CA2184489C - Improved paper making process - Google Patents
Improved paper making process Download PDFInfo
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- CA2184489C CA2184489C CA002184489A CA2184489A CA2184489C CA 2184489 C CA2184489 C CA 2184489C CA 002184489 A CA002184489 A CA 002184489A CA 2184489 A CA2184489 A CA 2184489A CA 2184489 C CA2184489 C CA 2184489C
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- 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
-
- 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
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular 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
- 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
- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/24—Addition to the formed paper during paper manufacture
- D21H23/26—Addition to the formed paper during paper manufacture by selecting point of addition or moisture content of the paper
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Abstract
A process for the manufacture of a paper having improved grease and water re sistance, yet facilitating recycling of the paper is achieved by applying recyclable plastic coating to a paper making machine.</ SDOAB>
Description
~ WO 96/21061 2 1 $ 4 4 8/ .:pL-'ztirs95ffiuX87 IIVIPROVED PAPER MAKlING PROCESS
Field of the Invention The present invention is directed to the papermaking arts, more particularly to a process for the manufacture of a paper having improved grease and water resistance, yet facilitating recycling of the paper. Such papers (throughout the specification and claims "papers" includes virgin or recycled paper, kraft stock and similar materials) find particular application in the container maldng art wherein such iinproved properties are desirable. The container making art, -particularly, in the field of corrugated containers, folding cartons, and the tray and box industries, consumes much of the natural timber resources. Thus, it would be beneficial to formulate new processes of forining papers of improved grease and water resistance properties which would be recyclable.
Description of the related art The art of "paperinaking" is an ancient one, being attributable to invention by the Chinese before the birth of Christ.
More modern developments resultecf in the widely accepted Fourdrinier process (See Kirk-OtTtmer= ErrchclupGdicr c?f Chcniicul Techltology, 3rd ed_, Voi_ 9, pp. 846-7, John Wiley & Sons, New York 1980) in which a"furnisli" (a "ftirnish" is predonlinantly water, e.g., 99.5% by weight and 0.5% "stock" ('stock" being virgin, recycled or mixed virgin and recycled pulp of wood fibers, fillers, sizing atidlor dyes) is deposited from a headbox on a "wire" (a fast-moving foraminous conveyor belt or screen) which serves as a table to fortn the paper. As the furnish moves alona, gravity and suction boxes under the wire draw the water out. The volume and density of the material and the speed at which it flows onto the wire determine the paper's final weight.
Typically, after the paper leaves the -wet end" of the papermaking machine, it still contains a predominant amount of water. Therefore, the paper enters a press section, which can be a series of heavy rotating cylinders, which press the water from the paper, further compacting.
it and reducing its water content, typically to 70% by weiglit.
Subsequent to pressing the paper enters a drying section. Typically, a drying section is the longest part of the paper machine. Hot air or stearn heated cylinders contact both sides of the paper, evaporating the water to a low level, e.g., 5% by weight of the paper.
The paper optionally passes through a sizing liquid to inake it less porous and to help printing inks remain on the surface instead of penetrating the paper. The paper can go through additional dryers that evaporate the liquid in the sizing and coating.
Calenders or polished steel rolls make the paper even smoother and more compact. Wliile most calenders add gloss, some calenders are used to create a dull or inatte finish.
The paper is wound onto a "parent" reel and taken off the paper inaking machine.
The paper on the parent reel can be further processed, such as on a slitter/winder, into rolls of smaller size or fed into sheeters, such as folio or cut-size sheeteA-L. for printing end uses or even office application.
In order to inake containers, rolls fornied by slitter/winder (e.g., of paper and kraft grades of liner) are unwound and coated with a wax, Waxes impart water resistance and wet strength to the liner btit inhibits recycling the ttsed containers incorporating them. Additionally, the prior art wax coated liners niust be adhered to the other components of the container with hot melt adhesives. These hot tnelt adhesives are a further impediinent to recycling of forined containers employing wax coated components. Thus, there still exists a need for manufacturing paper possessing superior wet strength and water and grease resistance properties but facilitating recycling thereof.
Stimmary of the Invention In one embodiment the invention is directed to a process for mal:ing paper wherein a furnish is deposited on a wire and dewatered, characterized in:
adding to the fumish a recyclable plastic coating.
In another embodirnent, the invention is directed to a process for making paper wherein a furnish is deposited on a wire and dewatered to form a paper, and the dewatered paper is subsequently pressed a number of times to further reduce the water content of the paper, characterized in adding a recyclable plastic coating to at least one side of the dewatered paper subsequent to a first pressing step.
In a still further etnbodiment, the invention is directed to a process for_ making paper wherein a furnish is deposited on a wire and dewatered, the dewatered paper is subsequently pressed to further reduce the water content of the paper and subsequently calendered, characterized in introducing to at least one side of the paper a recyclable plastic coating between the pressing and calendering steps.
A further embodiment discloses a process for inaking paper characterized in the following steps:
(a) applying a ftirnish to a wire, 2~g44;59 ~ WO 96121061 PCT/i3S95/00187 (b) dewatering the furnish and obtaining a water containing paper, (e) pressing the water containing paper to reduce the water content, (d) calendering the pressed paper, (e) recovering a finished paper, and (f) adding a recyclable plastic coating during the paper making process.
Brief Descri2tion of the 12f~wintrs Fig. I is a perspective, schematic view of a typical paper-making tnachine.
Fig. 2 is a schematic, side view of an alternative coating iiiethod.
Detailed Descripticm of the InvCntion A typical paper making machine is illtistrated generally at 10 in Fig. -1.
Normally it comprises a "wet end" 1 I including a headbox 12, a wire 13 and a press section 15, a drying section 16, a size press 18, calender section 20 and parent reel 22.
Optionally, a dandy roll 14 is positioned about two thirds of the way down the wire to level the fibers and make the sheet more uniform. Gravity and suction boxes (not sliowri) are positioned underneatti the wire to remove water from the furnish.
The stock fed to the headbox 12 can be virgin, recycled or a mixture of virgin and recycled pulp. In the headbox 12, the stock is mixed with water to for.m a furnish for deposit onto the wire.
In the invention, a recyclable plastic coating (RPC) is incorporated during the papermaking process. It should be understood that in this invention and throughout the specification and clainls, "coating" means "coating" or "impregnation" unless otherwise indicated.
For example, a typical (RPC) eonlposition is an aqueous acrylic resin based composition.
A preferred three-coiiiponent cornposition according to the following formula W096/21061 PGT1i3S95100187 ~
Field of the Invention The present invention is directed to the papermaking arts, more particularly to a process for the manufacture of a paper having improved grease and water resistance, yet facilitating recycling of the paper. Such papers (throughout the specification and claims "papers" includes virgin or recycled paper, kraft stock and similar materials) find particular application in the container maldng art wherein such iinproved properties are desirable. The container making art, -particularly, in the field of corrugated containers, folding cartons, and the tray and box industries, consumes much of the natural timber resources. Thus, it would be beneficial to formulate new processes of forining papers of improved grease and water resistance properties which would be recyclable.
Description of the related art The art of "paperinaking" is an ancient one, being attributable to invention by the Chinese before the birth of Christ.
More modern developments resultecf in the widely accepted Fourdrinier process (See Kirk-OtTtmer= ErrchclupGdicr c?f Chcniicul Techltology, 3rd ed_, Voi_ 9, pp. 846-7, John Wiley & Sons, New York 1980) in which a"furnisli" (a "ftirnish" is predonlinantly water, e.g., 99.5% by weight and 0.5% "stock" ('stock" being virgin, recycled or mixed virgin and recycled pulp of wood fibers, fillers, sizing atidlor dyes) is deposited from a headbox on a "wire" (a fast-moving foraminous conveyor belt or screen) which serves as a table to fortn the paper. As the furnish moves alona, gravity and suction boxes under the wire draw the water out. The volume and density of the material and the speed at which it flows onto the wire determine the paper's final weight.
Typically, after the paper leaves the -wet end" of the papermaking machine, it still contains a predominant amount of water. Therefore, the paper enters a press section, which can be a series of heavy rotating cylinders, which press the water from the paper, further compacting.
it and reducing its water content, typically to 70% by weiglit.
Subsequent to pressing the paper enters a drying section. Typically, a drying section is the longest part of the paper machine. Hot air or stearn heated cylinders contact both sides of the paper, evaporating the water to a low level, e.g., 5% by weight of the paper.
The paper optionally passes through a sizing liquid to inake it less porous and to help printing inks remain on the surface instead of penetrating the paper. The paper can go through additional dryers that evaporate the liquid in the sizing and coating.
Calenders or polished steel rolls make the paper even smoother and more compact. Wliile most calenders add gloss, some calenders are used to create a dull or inatte finish.
The paper is wound onto a "parent" reel and taken off the paper inaking machine.
The paper on the parent reel can be further processed, such as on a slitter/winder, into rolls of smaller size or fed into sheeters, such as folio or cut-size sheeteA-L. for printing end uses or even office application.
In order to inake containers, rolls fornied by slitter/winder (e.g., of paper and kraft grades of liner) are unwound and coated with a wax, Waxes impart water resistance and wet strength to the liner btit inhibits recycling the ttsed containers incorporating them. Additionally, the prior art wax coated liners niust be adhered to the other components of the container with hot melt adhesives. These hot tnelt adhesives are a further impediinent to recycling of forined containers employing wax coated components. Thus, there still exists a need for manufacturing paper possessing superior wet strength and water and grease resistance properties but facilitating recycling thereof.
Stimmary of the Invention In one embodiment the invention is directed to a process for mal:ing paper wherein a furnish is deposited on a wire and dewatered, characterized in:
adding to the fumish a recyclable plastic coating.
In another embodirnent, the invention is directed to a process for making paper wherein a furnish is deposited on a wire and dewatered to form a paper, and the dewatered paper is subsequently pressed a number of times to further reduce the water content of the paper, characterized in adding a recyclable plastic coating to at least one side of the dewatered paper subsequent to a first pressing step.
In a still further etnbodiment, the invention is directed to a process for_ making paper wherein a furnish is deposited on a wire and dewatered, the dewatered paper is subsequently pressed to further reduce the water content of the paper and subsequently calendered, characterized in introducing to at least one side of the paper a recyclable plastic coating between the pressing and calendering steps.
A further embodiment discloses a process for inaking paper characterized in the following steps:
(a) applying a ftirnish to a wire, 2~g44;59 ~ WO 96121061 PCT/i3S95/00187 (b) dewatering the furnish and obtaining a water containing paper, (e) pressing the water containing paper to reduce the water content, (d) calendering the pressed paper, (e) recovering a finished paper, and (f) adding a recyclable plastic coating during the paper making process.
Brief Descri2tion of the 12f~wintrs Fig. I is a perspective, schematic view of a typical paper-making tnachine.
Fig. 2 is a schematic, side view of an alternative coating iiiethod.
Detailed Descripticm of the InvCntion A typical paper making machine is illtistrated generally at 10 in Fig. -1.
Normally it comprises a "wet end" 1 I including a headbox 12, a wire 13 and a press section 15, a drying section 16, a size press 18, calender section 20 and parent reel 22.
Optionally, a dandy roll 14 is positioned about two thirds of the way down the wire to level the fibers and make the sheet more uniform. Gravity and suction boxes (not sliowri) are positioned underneatti the wire to remove water from the furnish.
The stock fed to the headbox 12 can be virgin, recycled or a mixture of virgin and recycled pulp. In the headbox 12, the stock is mixed with water to for.m a furnish for deposit onto the wire.
In the invention, a recyclable plastic coating (RPC) is incorporated during the papermaking process. It should be understood that in this invention and throughout the specification and clainls, "coating" means "coating" or "impregnation" unless otherwise indicated.
For example, a typical (RPC) eonlposition is an aqueous acrylic resin based composition.
A preferred three-coiiiponent cornposition according to the following formula W096/21061 PGT1i3S95100187 ~
COMPONEPiT A
TYPICAL CHARACTERISTICS Appearance Amber clear solution Non-voladle 34.0 0.5% resins solids pH
Viscosity, 2500 500 cps (Brookfield) Lbs./gal. 8.7 0.1 Density 1.07 Acid Number 70 Tg. 95"C
Flash point 115 P
Freeze/Thaw Stability Yes COMPONENT B
Appearance Translucent Bmulsion Non-volatiles 40%
pH 2.5 - 3.5 Viscosity 25 - 35 cps Weight per gallon 8.7 lbs.
M.F.T. 8 C.
Tg 00C
Acid number 58 (@ 100% NV) COMPONENT C
A 35 % solids polyethylene wax emulsion having the following typical properties:
Non-volatiles 34.7 -35_3%
pH 9.0-9.5 Weight per gallon 8.27 lbs.
is supplied to the headbox 12. Conlponents A. B and C are mixed in approximate parts by weight of 15:65:6 in admixture with 5.5 HOH, 0.5 NHaOH. 3 zinc oxide ~solution" (actually a dispersion), under strong agitation. All of the f'oregoing proportions can be varied plus or minus 10% and still display the performance of the. RPC. In fact, Component A
and B can be varied plus or minus 20% and Component C can be conipletely removed froin the forniulation or be substituted by otiier synthetic polyethylene waxes whiie still acliieving tlie desired results of the invention. The percent solids of the coEnposition supplied to lieadbox 12 or used at other coating locations according to the inventioil can typically be varied frotn abottt 3.0% to about 20% by weight.
Components A, B and C are mixed in approximate parts (by weight) of 15:65:6 in admixture with 5.5 HOH, 0.5 NH4OH, 3 zinc oxide solution, under strong agitation.
The Components A, B and C, to be used in formulating the composition of the invention, are commercially availabie from S.C. Johnson & Sons, Inc., U.S. Specialty Chemicals, 1525 5 Howe Street, Racine, ''Wisconsin under the trademarks JONCRYL 6I i.V, JONCRYL 82 and 7ONCRYL.28, respectively.
JONCRYL 82 is a polyn-eric composition compatible with various solvents including methanol, 3A ethanol, isopropanol, n-propanol, ethylene glycol monobutyl ether, diethylene glycol rnonoethyl ether, acetone, methylene ketone and methyl isobutyl ketone.
Heat resistance of JONCRYL 82 can be further increased by crosslinking the polymer with a zinc oxide solution which produces stable viscosities at higher pH. The maximuni workable pH of can be increased from 7 to 9 by incorporating a zinc oxide solution.
JONCRYL 61LV can be formulated in a ball-mill or high shear dispersion of up to 40%
organic and 70% inorganic pigment. Unlike other acrylic polymer dispersions, JONCRYL
61LV does not becon}e thixotropic at high pH. JONCRYL 61LV is compatible with caseins, shellacs and resin ester nialeics, as well as otlier acrylic resins.
However, more or less than 3.0-20% by weight of the aqueous composition can be incorporated in the stock or finished paper. The following Examples will demonstrate the wide variation in RPC content.
Example 1 _ Within the laboratory environment, liner board was repulped to conform with the consistency of pulped fiber processed in an average paper mill machine. At tliis point, the fiber was separated into foar separate beakers each with 100 grams of fiber. To beaker number 1, 5.0 grams of RPC was added. In beaker number 2, 10.0 grams of RPC was added.
In beaker number 3, 20.0 grams of RPC was added. In beaker number 4, 30.0 grams of RPC
was added.
After stirring the fiber mixed with RPC at variotis levels, the fiber from each beaker was applied to a wire mesh which would simulate the wire tnesh of a paper machine which allows the fiber to drain by gravity or assisted through a particle vacuum action that starts the renioval of fluids on the paper machine. Through gravity and compTession in the laboratory environment, excess fluids were driven out of the fiber of each test sample, one through four.
To simulate paper machine drying the fiber, still on the wire mesh, was dried bv infra-red heat.
After all four test satnples were drsed. the stirfaces were tested for grease resistance and water resistance. A fiftli saiiiple was repulped, screened and dried witliout any RPC to be the control.
Samples one through four showed improved grease and water resistance when compared to the control. The final phase was to repulp samples orie through four, rescreen and dry. The final =
step in the process to determine success is examining the dry reformed papen.under a microscope 5= to determine the presence of undissolved foreign niatter that would indicate a failure to repulp.
The examination revealed that no undissolved irlaterial were present, indicating success in ...
creating a barrier and having the barrier, RPC, dissolve and allow no foreign matter to be present in any beaker marked one through fottr. The foregoing experitnent is indicative of addition of RPC to the stock or furnish prior to deposit on the wire of a paper making machine.
The next step in taking the invention from the laboratory to a commercially viable process was to introduce the RPC at different locations in conventional paper making machines.
A position on the paper machine downstreatn of the lieadhox 12 was selected -for a manual "pour on" of liduid RPC on an edge of the paper approximately 24 inches (58.8 cm) of the width of the paper machine, in the amount of 5 galloiis (18.92 1). This section of treated paper was tracked through the paper machine and rotrieved at the dry end of the machine. This retrieval section was tested for grease and water resistaiice and stiowed itnprovement in both areas.
RPC was next applied witli a spraybar, the application rate applied t'rom a miniinum value, but sufficient to create perceptible enhancements to liner or mediuni, to approximately 40% by weight of paper, pH varied from 5.5 to 8Ø
The RPC was applied at the wet end via spray application to tiie top side of the slieet during a run of 26# mediuni. The trial spray head was positioned at:
(1) the wet/dry line on the wire, and (2) after the second press. before the dryer.
Subsequently, the RPC was applied via calender stock treatment to a 69#
special liner.
The purpose of this trial was to ascertain the viability of this application technique utilizing two water boxes on one side. The results of this latter trial is as follows:
TYPICAL CHARACTERISTICS Appearance Amber clear solution Non-voladle 34.0 0.5% resins solids pH
Viscosity, 2500 500 cps (Brookfield) Lbs./gal. 8.7 0.1 Density 1.07 Acid Number 70 Tg. 95"C
Flash point 115 P
Freeze/Thaw Stability Yes COMPONENT B
Appearance Translucent Bmulsion Non-volatiles 40%
pH 2.5 - 3.5 Viscosity 25 - 35 cps Weight per gallon 8.7 lbs.
M.F.T. 8 C.
Tg 00C
Acid number 58 (@ 100% NV) COMPONENT C
A 35 % solids polyethylene wax emulsion having the following typical properties:
Non-volatiles 34.7 -35_3%
pH 9.0-9.5 Weight per gallon 8.27 lbs.
is supplied to the headbox 12. Conlponents A. B and C are mixed in approximate parts by weight of 15:65:6 in admixture with 5.5 HOH, 0.5 NHaOH. 3 zinc oxide ~solution" (actually a dispersion), under strong agitation. All of the f'oregoing proportions can be varied plus or minus 10% and still display the performance of the. RPC. In fact, Component A
and B can be varied plus or minus 20% and Component C can be conipletely removed froin the forniulation or be substituted by otiier synthetic polyethylene waxes whiie still acliieving tlie desired results of the invention. The percent solids of the coEnposition supplied to lieadbox 12 or used at other coating locations according to the inventioil can typically be varied frotn abottt 3.0% to about 20% by weight.
Components A, B and C are mixed in approximate parts (by weight) of 15:65:6 in admixture with 5.5 HOH, 0.5 NH4OH, 3 zinc oxide solution, under strong agitation.
The Components A, B and C, to be used in formulating the composition of the invention, are commercially availabie from S.C. Johnson & Sons, Inc., U.S. Specialty Chemicals, 1525 5 Howe Street, Racine, ''Wisconsin under the trademarks JONCRYL 6I i.V, JONCRYL 82 and 7ONCRYL.28, respectively.
JONCRYL 82 is a polyn-eric composition compatible with various solvents including methanol, 3A ethanol, isopropanol, n-propanol, ethylene glycol monobutyl ether, diethylene glycol rnonoethyl ether, acetone, methylene ketone and methyl isobutyl ketone.
Heat resistance of JONCRYL 82 can be further increased by crosslinking the polymer with a zinc oxide solution which produces stable viscosities at higher pH. The maximuni workable pH of can be increased from 7 to 9 by incorporating a zinc oxide solution.
JONCRYL 61LV can be formulated in a ball-mill or high shear dispersion of up to 40%
organic and 70% inorganic pigment. Unlike other acrylic polymer dispersions, JONCRYL
61LV does not becon}e thixotropic at high pH. JONCRYL 61LV is compatible with caseins, shellacs and resin ester nialeics, as well as otlier acrylic resins.
However, more or less than 3.0-20% by weight of the aqueous composition can be incorporated in the stock or finished paper. The following Examples will demonstrate the wide variation in RPC content.
Example 1 _ Within the laboratory environment, liner board was repulped to conform with the consistency of pulped fiber processed in an average paper mill machine. At tliis point, the fiber was separated into foar separate beakers each with 100 grams of fiber. To beaker number 1, 5.0 grams of RPC was added. In beaker number 2, 10.0 grams of RPC was added.
In beaker number 3, 20.0 grams of RPC was added. In beaker number 4, 30.0 grams of RPC
was added.
After stirring the fiber mixed with RPC at variotis levels, the fiber from each beaker was applied to a wire mesh which would simulate the wire tnesh of a paper machine which allows the fiber to drain by gravity or assisted through a particle vacuum action that starts the renioval of fluids on the paper machine. Through gravity and compTession in the laboratory environment, excess fluids were driven out of the fiber of each test sample, one through four.
To simulate paper machine drying the fiber, still on the wire mesh, was dried bv infra-red heat.
After all four test satnples were drsed. the stirfaces were tested for grease resistance and water resistance. A fiftli saiiiple was repulped, screened and dried witliout any RPC to be the control.
Samples one through four showed improved grease and water resistance when compared to the control. The final phase was to repulp samples orie through four, rescreen and dry. The final =
step in the process to determine success is examining the dry reformed papen.under a microscope 5= to determine the presence of undissolved foreign niatter that would indicate a failure to repulp.
The examination revealed that no undissolved irlaterial were present, indicating success in ...
creating a barrier and having the barrier, RPC, dissolve and allow no foreign matter to be present in any beaker marked one through fottr. The foregoing experitnent is indicative of addition of RPC to the stock or furnish prior to deposit on the wire of a paper making machine.
The next step in taking the invention from the laboratory to a commercially viable process was to introduce the RPC at different locations in conventional paper making machines.
A position on the paper machine downstreatn of the lieadhox 12 was selected -for a manual "pour on" of liduid RPC on an edge of the paper approximately 24 inches (58.8 cm) of the width of the paper machine, in the amount of 5 galloiis (18.92 1). This section of treated paper was tracked through the paper machine and rotrieved at the dry end of the machine. This retrieval section was tested for grease and water resistaiice and stiowed itnprovement in both areas.
RPC was next applied witli a spraybar, the application rate applied t'rom a miniinum value, but sufficient to create perceptible enhancements to liner or mediuni, to approximately 40% by weight of paper, pH varied from 5.5 to 8Ø
The RPC was applied at the wet end via spray application to tiie top side of the slieet during a run of 26# mediuni. The trial spray head was positioned at:
(1) the wet/dry line on the wire, and (2) after the second press. before the dryer.
Subsequently, the RPC was applied via calender stock treatment to a 69#
special liner.
The purpose of this trial was to ascertain the viability of this application technique utilizing two water boxes on one side. The results of this latter trial is as follows:
7 69# Special Liner Reg 69#! Liner Treated One Side Ti-eated Two Sides Basis Wgt MSF 69 69.1 69.8 Caliper - 19.0 20.0 19.5 Mullen Min 128 117 120 CD 32-47 23.75 28.4 Cobb 1-min T/B gms. --- .37/.17 .20/.06 Scott plybond --- 95 100 Porosity Sec 8 700+ 1200+
Alternatively, as shown in Fig_ 2, coating on both sides of a nioving paper web 24 can be effected by passing web 24 between the nip of rollers 26, 28 in which a bank 30 of RPC
is found thereby applying the RPC to one side of web 24. After passing over idler roll 32, the other side of the web 24 can be coated by bank 40 and rollers 36, 38.
Additional layers of coating may be applied one or more tinies to either or both sides of web 24 by additional rollers 46, 48, 56, 58 and banks 50 and 60. Additional idler rolls 42, 52 may be provided to convey and tension web 24. The device of Fig. 2 can be: used prior to, subsequent to or in place of size press 18 of Fig. 1. It should be understood that additional rollers (not shown), banks (not shown) and even idler rolls (not shown) may be empioyed to apply as many additional layers of RPC as desired, Additionally, sizing agents may be incorporated into one or niore of the banks of RPC.
All of the foregoing tests prodticed a paper that was repulpable. In addition, the addition of RPC appears to dramatically increase fiber strengths. Using 100% recycled fiber treated with RPC increased fiber strengths, giving strengths of 90% of virgin fiber, whereas normal recycled fiber are approximately 60% of virgin fiber.
The process of paper inaking can be moditied to inciude [~"C addition at the headbox (or even upstream of the headbox when the stock is inixed with tiliers. si2ing or dyes), in the press section at any point subsequent to the first press, and subsequent to the drying section, either at or in piace of the size press but before the calenders.
The papers coated by the process find special use in the following industries, the label industry, especially the 60#13000 S.F. label industry, folding carton, tray and box (all board WO 96/21061 PCT/[1S95/00157 4D
Alternatively, as shown in Fig_ 2, coating on both sides of a nioving paper web 24 can be effected by passing web 24 between the nip of rollers 26, 28 in which a bank 30 of RPC
is found thereby applying the RPC to one side of web 24. After passing over idler roll 32, the other side of the web 24 can be coated by bank 40 and rollers 36, 38.
Additional layers of coating may be applied one or more tinies to either or both sides of web 24 by additional rollers 46, 48, 56, 58 and banks 50 and 60. Additional idler rolls 42, 52 may be provided to convey and tension web 24. The device of Fig. 2 can be: used prior to, subsequent to or in place of size press 18 of Fig. 1. It should be understood that additional rollers (not shown), banks (not shown) and even idler rolls (not shown) may be empioyed to apply as many additional layers of RPC as desired, Additionally, sizing agents may be incorporated into one or niore of the banks of RPC.
All of the foregoing tests prodticed a paper that was repulpable. In addition, the addition of RPC appears to dramatically increase fiber strengths. Using 100% recycled fiber treated with RPC increased fiber strengths, giving strengths of 90% of virgin fiber, whereas normal recycled fiber are approximately 60% of virgin fiber.
The process of paper inaking can be moditied to inciude [~"C addition at the headbox (or even upstream of the headbox when the stock is inixed with tiliers. si2ing or dyes), in the press section at any point subsequent to the first press, and subsequent to the drying section, either at or in piace of the size press but before the calenders.
The papers coated by the process find special use in the following industries, the label industry, especially the 60#13000 S.F. label industry, folding carton, tray and box (all board WO 96/21061 PCT/[1S95/00157 4D
weights) and liquid packs, stich as water, soda, and milk, ice cream, yogurt and delicatessen carry-out containers.
The fine paper industry for barrier containers and interleaves for between sensitive paper or metallized papers or photographic plates can also benefit from the #nc+ention.
By using the invention to apply a coating formulation into aõ~aper making machine the following benefits are achzeved:
(1) the overall cost of the finished coated/impregnated liner or paper is reduced, and (2) incorporating the technology into the paper inaking inachine (process) would allow the technology to reach its maximum potential.
Although the present invention has been described in terms of specif'ic embodiments, it will be apparent to one skilled in the art that various inodifications may be made according to those embodiments without departing from the scope of the applied ciaims and their equivalents.
Accordingly, the present invention should not be construed to be limited to the specific embodiments disclosed herein.
The fine paper industry for barrier containers and interleaves for between sensitive paper or metallized papers or photographic plates can also benefit from the #nc+ention.
By using the invention to apply a coating formulation into aõ~aper making machine the following benefits are achzeved:
(1) the overall cost of the finished coated/impregnated liner or paper is reduced, and (2) incorporating the technology into the paper inaking inachine (process) would allow the technology to reach its maximum potential.
Although the present invention has been described in terms of specif'ic embodiments, it will be apparent to one skilled in the art that various inodifications may be made according to those embodiments without departing from the scope of the applied ciaims and their equivalents.
Accordingly, the present invention should not be construed to be limited to the specific embodiments disclosed herein.
Claims (20)
1. In a process for making paper wherein a furnish is deposited on a wire and dewatered, the improvement comprising:
adding to the furnish an effective amount of a repulpable acrylic resin-containing composition wherein the acrylic resin-containing composition is at a pH of at least 5.5 and further comprises zinc oxide in an amount effective to crosslink the acrylic resin.
adding to the furnish an effective amount of a repulpable acrylic resin-containing composition wherein the acrylic resin-containing composition is at a pH of at least 5.5 and further comprises zinc oxide in an amount effective to crosslink the acrylic resin.
2. The process of claim 1 wherein the paper made is one selected from liner and medium.
3. The process of claim 1 wherein the furnish is a mixture of stock and water and said acrylic resin-containing composition is added to said mixture before the furnish is deposited on said wire.
4. The process of claim 1 wherein the furnish is a mixture of stock and water and said repulpable acrylic based resin composition is added to said mixture at the wet/dry line on said wire.
5. The process of claim 1 wherein the furnish is a mixture of stock and water and the stock is a pulp selected from the group consisting of virgin, recycled and mixtures thereof.
6. The process of claim 5 wherein the stock is a recycled pulp and said recycled pulp contains an acrylic based resin component.
7. In a process for making paper, wherein a furnish is deposited on a wire and dewatered to form a paper, and the dewatered paper is subsequently pressed a number of times to further reduce the water content of the paper, the improvement comprising adding an effective amount of a repulpable acrylic resin-containing composition at a pH of at least 5.5, said acrylic resin-containing composition including zinc oxide in an amount effective to crosslink the acrylic resin, to at least one side of the dewatered paper subsequent to a first pressing step.
8. The process of claim 7 wherein the repulpable acrylic resin-containing composition is applied to both sides of the dewatered paper subsequent to a first pressing step.
9. The process of claim 7 wherein the paper made is one selected from liner and medium.
10. In a process for making paper wherein a furnish is deposited on a wire and dewatered to form a paper, the dewatered paper is subsequently pressed to further reduce the water content of the paper and is subsequently calendered, the improvement comprising introducing to at least one side of the paper an effective amount of a repulpable acrylic resin-containing composition at a pH of at least 5.5, said acrylic resin-containing composition including zinc oxide in an amount effective to crosslink the acrylic resin, between the pressing and calendering steps.
11. The process of claim 10 wherein the paper made is one selected from liner and medium.
12. The process of claim 10 wherein the repulpable acrylic resin-containing composition is introduced to both sides of the paper.
13. A process for making paper comprising the following steps:
(A) applying a furnish to a wire;
(B) dewatering the furnish and obtaining a water containing paper;
(C) pressing the water containing paper to reduce the water content;
(D) calendaring the pressed paper;
(E) recovering a finished paper; and (F) adding an effective amount of a repulpable acrylic resin-containing composition containing zinc oxide in an amount effective to crosslink the acrylic resin, said resin composition having a pH of at least about 5.5, at any point during said paper making process.
(A) applying a furnish to a wire;
(B) dewatering the furnish and obtaining a water containing paper;
(C) pressing the water containing paper to reduce the water content;
(D) calendaring the pressed paper;
(E) recovering a finished paper; and (F) adding an effective amount of a repulpable acrylic resin-containing composition containing zinc oxide in an amount effective to crosslink the acrylic resin, said resin composition having a pH of at least about 5.5, at any point during said paper making process.
14. The process of claim 13 wherein said repulpable acrylic resin-containing composition is added more than once during said paper making process.
15. In a process for making paper wherein a furnish is deposited on a wire and dewatered, the improvement comprising adding to the furnish an effective amount of a repulpable acrylic based resin composition wherein the acrylic based resin composition consists of the following components:
(A) 15 parts by weight of an aqueous acrylic resin emulsion having 34Ø+-Ø5% non-volatiles, a pH of 8.3-8.6, a Brookfield viscosity of 2500 ~ 500 cps, a density of 1.07, an acid number of 70, a Tg of 95° C. and a flashpoint of 115°
C.;
(B) 65 parts by weight of an aqueous acrylic resin emulsion having 40% non-volatiles, a pH of 2.5-3.5, a viscosity of 25-35 cps, a weight per gallon of 8.7 pounds, an M.F.T. of 8° C., a T g of 0°C. and an acid number of 58 at 100%
non-volatiles;
(C) 6 parts by weight of an aqueous polyethylene was emulsion having 34.7-35.3%
non-volatiles, a pH of 9.0-9.5 and a weight per gallon of 8.27 pounds;
(D) 5.5 parts by weight HOH;
(E) 0.5 parts by weight NH4OH; and (F) 3 parts by weight zinc oxide solution.
(A) 15 parts by weight of an aqueous acrylic resin emulsion having 34Ø+-Ø5% non-volatiles, a pH of 8.3-8.6, a Brookfield viscosity of 2500 ~ 500 cps, a density of 1.07, an acid number of 70, a Tg of 95° C. and a flashpoint of 115°
C.;
(B) 65 parts by weight of an aqueous acrylic resin emulsion having 40% non-volatiles, a pH of 2.5-3.5, a viscosity of 25-35 cps, a weight per gallon of 8.7 pounds, an M.F.T. of 8° C., a T g of 0°C. and an acid number of 58 at 100%
non-volatiles;
(C) 6 parts by weight of an aqueous polyethylene was emulsion having 34.7-35.3%
non-volatiles, a pH of 9.0-9.5 and a weight per gallon of 8.27 pounds;
(D) 5.5 parts by weight HOH;
(E) 0.5 parts by weight NH4OH; and (F) 3 parts by weight zinc oxide solution.
16. In a process for making paper wherein a furnish is deposited on a wire and dewatered to form a paper, and the dewatered paper is subsequently pressed a number of times to further reduce the water content of the paper, the improvement comprising adding an effective amount of a repulpable acrylic based resin composition to at least one side of the dewatered paper subsequent to a first pressing step wherein the acrylic based resin composition consists of the following components:
(A) 15 parts by weight of an aqueous acrylic resin emulsion having 34Ø+-Ø5% non-volatiles, a pH of 8.3-8.6, a Brookfield viscosity of 2500 ~ 500 cps, a density of 1.07, an acid number of 70, a T. of 95°C and a flashpoint of 115°C.
(B) 65 parts by weight of an aqueous acrylic resin emulsion having 40% non-volatiles, a pH of 2.5-3.5, a viscosity of 25-35 cps, a weight per gallon of 8.7 pounds, an M.F.T. of 8°C, a T g of 0°C and an acid number of 58 at 100% non-volatiles;
(C) 6 parts by weight of an aqueous polyethylene wax emulsion having 34.7-35.3%
non-volatiles, a pH of 9.0-9.5 and a weight per gallon of 8.27 pounds;
(D) 5.5 parts by weight HOH;
(E) 0.5 parts by weight NH4OH; and (F) 3 parts by weight zinc oxide solution.
(A) 15 parts by weight of an aqueous acrylic resin emulsion having 34Ø+-Ø5% non-volatiles, a pH of 8.3-8.6, a Brookfield viscosity of 2500 ~ 500 cps, a density of 1.07, an acid number of 70, a T. of 95°C and a flashpoint of 115°C.
(B) 65 parts by weight of an aqueous acrylic resin emulsion having 40% non-volatiles, a pH of 2.5-3.5, a viscosity of 25-35 cps, a weight per gallon of 8.7 pounds, an M.F.T. of 8°C, a T g of 0°C and an acid number of 58 at 100% non-volatiles;
(C) 6 parts by weight of an aqueous polyethylene wax emulsion having 34.7-35.3%
non-volatiles, a pH of 9.0-9.5 and a weight per gallon of 8.27 pounds;
(D) 5.5 parts by weight HOH;
(E) 0.5 parts by weight NH4OH; and (F) 3 parts by weight zinc oxide solution.
17. In a process for making paper wherein a furnish is deposited on a wire and dewatered, the dewatered paper is subsequently pressed to further reduce the water content of the paper and subsequently calendared, the improvement comprising introducing to at least one side of the paper an effective amount of a repulpable acrylic resin based composition between the pressing and calendaring steps wherein the acrylic based resin composition consists of the following components:
(A) 15 parts by weight of an aqueous acrylic resin emulsion having 34.0 ~
0.5% non-volatile, a pH of 8.3-8.6, a Brookfield viscosity of 2500 ~ 500 cps, a density of 1.07, an acid number of 70, a T g of 95°C and a flashpoint of 115°C;
(B) 65 parts by weight of an aqueous acrylic resin emulsion having 40% non-volatiles, a pH of 2.5-3.5, a viscosity of 25-35 cps, a weight per gallon of 8.7 pounds, an M.F.T. of 8°C, a T, of 0°C and an acid number of 58 at 100% non-volatiles;
(C) 6 parts by weight of an aqueous polyethylene wax emulsion having 34.7-35.3% non-volatiles, a pH of 9.0-9.5 and a weight per gallon of 8.27 pounds;
(D) 5.5 parts by weight HOH;
(E) 0.5 parts by weight NH4OH; and (F) 3 parts by weight zinc oxide solution.
(A) 15 parts by weight of an aqueous acrylic resin emulsion having 34.0 ~
0.5% non-volatile, a pH of 8.3-8.6, a Brookfield viscosity of 2500 ~ 500 cps, a density of 1.07, an acid number of 70, a T g of 95°C and a flashpoint of 115°C;
(B) 65 parts by weight of an aqueous acrylic resin emulsion having 40% non-volatiles, a pH of 2.5-3.5, a viscosity of 25-35 cps, a weight per gallon of 8.7 pounds, an M.F.T. of 8°C, a T, of 0°C and an acid number of 58 at 100% non-volatiles;
(C) 6 parts by weight of an aqueous polyethylene wax emulsion having 34.7-35.3% non-volatiles, a pH of 9.0-9.5 and a weight per gallon of 8.27 pounds;
(D) 5.5 parts by weight HOH;
(E) 0.5 parts by weight NH4OH; and (F) 3 parts by weight zinc oxide solution.
18. The process of claim 1 wherein the recyclable plastic coating is an acrylic based resin composition consisting of the following components:
(A) 15 parts by weight of an aqueous acrylic resin emulsion having 34.0 non-volatiles, a pH of 8.3-8.6, a Brookfield viscosity of 2500 density of 1.07, an acid number of 70, a T, of 95°C and a flashpoint of 115°C;
(B) 65 parts by weight of an aqueous acrylic resin emulsion having 40% non-volatiles, a pH of 2.5-3.5, a viscosity of 25-35 cps, a weight per gallon of 8.7 pounds, an M.F.T. of 8°C, a T, of 0°C and an acid number of 58 at 100% non-volatiles;
(C) 6 parts by weight of an aqueous polyethylene wax emulsion having 34.7-35.3%
non-volatiles, a pH of 9.0-9.5 and a weight per gallon of 8.27 pounds;
(D) 5.5 parts by weight HOH;
(E) 0.5 parts by weight NH4OH; and (F) 3 parts by weight zinc oxide solution.
(A) 15 parts by weight of an aqueous acrylic resin emulsion having 34.0 non-volatiles, a pH of 8.3-8.6, a Brookfield viscosity of 2500 density of 1.07, an acid number of 70, a T, of 95°C and a flashpoint of 115°C;
(B) 65 parts by weight of an aqueous acrylic resin emulsion having 40% non-volatiles, a pH of 2.5-3.5, a viscosity of 25-35 cps, a weight per gallon of 8.7 pounds, an M.F.T. of 8°C, a T, of 0°C and an acid number of 58 at 100% non-volatiles;
(C) 6 parts by weight of an aqueous polyethylene wax emulsion having 34.7-35.3%
non-volatiles, a pH of 9.0-9.5 and a weight per gallon of 8.27 pounds;
(D) 5.5 parts by weight HOH;
(E) 0.5 parts by weight NH4OH; and (F) 3 parts by weight zinc oxide solution.
19. The process of claim 4 wherein the recyclable plastic coating is an acrylic based resin composition consisting of the following components:
(A) 15 parts by weight of an aqueous acrylic resin emulsion having 34.0 non-volatiles, a pH of 8.3-8.6, a Brookfield viscosity of 2500 density of 1.07, an acid number of 70, a T g of 95°C and a flashpoint of 115°C;
(B) 65 parts by weight of an aqueous acrylic resin emulsion having 40% non-volatiles, a pH of 2.5-3.5, a viscosity of 25-35 cps, a weight per gallon of 8.7 pounds, an M.F.T. of 8°C, a T, of 0°C and an acid number of 58 at 100% non-volatiles;
(C) 6 parts by weight of an aqueous polyethylene wax emulsion having 34.7-35.3%
non-volatiles, a pH of 9.0-9.5 and a weight per gallon of 8.27 pounds;
(D) 5.5 parts by weight HOH;
(E) 0.5 parts by weight NH4OH; and (F) 3 parts by weight zinc oxide solution.
(A) 15 parts by weight of an aqueous acrylic resin emulsion having 34.0 non-volatiles, a pH of 8.3-8.6, a Brookfield viscosity of 2500 density of 1.07, an acid number of 70, a T g of 95°C and a flashpoint of 115°C;
(B) 65 parts by weight of an aqueous acrylic resin emulsion having 40% non-volatiles, a pH of 2.5-3.5, a viscosity of 25-35 cps, a weight per gallon of 8.7 pounds, an M.F.T. of 8°C, a T, of 0°C and an acid number of 58 at 100% non-volatiles;
(C) 6 parts by weight of an aqueous polyethylene wax emulsion having 34.7-35.3%
non-volatiles, a pH of 9.0-9.5 and a weight per gallon of 8.27 pounds;
(D) 5.5 parts by weight HOH;
(E) 0.5 parts by weight NH4OH; and (F) 3 parts by weight zinc oxide solution.
20. The process of claim 6 wherein the recyclable plastic coating is an acrylic based resin composition consisting of the following components:
(A) 15 parts by weight of an aqueous acrylic resin emulsion having 34.0 non-volatiles, a pH of 8.3-8.6, a Brookfield viscosity of 2500 density of 1.07, an acid number of 70, a T., of 95°C and a flashpoint of 115°C;
(B) 65 parts by weight of an aqueous acrylic resin emulsion having 40% non-volatiles, a pH of 2.5-3.5, a viscosity of 25-35 cps, a weight per gallon of 8.7 pounds, an M.F.T. of 8°C, a T g of 0°C and an acid number of 58 100% non-volatiles;
(C) 6 parts by weight of an aqueous polyelthylene wax emulsion having 34.7-35.3%
non-volatiles, a pH of 9.0-9.5 and a weight per gallon of 8.27 pounds;
(D) 5.5 parts by weight HOH;
(E) 0.5 parts by weight NH4OH; and (F) 3 parts by weight zinc oxide solution.
(A) 15 parts by weight of an aqueous acrylic resin emulsion having 34.0 non-volatiles, a pH of 8.3-8.6, a Brookfield viscosity of 2500 density of 1.07, an acid number of 70, a T., of 95°C and a flashpoint of 115°C;
(B) 65 parts by weight of an aqueous acrylic resin emulsion having 40% non-volatiles, a pH of 2.5-3.5, a viscosity of 25-35 cps, a weight per gallon of 8.7 pounds, an M.F.T. of 8°C, a T g of 0°C and an acid number of 58 100% non-volatiles;
(C) 6 parts by weight of an aqueous polyelthylene wax emulsion having 34.7-35.3%
non-volatiles, a pH of 9.0-9.5 and a weight per gallon of 8.27 pounds;
(D) 5.5 parts by weight HOH;
(E) 0.5 parts by weight NH4OH; and (F) 3 parts by weight zinc oxide solution.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1995/000187 WO1996021061A1 (en) | 1995-01-06 | 1995-01-06 | Improved paper making process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2184489A1 CA2184489A1 (en) | 1996-07-11 |
| CA2184489C true CA2184489C (en) | 2007-12-11 |
Family
ID=22248465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002184489A Expired - Lifetime CA2184489C (en) | 1995-01-06 | 1995-01-06 | Improved paper making process |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0749508B1 (en) |
| AT (1) | ATE216742T1 (en) |
| AU (1) | AU1676195A (en) |
| CA (1) | CA2184489C (en) |
| DE (1) | DE69526495T2 (en) |
| FI (1) | FI121935B (en) |
| WO (1) | WO1996021061A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10232550C5 (en) * | 2002-07-18 | 2013-02-07 | Voith Patent Gmbh | Apparatus and method for impregnating a paper or board web |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2970079A (en) * | 1956-05-22 | 1961-01-31 | Du Pont | Surface coated impregnated waterleaf |
| US4313790A (en) * | 1980-03-31 | 1982-02-02 | Pulp And Paper Research Institute Of Canada | Additives for increased retention and pitch control in paper manufacture |
| US4510019A (en) * | 1981-05-12 | 1985-04-09 | Papeteries De Jeand'heurs | Latex containing papers |
| US5492733A (en) * | 1990-03-05 | 1996-02-20 | International Paper Company | High gloss ultraviolet curable coating |
| DE69322269T2 (en) * | 1992-05-27 | 1999-04-22 | Conagra, Inc., Omaha, Nebr. | FOOD CONTAINERS AND THE LIKE WITH PRESSURIZED LAYERS |
| US5393566A (en) * | 1992-10-27 | 1995-02-28 | Tim-Bar Coproration | Recyclable plastic coated containers |
| US5763100A (en) * | 1993-05-10 | 1998-06-09 | International Paper Company | Recyclable acrylic coated paper stocks and related methods of manufacture |
-
1995
- 1995-01-06 CA CA002184489A patent/CA2184489C/en not_active Expired - Lifetime
- 1995-01-06 AU AU16761/95A patent/AU1676195A/en not_active Abandoned
- 1995-01-06 EP EP95908441A patent/EP0749508B1/en not_active Expired - Lifetime
- 1995-01-06 DE DE69526495T patent/DE69526495T2/en not_active Expired - Lifetime
- 1995-01-06 AT AT95908441T patent/ATE216742T1/en not_active IP Right Cessation
- 1995-01-06 WO PCT/US1995/000187 patent/WO1996021061A1/en active IP Right Grant
-
1996
- 1996-09-05 FI FI963481A patent/FI121935B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FI963481L (en) | 1996-11-05 |
| EP0749508A4 (en) | 1997-10-22 |
| EP0749508B1 (en) | 2002-04-24 |
| FI963481A0 (en) | 1996-09-05 |
| DE69526495D1 (en) | 2002-05-29 |
| CA2184489A1 (en) | 1996-07-11 |
| EP0749508A1 (en) | 1996-12-27 |
| FI121935B (en) | 2011-06-15 |
| DE69526495T2 (en) | 2002-11-28 |
| ATE216742T1 (en) | 2002-05-15 |
| AU1676195A (en) | 1996-07-24 |
| WO1996021061A1 (en) | 1996-07-11 |
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| EEER | Examination request | ||
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