EP1759061A1 - Procede pour la conservation de materiaux cellulosiques - Google Patents

Procede pour la conservation de materiaux cellulosiques

Info

Publication number
EP1759061A1
EP1759061A1 EP05716817A EP05716817A EP1759061A1 EP 1759061 A1 EP1759061 A1 EP 1759061A1 EP 05716817 A EP05716817 A EP 05716817A EP 05716817 A EP05716817 A EP 05716817A EP 1759061 A1 EP1759061 A1 EP 1759061A1
Authority
EP
European Patent Office
Prior art keywords
cellulosic material
process according
stabilising agent
agent
cooled
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Withdrawn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
EP05716817A
Other languages
German (de)
English (en)
Inventor
Wolfgang WÄCHTER
Juan Solis
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.)
CONSERVACION DE SUSTRATOS CELULOSICOS SL
Original Assignee
CONSERVACION DE SUSTRATOS CELULOSICOS SL
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 CONSERVACION DE SUSTRATOS CELULOSICOS SL filed Critical CONSERVACION DE SUSTRATOS CELULOSICOS SL
Priority to EP05716817A priority Critical patent/EP1759061A1/fr
Publication of EP1759061A1 publication Critical patent/EP1759061A1/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Withdrawn legal-status Critical Current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
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents

Definitions

  • the present invention concerns a process for conservation of a cellulosic material.
  • the process is useful notably for conservation of valuable documents on cellulosic support such as books, manuscripts or works of art, clothes, flags and the like.
  • archives and libraries have struggled to prevent the aging of paper, i.e. notably yellowing and embrMement of paper in documents and books.
  • Many treatments to avoid or stop this aging have been proposed.
  • the primary goals of this treatment are either to transform the paper into another, more stable medium or stabilise the paper against degradation processes.
  • Above documents are subject to deterioration notably because of the acid content in most of the cellulosic materials.
  • the invention concerns in consequence a process for conservation of a cellulosic material, comprising a treatment wherein said cellulosic material is contacted with a stabilising agent, and at least one of the cellulosic material or the stabilising agent is cooled before and/or during the treatment.
  • the cellulosic material is generally a printed and/or coloured cellulosic material.
  • the process according to the invention is compatible with the presence of other materials such as in particular leather used e.g. in book covers.
  • at least one of the cellulosic material or the stabilising agent is generally cooled to a temperature which is less than 20°C. Often this temperature is equal to or less than 10°C. More often, this temperature is equal to or less than 0°C. Preferably, this temperature is equal to or less than -10°C. A temperature of about -15°C is particularly preferred.
  • at least one of the cellulosic material or the stabilising agent is generally cooled to a temperature which is equal to or higher than -50°C. Often, this temperature is equal to or higher than - 30°C.
  • a temperature equal to or higher than -25°C is particularly suitable.
  • the temperature is equal to or higher than -20°C.
  • at least the cellulosic material is cooled.
  • only the stabilising agent is cooled. If the stabilising agent is a composition of several constituents, one or more of the constituents can eventually be cooled before forming the composition.
  • the treatment is carried out at the abovementioned temperature. That means that the system consisting of cellulosic material and stabilising agent is brought to these temperatures. Generally, in this case, the system is kept at that temperature for a time sufficient to ensure the stabilising effect.
  • the cellulosic material and the stabilising agent have substantially the same temperature as they are being contacted.
  • Good results have been achieved with a temperature difference between the cellulosic material and the stabilising agent of less than 20°C.
  • this temperature difference is less than 10°C and more preferably, it is less than 5°C.
  • the temperature difference is about 1°C or less.
  • the process according to the invention is often carried out at a pressure at which the stabilising agent is in the liquid phase, being understood that suspensions, dispersions and slurries are also considered as liquid phases. A solution is preferred when the stabilising agent is in the liquid phase.
  • the process according to the invention can be carried out with a stabilising agent which is in the vapour phase under the treatment conditions.
  • Typical working pressures in the process according to the invention range from 1 to 10 bar.
  • the duration of the treatment is generally at most 50 hours, preferably at most 10 hours.
  • the duration of the treatment is more preferably less than or equal to about 3 hours.
  • a duration of the treatment equal to our less than 1 hour, for example 30-45 min is more particularly preferred.
  • treatment times of more than or equal to about 2 hours give also particularly good results. It has been found, surprisingly, that the process according to the invention allows for short treatment times in spite of cooling stabilising agent and/or cellulosic material.
  • the cellulosic material is not dried before the treatment.
  • the cellulosic material is slightly dried before the treatment so that it looses about 1 - 2% of moisture content by weight relative to the total weight of the cellulosic material before treatment. Such slight drying can be brought about by gentle heating of the cellulosic material to 30 to 50°C, preferably about 40°C.
  • a first particular ⁇ way of carrying out the process according to the invention comprises :
  • step (b) contacting the cellulosic material and the stabilising agent cooled in step (a), preferably in a treatment chamber which has optionally been cooled before introducing the cellulosic material;
  • a second particular way of carrying out the process according to the invention comprises :
  • a third particular way of carrying out the process according to the invention comprises :
  • step (b) contacting the cellulosic material cooled in step (a) and the stabilising agent optionally cooled in step (a) in a treatment chamber;
  • step (d) optionally, recovering excess quantities or constituents separated in step (c).
  • at least the cellulosic material, but optionally also the stabilizing agent are cooled before bringing them into contact. It is preferred to cool both cellulosic material and stabilizing agent before contacting them.
  • the treatment chamber may be of a simple type which comprises no cooling equipment or in which cooling equipment is not actuated.
  • the stabilising agent is often selected from fibre strengtheners, sizing agents, antioxidants, biocides and/or deacidification reagents. *- Among fibre strengtheners and sizing agents, cellulose derivatives and/or natural or non-natural polymers can suitably used.
  • cellulose derivatives are selected from carboxymethylcellulose, methylcellulose, ethylcellulose and cellulose ethers.
  • Specific examples of non-natural polymers are selected from styrene/acrylate copolymers, polyurethanes and polyamides.
  • a specific natural polymer is starch.
  • antioxidants derivatives of oxidizable arylcarboxylic acids, in particular hydroxyarylcarboxylic acids can suitably be used. Esters of arylcarboxylic acids are preferred.
  • the ester is generally an alkyl ester, preferably an alkyl ester derived from a linear, branched or cyclic alkyl radical having generally from 1 to 10, preferably from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl, isopropyl or butyl radicals, or their mixtures.
  • a derivative, in particular an alkyl ester of the p-hydroxibenzoic acid is used which is preferably selected among methyl p-hydroxibenzoate, ethyl p-hydroxibenzoate, propyl p-hydroxibenzoate, butyl p-hydroxibenzoate and their blends.
  • the stabilising agent is preferably a deacidification agent.
  • the deacidification agent generally comprises a base which can be selected for example from basic metal derivatives, from organometallic derivatives or from alkaline monomers such as acrylates.
  • Examples of particular basic metal derivatives suitable for use in the present invention include the oxides, hydroxides, carbonates and bicarbonates of zinc and metals in Group I, II and IV of the Periodic Table.
  • the bases are preferably oxides, hydroxides, carbonates and bicarbonates of magnesium, titanium, calcium, sodium, potassium, zinc, or combinations of two or more thereof.
  • agents include magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium methyl carbonate, titanium alcoholates, calcium oxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, zinc carbonate, zinc bicarbonate, zinc oxide, and combinations of two or more thereof.
  • Basic alkaline earth metal derivatives in particular magnesium compounds or salts are preferred.
  • Most preferred bases are selected from magnesium alkoxycarbonates such as carbonates derived from magnesiumdimethanolate, magnesiumdiethanolate and in particular magnesiumdipropanolate.
  • the deacidification agent may optionally comprise a solvent selected for example from alcohols, in particular having 1 to 4 carbon atoms, and non- halogenated or halogenated hydrocarbon solvents or ethers.
  • Such solvents include for example methanol, ethanol, isopropanoL n-propanol, isobutanol, propane, butanes, pentanes, isohexanes, heptanes, alkylsiloxanes, HFE-7100 and HFE-7200.
  • n-propanol is preferred.
  • the solvent comprises a fluorinated alcohol such as 2,2,3,3,3-pentafluoro-l -propanol.
  • Ihe stabilising agent in particular the deacidification agent comprises a hydrofluoroalkane. Suitable hydrofluoroalkanes generally comprise from 1 to 10, preferably from 2 to 6 carbon atoms.
  • hydrofluoroalkanes are selected from difluoromethane (HFC-32), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoro ⁇ ropane (HFC-236fa), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and 1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC-43-10mee).
  • HFC-227ea, HFC-134a and their mixtures are preferred.
  • a surfactant may optionally be present, in particular if no solvent is used.
  • the moisture content of optional solvent and hydrofluoroalkane is generally less than 1000 mg kg. This content can also be below 200 or lOO mg/kg.
  • the deacidification agent is a composition of magnesium propylcarbonate, propanol, in particular n-propanol, and HFC-227ea andor HFC-134a. This composition and its manufacture is described in EP-1111128 whose content is incorporated by reference in the present application.
  • This particular deacidification agent is generally in the form of a solution and is comprised of carbonated magnesium di-n-propylate preferably in n-propanol, and an HFC diluent selected from 1,1,1,2- tetrafluoroethane (HFC-134a) and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227).
  • Carbonated magnesium di-n-propylate is a solid with the formula (CH3CH2CH2O)2 MgOCO.
  • the concentration of carbonated magnesium di-n-propylate in n-propanol is preferably between 30 and 70% (weight by weight relative to the total weight of carbonated magnesium di-n-propylate and n-propanol).
  • a composition comprising 1.5 — 2.0% (weight by weight relative to the total weight of the composition) of carbonated magnesium di-n-propylate, 3.0 - 4.0% of n-propanol and the remainder consisting essentially of HFC is more particularly preferred.
  • the invention is illustrated in a non-limitative manner by the examples hereafter :
  • Example 1 Deacidification process performed in a cooled treatment chamber In a treatment chamber, a book from the set of books mentioned under
  • Example 2 Example 1 was repeated with the same type of book and the same deacidification reagent but the temperatures were -20°C. The treated book was effectively deacidified and showed no ink bleeding at the handwritten ink notes.
  • Example 3 Example 1 was repeated with the same type of book and the same deacidification reagent but the temperatures were -25°C. The treated book was effectively deacidified ⁇ nd showed no ink bleeding at the handwritten ink notes.
  • Example 4 Deacidification process performed in a treatment chamber without cooling equipment A book of the set of books as mentioned under "General remarks" above was cooled to a temperature of -15 °C. A deacidification reagent corresponding to the preferred embodiment described on p. 7, lines 12 to 20 was diluted with
  • the system reagent/book was kept together for 10 minutes for impregnation, then the chamber was drained for 30 minutes and then the remaining volatiles were removed by evaporation for 1.5 hours.
  • the treated book was effectively deacidified and showed no ink bleeding at the handwritten ink notes.
  • Example 5 Example 4 was repeated with the same type of book and the same deacidification reagent but the temperatures were -20°C. The treated book was effectively deacidified and showed no ink bleeding at the handwritten ink notes.
  • Example 6 Example 4 was repeated with the same type of book and same deacidification reagent but the temperatures were -25°C. The treated book was effectively deacidified and showed no ink bleeding at the handwritten ink notes. Of course, examples 4 to 6 as well could have been performed in a treatment chamber with cooling equipment kept switched off.
  • Example 7 (comparison) Example 1 was repeated with the same type of book and the same deacidification reagent but without temperature control, at room temperature. The treated book was deacidified but showed considerable ink bleeding at the handwritten ink notes.

Landscapes

  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paper (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

L'invention concerne un procédé de conservation de matériau cellulosique, comprenant un traitement consistant à faire entrer en contact le matériau cellulosique avec un agent stabilisateur, et à refroidir le matériau cellulosique et/ou l'agent stabilisateur avant et/ou pendant le traitement. L'agent stabilisateur préféré est un agent de désacidification contenant du dipropoxycarbonate de magnésium, du propanol, et un HFC choisi entre HFC-134a et HFC-227ea.
EP05716817A 2004-02-27 2005-02-25 Procede pour la conservation de materiaux cellulosiques Withdrawn EP1759061A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05716817A EP1759061A1 (fr) 2004-02-27 2005-02-25 Procede pour la conservation de materiaux cellulosiques

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP04100790 2004-02-27
PCT/EP2005/050827 WO2005083176A1 (fr) 2004-02-27 2005-02-25 Procede de conservation de materiaux cellulosiques
EP05716817A EP1759061A1 (fr) 2004-02-27 2005-02-25 Procede pour la conservation de materiaux cellulosiques

Publications (1)

Publication Number Publication Date
EP1759061A1 true EP1759061A1 (fr) 2007-03-07

Family

ID=34896107

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05716817A Withdrawn EP1759061A1 (fr) 2004-02-27 2005-02-25 Procede pour la conservation de materiaux cellulosiques

Country Status (6)

Country Link
US (1) US20080017336A1 (fr)
EP (1) EP1759061A1 (fr)
BR (1) BRPI0508056A (fr)
CA (1) CA2556626A1 (fr)
MX (1) MXPA06009765A (fr)
WO (1) WO2005083176A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SK287845B6 (sk) 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
SK50682009A3 (sk) * 2009-11-02 2011-05-06 Stu Fakulta Chemickej A Potravinárskej Technológie Zmes určená na jednostupňovú modifikáciu kyslých papierov a spôsob použitia tejto zmesi
EP2626464B1 (fr) * 2011-12-15 2017-03-22 Institutul National de Cercetare Dezvoltare Pentru Chimie si Petrochimie - Icechim Composition de désacidification de papier, procédé permettant de l'obtenir et son procédé d'application
DE102015107863A1 (de) * 2015-05-19 2016-11-24 GSK mbH - Gesellschaft zur Sicherung von schriftlichem Kulturgut mit beschränkter Haftung Vorrichtung und Verfahren zur Entfernung von Verunreinigungen und zur Desinfektion von Archivalien
CN105885547B (zh) * 2016-06-14 2017-05-17 陕西师范大学 一种醋酸纤维素酯胶片脱酸加固剂

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1271281A (en) * 1968-07-31 1972-04-19 Ethyl Corp Coating of webs by freeze-drying and products therefrom
US3676182A (en) * 1970-08-31 1972-07-11 Richard Daniel Smith Treatment of cellulosic materials
US4522843A (en) * 1984-01-25 1985-06-11 Kundrot Robert A Deacidification of library materials
US4860685A (en) * 1985-07-10 1989-08-29 Smith Richard D Treatment of cellulosic materials
AT391721B (de) * 1986-12-30 1990-11-26 Republik Oesterreich Diese Ver Verfahren und vorrichtung zur konservatorischen behandlung von papier
DE3904111A1 (de) * 1989-02-11 1990-08-16 Battelle Institut E V Verfahren und vorrichtung zur umweltfreundlichen massenentsaeuerung von buechern und anderen papiererzeugnissen
CA2142195A1 (fr) 1995-02-08 1996-08-09 D. James Worsfold Desacidification de matieres cellulosiques
EP1069237A1 (fr) * 1999-07-13 2001-01-17 Damir Turkovic Procédé pour lutter contre les parasites dans les livres
EP1468143A1 (fr) * 2002-01-15 2004-10-20 Consorzio Interuniversitario per lo Sviluppo dei Sistemi a Grande Interfase, C.S.G.I Suspension basique, elaboration de cette suspension, et procede de desacidification du papier

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005083176A1 *

Also Published As

Publication number Publication date
WO2005083176A1 (fr) 2005-09-09
BRPI0508056A (pt) 2007-07-17
US20080017336A1 (en) 2008-01-24
MXPA06009765A (es) 2007-03-23
CA2556626A1 (fr) 2005-09-09

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