WO1999024660A1 - Method for filling and coating cellulose fibers - Google Patents
Method for filling and coating cellulose fibers Download PDFInfo
- Publication number
- WO1999024660A1 WO1999024660A1 PCT/US1998/023067 US9823067W WO9924660A1 WO 1999024660 A1 WO1999024660 A1 WO 1999024660A1 US 9823067 W US9823067 W US 9823067W WO 9924660 A1 WO9924660 A1 WO 9924660A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- titanium
- organometallic compound
- zirconium
- pulp
- fibers
- Prior art date
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
Definitions
- metal oxides and metal hydroxides can be incorporated within the cell walls of papermaking fibers to serve as fillers or opacifiers for making various forms of paper from such modified fibers.
- These fibers are generally characterized by having increased strength and retention relative to conventionally filled products, improved retention over lumen loaded pulp and by having greater opacifying power relative to fibers modified by other methods which incorporate insoluble salts within the ceil walls.
- the invention resides in a method of making metal oxide - or metal hydroxide-modified cellulosic pulp fibers, such as papermaking fibers, comprising: (a) forming a non-aqueous slurry of the pulp fibers and a non-aqueous solvent, said fiber slurry having a consistency of about 10 weight percent or greater; (b) adding to the slurry an amount of a hydrolyzable organometallic compound of the general formula I KOR ⁇ OR, ⁇ such that the organometallic compound is absorbed by the fiber walls; (c) optionally removing any organometallic compound not absorbed by the fiber walls by filtration or distillation; and (d) adding water to the fiber to precipitate within the fiber walls a water-insoluble metal oxide of the formula M a O b or a water-insoluble metal hydroxide of the formula M c (OH) d , wherein "M” can be any metal which forms a water-insoluble oxide or hydroxide, "R" and
- Iigand can also be any Iigand, hereby defined as any organic or inorganic molecule or ion that has at least one electron pair which can be shared with the coordinating metal atom. Included within this definition are classical simple donor ligands which act as electron pair donors to acceptor ions or molecules and the nonclassical or ⁇ -bonding ligands where the metal has d orbitals that can be utilized in bonding and the iigand not only has donor capacity but itself contains molecular orbitals capable of accepting electrons.
- the invention resides in modified pulp fibers comprising from about 0.5 to about 60 weight percent of a metal oxide of the formula M a O b or a metal hydroxide of the formula M c (OH) d , wherein "M”, “a”, “b”, “c” and “d” are as defined above.
- the invention resides in paper, particularly soft tissue, comprising modified papermaking fibers containing from about 0.5 to about 60 weight percent of a metal oxide of the formula M a O b or a metal hydroxide of the formula M c (OH) d , wherein "M", "a", "b”, “c” and “d” are as defined above.
- water-insoluble means having solubility in cold (4°C.) water of less than 0.2 grams per 100 cubic centimeters.
- Suitable non-aqueous solvents include but are not limited to isopropyl alcohol, 1-propanol, 1-butanol, acetone, 2-ethylhexanol, methanol and ethanol. Generally polar solvents will be preferred but this again is not a critical aspect of the present invention.
- the consistency (percent solids) of the non-aqueous slurry of papermaking fibers is not critical and can be from about 10 to 100 weight percent. Although the organometallic compound can be introduced to the dry papermaking fibers (100 percent consistency), a non-aqueous slurry having a consistency of from about 20 to about 95 weight percent is preferred for improved wetting.
- suitable organic groups include, but are not limited to, methyl, ethyl, propyl, butyl, 2-ethylhexyl, isobutyl, isopropyl, hexyl, octyl, octadecyl, dodecyl, pentanedionate and acetylacetonate.
- R is a Iigand
- suitable compounds include, without limitation: substituted carboxylic acids such as methyl salicylate, malic acid, and glycine or dibutyl tartrate as disclosed by U.S. Patent No. 4,452,969 to McCready herein incorporated by reference; ortho substituted hydroxyaromatic compounds as disclosed by U.S Patent No. 4,452,970 to Brunelle, herein incorporated by reference; and phosphorous compounds such as phosphorous acid, diphenylphosphite, dibutyl phosphite, diisopropyl phosphite and diphenyl decyl phosphite as disclosed by U.S. Patent No. 5,453,479 to Borman, also herein incorporated by reference.
- the preferred organometallic compounds are those formed from the metals of groups IIIA and IVA ,with titanium and zirconium being most preferred.
- Suitable organometallic compounds include, but are not limited to, titanium (IV) isopropoxide, titanium (IV) butoxide, titanium (IV) 2-ethylhexoxide, titanium (IV) ethoxide, titanium (IV) propoxide, titanium diisopropoxide bis(2,4-pentanedionate), zirconium (IV) propoxide, zirconium (IV) ethoxide, zirconium (IV) butoxide, zirconium (IV) isopropoxide (and complex with isopropanol), zirconium (IV) t-butoxide, zirconium (IV) acetylacetonate, yttrium (III) isopropoxide, yttrium (III) ethoxide, yttrium oxide isopropoxide, hafn
- organometallic compounds can be added to the papermaking fibers neat or as a solution in a suitable organic solvent.
- a particularly suitable means of adding the organometallic compounds to the fibers is in the form of a solution of the same non- aqueous solvent used to slurry the papermaking fibers.
- Such a solution can contain from about 1 to about 100 weight percent of the organometallic compound, more specifically from about 10 to about 100 weight percent, depending on the concentration desired in the final product. Examples Example 1.
- This example illustrates the method of this invention to form titanium dioxide filled pulp.
- 200 milliliters of titanium(IV) isopropoxide (Aldrich, 97%) was introduced into the flask and the slurry allowed to stand for 30 minutes at room temperature. The slurry was then filtered to remove excess titanium(IV) isopropoxide.
- the fiber was then returned to the flask and 500 milliliters of distilled water was introduced into the flask. A white precipitate of titanium dioxide formed immediately.
- the pulp was allowed to sit in the water for 10 minutes before being filtered and washed several times with water to remove excess titanium dioxide.
- the pulp was then fiberized by beating at high speed in a Waring blender for four minutes until all nits were removed. The pulp was then washed until a clear filtrate was obtained through a 200 mesh screen.
- the pulp was dried and determined to have a titanium dioxide content of 39.8% as determined by ashing.
- Example 2 This example demonstrates the use of non-water displaced pulp.
- a sample of never- dried eucalyptus pulp was dried at 125°C. for 4 hours to a consistency of 99.5%. 10 grams of the dried pulp was placed in a 250 milliliter flask equipped with a nitrogen purge. 100 milliliters of titanium(IV) isopropoxide was introduced into the flask. Good wetting was noted. The sample was allowed to stand under nitrogen for 60 minutes. The pulp was filtered to remove excess titanium(IV) isopropoxide and returned to the reaction vessel. 100 milliliters of water was then introduced into the flask, at which time the appearance of a white precipitate of titanium dioxide was noted on the fibers.
- the pulp was allowed to sit in the water for 30 minutes before being filtered and rinsed to remove excess titanium dioxide precipitated on the fibers.
- the pulp was fiberized in a Waring blender for 4 minutes at high speed until all nits disappeared.
- the pulp was washed until the filtrate coming through a 200 mesh screen was clear.
- the pulp was dried and determined to have a titanium dioxide content of 27.8% as determined by ashing.
- This example demonstrates the treatment of eucalyptus fibers with an organometallic compound of a metal besides titanium.
- the pulp was allowed to sit in the water for 30 minutes before being filtered and rinsed to remove excess zirconium dioxide precipitated on the outside of the fibers.
- the fibers were washed until the filtrate coming through a 200 mesh screen was clear.
- the pulp was fiberized in a Waring blender for 4 minutes at high speed until all nits disappeared.
- the pulp was dried and determined to have a zirconium dioxide content of 44.5% as determined by ashing.
- Example 4 2.0 grams of the treated, washed pulp was taken and placed in a kitchen blender with 500cc of water. The sample was then blended on high speed for two minutes. The sample was filtered (a clear filtrate was obtained) and determined to have a zirconium dioxide content of 43.0% as determined by ashing. The 97% ash retention is indicative of filler being firmly embedded in the cell walls.
- Example 4
- Example 5 provides, for purposes of comparison in Example 5, a calcium carbonate fiber wall filled pulp as described by U.S. Patent No. 5,069,539 to Allan et. al.
- the pulp slurry was vacuum filtered to remove excess sodium bicarbonate and the resulting fiber mat was then broken up by hand and placed in a large beaker.
- 1766 grams of a 50 weight percent calcium chloride solution was prepared by slowly adding 1169 grams of reagent grade CaCI 2 2H 2 0 to 597 milliliters of water and raising the temperature to 90°C.
- the hot calcium chloride solution was added all at once to the dewatered fibers and mixed with a spatula. The mixture was then allowed to sit for 45 minutes. The fibers were then rinsed with water until the effluent passing through a 150 mesh screen was clear.
- the product of the precipitation step was divided into 3 equal parts.
- Each part was suspended in 3300 milliliters of water so as to obtain an approximately 2% consistency mixture and subjected to high shear mixing at high speed for 4 minutes in a 4L Waring blender. A small aliquot was removed and suspended in 500 milliliters of water in a glass beaker to check for fiber entanglements. After fiberization the material was washed on a 150 mesh screen with a stream of tap water until a clear effluent was obtained. The pulp was dried and determined to have a calcium carbonate content of 35.4% as determined by ashing.
- Example 5 This example describes the preparation of handsheets from the titanium dioxide fiber wall filled pulp.
- Ash content of the handsheets was 15.84%, indicating 100% retention of filler.
- control handsheets made with never-dried northern softwood kraft pulp and never-dried northern softwood kraft pulp filled with calcium carbonate and lumen loaded northern softwood kraft are also given in the table.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU12909/99A AU734350B2 (en) | 1997-11-07 | 1998-10-30 | Method for filling and coating cellulose fibers |
EP98956371A EP1029123A1 (en) | 1997-11-07 | 1998-10-30 | Method for filling and coating cellulose fibers |
JP2000519645A JP2001522951A (en) | 1997-11-07 | 1998-10-30 | Filling and coating method for cellulose fiber |
BR9813951-7A BR9813951A (en) | 1997-11-07 | 1998-10-30 | Method for filling and coating cellulose fibers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/966,090 | 1997-11-07 | ||
US08/966,090 US5928470A (en) | 1997-11-07 | 1997-11-07 | Method for filling and coating cellulose fibers |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999024660A1 true WO1999024660A1 (en) | 1999-05-20 |
Family
ID=25510900
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/023067 WO1999024660A1 (en) | 1997-11-07 | 1998-10-30 | Method for filling and coating cellulose fibers |
Country Status (14)
Country | Link |
---|---|
US (1) | US5928470A (en) |
EP (1) | EP1029123A1 (en) |
JP (1) | JP2001522951A (en) |
KR (1) | KR100530291B1 (en) |
CN (1) | CN1121533C (en) |
AR (1) | AR014007A1 (en) |
AU (1) | AU734350B2 (en) |
BR (1) | BR9813951A (en) |
CO (1) | CO5060554A1 (en) |
CR (1) | CR5901A (en) |
SV (1) | SV1998000132A (en) |
TW (1) | TWI224639B (en) |
WO (1) | WO1999024660A1 (en) |
ZA (1) | ZA989988B (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999064673A1 (en) * | 1998-06-12 | 1999-12-16 | Fort James Corporation | Method of making a paper web having a high internal void volume of secondary fibers and a product made by the process |
US6379498B1 (en) * | 2000-02-28 | 2002-04-30 | Kimberly-Clark Worldwide, Inc. | Method for adding an adsorbable chemical additive to pulp during the pulp processing and products made by said method |
US6458241B1 (en) * | 2001-01-08 | 2002-10-01 | Voith Paper, Inc. | Apparatus for chemically loading fibers in a fiber suspension |
US7749356B2 (en) | 2001-03-07 | 2010-07-06 | Kimberly-Clark Worldwide, Inc. | Method for using water insoluble chemical additives with pulp and products made by said method |
US6582560B2 (en) | 2001-03-07 | 2003-06-24 | Kimberly-Clark Worldwide, Inc. | Method for using water insoluble chemical additives with pulp and products made by said method |
US20040108083A1 (en) * | 2002-12-09 | 2004-06-10 | Specialty Minerals (Michigan) Inc. | Filler-fiber composite |
US20040108082A1 (en) * | 2002-12-09 | 2004-06-10 | Specialty Minerals (Michigan) Inc. | Filler-fiber composite |
US7186318B2 (en) * | 2003-12-19 | 2007-03-06 | Kimberly-Clark Worldwide, Inc. | Soft tissue hydrophilic tissue products containing polysiloxane and having unique absorbent properties |
US7811948B2 (en) * | 2003-12-19 | 2010-10-12 | Kimberly-Clark Worldwide, Inc. | Tissue sheets containing multiple polysiloxanes and having regions of varying hydrophobicity |
US7479578B2 (en) * | 2003-12-19 | 2009-01-20 | Kimberly-Clark Worldwide, Inc. | Highly wettable—highly flexible fluff fibers and disposable absorbent products made of those |
US7147752B2 (en) | 2003-12-19 | 2006-12-12 | Kimberly-Clark Worldwide, Inc. | Hydrophilic fibers containing substantive polysiloxanes and tissue products made therefrom |
US20050145354A1 (en) * | 2003-12-30 | 2005-07-07 | Swanson Stephen J. | Glitter paper product |
JP6520619B2 (en) * | 2015-09-30 | 2019-05-29 | 王子ホールディングス株式会社 | Fine fibrous cellulose content |
WO2018140252A1 (en) * | 2017-01-26 | 2018-08-02 | Kimberly-Clark Worldwide, Inc. | Treated fibers and fibrous structures comprising the same |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3969549A (en) * | 1974-12-24 | 1976-07-13 | The United States Of America As Represented By The Librarian Of Congress | Method of deacidifying paper |
WO1991001409A1 (en) * | 1989-07-24 | 1991-02-07 | The Board Of Regents Of The University Of Washington | Cell wall loading of never-dried pulp fibers |
EP0559300A2 (en) * | 1989-02-23 | 1993-09-08 | Philip Morris Products Inc. | Wrapper for smoking articles and method for preparing same |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2583548A (en) * | 1948-03-17 | 1952-01-29 | Vanderbilt Co R T | Production of pigmented cellulosic pulp |
US3029181A (en) * | 1959-05-18 | 1962-04-10 | Alfred M Thomsen | Method of increasing the opacity of cellulose fibers |
US4452970A (en) * | 1983-06-09 | 1984-06-05 | General Electric Company | Catalytic process for preparing poly(alkylene dicarboxylates) and catalysts for use therein |
US4452969A (en) * | 1983-06-09 | 1984-06-05 | General Electric Company | Poly(alkylene dicarboxylate) process and catalysts for use therein |
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 |
DE69125050T2 (en) * | 1990-05-14 | 1997-10-16 | New Oji Paper Co | Process for modifying cellulosic fibers with a practically water-insoluble inorganic compound |
US5223090A (en) * | 1991-03-06 | 1993-06-29 | The United States Of America As Represented By The Secretary Of Agriculture | Method for fiber loading a chemical compound |
US5275699A (en) * | 1992-10-07 | 1994-01-04 | University Of Washington | Compositions and methods for filling dried cellulosic fibers with an inorganic filler |
US5453479A (en) * | 1993-07-12 | 1995-09-26 | General Electric Company | Polyesterification catalyst |
-
1997
- 1997-11-07 US US08/966,090 patent/US5928470A/en not_active Expired - Fee Related
-
1998
- 1998-10-29 CO CO98063697A patent/CO5060554A1/en unknown
- 1998-10-30 EP EP98956371A patent/EP1029123A1/en not_active Withdrawn
- 1998-10-30 KR KR10-2000-7004927A patent/KR100530291B1/en not_active IP Right Cessation
- 1998-10-30 CN CN98810931A patent/CN1121533C/en not_active Expired - Fee Related
- 1998-10-30 JP JP2000519645A patent/JP2001522951A/en not_active Abandoned
- 1998-10-30 BR BR9813951-7A patent/BR9813951A/en not_active Application Discontinuation
- 1998-10-30 WO PCT/US1998/023067 patent/WO1999024660A1/en not_active Application Discontinuation
- 1998-10-30 AU AU12909/99A patent/AU734350B2/en not_active Ceased
- 1998-11-02 TW TW087118153A patent/TWI224639B/en active
- 1998-11-02 ZA ZA989988A patent/ZA989988B/en unknown
- 1998-11-03 AR ARP980105541A patent/AR014007A1/en unknown
- 1998-11-06 SV SV1998000132A patent/SV1998000132A/en not_active Application Discontinuation
- 1998-11-09 CR CR5901A patent/CR5901A/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3969549A (en) * | 1974-12-24 | 1976-07-13 | The United States Of America As Represented By The Librarian Of Congress | Method of deacidifying paper |
EP0559300A2 (en) * | 1989-02-23 | 1993-09-08 | Philip Morris Products Inc. | Wrapper for smoking articles and method for preparing same |
WO1991001409A1 (en) * | 1989-07-24 | 1991-02-07 | The Board Of Regents Of The University Of Washington | Cell wall loading of never-dried pulp fibers |
Also Published As
Publication number | Publication date |
---|---|
EP1029123A1 (en) | 2000-08-23 |
ZA989988B (en) | 1999-05-05 |
KR20010031854A (en) | 2001-04-16 |
CN1121533C (en) | 2003-09-17 |
AR014007A1 (en) | 2001-01-31 |
BR9813951A (en) | 2000-09-26 |
KR100530291B1 (en) | 2005-11-22 |
CR5901A (en) | 2000-06-16 |
TWI224639B (en) | 2004-12-01 |
CO5060554A1 (en) | 2001-07-30 |
US5928470A (en) | 1999-07-27 |
AU734350B2 (en) | 2001-06-14 |
SV1998000132A (en) | 1999-08-18 |
CN1278878A (en) | 2001-01-03 |
JP2001522951A (en) | 2001-11-20 |
AU1290999A (en) | 1999-05-31 |
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