EP1540081B1 - Papers comprising a boron-containing compound and a method of making same - Google Patents
Papers comprising a boron-containing compound and a method of making same Download PDFInfo
- Publication number
- EP1540081B1 EP1540081B1 EP03797461A EP03797461A EP1540081B1 EP 1540081 B1 EP1540081 B1 EP 1540081B1 EP 03797461 A EP03797461 A EP 03797461A EP 03797461 A EP03797461 A EP 03797461A EP 1540081 B1 EP1540081 B1 EP 1540081B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- starch
- boron
- containing compound
- paper
- web
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 67
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title 1
- 229920002472 Starch Polymers 0.000 claims abstract description 149
- 235000019698 starch Nutrition 0.000 claims abstract description 146
- 239000008107 starch Substances 0.000 claims abstract description 145
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000123 paper Substances 0.000 claims description 72
- 239000000835 fiber Substances 0.000 claims description 46
- 239000011087 paperboard Substances 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 14
- 229910021538 borax Inorganic materials 0.000 claims description 12
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- 238000003490 calendering Methods 0.000 claims description 10
- 238000004513 sizing Methods 0.000 claims description 10
- 239000004328 sodium tetraborate Substances 0.000 claims description 10
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 229920002261 Corn starch Polymers 0.000 claims description 3
- 240000003183 Manihot esculenta Species 0.000 claims description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 3
- 229920006320 anionic starch Polymers 0.000 claims description 3
- 239000008120 corn starch Substances 0.000 claims description 3
- 229940099112 cornstarch Drugs 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229920001592 potato starch Polymers 0.000 claims description 3
- 229940116317 potato starch Drugs 0.000 claims description 3
- 229940100486 rice starch Drugs 0.000 claims description 3
- 229940100445 wheat starch Drugs 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- 238000010411 cooking Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 16
- 239000000654 additive Substances 0.000 description 8
- 238000004061 bleaching Methods 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 7
- 229920001131 Pulp (paper) Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011121 hardwood Substances 0.000 description 5
- 239000011122 softwood Substances 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- -1 for example Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 235000009120 camo Nutrition 0.000 description 2
- 235000005607 chanvre indien Nutrition 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000011487 hemp Substances 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- ZCXUWYGUGJQPPR-UHFFFAOYSA-N trisodium;borate;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[Na+].[O-]B([O-])[O-] ZCXUWYGUGJQPPR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/12—Organo-metallic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
-
- 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
- D21H21/16—Sizing or water-repelling 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
- 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
Definitions
- the invention relates to the field of paper and paperboard products and, in particular, to paper and paperboard products having improved dimensional stability properties. Another aspect of this invention relates a process of making the paper and paperboard products of this invention.
- a continuing problem in the papermaking arts is the tendency of papers to expand or contract in size based on ambient moisture conditions.
- paper fibers will generally absorb moisture and expand.
- the dimensions of the overall paper also expand, a phenomena referred to as hygroexpansion.
- the paper fibers may give off previously retained moisture leading to fiber and paper shrinkage.
- variations in humidity conditions may lead to other variations and instabilities in the dimensions of the paper including curling and cockling.
- Paper and paperboard products sized with starch and boron-containing compounds with improved properties are known from JP 2002 266285 , TW 286 970 , JP 06 047826 , GB-A-2 137 613 , EP-A-0 148 647 and KR 2001 056 213 .
- the present invention provides a method for forming a paper or paperboard as defined in the present claims.
- the method includes providing a papermaking furnish comprising cellulosic fibers, starch and a boron-contaming compound.
- the amount of starch compound may vary widely as for example equal to or less than about 90.72kg (200 lbs) per ton of fiber and is preferably equal to or less than about 77,11kg (170 lbs) per ton of fiber, more preferably from about 0.91kg (2 lbs) to about 68,04kg (150 lbs) per ton of fiber and most preferably from about 0.91 kg (2 lbs) to about 45,36kg (100 lbs) per ton of fiber with amount of more preferably from about 1.36 kg (3 lbs) to about 22,68 kg (50 lbs) of starch per ton of fiber in the embodiments of choice,
- the amount of boron containing compound may also vary widely.
- the amount of boron containing compound will depend on the amount of starch.
- the compound is present in an amount equal to or less than about 7 % of the weight of starch added to the furnish, preferably equal to or less than about 5 % of the weight of starch added to the furnish, more preferably equal to or less than about 3 % of the weight of starch added to the furnish and most, preferably from about 0.2 % to about 2% of the weight of starch added to the furnish.
- the amount of starch is from about 0.7 % to about 0.8 % of the weight of starch added to the furnish.
- the method further includes forming a fibrous web from the papermaking furnish and drying the web. In the preferred embodiments of the invention, the dried web is calendered to provide a finished paper or paperboard.
- the invention relates to a paper or paperboard formed by the method of this invention.
- the paper or paperboard comprises a paper web formed from a pulp furnish comprising cellulosic fibers, starch and a boron-containing compound.
- the major portion e.g. greater than 50%, preferably greater than 75% and more preferably greater than about 80% to about 90%
- the major portion is at or about the surfaces of the web.
- the major portion e.g. greater then 50%, preferably greater than 75% and more preferably greater than about 80% to about 90%
- the starch and a boron-containing compound is dispersed through out the web the web.
- cooked starch and at least a portion of the boron-containing compound are premixed with one another to provide a slurry and the resultant slurry is then added to the pulp furnish.
- the boron-containing compound is added directly to the pulp furnish.
- the invention provides a method for forming a paper or paperboard as defined in present claim 2 including the steps of providing a papermaking furnish comprising cellulosic fibers, forming a fibrous web from the papermaking furnish, drying the web and sizing the web by applying a slurry to the web, the slurry comprises starch solids and a boron-containing compound.
- the amount of boron containing compound may also vary widely. In the preferred embodiments, the amount of boron containing compound will depend on the amount of starch.
- the compound is present in an amount equal to or less than about 7 % of the weight of starch added to the furnish, preferably equal to or less than about 5 % of the weight of starch added to the furnish, more preferably equal to or less than about 3 % of the weight of starch added to the furnish and most, preferably from about 0.2 % to about 2% of the weight of starch added to the furnish.
- the amount of starch is from about 0.7 % to about 0.8 % of the weight of starch added to the furnish.
- the dried web is calendered to provide a finished paper of paperboard.
- the invention relates to a paper or paperboard formed by the method of this invention
- the paper or paperboard comprises comprising a paper web formed from a pulp furnish including cellulosic fibers and having a sizing applied to the paper web, the sizing including starch solids and a boron-containing compound present in the amounts described above.
- boron containing compounds are boric acid and metal borate salts.
- Preferred boron-containing compounds for the practice of the invention may be selected from the group consisting of boric acid, borax, and zinc borate.
- the starch employed in the invention may be either an anionic starch, a cationic starch, or an amphipathic depending on the particular embodiment being practiced.
- Preferred starch sources may be selected from the group consisting of cornstarch, wheat starch, potato starch, rice starch, tapioca starch, and sago starch.
- the invention involves papers having either an internal starch or a size press applied starch and a boron-containing compound which is added in proportion to the starch and which is believed to interact with the starch to provide improved physical and mechanical properties in the paper.
- Apaper@ refers to and includes both paper and paperboard unless otherwise noted.
- the paper is provided as a web containing cellulosic pulp fibers such as fiber derived from hardwood trees, softwood trees, or a combination ef hardwood and softwood trees prepared for use in a papermaking furnish by any known suitable digestion, refining, and bleaching operations.
- the cellulosic fibers in the paper include from about 0 % to about 40 % by weight dry basis softwood fibers and from about 100 % to about 60 % by weight dry basis hardwood fibers.
- the fibers may be provided from non-woody herbaceous plants including, but not limited to, kenaf, hemp, jute, flax, sisal, or abaca although legal restrictions and other considerations may make the utilization of hemp and other fiber sources impractical or impossible.
- the paper may also include other conventional additives such as, for example, starch, mineral fillers, sizing agents, retention aids, and strengthening polymers.
- the fillers that may be used are organic and inorganic pigments such as, by way of example, polymeric particles such as polystyrene latexes and polymethylmethacrylate, and minerals such as calcium carbonate, kaolin, and talc.
- the papers may also include hollow microspheres.
- a variety of papers and paperboards may be provided by the invention having a wide variety of basis weights and formed from a wide variety of cellulosic fibers. These include but are not limited to, including office papers, forms papers, envelope papers, label stock, bristols, and printing and publication papers as well as bleached boards and linerboards.
- Office papers formed according to the present invention preferably have a final caliper, after calendering of the paper, and any nipping or pressing such as may be associated with subsequent coating of from about 0.089 mm (3.5) to about 0.254 mm (10 mils).
- Office papers of the invention also preferably exhibit basis weights of from about 0.066 kg/m 2 (18 lb/1300ft 2 ) to about 0.11 kg/m 2 (32 lb/1300ft 2 )
- Bleached boards formed according to the present invention preferably have a final caliper, after calendering of the board, and any nipping or pressing such as may be associated with subsequent coating o f up to about 1,14mm (45 mils).
- Bleached boards of the invention also typically exhibit basis weights of from about 0.19kg/m 2 (40 lb/1000 ft 2 ) to about 0.43kg/m 2 (90 lb/1000 ft 2 ).
- Linerboards formed according to the present invention preferably have a final caliper, after calendering of the board, and any nipping or pressing such as may be associated with subsequent coating of up to about 1.14mm (45 mils). Linerboards of the invention also preferably exhibit basis weights of from about 0.12 kg/m 2 (25lb/1000 ft 2 ) to about 0.48 kg/m 2 (100lb/1000 ft 2 ).
- the papers of the present invention include a boron-containing compound in combination with starch.
- the boron-containing compound is preferably selected from the group consisting of boric acid and anhydrous and hydrated metal borate salts.
- Particularly preferred boron-containing compounds include anhydrous and hydrated sodium borate (Borax), potassium borate, boric oxide, boric acid, and zinc borate.
- the boron-containing compound is added in proportion to the amount of starch being added and the amount may also vary widely. In the preferred embodiments the amount of boron containing compound will depend on the amount of starch.
- the compound is present in an amount equal to or less than about 7 % of the weight of starch added to the furnish, preferably equal to or less than about 5 % of the weight of starch added to the furnish, more preferably equal to or less than about 3 % of the weight of starch added to the furnish and most, preferably from about 0.2 % to about 2% of the weight of starch added to the furnish.
- the amount of starch is from about 0.7 % to about 0.8 % of the weight of starch added to the furnish.
- a starch solution is added to the paper in combination with the boron-containing compound.
- the starch solution may include a cationic starch, an anionic starch, an amphipathic starch, or a combination of more of more of these starches.
- Suitable starch sources include cornstarch, wheat starch, potato starch, rice starch, tapioca starch, and sago starch.
- the type and amount of starch added to the paper may vary depending on the particular embodiment of the invention as described in more detail herein below.
- starch and boron-containing compound added to the paper may vary depending on the particular embodiment of the invention.
- the starch and boron-containing compound are added to the furnish prior to the forming of the web on the papermaking machine.
- the combination of starch and boron-containing compound are added at the size press after the web has been formed and at least partially dried. Papers according to the invention have been observed to have improved resistance to moisture expansion and shrinkage.
- the papers exhibit less fiber expansion when in a moist or humid environment than conventional papers and also exhibit less fiber shrinkage when in a particularly arid environment
- the papers exhibit improvements in strength and stiffness properties including Gurley stiffness, modulus of elasticity, tensile energy absorption, and/or tensile strength.
- the method of forming the paper materials of the present invention includes providing an initial paper furnish.
- the cellulosic fibrous component of the furnish is suitably of the chemically pulped variety, such as a bleached kraft pulp, although the invention is not believed to be limited to kraft pulps, and may also be used with good effect with other chemical pulps such as sulfite pulps, mechanical pulps such as ground wood pulps, and other pulp varieties and mixtures thereof such as chemical-mechanical and thermo-mechanical pulps.
- the pulp is preferably bleached to remove lignins and to achieve a desired pulp brightness according to one or more bleaching treatments known in the art including, for example, elemental chlorine-based bleaching sequences, chlorine dioxide-based bleaching sequences, chlorine-free bleaching sequences, elemental chlorine-free bleaching sequences, and combinations or variations of stages of any of the foregoing and other bleaching related sequences and stages.
- bleaching treatments known in the art including, for example, elemental chlorine-based bleaching sequences, chlorine dioxide-based bleaching sequences, chlorine-free bleaching sequences, elemental chlorine-free bleaching sequences, and combinations or variations of stages of any of the foregoing and other bleaching related sequences and stages.
- the pulp After bleaching is completed and the pulp is washed and screened, it is generally subjected to one or more refining steps. Thereafter, the refined pulp is passed to a blend chest where it is mixed with various additives and fillers typically incorporated into a papermaking furnish as well as other pulps such as unbleached pulps and/or recycled or post-consumer pulps.
- the additives may include so-called Aintemal sizing@ agents used primarily to increase the contact angle of polar liquids contacting the surface of the paper such as alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD), and rosin sizes.
- Retention aids may also be added at this stage, including both cationic and anionic retention aids.
- an amount of internal starch is typically added to the paper furnish at this point as well.
- the boron-containing compound is added in to the furnish in combination with this starch.
- starch is typically added to the furnish in an amount as described above as for example an amount of about 1.36 kg (3 lb) of starch / ton of paper to about 13,61 kg (30 lbs) of starch / ton of paper.
- boron-containing compound is typically added to the furnish in an amount based on the weight of the starch added to the furnish in an amount as described above.
- the boron-containing compound has a relatively high water solubility. It is preferred to pre-mix the converted (cooked) starch solution and the boron-containing compound with one another, thereby providing a slurry of starch and boron-containing compound and then add this slurry mixture to the furnish as a later step.
- the preferred boron-containing compound is boric acid.
- the starch being added to the furnish is a cationic starch.
- the invention may employ a preconverted starch, that is, a starch which has been previously reacted with additives such as ammonium persulfate and / or conversion enzymes in order to partially convert the high ly branched molecular structure of the raw starch into a structure which is somewhat more linear and less branched.
- the starch may be cooked and converted in the slurry with the boron-containing compound at a temperature of about 95-100°C and then cooled to about 40-60°C prior to addition to the furnish.
- the boron-containing compound may be directly added to the furnish mixture, and separately, the starch solution may be directly added to the furnish. This is typically preferred if the boron-containing compound is one of relatively low aqueous solubility such as zinc borate for example.
- the furnish is formed into a single or multi-ply web on a papermaking machine such as a Fourdrinier machine or any other suitable papermaking machine known in the art, as well as those which may become known in the future.
- a papermaking machine such as a Fourdrinier machine or any other suitable papermaking machine known in the art, as well as those which may become known in the future.
- the basic methodologies involved in making paper on various papermaking machine configurations are well known to those of ordinary skill in the art and accordingly will not be described in detail herein.
- a furnish consisting of a relatively low consistency aqueous slurry of the pulp fibers (typically about 0.1 to about 1.0%) along with the microspheres and various additives and fillers dispersed therein is ejected from a headbox onto a porous endless moving forming sheet or wire where the liquid is gradually drained through shall openings in the wire until a mat of pulp fibers and the other materials is formed on the wire.
- the still-wet mat or web is transferred from the wire to a wet press where more fiber-to-fiber consolidation occurs and the moisture is further decreased.
- the web is then passed to an initial dryer section to remove most of the retained moisture and further consolidate the fibers in the web.
- the web may be further treated using a size press wherein additional starch, pigments, and other additives may be applied to the web and incorporated therein by the action of the press.
- the boron-containing compound may also be added to the paper along with this starch addition in addition to, or in place of, addition of the boron-containing compound with the wet end internal starch.
- starch is typically added at the size press in the desired amount as for example at a starch pickup rate of from about 18.14 (40) to about 68.04 kg (150 lbs) starch / ton of paper and the boron-con compound is typically added with the starch at the size press, in the desired amount and based on the weight of starch solids added as for example from about 0.2% to about 1.0% (preferably 0.7% to about 0.8%) by weight of the starch.
- the starch and the boron-containing compound be pre-mixed into a slurry.
- the starch is a raw, unconverted starch, such as a pearl starch
- the conversion may be aided by the use of additives such as ammonium persulfate and conversion enzymes.
- the conversion may be carried at a temperature of from about 100-105°C.
- the starch is then maintained at about 60-70°C until it is applied at the size press.
- a preferred boron-containing compound is borax (sodium borate).
- the paper is preferably calendered to achieve the desired final caliper as discussed above to improve the smoothness and other properties of the web.
- the calendering may be accomplished by steel-steel calendaring at nip pressures sufficient to provide a desired caliper. It will be appreciated that the ultimate caliper of the paper will be largely determined by the selection of the nip pressure.
- starch addition typically makes the paper more susceptible to hygroexpansion and other dimensional instability when in a high humidity environment.
- starch molecules by promoting complexing of starch molecules one with another, the amount of starch available to penetrate the cellulosic fibers, is reduced. Accordingly the fibers are less susceptible to moisture penetration and exhibit less dimensional variation with changing environmental conditions.
- the use of the boron-containing compounds leads to improvements in the end stiffness properties of the paper formed according to the invention.
- the papers may also exhibit improvements in Gurley stiffness, modulus of elasticity, tensile energy absorption, and/or tensile strength.
- a series of hand sheet samples of a linerboard were produced to determine the effect of addition of a boron-containing compound, together with starch, in a pulp furnish.
- the board was formed from a pulp mixture of about 80% hardwoods and about 20% softwoods.
- the first (control) sample was formed without any internal starch or boron-containing compound.
- Sample 2 was formed from the same furnish, except that starch was added to the furnish mixture at a ratio of about 9kg (20 lb) starch / ton of pulp fibers prior to the furnish being formed into the hand sheets. Again, no boron-containing, compound was included in the furnish.
- a series of hand sheet samples of an offset printing paper were produced to determine the effect of addition of a boron-containing compound, together with starch, in the sizing of a paper at the size press.
- the board was formed from a pulp mixture of about 80% hardwoods and about 20% softwoods.
- the first (control) sample was formed as a control. This sheet was not treated with either starch or boron-containing compound at the size press.
- Sample 2 a base sheet formed in accordance with Sample 1 was sized by applying a 16% starch solids mixture with a rod-metering device and sizing the sheet using a Beloit size press. No boron-containing compound was included with the sizing starch.
- the starch was a Staley Pearl AP starch that was converted using ammonium persulfate. The starch was applied at a pickup rate of about 45kg (100 lb) ton of base sheet.
- Sample 3 the sheet was formed and sized as in Sample 2, except that the starch solids were applied at 10 % solids rather than 16% solids. Again, no boron-containing compound was included with the sizing starch.
- a base sheet formed in accordance with Sample 1 was sized by applying a mixture comprising 16% starch solids and borax (sodium borate pentahydrate). The ratio (by weight) of the borax in the mixture to the starch solids was about 0.25 %. Prior to being applied to the sheet, the mixture of starch and borax was cooked with of ammonium persulphate in order to convert the starch. The mixture was applied with a rod-metering device, and the sheet was sized using a Beloit size press.
- borax sodium borate pentahydrate
Abstract
Description
- The invention relates to the field of paper and paperboard products and, in particular, to paper and paperboard products having improved dimensional stability properties. Another aspect of this invention relates a process of making the paper and paperboard products of this invention.
- A continuing problem in the papermaking arts is the tendency of papers to expand or contract in size based on ambient moisture conditions. In a high moisture environment, paper fibers will generally absorb moisture and expand. As the fibers expand, the dimensions of the overall paper also expand, a phenomena referred to as hygroexpansion. On the other hand, when papers are exposed to particularly dry ambient conditions, the paper fibers may give off previously retained moisture leading to fiber and paper shrinkage. Additionally, variations in humidity conditions may lead to other variations and instabilities in the dimensions of the paper including curling and cockling.
- Moreover, exposure to high humidity levels may lead to reductions in the strength and stiffness properties of papers. This is particularly problematic in heavier paperboards that are used for packaging wherein maintenance of high strength and stiffness is essential.
- Paper and paperboard products sized with starch and boron-containing compounds with improved properties are known from
JP 2002 266285 TW 286 970 JP 06 047826 GB-A-2 137 613 EP-A-0 148 647 andKR 2001 056 213 - Accordingly, there is a need for papers which are less sensitive to ambient conditions and which do not tend to expand or shrink due to local moisture conditions.
- With regard to the foregoing and other objects and advantages, the present invention provides a method for forming a paper or paperboard as defined in the present claims. The method includes providing a papermaking furnish comprising cellulosic fibers, starch and a boron-contaming compound. The amount of starch compound may vary widely as for example equal to or less than about 90.72kg (200 lbs) per ton of fiber and is preferably equal to or less than about 77,11kg (170 lbs) per ton of fiber, more preferably from about 0.91kg (2 lbs) to about 68,04kg (150 lbs) per ton of fiber and most preferably from about 0.91 kg (2 lbs) to about 45,36kg (100 lbs) per ton of fiber with amount of more preferably from about 1.36 kg (3 lbs) to about 22,68 kg (50 lbs) of starch per ton of fiber in the embodiments of choice, The amount of boron containing compound may also vary widely. In the preferred embodiments the amount of boron containing compound will depend on the amount of starch. In these preferred embodiments, the compound is present in an amount equal to or less than about 7 % of the weight of starch added to the furnish, preferably equal to or less than about 5 % of the weight of starch added to the furnish, more preferably equal to or less than about 3 % of the weight of starch added to the furnish and most, preferably from about 0.2 % to about 2% of the weight of starch added to the furnish. In the embodiments of choice, the amount of starch is from about 0.7 % to about 0.8 % of the weight of starch added to the furnish. The method further includes forming a fibrous web from the papermaking furnish and drying the web. In the preferred embodiments of the invention, the dried web is calendered to provide a finished paper or paperboard.
- In another aspect, the invention relates to a paper or paperboard formed by the method of this invention. The paper or paperboard comprises a paper web formed from a pulp furnish comprising cellulosic fibers, starch and a boron-containing compound. In one embodiment, the major portion (e.g. greater than 50%, preferably greater than 75% and more preferably greater than about 80% to about 90%) of the starch and a boron-containing compound is at or about the surfaces of the web. In another embodiment, the major portion (e.g. greater then 50%, preferably greater than 75% and more preferably greater than about 80% to about 90%) of the starch and a boron-containing compound is dispersed through out the web the web.
- In forming the paper or paperboard, it is preferred that cooked starch and at least a portion of the boron-containing compound are premixed with one another to provide a slurry and the resultant slurry is then added to the pulp furnish. In certain embodiments, it is further preferred to mix the unconverted starch and at least a portion of the boron-containing compound are premixed with one another to provide a slurry and the resultant slurry is then cooked to convert the starch prior to adding the slurry to the pulp furnish. However, in certain other embodiments of the invention, it may be preferred that the boron-containing compound is added directly to the pulp furnish.
- In still another aspect, the invention provides a method for forming a paper or paperboard as defined in present claim 2 including the steps of providing a papermaking furnish comprising cellulosic fibers, forming a fibrous web from the papermaking furnish, drying the web and sizing the web by applying a slurry to the web, the slurry comprises starch solids and a boron-containing compound. The amount of boron containing compound may also vary widely. In the preferred embodiments, the amount of boron containing compound will depend on the amount of starch. In these preferred embodiments, the compound is present in an amount equal to or less than about 7 % of the weight of starch added to the furnish, preferably equal to or less than about 5 % of the weight of starch added to the furnish, more preferably equal to or less than about 3 % of the weight of starch added to the furnish and most, preferably from about 0.2 % to about 2% of the weight of starch added to the furnish. In the embodiments of choice, the amount of starch is from about 0.7 % to about 0.8 % of the weight of starch added to the furnish. In the preferred embodiments of the invention, the dried web is calendered to provide a finished paper of paperboard.
- In yet another aspect, the invention relates to a paper or paperboard formed by the method of this invention The paper or paperboard comprises comprising a paper web formed from a pulp furnish including cellulosic fibers and having a sizing applied to the paper web, the sizing including starch solids and a boron-containing compound present in the amounts described above.
- Illustrative of useful boron containing compounds are boric acid and metal borate salts. Preferred boron-containing compounds for the practice of the invention may be selected from the group consisting of boric acid, borax, and zinc borate.
- The starch employed in the invention may be either an anionic starch, a cationic starch, or an amphipathic depending on the particular embodiment being practiced. Preferred starch sources may be selected from the group consisting of cornstarch, wheat starch, potato starch, rice starch, tapioca starch, and sago starch.
- The invention involves papers having either an internal starch or a size press applied starch and a boron-containing compound which is added in proportion to the starch and which is believed to interact with the starch to provide improved physical and mechanical properties in the paper. (As used herein, Apaper@ refers to and includes both paper and paperboard unless otherwise noted.)
- The paper is provided as a web containing cellulosic pulp fibers such as fiber derived from hardwood trees, softwood trees, or a combination ef hardwood and softwood trees prepared for use in a papermaking furnish by any known suitable digestion, refining, and bleaching operations. In a preferred embodiment, the cellulosic fibers in the paper include from about 0 % to about 40 % by weight dry basis softwood fibers and from about 100 % to about 60 % by weight dry basis hardwood fibers. In certain embodiments, at least a portion of the fibers may be provided from non-woody herbaceous plants including, but not limited to, kenaf, hemp, jute, flax, sisal, or abaca although legal restrictions and other considerations may make the utilization of hemp and other fiber sources impractical or impossible. The paper may also include other conventional additives such as, for example, starch, mineral fillers, sizing agents, retention aids, and strengthening polymers. Among the fillers that may be used are organic and inorganic pigments such as, by way of example, polymeric particles such as polystyrene latexes and polymethylmethacrylate, and minerals such as calcium carbonate, kaolin, and talc. In some instance, the papers may also include hollow microspheres.
- A variety of papers and paperboards may be provided by the invention having a wide variety of basis weights and formed from a wide variety of cellulosic fibers. These include but are not limited to, including office papers, forms papers, envelope papers, label stock, bristols, and printing and publication papers as well as bleached boards and linerboards.
- Office papers formed according to the present invention preferably have a final caliper, after calendering of the paper, and any nipping or pressing such as may be associated with subsequent coating of from about 0.089 mm (3.5) to about 0.254 mm (10 mils). Office papers of the invention also preferably exhibit basis weights of from about 0.066 kg/m2 (18 lb/1300ft2) to about 0.11 kg/m2(32 lb/1300ft2) Bleached boards formed according to the present invention preferably have a final caliper, after calendering of the board, and any nipping or pressing such as may be associated with subsequent coating o f up to about 1,14mm (45 mils). Bleached boards of the invention also typically exhibit basis weights of from about 0.19kg/m2 (40 lb/1000 ft2) to about 0.43kg/m2 (90 lb/1000 ft2).
- Linerboards formed according to the present invention preferably have a final caliper, after calendering of the board, and any nipping or pressing such as may be associated with subsequent coating of up to about 1.14mm (45 mils). Linerboards of the invention also preferably exhibit basis weights of from about 0.12 kg/m2 (25lb/1000 ft2) to about 0.48 kg/m2 (100lb/1000 ft2).
- Importantly, the papers of the present invention include a boron-containing compound in combination with starch. The boron-containing compound is preferably selected from the group consisting of boric acid and anhydrous and hydrated metal borate salts. Particularly preferred boron-containing compounds include anhydrous and hydrated sodium borate (Borax), potassium borate, boric oxide, boric acid, and zinc borate. The boron-containing compound is added in proportion to the amount of starch being added and the amount may also vary widely. In the preferred embodiments the amount of boron containing compound will depend on the amount of starch. In these preferred embodiments, the compound is present in an amount equal to or less than about 7 % of the weight of starch added to the furnish, preferably equal to or less than about 5 % of the weight of starch added to the furnish, more preferably equal to or less than about 3 % of the weight of starch added to the furnish and most, preferably from about 0.2 % to about 2% of the weight of starch added to the furnish. In the embodiments of choice, the amount of starch is from about 0.7 % to about 0.8 % of the weight of starch added to the furnish..
- A starch solution is added to the paper in combination with the boron-containing compound. The starch solution may include a cationic starch, an anionic starch, an amphipathic starch, or a combination of more of more of these starches. Suitable starch sources include cornstarch, wheat starch, potato starch, rice starch, tapioca starch, and sago starch. The type and amount of starch added to the paper may vary depending on the particular embodiment of the invention as described in more detail herein below.
- The addition of the starch and boron-containing compound to the paper may vary depending on the particular embodiment of the invention. In one embodiment of the invention, the starch and boron-containing compound are added to the furnish prior to the forming of the web on the papermaking machine. In another embodiment, the combination of starch and boron-containing compound are added at the size press after the web has been formed and at least partially dried. Papers according to the invention have been observed to have improved resistance to moisture expansion and shrinkage. That is the papers exhibit less fiber expansion when in a moist or humid environment than conventional papers and also exhibit less fiber shrinkage when in a particularly arid environment In some embodiments of the invention, the papers exhibit improvements in strength and stiffness properties including Gurley stiffness, modulus of elasticity, tensile energy absorption, and/or tensile strength.
- The method of forming the paper materials of the present invention includes providing an initial paper furnish. The cellulosic fibrous component of the furnish is suitably of the chemically pulped variety, such as a bleached kraft pulp, although the invention is not believed to be limited to kraft pulps, and may also be used with good effect with other chemical pulps such as sulfite pulps, mechanical pulps such as ground wood pulps, and other pulp varieties and mixtures thereof such as chemical-mechanical and thermo-mechanical pulps.
- While not essential to the invention, the pulp is preferably bleached to remove lignins and to achieve a desired pulp brightness according to one or more bleaching treatments known in the art including, for example, elemental chlorine-based bleaching sequences, chlorine dioxide-based bleaching sequences, chlorine-free bleaching sequences, elemental chlorine-free bleaching sequences, and combinations or variations of stages of any of the foregoing and other bleaching related sequences and stages.
- After bleaching is completed and the pulp is washed and screened, it is generally subjected to one or more refining steps. Thereafter, the refined pulp is passed to a blend chest where it is mixed with various additives and fillers typically incorporated into a papermaking furnish as well as other pulps such as unbleached pulps and/or recycled or post-consumer pulps. The additives may include so-called Aintemal sizing@ agents used primarily to increase the contact angle of polar liquids contacting the surface of the paper such as alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD), and rosin sizes. Retention aids may also be added at this stage, including both cationic and anionic retention aids.
- An amount of internal starch is typically added to the paper furnish at this point as well. In one embodiment of the invention, the boron-containing compound is added in to the furnish in combination with this starch. In this embodiment, starch is typically added to the furnish in an amount as described above as for example an amount of about 1.36 kg (3 lb) of starch / ton of paper to about 13,61 kg (30 lbs) of starch / ton of paper. Also, boron-containing compound is typically added to the furnish in an amount based on the weight of the starch added to the furnish in an amount as described above.
- In this embodiment, it is preferred that the boron-containing compound has a relatively high water solubility. It is preferred to pre-mix the converted (cooked) starch solution and the boron-containing compound with one another, thereby providing a slurry of starch and boron-containing compound and then add this slurry mixture to the furnish as a later step.
- In this embodiment, the preferred boron-containing compound is boric acid. It is also preferred that the starch being added to the furnish is a cationic starch. The invention may employ a preconverted starch, that is, a starch which has been previously reacted with additives such as ammonium persulfate and / or conversion enzymes in order to partially convert the high ly branched molecular structure of the raw starch into a structure which is somewhat more linear and less branched. However, if the starch has not been preconverted, then it may be cooked and converted in the slurry with the boron-containing compound at a temperature of about 95-100°C and then cooled to about 40-60°C prior to addition to the furnish.
- In another embodiment of the invention, the boron-containing compound may be directly added to the furnish mixture, and separately, the starch solution may be directly added to the furnish. This is typically preferred if the boron-containing compound is one of relatively low aqueous solubility such as zinc borate for example.
- Once prepared, the furnish is formed into a single or multi-ply web on a papermaking machine such as a Fourdrinier machine or any other suitable papermaking machine known in the art, as well as those which may become known in the future. The basic methodologies involved in making paper on various papermaking machine configurations are well known to those of ordinary skill in the art and accordingly will not be described in detail herein. In general, a furnish consisting of a relatively low consistency aqueous slurry of the pulp fibers (typically about 0.1 to about 1.0%) along with the microspheres and various additives and fillers dispersed therein is ejected from a headbox onto a porous endless moving forming sheet or wire where the liquid is gradually drained through shall openings in the wire until a mat of pulp fibers and the other materials is formed on the wire. The still-wet mat or web is transferred from the wire to a wet press where more fiber-to-fiber consolidation occurs and the moisture is further decreased. The web is then passed to an initial dryer section to remove most of the retained moisture and further consolidate the fibers in the web. After initial drying, the web may be further treated using a size press wherein additional starch, pigments, and other additives may be applied to the web and incorporated therein by the action of the press.
- In another embodiments of the invention, the boron-containing compound may also be added to the paper along with this starch addition in addition to, or in place of, addition of the boron-containing compound with the wet end internal starch. In this embodiment, starch is typically added at the size press in the desired amount as for example at a starch pickup rate of from about 18.14 (40) to about 68.04 kg (150 lbs) starch / ton of paper and the boron-con compound is typically added with the starch at the size press, in the desired amount and based on the weight of starch solids added as for example from about 0.2% to about 1.0% (preferably 0.7% to about 0.8%) by weight of the starch.
- In this embodiment as well, it may be preferred that the starch and the boron-containing compound be pre-mixed into a slurry. In addition, if the starch is a raw, unconverted starch, such as a pearl starch, then it may be preferred to mix the raw starch and the boron-containing compound, and then cook the resultant slurry to convert the starch prior to application at the size press. The conversion may be aided by the use of additives such as ammonium persulfate and conversion enzymes. The conversion may be carried at a temperature of from about 100-105°C. After conversion, the starch is then maintained at about 60-70°C until it is applied at the size press. For application at the size press, a preferred boron-containing compound is borax (sodium borate).
- After treatment in the size press and subsequent drying, the paper is preferably calendered to achieve the desired final caliper as discussed above to improve the smoothness and other properties of the web. The calendering may be accomplished by steel-steel calendaring at nip pressures sufficient to provide a desired caliper. It will be appreciated that the ultimate caliper of the paper will be largely determined by the selection of the nip pressure.
- As noted the resultant papers are observed to have improved resistance to hygroexpansion and to other detrimental effects of high humidity environments such as curling and cockling. Without being bound by theory, it is believed that the inclusion of the boron-containing compound achieves this affect by promoting formation of a complex between the starch molecules and the boron-containing compound. The complexing is believed to limit the penetration of the starch into the cellulosic fibers.
- Penetration of the starch solids into the cellulosic fibers is believed to provide a route for moisture to penetrate into the fibers as well. Thus, starch addition typically makes the paper more susceptible to hygroexpansion and other dimensional instability when in a high humidity environment. However, by promoting complexing of starch molecules one with another, the amount of starch available to penetrate the cellulosic fibers, is reduced. Accordingly the fibers are less susceptible to moisture penetration and exhibit less dimensional variation with changing environmental conditions.
- Surprisingly, it has also been observed that in some embodiments the use of the boron-containing compounds leads to improvements in the end stiffness properties of the paper formed according to the invention. The papers may also exhibit improvements in Gurley stiffness, modulus of elasticity, tensile energy absorption, and/or tensile strength.
- The following no limiting examples illustrate various additional aspects of the invention. Unless otherwise indicated, temperatures are in degrees Celsius, percentages are by weight and the percent of any pulp additive or moisture is based on the oven-dry weight of the pulp.
- A series of hand sheet samples of a linerboard were produced to determine the effect of addition of a boron-containing compound, together with starch, in a pulp furnish. The board was formed from a pulp mixture of about 80% hardwoods and about 20% softwoods. The first (control) sample was formed without any internal starch or boron-containing compound.
- Sample 2 was formed from the same furnish, except that starch was added to the furnish mixture at a ratio of about 9kg (20 lb) starch / ton of pulp fibers prior to the furnish being formed into the hand sheets. Again, no boron-containing, compound was included in the furnish.
- In Sample 3, the pulp mixture was used and in this sample, the furnish was combined with about 9kg (20 lb) starch/ ton of pulp fibers and about 1% of boric acid, based on the weight of starch added. The starch and boric acid were initially combined with one another to form slurry. This slurry was cooked and then added to the furnish prior to hand sheet formation.
- In Sample 4, zinc borate was added to the pulp mixture at a ratio of about 9 kg (20 lb) zinc borate / ton of pulp fibers. No internal starch was added to the pulp mixture.
- In Sample 5, about 9kg (20 lb) of starch / ton of pulp fibers and about 9kg (20 lb) of zinc borate / ton of pulp fibers were added to the furnish. No boric acid was included with the starch. Finally, in Sample 6, about 9kg (20 lb) of starch / ton of pulp fibers (with about 1% boric acid based on the weight of starch added) and about 9kg (20 lb) of zinc borate / ton of pulp fibers were added to the furnish.
- The physical and mechanical properties of each hand sheet sample were then measured. The results are listed in Table I.
Table I Property and Units Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Air Resistance Gurley s/100 cc 3.1 2.8 3.8 4.5 3.1 3.5 Apparent Density g/cm3 0.468 0.492 0.526 0.492 0.506 0.527 Basis weight g/m2 307 328 326 326 346 325 Basis weight (lb/1000 ft2) kg/m2 0.31
(62.9)0.32
(67.1)0.32
(66.7)0.32
(66.7)0.34
(70.6)0.32
(66.5)Bulk cm3/g 2.14 2.03 1.90 2.03 1.99 1.90 Burst factor gf/cm2/g/m2 20.2 23.8 25.7 23.6 24.5 24.9 Burst (lbf/in) kg/cm2 6.15
(88.1)7.75
(111)8.3
(119)7.61
(109)8.38
(120)8.03
(115)Caliper (mil) mm 0.657
(25.86)0.663
(26.11)0.617
(24.31)0.665
(26.18)0.613
(26.48)0.619
(24.35)Instron Breaking Length m 2940 3410 3290 3430 3180 3250 Instron Stretch at Peak % 2.18 2.65 2.84 2.76 2.74 2.74 Instron TEA at peak in (lbf/in2) kg/cm2 (0.825)
0.058(1.21)
0.085(1.26)
0.088(1.20)
0.084(1.16)
0.081(1.16)
0.081Instron tensile strength (lbf/in) kg/cm (50.5)
8.94(62.7)
11.09(60.1)
10.64(62.6)
11.08(61.5)
10.98(59.2)
10.48Instron Young's Modulus of Elasticity, 1E+3 (lbf/in2) kg/cm2 (159)
11.09(186)
12.98(176)
12.28(188)
13.12(179)
12.49(190)
13.26Internal Bond 1E-3 (ft*lb/in2) cm kg/cm2 (56)
119.3(65)
138.5(100)
213(80)
170.4(109)
232.2(93)
198Compressive strength, (lbf/in) kg/cm (26.32)
4.66(31.46)
5.57(32.06)
5.67(31.79)
5.63(35.15)
6.22(30.38)
5.38Stiffness Gurley mgf 8010 9930 8840 10000 12600 9500 Tear Factor 100 gf/g/m2 171 181 198 176 193 169 Tear gf 524 592 646 572 668 550 Z-direction direction tensile strength (lbf/in2) kg/cm2 (26)
1.81(30)
2.09(35)
2.44(33)
2.30(37)
2.58(42)
2.93 - A series of hand sheet samples of an offset printing paper were produced to determine the effect of addition of a boron-containing compound, together with starch, in the sizing of a paper at the size press. The board was formed from a pulp mixture of about 80% hardwoods and about 20% softwoods. The first (control) sample was formed as a control. This sheet was not treated with either starch or boron-containing compound at the size press. In Sample 2, a base sheet formed in accordance with Sample 1 was sized by applying a 16% starch solids mixture with a rod-metering device and sizing the sheet using a Beloit size press. No boron-containing compound was included with the sizing starch. The starch was a Staley Pearl AP starch that was converted using ammonium persulfate. The starch was applied at a pickup rate of about 45kg (100 lb) ton of base sheet.
- In Sample 3, the sheet was formed and sized as in Sample 2, except that the starch solids were applied at 10 % solids rather than 16% solids. Again, no boron-containing compound was included with the sizing starch.
- In Sample 4, a base sheet formed in accordance with Sample 1 was sized by applying a mixture comprising 16% starch solids and borax (sodium borate pentahydrate). The ratio (by weight) of the borax in the mixture to the starch solids was about 0.25 %. Prior to being applied to the sheet, the mixture of starch and borax was cooked with of ammonium persulphate in order to convert the starch. The mixture was applied with a rod-metering device, and the sheet was sized using a Beloit size press.
- In Sample 5, the sizing was carried out in accordance with Sample 4, except that the weight ratio of borax to starch solids was 0.50 % rather than 0.25%.
- In Sample 6, the starch was applied at a 10% starch solids concentration in the mixture. Borax was added in a ration of 0.50% borax to starch solids by weight. Finally, the pickup rate of the rod-metering device was lowered from 45.36kg (100 lb) ton to 27.22 kg (60 lb)/ton.
- The physical and mechanical properties of each hand sheet sample were then measured. The results are listed in Table II.
Table II Property and Units Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Hygroexpansion from 15% to 85% rel. humidity 0.87% 1.05% 1.08% 0.85% 1.10% Air Resistance Gurley s/100 cc 9.5 11.8 11.6 12.5 10.6 11.3 Apparent Density g/cm3 0.620 0.623 0.618 0.620 0.626 0.623 Basis Weight g/m2 69.7 70.4 70.0 71.0 71.1 70.7 Basis Weight kg/m2 (lb/1300 ft2) 0.068
(18.5)0.069
(18.7)0.069
(18.6)0.07
(18.9)0.07
(18.9)0.69
(18.8)Basis Weight kg/m2 (lb/3300 ft2) 0.071
(47.1)0.071
(47.6)0.071
(47.3)0.072
(48.0)0.072
(48.0)0.717
(47.8)Brightness Directional (GE), % FS 84.2 83.4 83.5 83.0 83.3 83.6 Brightness Directional (GE), % WS 84.2 83.8 83.8 83.6 83.7 83.7 Bulk ASV cm3/g 1.61 1.61 1.62 1.61 1.60 1.61 Caliper ? (mil) mm 0.11
(4.43)0.11
(4.46)0.11
(4.46)0.11
(4.52)0.11
(4.47)0.11
(4.48)COF Kinetic 0.353 0.306 0.304 0.312 0.258 0.266 COF Static 0.456 0.440 0.415 0.471 0.396 0.444 Dry Pick IGT, VVP FS 27.0 53.2 47.8 60.8 51.6 47.7 Dry Pick IGT, VVP WS 36.3 35.7 40.2 40.1 35.8 37.4 Instron stretch at peak, % (MD) 1.56 1.76 1.68 1.65 1.65 1.58 Instron stretch at peak, % (CD) 3.28 4.14 3.77 3.83 3.26 3.90 Instron TEA at peak cm.kg/cm2 (in*lbf/in2)(MD) (0.161)
0.028(0.216)
0.038(0.210)
0.037(0.194)
0.034(0.205)
0.036(0.197)
0.0349Instron TEA at peak cm.kg/cm2 (in*lbf/in2) (CD) (0.219)
0.038(0.290)
0.051(0.259)
0.046(0.302)
0.053(0.227)
0.040(0.259)
0.046Instron Tensile Strength WCD Ratio 2.01 2.21 2.35 1.92 2.19 2.35 Instron tensile strength kg/cm (lbf/in) (MD) (18.0)
3.18(19.9)
3.52(19.8)
3.50(19.8)
3.50(20.4)
3.61(20.5)
3.62Instron tensile strength kg/cm (lbf/in) (CD) (8.94)
1.58(9.01)
1.59(8.44)
1.49(10.3)
1.82(9.32)
1.65(8.74)
1.35Instron Young's Modulus. of Elasticity kg/cm2 1E+3 (lbf/in2) (MD) (469)
32.7(506)
35.3(524)
36.6(515)
35.9(533)
37.2(547)
38.2Instron Young's Modulus of Elasticity kg/cm2 1E+3 (lbf/in2) (CD) (209)
14.59(200)
14(190)
13.3(228)
15.96(209)
14.6(185)
12.95Instron Internal Bond, 1E-3 kg/cm2 ft*(lb/in2) (MD) (118)
8.26(127)
8.89(126)
8.82(126)
8.82(116)
8.12(118)
8.26Instron Internal Bond, 1E-3 kg/cm2 (ft*lb/in2) (CD) (114)
7.98(127)
8.89(124)
8.68(131)
9.17(113)
7.91(116)
8.12Opacity Tappi, % (89% backing) 89.1 98.8 88.9 89.0 89.2 89.0 Pick Velocity m/s FS 3.00 3.00 3.00 3.00 3.00 3.00 Pick Velocity m/s WS 3.00 3.00 3.00 3.00 3.00 3.00 Roughness Parker, um 10 kgf/cm2 softback FS 7.49 7.96 7.75 8.40 7.96 7.93 Roughness Parker, um 10 kgf/cm2 softback WS 9.73 10.07 10.00 9.72 9.68 9.96 Roughness Sheffield FS 258 263 270 270 266 281 Roughness Sheffield WS 302 323 320 320 313 329 Size Hercules, sec (1% ink, 80% endpt) FS 1 33 26 40 49 33 Size Hercules, sec (1% ink, 80% endpoint) WS 1 14 18 21 21 19 Stiffness Gurley, mgf (MD) 123 130 149 154 148 146 Stiffness Gurley, mgf (CD) 48.4 62.5 67.9 81.7 70.6 65.3 Tear factor 100 gf/g/m2 (MD) 15.8 15.6 15.7 14.1 15.5 15.6 Tear factor 100 gf/g/m2 (CD) 17.2 17.0 15.7 16.9 18.3 17.0 Tear gf(MD) 55.7 53.8 53.8 51.8 53.8 55.4 Tear gf (CD) 57.6 58.2 56.6 61.4 60.2 57.0 Wax pick, critical wax strength no. FS 7 11 10 14 11 11 Wax pick, critical wax strength no. WS 11 10 10 10 10 10 Z-direction tensile strength (lbf/in2) kg/cm2 (97)
6.79(106)
7.42(107)
7.49(112)
7.84(105)
7.35(110)
7.70 - Having now described various aspects of the invention and preferred embodiments thereof, it will be recognized by those of ordinary skill that numerous modifications, variations and substitutions may exist within scope of the appended claims.
Claims (15)
- A method for forming a paper or paperboard comprising:providing a papermaking furnish comprising cellulosic fibers, starch and a boron-containing compound; forming a fibrous web from the papermaking furnish; and drying the web; characterized in that the amount of starch is from about 0.91kg (2 lbs) to or less than about 92.72 kg (200 lbs) per ton of fiber; the amount of boron-containing compound is from about 0.24 to or less than about 7% by weight of the starch; and the web is further calendered to provide a finished paper or paperboard.
- A method for forming a paper or paperboard comprising:providing a papermaking furnish including cellulosic fibers; forming a fibrous web from the papermaking furnish; drying the web; and sizing the web by applying slurry to the web, the slurry including starch solids and a boron-containing compound; characterized in that the amount of starch is from about 0.91kg (2lbs) to or less than about 92.72 kg (200lbs) per ton of fiber; the amount of boron-containing compound is from about 0.24 to or less than about 7% by weight of the starch; and the web is further calendered to provide a finished paper or paperboard.
- The method of claim 1 which further comprises mixing converted starch and at least a portion of the boron-containing compound to provide a slurry and adding the slurry to a cellulosic fiber furnish to provide the papermaking furnish.
- The method of claim 3 which further comprises mixing unconverted starch and at least a portion of the boron-containing compound to provide a slurry, cooking the slurry to convert the starch and adding the cooked slurry to a cellulosic fiber furnish to provide the papermaking furnish.
- The method of claim 1 which further comprises adding the boron-containing compound and the converted starch individually to a cellulosic fiber furnish to provide the papermaking furnish.
- The method of claims 1 or 2 wherein the boron-containing compound is selected from the group consisting of boric acid and borate metal salts.
- The method of claim 6 wherein the boron-containing compound is selected from the group consisting of boric acid, borax, and zinc borate.
- The method of claims 1 or 2 wherein the boron-containing compound and the starch from a complex.
- The method of claims 1 or 2 wherein the starch is an anionic starch.
- The method of claims 1 or 2 wherein the starch is a cationic starch.
- The method of claims 1 or 2 wherein the starch is an amphipathic stanch.
- The method of claims 1 or 2 wherein the starch is selected from the group consisting of corn starch, wheat starch, potato starch, rice starch, tapioca starch, and sago starch.
- A paper or paperboard comprising a paper web prepared by a method according to anyone of claims 1 and 3 to 12.
- The method of claim 2 wherein the slurry is cooked to convert the starch prior to being applied to the web.
- A paper or paperboard comprising a paper web prepared by a method according to anyone of claims 2, 6 to 12 and 14.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US41131902P | 2002-09-17 | 2002-09-17 | |
US411319P | 2002-09-17 | ||
PCT/IB2003/003983 WO2004027149A1 (en) | 2002-09-17 | 2003-09-17 | Papers comprising a boron-containing compound and a method of making same |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1540081A1 EP1540081A1 (en) | 2005-06-15 |
EP1540081B1 true EP1540081B1 (en) | 2010-08-18 |
Family
ID=32030663
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03797461A Expired - Lifetime EP1540081B1 (en) | 2002-09-17 | 2003-09-17 | Papers comprising a boron-containing compound and a method of making same |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1540081B1 (en) |
CN (2) | CN1705797A (en) |
AT (1) | ATE478196T1 (en) |
AU (1) | AU2003260833A1 (en) |
BR (1) | BR0314311A (en) |
CA (1) | CA2513488C (en) |
DE (1) | DE60333841D1 (en) |
WO (1) | WO2004027149A1 (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7608166B2 (en) * | 2003-09-17 | 2009-10-27 | International Paper Company | Papers having borate-based complexing and method of making same |
AT413549B (en) * | 2003-11-03 | 2006-03-15 | Spezialpappenfabrik Rosegg Bet | NEW PAPER, CARTON BZW. CARDBOARD MATERIAL |
CN101365745B (en) * | 2005-11-04 | 2011-06-08 | 嘉吉有限公司 | Lecithin-containing starch compositions, preparation thereof and paper products having oil and grease resistance, and/or release properties |
KR101777888B1 (en) | 2009-11-06 | 2017-09-12 | 솔레니스 테크놀러지스 케이맨, 엘.피. | Surface application of polymers and polymer mixtures to improve paper strength |
PT2635645T (en) | 2010-11-05 | 2017-08-11 | Solenis Technologies Cayman Lp | Surface application of polymers to improve paper strength |
CN103966890B (en) * | 2013-02-05 | 2017-03-22 | 金东纸业(江苏)股份有限公司 | papermaking process |
CN103966892A (en) * | 2013-02-05 | 2014-08-06 | 金东纸业(江苏)股份有限公司 | Papermaking auxiliary agent, papermaking process and paper product |
CN103966886A (en) * | 2013-02-05 | 2014-08-06 | 金东纸业(江苏)股份有限公司 | Papermaking technology |
CN103966894A (en) * | 2013-02-05 | 2014-08-06 | 金东纸业(江苏)股份有限公司 | Papermaking process |
US8801899B1 (en) * | 2013-09-06 | 2014-08-12 | International Paper Company | Paperboards having improved bending stiffness and method for making same |
US20180209099A1 (en) | 2014-07-03 | 2018-07-26 | Basf Se | Aqueous surface-coating agent for paper and paperboard |
CN104389238A (en) * | 2014-10-09 | 2015-03-04 | 金东纸业(江苏)股份有限公司 | Papermaking method and sized paper and coated paper obtained by papermaking method |
CN107663813A (en) * | 2016-07-29 | 2018-02-06 | 华南理工大学 | A kind of damp-prrof packing paper and compound glue application solution and their preparation method |
EP4303358A1 (en) | 2022-07-04 | 2024-01-10 | Eti Maden Isletmeleri Genel Mudurlugu | The use of boron compounds in paper pulping, paper production and caustic recovery |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3112214A (en) * | 1962-10-24 | 1963-11-26 | Corn Products Co | Process for sizing cellulose sheets with a starch derivative bearing vicinalglycol groups |
US3740253A (en) * | 1968-12-13 | 1973-06-19 | T Hattori | Method for the manufacture of a highly water resistant paper |
JPS59144696A (en) * | 1983-02-07 | 1984-08-18 | 荒川化学工業株式会社 | Paper size agent |
FI72557C (en) * | 1984-01-11 | 1992-01-08 | Kemira Oy | Paper making process and blend composition for use therein |
JPH0647826A (en) * | 1992-07-29 | 1994-02-22 | Nitto Boseki Co Ltd | Manufacture of fiber plate for building |
TW268970B (en) * | 1994-08-16 | 1996-01-21 | Cheng Loong Co Ltd | Paper adhesive with improved wet adhesion strength and its production process |
KR100362082B1 (en) * | 1999-12-17 | 2002-11-23 | 한국조폐공사 | Process for preparing paper having good strength, dimensional stability and antibacterial property |
JP2002266285A (en) * | 2001-02-27 | 2002-09-18 | Unitika Chem Co Ltd | Paper coating agent and method for producing coated paper |
-
2003
- 2003-09-17 AU AU2003260833A patent/AU2003260833A1/en not_active Abandoned
- 2003-09-17 DE DE60333841T patent/DE60333841D1/en not_active Expired - Lifetime
- 2003-09-17 WO PCT/IB2003/003983 patent/WO2004027149A1/en not_active Application Discontinuation
- 2003-09-17 CA CA2513488A patent/CA2513488C/en not_active Expired - Fee Related
- 2003-09-17 BR BR0314311-2A patent/BR0314311A/en not_active Application Discontinuation
- 2003-09-17 EP EP03797461A patent/EP1540081B1/en not_active Expired - Lifetime
- 2003-09-17 CN CN03825229.5A patent/CN1705797A/en active Pending
- 2003-09-17 CN CN2012100796341A patent/CN102767114A/en active Pending
- 2003-09-17 AT AT03797461T patent/ATE478196T1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
CA2513488A1 (en) | 2004-04-01 |
CA2513488C (en) | 2010-12-07 |
ATE478196T1 (en) | 2010-09-15 |
AU2003260833A1 (en) | 2004-04-08 |
CN102767114A (en) | 2012-11-07 |
EP1540081A1 (en) | 2005-06-15 |
DE60333841D1 (en) | 2010-09-30 |
WO2004027149A1 (en) | 2004-04-01 |
BR0314311A (en) | 2005-07-26 |
CN1705797A (en) | 2005-12-07 |
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