WO1999035207A1 - Deacidification treatment of printed cellulosic materials - Google Patents
Deacidification treatment of printed cellulosic materials Download PDFInfo
- Publication number
- WO1999035207A1 WO1999035207A1 PCT/US1999/000434 US9900434W WO9935207A1 WO 1999035207 A1 WO1999035207 A1 WO 1999035207A1 US 9900434 W US9900434 W US 9900434W WO 9935207 A1 WO9935207 A1 WO 9935207A1
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- WIPO (PCT)
- Prior art keywords
- composition
- solvent
- alcohol
- deacidification
- organic metal
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
Definitions
- the present invention relates generally to compositions and methods for deacidification treatment and preservation of printed cellulosic materials, such as books, manuscripts and other image and information bearing documents and publications and works of art on paper, which may deteriorate or which may have become deteriorated through aging.
- Moisture variation in anhydrous raw materials presents a significant problem when using most known treatment methods.
- either powder or gel precipitates will be formed, depending on time, reactivity, temperature and pressure conditions. These precipitates may prevent (poison), impede (slow) a manufacture or reaction rate and detrimentally affect the deacidification workability of solutions (clog paper substrates).
- the precipitates also may deposit on and deface books and documents and block or clog filters, pipes, valves and other restricted passages in processing equipment. They may also deposit thick coatings on walls of tanks and, depending on relative densities, separate into top or bottom phase composition layers or even, in extreme cases, actually turn the treating solution (initially thinner than water) into an immobile gelatin-like gel.
- ultra-low moisture alcohol and aliphatic hydrocarbon solvents are not available commercially in standard containers, e.g. , in 5-gallon pails or 55-gallon drums.
- Industrial solvent manufacturers do not deliver their solvents in an ultra-dry condition, i.e. , below 15 or 25 ppm.
- the maximum moisture content specification for a 55-gallon drum of research grade "anhydrous" methanol from Fisher Scientific is 1,000 ppm.
- Sub-micron (less than 0.2 microns) coal black particles are known to precipitate in concentrates prepared for current treatment methods.
- the particles may be introduced as trace heavy metal (iron, cobalt, copper, etc.) impurities in the metals reacted with alcohols to produce alkoxide powders for use in treatment or by external conditions. These particles contaminate and discolor the treatment concentrate and must be removed before use in preservation.
- trace heavy metal iron, cobalt, copper, etc.
- a deacidification composition for treating printed cellulosic materials is provided.
- a method of making the composition and a method of preparing components of the composition also are provided.
- the composition comprises a metal carbonate, an ultra-dry alcohol having a moisture content of less than about 100 ppm and an ultra-dry solvent having a moisture content of less than about 100 ppm, the solvent selected from the group consisting of alcohols, aliphatic hydrocarbons, fluorocarbons and blends thereof, in amounts effective for treating and preserving printed cellulosic materials.
- the deacidification treatment compositions of the present invention are made by first treating alcohol, fluorocarbon, aromatic hydrocarbon or aliphatic hydrocarbon solvents with a molecular sieve or other desiccant to reduce the moisture content below 100 ppm, to produce ultralow moisture solvents.
- An organic metal alkoxide is blended with the ultralow moisture alcohol solvent and carbon dioxide to form an organic metal carbonate composition.
- Submicron-sized magnetic impurities from the organic metal carbonate composition are removed using magnetic filtration. Then the organic metal carbonate composition is filtered through a submicron filter to produce a deacidification treatment concentrate.
- the deacidification treatment concentrate is blended with the ultralow moisture solvent to provide a deacidification treatment solution having relatively inert solvation characteristics toward inks and structural components of printed cellulosic materials.
- This composition can be used in any known method of treating printed cellulosic materials.
- the ultra-dry solvents which generally are available in standard volume commercial containers, are made in a process comprising passing the solvent through one or more drying columns. The solvent then is recirculated to the container, with re-circulation of the solvent through the container and column occurring for a period effective for reducing the moisture content to less than about 100 ppm to provide an ultra-dry solvent.
- metal or “metal agent” means organic aluminum, magnesium, zinc or blends thereof.
- metal alkoxide means an organic aluminum alkoxide, magnesium alkoxide, zinc alkoxide or blends thereof.
- metal carbonate means an organic aluminum carbonate, magnesium carbonate, zinc carbonate or blends thereof.
- FIGURE 1 is a flow diagram showing the method of making compositions for treatment of printed cellulosic materials.
- FIGURE 2 is an illustration of an apparatus for drying deacidification solution solvents in accordance with the present invention.
- FIGURE 3 is second embodiment of the apparatus of FIGURE 2.
- the present invention is directed to a composition and method for treating printed cellulosic materials to preserve the materials with little to no negative impact on inks, images, bindings or other features.
- the invention also is directed to methods of making the composition. More particularly, the invention is directed to compositions including organic aluminum, magnesium, and/or zinc agents and ultra-dry solvents.
- the metal agents are blended with ultra-dry alcohol solvents with carbon dioxide to produce a non-aqueous deacidification concentrate composition.
- This concentrate composition is blended with ultra-dry solvents to produce a deacidification composition that can be used in sprays and solutions to protect books and documents against aging.
- metals 10 first are blended with an ultra-dry solvent 12 and carbon dioxide 14.
- the metals used in the composition are organic aluminum, magnesium, zinc or combinations thereof.
- the metal may be in the form of metal chips or a metal alkoxide.
- the solvent is an alcohol having 1 to 4 carbon atoms.
- the metal and solvent may be blended with stirring, shaking or other agitation as necessary to provide a blend composition.
- the metal, ultra-dry solvent and carbon dioxide react to provide a deacidification agent 16 comprising metal carbonate.
- Magnets 18 are immersed or otherwise contacted with the deacidification agent for removal of sub-micron particle impurities to provide a deacidification agent intermediate composition 20.
- the organic metal carbonate concentrates are refined and purified by removing iron and associated heavy metals (e.g. copper and cobalt) present in the black magnetic particles.
- the submicron particles are removed by attachment to magnets, agglomeration and filtration through membrane filters. Additionally, allowing the agglomerates to settle and decanting the concentrate may be used, as well as any combination of these procedures.
- Magnetic filtration may occur in single step (FIG. 1) or multiple step magnetic filtration (not shown).
- the primary advantages of a single step procedure are speed of removal and miriimization of the contamination from moisture. Additionally, the resulting concentrates are thinner and filter rapidly, subsequent blending, mixing, and transfer processes occur more readily, and costs of more processing and losses of concentrate composition during additional membrane filtration steps are avoided.
- Single step magnetic filtration emphasizes attracting particles to the magnetic poles. Though higher concentrations are possible, typically 25.0, 37.5, 50.0, 62.5, or 75.0 percent concentrations in methanol are manufactured. Concentrations in ethanol and isopropanol are typically 25.0 to 37.5 percent by weight. Magnets are immersed in the completed concentrate to agglomerate, attract, and collect the particles. Teflon coated rod (ALNICO V) magnets (1/2" by 6") designed for use as spin bars in magnetic mixers may be used. Other magnets, including electromagnets, magnetic grids, or magnetic particles which can readily be separated from the solutions being treated, and flow- through magnetic treatment chambers, may be substituted for the spin bar magnets.
- APNICO V Teflon coated rod
- Other magnets including electromagnets, magnetic grids, or magnetic particles which can readily be separated from the solutions being treated, and flow- through magnetic treatment chambers, may be substituted for the spin bar magnets.
- the magnets may be placed either in or outside of the concentrate solution being magnetically filtered.
- Multiple step filtration involves repeating the complete single step cycle at two or more pre-selected concentrations.
- the organic metal carbonate concentrate is initially manufactured to 37.5 percent by weight concentration, magnetically filtration treated, and membrane filtered through a 0.2 micron filter. Then 25 percent more organic metal carbonate is blended with the concentrate and the now 62.5 percent concentrate is again magnetically and membrane filtered. Finally, 12.5 percent more organic metal carbonate is blended in, magnetically and membrane filtered to produce a concentration level of 75.0 percent by weight in methanol.
- the primary advantages of the multi-step procedure are that stronger concentrates exceeding 100 percent by weight can be produced, and the quantities of fine black particulates do not build up because they are removed as they are formed.
- the potential for alcohols from multi-step concentrates to deface books and documents by dissolving inks is essentially eliminated.
- the quantity of free alcohol is very low, typically below 1 percent, and preferably below 0.5 percent by weight in the paper treating solutions.
- the composition is filtered 22 using membrane filtration.
- Sub-micron pleated membrane (0.2 micron or smaller pore size) filtration occurs after the desired concentration is attained, typically at the 37.5 and 62.5 percent concentrations, and after the solution has been separated from the magnets bearing the black magnetic particles.
- the 25.0 percent by weight organic metal carbonate concentrations can be filtered through a 0.2-micron filter after overnight treatment, the 37.5 percent concentrate two days after manufacture.
- the concentrates may be subjected to moderate warming during their manufacture. Additional amounts of ultra-dry solvents may be blended with the concentrates, as necessary for filtration. Filtration below the boiling point of the alcohol being used is essential. The heat reduces the viscosity of the concentrates, and improves magnetic filtration by reducing the required propelling pressure and increasing the rate of flow through membrane filters.
- Membrane filters commercially available having pores larger than 0.2-microns do not completely remove the agglomerated particles and residual fines from concentrate solutions.
- Ultra fine membrane filters e.g., 0.1, 0.05, and 0.01 -micron actual pore size (finest currently commercially available is 0.01- microns) may be substituted for the 0.2 micron filters to produce more pure filtrates.
- Filtration provides a deacidification concentrate 24.
- the deacidification concentrate then is blended with an ultra-dry solvent 26 to provide a deacidification composition 28.
- the solvent is an alcohol with 1 to 4 carbon atoms, an aliphatic hydrocarbon with 1 to 8 carbon atoms, a fluorocarbon hydrocarbon, or mixtures thereof.
- the deacidification concentrate and solvent may be blended with stirring, shaking or other agitation as necessary to provide a blend composition.
- organic aluminum alkoxides with or without a carbon dioxide adduct and either alone or in combination with organic magnesium or zinc agents, are also useful deacidification agents. They may be soluble directly in aliphatic and fluorocarbon solvents without an alcohol co- solvent.
- Ultra-Dry Solvents are also useful deacidification agents. They may be soluble directly in aliphatic and fluorocarbon solvents without an alcohol co- solvent.
- the commercially available solvents that may be used in the present invention include alcohols having 1 to 4 carbon atoms and aliphatic and halogenated hydrocarbon solvents.
- Such solvents include methanol, ethanol, isopropanol, isobutanol, propane, butanes, pentanes, isohexanes, heptanes, difluoroethane (HFC-152a), and tetrafluoroethane (HFC-134a), HFC-32, HFE- 7100, HFE-7200, and HFC-10-43MEE.
- Moisture which may be present in solvents presents a major problem in preparing stable and non defacing organic metal carbonate deacidification compositions, sprays, and solutions. Moisture, even under 50 or 100 ppm, may react with organic metal carbonates to form soluble hydrates or gels that may thicken the solution or produce precipitates.
- the moisture level of alcohol solvents is no more than about 100 ppm and in a very important aspect, no more than about 25-50 ppm.
- the moisture level of fluorocarbon and aliphatic solvents is no more than about 100 ppm and in a very important aspect, no more than about 5-15 ppm.
- the composition of the invention comprises fluorocarbon solvents.
- the fluorocarbon solvent is HFC- 134a.
- Mass deacidification solutions containing HFC- 134a solvent have almost no detrimental effect on all printing inks tested.
- Higher alkaline reserves are possible, if desired, because the metal carbonates, especially MMMC concentrates, have increased solubility in HFC- 134a. It is possible to achieve increased concentrate solubility using fluorocarbon solvents in the composition of the present invention, as compared to chlorofluorocarbon solvents.
- Previously soluble inks such as purple mimeograph, photocopy, and fast printing, offset inks that HCFC solvents such as HCFC-22 destroyed, are unaffected by treatment with HFC-134a or HFC-152a, with the same and far higher levels of alcohol.
- Solvents in the mass deacidification composition of the present invention can be completely recovered and recycled indefinitely with minimal benefaction requirements beyond adjustment for additional alcohol introduced in the make-up concentrate.
- Solids contents from about 25 to about 110 percent by weight of the organic metal carbonate in methanol may readily be produced, from about 25 to about 50 percent in ethanol, from about zero to about 40 percent in isopropanol and from about 0 to about 30 percent is isobutanol.
- HFC- 152a difluoroethane
- HFC- 134a tetrafluoroethane
- the concentrates may instantaneously precipitate out of solution on contact with HFC- 134a and slowly, over one to three or more days, gradually with agitation (shaking and stirring) form a stable solution.
- the concentrates tend to go into solution in HFC- 134a very rapidly when the HFC- 134a is added in increments, e.g. , 1:1, 1:4, 1:8, etc.; whereas direct blending at a 1:8 ratio produces a precipitate.
- a preferred deacidification composition for preserving paper includes from about 0.1 to about 4.0 percent of organic metal carbonate, from about 0.5 to about 10 percent by weight of ultra-dry alcohol and from about 86 to about 99 by weight aliphatic or fluorocarbon solvent, each based upon the weight of the total composition. In an important aspect, from about 0.5 to about 3.0 percent metal carbonate of the deacidification composition is thoroughly impregnated throughout the paper being protected against aging.
- One deacidification composition comprises methoxy magnesium methyl carbonate (MMMC) deacidification agent (which may include ethoxy components) blended with HFC- 134a at 0.5 to 4.0% by weight with a very low level, less than 1 % by weight, of free methanol in the treatment composition.
- MMMC methoxy magnesium methyl carbonate
- More methanol up to 10 percent may be used, if desired.
- a second composition comprises from about 0.25 to about 5.0 percent by weight of isopropoxy magnesium isopropyl carbonate (PMPC) blended with HFC-134a solvent including from about 1.0% to about 10% isopropanol.
- the PMPC concentrate may include methyl and/or ethyl carbonate components.
- Deacidification agents MMMC and PMPC produce similar deacidification treatment results with HFC- 134a.
- the MMMC is preferred because stronger concentrates may be prepared, the recovered solvents are easier to recycle, the treated books have a much lower odor level immediately after treatment and hazards are reduced because less flammable material is involved.
- Solutions of PMPC concentrate in aliphatic hydrocarbon solvents are extremely stable and combinations of solvents even dry to powder in open beakers in air without precipitation. Non-clogging aerosol sprays, solutions for brushing, and dipping paper may be prepared that do not produce white deposits during treatment.
- Ultra-drying in accordance with the present invention provides more stable deacidification products during shipment, storage, and use, as well as allows manufacture of products not possible until now.
- the compositions of the present invention are further blended with ultra-dried solvents to produce non-aqueous deacidification compositions for use as sprays and solutions for preserving books and documents.
- ultra-drying of the solvents With ultra-drying of the solvents, the quality and purity of starting solvents are established to a standard condition and can be used to produce finished products with predictable and reproducible properties.
- Solvents which are delivered in standard 55-gallon drums or similar containers, typically having moisture levels of at least about 1000 ppm, may be inexpensively transformed into ultra-dry solvents using the apparatus of the present invention, as shown in FIG. 2.
- the drums 50 have two threaded openings (one 2"
- I.D. opening 51 and one 3/4" I.D. opening 61).
- a dip tube 52 or similar piping extends into the drum through the 2 in. I.D. opening 51, preferably down to at or near the bottom of the drum.
- One or more pumps 56 draw the solvent from the drum 50 up through the dip tube 52 and through the inlet line 54 to one or more drying columns 58.
- the solvent is passed through the columns and returned back to the drum via a return line 60.
- the return line extends through the 3/4" I.D. opening 61.
- the returned solvent is discharged via a tube 62.
- the mbe 62 is angled or otherwise configured to promote splashing and circulation as the solvent is discharged in order to provide a mixing action.
- the solvent is recirculated through the drum and column until the moisture content is reduced to the desired level to provide an ultra-dry solvent.
- the solvent may be removed via a removal line 68 and transferred into smaller containers, such as 6.5 gallon carboys, for subsequent use, if desired.
- a source 64 of nitrogen gas, or equivalent, is connected to the headspace in the drum to provide an inert atmosphere and a pressure head for pumping. Valves 66 control the flow of gas into the drum.
- valves 72 control the flow through the drum and columns.
- Sight valves 74 are provided along the lines, as necessary.
- the preferred materials for transfer hoses, connections, and valves are Teflon and stainless steel. For safety's sake, equipment and hoses must be grounded because the flowing solvents can produce static electric charges that, if not discharged, may cause electric sparks.
- UOP Molecular Sieve M/S 3 A is effective in drying methanol, ethanol, and isopropanol; HFC and aliphatic hydrocarbon solvents.
- UOP Molecular Sieve M/S 4A, XH-7, and XH-9 may be used to dry and also remove alcohol from HFC, and aliphatic hydrocarbon solvents.
- Alternative drying products include highly desiccated silica gel and desiccant aluminum oxide and silicate powders. All of these desiccants may be used in alternate forms; e.g. , molded core dryers prepared to fit into a specific steel shell. Fluorocarbon solvents, such as HFC- 134a, may cause some of these desiccants, e.g. , UOP M/S 3A, to evolve a fine, white powder that can be removed during filtration.
- both lines extend through the same opening of the drum.
- the inlet line 54 and return line 60 both extend through the 2" I.D. opening 51.
- the removal line 80 extends from the return line 60 above the drum. The remaining features are as shown and described above for FIG. 2.
- the deacidification compositions of the present invention may be used in processes for treating and preserving printed cellulosic materials.
- the compositions can be used to prepare aerosols, solutions or other forms, as desired.
- the deacidification compositions may be used with any known treatment process.
- a process for mass deacidification using the composition in a solution form includes first thoroughly drying under vacuum the materials to be treated. The materials then are contacted with the composition for a period of time effective for thoroughly wetting the materials. During contact, the composition may be impregnated under pressure into the materials. After the solution is removed from the materials, any solution remaining in the materials is vaporized for recovery and recycling to vacuum conditions. In this process, it is possible to recover at least about 93-95% of the deacidification solution, which can be re-used in the process.
- Anhydrous methanol delivered in a 200 liter drum is treated using the apparatus of FIG. 1.
- the methanol initially contains 900 ppm water.
- the drying columns are 24" high columns filled with UOP molecular sieve desiccant
- Example 3 Ultra-Dry Isopentane
- Isopentane solvent is treated in a 55 gallon stainless steel drum with the apparatus of FIG. 3.
- the moisture content of the isopentanes solvent is reduced from 1,000 ppm at beginning to 15 ppm at end.
- Example 2 On Day 1 , four kilograms of granulated magnesium ethoxide and carbon dioxide gas are added to two 6.5-gallon flint glass carboy containing 14 liters of ultra-dry methanol prepared in Example 1. The components are reacted to produce a coal black, organic magnesium carbonate solution of MMMC in methanol. The magnesium ethoxide is kept in suspension in the methanol using an electromagnetic mixer; the carbon dioxide gas is added at ambient pressure at a rate of 5 cfm/hr. through a gas diffusion stone. On Day 2, two kilograms more magnesium ethoxide are reacted to produce a 37.5 percent concentrate.
- the mother liquor remains black and, after filtering through a 0.2-micron filter, is a blackish charcoal gray color.
- the PMPC concentrate Without magnetic filtration and concentrate heating, the PMPC concentrate needs weeks of natural aging for agglomeration before it can be filtered to a dark amber concentrate.
- Example 4 On Day 1, 1.5 kilograms of fine zinc chips with a catalyst is added to a magnetically stirred, 6.5-gallon flint glass carboy containing 14 liters of ultra-dry methanol prepared in Example 1, and reacted at 100° F to form zinc methoxide. Carbon dioxide is added as described in Example 4 to form methoxy zinc methyl carbonate (MZMC). On completion of the reactions, magnets are inserted to provide magnetic filtering, and the concentrates are maintained at 100°F as described in Example 4.
- MZMC methoxy zinc methyl carbonate
- Example 8 On Day 1 , one kilogram of fine zinc chips with a catalyst is added to a magnetically stirred, 6.5-gallon flint glass carboy containing 15 liters of ultra-dry Isopropanol prepared in Example 2, and reacted at 110°F to form zinc isopropoxide. Carbon dioxide is added as described in Example 4 to form isopropoxy zinc isopropyl carbonate (PZPC).
- magnets On completion of the reactions, magnets are inserted to provide magnetic filtering, and the concentrates are maintained at 110°F as described in Example 4.
- the magnets On Day 2, the magnets are removed and the mother liquor, now a translucent gray color, is filtered using 10 psig pressure through a 0.2 micron membrane filter in fifteen minutes to produce a water clear, near white concentrate filtrate.
- Example 8 Example 8
- MMMC MMMC
- a 37.5 percent concentrate of MMMC is prepared and magnetically filtered as described in Example 5. Also on Day 3, four kilograms more granulated magnesium ethoxide and carbon dioxide gas are reacted with the filtrate to produce a 62.5 percent, coal black MMMC concentrate. Again four magnets are inserted to provide magnetic filtration, and the concentrate is maintained at 110° F.
- Example 9 On Day 5, the four magnets are removed, cleaned, dried, and replaced. Their poles are coated with a fine black powder 1/16" to 1/8" thick when removed from the concentrate. The four cleaned magnets are re- inserted on Day 5, and contents kept at 110°F. On Day 7, the magnets (coated 1/16" to 1/8" thick) are again removed; and the 62.5 percent concentrate is filtered for the first time with a 20 psig. Nitrogen gas pressure through a 0.2-micron filter in 45 minutes. The concentrate filtrate is a light amber color that dries to a snow white powder.
- Example 9 Example 9
- Example 5 Forty-five pounds PMPC concentrate from Example 5 are added, under nitrogen gas, to a 16-gallon stainless steel tank, thinned with 45 pounds of HFC-134a, and mixed for 30 minutes on a seesaw shaker to produce a 1: 1 PMPC/HFC-134a ratio.
- the tank is pressurized to 160 psig with nitrogen gas in preparation for manufacture of a liquefied gas mass deacidification solution.
- HFC-134 Seventy pounds HFC-134, nine pounds of 50/50 PMPC HFC-134a concentrate, and 40.5 pounds HFC- 134a are transferred into a vacuum dried 12.5 gallon steel shipping cylinder, which is inverted and mixed for 30 minutes on a seesaw shaker.
- the PMPC solution initially hazy from fine bubbles, clears to give a crystal clear, water white solution in the sight glasses with no signs of discoloration, precipitation, or phase separation before and after use, as compared to HCFC-22 solution and previous CFC containing solutions which show a slight yellowing after use.
- the actual mass deacidification solution is prepared in clean, vacuum dried 12.5-gallon steel cylinders in four weighing and two mixing steps:
- the results equal or exceed the quality of treatments from all previous treatments including the PMPC/HFC-134a treatment of Example 9.
- the MMMC/HFC-134a solution treatment is preferred because it has less residual odor, is easier to manufacture and filter, is more readily recovered and recycled, and its stronger concentrates produce higher alkaline reserves.
- Zinc Mass Deacidification - MZMC MZMC concentrate (28.5-pounds) from Example 6 is diluted with
- HFC-134a 57-pounds of HFC- 134a in a 16-gallon tank and mixed for 15 minutes on a seesaw shaker. Fifty-seven more pounds of HFC- 134a are added, and mixed again for 15 minutes to form a 1:5 ratio solution.
- the actual mass deacidification solution is prepared in clean, vacuum dried 12.5 -gallon steel cylinders in four weighing and two mixing steps: (1) 26 lbs. HFC-134a Recovered Solvent; (2) 23.75 lbs. MZMC
- a 4.5-gallon cylinder of Soft Spray is prepared as is described in Example 11 except flammable solvents are substituted for HCFC-141B and HFC- 134a: (1) 1.00 lbs. Ultra-Dry Isopropanol (Example 3); (2) 10.00 lbs. Ultra-dry
- a 4.5-gallon cylinder of Soft Spray is prepared as is described in Example 12 except flammable solvents Pentane and HFC-152a are substituted for HCFC-141B and HFC-134a respectively.
- the weighing and preparation sequence is: (1) 1.00 lb. Ultra-Dry Isopropanol (Example 3); (2) 8.50 lbs. Ultra-dry
- a number of aerosol spray cans are filled with a non-flammable aerosol spray as follows.
- a non-pressurized formulation of solvents and concentrate is loaded into a stainless steel tank under nitrogen gas in the following order:
- the tank is closed and mixed, upside down, on a seesaw shaker for one hours, left stand over night and mixed again for one hour.
- the formulation is pressurized with ten psig of nitrogen gas, and is loaded 650 grams per unit into welded steel, epoxy-phenolic lined pint aerosol cans which are crimped closed with an all-steel, except neoprene gaskets, aerosol male tilt valve.
- the cans are pressurized with 125 grams of HFC-134a pressurized to 110 psig with nitrogen gas through the valve using a pressure burette, and subsequently mixed by vigorous manual shaking.
- a number of aerosol spray cans are filled with a non flammable aerosol spray as in Example 15 except the HFC- 134a propellant is replaced with HFC- 152a on a molecular weight basis.
- the cans are pressurized with 100 grams of HC-152a as in Example 15.
- Example 17
- a number of aerosol spray cans are filled with a flammable aerosol spray.
- the following non-pressurized formulation of solvents and concentrate is weighed (directly from their ultra-drying drums or filtrate container) into a 16- gallon stainless steel mixing tank under nitrogen gas in the following order:
- a number of aerosol spray cans are filled with a flammable aerosol spray as described in Example 17 according to the following formula:
- the tank is pressurized with 10-psig nitrogen gas, and the aerosol cans are filled 300 gms/can, and crimped shut with a metal/plastic, female aerosol valve.
- the cans are pressurized through the valve with 75 grams of HFC- 152a using a pressure burette pressurized with 100-psig nitrogen gas.
- a number of aerosol spray cans are filled with a flammable aerosol spray as described in Example 17 according to the following formula: (1) Ultra-dry Isopentanes 40 lbs. (Example 4) (2) PZPC concentrate 9 lbs. (Example 3)
- the tank is pressurized with 10-psig nitrogen gas, and the aerosol cans are filled 300 gms/can, and crimped shut with a metal/plastic, female aerosol valve.
- the cans are pressurized through the valve with 75 grams of HFC-152a using a pressure burette pressurized with 100-psig nitrogen gas.
- Aerosol - Barrier & Desiccant Protection Aerosol spray cans prepared according to the above examples may malfunction and clog as a consequence of inadvertent moisture contamination following manufacture and delivery. This malfunction can be avoided by preventing the moisture in air from contacting the valves as follows using a moisture barrier film (e.g. , polyvinylidene chloride film (Dow Chemical Saran Wrap 8)) and desiccant (e.g. , United Technologies silica gel or UOP M/S 3A).
- a moisture barrier film e.g. , polyvinylidene chloride film (Dow Chemical Saran Wrap 8)
- desiccant e.g. , United Technologies silica gel or UOP M/S 3A
- a number of glass quart bottles are filled with a flammable deacidification solution as follows.
- a non-pressurized formulation of solvent and concentrate is loaded into a stainless steel tank under nitrogen gas in the following order:
- the bottles are closed with a conventional plastic threaded cap whose liner (gasket) is composed of paperboard covered with a sealing composite composed of aluminum foil covered with a Mylar (polyester terephthalate) plastic film or equivalent barrier material to prevent the inward migration of moisture from ambient air.
- the bottles are shaken subsequently vigorously manually to insure mixing.
- the resulting solution may be applied by dipping, brushing, spraying or other technique to thoroughly wet paper objects.
- This solution can also be prepared in steel cylinders for spray application with nitrogen gas pressure, steel, phenolic-epoxy lined, or stainless steel cans, and other sizes of glass bottles, etc. with appropriate barrier closures as desired.
- Up to 10 percent, typically 3 to 5 percent, by weight of co-solvents bromopropane and/or diethylene chloride may be added to improve solubility of PMPC concentrate if desired.
- the proportions of the aliphatic solvents may be varied to customize the rate of drying from and treatment penetration into paper, and indirectly control the evolution of solvent vapors into workroom air.
- Example 22 The composition of the two papers tested is as follows: Paper A: an acid fine paper made of 50% hardwood bleached kraft, 50% softwood bleached kraft (post- industrial), 4% filler (clay), alum- rosin sizing and starch Paper B: an acid newsprint made of 100% thermomechanical pulp (TMP) with alum-rosin sizing The samples were conditioned at 23° C. and 50% RH prior to testing according to CPPA standard A.4.
- TMP thermomechanical pulp
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000527597A JP2002500289A (en) | 1998-01-09 | 1999-01-08 | Deoxidation of printed cellulose material |
CA002317564A CA2317564A1 (en) | 1998-01-09 | 1999-01-08 | Deacidification treatment of printed cellulosic materials |
BR9906824-9A BR9906824A (en) | 1998-01-09 | 1999-01-08 | "deacidification compositions for treatment of printed cellulosic materials and deacidification treatment for printed cellulosic materials, and processes for producing a deacidification treatment composition for printed cellulosic materials, for the treatment of deacidification of printed cellulosic materials and to reduce the content moisture in solvents. " |
EP99901377A EP1060220B1 (en) | 1998-01-09 | 1999-01-08 | Deacidification treatment of printed cellulosic materials |
DE69909762T DE69909762T2 (en) | 1998-01-09 | 1999-01-08 | METHOD FOR DEACIDIFYING PRINTED CELLULOSE CONTAINING MATERIAL |
AT99901377T ATE245685T1 (en) | 1998-01-09 | 1999-01-08 | METHOD FOR DEACIDIFICATION OF PRINTED CELLULOSE-CONTAINING MATERIAL |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US7110398P | 1998-01-09 | 1998-01-09 | |
US60/071,103 | 1998-01-09 |
Publications (1)
Publication Number | Publication Date |
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WO1999035207A1 true WO1999035207A1 (en) | 1999-07-15 |
Family
ID=22099279
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/000434 WO1999035207A1 (en) | 1998-01-09 | 1999-01-08 | Deacidification treatment of printed cellulosic materials |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1060220B1 (en) |
JP (1) | JP2002500289A (en) |
AT (1) | ATE245685T1 (en) |
BR (1) | BR9906824A (en) |
CA (1) | CA2317564A1 (en) |
DE (1) | DE69909762T2 (en) |
ES (1) | ES2201660T3 (en) |
WO (1) | WO1999035207A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000008250A2 (en) * | 1998-07-31 | 2000-02-17 | Universitat Politecnica De Catalunya | Product for desacidification of cellulose material, production and utilization thereof |
EP2522526A1 (en) * | 2011-05-13 | 2012-11-14 | Xerox Corporation | Storage stable images |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SK287845B6 (en) | 2007-09-18 | 2012-01-04 | Stu Fakulta Chemickej A Potravinarskej Technologie | Multifunction device for modification of cellulose materials and method for modification of cellulose materials |
CN112391872B (en) * | 2019-08-16 | 2022-10-11 | 鼎纳科技有限公司 | Using method of large book deacidification system |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3969549A (en) * | 1974-12-24 | 1976-07-13 | The United States Of America As Represented By The Librarian Of Congress | Method of deacidifying paper |
US4182801A (en) * | 1976-09-30 | 1980-01-08 | The Badger Company, Inc. | Method of drying liquid olefin monomer feed in a molecular sieve dryer in the polymerization of olefins from liquid olefin monomer |
US4318963A (en) * | 1980-01-21 | 1982-03-09 | Smith Richard D | Treatment of cellulosic materials |
US4401810A (en) * | 1981-09-08 | 1983-08-30 | United States Of America As Represented By The Librarian Of Congress | Method of stabilizing felted cellulosic sheet material with an alkali metal borohydride |
US5094888A (en) * | 1990-02-20 | 1992-03-10 | Fmc Corporation | Strengthening cellulosic materials |
US5264243A (en) * | 1992-06-16 | 1993-11-23 | Fmc Corporation | Mass cellulose deacidification process |
-
1999
- 1999-01-08 BR BR9906824-9A patent/BR9906824A/en not_active Application Discontinuation
- 1999-01-08 CA CA002317564A patent/CA2317564A1/en not_active Abandoned
- 1999-01-08 DE DE69909762T patent/DE69909762T2/en not_active Expired - Fee Related
- 1999-01-08 EP EP99901377A patent/EP1060220B1/en not_active Revoked
- 1999-01-08 AT AT99901377T patent/ATE245685T1/en not_active IP Right Cessation
- 1999-01-08 WO PCT/US1999/000434 patent/WO1999035207A1/en not_active Application Discontinuation
- 1999-01-08 ES ES99901377T patent/ES2201660T3/en not_active Expired - Lifetime
- 1999-01-08 JP JP2000527597A patent/JP2002500289A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3969549A (en) * | 1974-12-24 | 1976-07-13 | The United States Of America As Represented By The Librarian Of Congress | Method of deacidifying paper |
US4182801A (en) * | 1976-09-30 | 1980-01-08 | The Badger Company, Inc. | Method of drying liquid olefin monomer feed in a molecular sieve dryer in the polymerization of olefins from liquid olefin monomer |
US4318963A (en) * | 1980-01-21 | 1982-03-09 | Smith Richard D | Treatment of cellulosic materials |
US4401810A (en) * | 1981-09-08 | 1983-08-30 | United States Of America As Represented By The Librarian Of Congress | Method of stabilizing felted cellulosic sheet material with an alkali metal borohydride |
US5094888A (en) * | 1990-02-20 | 1992-03-10 | Fmc Corporation | Strengthening cellulosic materials |
US5264243A (en) * | 1992-06-16 | 1993-11-23 | Fmc Corporation | Mass cellulose deacidification process |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000008250A2 (en) * | 1998-07-31 | 2000-02-17 | Universitat Politecnica De Catalunya | Product for desacidification of cellulose material, production and utilization thereof |
WO2000008250A3 (en) * | 1998-07-31 | 2000-05-18 | Univ Catalunya Politecnica | Product for desacidification of cellulose material, production and utilization thereof |
EP2522526A1 (en) * | 2011-05-13 | 2012-11-14 | Xerox Corporation | Storage stable images |
Also Published As
Publication number | Publication date |
---|---|
JP2002500289A (en) | 2002-01-08 |
BR9906824A (en) | 2000-10-17 |
EP1060220A4 (en) | 2001-08-01 |
EP1060220B1 (en) | 2003-07-23 |
EP1060220A1 (en) | 2000-12-20 |
CA2317564A1 (en) | 1999-07-15 |
ATE245685T1 (en) | 2003-08-15 |
DE69909762D1 (en) | 2003-08-28 |
DE69909762T2 (en) | 2004-04-15 |
ES2201660T3 (en) | 2004-03-16 |
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