[go: up one dir, main page]

EP0543372A1 - Emulsions eau dans l'huile, et leur utilisation dans le traitement du papier - Google Patents

Emulsions eau dans l'huile, et leur utilisation dans le traitement du papier Download PDF

Info

Publication number
EP0543372A1
EP0543372A1 EP92119718A EP92119718A EP0543372A1 EP 0543372 A1 EP0543372 A1 EP 0543372A1 EP 92119718 A EP92119718 A EP 92119718A EP 92119718 A EP92119718 A EP 92119718A EP 0543372 A1 EP0543372 A1 EP 0543372A1
Authority
EP
European Patent Office
Prior art keywords
paper
microemulsion
surfactant
weight
water
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Withdrawn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
EP92119718A
Other languages
German (de)
English (en)
Inventor
Leonardo Borgioli
Mauro Chiavarini
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.)
Syremont SpA
Original Assignee
Syremont SpA
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 Syremont SpA filed Critical Syremont SpA
Publication of EP0543372A1 publication Critical patent/EP0543372A1/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Withdrawn legal-status Critical Current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

Definitions

  • the present invention relates to microemulsions of water-in-oil (W/O) type and to their use in the treatment of paper products.
  • W/O water-in-oil
  • the present invention relates to W/O microemulsions containing alkali metal and alkaline earth metal salts, and to their use for deacidifying paper and paper products, such as books, drawings, paintings on paper and printings.
  • Paper is known to undergo degradation over time. The most important factor among those factors which cause paper degradation is the acidity present in paper products.
  • Such an acidity may have several origins, such as, for example:
  • the acid-catalysed degradation process of paper products can be stopped by deacidification.
  • the most widely used deacidification process is based on the precipitation of an alkaline buffer on the cellulosic fibres of paper (W.J. Barrow, Restoration methods; Society of American Archivists, Richmond, Virginia, Oct. 27, 1942).
  • the sheets are soaked in a solution of calcium hydroxide, which neutralizes the acids present; residual calcium hydroxide is subsequently converted into carbonate by means of a bicarbonate solution.
  • Carbonate deposited on paper supplies an alkaline reserve which, during a certain time period, neutralizes the acids coming from same paper and from surrounding environment.
  • GB-A-2 180 248 discloses an expensive process for paper products preservation, in which a polymeric film is coated on paper sheets.
  • U.S. patent 3 676 055 proposes a post-treatment for acidic books.
  • the books are first dipped in a solution or suspension composed by alkali metal and alkaline earth metal oxides, and an organic solvent.
  • a solution of alkyl oxides, or of a mixture of alkyl oxides under pression developed by a propellant (Freon 12) is used.
  • Said process requires a very deep pre-drying because the reaction between water and diethilzinc is very fast; this pre-drying operation might cause damages to paper product.
  • diethylzinc is explosive, and process safety conditions must be carefully controlled.
  • Acid paper can be deacidified also in gas phase.
  • Such a process is disclosed in U.S. patent 4 619 735, which uses amines, such as melamine derivatives. Unfortunately, this process makes it possible a low alkaline reserve to be obtained, and furthermore causes paper yellowing and displays toxicity risks.
  • the purpose of the present invention is of overcoming the disadvantages of the processes known from the prior art and of supplying a low-cost product and process for deacidifying paper and paper products in bulk, which process renders such paper products resistant to the effect of acids present in paper and/or deriving from surrounding environment.
  • microemulsion makes it possible an alkaline reserve to be deposited and consequently a protection of paper to be achieved, with a simpple, low-cost and environmentally compatible process, because only surfactants are used, which can be recovered at process end.
  • Microemulsion means a dispersed system of oil-in-water or water-in-oil.
  • Oil means a hydrophobic, water immiscible liquid.
  • microemulsions are very stable, clear systems.
  • the stability of microemulsions is obtained by using surfactants (and, possibly, co-surfactants) which form a stabilizer monolayer around dispersed water droplets.
  • the subject-matter of the present invention is a microemulsion of water-in-oil type containing the following components:
  • the subject-matter of the present invention is a microemulsion of water-in-oil, characterized in that its essential components are the following:
  • the microemulsion possibly comprises from 1 to 20% by weight (based on surfactant) of an organic co-surfactant.
  • Particularly preferred according to the present invention is a microemulsion containing 5-10% by weight of a 10 ⁇ 2 - 10 ⁇ 1 M aqueous solution of alkali metal and alkaline earth metal salts, 70-90% by weight of a hydrophobic solvent, 5-25% by weight of a surfactant.
  • water is used in order to act as the vehicle for the alkalifying agent, therefore the amount of water used in the process is really kept at a minimum.
  • the salts of alkali metals and alkaline earth metals used in the emulsion according to the present invention can be oxides, hydroxides, carbonates and bicarbonates of the metals of Groups I and II, as well as diborates (e.g.: Na2B4O7); all of them being water-soluble.
  • Preferred compound are those containing Mg, Na, Ca; particularly preferred are non-toxicant compounds, such as magnesium ans sodium oxides, carbonates and bicarbonates, and calcium and magnesium hydroxides.
  • the hydrophobic organic solvent used in the microemulsion according to the present invention has a boiling point comprised within the range of from 0°C to 160°C, preferably comprised within the range of from 50°C to 100°C.
  • Exemplifying solvents are cyclohexane, n-heptane, n-hexane, isooctane.
  • the preferred solvent is heptane.
  • the surfactant present in the microemulsion according to the present invention is used in order to stabilize the small dispersed water droplets, reducing the interfacial tension of the system.
  • ionic surfactants examples include AOT (sodium dioctylsulfosuccinate) and SDS (sodium laurylsulfate).
  • a non-ionic surfactant When a non-ionic surfactant is used, the use of only one surfactant is enough. On the contrary, when a ionic surfactant is used, the use is sometimes required of a co-surfactant which decreases the density of surface charge generated by the ionic surfactant, reaching the interface and thus decreasing the interfacial tension. In that way, the co-surfactant makes it possible the dispersion of small water droplets to be achieved.
  • An example of such a co-surfactant is a linear-chain aliphatic alcohol with 3-16 carbon atoms, in particular n-butanol, n-pentanol, n-hexanol.
  • microemulsion according to the present invention obtained in that way is suitable for the treatment of acidic paper in order to decrease the acidity thereof, and considerably slow down its degradation over time and alteration of its mechanical properties.
  • Another object of the present invention is a process for the treatment of paper products, charaterized in that said products are impregnated by dipping into the above disclosed microemulsion, and the surfactant is subsequently removed by washing with solvent and the products are dried.
  • the impregnation of paper with the emulsion is carried out at room temperature (25°C).
  • the weight ratio of microemulsion to paper is comprised within the range of from 1:1 to 50:1.
  • the washing of the impregnated paper is carried out with a solvent, for example with an apolar solvent, such as n-heptane, or an alcohol, such as ethanol.
  • a solvent for example with an apolar solvent, such as n-heptane, or an alcohol, such as ethanol.
  • the resulting treated paper is dried at a temperature comprised within the range of from 0°C to 80°C, preferably comprised within the range of from 25°C to 60°C.
  • the evaluation of the treatment is carried out by means of measurement of pH value and of alkaline reserve of paper.
  • the W/O microemulsion is prepared by starting from an aqueous solution containing salts of alkali metals or alkaline earth metals, a hydrophobic solvent and a surfactant.
  • the acidic paper is impregnated by being dipped into this microemulsion at room temperature.
  • the ratio of microemulsion to paper, by weight, is comprised within the range of from 2:1 to 20:1.
  • the process according to the present invention make it possible paper products, such as books (without that they have to be disassembled), drawings, paintings on paper, paintings, documents, and so forth, to be treated in bulk; the fast deposition of alkalifier agents on paper fibres, or fast deacidification of paper; and the removal of soil from paper.
  • the process according to the present invention is suitable for deacidifying cellulose-based paper, as well as pulp-containing paper.
  • the process according to the present invention is simple and cheap, because it does not require special equipment, and is environmentally compatible, because the reactants used can be recycled without releasing eco-toxic substances into the environment.
  • a water-in-oil (W/O) microemulsion was prepared by simply mixing the following components: 77% of heptane, 15% of sodium dioctylsulfosuccinate, and 8% of an aqueous solution of sodium bicarbonate at 5% by weight.
  • a sheet of pure cellulose Whatman paper with pH 5.7 was immersed in this microemulsion.
  • the paper was soaked for one hour at room temperature (25°C).
  • the ratio of microemulsion to paper, by weight, was 5:1.
  • So treated paper was sussequently washed with ethanol, and then was dried inside an air-circulation oven at 50°C for 30 minutes.
  • a water-in-oil (W/O) microemulsion was prepared by simply mixing the following components: 80,0% by weight of heptane, 11,5% by weight of sodium dioctylsulfosuccinate, and 8,5% by weight of an aqueous solution of magnesium bicarbonate at 4% by weight.
  • a sheet of pure cellulose Whatman paper with pH 5.7 was immersed in this microemulsion.
  • the paper was soaked for one hour at room temperature (25°C).
  • the ratio of microemulsion to paper, by weight, was 5:1.
  • So treated paper was subsequently washed with ethanol and then was dried inside an air-circulation oven at 50°C for 30 minutes.
  • a water-in-oil (W/O) microemulsion was prepared by simply mixing the following components: 80 % of heptane, 11,5% of sodium dioctylsulfosuccinate, and 8,5% of an aqueous solution of magnesium bicarbonate at 4% by weight.
  • So treated paper was subsequently washed with ethanol and then was dried inside an air-circulation oven at 50°C for 30 minutes.
  • the resulting paper was exposed to those conditions which are known to cause an accelerated paper ageing. Therefore, paper was kept stored inside an oven at 90°C with a relative humidity of 50%.
  • a water-in-oil (W/O) microemulsion was prepared by simply mixing the following components: 80 % of heptane, 11,5% of sodium dioctylsulfosuccinate, and 8,5% of an aqueous solution of magnesium hydrogen carbonate at 4% by weight
  • a book (tied paper sheets having a pH value of 5.1) was dipped into this microemulsion. The book was soaked for one hour at room temperature (25°C). The ratio of microemulsion to book, by weight, was 2:1.
  • the so treated book was subsequently washed with ethanol and then was air-dried, at room temperature.
  • the treated books had a pH value of 7.2.
  • a water-in-oil (W/O) microemulsion was prepared by simply mixing the following components: 67,5% of heptane, 22,5% of LIALET 125/2 (R) (a mixture of diethoxylated C12OH and C15OH), 10,0% of an aqueous solution of magnesium bicarbonate at 4% by weight.
  • a sheet of pure cellulose Whatman paper with pH 5.7 was immersed in this microemulsion.
  • the paper was soaked for one hour at room temperature (25°C).
  • the ratio of microemulsion to paper, by weight, was 5:1.
  • So treated paper was subsequently washed with ethanol and then was dried inside an air-circulation oven at 50°C for 30 minutes.

Landscapes

  • Paper (AREA)
  • Colloid Chemistry (AREA)
EP92119718A 1991-11-20 1992-11-19 Emulsions eau dans l'huile, et leur utilisation dans le traitement du papier Withdrawn EP0543372A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI913102A IT1252006B (it) 1991-11-20 1991-11-20 Microemulsioni di acqua in olio e loro impiego nel trattamento di carta
ITMI913102 1991-11-20

Publications (1)

Publication Number Publication Date
EP0543372A1 true EP0543372A1 (fr) 1993-05-26

Family

ID=11361147

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92119718A Withdrawn EP0543372A1 (fr) 1991-11-20 1992-11-19 Emulsions eau dans l'huile, et leur utilisation dans le traitement du papier

Country Status (4)

Country Link
EP (1) EP0543372A1 (fr)
JP (1) JPH0615161A (fr)
CA (1) CA2083460A1 (fr)
IT (1) IT1252006B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999051819A1 (fr) * 1998-04-03 1999-10-14 Preservation Technologies, L.P. Desacidification de matieres a base de cellulose a l'aide de vehicules hydrofluoroether
WO2003060234A1 (fr) * 2002-01-15 2003-07-24 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
ITUA20161894A1 (it) * 2016-03-22 2017-09-22 Univ Degli Studi Di Palermo Composizione per la deacidificazione e la riduzione della carta e relativo metodo per il restauro della carta
CN112962348A (zh) * 2021-02-05 2021-06-15 青岛大学 一种修复破损老化纸质档案纸张的方法
CN115787350A (zh) * 2022-11-04 2023-03-14 国家图书馆 一种纸张含氟脱酸液

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003903296A0 (en) * 2003-06-30 2003-07-10 Raustech Pty Ltd Chemical compositions of matter

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3898356A (en) * 1974-02-28 1975-08-05 Us Army Method of deacidifying paper
FR2578198A1 (fr) * 1984-01-25 1986-09-05 Koppers Co Inc Procede de desacidification de materiaux de bibliotheque, livres et papier portant des images a base de cellulose

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3898356A (en) * 1974-02-28 1975-08-05 Us Army Method of deacidifying paper
FR2578198A1 (fr) * 1984-01-25 1986-09-05 Koppers Co Inc Procede de desacidification de materiaux de bibliotheque, livres et papier portant des images a base de cellulose

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999051819A1 (fr) * 1998-04-03 1999-10-14 Preservation Technologies, L.P. Desacidification de matieres a base de cellulose a l'aide de vehicules hydrofluoroether
US6080448A (en) * 1998-04-03 2000-06-27 Preservation Technologies Lp Deacidification of cellulose based materials using hydrofluoroether carriers
US6342098B1 (en) 1998-04-03 2002-01-29 Preservation Technologies Lp Deacidification of cellulose based materials using hydrofluoroether carriers
WO2003060234A1 (fr) * 2002-01-15 2003-07-24 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
ITUA20161894A1 (it) * 2016-03-22 2017-09-22 Univ Degli Studi Di Palermo Composizione per la deacidificazione e la riduzione della carta e relativo metodo per il restauro della carta
CN112962348A (zh) * 2021-02-05 2021-06-15 青岛大学 一种修复破损老化纸质档案纸张的方法
CN115787350A (zh) * 2022-11-04 2023-03-14 国家图书馆 一种纸张含氟脱酸液
CN115787350B (zh) * 2022-11-04 2024-05-31 国家图书馆 一种纸张含氟脱酸液

Also Published As

Publication number Publication date
ITMI913102A0 (it) 1991-11-20
ITMI913102A1 (it) 1993-05-20
CA2083460A1 (fr) 1993-05-21
IT1252006B (it) 1995-05-27
JPH0615161A (ja) 1994-01-25

Similar Documents

Publication Publication Date Title
US3676182A (en) Treatment of cellulosic materials
EP1068395B1 (fr) Desacidification de matieres a base de cellulose a l'aide de vehicules hydrofluoroether
US4522843A (en) Deacidification of library materials
EP0717803B1 (fr) Desacidification de materiaux a base de cellulose a l'aide de vecteurs perfluores
CA1147510A (fr) Methode de traitement de celluloses
JP2797194B2 (ja) 印刷されたセルロース物質の保存のためのプロセス
US3898356A (en) Method of deacidifying paper
EP0543372A1 (fr) Emulsions eau dans l'huile, et leur utilisation dans le traitement du papier
US5322558A (en) Neutralizing agent for paper products
US20140356542A1 (en) Deacidification Treatments Of Printed Cellulosic Materials
US20130302524A1 (en) Deacidification Treatment Of Printed Cellulosic Materials
US5137760A (en) Deacidification process
KR100238837B1 (ko) 케텐 이량체 사이즈와 콜로이드 실리카의 안정한 블렌드
Wittekind The Battelle mass deacidification process: a new method for deacidifying books and archival materials
US5277842A (en) Solvents for agents to mass deacidify books and other paper products in an environmentally safe manner
EP0003186A1 (fr) Serviette humide emballée et méthode pour sa fabrication
DE2557409C2 (de) Emulsion von Harzsäureisocyanaten als Leimungsmittel für Papier
US4548841A (en) Activated silicon-containing aluminum complex flame retardant and method for flameproofing
EP1060220B1 (fr) Traitement de desacidification de matieres cellulosiques imprimees
US20040031415A1 (en) Activated silicon-containing-aluminum complex explosion-proof flame retardant and method for flame-proofing
US20080011988A1 (en) Activated silicon-containing-aluminum complex flame retardant and method for flame-proofing
US20040031414A1 (en) Activated silicon-containing-aluminum complex flame retardant and method for flame-proofing
US4666746A (en) Method for the impregnation of water-repellent paper
KR20030045477A (ko) 휘발된 청색잉크 복원제 및 이의 제조방법

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE

17P Request for examination filed

Effective date: 19931021

17Q First examination report despatched

Effective date: 19941020

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19950301