EP0499076A1 - Solvent for ecologically mass deacidifying book and other paper articles - Google Patents
Solvent for ecologically mass deacidifying book and other paper articles Download PDFInfo
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- EP0499076A1 EP0499076A1 EP92101209A EP92101209A EP0499076A1 EP 0499076 A1 EP0499076 A1 EP 0499076A1 EP 92101209 A EP92101209 A EP 92101209A EP 92101209 A EP92101209 A EP 92101209A EP 0499076 A1 EP0499076 A1 EP 0499076A1
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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
- 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 invention relates to solvents for agents in the form of neutralizing agents for the efficient mass deacidification of books, printed and other paper products, as well as all kinds of archives, such as magazines, files or documents.
- the books for deacidification are treated with vapors of metal alkyls, for example with vapors of diethyl zinc (US Pat. No. 3,969,549).
- the moisture in the paper transforms the metal alkyls into the oxides of the metals, eg in zinc oxide, which remains in the paper and neutralizes the free acids.
- This process is to be regarded as a "dry” process, which means that the books only come into contact with the vapors of the metal alkyls, ie they are not soaked in a liquid.
- the metal alkyls suitable for this application are self-igniting substances in the air, which represent a great fire and explosion risk potential and require an extremely high level of care and complex safety measures to avoid serious accidents.
- the books are treated with solutions of an organometallic compound, such as, for example, methyl magnesium carbonate, in a suitable solvent, such as the solvents mentioned below.
- organometallic compound such as, for example, methyl magnesium carbonate
- the moisture in the paper in turn converts it to magnesium oxide and magnesium carbonate, both of which are able to neutralize the acids in the paper.
- this process soaks the books with a solution.
- the solvents used for deacidification must not attack or damage the paper or the tools used for book production in any way. Since after the deacidification of the books, the solvents are removed from the books in a drying process, the solvents must evaporate at temperatures at which the books are not yet damaged.
- Fluorocarbons and chlorofluorocarbons with the addition of alcohols such as e.g. Methanol or ethanol used.
- the fluorocarbons and chlorofluorocarbons mentioned have sufficient compatibility with most book materials and evaporate at temperatures at which the one does not yet experience excessive evaporation losses during handling, and secondly the books are not yet damaged.
- the invention is therefore based on the object of specifying new solvents which are suitable for the mass deacidification of paper products and permit their deacidification with the greatest possible protection of the products and avoiding environmentally harmful substances.
- organosiloxanes have similarly good solvent properties for book deacidification as the previously used chlorofluorocarbons, without having the environmental problems of these substances and, moreover, can also be used very well in the proposed rational processes.
- the novelty consists in particular in the knowledge according to the invention that the particular siloxanes with 2 to 4 units (also called siloxane units) each having 2 to 4 units (also called siloxane units) make these siloxanes particularly suitable as solvents for book deacidification.
- the organo groups marked with R are occupied by CH3 groups since these siloxanes have a low boiling point and are therefore particularly suitable for the use according to the invention.
- n 0 to 2, corresponding to a number of silicon atoms from 2 to 4.
- CH3 groups can also occur, the compounds then having a particularly high chemical stability.
- hydrogen atoms or functional groups which can react with the paper fiber can take the place of the x or R atoms.
- the structure of the paper fiber can be positively influenced and re-consolidation of already damaged paper can thus be achieved.
- these siloxanes are not suitable for the intended application, since unacceptably high temperatures would have to be used to dry the books even in a vacuum.
- methylsiloxanes with 2-4 silicon atoms or silicon atom units have boiling points of 100-150 ° C at atmospheric pressure and viscosities from 0.65 mm2 / s to 1 mm2 / s.
- these siloxanes have proven in experiments to be excellent solvents for book deacidification.
- the substances mentioned are colorless, odorless liquids with very low viscosity and very low surface tension, which can be evaporated without residue at comparatively low temperatures.
- the low viscosity and surface tension make these compounds particularly suitable for the purpose mentioned, since this enables good and uniform impregnation of the books.
- the boiling point of the latter compound which at 150 ° C is already too high for gentle treatment of books, can be reduced by applying a vacuum when drying the books, as is often the case in the art and also in the art DE 39 04 111 A1 is specified, can be reduced to about 70 ° C at about 100 mbar.
- Siloxanes of the type mentioned are compatible with many other solvents, e.g. Alcohols, which are used as solubilizers for methyl magnesium carbonate and to stabilize it, are miscible and are good solvents for many organometallic compounds, while the common materials and auxiliaries used for book production, e.g. Printing inks, glue and adhesives, plastics for cover covers as well as inks and stamping inks, can neither be loosened nor damaged in any other way by siloxanes.
- solvents e.g. Alcohols, which are used as solubilizers for methyl magnesium carbonate and to stabilize it, are miscible and are good solvents for many organometallic compounds, while the common materials and auxiliaries used for book production, e.g. Printing inks, glue and adhesives, plastics for cover covers as well as inks and stamping inks, can neither be loosened nor damaged in any other way by siloxanes.
- Rubber if it is not a special type of rubber - is destroyed by mineral oils and solvents such as petroleum hydrocarbons, aromatics, esters and alcohols or experiences a strong swelling due to these substances, whereas polysiloxanes of the type mentioned are excellent lubricants and care agents for rubber represent.
- the aforementioned DE 390411 A1 specifies the use of microwaves for drying the books after the treatment; this enables both quick and gentle handling of the books.
- the heatability of a substance in the microwave field is essentially dependent on its dielectric constant ⁇ r and the dielectric loss factor tan ⁇ , both of which are specific properties of the substance are dependent; the higher these values are, the better the material can be heated in the microwave field.
- the solvents according to the invention are therefore just as suitable as the previous solvents for use in rational processes of the type mentioned with microwave drying. However, it can also be used in other conventional drying processes that do not use microwaves.
- siloxanes according to the invention are very suitable for the known neutralizing agent methyl magnesium carbonate. However, they can also be used for other organometallic compounds which may be determined in the future and which in some way turn out to be an effective treatment agent for mass deacidification.
- Methyl magnesium carbonate solution magnesium content 3%, dissolved in alcohol and 87.5 g hexamethyldisiloxane instead of the usual CFC solvent for deacidification.
- the pH value of 4.5 of the untreated paper could be raised to 8.5
- the free acids in the paper were neutralized, at the same time an alkaline buffer reserve was introduced into the paper, and no damage to the paper or the lettering was observed.
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Abstract
Description
Die Erfindung betrifft Lösemittel für Agentien in Form von Neutralisationsmitteln zur rationellen Massenentsäuerung von Büchern, Druck- und anderen Papiererzeugnissen sowie Archivalien aller Art wie Zeitschriften, Akten oder Dokumenten.The invention relates to solvents for agents in the form of neutralizing agents for the efficient mass deacidification of books, printed and other paper products, as well as all kinds of archives, such as magazines, files or documents.
Bei allen Druck- und Papiererzeugnissen, insbesondere bei Büchern, tritt während der Lagerung eine Alterung der Papiersubstanz ein, in deren Verlauf im Papier Spuren von Säuren freigesetzt werden, die zu einer fortschreitenden Schädigung der Papiersubstanz führen.In all printed and paper products, especially books, the paper substance ages during storage, during which time traces of acids are released in the paper, which lead to progressive damage to the paper substance.
Werden keine Gegenmaßnahmen getroffen, so kann diese Schädigung nach einigen Jahrzehnten bis zu einem völligen Zerfall des Papiers führen.If no countermeasures are taken, this damage can lead to a complete decay of the paper after a few decades.
Zur Erhaltung der Bestände von Archiven und Bibliotheken von weltweit einigen hundert Millionen Büchern ist es daher erforderlich, die Säuren im Papier zu neutralisieren und gleichzeitig im Papier eine Puffersubstanz in hinreichender Menge zu verankern, die auch die zukünftig im Papier freigesetzte Säure neutralisiert.To preserve the archives and libraries of several hundred million books worldwide, it is therefore necessary to neutralize the acids in the paper and at the same time anchor a sufficient amount of a buffer substance in the paper, which will also neutralize the acid released in the paper in the future.
In Anbetracht der sehr großen Büchermengen kommen hierfür nur Verfahren in Betracht, die eine rationelle Massenbehandlung großer Mengen der ganzen Bücher gestatten, d.h. Verfahren, bei denen es nicht notwendig ist, die Buchbindung zu öffnen und die Seiten einzeln zu behandeln.In view of the very large volumes of books, only processes that allow rational mass treatment of large quantities of the entire books, i.e. Procedures where it is not necessary to open the book binding and treat the pages individually.
Nach einem bekannten Verfahren werden die Bücher zur Entsäuerung mit Dämpfen von Metallalkylen, z.B. mit Dämpfen von Diethylzink (US-PS 3,969,549) behandelt. Durch die Feuchtigkeit im Papier erfolgt eine Umwandlung der Metallalkyle in die Oxide der Metalle, z.B. in Zinkoxid, das im Papier verbleibt und die freien Säuren neutralisiert.According to a known method, the books for deacidification are treated with vapors of metal alkyls, for example with vapors of diethyl zinc (US Pat. No. 3,969,549). The moisture in the paper transforms the metal alkyls into the oxides of the metals, eg in zinc oxide, which remains in the paper and neutralizes the free acids.
Dieses Verfahren ist als ein "trockenes" Verfahren anzusehen, das heißt, die Bücher kommen nur mit den Dämpfen der Metallalkyle in Kontakt, werden also nicht mit einer Flüssigkeit durchtränkt.This process is to be regarded as a "dry" process, which means that the books only come into contact with the vapors of the metal alkyls, ie they are not soaked in a liquid.
Nach diesem Verfahren werden gute Entsäuerungsergebnisse bei einer schonenden Behandlung der Bücher erzielt.This process produces good deacidification results with careful treatment of the books.
Die für diesen Anwendungszweck geeigneten Metallalkyle sind jedoch an der Luft selbstentzündliche Stoffe, die ein großes Brand- und Explosionsgefahrpotential darstellen und zur Vermeidung von schweren Unfällen ein äußerstes Maß an Sorgfalt und aufwendige Sicherheitsmaßnahmen erfordern.However, the metal alkyls suitable for this application are self-igniting substances in the air, which represent a great fire and explosion risk potential and require an extremely high level of care and complex safety measures to avoid serious accidents.
Nach einem anderen bekannten Verfahren, dem sogenannten Wei-T'o-Verfahren werden die Bücher mit Lösungen einer metallorganischen Verbindung, wie beispielsweise Methylmagnesiumcarbonat, in einem geeigneten Lösemittel wie den weiter unten erwähnten Lösemitteln behandelt.According to another known process, the so-called Wei-T'o process, the books are treated with solutions of an organometallic compound, such as, for example, methyl magnesium carbonate, in a suitable solvent, such as the solvents mentioned below.
Beim Beispiel des Methylmagnesiumcarbonats wird dieses wiederum durch die Feuchtigkeit im Papier in Magnesiumoxid und Magnesiumcarbonat umgewandelt, die beide in der Lage sind, die Säuren im Papier zu neutralisieren.In the example of methyl magnesium carbonate, the moisture in the paper in turn converts it to magnesium oxide and magnesium carbonate, both of which are able to neutralize the acids in the paper.
Im Gegensatz zum erstgenannten "trockenen" Verfahren werden bei diesem Verfahren die Bücher mit einer Lösung durchtränkt.In contrast to the former "dry" process, this process soaks the books with a solution.
Neben der schon erwähnten Hauptaufgabe, nämlich der Entsäuerung der Bücher, wird bei diesem Verfahren weiterhin ein Abschwemmen von Staub und Schmutzpartikeln ähnlich wie bei der chemischen Reinigung von Textilien erreicht. Hierin ist neben der Sicherheit dieses Verfahrens ein weiterer großer Vorteil zu sehen.In addition to the main task already mentioned, namely deacidification of the books, this process continues to wash away dust and dirt particles similar to the chemical cleaning of textiles. In addition to the safety of this process, this is another great advantage.
Es gilt zwangsläufig, daß an das chemisch-physikalische Verhalten der verwendeten Lösemittel sehr hohe Anforderungen gestellt werden müssen, um eine schonende Behandlung der Bücher zu ermöglichen.It is inevitable that the chemical-physical behavior of the solvents used must meet very high requirements in order to enable the books to be handled gently.
Bei der Herstellung der Bücher wurden und werden neben dem Papier Hilfsmittel der unterschiedlichsten Art verwendet, wie z.B. Leim, Klebstoffe, Druckfarben, Tinten, Karton, Textilien, Leder und Kunststoffe.In addition to paper, a wide variety of tools have been used in the production of the books, such as Glue, adhesives, printing inks, inks, cardboard, textiles, leather and plastics.
Die zur Entsäuerung eingesetzten Lösemittel dürfen weder das Papier noch die zur Buchherstellung verwendeten Hilfsmittel in irgendeiner Weise angreifen oder schädigen. Da nach der Entsäuerung der Bücher die Lösemittel in einem Trocknungsverfahren aus den Büchern entfernt werden, müssen die Lösemittel bei Temperaturen verdampfen, bei denen noch keine Beschädigung der Bücher eintritt.The solvents used for deacidification must not attack or damage the paper or the tools used for book production in any way. Since after the deacidification of the books, the solvents are removed from the books in a drying process, the solvents must evaporate at temperatures at which the books are not yet damaged.
Als solche schonenden Lösemittel wurden bisher Fluorkohlenwasserstoffe und Fluorchlorkohlenwasserstoffe (FCKW) unter Zusatz von Alkoholen wie z.B. Methanol oder Ethanol verwendet.Fluorocarbons and chlorofluorocarbons (CFCs) with the addition of alcohols such as e.g. Methanol or ethanol used.
Die genannten Fluorkohlenwasserstoffe und Fluorchlorkohlenwasserstoffe haben eine ausreichende Verträglichkeit mit den meisten Buchmaterialien und verdampfen bei Temperaturen, bei denen zum einen noch keine zu hohen Verdunstungsverluste bei der Handhabung eintreten, zum anderen die Bücher noch nicht geschädigt werden.The fluorocarbons and chlorofluorocarbons mentioned have sufficient compatibility with most book materials and evaporate at temperatures at which the one does not yet experience excessive evaporation losses during handling, and secondly the books are not yet damaged.
Insbesondere für die Fluorchlorkohlenwasserstoffe gelten jedoch wegen ihres hohen umwelt- und ozonschädigenden Potentials starke Anwendungs- und Herstellungsbeschränkungen.For chlorofluorocarbons in particular, however, there are severe restrictions on their use and production because of their high environmental and ozone-depleting potential.
Im Zuge dieser weltweiten Beschränkungen und deren jetzt schon in Verträgen verankerten Verschärfungen ist ein weltweites Anwendungsverbot abzusehen.In the course of these worldwide restrictions and their tightening, which are already enshrined in contracts, a worldwide ban on use is foreseeable.
Die DE 39 04 111 A1 beschreibt zwar ein Verfahren zur umweltfreundlichen Massenentsäuerung von Büchern und anderen Papiererzeugnissen, bei dem durch eine geschlossene Verfahrensweise und durch konsequente Abluftreinigung Emissionen weitestgehend vermieden werden. Wenn jedoch durch ein Anwendungsverbot und/oder oder infolge freiwilliger Einstellung der Produktion Fluorkohlenwasserstoffe oder Fluorchlorkohlenwasserstoffe in absehbarer Zeit nicht mehr zur Verfügung stehen werden, fehlen die für dieses wirkungsvolle, handhabungssichere und rationelle Verfahren zunächst und beispielhalber in Betracht gezogenen, geeigneten Lösemittel.DE 39 04 111 A1 describes a process for environmentally friendly mass deacidification of books and other paper products, in which emissions are largely avoided by a closed procedure and by consistent exhaust air purification. However, if fluorocarbons or chlorofluorocarbons will no longer be available in the foreseeable future due to a ban on use and / or as a result of the voluntary cessation of production, the suitable solvents that are effective and safe to use and rational are initially lacking and are considered as examples.
Der Erfindung liegt daher die Aufgabe zugrunde, neue Lösemittel anzugeben, die sich für die Massenentsäuerung von Papiererzeugnissen eignen und deren Entsäuerung unter größtmöglicher Schonung der Erzeugnisse und unter Vermeidung umweltbelastender Stoffe gestatten.The invention is therefore based on the object of specifying new solvents which are suitable for the mass deacidification of paper products and permit their deacidification with the greatest possible protection of the products and avoiding environmentally harmful substances.
Diese Aufgabe wird durch den Gegenstand des Patentanspruchs 1 gelöst. Danach werden als Alternative zu den umweltbelastenden Fluorchlorkohlenwasserstoffen Methylsiloxane mit mindestens 2 und maximal 4 Siliziumatomen bzw. Siloxaneinheiten angegeben. Diese können sowohl linearkettenförmige als auch zyklische Verbindungen sein.This object is achieved by the subject matter of patent claim 1. Thereafter, as an alternative to the environmentally harmful chlorofluorocarbons, methylsiloxanes with at least 2 and a maximum of 4 silicon atoms or siloxane units specified. These can be linear chain as well as cyclic connections.
Die Erfinder stellten überraschenderweise fest, daß Organosiloxane ähnlich gute Lösemitteleigenschaften zur Bücherentsäuerung haben wie die bisher verwendeten Fluorchlorkohlenwasserstoffe, ohne die Umweltproblematik dieser Stoffe aufzuweisen und darüberhinaus auch sehr gut in den vorgeschlagenen rationellen Verfahren einsetzbar sind.The inventors surprisingly found that organosiloxanes have similarly good solvent properties for book deacidification as the previously used chlorofluorocarbons, without having the environmental problems of these substances and, moreover, can also be used very well in the proposed rational processes.
Organosiloxane - in höhermolekularer Form bekannt unter dem Namen Siliconöle - haben an sich wegen ihrer guten chemischen und physikalischen Eigenschaften eine Reihe von Anwendungen in der Technik, Kosmetik und Pharmazeutik gefunden.Organosiloxanes - known in higher molecular weight under the name silicone oils - have found a number of applications in technology, cosmetics and pharmaceuticals because of their good chemical and physical properties.
Die Neuheit besteht insbesondere in der erfindungsgemäßen Erkenntnis, daß die im Patentanspruch 1 angegebenen bestimmten Siloxane mit 2 bis 4 jeweils 1 Siliziumatom aufweisenden Einheiten (auch Siloxaneinheiten genannt) diese Siloxane als Lösemittel zur Bücherentsäuerung besonders gut geeignet machen.The novelty consists in particular in the knowledge according to the invention that the particular siloxanes with 2 to 4 units (also called siloxane units) each having 2 to 4 units (also called siloxane units) make these siloxanes particularly suitable as solvents for book deacidification.
Die allgemeine Struktur von z.B. linearkettenförmigen Siloxanen läßt sich mit folgender Formel beschreiben:
Erfindungsgemäß sind hierbei die mit R gekennzeichneten Organogruppen von CH₃-Gruppen besetzt, da diese Siloxane einen niedrigen Siedepunkt haben und somit für die erfindungsgemäße Anwendung besonders geeignet sind. Erfindungsgemäß beträgt n = 0 bis 2 entsprechend einer Anzahl von Siliziumatomen von 2 bis 4.According to the invention, the organo groups marked with R are occupied by CH₃ groups since these siloxanes have a low boiling point and are therefore particularly suitable for the use according to the invention. According to the invention, n = 0 to 2, corresponding to a number of silicon atoms from 2 to 4.
Anstelle der x (der terminalen Siliziumvalenzen) können ebenfalls CH₃-Gruppen treten, wobei die Verbindungen dann eine besonders hohe chemische Stabilität aufweisen. Alternativ können anstelle der x oder R Wasserstoffatome oder funktionelle Gruppen treten, die mit der Papierfaser reagieren können.Instead of the x (the terminal silicon valences), CH₃ groups can also occur, the compounds then having a particularly high chemical stability. Alternatively, hydrogen atoms or functional groups which can react with the paper fiber can take the place of the x or R atoms.
Bei Anwendung dieser Siloxane, die in Mischung mit Siloxanen der erstgenannten Gruppe eingesetzt werden können, läßt sich die Struktur der Papierfaser positiv beeinflussen und damit eine Wiederverfestigung von bereits geschädigtem Papier erreichen.When using these siloxanes, which can be used in a mixture with siloxanes from the first-mentioned group, the structure of the paper fiber can be positively influenced and re-consolidation of already damaged paper can thus be achieved.
Somit sind auch Mischungen von Siloxanen der oben angegebenen n-Werte sowie auch unterschiedlicher Besetzung der z.B. terminalen und anderen Siliziumvalenzen denkbar, die zur Optimierung der in Frage stehenden Anwendung als Lösemittel führen.Mixtures of siloxanes with the n values given above and also with different compositions of e.g. terminal and other silicon valences conceivable, which lead to the optimization of the application in question as a solvent.
Linearkettenförmige Methylsiloxane, deren R- und X-Valenzen mit CH₃-Gruppen abgesättigt sind die 5 Siliziumatome oder mehr aufweisen und deren n > 3 ist, haben mit steigendem n einen zunehmend öligen Charakter und einen ansteigenden Siedepunkt, der z. B. für n = 5 bei 0,6 mbar 120°C beträgt. Infolge der hohen Siedepunkte sind diese Siloxane für die vorgesehene Anwendung nicht geeignet, da zur Trocknung für die Bücher auch im Vakuum unzuträglich hohe Temperaturen angewendet werden müßten.Linear chain-shaped methylsiloxanes, the R and X valences of which are saturated with CH₃ groups and which have 5 silicon atoms or more and whose n is> 3, have an increasingly oily character and an increasing boiling point with increasing n, the z. B. for n = 5 at 0.6 mbar is 120 ° C. As a result of the high boiling points, these siloxanes are not suitable for the intended application, since unacceptably high temperatures would have to be used to dry the books even in a vacuum.
Dagegen haben Methylsiloxane mit 2-4 Siliziumatomen bzw. Siliziumatomeinheiten (n = 0 bis 2) Siedepunkte von 100-150°C bei Atmosphärendruck und Viskositäten von 0,65 mm²/s bis 1 mm²/s. Diese Siloxane haben sich überraschenderweise infolge ihres vergleichsweise niedrigen Siedepunktes, infolge ihrer niedrigen Viskosität und ihrer sonstigen guten chemischen und physikalischen Eigenschaften in Versuchen als ausgezeichnete Lösemittel zur Bücherentsäuerung erwiesen. Die genannten Stoffe sind farblose, geruchslose Flüssigkeiten mit sehr niedriger Viskosität und sehr geringer Oberflächenspannung, die bei vergleichsweise niedrigen Temperaturen rückstandlos verdampft werden können.In contrast, methylsiloxanes with 2-4 silicon atoms or silicon atom units (n = 0 to 2) have boiling points of 100-150 ° C at atmospheric pressure and viscosities from 0.65 mm² / s to 1 mm² / s. Surprisingly, due to their comparatively low boiling point, their low viscosity and their other good chemical and physical properties, these siloxanes have proven in experiments to be excellent solvents for book deacidification. The substances mentioned are colorless, odorless liquids with very low viscosity and very low surface tension, which can be evaporated without residue at comparatively low temperatures.
Insbesondere auch die niedrige Viskosität und Oberflächenspannung machen diese Verbindungen für den genannten Zweck besonders geeignet, da hierdurch eine gute und gleichmäßige Durchtränkung der Bücher möglich wird.In particular, the low viscosity and surface tension make these compounds particularly suitable for the purpose mentioned, since this enables good and uniform impregnation of the books.
So hat z.B. Hexamethyldisiloxan - ein Siloxan, das zwei Siliziumatome aufweist (n = 0) - eine Viskosität von 0,65 mm²/s, einen Siedepunkt von 100°C bei Atmosphärendruck und eine Oberflächenspannung von 15,9 mN/m; ein Siloxan, bestehend aus vier Siliziumatomen (n = 2), hat einen Siedepunkt von 150°C, eine Viskosität von 1,0 mm²/s und eine Oberflächenspannung von 16 mN/m.For example, Hexamethyldisiloxane - a siloxane that has two silicon atoms (n = 0) - a viscosity of 0.65 mm² / s, a boiling point of 100 ° C at atmospheric pressure and a surface tension of 15.9 mN / m; a siloxane consisting of four silicon atoms (n = 2) has a boiling point of 150 ° C, a viscosity of 1.0 mm² / s and a surface tension of 16 mN / m.
Der Siedepunkt letzterer Verbindung, der mit 150°C an sich bereits zu hoch für eine schonende Behandlung von Büchern ist, kann durch Anwendung von Vakuum bei der Trocknung der Bücher, wie dies in der Technik in vielen Fällen angewendet und auch in der
DE 39 04 111 A1 angegeben wird, auf ca. 70°C bei etwa 100 mbar verringert werden.The boiling point of the latter compound, which at 150 ° C is already too high for gentle treatment of books, can be reduced by applying a vacuum when drying the books, as is often the case in the art and also in the art
DE 39 04 111 A1 is specified, can be reduced to about 70 ° C at about 100 mbar.
Siloxane der genannten Art sind mit vielen anderen Lösemitteln, z.B. Alkoholen, die als Lösevermittler für Methylmagnesiumcarbonat und zu dessen Stabilisierung eingesetzt werden, mischbar und sind gute Lösemittel für viele metallorganische Verbindungen, während die gebräuchlichen Materialien und Hilfsmittel, die zur Bücherherstellung verwendet werden, wie z.B. Druckfarben, Leim und Klebemittel, Kunststoffe für Einbanddeckel sowie auch Tinten und Stempelfarben, von Siloxanen weder gelöst noch in einer anderen Art geschädigt werden.Siloxanes of the type mentioned are compatible with many other solvents, e.g. Alcohols, which are used as solubilizers for methyl magnesium carbonate and to stabilize it, are miscible and are good solvents for many organometallic compounds, while the common materials and auxiliaries used for book production, e.g. Printing inks, glue and adhesives, plastics for cover covers as well as inks and stamping inks, can neither be loosened nor damaged in any other way by siloxanes.
Zur Veranschaulichung sei folgendes Beispiel aufgeführt: Gummisofern es sich nicht um Spezialgummitypen handelt - wird von Mineralölen und Lösemitteln wie Benzinkohlenwasserstoffen, Aromaten, Estern und Alkoholen zerstört oder erfährt durch diese Stoffe eine starke Quellung, wohingegen Polysiloxane der genannten Art vorzügliche Schmier- und Pflegemittel für Gummi darstellen.The following example is used to illustrate this: Rubber, if it is not a special type of rubber - is destroyed by mineral oils and solvents such as petroleum hydrocarbons, aromatics, esters and alcohols or experiences a strong swelling due to these substances, whereas polysiloxanes of the type mentioned are excellent lubricants and care agents for rubber represent.
Der Grund für diese gute Verträglichkeit ist in dem von Gummielastomeren stark abweichenden chemischen Aufbau der Siloxane zu sehen, der sich in seiner chemischen Konfiguration mehr den zur Bücherentsäuerung verwendeten metallorganischen Verbindungen annähert.The reason for this good compatibility can be seen in the chemical structure of the siloxanes, which differs greatly from that of rubber elastomers. Its chemical configuration more closely approximates the organometallic compounds used for book deacidification.
Die bereits genannte DE 390411 A1 gibt zur Trocknung der Bücher nach der Behandlung die Anwendung von Mikrowellen an; dadurch wird sowohl eine rasche als auch schonende Behandlung der Bücher ermöglicht.The aforementioned DE 390411 A1 specifies the use of microwaves for drying the books after the treatment; this enables both quick and gentle handling of the books.
Die Erwärmbarkeit eines Stoffes im Mikrowellenfeld ist dabei im wesentlichen von dessen Dielektrizitätszahl εr und dem dielektrischen Verlustfaktor tan δ, die beide spezifische Stoffeigenschaften sind, abhängig; je höher diese Werte sind, desto besser ist der Stoff im Mikrowellenfeld erwärmbar.The heatability of a substance in the microwave field is essentially dependent on its dielectric constant ε r and the dielectric loss factor tan δ, both of which are specific properties of the substance are dependent; the higher these values are, the better the material can be heated in the microwave field.
Die Literatur gibt für Siloxane der genannten Art vergleichsweise niedrige Werte für diese Kennzahlen an mit εr = ca. 2-3 und tan δ = ca. 1-2x10⁻⁵.The literature gives comparatively low values for these key figures for siloxanes of the type mentioned, with ε r = approx. 2-3 and tan δ = approx. 1-2x10⁻⁵.
Überraschenderweise zeigte es sich jedoch, daß Bücher, die mit Siloxanen mit einer Kettenlänge von 2-4 Siliziumatomen getränkt sind, im Mikrowellenfeld in kurzer Zeit auf ausreichende Temperaturen erwärmt werden können.Surprisingly, however, it was found that books which are impregnated with siloxanes with a chain length of 2-4 silicon atoms can be heated to sufficient temperatures in the microwave field in a short time.
So konnte z.B. eine linearkettige Siloxanprobe mit 4 Siliziumatomen (n = 2) und einem Gewicht von 1 kg bei einer Frequenz von 2450 MHz und einer Mikrowellenleistung von 600 W innerhalb weniger Minuten auf 80°C erwärmt werden.For example, a linear chain siloxane sample with 4 silicon atoms (n = 2) and a weight of 1 kg at a frequency of 2450 MHz and a microwave power of 600 W can be heated to 80 ° C within a few minutes.
Damit sind die erfindungsgemäßen Lösemittel ebensogut wie die bisherigen Lösemittel zur Verwendung in rationellen Verfahren der genannten Art mit Mikrowellentrocknung geignet. Jedoch ist daneben auch die Verwendung in konventionellen Trocknungsververfahren anderer Art, die keine Mikrowellen benutzen, möglich.The solvents according to the invention are therefore just as suitable as the previous solvents for use in rational processes of the type mentioned with microwave drying. However, it can also be used in other conventional drying processes that do not use microwaves.
Gerade diese relativ schwache, hochfrequente Energieankopplung ermöglicht eine besonders schonende Trocknung der Bücher; im Falle einer sehr starken Ankopplung und damit sehr raschen Erwärmung der lösemittelgetränkten Bücher besteht die Gefahr, daß die Bücher durch spontane Dampfbildung im Buchblock beschädigt oder gar zerstört werden.It is this relatively weak, high-frequency coupling of energy that enables the books to be dried gently; in the case of a very strong coupling and thus very rapid heating of the solvent-soaked books, there is a risk that the books will be damaged or even destroyed by spontaneous steam formation in the book block.
Ein weiterer Vorteil bei Verwendung der genannten Siloxane zur Bücherentsäuerung ergibt sich aus der geringen Dichte dieser Siloxane, die z. B. 0,761 g/cm³ (für n = 0) bzw. 0,818 g/cm³ (für n = 1) beträgt.Another advantage of using the aforementioned siloxanes for book deacidification results from their low density Siloxanes, e.g. B. 0.761 g / cm³ (for n = 0) or 0.818 g / cm³ (for n = 1).
Während bei Verwendung von Fluor- und Fluorchlorkohlenwasserstoffen infolge der hohen Dichte dieser Lösemittel die Bücher bei der Behandlung aufschwimmen, wird dies bei den erfindungsgemäßen Lösemitteln vermieden, wodurch sich apparative Vereinfachungen ergeben.While when using fluorocarbons and chlorofluorocarbons due to the high density of these solvents, the books float during treatment, this is avoided with the solvents according to the invention, which results in simplifications of the apparatus.
Bei Verwendung von Fluor- und Fluorchlorkohlenwasserstoffen muß das Aufschwimmen der Bücher in der Behandlungslösung durch zeitraubende Maßnahmen verhindert werden. Außerdem können Einbauten, die das Aufschwimmen verhindern sollen, Störungen des Mikrowellenfeldes bei der Trocknung verursachen.When using fluorocarbons and chlorofluorocarbons, the floating of the books in the treatment solution must be prevented by time-consuming measures. In addition, installations that are intended to prevent floating can cause disturbances in the microwave field during drying.
Die erfindungsgemäßen Siloxane eignen sich sehr gut für das bekannte Neutralisationsmittel Methylmagnesiumcarbonat. Jedoch sind sie auch für andere, gegebenenfalls zukünftig ermittelte metallorganische Verbindungen, die sich in irgendeiner Weise als wirkungsvolles Behandlungsagens zur Massenentsäuerung herausstellen, einsetzbar.The siloxanes according to the invention are very suitable for the known neutralizing agent methyl magnesium carbonate. However, they can also be used for other organometallic compounds which may be determined in the future and which in some way turn out to be an effective treatment agent for mass deacidification.
In einem der Versuche wurden z.B. Methylmagnesiumcarbonatlösung (Magnesiumgehalt 3 %, gelöst in Alkohol und 87,5 g Hexamethyldisiloxan anstelle des üblichen FCKW-Lösemittels für die Entsäuerung eingesetzt. Bei einem mit dieser Lösung behandelten Papier konnte der pH-Wert von 4,5 des unbehandelten Papiers auf 8,5 angehoben werden; die freien Säuren im Papier wurden neutralisiert, gleichzeitig wurde eine alkalische Pufferreserve in das Papier eingebracht. Eine Schädigung des Papiers bzw. der Beschriftung war nicht zu beobachten.In one of the experiments e.g. Methyl magnesium carbonate solution (magnesium content 3%, dissolved in alcohol and 87.5 g hexamethyldisiloxane instead of the usual CFC solvent for deacidification. With a paper treated with this solution, the pH value of 4.5 of the untreated paper could be raised to 8.5 The free acids in the paper were neutralized, at the same time an alkaline buffer reserve was introduced into the paper, and no damage to the paper or the lettering was observed.
Claims (6)
dadurch gekennzeichnet,
daß das Lösemittel ein Methylsiloxan das 2, 3 oder 4 Siliziumatome enthält,ist oder verschiedene derartiger Methylsiloxane umfaßt.Solvents for agents for environmentally friendly mass deacidification of books and other paper products,
characterized,
that the solvent is a methyl siloxane containing 2, 3 or 4 silicon atoms, or includes various such methyl siloxanes.
dadurch gekennzeichnet,
daß das Lösemittel Hexamethyldisiloxan ist oder umfaßt.Solvent according to claim 1,
characterized,
that the solvent is or comprises hexamethyldisiloxane.
dadurch gekennzeichnet,
daß auch terminale Siliziumvalenzen sämtlicher oder einiger der Methylsiloxane von Methylgruppen besetzt sind.Solvent according to claim 1 or 2,
characterized,
that terminal silicon valences of all or some of the methylsiloxanes are also occupied by methyl groups.
dadurch gekennzeichnet,
daß ein oder mehrere Siliziumvalenzen sämtlicher oder einiger Methylsiloxane von H-Atomen besetzt sind.Solvent according to claim 1 or 2,
characterized,
that one or more silicon valences of all or some methylsiloxanes are occupied by hydrogen atoms.
dadurch gekennzeichnet,
daß ein oder mehrere Siliziumvalenzen sämtlicher oder einiger der Methylsiloxane von funktionellen Gruppen besetzt sind, die in der Lage sind, mit der Zellulose des Papiers zu reagieren.Solvent according to claim 1 or 2,
characterized,
that one or more silicon valences of all or some of the methylsiloxanes are occupied by functional groups that are able to react with the cellulose of the paper.
dadurch gekennzeichnet,
daß ein oder mehrere nicht mit Methylgruppen besetzte Siliziumvalenzen der Methylsiloxane wahlweise mit H-Atomen und/oder mit funktionellen Gruppen besetzt sind, die in der Lage sind, mit der Zellulose des Papiers zu reagieren.Solvent according to claim 1 or 2,
characterized,
that one or more silicon valences of the methylsiloxanes not occupied by methyl groups are optionally occupied by H atoms and / or by functional groups which are able to react with the cellulose of the paper.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4104515 | 1991-02-14 | ||
| DE4104515A DE4104515C1 (en) | 1991-02-14 | 1991-02-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0499076A1 true EP0499076A1 (en) | 1992-08-19 |
| EP0499076B1 EP0499076B1 (en) | 1995-08-02 |
Family
ID=6425050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92101209A Expired - Lifetime EP0499076B1 (en) | 1991-02-14 | 1992-01-25 | Solvent for ecologically mass deacidifying book and other paper articles |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0499076B1 (en) |
| JP (1) | JPH0693245A (en) |
| AT (1) | ATE125896T1 (en) |
| CA (1) | CA2060926C (en) |
| DE (2) | DE4104515C1 (en) |
| ES (1) | ES2077885T3 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0582265A1 (en) * | 1992-08-04 | 1994-02-09 | BATTELLE INGENIEURTECHNIK GmbH | Process for restoring damaged papier |
| WO2002042557A1 (en) * | 2000-11-21 | 2002-05-30 | ZFB Zentrum für Bucherhaltung GmbH | Solidifying agent and/or stabilizer |
| FR2825726A1 (en) * | 2001-06-12 | 2002-12-13 | Herve Cheradame | Deacidification of paper, useful for preserving or restoring old documents, by treatment with solution containing polymerizable amino-substituted alkoxysilane |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010070082A (en) * | 2000-01-10 | 2001-07-25 | 이인수 | The Agent using a Si-Compound Carrier for Long-Term Storage of Prints |
| SK287845B6 (en) * | 2007-09-18 | 2012-01-04 | Stu Fakulta Chemickej A Potravinarskej Technologie | Multifunction device for modification of cellulose materials and method for modification of cellulose materials |
| CN105862513B (en) * | 2016-04-22 | 2018-06-19 | 国家图书馆 | A kind of paper deacidification liquid and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3969549A (en) * | 1974-12-24 | 1976-07-13 | The United States Of America As Represented By The Librarian Of Congress | Method of deacidifying paper |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3904111A1 (en) * | 1989-02-11 | 1990-08-16 | Battelle Institut E V | METHOD AND DEVICE FOR THE ENVIRONMENTALLY FRIENDLY MASS DEIFICATION OF BOOKS AND OTHER PAPER PRODUCTS |
-
1991
- 1991-02-14 DE DE4104515A patent/DE4104515C1/de not_active Expired - Lifetime
-
1992
- 1992-01-25 AT AT92101209T patent/ATE125896T1/en not_active IP Right Cessation
- 1992-01-25 ES ES92101209T patent/ES2077885T3/en not_active Expired - Lifetime
- 1992-01-25 DE DE59203063T patent/DE59203063D1/en not_active Expired - Lifetime
- 1992-01-25 EP EP92101209A patent/EP0499076B1/en not_active Expired - Lifetime
- 1992-02-03 JP JP4047516A patent/JPH0693245A/en active Pending
- 1992-02-10 CA CA002060926A patent/CA2060926C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3969549A (en) * | 1974-12-24 | 1976-07-13 | The United States Of America As Represented By The Librarian Of Congress | Method of deacidifying paper |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0582265A1 (en) * | 1992-08-04 | 1994-02-09 | BATTELLE INGENIEURTECHNIK GmbH | Process for restoring damaged papier |
| WO2002042557A1 (en) * | 2000-11-21 | 2002-05-30 | ZFB Zentrum für Bucherhaltung GmbH | Solidifying agent and/or stabilizer |
| FR2825726A1 (en) * | 2001-06-12 | 2002-12-13 | Herve Cheradame | Deacidification of paper, useful for preserving or restoring old documents, by treatment with solution containing polymerizable amino-substituted alkoxysilane |
| WO2002101148A1 (en) * | 2001-06-12 | 2002-12-19 | Cheradame Herve | Method for treating paper and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0499076B1 (en) | 1995-08-02 |
| DE4104515C1 (en) | 1992-08-06 |
| ATE125896T1 (en) | 1995-08-15 |
| ES2077885T3 (en) | 1995-12-01 |
| DE59203063D1 (en) | 1995-09-07 |
| JPH0693245A (en) | 1994-04-05 |
| CA2060926C (en) | 2003-09-30 |
| CA2060926A1 (en) | 1992-08-15 |
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