CA2372697A1 - Preservation of paper and textile materials - Google Patents
Preservation of paper and textile materials Download PDFInfo
- Publication number
- CA2372697A1 CA2372697A1 CA002372697A CA2372697A CA2372697A1 CA 2372697 A1 CA2372697 A1 CA 2372697A1 CA 002372697 A CA002372697 A CA 002372697A CA 2372697 A CA2372697 A CA 2372697A CA 2372697 A1 CA2372697 A1 CA 2372697A1
- Authority
- CA
- Canada
- Prior art keywords
- fluoropolymer
- article
- paper
- textile
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44D—PAINTING OR ARTISTIC DRAWING, NOT OTHERWISE PROVIDED FOR; PRESERVING PAINTINGS; SURFACE TREATMENT TO OBTAIN SPECIAL ARTISTIC SURFACE EFFECTS OR FINISHES
- B44D7/00—Preserving paintings, e.g. by varnishing
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/08—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with halogenated hydrocarbons
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
- D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
- D06M15/3335—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol fluorinated
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
- D06M15/353—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Paper (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Paints Or Removers (AREA)
Abstract
A method is disclosed for strengthening a paper or textile article. The method involves (a) applying to the article a solution of an amorphous fluoropolymer in a perfluoroalkane solvent; and (b) drying the article. Also disclosed are strengthened paper and textile articles which include a fibrous paper or textile substrate, and amorphous fluoropolymer interconnecting fibers of the substrate.
Description
r j ~_OE_?:00~ 1 ~. COCA ~- ~ : ~e~~-' NG, , ~ . !.~~ 0000? 6?
CA 02372697 2001-10-30 IO~~, f, ~ , CL1446 PCT . .
TALE
PRESERVATION OF PAPER AND TEXTILE MATERIALS
FIEL OF THE INVENTION
The p~tesent invention relates to the preservation of paper articles (e.g., books, manuscripts, documents) and textiles articles (e.g., paintings on canvas, clothing, etc.) through the application of an amorphous fluoropolymer by, for example, spraying, dipping or brushing the article to be preserved with a solution of the fiuoropolymer.
BACKGROUND
Commonly owned and eopending PCT International Application No. PCT/US98/26903 discloses coating a substrate (e.g., a metal, ceramic or composite) including the application of a fluompolymer solution to seal pores.
The use of fluoropolymer dispersions to coat and protect paper and fabrics is known (see e.g., U.S. Patent Nos. 4,742,140 and 5,674,96/). Generally, these dispersions are comprised of particles in the neighborhood of 80 to 400 nm in ' i diameter in as aqueous medium. The particles arc not intcndod 'to fully or uniformly coat the fibers of paper or fabric. Also, because they are generally aqueous dispersions, items containing water-soluble dyes would be damaged by contact with water.
WO A 92/10532 teaches fluoimating the surface of polymers by deposition of fluorocarbons from solution. WO A 97/19224 is a process for preserving paper by polymerizing polycondensates in situ. GB A 007 981 .
discloses lamination of paper or textile articles. US 5,509,736 describes , itapregauoa of paper with paiiicies of oXides viinicil hyarate io-bases:
SUMMARY OF 'f~ INVENT1(~N
The present invention provides a method for strengthening a cellulosic paper or textile article, comprising the steps of (a) applying to the article a solution of an amorphous fluoropolymer in a pcrfluoroalkane solvent; and (b) drying the article so that the solvent is essentially removed.
The present invention also relates to a strengthened cellulosic pager or textile article comprising (i) a f brows cellulosic paper or textile substrate and (ii) amorphous fluompolymer interconnecting fibers of said substrate.
BRIEF DESCRIPTION OF T~ DRA
Figure 1 represents a plot of data from Table 1.
DETAILED DESCRIPTION
The present invention employs amorphous fluoropolymers which, for application, are dissolved in a perfluoroalkaae solvent. Articles to be preserved are treated with the fluoropolymer solution by any suitable method, including but AMENDED SHEET
EMPFAPlGSZEIT 15. JUN. 19;56 HuSUKUCKC7FrT 1~ IIIAI ~n.n~
~-0~-20f ~ ' not limited to dipping, spraying and brushing. The article may be, but is not limited to, a book, manuscript, paper, fabric, article of clothing, painting, and the like. Normally, the amorphous fluoropolymer is used substantially transparent, and consequently there is no substantial difference in appearance between the treated article and the untreated article.
~hcn fluoropolymer is deposited from solution onto a non-porous surface, a coating of about 5 to 20 ~.rn thick typically results. This thickness is related to the concentration of the solution used is the deposition. Generally, a 1 %
solution will produce a film about 5 Eun thick, and a 6% solution yields a film thickness of about 50 pm. However, when the object on which the fluoropolymer is deposited is f brows or porous, the fluoropolymer penetrates into the obj oct. Commonly owned and copending PCT International Application No. PCT/US98I26903 and U.S. Patent Application Serial No. 215,441 describe the penetration of fluoropolymer solutions into pores in thermal spray coatings which are used for corrosion protection. Fluorine x-ray fluorescence micrographs were used to demonstrate fluoropolymer penetration into the pores.
Useful herein are solutions of fluoropolymers with molecular weights in the range of from 200,000 to 400,000. These fluoropolymers are known to have excellent chemical resistance; and their solutions generally have relatively low viscosities, on the order of about 0.050-0.300 pastel seconds (60 to 300 centipoise) at shear rates from about 50 to 300 sec-1, which enables them to flow into the pores. The location of the fluoropolymer in the pores is also important because, unlike purely surface films, the material is not easily abraded or word$waY: i~aine=; W o ituorbpoiytner~in W a pole is protected fr'oni abrasion - -I
by the surrounding porous coating as well as nay surface coating. Moreover, the fibers of the substrate are interconnected with fluoropolymer, thereby strengthening the atticle_ Treating paper with fluoropolymer solutions can significantly increase the tensile strength of paper, as shown in Example 2 below, as well as typically impart other desirable properties. The films or deposits have very low surface energies compared to untreated paper (e.g., in the range of 15 to 19 dynes/cm).
Thus, they are generally difficult to wet with liquids such as water. Solid deposits like dirt, dust or inks will not easily adhere to such surfaces. The permeation of aggressive chemical eonstxtuents of the environment which may degrade or corrode the object is retarded, as the solutions penetrate into the bulk of the material as well as depositing on the surface. Finally, the fluoropolymer film or deposit itself is very inert to degradation from environmental chemicals.
CA 02372697 2001-10-30 IO~~, f, ~ , CL1446 PCT . .
TALE
PRESERVATION OF PAPER AND TEXTILE MATERIALS
FIEL OF THE INVENTION
The p~tesent invention relates to the preservation of paper articles (e.g., books, manuscripts, documents) and textiles articles (e.g., paintings on canvas, clothing, etc.) through the application of an amorphous fluoropolymer by, for example, spraying, dipping or brushing the article to be preserved with a solution of the fiuoropolymer.
BACKGROUND
Commonly owned and eopending PCT International Application No. PCT/US98/26903 discloses coating a substrate (e.g., a metal, ceramic or composite) including the application of a fluompolymer solution to seal pores.
The use of fluoropolymer dispersions to coat and protect paper and fabrics is known (see e.g., U.S. Patent Nos. 4,742,140 and 5,674,96/). Generally, these dispersions are comprised of particles in the neighborhood of 80 to 400 nm in ' i diameter in as aqueous medium. The particles arc not intcndod 'to fully or uniformly coat the fibers of paper or fabric. Also, because they are generally aqueous dispersions, items containing water-soluble dyes would be damaged by contact with water.
WO A 92/10532 teaches fluoimating the surface of polymers by deposition of fluorocarbons from solution. WO A 97/19224 is a process for preserving paper by polymerizing polycondensates in situ. GB A 007 981 .
discloses lamination of paper or textile articles. US 5,509,736 describes , itapregauoa of paper with paiiicies of oXides viinicil hyarate io-bases:
SUMMARY OF 'f~ INVENT1(~N
The present invention provides a method for strengthening a cellulosic paper or textile article, comprising the steps of (a) applying to the article a solution of an amorphous fluoropolymer in a pcrfluoroalkane solvent; and (b) drying the article so that the solvent is essentially removed.
The present invention also relates to a strengthened cellulosic pager or textile article comprising (i) a f brows cellulosic paper or textile substrate and (ii) amorphous fluompolymer interconnecting fibers of said substrate.
BRIEF DESCRIPTION OF T~ DRA
Figure 1 represents a plot of data from Table 1.
DETAILED DESCRIPTION
The present invention employs amorphous fluoropolymers which, for application, are dissolved in a perfluoroalkaae solvent. Articles to be preserved are treated with the fluoropolymer solution by any suitable method, including but AMENDED SHEET
EMPFAPlGSZEIT 15. JUN. 19;56 HuSUKUCKC7FrT 1~ IIIAI ~n.n~
~-0~-20f ~ ' not limited to dipping, spraying and brushing. The article may be, but is not limited to, a book, manuscript, paper, fabric, article of clothing, painting, and the like. Normally, the amorphous fluoropolymer is used substantially transparent, and consequently there is no substantial difference in appearance between the treated article and the untreated article.
~hcn fluoropolymer is deposited from solution onto a non-porous surface, a coating of about 5 to 20 ~.rn thick typically results. This thickness is related to the concentration of the solution used is the deposition. Generally, a 1 %
solution will produce a film about 5 Eun thick, and a 6% solution yields a film thickness of about 50 pm. However, when the object on which the fluoropolymer is deposited is f brows or porous, the fluoropolymer penetrates into the obj oct. Commonly owned and copending PCT International Application No. PCT/US98I26903 and U.S. Patent Application Serial No. 215,441 describe the penetration of fluoropolymer solutions into pores in thermal spray coatings which are used for corrosion protection. Fluorine x-ray fluorescence micrographs were used to demonstrate fluoropolymer penetration into the pores.
Useful herein are solutions of fluoropolymers with molecular weights in the range of from 200,000 to 400,000. These fluoropolymers are known to have excellent chemical resistance; and their solutions generally have relatively low viscosities, on the order of about 0.050-0.300 pastel seconds (60 to 300 centipoise) at shear rates from about 50 to 300 sec-1, which enables them to flow into the pores. The location of the fluoropolymer in the pores is also important because, unlike purely surface films, the material is not easily abraded or word$waY: i~aine=; W o ituorbpoiytner~in W a pole is protected fr'oni abrasion - -I
by the surrounding porous coating as well as nay surface coating. Moreover, the fibers of the substrate are interconnected with fluoropolymer, thereby strengthening the atticle_ Treating paper with fluoropolymer solutions can significantly increase the tensile strength of paper, as shown in Example 2 below, as well as typically impart other desirable properties. The films or deposits have very low surface energies compared to untreated paper (e.g., in the range of 15 to 19 dynes/cm).
Thus, they are generally difficult to wet with liquids such as water. Solid deposits like dirt, dust or inks will not easily adhere to such surfaces. The permeation of aggressive chemical eonstxtuents of the environment which may degrade or corrode the object is retarded, as the solutions penetrate into the bulk of the material as well as depositing on the surface. Finally, the fluoropolymer film or deposit itself is very inert to degradation from environmental chemicals.
AMENDED SHEET
-.~..~.mwn~rrr .r IIIU ~n ~/ nnen~nr~lc7GtT 1~ ~~~N ~n ~-O6-2OO' ' =~ ?OL'! r ' : O9°h -, ,_ CA 02372697 2001-10-30 v~ ~~~L 1 v~~
Nf i0~~ ~' h ;
. I
' , One use for this invention is the preservation of a variety of papers, !
including books, newspaper pages and documents, As paper ages, it frequently becomes more brittle. This is a problem for historic books and documents of great age. Treatment of these papers with the fluoropolymer solutions, as described in this invention, have been shown to increase the tensile strength of the paper, as shown is the Irxatnples below. As outlined is Examples 1 and 2 below, a paper or book can be dipped into the fluoropolymerlperfluoroalkane solution and air dried i EMPFANGSZEIT I5, ~~N, Ig:56 AMENDED SHEET
nu~utcuCKSZEIT i5 .IIIN ~n.n~
'r 5-0~-200' I''. : ~, ?~C:'- _ : ~~ai' - ''' 000''' "'=0 .., ~ ~.< < ~_ -N0, l 608 P. 9 Minneapolis, MN). In general, the perfluoroalkaae solvents used la these solutions are not considered aggressive to many paper and textile articles.
Most inks will not dissolve in perfluorinated solvents. Similarly, many substrates sre tnnaffected by exposure to these solvents.
. The fluoropolymer solutions may be applied to the fibrous articles by common coating methods, including but not limited to spray application, dipping and brushing. After application of the solutions, the articles can be dried by conventional methods (e.g., air or vacuum drying), EXAMPLES
Fluoroflo~ymer Solution Preoaration~
Teflon~ AF solutions were used in the examples below, and were used as received from E. I. du Pont de Nemours and Company, Wilmington, DE, unless otherwise noted. To dilute the Teflon~ AF2130, solvent (FC-75, 3M, Minneapolis, MN) was weighed and was placed into a containcz, with the calculated amount of Teflon~ AF2130 added to the solvent. The samples were mixed before use.
Paper reatment Several types of paper, including newsprint and copier paper were dipped for about 30 seconds into several Teflon~ AF solutions, having concentrations between 1 and 6% solids by weight, such that about half the sheet was impregnated with the solution. The papers were removed from the solution and I
dried for about 30 minutes. The entire sheets of paper were immersed in water at room temperature. The treated portion emerged in undamaged condition while r the untreated papez fell apart. No dissolution or blurring of ink was observed in the treated portion of the newsprint.
I
Strength Testine of Payer The strength of treated paper was compared to that of an untreated paper. ' Strips of paper (20 pound White Wove, Gilbert, Tnc., Menasha, WI) about 2.5 cm (1 inch) wide, 20.3 em (8 inches) long, and 0.010 cm (0.004 inches) thick, were immersed for 10 minutes in solutions with varying concentrations of .
fluoropolymer_ The strips were removed and dried, leaving a fluoropolymer deposit in the paper. The tensile strengths of the strips were measured using a r model I 122 Instron test machine (Instroa Corp., Canton, MA) and ASTM Method D 828 procedures (the test bars were held in grips with a separation of 5 inches, . .
and the cross head speed was 2 incheslminute). The fluoropolymer treatment EMPFANGSZE IT 15. JUN. ~ g; 5b AMENDED SHEET
r,vovnut,KSZEIT 15 .Illel ~n.n.
mnu I ~. ~U~~: v , j _ n ~ .t CA 02372697 2001-10-30 ~'' ' ~' ~ ~ ~ j "~_ ,L
increased the st~ngth of the paper. Z'he results are shown in Table 1 below, as well as in Figgie 1. ' Fluoropolymer Concenvation S~g~~ % Iaereas~ !n Solution Ideocificatioaof Mpa ~1 Stren va. Control Fluoropolymer, /o None 0 44.0 6.38 ...
TEFLON~ AF 3 512 7.42 16.3 1600 6 ' 56.1 8.14 27.6 TFrFLON~ AF1601 'TEFLON AF2400I 48.9 7.09 11.1 TEFLON~ AFZ1306 59.3 8.60 34.8 , TEFLON~ AF2130'3 59.0 8.55 34_0 TEFLON~ AF21301 47.8 6.94 8.8 .
AMENDED SHEET , EMPFANGSZEIT 15. JUN. 19:56 enenenrve~rrT ,r ...,.
-.~..~.mwn~rrr .r IIIU ~n ~/ nnen~nr~lc7GtT 1~ ~~~N ~n ~-O6-2OO' ' =~ ?OL'! r ' : O9°h -, ,_ CA 02372697 2001-10-30 v~ ~~~L 1 v~~
Nf i0~~ ~' h ;
. I
' , One use for this invention is the preservation of a variety of papers, !
including books, newspaper pages and documents, As paper ages, it frequently becomes more brittle. This is a problem for historic books and documents of great age. Treatment of these papers with the fluoropolymer solutions, as described in this invention, have been shown to increase the tensile strength of the paper, as shown is the Irxatnples below. As outlined is Examples 1 and 2 below, a paper or book can be dipped into the fluoropolymerlperfluoroalkane solution and air dried i EMPFANGSZEIT I5, ~~N, Ig:56 AMENDED SHEET
nu~utcuCKSZEIT i5 .IIIN ~n.n~
'r 5-0~-200' I''. : ~, ?~C:'- _ : ~~ai' - ''' 000''' "'=0 .., ~ ~.< < ~_ -N0, l 608 P. 9 Minneapolis, MN). In general, the perfluoroalkaae solvents used la these solutions are not considered aggressive to many paper and textile articles.
Most inks will not dissolve in perfluorinated solvents. Similarly, many substrates sre tnnaffected by exposure to these solvents.
. The fluoropolymer solutions may be applied to the fibrous articles by common coating methods, including but not limited to spray application, dipping and brushing. After application of the solutions, the articles can be dried by conventional methods (e.g., air or vacuum drying), EXAMPLES
Fluoroflo~ymer Solution Preoaration~
Teflon~ AF solutions were used in the examples below, and were used as received from E. I. du Pont de Nemours and Company, Wilmington, DE, unless otherwise noted. To dilute the Teflon~ AF2130, solvent (FC-75, 3M, Minneapolis, MN) was weighed and was placed into a containcz, with the calculated amount of Teflon~ AF2130 added to the solvent. The samples were mixed before use.
Paper reatment Several types of paper, including newsprint and copier paper were dipped for about 30 seconds into several Teflon~ AF solutions, having concentrations between 1 and 6% solids by weight, such that about half the sheet was impregnated with the solution. The papers were removed from the solution and I
dried for about 30 minutes. The entire sheets of paper were immersed in water at room temperature. The treated portion emerged in undamaged condition while r the untreated papez fell apart. No dissolution or blurring of ink was observed in the treated portion of the newsprint.
I
Strength Testine of Payer The strength of treated paper was compared to that of an untreated paper. ' Strips of paper (20 pound White Wove, Gilbert, Tnc., Menasha, WI) about 2.5 cm (1 inch) wide, 20.3 em (8 inches) long, and 0.010 cm (0.004 inches) thick, were immersed for 10 minutes in solutions with varying concentrations of .
fluoropolymer_ The strips were removed and dried, leaving a fluoropolymer deposit in the paper. The tensile strengths of the strips were measured using a r model I 122 Instron test machine (Instroa Corp., Canton, MA) and ASTM Method D 828 procedures (the test bars were held in grips with a separation of 5 inches, . .
and the cross head speed was 2 incheslminute). The fluoropolymer treatment EMPFANGSZE IT 15. JUN. ~ g; 5b AMENDED SHEET
r,vovnut,KSZEIT 15 .Illel ~n.n.
mnu I ~. ~U~~: v , j _ n ~ .t CA 02372697 2001-10-30 ~'' ' ~' ~ ~ ~ j "~_ ,L
increased the st~ngth of the paper. Z'he results are shown in Table 1 below, as well as in Figgie 1. ' Fluoropolymer Concenvation S~g~~ % Iaereas~ !n Solution Ideocificatioaof Mpa ~1 Stren va. Control Fluoropolymer, /o None 0 44.0 6.38 ...
TEFLON~ AF 3 512 7.42 16.3 1600 6 ' 56.1 8.14 27.6 TFrFLON~ AF1601 'TEFLON AF2400I 48.9 7.09 11.1 TEFLON~ AFZ1306 59.3 8.60 34.8 , TEFLON~ AF2130'3 59.0 8.55 34_0 TEFLON~ AF21301 47.8 6.94 8.8 .
AMENDED SHEET , EMPFANGSZEIT 15. JUN. 19:56 enenenrve~rrT ,r ...,.
Claims (10)
1. A method for strengthening a cellulosic paper or textile article, comprising the steps of:
(a) applying to the article a solution of an amorphous fluoropolymer in a perfluoroalkane solvent; and (b) drying the article so that the solvent is essentially removed.
(a) applying to the article a solution of an amorphous fluoropolymer in a perfluoroalkane solvent; and (b) drying the article so that the solvent is essentially removed.
2. The method of Claim 1 wherein the fluoropolymer has a molecular weight in the range of from 200,000 to 400,000.
3. The method of Claim 1 wherein the fluoropolymer is a copolymer of 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole with either tetrafluoroethylene or chlorotrifluoroethylene.
4. The method of Claim 1 wherein the fluoropolymer is a copolymer of tetrafluoroethylene with a monomer selected from fluoroolefins having from 2 to 8 carbon atoms and fluorinated alkyl vinyl ethers where the alkyl group contains from 1 to 5 carbons.
5. A strengthened cellulosic paper ar textile article, comprising:
(i) a fibrous cellulosic paper or textile substrate; and (ii) amorphous fluoropolymer interconnecting fibers of said substrate.
(i) a fibrous cellulosic paper or textile substrate; and (ii) amorphous fluoropolymer interconnecting fibers of said substrate.
6. The strengthened cellulosic paper or textile article of Claim 5 wherein the fluoropolymer has a molecular weight in the range of from 200,000 to 400,000.
7. The strengthened cellulosic paper or textile article of Claim S wherein the fluoropolymer is a copolymer of 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole with either tetrafluoroethylene or chlorotrifluoroethylene.
8. The strengthened cellulosic paper or textile article of Claim 5 wherein the fluoropolymer is a copolymer of tetrafluoroethylene with a monomer selected from fluoroolefins having from 2 to 8 carbon atoms and fluorinated alkyl vinyl ethers where the alkyl group contains from 1 to 5 carbons.
9. A strengthened article of paper or textile, comprising:
a) a pattern or printing, and b) an amorphous fluoropolymer coating applied from an amorphous fluoropolymer solution such that the information conveyed by the pattern or printing is not obscured or distorted.
a) a pattern or printing, and b) an amorphous fluoropolymer coating applied from an amorphous fluoropolymer solution such that the information conveyed by the pattern or printing is not obscured or distorted.
10. The process of treating a patterned or printed article of paper or textile comprising: applying to the article a solution of an amorphous fluoropolymer in a perfluoroalkane solvent; and drying the article so that the solvent is essentially removed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13965199P | 1999-06-17 | 1999-06-17 | |
| US60/139,651 | 1999-06-17 | ||
| PCT/US2000/016234 WO2000079051A1 (en) | 1999-06-17 | 2000-06-13 | Preservation of paper and textile materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2372697A1 true CA2372697A1 (en) | 2000-12-28 |
Family
ID=22487669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002372697A Abandoned CA2372697A1 (en) | 1999-06-17 | 2000-06-13 | Preservation of paper and textile materials |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1190140A1 (en) |
| JP (1) | JP2003502531A (en) |
| KR (1) | KR20020047051A (en) |
| AU (1) | AU5485900A (en) |
| CA (1) | CA2372697A1 (en) |
| IL (1) | IL146189A0 (en) |
| WO (1) | WO2000079051A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100453205B1 (en) * | 2001-07-11 | 2004-10-15 | 주식회사 흥인화학 | A Long Term Preservative For Cellulose Materials Using A Mixture Of Fluorine Compounds Having Low Molecular Weight As A Carrier |
| KR100970953B1 (en) * | 2009-07-06 | 2010-07-20 | (주)노바텍인코퍼레이션 | Writable decoration wallpaper |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1007981A (en) * | 1961-04-17 | 1965-10-22 | William Herbert Langwell | Improvements in or relating to the preservation of documents for storage |
| GB9026687D0 (en) * | 1990-12-07 | 1991-01-23 | Vascutek Ltd | Process for providing a low-energy surface on a polymer |
| US5409736A (en) * | 1993-08-31 | 1995-04-25 | Preservation Technologies, Inc. | Deacidification of cellulose based materials using perfluorinated carriers |
| DE19543707A1 (en) * | 1995-11-23 | 1997-05-28 | Inst Neue Mat Gemein Gmbh | Process for preserving paper |
-
2000
- 2000-06-13 CA CA002372697A patent/CA2372697A1/en not_active Abandoned
- 2000-06-13 AU AU54859/00A patent/AU5485900A/en not_active Abandoned
- 2000-06-13 WO PCT/US2000/016234 patent/WO2000079051A1/en not_active Application Discontinuation
- 2000-06-13 KR KR1020017016148A patent/KR20020047051A/en not_active Application Discontinuation
- 2000-06-13 EP EP00939840A patent/EP1190140A1/en not_active Withdrawn
- 2000-06-13 IL IL14618900A patent/IL146189A0/en unknown
- 2000-06-13 JP JP2001505390A patent/JP2003502531A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020047051A (en) | 2002-06-21 |
| WO2000079051A1 (en) | 2000-12-28 |
| AU5485900A (en) | 2001-01-09 |
| IL146189A0 (en) | 2002-07-25 |
| EP1190140A1 (en) | 2002-03-27 |
| JP2003502531A (en) | 2003-01-21 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |