser und Trocknen wird das neue Polymere in Ausbeuten von über 90 % in Form eines groben Pulvers erhalten.To carry out the polymerization without solvent, the monomer mixture, consisting of basic vinyl heterocycle, the crosslinking agent and optionally N-vinyllactam or another comonomer, is rendered inert by introducing nitrogen and then heated to 100 to 200, preferably 150 to 180 ° C. It is advantageous if a weak stream of nitrogen is further introduced into the mixture. It is particularly advantageous if the batch is brought to the boil by applying a vacuum. Depending on the type of monomers used and the temperature selected, the mixture then polymerizes within 1 to 20 hours. For example, in the polymerization of 2Methyl-vinylimidazole with 2% N, N'-divinylethyleneurea at 150 ° C with stirring with a vigorous stirrer and a pressure of 310 mbar after 2.5 h, the first polymer particles slowly increase until after 10 h the batch consists of a brownish powder. After washing with water and drying, the new polymer is obtained in yields of over 90% in the form of a coarse powder.

Eine bevorzugte Herstellungsart ist die Fällungspolymerisation in Wasser. Die Konzentration der Monomeren im Reaktionsansatz wird zweckmäßigerweise so gewählt, daß der Ansatz über die gesamte Reaktionsdauer hinweg gut rührbar bleibt. Bei zu wenig Wasser werden die Polymerisatkörner nämlich klebrig, so daß ein Rühren schwieriger wird als ganz ohne Wasser. Bei den üblichen Rührkesseln liegt die zweckmäßige Monomerenkonzentration, bezogen auf die wäßrige Mischung, bei ca. 5 bis 30, vorzugsweise 8 bis 15 Gew.-%. Man kann sie bis auf 50 Gew.-% steigern, wenn kräftige Rührwerke zur Verfügung stehen. Es kann auch zweckmäßig sein, die Polymerisation mit einer relativ konzentrierten Lösung zu beginnen und dann im Verlauf der Reaktion mit Wasser zu verdünnen. Die Polymerisation wird zweckmäßigerweise bei pH-Werten über 6 durchgeführt, um eine eventuell mögliche Verseifung der Comonomeren und/oder Vernetzer zu vermeiden. Die Einstellung des pH-Wertes kann durch Zugabe geringer Mengen Basen wie Natriumhydroxid oder Ammoniak oder der üblichen Puffersalze wie Soda, Natriumhydrogencarbonat oder Natriumphosphat erfolgen. Der Ausschluß von Sauerstoff läßt sich dabei dadurch erreichen, daß der Polymerisationsansatz am Sieden gehalten wird, und/oder wie erwähnt mit Hilfe eines Inertgases wie Stickstoff. Die Polymerisationstemperatur kann hier 30 bis 150°C betragen. Vorzugsweise arbeitet man bei 40 bis 100°C.A preferred method of preparation is precipitation polymerization in water. The concentration of the monomers in the reaction mixture is expediently chosen so that the mixture remains readily stirrable over the entire duration of the reaction. If the water is too little, the polymer grains become sticky, so that stirring becomes more difficult than without water. In the conventional stirred kettles, the appropriate monomer concentration, based on the aqueous mixture, is about 5 to 30, preferably 8 to 15,% by weight. They can be increased to 50% by weight if powerful stirrers are available. It may also be appropriate to start the polymerization with a relatively concentrated solution and then to dilute it with water in the course of the reaction. The polymerization is expediently carried out at pH values above 6 in order to avoid possible saponification of the comonomers and / or crosslinking agents. The pH can be adjusted by adding small amounts of bases such as sodium hydroxide or ammonia or the usual buffer salts such as soda, sodium bicarbonate or sodium phosphate. The exclusion of oxygen can be achieved by keeping the polymerization batch at the boil and / or, as mentioned, using an inert gas such as nitrogen. The polymerization temperature can be 30 to 150 ° C here. Is preferably carried out at 40 to 100 ° C.

Bisweilen kann es von Vorteil sein, zur völligen Entfernung von gelöstem Sauerstoff vor oder zu Beginn der Polymerisation geringe Mengen - 0,01 bis 1 Gew.-%, bezogen auf die Monomermischung, - eines Reduktionsmittels wie Natriumsulfit, Natriumpyrosulfit, Natriumdithionit, Ascorbinsäure und dergleichen zuzusetzen.Sometimes it may be advantageous to remove small amounts - 0.01 to 1% by weight, based on the monomer mixture - of a reducing agent such as sodium sulfite, sodium pyrosulfite, sodium dithionite, ascorbic acid and the like in order to completely remove dissolved oxygen before or at the start of the polymerization to add.

Bei einer besonders bevorzugten Ausführungsform der Fällungspolymerisation wird das wasserlösliche Comonomere (vorzugsweise NVP oder ein N-Vinyllactam), ein Teil des Vernetzers, Wasser und gegebenenfalls ein Puffer und ein Reduktionsmittel in einem schwachen Stickstoffstrom erhitzt, bis sich die ersten Polymerisatteilchen zeigen. Dann wird eine vorher durch Einblasen von Stickstoff inertisierte Mischung aus dem Vinylheterocyclus und dem restlichen Vernetzer und gegebenenfalls Wasser als Verdünnungsmittel innerhalb 0,2 bis 6 Stunden zugegeben.In a particularly preferred embodiment of the precipitation polymerization, the water-soluble comonomer (preferably NVP or an N-vinyllactam), part of the crosslinking agent, water and, if appropriate, a buffer and a reducing agent are heated in a gentle stream of nitrogen until the first polymer particles show up. Then a mixture of the vinyl heterocycle and the remaining crosslinking agent and optionally water, which had been rendered inert by blowing in nitrogen, is added as a diluent within 0.2 to 6 hours.

Häufig kann der Start der Polymerisation durch Zugabe von 0,01 bis 5 Gew.-%, bezogen auf die Monomermischung, eines vernetzten, wenig quellbaren Polymerisates auf Basis von basischen Vinylheterocyclen mit einem pKa-Wert von mindestens 3,8 oder Vinyllactamen, insbesondere N-Vinylimidazol und N-Vinylpyrrolidon, beschleunigt werden.The start of the polymerization can often be started by adding from 0.01 to 5% by weight, based on the monomer mixture, of a crosslinked, less swellable polymer based on basic vinyl heterocycles with a pK a value of at least 3.8 or vinyl lactams, in particular N-vinylimidazole and N-vinylpyrrolidone, are accelerated.

Die Isolierung des anfallenden Polymeren aus der wäßrigen Suspension kann durch Filtration oder Zentrifugieren mit anschließendem Auswaschen mit Wasser und Trocknen in üblichen Trocknern wie Umluft- oder Vakuumtrockenschrank, Schaufeltrockner oder Stromtrockner erfolgen.The polymer obtained from the aqueous suspension can be isolated by filtration or centrifugation, followed by washing with water and drying in conventional dryers such as a circulating air or vacuum drying cabinet, paddle dryer or current dryer.

Das Polymerisat wird für die erfindungsgemäße Verwendung in der Regel in Mengen von 0,5-90, vorzugsweise 2-20 Gew.-%, bezogen auf die gesamte Trockenmasse der Beschichtungsformulierung, eingesetzt. Die Korngrößenverteilung der Polymerisatpartikel liegt üblicherweise im Bereich von 0,01-100 µm, bevorzugt im Bereich von 0,3-20 µm.For the use according to the invention, the polymer is generally used in amounts of 0.5-90, preferably 2-20,% by weight, based on the total dry weight of the coating formulation. The particle size distribution of the polymer particles is usually in the range from 0.01-100 μm, preferably in the range from 0.3-20 μm.

Ein weiterer Bestandteil der Beschichtungsformulierung ist ein Bindemittel. Als Bindemittel sind beispielsweise Polyvinylalkohole oder Polyvinylpyrrolidone mit K-Werten zwischen 60 und 90 gut geeignet.Another component of the coating formulation is a binder. For example, polyvinyl alcohols or polyvinylpyrrolidones with K values between 60 and 90 are well suited as binders.

Als weitere Bestandteile der Beschichtungsformulierung können aus der Papierherstellung bekannte Füllstoffe wie Bariumsulfat, Kalziumkarbonat, Kaolin, Talk, Titandioxid oder Silicate zugegeben werden.Fillers known from paper production, such as barium sulfate, calcium carbonate, kaolin, talc, titanium dioxide or silicates, can be added as further constituents of the coating formulation.

Die Bestandteile werden in einem flüssigen Medium, bevorzugt in Wasser. suspendiert, wobei der Feststoffgehalt üblicherweise zwischen 30 und 80 % liegt und eine Viskosität (Brookfield) zwischen 100 und 3000 mPas erzielt wird.The ingredients are in a liquid medium, preferably in water. suspended, the solids content usually being between 30 and 80% and a viscosity (Brookfield) between 100 and 3000 mPas being achieved.

Diese Suspension wird direkt zur Beschichtung der zu bedruckenden Materialien eingesetzt.This suspension is used directly to coat the materials to be printed.

Als Materialien für die erfindungsgemäße Verwendung sind vor allem Papiere und Pappen sowie Kunststoffolien geeignet.Papers and cardboards as well as plastic films are particularly suitable as materials for the use according to the invention.

Die bedruckbaren Materialien brauchen in der Regel nicht vorbehandelt zu werden, bevor die das Polymerisat enthaltende Beschichtungsmasse aufgetragen wird.The printable materials generally do not need to be pretreated before the coating composition containing the polymer is applied.

Die folgenden Beispiele dienen der weiteren Veranschaulichung der Erfindung.The following examples serve to further illustrate the invention.

Beispiel 1example 1

In einem Rührgefäß mit Rückflußkühler wurde ein Gemisch aus 50 Teilen N-Vinylimidazol, 30 Teilen 2-Methyl-1-vinylimidazol und 30 Teilen N-Vinylpyrrolidon unter Zusatz von 3 Teilen N,N'-Divinylethylenharnstoff bei 250 mbar auf 160°C erhitzt. Nach ca. 90 min traten die ersten unlöslichen Polymerisatpartikel auf. Nach weiteren 2 Stunden Rühren bestand der Reaktionsansatz aus einem trockenen Pulver, das anschließend auf einer Nutsche gewaschen und im Umluftschrank bei 60°C getrocknet wurde. Die Ausbeute betrug 93,5 %.In a stirred vessel with reflux condenser, a mixture of 50 parts of N-vinylimidazole, 30 parts of 2-methyl-1-vinylimidazole and 30 parts of N-vinylpyrrolidone was heated to 160 ° C. at 250 mbar with the addition of 3 parts of N, N'-divinylethylene urea. The first insoluble polymer particles appeared after about 90 minutes. After stirring for a further 2 hours, the reaction mixture consisted of a dry powder, which was then washed on a suction filter and dried in a circulating air cabinet at 60 ° C. The yield was 93.5%.

Beispiel 2Example 2

In einem Rührgefäß wurde ein Gemisch aus 4 Teilen N-Vinylpyrrolidon, 0,1 Teilen N,N'-Divinylethylenharnstoff (DVEH), 50 Teilen Wasser und 0,5 Teilen Natronlauge (5 %ig) vorgelegt und im Stickstoffstrom auf 60°C erwärmt. Nach Zugabe von 0,01 Teilen Natriumdithionit wurde 60 min bei 70°C gerührt. Zu der so erhaltenen Suspension wurde eine Lösung von 37 Teilen N-Vinylimidazol und 1,2 Teilen DVEH in 50 Teilen Wasser innerhalb von 3 Stunden dosiert. Anschließend wurde 2 Stunden bei 70°C nachpolymerisiert. Die Aufarbeitung erfolgte durch Waschen auf einer Nutsche, Nachwaschen mit Wasser und Trocknen im Umluftschrank bei 60°C. Man erhielt ein weißes feinkörniges Produkt in einer Ausbeute von 95 %.A mixture of 4 parts of N-vinylpyrrolidone, 0.1 part of N, N'-divinylethylene urea (DVEH), 50 parts of water and 0.5 part of sodium hydroxide solution (5% strength) was placed in a stirred vessel and heated to 60 ° C. in a stream of nitrogen . After addition of 0.01 part of sodium dithionite, the mixture was stirred at 70 ° C. for 60 min. A solution of 37 parts of N-vinylimidazole and 1.2 parts of DVEH in 50 parts of water was metered into the suspension thus obtained within 3 hours. The mixture was then polymerized at 70 ° C for 2 hours. The preparation was carried out by washing on a suction filter, washing with water and drying in a circulating air cabinet 60 ° C. A white fine-grained product was obtained in a yield of 95%.

Beispiel 3Example 3

Eine Lösung eines Gemisches aus 15 Teilen N-Vinyl-1,4-dihydropyridin und 15 Teilen N-Vinylpyrrolidon wurde in einer mit einem Rückflußkühler ausgestatteten Rührapparatur in 200 Teilen Wasser unter Zusatz von 0,6 Teilen N,N'-Divinylethylenharnstoff zunächst bei einer Temperatur von 60°C unter Rühren mit Stickstoff begast und anschließend mit 1 Teil Natriumdithionit versetzt. Nach einer Stunde wurde zu der so erhaltenen Primärsuspension eine Lösung von 70 Teilen N-Vinylimidazol und 1,4 Teilen N,N'-Divinylethylenharnstoff in 200 Teilen Wasser zugesetzt. Der Ansatz wurde unter Rühren auf 80°C erhitzt und 8 Stunden lang polymerisiert. Nach Abtrennung des erhaltenen Fällungspolymerisats auf einer Nutsche wurde mit Wasser sorgfältig gewaschen und im Vakuumtrockenschrank bei 50°C getrocknet. Die Ausbeute an weißem feinkörnigen und geruchsneutralem Pulver betrug 94,7 %.A solution of a mixture of 15 parts of N-vinyl-1,4-dihydropyridine and 15 parts of N-vinylpyrrolidone was in a stirrer equipped with a reflux condenser in 200 parts of water with the addition of 0.6 part of N, N'-divinylethylene urea, first in a Temperature of 60 ° C with nitrogen gassing and then mixed with 1 part of sodium dithionite. After one hour, a solution of 70 parts of N-vinylimidazole and 1.4 parts of N, N'-divinylethylene urea in 200 parts of water was added to the primary suspension thus obtained. The mixture was heated to 80 ° C. with stirring and polymerized for 8 hours. After the precipitation polymer obtained had been separated off on a suction filter, it was carefully washed with water and dried in a vacuum drying cabinet at 50.degree. The yield of white fine-grained and odorless powder was 94.7%.

Beispiel 4Example 4

10 Teile des zerkleinerten Polymers gemäß Beispiel 2 wurden mit 80 Teilen Kalziumkarbonat (95 %) mit einem Partikeldurchmesser kleiner 2 µm sowie 10 Teilen Luviskol K 90® (Polyvinylpyrrolidon) in 100 Teilen Wasser eingearbeitet und homogenisiert. Die so erhaltene Dispersion wurde mittels einem Rollrakel, einem Rakel, einer Filmpresse, einer Luftbürste oder einer Streichpresse auf dem Papier egalisiert. Die Auf tragsmenge lag zwischen 2 und 15 g pro m2 Papier.10 parts of the comminuted polymer according to Example 2 were incorporated and homogenized with 80 parts of calcium carbonate (95%) with a particle diameter of less than 2 μm and 10 parts of Luviskol K 90® (polyvinylpyrrolidone) in 100 parts of water. The dispersion obtained in this way was leveled out on the paper using a doctor blade, a doctor blade, a film press, an air brush or a coating press. The order quantity was between 2 and 15 g per m 2 of paper.

Beispiel 5Example 5

10 Teile des zerkleinerten Polymers gemäß Beispiel 2 wurden mit 75 Teilen Kalziumkarbonat (95 %) mit einem Partikeldurchmesser kleiner 2 µm sowie 10 Teilen Poly(trimethylammoniummethylmethacrylat) und 5 Teilen Polyvinylalkohol Kurraray R1130® in 100 Teilen Wasser eingearbeitet und homogenisiert.
Die so erhaltene Dispersion wurde mittels einem Rollrakel, einem Rakel, einer Filmpresse, einer Luftbürste oder einer Streichpresse auf dem Papier egalisiert. Die Auftragsmenge lag zwischen 2 und 15 g pro m2 Papier.10 parts of the comminuted polymer according to Example 2 were incorporated with 75 parts of calcium carbonate (95%) with a particle diameter of less than 2 μm and 10 parts of poly (trimethylammonium methyl methacrylate) and 5 parts of Kurraray R1130® polyvinyl alcohol in 100 parts of water and homogenized.
The dispersion obtained in this way was leveled out on the paper using a doctor blade, a doctor blade, a film press, an air brush or a coating press. The application quantity was between 2 and 15 g per m 2 of paper.

Claims (10)

Verwendung eines Polymerisats aus (a) 50 bis 99,5 Gew.-% mindestens eines basischen Vinylheterocyclus mit einem pka-Wert von mindestens 3,8, (b) 0 bis 49,5 Gew.-% eines weiteren copolymerisierbaren Monomeren und (c) 0,5 bis 10 Gew.-%, eines Vernetzers zur Beschichtung von bedruckbaren Materialien.Use of a polymer (a) 50 to 99.5% by weight of at least one basic vinyl heterocycle with a pk a value of at least 3.8, (b) 0 to 49.5% by weight of a further copolymerizable monomer and (c) 0.5 to 10% by weight of a crosslinker for coating printable materials. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß ein Polymerisat eingesetzt wird, das als basischen Vinylheterocyclus N-Vinylimidazol oder 2-Methyl-1-vinylimidazol oder eine Mischung von beiden einpolymerisiert enthält.Use according to claim 1, characterized in that a polymer is used which contains N-vinylimidazole or 2-methyl-1-vinylimidazole or a mixture of the two in copolymerized form as the basic vinyl heterocycle. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß ein Polymerisat eingesetzt wird, das als Comonomer (b) ausschließlich N-Vinylpyrrolidon, N-Vinylcaprolactam, N-Vinyl-1,4-dihydropyridin oder eine Mischung dieser Comonomeren einpolymerisiert enthält.Use according to claim 1 or 2, characterized in that a polymer is used which, as comonomer (b), contains only N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyl-1,4-dihydropyridine or a mixture of these comonomers in copolymerized form. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß ein Polymerisat eingesetzt wird, das als Vernetzer (c) N,N-Divinylethylenharnstoff einpolymerisiert enthält.Use according to one of Claims 1 to 3, characterized in that a polymer is used which contains N, N-divinylethyleneurea in copolymerized form as crosslinking agent (c). Verwendung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß ein Polymerisat eingesetzt wird, das in Gegenwart eines Reduktionsmittels hergestellt worden ist.Use according to one of claims 1 to 4, characterized in that a polymer is used which has been prepared in the presence of a reducing agent. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß ein Polymerisat eingesetzt wird, das in Gegenwart von Wasser bei 30 bis 150°C hergestellt worden ist.Use according to one of claims 1 to 5, characterized in that a polymer is used which has been prepared in the presence of water at 30 to 150 ° C. Verwendung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Polymerisat eine Korngröße zwischen 0,01 und 100 µm besitzt.Use according to one of claims 1 to 6, characterized in that the polymer has a grain size between 0.01 and 100 µm. Verwendung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das Polymerisat zur Beschichtung von Papier oder Pappe eingesetzt wird.Use according to one of claims 1 to 7, characterized in that the polymer is used for coating paper or cardboard. Verwendung nach Anspruch 8 zur Beschichtung von Materialien für den ink-jet Druck.Use according to claim 8 for coating materials for ink-jet printing. Für den ink-jet Druck geeignete bedruckbare Materialien, die vor dem Druck mit einem Polymerisat gemäß einem der vorstehenden Ansprüche beschichtet worden sind.Printable materials suitable for ink-jet printing which have been coated with a polymer according to one of the preceding claims before printing.
EP19970106530 1996-04-25 1997-04-21 Use of a polymer on the basis of basic vinyl heterocyclic compounds for the coating of printable material Ceased EP0803373A1 (en)

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