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.
• Canadian patent application CA-A-2142195 describes paper deacidification compositions containing methoxymagnesium methylcarbonate or ethoxymagnesium ethylcarbonate in a solvent diluted with a hydrochlorofluorocarbon or a hydrofluorocarbon.
• 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. Preferably, the temperature is equal to or higher than ⁇ 20° C.
• At least the cellulosic material is cooled.
• 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.
• 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:
• 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:
• 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.
• cellulose derivatives and/or natural or non-natural polymers can suitably used.
• cellulose derivatives are selected from carboxymethylcellulose, methylcellulose, ethylcellulose and cellulose ethers.
• non-natural polymers are selected from styrene/acrylate copolymers, polyurethanes and polyamides.
• a specific natural polymer is starch.
• esters of arylcarboxylic acids are preferred.
• the ester is generally an alkyl ester, preferably an allyl 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.
• Preferred biocides correspond to the antioxidants described herebefore.
• 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.
• 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-1-propanol.
• the 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 (C-32), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (EFC-134a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (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 100 mg/kg.
• the deacidification agent is a composition of magnesium propylcarbonate, propanol, in particular n-propanol, and HFC-227ea and/or 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.
• 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.
• a set of books printed on acidic paper in the first half of the twentieth century and having handwritten ink notes written on several pages is selected due to the sensitivity of the mentioned inks to deacidification treatments.
• Examples 1 to 3 were performed using a chamber with cooling equipment which was cooled during the contact of books and stabilizing agent.
• Examples 4 to 6 were performed in a simple treatment chamber without cooling equipment.
• Example 7 (comparison example) was performed without cooling book and stabilizing agent before and during contact.
• a book from the set of books 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 HFC-227ea and the diluted reagent was cooled to ⁇ 15° C. It was then introduced into the treatment chamber while controlling the temperature so as to make sure that the difference between the deacidification reagent and the book did not exceed about 3° C.
• the system reagent/book was kept together for 10 minutes at ⁇ 15° C. 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 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 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, and showed no ink bleeding at the handwritten ink notes.
• 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 HFC-227ea and the diluted reagent was cooled to ⁇ 15° C. Both book and deacidification reagent were then introduced into a simple treatment chamber. 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 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 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.
• 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.

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

Applications Claiming Priority (3)

Publications (1)

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Country Status (6)

Cited By (2)

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Citations (5)

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• 2005
  • 2005-02-25 MX MXPA06009765A patent/MXPA06009765A/es unknown
  • 2005-02-25 US US10/590,977 patent/US20080017336A1/en not_active Abandoned
  • 2005-02-25 CA CA002556626A patent/CA2556626A1/fr not_active Abandoned
  • 2005-02-25 EP EP05716817A patent/EP1759061A1/fr not_active Withdrawn
  • 2005-02-25 WO PCT/EP2005/050827 patent/WO2005083176A1/fr active Application Filing
  • 2005-02-25 BR BRPI0508056-8A patent/BRPI0508056A/pt not_active IP Right Cessation

Patent Citations (5)

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