EP1341966A1 - Agent de consolidation et/ou de stabilisation - Google Patents

Agent de consolidation et/ou de stabilisation

Info

Publication number
EP1341966A1
EP1341966A1 EP01997592A EP01997592A EP1341966A1 EP 1341966 A1 EP1341966 A1 EP 1341966A1 EP 01997592 A EP01997592 A EP 01997592A EP 01997592 A EP01997592 A EP 01997592A EP 1341966 A1 EP1341966 A1 EP 1341966A1
Authority
EP
European Patent Office
Prior art keywords
derivatives
paper
organic material
fixing
agent according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01997592A
Other languages
German (de)
English (en)
Inventor
Manfred Anders
Karl Bredereck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zfb Zentrum Fur Bucherhaltung GmbH
Original Assignee
Zfb Zentrum Fur Bucherhaltung GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zfb Zentrum Fur Bucherhaltung GmbH filed Critical Zfb Zentrum Fur Bucherhaltung GmbH
Publication of EP1341966A1 publication Critical patent/EP1341966A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose

Definitions

  • the present invention relates to strengthening agents and / or stabilizing agents for organic material, a method for strengthening / stabilizing organic material and the use of the strengthening or stabilizing agents.
  • Paper is also stabilized by lamination, with a thin polymer film being applied to the paper on one or both sides by melting or gluing.
  • the disadvantage of this single sheet process is the increasing paper thickness, so that after treatment and consolidation the cover intended for the book no longer fits. As a further side effect, the handle and the appearance of the paper are changed significantly and the durability of the polymers used is not guaranteed. In addition, no simultaneous deacidification or mass treatment is possible.
  • the Batmaschine Institute has also increased the strength of paper by up to 100% using hexamethyl diisocyanate as a strengthening agent.
  • isocyanates are not compatible with any known soluble deacidifying agent and, when applied directly to the paper, form crosslinked polyureas, a further disadvantage being the increase in hardness of the paper.
  • the object of the invention is therefore to provide a setting agent and / or stabilizing agent, a method for setting and / or stabilizing organic material in bulk and the use of this setting agent for the preservation and restoration of organic material, in which the further decomposition of the organic material prevented and the renewed stabilization by deacidification and consolidation can take place in one step and the stabilization of damaged objects to usable material is achieved.
  • this object is achieved by claims 1, 7, 8 and 10. Preferred further developments result from the subclaims.
  • a strengthening agent for organic material which contains a silylated derivative of a compound containing hydroxyl and / or carboxyl and / or amino groups in a non-polar solvent.
  • the agent according to the invention acts as a protective colloid against hydrolysis-sensitive deacidifying agents and thus delays the reaction of this deacidifying agent with water. This promotes the even distribution of the deacidifying agent with paper, whereby the pre-drying of the paper before deacidification no longer needs to be as extreme.
  • the degree of silylation of the various polyhydroxy compounds allows the solubility to be controlled in a targeted manner, and in principle solvents of the most varied polarity can be used universally.
  • the modified polyhydroxy compounds used according to the invention can generally be adapted to almost all solvents, up to supercritical carbon dioxide as the solvent.
  • the combinations of silylated cellulose ethers with METE show an amazing further effect.
  • the strong interaction between the polyvalent cations of the deacidifying agent and the post-sizing agent also has a positive effect on the distribution of the deacidifying agent on the paper.
  • the silylated compounds act like a protective colloid on the METE because the treatment solution can be easily applied to the non-pre-dried paper without immediate hydrolysis.
  • the hydrophobic silylated cellulose agents wrap around the deacidifying agent, protecting it from moisture and delaying hydrolysis.
  • the silylated polyhydroxy compounds, in particular the silylated cellulose ethers form a transparent film with the METE, which also prevents the formation of coarse crystallites from the deacidifying agent.
  • Organosilyl compounds have been found to be suitable for the invention, the masking of the hydroxyl groups as a rule to trialkylsilyl ethers, usually trimethylsilyl ether, being a suitable method.
  • Trimethylchlorosilane or hexamethyldisilazane can be used as the silylating agent, trialkylsilyl groups being preferred.
  • compounds containing hydroxyl, carboxyl or amino groups have been polysaccharides, carbohydrates and their derivatives, such as alkyl glycosides (e.g. butyl glucoside, octyl glucoside) and alkyl polyglycosides, cellulose and cellulose derivatives (e.g. cellulose ether), Starch and starch derivatives (e.g.
  • starch ether starch ether
  • hemicellulose and hemicellulose derivatives galactomannans and galactomannan derivatives, guar and guar derivatives, chitin and chitin derivatives, chitosan and chitosan derivatives, dextrans and dextran derivatives, dextrins and dextrin derivatives, xanthans and xanthene derivatives, polyvinyl alcohol derivate and polyvinyl , Gelatin and gelatin derivatives or polyethylene amines and their derivatives are shown to be promising.
  • the conversion z. B. the cellulose or the cellulose derivative in the corresponding silylated cellulose derivative makes the resulting compound soluble in non-polar solvents.
  • organic solvents such as alkanes, alkenes or hexamethyldisiloxane (HMDO), supercritical carbon dioxide or halogenated hydrocarbons have proven to be suitable as non-polar solvents, the persilylated or almost persilylated compounds containing hydroxyl or amino groups, e.g. B. polysaccharides or the like, solve well and these are compatible as a solution with the deacidifying agents used in mass deacidification.
  • HMDO hexamethyldisiloxane
  • the silylated compounds are moreover compatible with the hydrolysis-sensitive deacidifying agents, such as magnesium alcoholates, titanium / magnesium alcoholates or the like, which are used in the various mass deacidification processes.
  • the hydrolysis-sensitive deacidifying agents such as magnesium alcoholates, titanium / magnesium alcoholates or the like, which are used in the various mass deacidification processes.
  • This method can also be used to integrate new additives into the chemical system of mass deacidification which, because of their polar nature, could not previously be used. These groups can also be masked here by means of an intermediate silylation of the polar hydroxyl, amine or carboxyl functions. In this way, silylated antioxidants, complexing agents (metal ion deactivators), radical scavengers, light stabilizers (UV stabilizers), peroxide decomposers, antiozonants or pesticides, in particular fungicides, bactericides or insecticides, can be incorporated into the chemical system of mass deacidification.
  • silylated antioxidants complexing agents (metal ion deactivators), radical scavengers, light stabilizers (UV stabilizers), peroxide decomposers, antiozonants or pesticides, in particular fungicides, bactericides or insecticides.
  • HMDO hexamethyldisiloxane
  • HMDO HMDO.
  • the hydrolysis of the unstable (cellulose) silyl ethers is catalyzed by acids, but also by bases.
  • Persilylated polysaccharide derivatives are relatively stable due to their hydrophobic character and hydrolyze only very slowly.
  • the voluminous trimethylsilyl groups make it difficult for water to reach the ether oxygen atom (steric hindrance).
  • celluloses with an average degree of substitution (MS) of 1, 5 or less hydrolyze very quickly because they do not have this steric hindrance.
  • MS average degree of substitution
  • the degree of substitution makes it possible, on the one hand, to vary the solubility of (polyhydroxy) compounds, in particular polysaccharides, from polar (water) to nonpolar (petroleum ether) and, on the other hand, to specifically control the sensitivity to hydrolysis.
  • the substances known from aqueous treatment can also be used from non-polar solvents, whereby the compatibility with hydrolysis-sensitive deacidifying agents enables simultaneous deacidification of the organic material to be treated.
  • paper is preserved and restored; Wood, textiles, paints and inks, as well as a fixation of soluble inks before an aqueous treatment possible.
  • the results of the paper strengths were determined by elongation at break test in the running direction of the papers as work load [J / m 2 ].
  • the mechanical strength of the samples was tested both immediately after the treatment and after five weeks (35 days) of artificial aging at 80 ° C., 65% relative atmospheric humidity.
  • silylated cellulose derivatives compensate for part of the loss of strength due to deacidification.
  • the silyl groups on the cellulose ethers split off, the molecules becoming more polar and thus also being able to form stronger interactions with the paper fibers.
  • the strength of the paper increases.
  • Papers treated with strengthening agents and deacidifying agents have a higher strength after the artificial aging than the untreated paper before the artificial aging.
  • the strengthening agent used according to the invention in the present case a silylated cellulose ether, significantly delays the hydrolysis of the deacidifying agent.
  • the hydrophobic silylated cellulose ethers encase the deacidifying agent. This protects it against moisture and hydrolysis delayed.
  • the treatment solution can easily be applied to the (not pre-dried) paper without immediate hydrolysis.
  • the silylated cellulose ethers form a transparent film with the METE. This is also shown by the following scanning electron microscopic images. While the paper that has only been deacidified with METE is completely coated with fine crystallites of the hydrolyzed deacidifying agent (Fig.
  • the very hydrolysis-sensitive deacidifying agents of the mass deacidification processes can be used directly in single sheet treatment, even without pre-drying the paper.
  • Example 3 Deacidification and consolidation with METE in HMDO as deacidifying agent in the
  • the strengthening agent for organic material according to the invention leads to a significant and permanent improvement in the mechanical strength of the paper.
  • the hydrolysis of the deacidifying agent can be retarded to such an extent that such extreme predrying, as is common today, is no longer necessary in mass deacidification.
  • Old and partly moldy wooden objects, in which the cellulose part has already largely decomposed, are treated with a persylated trimethylsilyl cellulose (TMSC) dissolved in pentane. After filling the voids in the wooden article with this solution, e.g. through a vacuum impregnation, the volatile pentane evaporates.
  • TMSC persylated trimethylsilyl cellulose
  • TMSC hydrolyzes to pure cellulose at room temperature in about 6 months.
  • the cellulose formed in this way is again in the interior of the wood, which is therefore as fiber-forming semi-crystalline substance again contributes to a considerable stabilization of the wood.
  • Paints and inks that bleed easily in water can be fixed with highly substituted polysaccharide silyl ethers before aqueous treatment.
  • the effectiveness is best if the paper to be treated is coated on both sides with a solution of highly substituted polysaccharide silyl ethers. At these points, the paper becomes so hydrophobic that no polar solvent (water) reaches the colors and inks and bleeding does not occur.
  • a deacidifying agent that is also dissolved in the treatment solution, e.g. METE the paper to be deacidified at these areas.
  • a 0.5 to 5% by weight solution with heptane or pentane is preferably used as the solvent.

Landscapes

  • Paper (AREA)

Abstract

La présente invention concerne un agent de consolidation et/ou de stabilisation destiné à une matière organique, qui renferme un dérivé silylé d'un composé contenant des groupes hydroxyle, carboxyle ou amino dans un solvant non polaire. La présente invention concerne également un procédé pour consolider et/ou stabiliser une matière organique, procédé dans lequel cet agent de consolidation est utilisé. Ledit agent de consolidation peut, entre autres, être utilisé pour conserver et restaurer du papier, du bois, des matières textiles, des peintures et des encres.
EP01997592A 2000-11-21 2001-11-21 Agent de consolidation et/ou de stabilisation Withdrawn EP1341966A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE2000157554 DE10057554B4 (de) 2000-11-21 2000-11-21 Festigungs- und/oder Stabilisierungsmittel, Verfahren zur Festigung/Stabilisierung und Verwendung
DE10057554 2000-11-21
PCT/EP2001/013567 WO2002042557A1 (fr) 2000-11-21 2001-11-21 Agent de consolidation et/ou de stabilisation

Publications (1)

Publication Number Publication Date
EP1341966A1 true EP1341966A1 (fr) 2003-09-10

Family

ID=7663989

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01997592A Withdrawn EP1341966A1 (fr) 2000-11-21 2001-11-21 Agent de consolidation et/ou de stabilisation

Country Status (3)

Country Link
EP (1) EP1341966A1 (fr)
DE (1) DE10057554B4 (fr)
WO (1) WO2002042557A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10343047B4 (de) * 2003-09-16 2008-08-07 Zfb Project-Management Gmbh Antioxidationsmittel für organisches Material und Verfahren zur Behandlung desselben
DE102007017303A1 (de) * 2007-04-11 2008-10-16 Institut für Textil- und Verfahrenstechnik der Deutschen Institute für Textil- und Faserforschung Denkendorf - Stiftung des öffentlichen Rec Antibakteriell wirksames Mittel und dessen Verwendung
EP3072933B1 (fr) * 2015-03-23 2021-05-05 Universität Graz Nanoparticules composites alcalines stabilisées, procédé de production et utilisation de celles-ci
DE102017214349B4 (de) * 2017-08-17 2021-06-10 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung von silylierten Alkylcellulosen als Klebstoff
EP3670713A1 (fr) * 2018-12-21 2020-06-24 PresCon AG Utilisation du procédé d'électrofilage destinée à la conservation et à la restauration des biens culturels et dispositif correspondant
CN110106743A (zh) * 2019-05-31 2019-08-09 华南理工大学 一种酸化老化纸质文献脱酸增强剂的制备及使用方法
CN112962348B (zh) * 2021-02-05 2022-11-29 青岛大学 一种修复破损老化纸质档案纸张的方法
CN118979410A (zh) * 2024-08-13 2024-11-19 陕西师范大学 一种改良乙基纤维素加固剂及其制备方法和在铁盐晒图纸加固中的应用

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2532622A (en) * 1949-02-23 1950-12-05 Dow Corning Organo silicon derivatives of cellulose
US3418312A (en) * 1966-09-09 1968-12-24 Gen Electric Process for producing soluble trimethylsilylated cellulose
US3941733A (en) * 1975-01-02 1976-03-02 Minnesota Mining And Manufacturing Company Silanol-containing urethane dispersions
US4992538A (en) * 1989-06-05 1991-02-12 Aqualon Company Silated polysaccharides
DD299314A5 (de) * 1989-11-23 1992-04-09 Friedrich-Schiller-Universitaet Jena,De Verfahren zur herstellung von o-trialkylsilylcellulosen
US5059686A (en) * 1990-09-28 1991-10-22 Aqualon Company Silated polysaccharides
DE4104515C1 (fr) * 1991-02-14 1992-08-06 Battelle-Institut Ev, 6000 Frankfurt, De
DE4138750A1 (de) * 1991-11-26 1993-05-27 Battelle Institut E V Neutralisationsmittel zur wirkungsvollen und schonenden massenentsaeuerung von buechern und anderen papiererzeugnissen
DE19543707A1 (de) * 1995-11-23 1997-05-28 Inst Neue Mat Gemein Gmbh Verfahren zum Konservieren von Papier
US5990333A (en) * 1996-06-19 1999-11-23 Hercules Incorporated Silyl-linked polyamidoamines and their preparation
EP1001084A3 (fr) * 1998-11-16 2002-01-16 ZFB Zentrum für Bucherhaltung GmbH Agent de déacidification

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0242557A1 *

Also Published As

Publication number Publication date
WO2002042557A1 (fr) 2002-05-30
DE10057554A1 (de) 2002-06-06
DE10057554B4 (de) 2007-05-24

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