EP0253285A1 - Co-binder for coating compositions - Google Patents

Co-binder for coating compositions Download PDF

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Publication number
EP0253285A1
EP0253285A1 EP87109835A EP87109835A EP0253285A1 EP 0253285 A1 EP0253285 A1 EP 0253285A1 EP 87109835 A EP87109835 A EP 87109835A EP 87109835 A EP87109835 A EP 87109835A EP 0253285 A1 EP0253285 A1 EP 0253285A1
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Prior art keywords
weight
units
vinyl
cobinder
parts
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EP87109835A
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German (de)
French (fr)
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EP0253285B1 (en
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Bernd Dr. Schilling
Karl-Ernst Fickert
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Wacker Chemie AG
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Wacker Chemie AG
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    • 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
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters

Definitions

  • coating slips are known to be used which essentially consist of a pigment suspended in water with the aid of a dispersant, e.g. B. kaolin, satin white or calcium carbonate and binders.
  • a dispersant e.g. B. kaolin, satin white or calcium carbonate and binders.
  • Cobinder based on polymers of special acrylic esters.
  • Cobinder controls accordinging to G. Hirsch, Das Textil 32 (10A), 1978, 66-72 above all the viscosity and water retention of coating colors, improve individual coating properties such as pick resistance or Ink absorption and above all have an excellent activator effect for optical brighteners.
  • semi-synthetic, water-soluble polymers such as the sodium salt of carboxymethyl cellulose and fully synthetic polymers such as copolymers of vinyl acetate and acrylamide (DE-A-2450039) and copolymers of unsaturated acid amides with vinyl or allyl alcohol (DE-A-2933765 & CA 1163395) is used.
  • Polymers containing acrylic esters are also used as cobinders, which are added to the coating color as acidic aqueous dispersions and only develop their effect when the alkali is in place (see G. Hirsch, Das Textil 32 (10 A1), 1978, 66-72).
  • polyvinyl alcohols are not only excellent binders for pigments, but above all their carrier properties for optical brighteners exceed all of the above-mentioned cobinder systems (see H.G.'-. Oesterlin, Das Textil 36, 1982, 66-72, 121-126, 170-175). According to their degree of hydrolysis, a distinction is made between polyvinyl alcohols (PVAL) so-called fully saponified types (degree of hydrolysis 98-100 mol%) and partially saponified types with degrees of hydrolysis of 70-90 mol%. In the paper coating shop, after extensive investigations (H.G.
  • the polymers preferably consist of 60-95% by weight, in particular 70-95% by weight, units a, 5-40% by weight, in particular 5-20% by weight of units b, and 0-10% by weight, in particular each 0 - 5 wt% units c and d.
  • the amount of the comonomer units b - e is in the range from 5 to 20% by weight, in particular 7.5 to 10% by weight, the amounts of the vinyl acylate units being particularly preferably as small as possible, i.e. H. at z. B. 0-2% by weight.
  • the amount of units e is also preferably 0-1% by weight, in particular still in the lower half of this range, e.g. even below 0.2% by weight.
  • the polymers mentioned according to the invention are not only distinguished by the better miscibility of their solutions with the pigment slurry, the pigment shock being significantly reduced, if it still occurs, compared to the addition of solutions of polyvinyl alcohols comparable in viscosity and degree of hydrolysis Surprisingly also in that they can be stirred directly into pigment suspensions in bulk without prior dissolution or dilution.
  • the polymers used according to the invention have a stronger pigment binding capacity and higher water retention values than comparable, technically used, fully hydrolyzed polyvinyl alcohols, which expands their field of use as cobinder.
  • the methyl radical is preferred as the alkyl group in units b; however, branched and unbranched C 2 to C 4 alkyl groups can also be used.
  • the polymers which have hitherto been used as protective colloids for radical polymerization (DE-C-1026074, cf. Chem. Abstr. 54, 16024 h) or as base material for the production of moldings (Chem. Abstr. 87, 118 700c) or in a mixture with glycerol as a water-soluble hot melt adhesive (Chem. Abstr.
  • 91, 176392 x can be prepared in a two-stage process, in the first stage by copolymerization of vinyl acylate, in particular vinyl acetate and / or vinyl propionate, with 1-alkyl vinyl acylate, in particular isopropenyl acetate and / or -propionate, and optionally allyl acylate, in particular allyl acetate and / or -propionate in the usual manner by radical suspension or emulsion polymerization in water or by radical polymerization in bulk or in a suitable organic solvent - such as. B. alcohols or esters.
  • reactants e.g. B. of metal hydroxides
  • the molecular weights can be adjusted in the customary manner by varying the initiator concentrations, temperature and addition of polymerization regulators such as, for example, bromotrichloromethane and thioacetic acid during the polymerization. Higher molecular weights can also be set by adding small amounts of polyethylenically unsaturated compounds such as divinyl adipate and allyl methacrylate.
  • the compounds according to the invention with their use as cobinders preferably have Höppler viscosities of 3-20, in particular 4 to 12 mPas (measured as a 4% strength aqueous solution).
  • Another possibility of varying the polymers used according to the invention is the incorporation (copolymerization) of units which are derived from vinyl esters of increased hydrophobicity, that is to say, for. B. of the vinyl fatty acid esters, e.g. B. vinyl stearate and / or vinyl laurate and / or from Versatic (R) acid vinyl esters (VeoVa ( R ), esters of branched carboxylic acids produced by the so-called Koch synthesis with mostly 10 to 20 carbon atoms, Shell AG).
  • These units increase e.g. B. the surface-active effect of the polymers.
  • They are preferably polymerized in amounts of 0-1, in particular 0-0.5,% by weight, based on the total amount of the monomer units.
  • ethylene for example, can also be polymerized in amounts of 0-5, in particular 0-1,% by weight of ethylene units.
  • coating slips for flat substrates in particular for coated printing substrates, which include paper, cardboard and cardboard in particular, are known in principle. Reference is only made, for example, to DE-A-2933765 and DE-A-2450039.
  • the polymer used according to the invention can be used as a cobinder in known coating compositions in customary amounts and can at least partially, preferably entirely, replace the cobinder used there, e.g. B. the polymer B of DE-A-2933765 or the copolymer of acrylamide of DE-A-2450039.
  • the results are shown in Table 2.
  • the first value represents the result at 10 rpm
  • the second value represents the result at 100 rpm Lichen polyvinyl alcohols practically only act as another filler.
  • a paper coating slip with the following composition (FG 61%) was produced and the water retention capacity was measured using the Venema method 6) .
  • the coating colors were spread on one side on a test coating system by means of a scraper applicator at a speed of 100 m / min onto a wood-containing base paper with a basis weight of approx. 35 g / m.
  • the 2 application weight was 10.3 g / m.
  • Underlined papers on a 2-roll laboratory calendar sati - then ge were and the degree of whiteness was measured using a reflectance photometer (from Zeiss) with the filters R 457 (+ UV) and R 400 (-UV).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Amplifiers (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Oscillators With Electromechanical Resonators (AREA)
  • Indole Compounds (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

In a coating slip for coating flat surfaces comprising an aqueous dispersion, with a solids content of 8 to 65% by weight, of 100 parts by weight of a pigment, 3 to 30 parts by weight of synthetic high-molecular-weight binder based on copolymers of acrylates, styrene, butadiene and unsaturated carboxylic acid esters and 0.5 to 2 parts by weight of a cobinder the improvement comprising using a cobinder polymer containing a large degree of hydroxyl groups comprising (a) 50 to 95% by weight of vinyl alcohol units, (b) 5 to 50% by weight of 1-alkylvinyl alcohol units of 1 to 4 alkyl carbon atoms, (c) 0 to 20% by weight of vinyl acylate units, (d) 0 to 20% by weight of allyl alcohol units and (e) 0 to 5% by weight of other polymerizable monomers having improved pigment shock behavior and very good activity as an optical brightener support.

Description

Zur Herstellung von gestrichenen flächigen Substraten, insbesondere von gestrichenen Druckträgern werden bekanntlich Streichmassen verwendet, die im wesentlichen aus einem in Wasser mit Hilfe eines Dispergiermittels suspendierten Pigments, z. B. Kaolin, Satinweiß öder Calciumcarbonat und Bindemitteln bestehen. Während früher als Bindemittel hochmolekulare Naturprodukte wie Stärke oder Casein verwendet wurden, versucht man heute, zur Erzeugung hochwertiger gegestrichener Druckträger mehr und mehr diese natürlichen Bindemittel wegen ihrer Nachteile, daß sie nicht immer in gleicher Qualität anfallen, oftmals eine störende Färbung aufweisen, empfindlich gegen den Befall durch Mikroorganismen sind, durch aufwendige Verfahren aufgeschlossen werden müssen und spröde Striche ergeben, durch synthetische hochmolekulare Bindemittel auf Basis von Copolymeren aus Acrylsäureestern,Styrol, Butadien und ungesättigten Carbonsäureestern in Form wäßriger Dispersionen zu ersetzen. Obwohl die synthetischen hochmolekularen Bindemittel die geschilderten Nachteile der natürlichen Polymeren nicht aufweisen, sind sie dennoch wegen der weiter steigenden Anforderungen an die Qualität des bedruckten Papiers noch verbesserungsbedürftig.For the production of coated flat substrates, in particular coated printing substrates, coating slips are known to be used which essentially consist of a pigment suspended in water with the aid of a dispersant, e.g. B. kaolin, satin white or calcium carbonate and binders. While previously high molecular weight natural products such as starch or casein were used as binders, attempts are being made today to produce high-quality coated printing media more and more these natural binders because of their disadvantages that they are not always of the same quality, often have an annoying color, sensitive to the Infestation by microorganisms, which have to be disrupted by complex processes and produce brittle lines, are to be replaced by synthetic high-molecular binders based on copolymers of acrylic acid esters, styrene, butadiene and unsaturated carboxylic acid esters in the form of aqueous dispersions. Although the synthetic high-molecular-weight binders do not have the disadvantages described for natural polymers, they are still in need of improvement because of the ever increasing demands on the quality of the printed paper.

Verbesserungen in dieser .Hinsicht erreicht man z. B. durch die Zugabe von sogenannten "Cobindern" auf der Basis von Polymeren spezieller Acrylester. Cobinder steuern (nach G. Hirsch, Das Papier 32 (10A), 1978, 66-72) vor allem die Viskosität und Wasserretention von Streichfarben, verbessern einzelne Stricheigenschaften wie Rupffestigkeiten oder Druckfarbenaufnahme und besitzen vor allem eine ausgezeichnete Aktivatorwirkung für optische Aufheller.Improvements in this regard can be achieved e.g. B. by the addition of so-called "cobinder" based on polymers of special acrylic esters. Cobinder controls (according to G. Hirsch, Das Papier 32 (10A), 1978, 66-72) above all the viscosity and water retention of coating colors, improve individual coating properties such as pick resistance or Ink absorption and above all have an excellent activator effect for optical brighteners.

In der Praxis werden als Cobinder halbsynthetische, wasserlösliche Polymere wie beispielsweise das Natriumsalz der Carboxymethylcellulose und vollsynthetische Polymere wie beispielsweise Mischpolymerisate aus Vinylacetat und Acrylamid (DE-A-2450039), und Copolymerisate ungesättigter Säureamide mit Vinyl- oder Allylalkohol (DE-A-2933765 & CA 1163395) eingesetzt. Verwendung als Cobinder finden auch acrylesterhaltige Polymerisate , die als saure wäßrige Dispersionen der Streichfarbe zugesetzt werden und ihre Wirkung erst bei der Alkalistellung entfalten (siehe G. Hirsch, Das Papier 32 (10 A1), 1978, 66-72).In practice, semi-synthetic, water-soluble polymers such as the sodium salt of carboxymethyl cellulose and fully synthetic polymers such as copolymers of vinyl acetate and acrylamide (DE-A-2450039) and copolymers of unsaturated acid amides with vinyl or allyl alcohol (DE-A-2933765 & CA 1163395) is used. Polymers containing acrylic esters are also used as cobinders, which are added to the coating color as acidic aqueous dispersions and only develop their effect when the alkali is in place (see G. Hirsch, Das Papier 32 (10 A1), 1978, 66-72).

Besondere Bedeutung aber auf dem Gebiet der Cobinder kommt der Verbindungsklasse der Polyvinylalkohole zu. Polyvinylalkohole stellen nicht nur hervorragende Bindemittel für Pigmente dar, sondern übertreffen vor allem in ihren Trägereigenschaften für optische Aufheller alle vorgenannten Cobindersysteme (siehe H.G.'-.Oesterlin, Das Papier 36, 1982, 66-72, 121-126, 170-175). Nach ihrem Hydrolysegrad unterscheidet man bei den Polyvinylalkoholen (PVAL) sogenannte vollverseifte Typen (Hydrolysegrad 98-100 mol%) und teilverseifte Typen mit Hydrolysegraden von 70-90 mol%. In der Papierstreicherei werden nach umfangreichen Untersuchungen (H.G. Oesterlin, Das Papier 32 (10 A), 1978, V 13-19) vollverseifte Typen, die praktisch auch nur als Cobinder Verwendung finden, eindeutig bevorzugt. Die Viskositäten der in der Praxis eingesetzten vollverseiften Polyvinylalkoholtypen liegen, gemessen als 4%ige wäßrige Lösungen(Höppler- viskosität), bei 4-10 mPas, was mittleren Molekulargewichten von ca. 20.000 - 50.000 entspricht.However, the compound class of polyvinyl alcohols is of particular importance in the field of cobinders. Polyvinyl alcohols are not only excellent binders for pigments, but above all their carrier properties for optical brighteners exceed all of the above-mentioned cobinder systems (see H.G.'-. Oesterlin, Das Papier 36, 1982, 66-72, 121-126, 170-175). According to their degree of hydrolysis, a distinction is made between polyvinyl alcohols (PVAL) so-called fully saponified types (degree of hydrolysis 98-100 mol%) and partially saponified types with degrees of hydrolysis of 70-90 mol%. In the paper coating shop, after extensive investigations (H.G. Oesterlin, Das Papier 32 (10 A), 1978, V 13-19), fully saponified types, which are also used practically only as cobinders, are clearly preferred. The viscosities of the fully saponified polyvinyl alcohol types used in practice, measured as 4% aqueous solutions (Höppler viscosity), are 4-10 mPas, which corresponds to average molecular weights of approx. 20,000 - 50,000.

Wegen ihrer hervorragenden Pigmentbindekraft und Trägerwirkung für optische Aufheller nimmt man 2 gravierende Nachteile dieser Cobinder bei der technischen Applikation in der Praxis in Kauf.Because of their excellent pigment binding power and carrier effect for optical brighteners, 2 serious ones are used Disadvantages of these Cobinder in the technical application in practice in purchase.

Vollverseifte Polyvinylalkohole sind praktisch bei Raumtemperatur in Wasser unlöslich. Zur Überführung in eine wäßrige Lösung muß eine Polyvinylalkohol-Suspension längere Zeit intensiv bei mindestens 90° C gerührt werden, was den Papierherstellungsprozeß letzten Endes"durch Vorhaltung von Lösestationen und zusätzliche Energiekosten belastet. Der zweite Nachteil ist mit dem Begriff "Pigmentschock" verknüpft. Bei Zugabe der Polyvinylalkohollösung zur Pigmentslurry kommt es momentan zu einem starken Viskositätsanstieg der Streichmassen, der nur durch geeigneteRührmischwerke, die sehr hohe Scherkräfte aufbringen, rasch abgebaut werden kann oder durch Zugabe von zusätzlichen Hilfsstoffen, den sogenannten "Antischockmitteln".Fully hydrolyzed polyvinyl alcohols are practically insoluble in water at room temperature. In order to convert it into an aqueous solution, a polyvinyl alcohol suspension has to be stirred intensively for a long time at at least 90 ° C., which in the end places a burden on the paper production process "by providing dissolving stations and additional energy costs. The second disadvantage is linked to the term" pigment shock " When the polyvinyl alcohol solution is added to the pigment slurry, there is currently a sharp increase in the viscosity of the coating slips, which can only be rapidly degraded by using suitable agitating mixers which apply very high shear forces or by adding additional auxiliaries, the so-called "anti-shock agents".

Es bestand daher die Aufgabe, bei der Herstellung gestrichener flächiger Gebilde, z. B. von Druckträgern, insbesondere gestrichener Papiere, Pappen und/oder Kartone,Wege zu finden, die vorstehend beschriebenen Schwierigkeiten und Nachteile zu vermeiden, ohne die Vorteile der bisherigen Massen aufs Spiel zu setzen.It was therefore the task in the manufacture of coated flat structures, for. B. of print media, especially coated paper, cardboard and / or cardboard, to find ways to avoid the difficulties and disadvantages described above, without jeopardizing the advantages of the previous masses.

Überraschenderweise wurde nun gefunden, daß diese Aufgabe gelöst werden kann, wenn als Cobinder polyhydroxylgruppenhaltige Polymere eingesetzt werden, die aus

  • a) 50 - 95 Gew.% Vinylalkoholeinheiten,
  • b) 5 - 50 Gew.% Einheiten von 1-Alkylvinylalkoholen mit Cl-bis C4-Alkylgruppen, insbesondere Methylgruppen,
  • c) 0 - 20 Gew.% Vinylacylateinheiten, vorzugsweise Vinyl-C1- bis-C20-acylateinheiten,
  • d) 0 - 20 Gew.% Allylalkoholeinheiten und
  • e) 0 - 5 Gew.% weiteren einpolymerisierten Einheiten bestehen und die vorzugsweise ein mittleres vorzugsweise viskosimetrisch bestimmtes Molekulargewicht von 20.000 - 100.000 aufweisen.
Surprisingly, it has now been found that this object can be achieved if, as cobinder, polyhydroxyl-containing polymers are used which consist of
  • a) 50-95% by weight of vinyl alcohol units,
  • b) 5-50% by weight of units of 1-alkylvinyl alcohols with C 1 -C 4 -alkyl groups, in particular methyl groups,
  • c) 0-20% by weight of vinyl acylate units, preferably vinyl C 1 -C 20 -acylate units,
  • d) 0-20% by weight of allyl alcohol units and
  • e) 0 - 5% by weight of further polymerized units exist and which preferably have an average preferably viscosimetrically determined molecular weight of 20,000-100,000.

Vorzugsweise bestehen die Polymeren aus 60 - 95 Gew.%, insbesondere 70 - 95 Gew.% Einheiten a, 5 - 40 Gew.%, insbesondere 5 - 20 Gew.% Einheiten b, sowie je 0 - 10 Gew.%, insbesondere je 0 - 5 Gew.% Einheiten c und d. Gemäß einer besonders bevorzugten Ausführungsform liegt die Menge der Comonomereinheiten b - e im Bereich 5 bis 20. Gew.%, insbesondere 7,5 - 10 Gew.%, wobei die Mengen der Vinylacylat-Einheiten besonders vorzugsweise möglichst gering ist, d. h. bei z. B. 0 - 2 Gew.% liegt. Auch die Menge der Einheiten e liegt vorzugsweise bei 0 - 1 Gew.%, insbesondere noch in der unteren Hälfte dieses Bereiches, z.B. sogar unter 0,2 Gew.%. Die genannten erfindungsgemäß verwendeten Polymeren zeichnen sich nicht nur durch die bessere Vermischbarkeit ihrer Lösungen mit dem Pigmentslurry aus, wobei der Pigmentschock, verglichen mit dem bei Zugabe von Lösungen von in Viskosität und Hydrolysegrad vergleichbaren Polyvinylalkoholen, deutlich vermindert ist, sofern er überhaupt noch auftritt, sondern überraschenderweise auch dadurch, daß sie in Substanz ohne vorherige Auflösung oder Verdünnung direkt in Pigmentsuspensionen eingerührt werden können.The polymers preferably consist of 60-95% by weight, in particular 70-95% by weight, units a, 5-40% by weight, in particular 5-20% by weight of units b, and 0-10% by weight, in particular each 0 - 5 wt% units c and d. According to a particularly preferred embodiment, the amount of the comonomer units b - e is in the range from 5 to 20% by weight, in particular 7.5 to 10% by weight, the amounts of the vinyl acylate units being particularly preferably as small as possible, i.e. H. at z. B. 0-2% by weight. The amount of units e is also preferably 0-1% by weight, in particular still in the lower half of this range, e.g. even below 0.2% by weight. The polymers mentioned according to the invention are not only distinguished by the better miscibility of their solutions with the pigment slurry, the pigment shock being significantly reduced, if it still occurs, compared to the addition of solutions of polyvinyl alcohols comparable in viscosity and degree of hydrolysis Surprisingly also in that they can be stirred directly into pigment suspensions in bulk without prior dissolution or dilution.

Ferner weisen die erfindungsgemäß verwendeten Polymeren neben ihren ausgezeichneten Trägereigenschaften für optische Aufheller ein stärkeres Pigmentbindevermögen und höhere Wasserretentionswerte als vergleichbare technisch eingesetzte vollverseifte Polyvinylalkohole auf, was ihren Einsatzbereich als Cobinder erweitert.Furthermore, in addition to their excellent carrier properties for optical brighteners, the polymers used according to the invention have a stronger pigment binding capacity and higher water retention values than comparable, technically used, fully hydrolyzed polyvinyl alcohols, which expands their field of use as cobinder.

In der Praxis tritt bei den heute üblichen schnellaufenden Auftragsapparaturen bei Verwendung bisher bekannter Streichmassen das Problem der Dilatanz auf. Dieser Dilatanzstreifen wird bei der Verwendung der erfindungsgemäßen Cobinder nicht gebildet; es wird damit ein gleichmäßigerer Auftrag der Streichmasse erhalten.In practice, the problem of dilatancy arises with today's high-speed application equipment when using previously known coating slips. This dilatancy strip is not formed when using the cobinder according to the invention; a more even application of the coating slip is thus obtained.

Als Alkylgruppe in den Einheiten b wird der Methylrest bevorzugt; es können aber auch verzweigte und unverzweigte C2bis C 4-Alkylgruppen eingesetzt werden.The methyl radical is preferred as the alkyl group in units b; however, branched and unbranched C 2 to C 4 alkyl groups can also be used.

Die Polymeren, die bisher schon als Schutzkolloid für die Radikalpolymerisation (DE-C-1026074, cf. Chem. Abstr. 54 , 16024 h) oder als Grundmaterial zur Herstellung von Formkörpern (Chem. Abstr. 87, 118 700c) oder auch im Gemisch mit Glycerin als wasserlöslicher Heißklebstoff (Chem. Abstr. 91, 176392 x) beschrieben worden sind, können in einem zweistufigen Verfahren hergestellt werden, in erster Stufe durch Copolymerisation von Vinylacylat, insbesondere Vinylacetat und/oder Vinylpropionat, mit 1-Alkylvinylacylat, insbesondere Isopropenylacetat und/oder -propionat, sowie ggf. Allylacylat, insbesondere Allylacetat und/oder -propionat in üblicher Weise durch radikalische Suspensions- oder Emulsionspolymerisation in Wasser oder durch radikalische Polymerisation in Substanz oder in einem geeigneten organischen Lösungs- mittel wie z. B. Alkoholen oder Estern. Als Beispiele hierfür seien genannt: Methanol, Ethanol, Isopropanol, Methyl-, Ethyl-, Isopropyl- und Butylacetat. In zweiter Stufe wird das so erhaltene Copolymerisat entsprechend den bei der Herstellung von Polyvinylalkoholen, bzw. von (teil-)verseiften Polyvinylestern bekannten Verfahren im Alkalischen oder Sauren unter Zugabe von Solvolyse- bzw. Hydrolysekatalysator oder von stöchiometrischen Mengen entsprechender Reaktionspartner, z. B. von Metallhydroxiden, vorzugsweise möglichst vollständig solvolysiert oder hydrolysiert, z. B. durch Umesterung der Acylatreste der Polymeren.The polymers, which have hitherto been used as protective colloids for radical polymerization (DE-C-1026074, cf. Chem. Abstr. 54, 16024 h) or as base material for the production of moldings (Chem. Abstr. 87, 118 700c) or in a mixture with glycerol as a water-soluble hot melt adhesive (Chem. Abstr. 91, 176392 x) can be prepared in a two-stage process, in the first stage by copolymerization of vinyl acylate, in particular vinyl acetate and / or vinyl propionate, with 1-alkyl vinyl acylate, in particular isopropenyl acetate and / or -propionate, and optionally allyl acylate, in particular allyl acetate and / or -propionate in the usual manner by radical suspension or emulsion polymerization in water or by radical polymerization in bulk or in a suitable organic solvent - such as. B. alcohols or esters. Examples include: methanol, ethanol, isopropanol, methyl, ethyl, isopropyl and butyl acetate. In a second stage, the copolymer obtained in accordance with the processes known in the preparation of polyvinyl alcohols or (partially) saponified polyvinyl esters in alkaline or acidic form with the addition of solvolysis or hydrolysis catalyst or of stoichiometric amounts of corresponding reactants, e.g. B. of metal hydroxides, preferably as completely as possible solvolysed or hydrolyzed, e.g. B. by transesterification of the acylate residues of the polymers.

Die Einstellung der Molekulargewichte kann in üblicher Weise durch Variation von Initiatorkonzentrationen, Temperatur und Zusatz von Polymerisationsreglern wie beispielsweise Bromtrichlormethan und Thioessigsäure bei der Polymerisation erfolgen. Höhere Molekulargewichte können auch durch Zugabe von geringen Mengen mehrfach ethylenisch ungesättigter Verbindungen wie Divinyladipat und Allylmethacrylat eingestellt werden. Die erfindungsgemäßen Verbindungen mit ihrer Anwendung als Cobinder weisen bevorzugt Höpplerviskositäten von 3-20, inbesondere 4 bis 12 mPas (gemessen als 4%ige wäßrige Lösung) auf.The molecular weights can be adjusted in the customary manner by varying the initiator concentrations, temperature and addition of polymerization regulators such as, for example, bromotrichloromethane and thioacetic acid during the polymerization. Higher molecular weights can also be set by adding small amounts of polyethylenically unsaturated compounds such as divinyl adipate and allyl methacrylate. The compounds according to the invention with their use as cobinders preferably have Höppler viscosities of 3-20, in particular 4 to 12 mPas (measured as a 4% strength aqueous solution).

Eine weitere Möglichkeit, die erfindungsgemäß verwendeten Polymeren zu variieren, bietet der Einbau (die Einpolymerisa- tion)von Einheiten, die sich von Vinylestern erhöhter Hydrophobie ableiten, also z. B. von den Vinylfettsäureestern, z. B. Vinylstearat und/oder Vinyllaurat und/oder von Versatic(R) säurevinylestern (VeoVa (R) , Esternvon durch die sogenannte Koch-Synthese hergestellten verzweigten Carbonsäuren mit meist 10 bis 20 C-Atomen, Shell AG). Diese Einheiten erhöhen z. B. die grenzflächenaktive Wirkung der Polymeren. Sie sind vorzugsweise in Mengen von 0 - 1, insbesondere 0 - 0,5 Gew.%, bezogen auf die Gesamtmenge der Monomer-Einheiten, einpolymerisiert. Des weiteren kann auch z.B: Ethylen einpolymerisiert werden in Mengen von 0-5, insbesondere 0-1 Gew.%, Ethyleneinheiten.Another possibility of varying the polymers used according to the invention is the incorporation (copolymerization) of units which are derived from vinyl esters of increased hydrophobicity, that is to say, for. B. of the vinyl fatty acid esters, e.g. B. vinyl stearate and / or vinyl laurate and / or from Versatic (R) acid vinyl esters (VeoVa ( R ), esters of branched carboxylic acids produced by the so-called Koch synthesis with mostly 10 to 20 carbon atoms, Shell AG). These units increase e.g. B. the surface-active effect of the polymers. They are preferably polymerized in amounts of 0-1, in particular 0-0.5,% by weight, based on the total amount of the monomer units. Furthermore, ethylene, for example, can also be polymerized in amounts of 0-5, in particular 0-1,% by weight of ethylene units.

Die Herstellung und Zusammensetzung von Streichmassen für flächige Substrate, insbesondere für gestrichene Druckträger, zu denen insbesondere Papiere, Pappen und Kartone zu zählen sind, sind im Prinzip bekannt. Es sei nur beispielsweise auf die DE-A-2933765 und die DE-A-2450039 verwiesen.The production and composition of coating slips for flat substrates, in particular for coated printing substrates, which include paper, cardboard and cardboard in particular, are known in principle. Reference is only made, for example, to DE-A-2933765 and DE-A-2450039.

Das erfindungsgemäß verwendete Polymere kann als Cobinder in bekannten Streichmassen in üblichen Mengen eingesetzt werden und die dort ggf. eingesetzten Cobinder zumindest teilweise, vorzugsweise zur Gänze ersetzen, z. B. das Polymerisat B der DE-A-2933765 oder das Copolymere des Acrylamids der DE-A-2450039.The polymer used according to the invention can be used as a cobinder in known coating compositions in customary amounts and can at least partially, preferably entirely, replace the cobinder used there, e.g. B. the polymer B of DE-A-2933765 or the copolymer of acrylamide of DE-A-2450039.

Zur Straffung der vorliegenden Anmeldung wird hinsichtlich der übrigen Komponenten solcher Streichmassen auf die genannten beiden DE-Offenlegungsschriften ausdrücklich Bezug genommen.In order to streamline the present application, reference is expressly made to the two DE published documents mentioned with regard to the other components of such coating slips.

In den folgenden Beispielen und Vergleichsversuchen, die der weiteren Erläuterung der Erfindung dienen sollen, verstehen sich Mengenangaben stets als Gewichtsangaben, soweit nichts anderes angegeben ist. %-Angaben addieren sich stets zu 100 % (gilt für die gesamte Offenbarung).In the following examples and comparative experiments, which are intended to further explain the invention, quantities are always to be understood as weights unless otherwise stated. % Figures always add up to 100% (applies to the entire disclosure).

In diesen Beispielen und Vergleichsversuchen wurden folgende in Tabelle 1 charakterisierte Cobinder eingesetzt. Deren Zusammensetzung ergibt sich wie folgt:

  • Copolymere aus (A) Vinylacetat, (B) Isopropenylacetat und ggf. (C) Allylacetat wurden gemäß der Angabe der Verseifungszahl, bzw. des Solvolysegrades solvolysiert und zeigten danach die angegebene Viskosität und den angegebenen K-Wert. Die Vergleichsproben sind handelsübliche "vollverseifte" Polyvinylalkohole. Die Eigenschaften wurden nach folgenden Meßvorschriften bestimmt:
    • 1) Auslaufviskosität mit einem Kugelfall-Viskosimeter nach Höppler (DIN 53015) als 4 Gew.%ige wäßrige Lösung bei 20° C; n.b. = nicht bestimmt
    • 2) K-Wert nach Fikentscher, Cellulosechemie 13, 58 (1932)
    • 3) Verseifungszahl nach DIN 53401
The following cobinders characterized in Table 1 were used in these examples and comparative experiments. Their composition is as follows:
  • Copolymers of (A) vinyl acetate, (B) isopropenylacetate and optionally (C) allyl acetate were solvolysed in accordance with the specification of the saponification number or the degree of solvolysis and then showed the stated viscosity and the stated K value. The comparison samples are commercially available "fully hydrolyzed" polyvinyl alcohols. The properties were determined according to the following measurement regulations:
    • 1) discharge viscosity with a falling ball viscometer according to Höppler (DIN 53015) as a 4% by weight aqueous solution at 20 ° C .; nb = not determined
    • 2) K value according to Fikentscher, Cellulosechemie 13, 58 (1932)
    • 3) Saponification number according to DIN 53401

Beispiel 1example 1

Viskositätsverhalten beim Einrühren der erfindungsgemäßen Cobinder im Vergleich zu den Vergleichsprodukten in Kaolin-Slurries'. Zugabe als Feststoff.Viscosity behavior on stirring the co-binders according to the invention compared to the comparative products in kaolin slurries'. Add as a solid.

In eine wäßrige Lösung von 0,25 Teilen Natriumpolyacrylat und 0,1 Teilen Natronlauge wurden mit Hilfe eines Schnellrührers 99 Teile China-Clay eingerührt und zu einer homogenen Suspension dispergiert. Bei 1000 U/min des Rührers wurden anschließend jeweils 1 Teil Cobinder portionsweise eingetragen und nach 30 min. die Brookfieldviskositäten gemessen. Die Wassermenge wurde so bemessen, daß ein Gesamtfestgehalt der Pigment-Suspension von 60 % resultierte.99 parts of china clay were stirred into an aqueous solution of 0.25 part of sodium polyacrylate and 0.1 part of sodium hydroxide solution using a high-speed stirrer and dispersed to form a homogeneous suspension. At 1000 rpm of the stirrer, 1 part of cobinder was then added in portions and after 30 min. the Brookfield viscosities measured. The amount of water was measured so that a total solids content of the pigment suspension of 60% resulted.

Die Ergebnisse sind in Tabelle 2 dargestellt. Dabei stellt der erste Wert jeweils das Ergebnis bei 10 U/min., der zweite Wert jeweils das Ergebnis bei 100 U/min dar. Die herkömmlichen Polyvinylalkohole wirken dabei praktisch nur wie ein weiterer Füllstoff.

Figure imgb0001
The results are shown in Table 2. The first value represents the result at 10 rpm, the second value represents the result at 100 rpm Lichen polyvinyl alcohols practically only act as another filler.
Figure imgb0001

Beispiel 2:Example 2:

"Schockverhalten" beim Einrühren eines erfindungsgemäß verwendeten Cobinders in eine Kaolin-Pigment-Suspension im Vergleich zu einem PVAL."Shock behavior" when stirring a cobinder used according to the invention into a kaolin pigment suspension compared to a PVAL.

In eine wäßrige Lösung von 0,25 Teilen Natriumpolyacrylat und 0,1 Teilen Natronlauge wurden mit Hilfe eines Schnellrührers 99 Teile China-Clay eingerührt und zu einer homogenen Suspension dispergiert. Bei 100 U/min des Rührers wurde 1 Teil Polyvinylalkohol bzw. Cobinder als 10 %ige Lösung zugegeben und die Leistungsaufnahme des Rührers zeitabhängig gemessen. Die Wassermenge wurde so bemessen, daß ein Gesamtfestgehalt der Pigmentsuspension von 60 % resultierte.

Figure imgb0002
Figure imgb0003
 99 parts of china clay were stirred into an aqueous solution of 0.25 part of sodium polyacrylate and 0.1 part of sodium hydroxide solution using a high-speed stirrer and dispersed to form a homogeneous suspension. At 100 rpm of the stirrer, 1 part of polyvinyl alcohol or cobinder was added as a 10% solution and the power consumption of the stirrer was measured as a function of time. The amount of water was measured so that a total solids content of the pigment suspension of 60% resulted.
Figure imgb0002
Figure imgb0003

Beispiel 3:Example 3:

Es wurde eine Papierstreichfarbe mit folgender Zusammensetzung (FG 61 %) hergestellt und das Wasserretentionsvermögen nach der Venema-Methode6)gemessen.

Figure imgb0005
Figure imgb0006
 A paper coating slip with the following composition (FG 61%) was produced and the water retention capacity was measured using the Venema method 6) .
Figure imgb0005
Figure imgb0006

Beispiel 4:Example 4:

Es wurden Papierstreichfarben mit folqender Zusammensetzung hergestellt:

Figure imgb0007
Paper coating colors with the following composition were produced:
Figure imgb0007

Die Streichfarben wurden auf einer Versuchsstreichanlage mittels eines Schaber-Auftragswerkes bei einer Geschwindigkeit von 100 m/min auf ein holzhaltiges Rohpapier mit einem 2 Flächengewicht von ca. 35 g/m einseitig aufgestrichen. Das 2 Auftragsgewicht betrug 10,3 g/m . Anschließend wurden die ge- strichenen Papiere über einen 2-Walzen-Laborkalender satiniert und der Weißgrad mit Hilfe eines Remissionsphotometers (Fa. Zeiss) mit den Filtern R 457 (+UV) und R 400 (-UV) gemessen.

Figure imgb0008
The coating colors were spread on one side on a test coating system by means of a scraper applicator at a speed of 100 m / min onto a wood-containing base paper with a basis weight of approx. 35 g / m. The 2 application weight was 10.3 g / m. Underlined papers on a 2-roll laboratory calendar sati - then ge were and the degree of whiteness was measured using a reflectance photometer (from Zeiss) with the filters R 457 (+ UV) and R 400 (-UV).
Figure imgb0008

Claims (1)

Verwendung polyhydroxylgruppenhaltiger Polymeren aus a) 50 - 95 Gew.% Vinylalkoholeinheiten, b) 5 - 50 Gew.% Einheiten von 1-Alkylvinylalkoholen mit C1-bis C4-Alkylgruppen, c) 0 - 20 Gew.% Vinylacylateinheiten, d) 0 - 20 Gew.% Allylalkoholeinheiten und e) 0 - 5 Gew.% weiteren einpolymerisierten Einheiten als Cobinder in Streichmassen für flächige Substrate, insbesondere Papiere, Pappen und Kartone. Use of polyhydroxyl group-containing polymers a) 50-95% by weight of vinyl alcohol units, b) 5-50% by weight units of 1-alkylvinyl alcohols with C 1 to C 4 alkyl groups, c) 0-20% by weight of vinyl acylate units, d) 0-20% by weight of allyl alcohol units and e) 0 - 5% by weight of further polymerized units as cobinder in coating slips for flat substrates, in particular papers, cardboards and cardboard boxes.
EP87109835A 1986-07-08 1987-07-08 Co-binder for coating compositions Expired - Lifetime EP0253285B1 (en)

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AT87109835T ATE56767T1 (en) 1986-07-08 1987-07-08 COBINDER FOR COATING COMPOUNDS.

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WO2012080007A1 (en) * 2010-12-17 2012-06-21 Wacker Chemie Ag Paper coating slips comprising a combination of styrene-butadiene copolymer and/or styrene-acrylic ester copolymer and vinyl acetate-ethylene copolymer
CN104628930A (en) * 2015-02-15 2015-05-20 北京工业大学 Method for synthesizing cement dispersing agent by copolymerization of fatty acid vinyl ester monomers

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CA2110448A1 (en) * 1992-12-08 1994-06-09 Helen H.Y. Pak-Harvey Redispersible acrylic polymer powder for cementitious compositions
DE19641064A1 (en) * 1996-10-04 1998-04-09 Wacker Chemie Gmbh Modified polyvinyl butyrals with low solution viscosity
ATE321079T1 (en) 1999-12-21 2006-04-15 Omnova Solutions Inc POLYVINYL ALCOHOL COPOLYMER COMPOSITION
DE10232666A1 (en) * 2002-07-18 2004-02-05 Wacker Polymer Systems Gmbh & Co. Kg Polyvinyl alcohol containing silane for paper coating slips
DE10323203A1 (en) * 2003-05-22 2004-12-23 Wacker Polymer Systems Gmbh & Co. Kg Use of silane-functional polyvinyl alcohols in primers for release papers and films
DE10323204A1 (en) * 2003-05-22 2004-12-16 Wacker Polymer Systems Gmbh & Co. Kg Primer for release papers and films
CA2547469A1 (en) * 2003-12-09 2005-06-23 Celanese International Corporation Optical brightener and method of preparing it
US20060058486A1 (en) * 2004-09-16 2006-03-16 Wacker-Chemie Gmbh Alkenyl-functional organopolysiloxanes
EP1712677A1 (en) * 2005-04-08 2006-10-18 Clariant International Ltd. Aqueous solutions of optical brighteners
CN104053719B (en) 2011-11-18 2018-07-20 国际人造丝公司 Polymer emulsion blend and its application
TWI637969B (en) * 2013-12-26 2018-10-11 可樂麗股份有限公司 Modified polyvinyl alcohol and production method thereof

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DE1913667A1 (en) * 1968-03-18 1969-09-25 Denki Kagaku Kogyo Kk Pigment binder for paper coating slips

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WO2012080007A1 (en) * 2010-12-17 2012-06-21 Wacker Chemie Ag Paper coating slips comprising a combination of styrene-butadiene copolymer and/or styrene-acrylic ester copolymer and vinyl acetate-ethylene copolymer
CN104628930A (en) * 2015-02-15 2015-05-20 北京工业大学 Method for synthesizing cement dispersing agent by copolymerization of fatty acid vinyl ester monomers
CN104628930B (en) * 2015-02-15 2016-08-24 北京工业大学 Fatty acid vinyl ester monomer copolymerization is synthesized the method for cement dispersants

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