EP0545180B1 - Neutralization composition for effectively and gently deacidifying books and other paper articles - Google Patents

Neutralization composition for effectively and gently deacidifying books and other paper articles Download PDF

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Publication number
EP0545180B1
EP0545180B1 EP92119850A EP92119850A EP0545180B1 EP 0545180 B1 EP0545180 B1 EP 0545180B1 EP 92119850 A EP92119850 A EP 92119850A EP 92119850 A EP92119850 A EP 92119850A EP 0545180 B1 EP0545180 B1 EP 0545180B1
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Prior art keywords
paper
alkoxide
metals
neutralizing agent
books
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EP92119850A
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German (de)
French (fr)
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EP0545180A1 (en
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Jürgen Dr. Wittekind
Rolf Eggersdorfer
Peter Schwerdt
Karl-Heinz Scherer
Rolf-Erhard Dr. Schmitt
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Zfb Zentrum Fur Bucherhaltung GmbH
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Battelle Ingenieurtechnik GmbH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0063—Preservation or restoration of currency, books or archival material, e.g. by deacidifying
    • 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
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/18—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00 of old paper as in books, documents, e.g. restoring

Definitions

  • the present invention relates to neutralizing agents for the effective and gentle mass deacidification of books and other printed and paper products of all kinds, such as e.g. Magazines or files.
  • Alkaline earth metals form very stable salts with the acids in the paper, which ensure reliable preservation, and as an alkaline reserve in the paper give pH values of around 8-9, which are beneficial to the paper and do not cause any alkaline damage.
  • a known method for deacidifying archive material (US Pat. No. 3,969,549) is to treat the books with vapors of metal alkyls, in particular with vapors of diethyl zinc. Due to the moisture in the paper, the metal alkyls are converted into the oxides of the metals, e.g. converted into zinc oxide, which remains in the paper and is a good neutralizing agent for free acids.
  • the metal alkyls suitable for this purpose are self-igniting substances in the air, which represent a constant fire and explosion hazard during handling and therefore require an extremely high level of care and appropriate qualifications.
  • the Wei T'O process therefore uses book-compatible solvents such as chlorofluorocarbons, the solubility of methyl magnesium carbonate being achieved by adding 10-20% low-boiling alcohols such as methanol or ethanol. Practice shows, however, that this alcohol addition can already be sufficient for inks and stamp inks to wash out and rub off on the neighboring sides.
  • the present invention has for its object to provide neutralizing agents that avoid the disadvantages of the known methods and allow effective, gentle and rational deacidification of archive material, in particular without the risk of damage to printing ink, glue or paper, and without after treatment in Paper of remaining interfering substances.
  • alkoxides and in particular mixtures of alkoxides have continued to be used for about twenty years (WO-A-90/03466 and US-A-3 676 182), whereby the solubility in organic solvents is achieved that at least one of the metal valences is occupied with polyhydric alcohols and / or with ethers of polyhydric alcohols or with amino compounds.
  • these substances remain in the paper due to their relatively high boiling point.
  • the short-chain monohydric alcohols possible in the invention for the formation of the double alkoxides are volatile and do not have this disadvantage.
  • the hydroxyl hydrogen of an alcohol is replaced by a metal
  • the double alkoxides according to the invention are salts, e.g. from Mg or Ca alkoxide with the acid-reacting esters of orthotitanic acid or orthozirconic acid.
  • MeI is particularly advantageously formed from the metals titanium and zirconium, while the metals magnesium and calcium are particularly advantageously substituted for MeII.
  • the OR groups can be formed from alcohols of different types, for example (mono- or polyhydric alcohols with 1 to 5 carbon atoms). However, monohydric alcohols having 1 to 5, preferably 2 to 4, carbon atoms which are readily volatile are preferably used according to the invention.
  • Double alkoxides e.g. Titanium and zirconium have so far been used as catalysts in organic chemistry. The fact that they are outstandingly suitable for the mass deacidification of paper has not yet been recognized.
  • the metal MeII takes over in the form of an alkaline earth metal (for example calcium, magnesium) or alkali metal (for example potassium or sodium) by reaction with the moisture in the paper and the formation of oxides or hydroxides (for example calcium or magnesium oxides and hydroxides) the neutralization of free acids and the formation of an alkaline reserve, while the Metal MeI (preferably titanium or zirconium) causes the good solubility of these compounds.
  • an alkaline earth metal for example calcium, magnesium
  • alkali metal for example potassium or sodium
  • alkaline earth metals An advantage of the alkaline earth metals is that the hydroxides are only moderately alkaline, so that alkaline damage to the paper is avoided.
  • the alkoxide component of the metal components MeI (preferably titanium or zirconium) is also hydrolyzed to the hydroxides of these metals in contact with the paper moisture. However, these hydroxides are very quickly converted into the respective oxides, which due to their chemical inertness are irrelevant for the neutralization.
  • double alkoxides mentioned are used as a solution in a siloxane, for example hexamethyldisiloxane as a solvent which contains, for example, 0.1-0.5% by weight of magnesium or calcium.
  • solubilizer e.g. alcohol
  • the use of the neutralizing agents according to the invention can be carried out using processes known per se for deacidification, in particular for the mass deacidification of archive materials, e.g. with the method specified in DE-A-3904 111. It is generally advantageous to dry the archival material, which will have a storage moisture content of around 5-10% by weight, in a predrying step to a residual moisture content of around 0.5% by weight. The degree of this predrying provides a good opportunity to regulate the amount of neutralizing metal oxides installed in the paper, with a greater amount of oxide precipitating out of the solution and becoming anchored in the paper with increasing moisture.
  • Titanium tetrabutylateMagnesium diethylate Ti (O4H9) 4 ⁇ Mg (OC2H5) 2 dissolved in 950 g Hexamethyldisiloxane Humidity pH before treatment pH after treatment * Alkaline buffer reserve (calculated weight% MgCO3) Uncoated 0.5% by weight 4.5 7.6 0.82 Paper number I 4.7% by weight 4.5 8.8 1.79 Uncoated 0.5% by weight 4.2 8.5 0.79 Paper No. II 5.0% by weight 4.2 9.5 2.32 Uncoated 0.5% by weight 4.1 8.2 1.08 Paper No. III 5.0% by weight 4.1 8.9 1.77 Deleted 0.5% by weight 7.5 8.2 2.51 paper 5.0% by weight 7.5 8.3 2.99
  • alkaline buffer reserve was taken from the language of conservation practice and is calculated in wt.% MgCO3. The alkaline component was determined by titration and converted to magnesium carbonate.
  • Microwave heating was used for predrying to a residual moisture of 0.5% by weight.
  • the actual treatment was carried out in the form of vacuum drying in order to ensure a good and even soaking of the books.
  • the duration of exposure of the treatment solutions was then 10 minutes in each case.
  • the tables show, on the one hand, the successful binding of the acids by shifting the pH value (although the initial pH value of the coated paper is already higher due to the calcium carbonate component already present there by coating) and, on the other hand, that an adequate buffer reserve is anchored in the paper could.
  • the tables also show that this can be regulated over a wide range via the paper moisture.
  • hafnium can also be used, for example, which also acts as an ingredient which ensures sufficient solubility, but is somewhat more expensive than zirconium or titanium.
  • Aluminum and tin can also be used.
  • all alkaline earth metals or alkali metals can be used, the salts of which are able to form the acids neutralize in paper.
  • Strontium for example, can also be used as an alkaline earth metal component; Barium is less suitable because of its toxicity.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Neutralising agent for effective and gentle mass deacidification of books and other paper products, consisting of a solution of double alkoxides of one or more types each with an alkoxide of metals assisting the solubility, such as metals of subgroup IV, aluminium or tin, and an alkoxide of metals which bind the free acids in the paper, such as alkali metals or alkaline earth metals, it being possible to use a non-polar solvent, which is well compatible with the archive materials, for dissolution.

Description

Die vorliegende Erfindung betrifft Neutralisationsmittel zur wirkungsvollen und schonenden Massenentsäuerung von Büchern sowie anderen Druck- und Papiererzeugnissen aller Art, wie z.B. Zeitschriften oder Akten.The present invention relates to neutralizing agents for the effective and gentle mass deacidification of books and other printed and paper products of all kinds, such as e.g. Magazines or files.

Die bei allen Druck- und Papiererzeugnissen und insbesondere bei Büchern während der Lagerung auftretende Alterung führt vor allem durch Spuren von im Papier freigesetzten Säuren zu einer fortschreitenden Schädigung der Papiersubstanz. Werden keine Gegenmaßnahmen in Form einer Neutralisation dieser Säuren getroffen, so führt diese Schädigung nach einigen Jahrzehnten zu einem völligen Zerfall des Papiers. Zur Erhaltung von Archiv- und Bibliotheksbeständen von weltweit einigen hundert Millionen Büchern und anderen Archivalien ist es daher erforderlich, die Säuren im Papier zu neutralisieren und gleichzeitig im Papier eine hinreichende Menge einer Substanz zu verankern, die als alkalische Reserve auch zukünftig im Papier noch freigesetzte Säuren neutralisiert. In Anbetracht der sehr großen Büchermengen sind hierzu nur Verfahren geeignet, die die Behandlung der ganzen Bücher gestattet, d.h. Verfahren, bei denen es nicht notwendig ist, die Buchbindung zu öffnen und die Seiten einzeln zu behandeln. Gleiches gilt auch für Archivbestände aller Art, die ebenfalls eine Behandlung von gebundenen oder andersartig zusammengefaßten Papierseiten erfordern. Aus der Notwendigkeit, gebundene Archivalien zu behandeln, ergibt sich die sehr wichtige Anforderung, daß die Neutralisationsmittel und vor allem die zur Behandlung notwendigen Lösemittel in keiner Weise die Komponenten der Archivalien wie z.B. Leime und Klebemittel, Einbandmaterialien, Druck- und Stempelfarben sowie Tinten in irgendeiner Weise angreifen oder verändern. Da die Archivalien in gebundener Form behandelt werden, ist es unvermeidbar, daß die einzelnen Seiten während der Behandlung mehr oder weniger dicht aufeinander liegen. Aus diesem Grunde ist es besonders wichtig, daß Druckfarben, Stempelfarben und auch Tinten, mit denen z.B. Bücher in vielen Fällen signiert sind, in keiner Weise angelöst werden, damit ein Abfärben der Schrift auf die Nachbarseiten vermieden wird.The aging that occurs in all printed and paper products and especially in books during storage leads to progressive damage to the paper substance, in particular due to traces of acids released in the paper. If no countermeasures are taken in the form of neutralization of these acids, this damage leads to a complete decay of the paper after a few decades. To preserve archive and library holdings from a few hundred million books and other archive materials worldwide, it is therefore necessary to neutralize the acids in the paper and, at the same time, anchor a sufficient amount of a substance in the paper that will continue to be released in the paper as an alkaline reserve neutralized. In view of the very large volumes of books, only procedures which allow the treatment of the entire books are suitable for this, ie procedures in which it is not necessary to open the book binding and to treat the pages individually. The same applies to all types of archives that also require the treatment of bound or otherwise summarized paper pages. From the need to treat bound archives, there is the very important requirement that the neutralizing agents and especially those for treatment necessary solvents in no way attack or change the components of the archival documents such as glues and adhesives, cover materials, printing and stamping inks and inks in any way. Since the archival material is treated in a bound form, it is inevitable that the individual pages are more or less close to one another during the treatment. For this reason, it is particularly important that printing inks, stamping inks and also inks, with which books are signed in many cases, for example, are not dissolved in any way so that the writing on the neighboring pages is not discolored.

Von den bekannten Verfahren zur Entsäuerung kommt besondere Bedeutung den Verfahren zu, die zur Neutralisation Verbindungen der Erdalkalimetalle verwenden. Erdalkalimetalle bilden mit den Säuren im Papier sehr stabile Salze, die eine zuverlässige Konservierung gewährleisten, und ergeben als alkalische Reserve im Papier pH-Werte von etwa 8-9, die dem Papier zuträglich sind und keine alkalische Schädigung bewirken.Of the known processes for deacidification, the processes which use compounds of the alkaline earth metals for neutralization are of particular importance. Alkaline earth metals form very stable salts with the acids in the paper, which ensure reliable preservation, and as an alkaline reserve in the paper give pH values of around 8-9, which are beneficial to the paper and do not cause any alkaline damage.

Ein bekanntes Verfahren zur Entsäuerung von Archivalien (US-A-3 969 549) besteht in der Behandlung der Bücher mit Dämpfen von Metallalkylen, insbesondere mit Dämpfen von Diethylzink. Durch die Feuchtigkeit im Papier werden die Metallalkyle in die Oxide der Metalle, z.B. in Zinkoxid, umgewandelt, das im Papier verbleibt und ein gutes Neutralisationsmittel für freie Säuren darstellt. Die für diesen Anwendungszweck geeigneten Metallalkyle sind jedoch an der Luft selbstentzündliche Stoffe, die bei der Handhabung ein ständiges Brand- und Explosionsgefahrpotential darstellen und daher ein äußerstes Maß an Sorgfalt und entsprechende Qualifikation voraussetzen.A known method for deacidifying archive material (US Pat. No. 3,969,549) is to treat the books with vapors of metal alkyls, in particular with vapors of diethyl zinc. Due to the moisture in the paper, the metal alkyls are converted into the oxides of the metals, e.g. converted into zinc oxide, which remains in the paper and is a good neutralizing agent for free acids. However, the metal alkyls suitable for this purpose are self-igniting substances in the air, which represent a constant fire and explosion hazard during handling and therefore require an extremely high level of care and appropriate qualifications.

Nach einem anderen bekannten Verfahren (EP-A-0273 902) werden die Bücher mit einer wässrigen Lösung von Kalziumhydroxid getränkt, wobei freie Säuren als Kalziumsalze gebunden werden. Die behandelten, noch nassen Bücher werden schockgefroren und gefriergetrocknet. Mit diesem Verfahren ist zwar eine wirkungsvolle Entsäuerung möglich, es ist jedoch zu beachten, daß sich Wasser bekanntermaßen nachteilig auf Papier und insbesondere auf Bücher auswirkt. Neben dem Wellen des Papiers und insbesondere der Buchdeckel besteht die Gefahr, daß die Buchleimung beschädigt wird und daß Tinten- und Stempelfarben ausgewaschen werden. Ferner besteht bei der Gefriertrocknung trotz Schockgefrieren die Gefahr, daß die Eiskristalle das Papier schädigen. Unvermeidbar sind mit der Gefriertrocknung sehr lange Trocknungszeiten verbunden, die bis zu 34 Stunden betragen können und eine rationelle Arbeitsweise unmöglich machen.According to another known method (EP-A-0273 902) the books are washed with an aqueous solution of calcium hydroxide soaked, whereby free acids are bound as calcium salts. The treated, still wet books are snap-frozen and freeze-dried. With this method, effective deacidification is possible, but it should be noted that water is known to have a disadvantageous effect on paper and in particular on books. In addition to the corrugation of the paper and in particular the book cover, there is a risk that the book sizing is damaged and that ink and stamp colors are washed out. In addition, freeze-drying, despite shock freezing, poses the risk that the ice crystals damage the paper. Freeze drying is inevitably associated with very long drying times, which can be up to 34 hours and make efficient operation impossible.

Ein weiteres bekanntes Verfahren, das sogenannte Wei T'O-Verfahren, das seit 1974 in der konservatorischen Praxis angewandt wird, verwendet zur Behandlung eine Lösung einer magnesiumorganischen Verbindung wie beispielsweise Methylmagnesiumcarbonat. Auf dieses Verfahren wird auch in dem Artikel "Mass- deacidification in France" von Jean-Marie Arnoult, Restaurator 22/13 984, 1987 Bezug genommen. Auch bei diesem Verfahren wird die Magnesiumverbindung durch die Feuchtigkeit im Papier in Magnesiumoxid und Magnesiumcarbonat umgewandelt, die beide in der Lage sind, Säuren zu neutralisieren. Methylmagnesiumcarbonat ist jedoch wie auch alle Alkoholate der Alkali- und Erdalkalimetalle in unpolaren Lösemitteln unlöslich. Gerade jedoch die unpolaren Lösemittel sind im Hinblick auf die Verträglichkeit mit den Archivalien besonders geeignete Lösemittel. Das Wei T'O-Verfahren verwendet daher als Lösemittel buchverträgliche Lösemittel wie z.B. Fluorchlorkohlenwasserstoffe, wobei die Löslichkeit des Methylmagnesiumcarbonat durch Zusätze von 10-20 % niedersiedender Alkohole wie Methanol oder Ethanol erreicht wird. Die Praxis zeigt jedoch, daß dieser Alkoholzusatz bereits ausreichen kann, bei Tinten und Stempelfarben ein Auswaschen und ein Abfärben auf die Nachbarseiten zu bewirken.Another known method, the so-called Wei T'O method, which has been used in conservation practice since 1974, uses a solution of an organomagnesium compound, such as methyl magnesium carbonate, for the treatment. This method is also referred to in the article "Massacidification in France" by Jean-Marie Arnoult, restorer 22/13 984, 1987. In this process too, the moisture in the paper converts the magnesium compound into magnesium oxide and magnesium carbonate, both of which are able to neutralize acids. However, like all alcoholates of the alkali and alkaline earth metals, methyl magnesium carbonate is insoluble in non-polar solvents. However, the non-polar solvents are particularly suitable solvents in terms of compatibility with the archival documents. The Wei T'O process therefore uses book-compatible solvents such as chlorofluorocarbons, the solubility of methyl magnesium carbonate being achieved by adding 10-20% low-boiling alcohols such as methanol or ethanol. Practice shows, however, that this alcohol addition can already be sufficient for inks and stamp inks to wash out and rub off on the neighboring sides.

Die genannten, die Lösemittel betreffenden Probleme werden bei einem anderen bekannten Verfahren (WO-A-90 03 466), bei dem Magnesiumglykolate verwendet werden, vermieden. Diese Glykolate lösen sich auch in unpolaren Lösemitteln wie z.B. Trichlortrifluorethan oder Hexan. Während jedoch bei Verwendung von Magnesiumalkoholaten niederer Alkohole wie die des Methanols, Ethanols, Butanols oder auch der Propanole bei der Reaktion mit der Feuchtigkeit im Papier neben Magnesiumhydroxid eben diese Alkohole gebildet werden, die infolge ihrer Flüchtigkeit bei der nachfolgenden Trocknung verdampfen, entstehen bei Anwendung der Glykolate Glykole, die infolge ihres hohen Siedepunktes im Papier verbleiben. Wird nun eine für die Neutralisation und für die Bildung einer zusätzlichen alkalischen Reserve im Papier hinreichende Menge Magnesiumhydroxid in das Papier eingebracht, so entsteht unvermeidlich auch eine entsprechend große Menge Glykol, die im Papier verbleibt und diesem einen feuchten bis fettigen Charakter verleiht.The problems mentioned relating to the solvents are avoided in another known process (WO-A-90 03 466) in which magnesium glycolates are used. These glycolates also dissolve in non-polar solvents such as Trichlorotrifluoroethane or hexane. However, while using magnesium alcoholates of lower alcohols such as methanol, ethanol, butanol or also propanols in the reaction with the moisture in the paper, in addition to magnesium hydroxide, these alcohols are formed, which evaporate due to their volatility in the subsequent drying Glycolates Glycols that remain in the paper due to their high boiling point. If a sufficient amount of magnesium hydroxide is now introduced into the paper for neutralization and for the formation of an additional alkaline reserve in the paper, a correspondingly large amount of glycol is inevitably formed, which remains in the paper and gives it a moist to greasy character.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, Neutralisationsmittel anzugeben, die die geschilderten Nachteile der bekannten Verfahren vermeiden und eine wirkungsvolle, schonende und rationelle Entsäuerung von Archivalien ermöglichen, insbesondere ohne die Gefahr der Beschädigung von Druckfarbe, Leim oder Papier, sowie ohne nach der Behandlung im Papier verbleibender störender Begleitstoffe.The present invention has for its object to provide neutralizing agents that avoid the disadvantages of the known methods and allow effective, gentle and rational deacidification of archive material, in particular without the risk of damage to printing ink, glue or paper, and without after treatment in Paper of remaining interfering substances.

Diese Aufgabe wird durch die kennzeichnenden Merkmale des Patentanspruchs 1 gelöst. Danach wurde gefunden, daß sich Doppelalkoxide aus Alkoxiden von die Löslichkeit unterstützenden Metallen in Form von Metallen der IV. Nebengruppe des periodischen Systems der Elemente und Aluminium sowie Zinn und Alkoxiden von Metallen, die die freien Säuren im Papier binden, wie Erdalkalimetallen oder Alkalimetallen die geforderten Eigenschaften erbringen und sich hervorragend für die Massenentsäuerung eignen.This object is achieved by the characterizing features of patent claim 1. Thereafter it was found that double alkoxides from alkoxides of solubility-supporting metals in the form of metals of subgroup IV of the periodic system of the elements and aluminum and tin and alkoxides of metals which bind the free acids in the paper, such as Alkaline earth metals or alkali metals provide the required properties and are ideal for mass deacidification.

Dies ist bemerkenswert, weil z.B. die Alkoholate oder auch Alkoxide der Erdalkalimetalle Calcium und Magnesium in unpolaren Lösemitteln bekanntermaßen unlöslich sind. Es zeigte sich demgegenüber, daß z.B. die Doppelalkoxide dieser Metalle mit Elementen der IV. Nebengruppe in einer Vielzahl unpolarer und mit Archivalien sehr gut verträglichen Lösemitteln vorzüglich lösbar sind.This is remarkable because e.g. the alcoholates or alkoxides of the alkaline earth metals calcium and magnesium are known to be insoluble in non-polar solvents. In contrast, it was found that e.g. the double alkoxides of these metals with elements of subgroup IV are excellently soluble in a large number of non-polar solvents which are very well compatible with archival documents.

Dies ist bislang nicht erkannt worden, obgleich seit etwa zwanzig Jahren fortgesetzt mit Alkoxiden und insbesondere mit Mischungen von Alkoxiden gearbeitet wird (WO-A-90/03466 und US-A-3 676 182), wobei die Löslichkeit in organischen Lösemitteln dadurch erzielt wird, daß mindestens eine der Metallvalenzen mit mehrwertigen Alkoholen und/oder mit Äthern mehrwertiger Alkohole oder mit Aminoverbindungen belegt wird. Diese Stoffe bleiben jedoch infolge ihres relative hohen Siedepunktes im Papier. Wie weiter unten ausgeführt ist, sind hingegen die in der Erfindung möglichen kurzkettigen einwertigen Alkohole zur Bildung der Doppelalkoxide leicht flüchtig und weisen diesen Nachteil nicht auf. Schließlich ist auf die grundsätzlichen Unterschiede zwischen Alkoxiden (oder Alkoholaten) und Doppelalkoxiden hinzuweisen. Bei ersteren ist der Hydroxylwasserstoff eines Alkohols durch ein Metall ersetzt, bei den erfindungsgemäßen Doppelalkoxiden handelt es sich demgegenüber um Salze z.B. aus Mg- oder Ca-Alkoxid mit den sauer reagierenden Estern der Orthotitansäure bzw. Orthozirkonsäure.This has not been recognized until now, although alkoxides and in particular mixtures of alkoxides have continued to be used for about twenty years (WO-A-90/03466 and US-A-3 676 182), whereby the solubility in organic solvents is achieved that at least one of the metal valences is occupied with polyhydric alcohols and / or with ethers of polyhydric alcohols or with amino compounds. However, these substances remain in the paper due to their relatively high boiling point. In contrast, as explained further below, the short-chain monohydric alcohols possible in the invention for the formation of the double alkoxides are volatile and do not have this disadvantage. Finally, the fundamental differences between alkoxides (or alcoholates) and double alkoxides should be pointed out. In the former, the hydroxyl hydrogen of an alcohol is replaced by a metal, whereas the double alkoxides according to the invention are salts, e.g. from Mg or Ca alkoxide with the acid-reacting esters of orthotitanic acid or orthozirconic acid.

Diese Doppelalkoxide sind durch die allgemeine Formel

        MeI(OR)x · MeII(OR)y

charakterisierbar. MeI wird erfindungsgemäß besonders vorteilhaft von den Metallen Titan und Zirkonium gebildet, während an die Stelle von MeII besonders vorteilhaft die Metalle Magnesium und Calcium treten. Die OR-Gruppen können prinzipiell von Alkoholen unterschiedlicher Art z.B. (ein- oder mehrwertigen Alkoholen mit 1 bis 5 C-Atomen) gebildet werden. Vorzugsweise werden jedoch erfindungsgemäß einwertige Alkoholen mit 1 bis 5, vorzugsweise 2 bis 4 C-Atomen eingesetzt, die leicht flüchtig sind.These double alkoxides are of the general formula

Mel (OR) x Me II (OR) y

characterizable. According to the invention, MeI is particularly advantageously formed from the metals titanium and zirconium, while the metals magnesium and calcium are particularly advantageously substituted for MeII. In principle, the OR groups can be formed from alcohols of different types, for example (mono- or polyhydric alcohols with 1 to 5 carbon atoms). However, monohydric alcohols having 1 to 5, preferably 2 to 4, carbon atoms which are readily volatile are preferably used according to the invention.

Doppelalkoxide z.B. des Titans und Zirkoniums werden bislang als Katalysatoren in der organischen Chemie eingesetzt. Die Tatsache ihrer hervorragenden Eignung zur Massenentsäuerung von Papier wurde bisher nicht erkannt.Double alkoxides e.g. Titanium and zirconium have so far been used as catalysts in organic chemistry. The fact that they are outstandingly suitable for the mass deacidification of paper has not yet been recognized.

Von Bedeutung ist hierbei noch folgende Tatsache. Es wäre zunächst bei derartigen Doppelalkoxiden zu erwarten, daß bei der Säurebindung im Papier neben der erwünschten Bildung von stabilen Mg- bzw. Ca-Salzen auch Ti- bzw. Zr-Salze entstehen. Diese nur wenig stabilen Salze könnten ihrerseits durch Säurefreisetzung das Papier gefährden. Überraschenderweise wurde jedoch festgestellt, daß diese Salze nicht entstehen.The following fact is important here. In the case of double alkoxides of this type, it would initially be expected that, in addition to the desired formation of stable Mg or Ca salts, Ti or Zr salts also form in the acid binding in the paper. These salts, which are not very stable, could themselves endanger the paper through acid release. Surprisingly, however, it was found that these salts do not arise.

Ferner wurde beobachtet, daß durch Titan zudem eine vorteilhafte Verfestigung des Papiers bewirkt wird.It was also observed that titanium also causes the paper to be advantageously strengthened.

Bei den erfindungsgemäßen Doppelalkoxiden übernimmt das Metall MeII in Form eines Erdalkalimetalls (z.B. Calcium, Magnesium) oder Alkalimetalls (z.B. Kalium oder Natrium) durch Reaktion mit der Feuchte im Papier und die Bildung von Oxiden oder Hydroxiden (z.B. Calcium- oder Magnesiumoxiden und -hydroxiden) die Neutralisation freier Säuren und die Bildung einer alkalischen Reserve, während das Metall MeI (vorzugsweise Titan oder Zirkonium) die gute Löslichkeit dieser Verbindungen bewirkt.In the double alkoxides according to the invention, the metal MeII takes over in the form of an alkaline earth metal (for example calcium, magnesium) or alkali metal (for example potassium or sodium) by reaction with the moisture in the paper and the formation of oxides or hydroxides (for example calcium or magnesium oxides and hydroxides) the neutralization of free acids and the formation of an alkaline reserve, while the Metal MeI (preferably titanium or zirconium) causes the good solubility of these compounds.

Bei den Erdalkalimetallen ist von Vorteil, daß die Hydroxide nur mäßig alkalisch sind, so daß eine alkalische Schädigung des Papiers vermieden wird.An advantage of the alkaline earth metals is that the hydroxides are only moderately alkaline, so that alkaline damage to the paper is avoided.

Die Alkoxidkomponente der Metallkomponenten MeI (vorzugsweise Titan oder Zirkonium) wird in Kontakt mit der Papierfeuchte ebenfalls zu den Hydroxiden dieser Metalle hydrolysiert. Diese Hydroxide werden jedoch sehr schnell in die jeweiligen Oxide umgewandelt, die infolge ihrer chemischen Inertheit für die Neutralisation bedeutungslos sind.The alkoxide component of the metal components MeI (preferably titanium or zirconium) is also hydrolyzed to the hydroxides of these metals in contact with the paper moisture. However, these hydroxides are very quickly converted into the respective oxides, which due to their chemical inertness are irrelevant for the neutralization.

Da diese Oxide zudem andererseits als sehr feine Pulver vorliegen, ergibt sich ein weiterer, erfindungsgemäßer Vorteil dadurch, daß diese feinen Pulver ein eventuelles Verkleben der Seiten verhindern, ähnlich wie dies in anderen Bereichen der Technik z.B. durch Talkum bewirkt wird, ohne jedoch dabei störend in Erscheinung zu treten.Since these oxides are also present on the other hand as very fine powders, a further advantage according to the invention results from the fact that these fine powders prevent the sides from possibly sticking, in a manner similar to that in other areas of technology, e.g. is caused by talc, but without appearing disturbing.

Im Falle eines Doppelalkoxids mit Calcium als MeII ergibt sich erfindungsgemäß weiterhin der wichtige Vorteil, daß Calcium mit den Schwefelsäurespuren im Papier unlösliches und chemisch besonders inertes Calciumsulfat (Gips) bildet. Bei bekannten Verfahren war es bisher nur möglich, Calcium in wässriger Lösung in das Papier einzubringen.In the case of a double alkoxide with calcium as MeII, there is also the important advantage according to the invention that calcium forms calcium sulfate (gypsum) which is insoluble and chemically particularly inert with the traces of sulfuric acid in the paper. In the case of known processes, it was previously only possible to introduce calcium into the paper in aqueous solution.

Die genannten Doppelalkoxide werden als Lösung in einem Siloxan, z.B. Hexamethyldisiloxan als Lösemittel angewendet, die z.B. 0,1-0,5 Gew.-% Magnesium oder Calcium enthält.The double alkoxides mentioned are used as a solution in a siloxane, for example hexamethyldisiloxane as a solvent which contains, for example, 0.1-0.5% by weight of magnesium or calcium.

Von besonderer Bedeutung ist, daß erfindungsgemäß kein Zusatz eines Lösevermittlers, z.B. eines Alkohols, notwendig ist.It is of particular importance that, according to the invention, no addition of a solubilizer, e.g. alcohol, is necessary.

Die Anwendung der erfindungsgemäßen Neutralisationsmittel kann mit an sich bekannten Verfahren zur Entsäuerung, insbesondere zur Massenentsäuerung von Archivalien, z.B. mit dem in der DE-A-3904 111 angegebenen Verfahren erfolgen. Es ist in der Regel dabei von Vorteil, die Archivalien, die eine Lagerfeuchte von etwa 5-10 Gew.- % haben werden, in einem Vortrocknungsschritt auf eine Restfeuchte von ca. 0,5 Gew.-% zu trocknen. Der Grad dieser Vortrocknung gibt eine gute Möglichkeit, die Menge der im Papier installierten, neutralisierenden Metalloxide zu regulieren, wobei mit zunehmender Feuchte eine größere Menge Oxid aus der Lösung ausgefällt und im Papier verankert wird.The use of the neutralizing agents according to the invention can be carried out using processes known per se for deacidification, in particular for the mass deacidification of archive materials, e.g. with the method specified in DE-A-3904 111. It is generally advantageous to dry the archival material, which will have a storage moisture content of around 5-10% by weight, in a predrying step to a residual moisture content of around 0.5% by weight. The degree of this predrying provides a good opportunity to regulate the amount of neutralizing metal oxides installed in the paper, with a greater amount of oxide precipitating out of the solution and becoming anchored in the paper with increasing moisture.

Im folgenden werden zwei Ausführungsbeispiele der Erfindung anhand tabellarisch zusammengefaßter Versuchsergebnisse zur Erläuterung der Erfindung und deren Vorteile angegeben.In the following, two exemplary embodiments of the invention are given on the basis of experimental results summarized in a table to explain the invention and its advantages.

Beispiel 1:Example 1:

50 g50 g Titantetrabutylat · MagnesiumdiethylatTitanium tetrabutylateMagnesium diethylate Ti(O₄H₉)₄ · Mg(OC₂H₅)₂ gelöst inTi (O₄H₉) ₄ · Mg (OC₂H₅) ₂ dissolved in 950 g950 g HexamethyldisiloxanHexamethyldisiloxane FeuchteHumidity pH-Wert vor der BehandlungpH before treatment pH-Wert nach der BehandlungpH after treatment * Alkalische Pufferreserve (ber.a.Gew.% MgCO₃)* Alkaline buffer reserve (calculated weight% MgCO₃) UngestrichenesUncoated 0.5 Gew.-%0.5% by weight 4,54.5 7,67.6 0,820.82 Papier Nr. IPaper number I 4,7 Gew.-%4.7% by weight 4,54.5 8,88.8 1,791.79 UngestrichenesUncoated 0,5 Gew.-%0.5% by weight 4,24.2 8,58.5 0,790.79 Papier Nr. IIPaper No. II 5,0 Gew.-%5.0% by weight 4,24.2 9,59.5 2,322.32 UngestrichenesUncoated 0,5 Gew.-%0.5% by weight 4,14.1 8,28.2 1,081.08 Papier Nr. IIIPaper No. III 5,0 Gew.-%5.0% by weight 4,14.1 8,98.9 1,771.77 GestrichenesDeleted 0,5 Gew.-%0.5% by weight 7,57.5 8,28.2 2,512.51 Papierpaper 5,0 Gew.-%5.0% by weight 7,57.5 8,38.3 2,992.99

Beispiel 2:Example 2:

110 g110 g Titantetraethylat · CalciumdiethylatTitanium tetraethylate · Calcium diethylate Ti(OC₂H₅)₄ · Ca(OC₂H₅)₂ gelöst inTi (OC₂H₅) ₄Ca (OC₂H₅) ₂ dissolved in 890 g890 g HexamethyldisiloxanHexamethyldisiloxane FeuchteHumidity pH-Wert vor der BehandlungpH before treatment pH-Wert nach der BehandlungpH after treatment *Alkalische Pufferreserve (ber. als Gew.-%)* Alkaline buffer reserve (calculated as% by weight) UngestrichenesUncoated 0,5 Gew.-%0.5% by weight 4,24.2 7,57.5 1,581.58 Papier Nr. IIPaper No. II 5,0 Gew.-%5.0% by weight 4,24.2 7,77.7 2,262.26

Der Begriff "alkalische Pufferreserve" wurde dem Sprachgebrauch der konservatorischen Praxis entnommen und ist jeweils in Gew.% MgCO₃ berechnet. Der alkalische Bestandteil wurde hierzu titrimetisch bestimmt und auf Magnesiumcarbonat umgerechnet.The term "alkaline buffer reserve" was taken from the language of conservation practice and is calculated in wt.% MgCO₃. The alkaline component was determined by titration and converted to magnesium carbonate.

1. Wie aus den Tabellen hervorgeht, wurden sowohl ungetrocknete, d.h. lagerfeuchte Papiere als auch vorgetrocknete Papiere behandelt.1. As can be seen from the tables, both undried, i.e. treated papers and pre-dried papers.

Es handelte sich dabei um Bücher mit unterschiedlichen Papiersorten.These were books with different types of paper.

Zur Vortrocknung auf eine Restfeuchte von 0,5 Gew. % wurde eine Mikrowellenbeheizung angewandt.Microwave heating was used for predrying to a residual moisture of 0.5% by weight.

Die eigentliche Behandlung erfolgte in Form einer Vakuumtrocknung, um eine gute und gleichmäßige Durchtränkung der Bücher zu gewährleisten. Die Einwirkungsdauer der Behandlungslösungen betrug dann jeweils 10 Minuten.The actual treatment was carried out in the form of vacuum drying in order to ensure a good and even soaking of the books. The duration of exposure of the treatment solutions was then 10 minutes in each case.

Die Tabellen zeigen einerseits die erfolgreiche Bindung der Säuren durch die Verschiebung des pH-Wertes, (wobei beim gestrichenen Papier infolge des dort durch das Streichen bereits vorliegenden Calciumcarbonatbestandteils der pH-Ausgangswert bereits höher ist) und andererseits, daß eine ausreichende Pufferreserve im Papier verankert werden konnte. Die Tabellen zeigen ferner, daß diese über die Papierfeuchte über einen weiten Bereich regulierbar ist.The tables show, on the one hand, the successful binding of the acids by shifting the pH value (although the initial pH value of the coated paper is already higher due to the calcium carbonate component already present there by coating) and, on the other hand, that an adequate buffer reserve is anchored in the paper could. The tables also show that this can be regulated over a wide range via the paper moisture.

Neben den angegebenen Metallen der IV. Nebengruppe ist beispielsweise auch Hafnium verwendbar, das ebenfalls als für eine ausreichende Löslichkeit sorgender Bestandteil wirkt, jedoch um einiges teurer ist als Zirkonium oder Titan. Ferner sind Aluminium und Zinn einsetzbar. Prinzipiell sind sämtliche Erdalkalimetalle oder Alkalimetalle verwendbar, deren Salze in der Lage sind, die Säuren im Papier zu neutralisieren. Als Erdalkalimetallbestandteil ist z.B. auch Strontium einsetzbar; Barium ist wegen seiner Giftigkeit weniger geeignet.In addition to the specified metals of subgroup IV, hafnium can also be used, for example, which also acts as an ingredient which ensures sufficient solubility, but is somewhat more expensive than zirconium or titanium. Aluminum and tin can also be used. In principle, all alkaline earth metals or alkali metals can be used, the salts of which are able to form the acids neutralize in paper. Strontium, for example, can also be used as an alkaline earth metal component; Barium is less suitable because of its toxicity.

Claims (7)

  1. A neutralizing agent for effective but mild mass de-acidification of books and other paper products,
    characterized in that
    the neutralizing agent consists of a solution of at least one kind of double alkoxides in a siloxane each with one alkoxide of a group IV metal or aluminium or tin promoting solubility and one alkoxide of a metal binding the acids in the paper.
  2. A neutralizing agent according to claim 1,
    characterized in that
    the group IV alkoxide is a titanium alkoxide.
  3. A neutralizing agent according to claim 1,
    characterized in that
    the group IV alkoxide is a zirconium alkoxide.
  4. A neutralizing agent according to any preceding claim,
    characterized in that
    the alkoxide of the metal binding the acids is an alkaline earth metal or an alkali metal alkoxide.
  5. A neutralizing agent according to claim 4,
    characterized in that
    the alkaline earth metal alkoxide is a magnesium alkoxide.
  6. A neutralizing agent according to claims 1 to 4,
    characterized in that
    the alkaline earth metal alkoxide is a calcium alkoxide.
  7. A neutralizing agent according to any preceding claim,
    characterized in that
    the double alkoxide is formed from univalent alcohols with 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms.
EP92119850A 1991-11-26 1992-11-21 Neutralization composition for effectively and gently deacidifying books and other paper articles Expired - Lifetime EP0545180B1 (en)

Applications Claiming Priority (2)

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DE4138750A DE4138750A1 (en) 1991-11-26 1991-11-26 NEUTRALIZING AGENTS FOR THE EFFECTIVE AND GENTLE MASS DE-ACIDIFICATION OF BOOKS AND OTHER PAPER PRODUCTS
DE4138750 1991-11-26

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DE4300185A1 (en) * 1993-01-07 1994-07-14 Huels Chemische Werke Ag Storage-stable solutions of a mixture of carbonized magnesium methylate, carbonized magnesium ethylate and their carbonized mixed alkoxide in a mixture of methanol and ethanol and their preparation and use
DE4300186A1 (en) * 1993-01-07 1994-07-14 Huels Chemische Werke Ag Storage-stable solutions of carbonized magnesium methylate in methanol as well as their production and use
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ATE136078T1 (en) 1996-04-15
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DE4138750A1 (en) 1993-05-27
DE59205843D1 (en) 1996-05-02
US5322558A (en) 1994-06-21
ES2087406T3 (en) 1996-07-16
CA2083549A1 (en) 1993-05-27

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