US3778401A - Restoring and/or preserving papers or like materials - Google Patents

Restoring and/or preserving papers or like materials Download PDF

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Publication number
US3778401A
US3778401A US00221102A US3778401DA US3778401A US 3778401 A US3778401 A US 3778401A US 00221102 A US00221102 A US 00221102A US 3778401D A US3778401D A US 3778401DA US 3778401 A US3778401 A US 3778401A
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United States
Prior art keywords
solution
isopropanol
water
added
papers
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Expired - Lifetime
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US00221102A
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English (en)
Inventor
C Hayworth
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World Patent Development Corp
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World Patent Development Corp
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones

Definitions

  • a stable monophasic composition consisting of a solution of polyvinyl acetals in a solvent mix ture consisting of a chlorinated hydrocarbon containing two carbon atoms such as trichloroethylene and basic agents in aqueous solution useful for restoring and preserving papers and similar materials while providing desired basicity.
  • This invention relates generally to new and useful improvements in prolonged preservation of degradable sheet materials and particularly seeks to provide novel means and methods for prolonging the life of original paper documents and the like and for restoring and preserving such materials after damage or degradation has occurred.
  • papyrus and papers particularly those made from vegetable or wood cellulose fibers, as well as textiles and binding leathers are subject to degradation with age and frequently become stained and brittle. Accordingly, any cultural items such as manuscripts, books, prints, drawings, paintings, maps, photographs, photoreproductions and the like when applied to such papyrus, papers, textiles or binding leathers will suflfer comparable damage.
  • compositions and methods of the above-identified patent application provide for safe and permanent restoration of many sheet materials.
  • these solutions do not provide adequate protection against deterioration due to acidic materials.
  • acidic materials either in the paper itself (e.g. alum) or in the atmosphere (e.g. carbon dioxide, sulfur dioxide, and nitric oxides).
  • the treatmets of sheet materials with solutions of polyvinyl acetals in organic solvents avoids need for treating each page separately.
  • An entire book, for example, can be immersed directly into such solutions. It would accordingly be desirable to incorporate basic agents in such solutions and thereby avoid need for treating each page separately.
  • basic agents such as, for example, magnesium acetate, which are soluble in organic solvents (such as ethanol) and to add such agents to ethanolic solutions of polyvinyl acetals
  • the absence of water from such solutions seriously reduces the neutralizing effect of these basic agents.
  • ethanolic solutions of polyvinyl acetals have been found to be unsuitable for preservation of materials printed after 1900 because of solubility of some printing inks used after 1900, in ethanol.
  • diiferent organic solvents have been used.
  • a chlorinated hydrocarbon such as, for example, trichloroethylene, has been found useful because post-1900 inks are practically insoluble in this solvent.
  • an object of the present invention to provide stable solutions containing both a chlorinated hydrocarbon solution of polyvinyl acetals of the composition described above and an aqueous solution of a basic agent.
  • the chlorinated hydrocarbon solvent contains 2 carbon atoms.
  • solvents are ethylene chloride, ethylidene dichloride, 1,1,1-trichloroethane, 1,1,2-trichloroethylene, 1,1,2,2-tetrachloroethylene and 1,1,1,2-tetrachloroethylene, 1,1,2-trichloroethylene is preferred.
  • stable monophasic solutions of a 1,1,2-trichloroethylene solution of polyvinyl acetals and an aqueous solution of a basic agent obtained by dissolving the polyvinyl acetal in a solution of trichloroethylene and either isopropanol or methyl isobutyl ketone or a mixture of isopropanol and isobutyl ketone, and adding thereto an alcoholic solution of either an aqueous solution of the basic agent or of a hydrated basic agent.
  • polyvinyl acetal is dissolved in cc. of a solution containing from 60-95 cc. of trichloroethylene and from 5-40 cc. of the isopropanol or methyl isobutyl ketone or mixture thereof.
  • 1 cc. of water may be added in place of either 1 cc. of the isopropanol or the ketone.
  • Other water-miscible solvents such as methanol, ethanol, propanol, acetone or methyl ethyl ketone may be used in place of the isopropanol or the methyl isobutyl ketone.
  • the basic agent which may be a hydroxide of sodium, potassium, strontium, barium or lithium; a carbonate of sodium or potassium, a bicarbonate of sodium, potassium or lithium; an acetate of sodium, potassium, lithium, barium or magnesium; or hydrates of said compounds, is first dissolved in water and the aqueous solution then dissolved in about 100 cc. of a watermiscible alcohol.
  • Suitable alcohols include methanol, ethanol, propanol, isopropanol and mixtures thereof.
  • a hydrate of the basic agent may be added to the alcohol. From about 0.5 to 20 g. of the basic agent can be present in about 100 cc. of the alcoholic solution.
  • Example 1 1 g. NaOH was dissolved in cc. water, added to cc. methanol and then diluted with 90 cc. isopropanol.
  • solution A consisting of: 3.5 g. of polyvinyl acetal dissolved in a mixture of:
  • Example 3 Mg(CH COO 2 4H O 10 g. Mg(CH COO) -4H O was dissolved in 10 cc. of water and 90 cc. isopropanol added. 2 cc. of this solution added to 100 cc. of solution A.
  • the pH of the treated pages can be established either by a universal indicator or by cold water extraction whereby samples of the treated pages are extracted in distilled water for a period of one hour, and the pH of the distilled water is determined.
  • Example 4 Mg(CH COO 2 4H O +NaOH 10 g. NaOH was dissolved in a mixture of 7.5 cc. of water and 117.5 cc. of methanol. 125 cc. of isopropyl alcohol was then added. This is solution B.
  • solution D 150 cc. of solution B was added with stirring, and the mixture slightly warmed to dissolve precipitate which formed on addition. This is solution D.
  • Example 6 10 g. Mg(CH COO) -4H O was dissolved in 3 cc. Water and 97 cc. of ethyl alcohol. 10 cc. of this solution, together with 20 cc. of isopropyl alcohol, were added to 100 cc. of solution B. After thorough mixing, a clear solution resulted which neutralized newspaper after five minutes dipping and drying to a pH of about 6.5. This solution showed a trace of crystals on the bottom of the flask after standing about fifty hours, indicating a saturated solution of magnesium salt.
  • Example 7 Mg(CH COO 4H O This example is identical to Example 6 with the exception that 20 g. of Mg(CH COO) -4H O was dissolved in the water-ethanol mixture. Again, a newspaper dipped in 100 cc. copolymer solution to which was added 10 cc. of this magnesium solution, plus 20 cc. of isopropyl alcohol, showed a deposition of crystals and a heavy layer of crystals were present on the bottom of the flask after fifty hours standing, confirming that Example 6 resulted in a saturated solution.
  • Example 8 Mg(OH COO) -4H O+NaOH 50 g. of Mg(CH COO) -4H O was dissolved in 7.5 cc. of water and 242.5 cc. of ethyl alcohol. Then 250 cc. of ispropyl alcohol was added and finally 200 cc. of methyl alcohol. This is solution F. To this solution F, 50 cc. of solution B as prepared in Example 4 was added with stirring, and the mixture slightly warmed to dissolve precipitate which formed on adidtion. This is solution G.
  • a composition for restoring and preserving papers consisting of a solution of a polyvinyl acetal in a solvent mixture consisting of a chlorinated hydrocarbon containing 2 carbon atoms and a solvent selected from the group consisting of isopropanol, methyl isobutyl ketone and mixtures of isopropanol and methyl isobutyl ketone, to
  • composition according to claim 1 wherein the chlorinated hydrocarbon is 1,1,2-trichloroethylene.
  • composition according to claim 3 wherein the water-miscible alcohol is selected from the group consisting of methanol, ethanol, propanol and isopropanol.
  • composition according to claim 4 wherein about 0.5 to 20 g. of the basic agent is present in solution in about 100 cc. of the alcohol.
  • composition according to claim 6 wherein 1 cc. of the solvent selected from the group consisting of isopropanol, methyl isobutyl ketone and mixtures of isopropanol and methyl isobutyl ketone is replaced by 1 cc. of water.
  • a composition according to claim 7 wherein 2 cc. of a solution of 10 g. barium hydroxide octahydrate in 100 cc. methanol, is added to 100 cc. of a solution of 3.5 g. of polyvinyl acetal in 79 cc. 1,1,2-trichloroethylene, 15 cc. isopropanol, 5 cc. methyl isobutyl isobutyl ketone, and 1 cc. water.
  • composition according to claim 1 wherein the chlorinate hydrocarbon is 1,1,l-trichloroethane.
  • a composition according to claim 12 wherein the basic agent is selected from the group consisting of a hydroxide of sodium, potassium, strontium, barium or lithium, a carbonate of sodium or potassium, a bicarbonate of sodium, potassium or lithium, an acetate of sodium, potassium, lithium, barium or magnesium, and hydrates thereof.
  • a composition according to claim 13 wherein the water-miscible alcohol is selected from the group consisting of methanol, ethanol, propanol and isopropanol.
  • composition according to claim 14 wherein about 0.5 to 20 g. of the basic agentis present in solution in about 100 cc. of the alcohol.
  • composition according to claim 16 wherein 1 cc. of the solvent selected from the group consisting of isopropanol, methyl isobutyl ketone and mixtures of isopropanol and methyl isobutyl ketone is replaced by 1 cc. of water.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paper (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
US00221102A 1972-01-26 1972-01-26 Restoring and/or preserving papers or like materials Expired - Lifetime US3778401A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US22110272A 1972-01-26 1972-01-26

Publications (1)

Publication Number Publication Date
US3778401A true US3778401A (en) 1973-12-11

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US00221102A Expired - Lifetime US3778401A (en) 1972-01-26 1972-01-26 Restoring and/or preserving papers or like materials

Country Status (5)

Country Link
US (1) US3778401A (enrdf_load_stackoverflow)
JP (1) JPS4882107A (enrdf_load_stackoverflow)
DE (1) DE2303154A1 (enrdf_load_stackoverflow)
FR (1) FR2169235A2 (enrdf_load_stackoverflow)
IT (1) IT1046203B (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4131700A (en) * 1976-07-12 1978-12-26 Guglielmo Richard J Sr Composition of matter for treating a closed cell foam substrate
US5104997A (en) * 1988-09-30 1992-04-14 Fmc Corporation Mass treatment of cellulosic materials
US5208072A (en) * 1988-09-30 1993-05-04 Fmc Corporation Mass treatment of cellulosic materials
US5264243A (en) * 1992-06-16 1993-11-23 Fmc Corporation Mass cellulose deacidification process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4131700A (en) * 1976-07-12 1978-12-26 Guglielmo Richard J Sr Composition of matter for treating a closed cell foam substrate
US5104997A (en) * 1988-09-30 1992-04-14 Fmc Corporation Mass treatment of cellulosic materials
US5208072A (en) * 1988-09-30 1993-05-04 Fmc Corporation Mass treatment of cellulosic materials
US5264243A (en) * 1992-06-16 1993-11-23 Fmc Corporation Mass cellulose deacidification process

Also Published As

Publication number Publication date
DE2303154A1 (de) 1973-08-02
JPS4882107A (enrdf_load_stackoverflow) 1973-11-02
IT1046203B (it) 1980-06-30
FR2169235A2 (enrdf_load_stackoverflow) 1973-09-07

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