WO2003104559A1 - Papier a faible teneur en eau - Google Patents
Papier a faible teneur en eau Download PDFInfo
- Publication number
- WO2003104559A1 WO2003104559A1 PCT/US2003/017922 US0317922W WO03104559A1 WO 2003104559 A1 WO2003104559 A1 WO 2003104559A1 US 0317922 W US0317922 W US 0317922W WO 03104559 A1 WO03104559 A1 WO 03104559A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- paper product
- water
- wood pulp
- polyhydroxy polymer
- pulp
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0004—Use of compounding ingredients, the chemical constitution of which is unknown, broadly defined, or irrelevant
-
- 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
- D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels
-
- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/26—Polyamides; Polyimides
-
- 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
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
- D21H27/38—Multi-ply at least one of the sheets having a fibrous composition differing from that of other sheets
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
Definitions
- the present invention relates to a low water paper product. More specifically, the paper product of the present invention is comprised of wood pulp having at least some of the water present in the amorphous regions replaced with polyhydroxy polymer. The resulting paper product is more rigid and dimensionally stable, and has a lower equilibrium moisture content.
- Cellulose is a rigid polymer which is composed of linear chains of polymerized glucose units.
- living wood and in cellulose isolated at low temperature from wood there is a low degree of lateral order.
- the cellulose chains become more ordered or crystalline.
- regions of low lateral order are easily penetrated by water. It has been found that the water is present as a liquid in the non- crystalline regions. The presence of the water in the non-crystalline regions satisfies the need in the structure for hydrogen bonding. However, the presence of the water also makes the fibers more plastic and swellable when exposed to water vapor or liquid water.
- the presence of the water adversely affects the dimensional stability of the paper. It is known that many paper products exhibit failures in the presence of water. This is of particular relevance when a cellulose or paper-based product is used as insulation in a transformer.
- the weakest link of any transformer insulation system is the cellulose. In the majority of cases, the failure of a transformer is related to insulation breakdown. Practically speaking, the lifespan of the transformer is really the lifespan of the cellulose insulation.
- the Achilles' heel of cellulose used in the oil filled electrical transformer is thermal degradation.
- the combination of water, oxygen, and heat break down the physical strength of the cellulose fiber.
- the aging process is accelerated. For example, a one percent water content will age the cellulose ten times faster than if the water content was 0.1 percent. If the effects of oxygen and the presence of water are combined, aging can increase by an order of 25 times. This is the reason transformer manufacturers have begun making sealed transformers and transformers with expansion reservoirs equipped with a bladder. These technologies are aimed at countering the migration of water and oxygen towards the main tank. It is understood in the prior art that water in paper may generally be found in four external states . The water can be absorbed to the surface, the water can be present as a vapor (a high humidity environment) , as free water in capillaries, and as embibed free water.
- Another object of the present invention is to provide a paper product with improved stiffness. Still another object of the present invention is to provide a paper product having excellent dielectric properties.
- Yet another object of the present invention is to provide a novel paper product useful as a heat transformer paper, or circuit board paper, or in graphic arts .
- Another object of the present invention is to provide a process for preparing such paper products.
- a low water paper product comprised of cellulosic pulp, with the cellulosic (wood) pulp having at least some of the water present in the amorphous regions of the fiber structure replaced with a polyhydroxy polymer, preferably polyvinyl alcohol.
- a polyhydroxy polymer preferably polyvinyl alcohol.
- sufficient water in the structure is replaced with the polyvinyl alcohol such that the treated pulp contains at least 0.70 wt.%, and more preferably at least 1.0 wt.% of the polyvinyl alcohol.
- the resulting paper product made from the pulp is more rigid and dimensionally stable. When dried it reaches a lower water content. This is particularly useful for paper used in the manufacture of transformers. In use, transformers generate heat.
- the present invention provides a process for preparing such a low water paper product . Wood pulp is exposed to a solution of polyhydroxy polymer until at least some of the water present in the amorphous regions of the wood pulp fiber structure are replaced with the polyhydroxy polymer.
- the exposure generally employs soaking the wood pulp in a solution of the polyhydroxy polymer, preferably polyvinyl alcohol .
- the soaking of the wood pulp generally occurs such that the treated wood pulp, and hence the final paper product made therefrom, will contain from 0.5 wt % to 3.0 wt % of the polyvinyl alcohol, and preferably at least 1.0 wt.%.
- the present invention is based upon the discovery that the water contained in the non- crystalline regions of a cellulose fiber structure can in fact be replaced with a polyhydroxy polymer, such as polyvinyl alcohol, and provide a useful cellulosic product.
- the water is generally present to satisfy the need in the structure for hydrogen bonding, and it is believed that the polyhydroxy polymer somehow replaces the water, thereby removing the water from the structure and creating a low water paper product.
- a more dimensionally stable paper product is achieved, particularly when that paper product is exposed to water vapor or water.
- the paper product also has a lower equilibrium moisture content, reducing the chance of hydrolysis.
- the reduced water content paper would also exhibit excellent dielectric properties.
- paper with lower moisture content would pick up less water during an aqueous saturation since the fibers will swell less, which would be useful in many different types of paper products.
- Cellulose is a polymer made of beta linked glucose units.
- the polymer is linear and ordered. The degree of lateral order is commonly referred to as crystallinity.
- the wood fiber used in the paper made for transformer wire coil insulation is less crystalline than the fiber of cotton.
- the crystallinity of wood fiber is approximately 45-65% while the crystallinity of cotton fiber is up to 90%. (Wood Chemistry, Vol. 1, Louis E. Wise and Edwin C. Jahn, Reinhold Publishing, 1952, p. 157.) It is the amorphous portion of the cellulose that is penetrated by water.
- a lower water paper product is provided, as compared to one which has not been treated with a polyhydroxy polymer in accordance with the present invention.
- cellulose is composed of crystalline and amorphous areas, and liquid water exists in the amorphous areas, even in air dried pulp.
- a cellulose structure will contain at least 3 wt % by water. It has been found that by removing at least some of the water, or in effect replacing it in the cellulose structure, that an improved paper product with regard to rigidity and dimensional stability, particularly when exposed to water vapor or water in its final form, can be obtained.
- the type of pulp to which the present invention relates can be any wood pulp. Particularly good results have been achieved with northern pine Kraft pulp.
- the water in the structure of the wood pulp is replaced at least partially with a polyhydroxy polymer.
- the preferred polyhydroxy polymer is that of polyvinyl alcohol. Any commercially available polyvinyl alcohol can generally be used, and many appropriate polyvinyl alcohols are available from Celanese of New Jersey. For example, their Celvol 165, Celvol 203 and Celvol 205 SF polyvinyl alcohol has been found to be suitable in connection with the present invention.
- the polyvinyl alcohol be water soluble, which will enhance the amount of polymer that replaces water in the cellulosic structure.
- the polyvinyl alcohol can be hydrolyzed (e.g., about 89%), but is preferably not super-hydrolyzed (e.g., at least 98%) .
- Super-hydrolyzed polyvinyl alcohol can also be used, but due to its limited solubility in water, less polymer is available for replacing water in the cellulosic structure.
- replacement of water in the structure can amount to more than 0.70 wt.% of the treated pulp (when dried), and more preferably at least 1.0 wt.%. Replacement of greater than 1.5 or 2.0 wt.%, up to 3.0 wt.%, can therefore be achieved.
- the low water paper product of the present invention comprises a wood pulp having at least some of the water present in the amorphous regions of the wood pulp fiber structure replaced with a polyhydroxy polymer.
- the polyhydroxy polymer is preferably polyvinyl alcohol.
- the resulting paper product prepared from such wood pulp is more rigid and dimensionally stable when exposed to water.
- The- water in the structure is replaced by the polyhydroxy polymer upon exposing the wood pulp to a solution of the polyhydroxy polymer until at least some of the water present in the amorphous regions of the wood pulp fiber structure are replaced.
- the wood pulp is generally exposed to the solution of the polyhydroxy polymer for a period of time ranging from 1 to 120 minutes, more preferably from 5 to 60 minutes, and most preferably from about 10 to 30 minutes. It is preferred that the wood pulp is simply soaked in a solution, i.e., aqueous solution, of the polyhydroxy polymer, as this is the easiest and most efficient way in order to effect the replacement of the water with the polyvinyl alcohol .
- the treatment generally continues until the amount of polyvinyl alcohol contained in the cellulosic product ranges from 0.5 wt % to 3.0 wt %, more preferably from about 1.0 to 3.0 wt %, and most preferably from about 1.5 to 2.5 wt % .
- the exact amount of polyhydroxy polymer of course will depend on the amount of water in the wood pulp, e.g., how many amorphous sites and regions there are.
- the wood pulp used or treated can be dried or not dried. The process of the present invention works equally well with any pulp, in any state of refinement.
- the wood pulp itself is exposed to the polyhydroxy polymer solution.
- the wood chips used to make the pulp can also be treated to effect the polymer exchange in the cellulosic structure.
- the wood pulp can then subsequently be refined and formed into a paper product using conventional methods.
- the resulting paper product prepared from the treated wood pulp as discussed above exhibits improved rigidity and dimensional stability, particularly when exposed to water or water vapor, and a lower equilibrium moisture content.
- the paper of the present invention would suffer less hydrolytic degradation during heat aging (needed for heat resistant transformer paper) , would exhibit excellent dielectric properties (needed in circuit board ⁇ paper) , respond less to changes in humidity levels in air (improved dimensional stability for printed and graphic art papers), and exhibit superior stiffness.
- the paper product of the present invention finds great applicability as dried E-board in transformers since the lower equilibrium moisture content minimizes the water available for any hydrolysis in the heated environment of a transformer. This will extend the useful life of the paper insulation, and hence, the transformer itself.
- a transformer comprised of the paper product of the present invention is provided.
- a three ply paper structure employing a layer comprised of a wood pulp in accordance with the present invention was prepared.
- a cylinder machine was used where separate stock was employed for the outside layers and the inside layer.
- the outside layers were fed a furnish of cellulosic pulp.
- the furnish for the inside layer comprised 70% by weight of a cellulosic pulp, 20% by weight of a polymeric binder, i.e., polyvinyl alcohol, and 10% by weight of a polyaramide fiber.
- the polymeric binder was comprised of Celvol 165 SF polyvinyl alcohol, and the high temperature fiber was NOMEX ® fiber, one-quarter inch length and 2.0 denier.
- the polyvinyl alcohol, wood pulp and high temperature fiber were blended in a pulper for 15 minutes.
- the cellulosic pulp was exposed to the polyvinyl alcohol (polyhydroxy polymer) for a significant amount of time to have at least some of the water present in the amorphous regions of the cellulosic pulp fiber structure be replaced with the polyhydroxy polymer.
- a three ply paper structure was prepared.
- the outer layers were comprised of solely cellulosic pulp, and the inside layer was comprised of the cellulosic pulp in combination with the high temperature fiber and the polymeric binder.
- the resulting paper structure was then pressed, dried and calendared in conventional fashion. The drying was conducted at a temperature sufficient to activate the polyvinyl alcohol polymeric binder.
- the resulting paper structure exhibited good strength properties, and is believed useful as electrical insulation in transformer coils.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Insulating Materials (AREA)
- Paper (AREA)
Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003240573A AU2003240573A1 (en) | 2002-06-07 | 2003-06-06 | Low water paper |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US38641002P | 2002-06-07 | 2002-06-07 | |
US60/386,410 | 2002-06-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003104559A1 true WO2003104559A1 (fr) | 2003-12-18 |
Family
ID=29736160
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2003/017922 WO2003104559A1 (fr) | 2002-06-07 | 2003-06-06 | Papier a faible teneur en eau |
Country Status (3)
Country | Link |
---|---|
US (1) | US20030226649A1 (fr) |
AU (1) | AU2003240573A1 (fr) |
WO (1) | WO2003104559A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2617896A1 (fr) | 2012-01-20 | 2013-07-24 | ABB Technology Ltd | Matériau isolant électrique à base de cellulose |
WO2015113012A1 (fr) * | 2014-01-27 | 2015-07-30 | 3M Innovative Properties Company | Matériau isolant électrique et transformateur |
WO2015113013A1 (fr) * | 2014-01-27 | 2015-07-30 | 3M Innovative Properties Company | Matériau électriquement isolant et bande d'enveloppement de conducteurs pour équipements électriques tels que transformateurs |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2330314A (en) * | 1940-08-23 | 1943-09-28 | Du Pont | Manufacture of nonwoven fabrics |
US3674632A (en) * | 1968-09-10 | 1972-07-04 | Johan Jakob Wennergren | Process for moisture stabilizing cellulosic sheet material using a polyoxyalkylene glycol and a polyoxyethylene-oxypropylene glycol block polymer |
US3736178A (en) * | 1971-01-14 | 1973-05-29 | Mc Graw Edison Co | Cellulose material treated with a cellulose derivative,diglycolamine and an alkylketene dimer |
US5391473A (en) * | 1991-08-19 | 1995-02-21 | Eastman Kodak Company | Photographic paper with low oxygen permeability |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3903352A (en) * | 1971-04-05 | 1975-09-02 | Kimberly Clark Co | Coated electrical insulating paper and method of making it |
US5096539A (en) * | 1989-07-24 | 1992-03-17 | The Board Of Regents Of The University Of Washington | Cell wall loading of never-dried pulp fibers |
US5466336A (en) * | 1992-02-10 | 1995-11-14 | Cpg Holdings Inc. | Process for making a paper based product employing a polymeric latex binder |
US5498314A (en) * | 1992-02-10 | 1996-03-12 | Cpg Holdings Inc. | Process for making a paper based product containing a binder |
US5328567A (en) * | 1992-02-10 | 1994-07-12 | Custom Papers Group Inc. | Process for making a paper based product containing a binder |
US5275699A (en) * | 1992-10-07 | 1994-01-04 | University Of Washington | Compositions and methods for filling dried cellulosic fibers with an inorganic filler |
-
2003
- 2003-06-06 AU AU2003240573A patent/AU2003240573A1/en not_active Abandoned
- 2003-06-06 US US10/455,332 patent/US20030226649A1/en not_active Abandoned
- 2003-06-06 WO PCT/US2003/017922 patent/WO2003104559A1/fr not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2330314A (en) * | 1940-08-23 | 1943-09-28 | Du Pont | Manufacture of nonwoven fabrics |
US3674632A (en) * | 1968-09-10 | 1972-07-04 | Johan Jakob Wennergren | Process for moisture stabilizing cellulosic sheet material using a polyoxyalkylene glycol and a polyoxyethylene-oxypropylene glycol block polymer |
US3736178A (en) * | 1971-01-14 | 1973-05-29 | Mc Graw Edison Co | Cellulose material treated with a cellulose derivative,diglycolamine and an alkylketene dimer |
US5391473A (en) * | 1991-08-19 | 1995-02-21 | Eastman Kodak Company | Photographic paper with low oxygen permeability |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2617896A1 (fr) | 2012-01-20 | 2013-07-24 | ABB Technology Ltd | Matériau isolant électrique à base de cellulose |
WO2013107802A1 (fr) | 2012-01-20 | 2013-07-25 | Abb Technology Ltd | Matériau électro-isolant à base de cellulose |
WO2015113012A1 (fr) * | 2014-01-27 | 2015-07-30 | 3M Innovative Properties Company | Matériau isolant électrique et transformateur |
WO2015113013A1 (fr) * | 2014-01-27 | 2015-07-30 | 3M Innovative Properties Company | Matériau électriquement isolant et bande d'enveloppement de conducteurs pour équipements électriques tels que transformateurs |
CN105934801A (zh) * | 2014-01-27 | 2016-09-07 | 3M创新有限公司 | 电绝缘材料和变压器 |
Also Published As
Publication number | Publication date |
---|---|
AU2003240573A1 (en) | 2003-12-22 |
US20030226649A1 (en) | 2003-12-11 |
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