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
  • D21H25/02—Chemical or biochemical treatment
• • 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
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/03—Non-macromolecular organic compounds
  • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
  • D21H17/11—Halides
• • 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
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/63—Inorganic compounds
  • D21H17/64—Alkaline compounds
• • 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
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
  • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
• • 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
  • D21H21/22—Agents rendering paper porous, absorbent or bulky
  • D21H21/24—Surfactants

Definitions

• the present invention relates, in part, to the deacidification of cellulose-based materials.
• the present invention relates to the use of hydrofluoro-olefins and/or hydrochlorofluoro-olefins to reduce the acidity associated with certain cellulose-based materials.
• a major cause associated with the deterioration of cellulose-based materials is the inherent acidity of such materials.
• the manufacture of paper and other cellulose materials often requires the addition of acids and acidic chemicals to reduce absorbency and to allow the paper products to accept inks and dyes.
• the manufacturing processes of these materials often include the introduction of additives via acidic mechanisms.
• these manufacturing processes often result in cellulose-based products having residual acidic material.
• the cellulose-based products tend to have low pH values and, accordingly, tend to undergo slow, but relentless, acid deterioration.
• U.S. Pat. No. 4,522,843 suggests that this problem can be solved by using a dispersion of a basic metal salt into a chlorofluorocarbon such as trichlorofluoromethane, trichlorotrifluoroethane and dichlorotetrafluoroethane and mixtures therof.
• a chlorofluorocarbon such as trichlorofluoromethane, trichlorotrifluoroethane and dichlorotetrafluoroethane and mixtures therof.
• the inventors point out that these substances are chlorofluorocarbons and contribute significantly to the depletion of the atmospheric ozone layer. They propose the use hydrofluorocarbons which do not contribute to the depletion of the ozone layer and also have physical properties that are appropriated for this application.
• the present invention relates to a deacidification composition
• a deacidification composition comprising (a) dispersing medium comprising, and preferably comprising in major proportion by weight, one or more hydrohalo-olefin(s) and (b) a deacidification agent dispersed in the dispersing medium, and even more preferably dispersed in the one or more hydrohalo-olefin(s).
• the one or more hydrohalo-olefin(s) contain from two to six carbon atoms, and more preferably in certain embodiments three to five carbon atoms.
• the one or more hydrohalo-olefin(s) have a boiling point or boiling range of from about ⁇ 29.0° C. to about 50° C.
• the preferred hydrohalo-olefin of the present invention comprises a compound according to formula I
• the deacidification agent comprises metal oxides, metal hydroxides, metal carbonates, metal salts, and combinations of two or more thereof. In certain aspects, it is a Group IA or Group IIA metal, which may include Group IA or Group IIA metal oxides, metal hydroxides, metal carbonates, and combinations thereof. In certain preferred embodiments, the deacidification agent comprises magnesium oxide. In certain preferred embodiments, the deacidification agent is in particle form and may have a predominant particle size of from about 0.01 to about 1.0 micron.
• the dispersing medium may include, in addition to the one or more hydrohalo-olefins, any one or more of several components in order to aid in, modulate and/or enhance the dispersing function or to provide any other desired function to the composition consistent with intended purpose.
• the dispersing medium may also include one or more surfactants, which may be provided to aid dispersion of the deacidification agent within the hydrohalo-olefin.
• surfactants may include a fluorinated surfactant or any other surfactant able to obtain the effects provided herein.
• the present invention also relates to methods of deacidifying a cellulose based material by providing a composition according to the present invention; and increasing the pH of a cellulose-based material by contacting said material with the composition.
• the contacting step may include immersing at least a portion of the cellulose-based material in the composition.
• the contacting step may also, or alternatively, include spraying the composition onto said cellulose-based material.
• the hydrohalo-olefin in preferred embodiments is then evaporated to deposit at least a portion of the deacidifying agent on the cellulose-based material.
• the present invention relates, in part, to compositions and methods of deacidifying cellulose-based materials that are not only adaptable for use with a wide range of deacidification agents, but also tend to be more environmentally-friendly and less costly than prior art processes.
• the present invention relates to the discovery that halogenated olefins, including hydrofluoro-olefins (“HFO”) and hydrochlorofluoro-olefins (“HCFO”), can be used in conjunction with a wide variety of basic materials to form compositions suitable for use in deacidifying acidic cellulosic materials.
• HFO hydrofluoro-olefins
• HCFO hydrochlorofluoro-olefins
• halogenated olefins having a boiling point of, or mixtures or blends of halogenated olefins having a boiling range within, from about ⁇ 29.0° C. to about 50° C. are capable of dispersing effective amounts of deacidifying agents therein such that the composition comprising the halogenated olefins and deacidifying agents may be advantageously introduced to acidic materials to increase the pH associated therewith.
• the preferred forms of the present compositions are similarly advantageous because they do not contribute to ozone depletion and have minimal ODP values. Thus, they are environmentally benign.
• compositions of the present method are also relatively volatile, and thus, can be removed easily from the cellulosic materials without the need to resort to conventional drying methods that are expensive and time-consuming.
• compositions of the present method are also relatively inexpensive, and exhibit additional beneficial properties such as, low flammability, low toxicity, and low reactivity.
• hydrohalo-olefins relates to any organic compound having at least one double bond between two carbon atoms, at least one halogen and at least one hydrogen. Such compounds are inclusive of, but not limited to, hydrofluoro-olefins and hydrochlorofluoro-olefins.
• hydrofluoro-olefin or “HFO” relates to any organic compound having at least one double bond between two carbon atoms, at least one fluorine and at least one hydrogen.
• hydroochlorofluoro-olefin or “HCFO” relates to any organic compound having at least one double bond between two carbon atoms, at least one fluorine, at least one chlorine, and at least one hydrogen.
• the hydrohalo-olefin contains C2 to C6 carbon atoms, or C3 to C5 carbon atoms, wherein the double bond is between two of the carbons.
• C2 to C6 refers to any olefin having from two to six carbon atoms in the backbone
• C3 to C5 means any olefin having from three to five carbon atoms in the backbone.
• hydrohalo-olefin hydrofluoro-olefin, and/or hydrochlorofluoro-olefin is compound according the following formula I:
• Useful hydrofluoro-olefins include but are not limited to one or more tetrafluoropropenes (HFO-1234), trifluoropropene (HFO-1243), heptafluorobutene (HFO-1327), heptafluoropentene (HFO-1447) and/or a fluorohexene.
• Useful hydrochlorofluoro-olefins include but are not limited to chlorotrifluoropropene (HCFO-1233) and/or a chlorofluorohexene.
• the hydrohalo-olefin, hydrofluoro-olefin and/or hydrochlorofluoro-olefin is substantially non-toxic. That is, in certain aspects, the hydrohalo-olefin, hydrofluoro-olefin and/or hydrochlorofluoro-olefin has a very low acute toxicity level, as measured by inhalation exposure to mice and/or rats.
• HFO-1234 is used herein to refer to all tetrafluoropropenes. Among the tetrafluoropropenes are included, but not limited to, 2,3,3,3-tetrafluoropropene (HFO-1234yf) or cis- and/or trans-1,1,1,3-tetrafluoropropene (HFO-1234ze).
• HFO-1234ze is used herein generically to refer to 1,1,1,3-tetrafluoropropene, independent of whether it is the cis- or trans- form.
• hydrofluoro-olefin comprises, consists essentially of, or consists of cisHFO-1234ze.
• the hydrofluoro-olefin comprises, consists essentially of, or consists of transHFO-1234ze, and in even further embodiments the hydrofluoro-olefin comprises, consists essentially of, or consists of cisHFO-1234ze and transHFO-1234ze.
• HCFO-1233 is used herein to refer to all trifluoromonochloropropenes. Among the trifluoromonochloropropenes are included, but not limited to, cis- and/or trans-1,1,1-trifluoro-3-chlororopropene (HCFO-1233zd).
• cisHCFO-1233zd and “transHCFO-1233zd” are used herein to describe the cis- and trans- forms of 1,1,1-trifluoro-3-chlororopropene, respectively.
• HCFO-1233zd therefore includes within its scope cisHCFO-1233zd, transHCFO-1233zd, and all combinations and mixtures of these.
• the hydrochlorofluoro-olefin comprises, consists essentially of, or consists of cisHCFO-1233zd. In further embodiments, the hydrochlorofluoro-olefin comprises, consists essentially of, or consists of transHCFO-1233zd, and in even further embodiments the hydrochlorofluoro-olefin comprises, consists essentially of, or consists of cisHCFO-1233zd and transHFO-1233zd.
• compositions are not limiting to broad scope the invention.
• Compounds of the present invention may also include any and all isomers thereof and/or alternative compounds in accordance with the foregoing.
• compositions of the present invention include, and preferably in major proportion by weight, and even more preferably in certain embodiments consist essentially of 1233zd, which exhibits desirable non-
• the dispersing medium, and in particular the hydrohalo-olefin(s), may be provided in any effective amount to act as a carrier for the deacidification agent and deliver it to the target substrate of interest.
• the compositions of the present invention comprise greater than 50 wt % of one of more hydrohalo-olefins, based on the total weight of the composition.
• the compositions comprise about 75 wt. % or more, about 80 wt. % or more, about 85 wt. % or more, about 90 wt. % or more, about 95 wt. % or more, or about 99 wt. % or more of the hydrohalo-olefin(s).
• the hydrohalo-olefin(s) comprises from about 1 to about 99 weight percent of the composition, from about 50 to about 99 wt. % of the composition, from about 75 to about 99 wt. % of the composition, from about 80 to about 99 wt. % of the composition, from about 90 to about 99 wt. % of the composition, or from about 90 to about 95 wt. % of the composition, based on the total weight of the composition.
• compositions of the present invention include one or more deacidification agents.
• a “deacidification agent,” as used herein, means a basic substance that can be used in conjunction with one or more of the hydrohalo-olefins provided herein to deacidify cellulose-based materials. Examples include oxides, hydroxides, carbonates, and bicarbonates of zinc and metals in Group 1 and Group II of the Periodic Table. According to certain embodiments, the deacidification agents of the present invention are oxides, hydroxides, carbonates and bicarbonates of zinc, magnesium, sodium, potassium, calcium, or combinations of two or more thereof.
• Non-limiting examples of such agents include zinc carbonate, zinc bicarbonate, zinc oxide, magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium methyl carbonate, calcium oxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and combinations of two or more thereof. More preferred, but non-limiting, deacidification agents include magnesium oxide and magnesium methyl carbonate. An especially preferred, but non-limiting, deacidification agent is magnesium oxide.
• the deacidification agents of the present invention are used in particle form.
• the deacidification agent particles are of a size suitable for being depositing on a cellulose-based material to cause deacidification of the material without substantially impairing images, if any, thereon.
• the predominant particle size i.e. the size of from about 90 to about 99%, or from about 95 to about 99% of the particles
• the predominant particle size is from about 0.01 to about 1.0 micron.
• the predominant particle size is from about 0.2 to about 0.5 micron.
• the particle surface area is from about 50 to about 200 m 2 /g BET, from about 100 to about 200 m 2 /g, or about 170 m 2 /g.
• deacidification agent particles suitable for use in the present invention are available commercially and/or can be prepared using processes known in the art.
• processes for preparing alkaline metal particles include burning elemental metals and collecting the resulting smoke, attrition of preformed oxides, calcination of elemental salts, and the like.
• processes for preparing alkaline metal particles include burning elemental metals and collecting the resulting smoke, attrition of preformed oxides, calcination of elemental salts, and the like.
• those of skill in the art will readily be able to obtain deacidification agent particles suitable for use in the present invention.
• the deacidification agent may be provided in any effective amount to achieve the objectives identified herein.
• the compositions of the present invention comprise about 50 wt % or less of the deacidification agent, based on the total weight of the composition.
• the compositions comprise about 25 wt. % or less, about 20 wt. % or less, about 15 wt. % or less, about 10 wt. % or less, about 5 wt. % or less, or about 1 wt. % or less of the deacidification agent.
• the deacidification agent comprises from about 1 to about 99 weight percent of the composition, from about 1 to about 50 wt.
• composition from about 1 to about 25 wt. % of the composition, from about 1 to about 15 wt. % of the composition, from about 1 to about 10 wt. % of the composition, or from about 5 to about 10 wt. % of the composition, based on the total weight of the composition.
• compositions used in the present invention further comprise a surfactant, which may aid in the dispersion of the dacidification agent in the hydrohalo-olefin.
• a surfactant which may aid in the dispersion of the dacidification agent in the hydrohalo-olefin.
• Any of a wide range of surfactants are suitable for use in the present invention and may include, but are not limited to ionic surfactants, anionic surfactants, cationic surfactants, and/or non-ionic surfactants, any one of which may optionally be halogenated.
• preferred, but non-limiting, surfactants used in the present invention are fluorinated surfactants, such as, for example, Fluorad, FC740 (approximately 50% petroleum naptha and 50% fluoroaliphatic polymeric esters) and FC721 available commercially from 3M and Solsperse 3000 and 6000 available from ICI Corporation.
• fluorinated surfactants such as, for example, Fluorad, FC740 (approximately 50% petroleum naptha and 50% fluoroaliphatic polymeric esters) and FC721 available commercially from 3M and Solsperse 3000 and 6000 available from ICI Corporation.
• deacidification agent hydrohalo-olefin
• surfactant may help increase the dispersibility of deacidification agent in the hydrohalo-olefin.
• the concentration of the deacidification agent in the composition is from about 0.001 to about 0.5 weight percent based on the total weight of the compositions. According to other embodiments, the deacidification agent concentration is from about 0.01 to about 0.4 weight percent.
• the surfactant has a concentration of from about 0.005 to about 1.0 weight percent based on the total weight of the deacidifying composition. Alternatively, the concentration is from about 0.005 and 0.5 weight percent.
• the contacting step of the present invention involves contacting at least a portion of a cellulose-based material with a composition of the present invention to increase the pH associated with the cellulose material.
• a cellulose-based material Any of a wide range of cellulose-based materials can be used in the present methods.
• suitable materials include paper and paper products, books, wood and wood products, combinations of two or more thereof, and the like.
• any of a wide range of methods for contacting the acidic cellulose material with a composition of the present invention can be used.
• suitable contacting methods include immersion of the cellulose material in the composition, adding the composition dropwise to the cellulose material, spraying the composition onto the cellulose material, combinations of two or more thereof, and the like.
• the composition may be provided as an aerosol using any of the foregoing or otherwise known propellants.
• the use of electrostatic attraction may be used in conjunction with the above methods to enhance deposit of materials on paper.
• the step of contacting the cellulose material involves contacting substantially the entire surface area of the cellulose material with the composition such that removal of the composition results in lowering the acidity of the cellulose material.
• the contacting step of the present invention may further comprise the step of removing the hydrohalo-olefin from the cellulosic material to deposit at least a portion of the deacidification agent on the cellulosic material. Any known methods for removing the hydrohalo-olefin may be used according to the present invention.
• the removing step comprises evaporating the hydrohalo-olefin from the cellulosic material.
• the evaporating step comprises changing the pressure and/or temperature to which the hydrohalo-olefin and cellulosic material are exposed such that the hydrohalo-olefin is converted to the gaseous state.
• the removed hydrohalo-olefin solvent can be recycled for further use.
• the present invention allows for the deacidification of cellulosic materials without the need for time-consuming solvent-removing drying steps and excess clean-up.
• This example illustrates one method of deacidifying paper according to the present invention.
• This example illustrates another method of deacidifying paper according to the present invention.
• a 150 cc aerosol can is loaded with 50 grams of a suspension prepared according to Example 1.
• One of HFC-134a (1.5 grams), HFO-1243zf, HFO-1234ze(E), (1.5 grams) or HFO-1234yf (1.5 grams) is added to the can to act as a propellant for the suspension.
• a sample of 63 year old paper as described in Example 1 is sprayed with the suspension from the aerosol can. The pH of the paper after spraying is measured to be 9.0
• This example illustrates one method of deacidifying paper according to the present invention.
• This example illustrates another method of deacidifying paper according to the present invention.
• a 150 cc aerosol can is loaded with 50 grams of a suspension prepared according to Example 3.
• One of HFC-134a (1.5 grams), HFO-1243zf, HFO-1234ze(E) (1.5 grams) or HFO-1234yf (1.5 grams) is added to the can to act as a propellant for the suspension.
• a sample of 63 year old paper as described in Example 1 is sprayed with the suspension from the aerosol can.
• the pH of the paper after spraying is measured to be 9.0
• This example illustrates one method of deacidifying paper according to the present invention.
• This example illustrates another method of deacidifying paper according to the present invention.
• a 150 cc aerosol can is loaded with 50 grams of a suspension prepared according to Example 5.
• One of HFC-134a (1.5 grams), HFO-1243zf, HFO-1234ze (E) (1.5 grams) or HFO-1234yf (1.5 grams) is added to the can to act as a propellant for the suspension.
• a sample of 63 year old paper as described in Example 1 is sprayed with the suspension from the aerosol can. The pH of the paper after spraying is measured to be 9.0

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• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
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• General Chemical & Material Sciences (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2012
  • 2012-12-13 US US13/713,833 patent/US20130158250A1/en not_active Abandoned
  • 2012-12-14 EP EP12858381.2A patent/EP2791417A4/fr not_active Withdrawn
  • 2012-12-14 WO PCT/US2012/069690 patent/WO2013090684A1/fr unknown

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