CA2556626A1 - Process for preservation of cellulosic materials - Google Patents
Process for preservation of cellulosic materials Download PDFInfo
- Publication number
- CA2556626A1 CA2556626A1 CA002556626A CA2556626A CA2556626A1 CA 2556626 A1 CA2556626 A1 CA 2556626A1 CA 002556626 A CA002556626 A CA 002556626A CA 2556626 A CA2556626 A CA 2556626A CA 2556626 A1 CA2556626 A1 CA 2556626A1
- Authority
- CA
- Canada
- 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.)
- Abandoned
Links
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000004321 preservation Methods 0.000 title description 2
- 239000003381 stabilizer Substances 0.000 claims abstract description 54
- 238000011282 treatment Methods 0.000 claims abstract description 47
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 claims abstract description 10
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000470 constituent Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 150000005828 hydrofluoroalkanes Chemical class 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000003139 biocide Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- XOSPKEFUTSNHHS-UHFFFAOYSA-L magnesium;propyl carbonate Chemical group [Mg+2].CCCOC([O-])=O.CCCOC([O-])=O XOSPKEFUTSNHHS-UHFFFAOYSA-L 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229940043430 calcium compound Drugs 0.000 claims 1
- 150000001674 calcium compounds Chemical class 0.000 claims 1
- 239000000976 ink Substances 0.000 description 18
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- 230000000740 bleeding effect Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- -1 cyclic alkyl radical Chemical class 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229920005615 natural polymer Polymers 0.000 description 3
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- YUHZIUAREWNXJT-UHFFFAOYSA-N (2-fluoropyridin-3-yl)boronic acid Chemical class OB(O)C1=CC=CN=C1F YUHZIUAREWNXJT-UHFFFAOYSA-N 0.000 description 1
- RIQRGMUSBYGDBL-UHFFFAOYSA-N 1,1,1,2,2,3,4,5,5,5-decafluoropentane Chemical compound FC(F)(F)C(F)C(F)C(F)(F)C(F)(F)F RIQRGMUSBYGDBL-UHFFFAOYSA-N 0.000 description 1
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 1
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 1
- 229940044613 1-propanol Drugs 0.000 description 1
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005376 alkyl siloxane group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- NWXABJPNOZDLKI-UHFFFAOYSA-M magnesium;ethanolate;ethyl carbonate Chemical compound [Mg+2].CC[O-].CCOC([O-])=O NWXABJPNOZDLKI-UHFFFAOYSA-M 0.000 description 1
- PNVKCUSCADAAMP-UHFFFAOYSA-M magnesium;methanolate;methyl carbonate Chemical compound [Mg+2].[O-]C.COC([O-])=O PNVKCUSCADAAMP-UHFFFAOYSA-M 0.000 description 1
- CHKVEDLTACTUAS-UHFFFAOYSA-L magnesium;methyl carbonate Chemical compound [Mg+2].COC([O-])=O.COC([O-])=O CHKVEDLTACTUAS-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- WNJYXPXGUGOGBO-UHFFFAOYSA-N magnesium;propan-1-olate Chemical compound CCCO[Mg]OCCC WNJYXPXGUGOGBO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229960005335 propanol Drugs 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical compound [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 description 1
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
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Paper (AREA)
Abstract
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. A deacidification agent comprising magnesiumdipropoxycarbonate, propanol and an HFC selected from HFC-134a and HFC-227ea is particularly preferred as stabilising agent.
Description
PROCESS FOR PRESERVATION OF CELLULOSIC MATERIALS
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.
During the past 150 years, archives and libraries have struggled to prevent the aging of paper, i.e. notably yellowing and embrittlement 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. Another serious problem encountered in the conservation of books and documents made of paper stems from the readily oxidizable nature of the material. Oxidation not only results in the discoloration of paper but also a considerable mechanical weakening of the text's support. Such discoloration is favoured by light radiation, which constitutes other significant source of degradation in paper. The auto-oxidizing mechanism of degradation which occurs in cellulose during the ageing process (in atmospheric oxygen) is also important in library conservation.
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.
This and other known conservation techniques are not entirely satisfactory as they may cause harm to inks and colours, thus giving rise to problems like ink or colour bleeding, formation of Newton rings and/or white deposits.
It was desirable to find a conservation process, notably a deacidification process which is effective and does not display the problems above, or which at least allows to minimise said problems.
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 andlor 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.
In the process according to the invention, 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.
In the process according to the invention, 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.
In a first preferred embodiment, at least the cellulosic material is cooled.
In a second embodiment, only the stabilising agent is cooled. If the stabilising agent is a composition of several constituents, one or more ofthe constituents can eventually be cooled before forming the composition.
In a third, preferred, embodiment 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.
It is advantageous, in particular in the third embodiment, to ensure that 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. Preferably, this temperature difference is less than 10°C and more preferably, it is less than 5°C. Most preferably, the temperature difference is about 1 °C or less.
The process according to the invention is often carned 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 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.
During the past 150 years, archives and libraries have struggled to prevent the aging of paper, i.e. notably yellowing and embrittlement 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. Another serious problem encountered in the conservation of books and documents made of paper stems from the readily oxidizable nature of the material. Oxidation not only results in the discoloration of paper but also a considerable mechanical weakening of the text's support. Such discoloration is favoured by light radiation, which constitutes other significant source of degradation in paper. The auto-oxidizing mechanism of degradation which occurs in cellulose during the ageing process (in atmospheric oxygen) is also important in library conservation.
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.
This and other known conservation techniques are not entirely satisfactory as they may cause harm to inks and colours, thus giving rise to problems like ink or colour bleeding, formation of Newton rings and/or white deposits.
It was desirable to find a conservation process, notably a deacidification process which is effective and does not display the problems above, or which at least allows to minimise said problems.
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 andlor 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.
In the process according to the invention, 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.
In the process according to the invention, 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.
In a first preferred embodiment, at least the cellulosic material is cooled.
In a second embodiment, only the stabilising agent is cooled. If the stabilising agent is a composition of several constituents, one or more ofthe constituents can eventually be cooled before forming the composition.
In a third, preferred, embodiment 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.
It is advantageous, in particular in the third embodiment, to ensure that 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. Preferably, this temperature difference is less than 10°C and more preferably, it is less than 5°C. Most preferably, the temperature difference is about 1 °C or less.
The process according to the invention is often carned 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.
Alternatively, 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.
In the process according to the invention, 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. However, 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.
In a particular embodiment of the process according to the invention, the cellulosic material is not dried before the treatment.
In another particular embodiment of the process according to the invention, 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) cooling the stabilising agent;
(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;
(c) optionally, separating excess quantities of stabilising agent or constituents of the stabilising agent from the cellulosic material;
(d) optionally, recovering excess quantities or constituents separated in step (c).
A second particular way of carrying out the process according to the invention comprises (a) providing a treatment chamber equipped with a cooling device, which treatment chamber is cooled down before the treatment;
(b) introducing cooled cellulosic material into the treatment chamber;
(c) supplying the optionally cooled stabilising agent to said treatment chamber so as to contact the stabilising agent with the cellulosic material;
Typical working pressures in the process according to the invention range from 1 to 10 bar.
In the process according to the invention, 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. However, 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.
In a particular embodiment of the process according to the invention, the cellulosic material is not dried before the treatment.
In another particular embodiment of the process according to the invention, 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) cooling the stabilising agent;
(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;
(c) optionally, separating excess quantities of stabilising agent or constituents of the stabilising agent from the cellulosic material;
(d) optionally, recovering excess quantities or constituents separated in step (c).
A second particular way of carrying out the process according to the invention comprises (a) providing a treatment chamber equipped with a cooling device, which treatment chamber is cooled down before the treatment;
(b) introducing cooled cellulosic material into the treatment chamber;
(c) supplying the optionally cooled stabilising agent to said treatment chamber so as to contact the stabilising agent with the cellulosic material;
(d) optionally, separating excess quantities of stabilising agent or constituents of the stabilising agent from the cellulosic material;
(e) optionally, recovering excess quantities or constituents separated in step (d).
A third particular way of carrying out the process according to the S invention comprises (a) cooling the cellulosic material and optionally cooling the stabilising agent;
(b) contacting the cellulosic material cooled in step (a) and the stabilising agent optionally cooled in step (a) in a treatment chamber;
(c) optionally, separating excess quantities of stabilising agent or constituents of the stabilising agent from the cellulosic material;
(d) optionally, recovering excess quantities or constituents separated in step (c).
In the third particular way of carrying out the process according to the invention, 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.
In the process according to the invention, 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. Specific examples of cellulose derivatives are selected from carboxymethylcellulose, methylcellulose, ethylcellulose and cellulose ethers. Specific examples of non-natural polymers 2S are selected from styrene/acryIate copolymers, polyurethanes and polyamides. A
specific natural polymer is starch.
Among antioxidants, derivatives of oxidizable arylcarboxylic acids, in particular hydroxyarylcarboxylic acids can suitably be used Esters of arylcarboxylic acids are preferred. In this case 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.
In a particularly preferred embodiment a derivative, in particular an alkyl ester of the p-hydroxibenzoic acid is used which is preferably selected among 3S methyl p-hydroxibenzoate, ethyl p-hydroxibenzoate, propyl p-hydroxibenzoate, butyl p-hydroxibenzoate and their blends.
(e) optionally, recovering excess quantities or constituents separated in step (d).
A third particular way of carrying out the process according to the S invention comprises (a) cooling the cellulosic material and optionally cooling the stabilising agent;
(b) contacting the cellulosic material cooled in step (a) and the stabilising agent optionally cooled in step (a) in a treatment chamber;
(c) optionally, separating excess quantities of stabilising agent or constituents of the stabilising agent from the cellulosic material;
(d) optionally, recovering excess quantities or constituents separated in step (c).
In the third particular way of carrying out the process according to the invention, 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.
In the process according to the invention, 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. Specific examples of cellulose derivatives are selected from carboxymethylcellulose, methylcellulose, ethylcellulose and cellulose ethers. Specific examples of non-natural polymers 2S are selected from styrene/acryIate copolymers, polyurethanes and polyamides. A
specific natural polymer is starch.
Among antioxidants, derivatives of oxidizable arylcarboxylic acids, in particular hydroxyarylcarboxylic acids can suitably be used Esters of arylcarboxylic acids are preferred. In this case 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.
In a particularly preferred embodiment a derivative, in particular an alkyl ester of the p-hydroxibenzoic acid is used which is preferably selected among 3S methyl p-hydroxibenzoate, ethyl p-hydroxibenzoate, propyl p-hydroxibenzoate, butyl p-hydroxibenzoate and their blends.
Preferred biocides correspond to the antioxidants described herebefore.
In the process according to the invention, the stabilising agent is preferably a deacidification agent.
In this case, the deacidificatioti agent generally comprises a base which can be selected for example from basic metal derivatives, from organometallic derivatives or from alkaline monomers such as a~crylates.
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. According to certain embodiments, the bases are preferably oxides, hydroxides, carbonates and bicarbonates of magnesium, titanium, calcium, sodium, potassium, zinc, or combinations of two or more thereof. Examples of 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 ar salts are preferred Most preferred bases are selected from magnesium alkoxycarbonates such as carbonates derived from magnesiumdimethanolate, magnesiumdsethanolate 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, isoprapanol, n-propanol, isobutanol, propane, butanes, pentanes, isohexanes, heptanes, alkylsiloxanes, HFE-7100 and HFE-7200. n-propanol is preferred.
In another embodiment, the solvent comprises a fluorinated alcohol such as 2,2,3,3,3 pentafluoxo-1 propanol.
In a preferred embodiment of the invention, 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.
Specific hydrofluoroalkanes are selected from difluoromethane (IIFC-32), 1,I-difluoroethane (FCC-ISZa), 1,1,1-trifluoroethane (IIFC-143a), 1,1,1,2-tetrafluoroethane (IBC-134a),1,1,1,3,3-pentafluoropropane (IBC-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 (I-~C-365mfc) and 1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC-43-lOmee).
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.
In a most preferred embodiment, 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 (IBC-134a) and 1,1,1,2,3,3,3-heptafluoropropane (IBC-227).
Carbonated magnesium di-n-propylate is a solid with the formula (CH3CH2CH20)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 General remarks 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.
Examples Example 1 : Deacidificafiion process performed in a cooled treatment chamber In a treatment chamber, 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 reagentlbook 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 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~~and 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 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 5 _g_ 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.
In the process according to the invention, the stabilising agent is preferably a deacidification agent.
In this case, the deacidificatioti agent generally comprises a base which can be selected for example from basic metal derivatives, from organometallic derivatives or from alkaline monomers such as a~crylates.
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. According to certain embodiments, the bases are preferably oxides, hydroxides, carbonates and bicarbonates of magnesium, titanium, calcium, sodium, potassium, zinc, or combinations of two or more thereof. Examples of 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 ar salts are preferred Most preferred bases are selected from magnesium alkoxycarbonates such as carbonates derived from magnesiumdimethanolate, magnesiumdsethanolate 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, isoprapanol, n-propanol, isobutanol, propane, butanes, pentanes, isohexanes, heptanes, alkylsiloxanes, HFE-7100 and HFE-7200. n-propanol is preferred.
In another embodiment, the solvent comprises a fluorinated alcohol such as 2,2,3,3,3 pentafluoxo-1 propanol.
In a preferred embodiment of the invention, 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.
Specific hydrofluoroalkanes are selected from difluoromethane (IIFC-32), 1,I-difluoroethane (FCC-ISZa), 1,1,1-trifluoroethane (IIFC-143a), 1,1,1,2-tetrafluoroethane (IBC-134a),1,1,1,3,3-pentafluoropropane (IBC-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 (I-~C-365mfc) and 1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC-43-lOmee).
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.
In a most preferred embodiment, 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 (IBC-134a) and 1,1,1,2,3,3,3-heptafluoropropane (IBC-227).
Carbonated magnesium di-n-propylate is a solid with the formula (CH3CH2CH20)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 General remarks 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.
Examples Example 1 : Deacidificafiion process performed in a cooled treatment chamber In a treatment chamber, 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 reagentlbook 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 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~~and 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 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 5 _g_ 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.
Claims (4)
1- 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.
2 - Process according to claim 1, wherein at least one of the cellulosic material or the stabilising agent is cooled to a temperature which is less than 20degree.C.
3 - Process according to claim 2, wherein the temperature is from -50degree.C
to 0degree.C, preferably from -20degree.C to -5degree.C.
to 0degree.C, preferably from -20degree.C to -5degree.C.
4 - Process according to claim 2 or 3, wherein the treatment is carried out at said temperature.
- Process according to anyone of claims 1 to 4, wherein the cellulosic material and the stabilising agent have substantially the same temperature as they are being contacted 6 - Process according to anyone of claims 1 to 4, wherein the stabilising agent is selected from fibre strengtheners, sizing agents, antioxidants, biocides and/or deacidification agents.
7 - Process according claims 6, wherein the stabilising agent is a deaciclification agent.
8 - Process according to claim 7, wherein the deacidification agent comprises a base selected from basic alkaline earth metal derivatives, in particular magnesium or calcium compounds or salts.
9 - Process according to claim 7 or 8, wherein the deacidification agent comprises a solvent selected from alcohols, in particular having 1 to 4 carbon atoms, and non-halogenated or halogenated hydrocarbon solvents or ethers.
- Process according to anyone of claims 7 to 9, wherein the deacidification agent comprises a hydrofluoroalkane, preferably selected from HFC-227ea and HFC-134a.
11-Process according to claim 10, wherein the deacidification agent is a composition of magnesium propylcarbonate, propanol and HFC-227ea.
12 - Process according to anyone of claims 1 to 11, wherein the treatment is carried out for a duration of from 1 to 50 hours.
13 - Process according to anyone of claims 1 to 12, wherein the cellulosic material is not dried before the treatment.
14 - Process according to anyone of claims 1 to 12, wherein the cellulosic material is dried before the treatment so that it looses about 1% or 2% of moisture content weight by weight.
15 -Process according to anyone of claims 1 to 14, which comprises:
(a) cooling the stabilising agent;
(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;
(c) optionally, separating excess quantities of stabilising agent or constituents of the stabilising agent from the cellulosic material;
(d) optionally, recovering excess quantities or constituents separated in step (c).
16 - Process according to anyone of claims 1 to 14, which comprises (a) providing a treatment chamber equipped with a cooling device, which treatment chamber is cooled before the treatment;
(b) introducing cooled cellulosic material into the treatment chamber;
(c) supplying the optionally cooled stabilising agent to said treatment chamber so as to contact the stabilising agent with the cellulosic material;
(d) optionally, separating excess quantities of stabilising agent or constituents of the stabilising agent from the cellulosic material;
(e) optionally, recovering excess quantities or constituents separated in step (d).
17 - Process according to anyone of claims 1 to 14, which comprises (a) cooling the cellulosic material and optionally cooling the stabilising agent;
(b) contacting the cellulosic material cooled in step (a) and the stabilising agent optionally cooled in step (a) in a treatment chamber;
(c) optionally, separating excess quantities of stabilising agent or constituents of the stabilising agent from the cellulosic material;
(d) optionally, recovering excess quantities or constituents separated in step (c).
18 - Process according to claim 17, whereby the treatment chamber is not cooled in step (b).
19 - Process according to claim 17 or claim 18, wherein both cellulosic material and stabilizing agent are cooled prior to contacting them in the treatment chamber.
- Process according to anyone of claims 1 to 4, wherein the cellulosic material and the stabilising agent have substantially the same temperature as they are being contacted 6 - Process according to anyone of claims 1 to 4, wherein the stabilising agent is selected from fibre strengtheners, sizing agents, antioxidants, biocides and/or deacidification agents.
7 - Process according claims 6, wherein the stabilising agent is a deaciclification agent.
8 - Process according to claim 7, wherein the deacidification agent comprises a base selected from basic alkaline earth metal derivatives, in particular magnesium or calcium compounds or salts.
9 - Process according to claim 7 or 8, wherein the deacidification agent comprises a solvent selected from alcohols, in particular having 1 to 4 carbon atoms, and non-halogenated or halogenated hydrocarbon solvents or ethers.
- Process according to anyone of claims 7 to 9, wherein the deacidification agent comprises a hydrofluoroalkane, preferably selected from HFC-227ea and HFC-134a.
11-Process according to claim 10, wherein the deacidification agent is a composition of magnesium propylcarbonate, propanol and HFC-227ea.
12 - Process according to anyone of claims 1 to 11, wherein the treatment is carried out for a duration of from 1 to 50 hours.
13 - Process according to anyone of claims 1 to 12, wherein the cellulosic material is not dried before the treatment.
14 - Process according to anyone of claims 1 to 12, wherein the cellulosic material is dried before the treatment so that it looses about 1% or 2% of moisture content weight by weight.
15 -Process according to anyone of claims 1 to 14, which comprises:
(a) cooling the stabilising agent;
(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;
(c) optionally, separating excess quantities of stabilising agent or constituents of the stabilising agent from the cellulosic material;
(d) optionally, recovering excess quantities or constituents separated in step (c).
16 - Process according to anyone of claims 1 to 14, which comprises (a) providing a treatment chamber equipped with a cooling device, which treatment chamber is cooled before the treatment;
(b) introducing cooled cellulosic material into the treatment chamber;
(c) supplying the optionally cooled stabilising agent to said treatment chamber so as to contact the stabilising agent with the cellulosic material;
(d) optionally, separating excess quantities of stabilising agent or constituents of the stabilising agent from the cellulosic material;
(e) optionally, recovering excess quantities or constituents separated in step (d).
17 - Process according to anyone of claims 1 to 14, which comprises (a) cooling the cellulosic material and optionally cooling the stabilising agent;
(b) contacting the cellulosic material cooled in step (a) and the stabilising agent optionally cooled in step (a) in a treatment chamber;
(c) optionally, separating excess quantities of stabilising agent or constituents of the stabilising agent from the cellulosic material;
(d) optionally, recovering excess quantities or constituents separated in step (c).
18 - Process according to claim 17, whereby the treatment chamber is not cooled in step (b).
19 - Process according to claim 17 or claim 18, wherein both cellulosic material and stabilizing agent are cooled prior to contacting them in the treatment chamber.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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EP04100790.7 | 2004-02-27 | ||
EP04100790 | 2004-02-27 | ||
PCT/EP2005/050827 WO2005083176A1 (en) | 2004-02-27 | 2005-02-25 | Process for preservation of cellulosic materials |
Publications (1)
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CA2556626A1 true CA2556626A1 (en) | 2005-09-09 |
Family
ID=34896107
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CA002556626A Abandoned CA2556626A1 (en) | 2004-02-27 | 2005-02-25 | Process for preservation of cellulosic materials |
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US (1) | US20080017336A1 (en) |
EP (1) | EP1759061A1 (en) |
BR (1) | BRPI0508056A (en) |
CA (1) | CA2556626A1 (en) |
MX (1) | MXPA06009765A (en) |
WO (1) | WO2005083176A1 (en) |
Cited By (1)
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DE102008034100A1 (en) | 2007-09-18 | 2009-03-19 | Stu Fakulta Chemickej A Potravinárskej Technológie | Multifunctional device for modification of cellulose material such as printed- and paper products from books, magazines, manuscripts, maps and works of art on paper, technical drawings and other documents, comprises a drying chamber |
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SK50682009A3 (en) * | 2009-11-02 | 2011-05-06 | Stu Fakulta Chemickej A Potravinárskej Technológie | A mixture for a single-step modification of acidic papers and use this mixture |
EP2626464B1 (en) * | 2011-12-15 | 2017-03-22 | Institutul National de Cercetare Dezvoltare Pentru Chimie si Petrochimie - Icechim | Composition for paper deacidification, process to obtain it and method for its application |
DE102015107863A1 (en) * | 2015-05-19 | 2016-11-24 | GSK mbH - Gesellschaft zur Sicherung von schriftlichem Kulturgut mit beschränkter Haftung | Apparatus and method for removing contaminants and for disinfecting archives |
CN105885547B (en) * | 2016-06-14 | 2017-05-17 | 陕西师范大学 | Deacidifying and strengthening agent for cellulose acetate film |
Family Cites Families (9)
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 (en) * | 1986-12-30 | 1990-11-26 | Republik Oesterreich Diese Ver | METHOD AND DEVICE FOR THE PRESERVATIVE TREATMENT OF PAPER |
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 |
CA2142195A1 (en) | 1995-02-08 | 1996-08-09 | D. James Worsfold | Deacidification of cellulosic material |
EP1069237A1 (en) * | 1999-07-13 | 2001-01-17 | Damir Turkovic | Process for controlling pests in books |
AU2002246036A1 (en) * | 2002-01-15 | 2003-07-30 | Consorzio Interuniversitario Per Lo Sviluppo Dei Sistemi A Grande Interfase C.S.G.I. | Basic suspension, its preparation and process for paper deacidification |
-
2005
- 2005-02-25 MX MXPA06009765A patent/MXPA06009765A/en unknown
- 2005-02-25 BR BRPI0508056-8A patent/BRPI0508056A/en not_active IP Right Cessation
- 2005-02-25 CA CA002556626A patent/CA2556626A1/en not_active Abandoned
- 2005-02-25 US US10/590,977 patent/US20080017336A1/en not_active Abandoned
- 2005-02-25 WO PCT/EP2005/050827 patent/WO2005083176A1/en active Application Filing
- 2005-02-25 EP EP05716817A patent/EP1759061A1/en not_active Withdrawn
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008034100A1 (en) | 2007-09-18 | 2009-03-19 | Stu Fakulta Chemickej A Potravinárskej Technológie | Multifunctional device for modification of cellulose material such as printed- and paper products from books, magazines, manuscripts, maps and works of art on paper, technical drawings and other documents, comprises a drying chamber |
Also Published As
Publication number | Publication date |
---|---|
BRPI0508056A (en) | 2007-07-17 |
MXPA06009765A (en) | 2007-03-23 |
EP1759061A1 (en) | 2007-03-07 |
US20080017336A1 (en) | 2008-01-24 |
WO2005083176A1 (en) | 2005-09-09 |
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