(19)
(11) EP 1 540 081 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Mention of the grant of the patent:
18.08.2010 Bulletin 2010/33

(21) Application number: 03797461.5

(22) Date of filing: 17.09.2003
(51) International Patent Classification (IPC): 
D21H 21/16(2006.01)
D21H 27/00(2006.01)
D21H 17/28(2006.01)
D21H 21/18(2006.01)
D21H 17/12(2006.01)
(86) International application number:
PCT/IB2003/003983
(87) International publication number:
WO 2004/027149 (01.04.2004 Gazette 2004/14)

(54)

PAPERS COMPRISING A BORON-CONTAINING COMPOUND AND A METHOD OF MAKING SAME

PAPIERE MIT BORHALTIGER VERBINDUNG UND VERFAHREN ZU IHRER HERSTELLUNG

PAPIERS COMPRENANT UN COMPOSE CONTENANT DU BORE ET PROCEDE DE FABRICATION CORRESPONDANT


(84) Designated Contracting States:
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

(30) Priority: 17.09.2002 US 411319 P

(43) Date of publication of application:
15.06.2005 Bulletin 2005/24

(73) Proprietor: INTERNATIONAL PAPER COMPANY
Stamford, CT 06921 (US)

(72) Inventors:
  • Huang, Yan C.
    Stamford, CT 06921 (US)
  • Lyne, M. Bruce
    Stamford, CT 06921 (US)
  • Singh, Kapil M.
    Stamford, CT 06921 (US)
  • Hong, Yaoliang
    Stamford, CT 06921 (US)

(74) Representative: Schneider, Michael et al
Heisse Kursawe Eversheds Rechtsanwälte Partnerschaft Maximiliansplatz 5
80333 München
80333 München (DE)


(56) References cited: : 
EP-A- 0 148 647
GB-A- 2 137 613
   
  • DATABASE WPI Section Ch, Week 200338 Derwent Publications Ltd., London, GB; Class A11, AN 2003-397136 XP002266048 & JP 2002 266285 A (UNICHIKA CHEM KK), 18 September 2002 (2002-09-18)
  • DATABASE WPI Section Ch, Week 199615 Derwent Publications Ltd., London, GB; Class A81, AN 1996-150171 XP002266049 & TW 268 970 A (CHENG LOONG CO LTD), 21 January 1996 (1996-01-21)
  • DATABASE WPI Section Ch, Week 199412 Derwent Publications Ltd., London, GB; Class A14, AN 1994-097406 XP002266050 & JP 06 047826 A (KAIHATSU BOARD KK), 22 February 1994 (1994-02-22)
  • DATABASE WPI Section Ch, Week 200219 Derwent Publications Ltd., London, GB; Class A97, AN 2002-145939 XP002266051 & KR 2001 056 213 A (KOREA SECURITY PRINTING & MINTING CORP), 4 July 2001 (2001-07-04)
   
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

FIELD OF THE INVENTION



[0001] 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.

BACKGROUND OF THE INVENTION



[0002] 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.

[0003] 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.

[0004] 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.

[0005] 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.

SUMMARY OF THE INVENTION



[0006] 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.

[0007] 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.

[0008] 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.

[0009] 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.

[0010] 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.

[0011] 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.

[0012] 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.

DETAILED DESCRIPTION OF THE INVENTION



[0013] 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.)

[0014] 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.

[0015] 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.

[0016] 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).

[0017] 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).

[0018] 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..

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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).

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

Example I



[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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)
0.081
Instron 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)
10.48
Instron 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)
13.26
Internal Bond 1E-3 (ft*lb/in2) cm kg/cm2 (56)
119.3
(65)
138.5
(100)
213
(80)
170.4
(109)
232.2
(93)
198
Compressive 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)
5.38
Stiffness 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

Example II



[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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%.

[0046] 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.

[0047] 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)
0.0349
Instron 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)
0.046
Instron 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)
3.62
Instron 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)
1.35
Instron 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)
38.2
Instron 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)
12.95
Instron 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)
8.26
Instron 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)
8.12
Opacity 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


[0048] 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

1. 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.


 
2. 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.


 
3. 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.
 
4. 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.
 
5. 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.
 
6. 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.
 
7. The method of claim 6 wherein the boron-containing compound is selected from the group consisting of boric acid, borax, and zinc borate.
 
8. The method of claims 1 or 2 wherein the boron-containing compound and the starch from a complex.
 
9. The method of claims 1 or 2 wherein the starch is an anionic starch.
 
10. The method of claims 1 or 2 wherein the starch is a cationic starch.
 
11. The method of claims 1 or 2 wherein the starch is an amphipathic stanch.
 
12. 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.
 
13. A paper or paperboard comprising a paper web prepared by a method according to anyone of claims 1 and 3 to 12.
 
14. The method of claim 2 wherein the slurry is cooked to convert the starch prior to being applied to the web.
 
15. A paper or paperboard comprising a paper web prepared by a method according to anyone of claims 2, 6 to 12 and 14.
 


Ansprüche

1. Verfahren zum Formen von Papier oder Pappe, umfassend folgende Schritte:

Bereitstellen einer Papiermasse zur Papierherstellung, die Zellulosefasern, Stärke und eine borhaltige Verbindung umfasst;

Formen einer Faserbahn aus der Papiermasse zur Papierherstellung; und

Trocknen der Bahn;

dadurch gekennzeichnet, dass

die Stärkemenge von ungefähr 0,91 kg (21 lbs) bis zu oder weniger als ungefähr 92,72 kg (200 lbs) pro Fasertonne reicht;

die Menge der borhaltigen Verbindung von ungefähr 0,2 bis zu oder weniger als ungefähr 7 Gewichtsprozent der Stärke reicht; und

die Bahn ferner satiniert wird, um fertiges Papier oder fertige Pappe bereitzustellen.


 
2. Verfahren zum Formen von Papier oder Pappe, umfassend folgende Schritte:

Bereitstellen einer Papiermasse zur Papierherstellung, die Zellulosefasern umfasst;

Formen einer Faserbahn aus der Papiermasse zur Papierherstellung;

Trocknen der Bahn; und

Dimensionieren der Bahn durch Auftragen von Schlamm auf die Bahn, wobei der Schlamm Stärkefeststoffe und eine borhaltige Verbindung umfasst;

dadurch gekennzeichnet, dass

die Stärkemenge von ungefähr 0,91 kg (21 lbs) bis zu oder weniger als ungefähr 92,72 kg (200 lbs) pro Fasertonne reicht;

die Menge der borhaltigen Verbindung von ungefähr 0,2 bis zu oder weniger als ungefähr 7 Gewichtsprozent der Stärke reicht; und

die Bahn ferner satiniert wird, um fertiges Papier oder fertige Pappe bereitzustellen.


 
3. Verfahren nach Anspruch 1, ferner umfassend das Mischen konvertierter Stärke und mindestens eines Teils der borhaltigen Verbindung, um Schlamm bereitzustellen und den Schlamm einer Zellulosefaser-Papiermasse hinzuzufügen, um die Papiermasse zur Papierherstellung bereitzustellen.
 
4. Verfahren nach Anspruch 3, ferner umfassend das Mischen nicht konvertierter Stärke und mindestens eines Teils der borhaltigen Verbindung, um Schlamm bereitzustellen, das Kochen des Schlamms, um die Stärke zu konvertieren, und das Hinzufügen des gekochten Schlamms zu einer Zellulosefaser-Papiermasse, um die Papiermasse zur Papierherstellung bereitzustellen.
 
5. Verfahren nach Anspruch 1, ferner umfassend das einzelne Hinzufügen der borhaltigen Verbindung und der konvertierten Stärke zu einer Zellulosefaser-Papiermasse, um die Papiermasse zur Papierherstellung bereitzustellen.
 
6. Verfahren nach Anspruch 1 oder 2, wobei die borhaltige Verbindung aus der Gruppe ausgewählt wird, die aus Borsäure und Metallboratsalzen besteht.
 
7. Verfahren nach Anspruch 6, wobei die borhaltige Verbindung aus der Gruppe ausgewählt wird, die aus Borsäure, Borax und Zinkborat besteht.
 
8. Verfahren nach Anspruch 1 oder 2, wobei die borhaltige Verbindung und die Stärke einen Komplex bilden.
 
9. Verfahren nach Anspruch 1 oder 2, wobei die Stärke eine anionische Stärke ist.
 
10. Verfahren nach Anspruch 1 oder 2, wobei die Stärke eine kationische Stärke ist.
 
11. Verfahren nach Anspruch 1 oder 2, wobei die Stärke eine amphipathische Stärke ist.
 
12. Verfahren nach Anspruch 1 oder 2, wobei die Stärke aus der Gruppe ausgewählt wird, die aus Maisstärke, Weizenstärke, Kartoffelstärke, Reisstärke, Tapiokastärke und Sagostärke besteht.
 
13. Papier oder Pappe, umfassend eine Papierbahn, die mit einem Verfahren nach einem der Ansprüche 1 und 3 bis 12 angefertigt wird.
 
14. Verfahren nach Anspruch 2, wobei der Schlamm gekocht wird, um die Stärke zu konvertieren, bevor er auf die Bahn aufgetragen wird.
 
15. Papier oder Pappe, umfassend eine Papierbahn, die mit einem Verfahren nach einem der Ansprüche 2, 6 bis 12 und 14 angefertigt wird.
 


Revendications

1. Procédé de formage d'un papier ou carton comprenant les opérations consistant à :

se procurer une composition de fabrication de papier comprenant des fibres cellulosiques, de l'amidon et un composé contenant du bore ; former une bande fibreuse à partir de la composition de fabrication de papier ; et sécher la bande ; caractérisé par le fait que la quantité d'amidon est d'environ 0,91 kg (2 livres) à environ 92,72 kg (200 livres) ou moins par tonne de fibres ; la quantité de composé contenant du bore est d'environ 0,2 % à environ 7 % ou moins en poids de l'amidon ; et la bande est en outre calandrée pour obtenir un papier ou carton fini.


 
2. Procédé de formage d'un papier ou carton comprenant les opérations consistant à:

se procurer une composition de fabrication de papier comprenant des fibres cellulosiques ; former une bande fibreuse à partir de la composition de fabrication de papier ; sécher la bande ; et encoller la bande par application de bouillie sur la bande, la bouillie comprenant des matières solides d'amidon et un composé contenant du bore ; caractérisé par le fait que la quantité d'amidon est d'environ 0,91 kg (2 livres) à environ 92,72 kg (200 livres) ou moins par tonne de fibres ; la quantité de composé contenant du bore est d'environ 0,2 % à environ 7 % ou moins en poids de l'amidon ; et la bande est en outre calandrée pour obtenir un papier ou carton fini.


 
3. Procédé selon la revendication 1, qui comprend en outre les opérations consistant à mélanger de l'amidon converti et au moins une partie du composé contenant du bore pour produire une bouillie et à ajouter la bouillie à une composition de fibres cellulosiques pour obtenir la composition de fabrication de papier.
 
4. Procédé selon la revendication 3, qui comprend en outre les opérations consistant à mélanger de l'amidon non converti et au moins une partie du composé contenant du bore pour produire une bouillie, à cuire la bouillie pour convertir l'amidon et à ajouter la bouillie cuite à une composition de fibres cellulosiques pour obtenir la composition de fabrication de papier.
 
5. Procédé selon la revendication 1, qui comprend en outre les opérations consistant à ajouter individuellement le composé contenant du bore et l'amidon converti à une composition de fibres cellulosiques pour obtenir la composition de fabrication de papier.
 
6. Procédé selon l'une des revendications 1 ou 2, dans lequel le composé contenant du bore est choisi dans le groupe constitué par l'acide borique et les sels métalliques borates.
 
7. Procédé selon la revendication 6, dans lequel le composé contenant du bore est choisi dans le groupe constitué par l'acide borique, le borax et le borate de zinc.
 
8. Procédé selon l'une des revendications 1 ou 2, dans lequel le composé contenant du bore et l'amidon forment un complexe.
 
9. Procédé selon l'une des revendications 1 ou 2, dans lequel l'amidon est un amidon anionique.
 
10. Procédé selon l'une des revendications 1 ou 2, dans lequel l'amidon est un amidon cationique.
 
11. Procédé selon l'une des revendications 1 ou 2, dans lequel l'amidon est un amidon amphipathique.
 
12. Procédé selon l'une des revendications 1 ou 2, dans lequel l'amidon est choisi dans le groupe constitué par l'amidon de maïs, l'amidon de blé, l'amidon de pomme de terre, l'amidon de riz, l'amidon de tapioca et l'amidon de sagou.
 
13. Papier ou carton comprenant une bande de papier préparée par un procédé selon l'une quelconque des revendications 1 et 3 à 12.
 
14. Procédé selon la revendication 2, dans lequel la bouillie est cuite pour convertir l'amidon avant d'être appliquée sur la bande.
 
15. Papier ou carton comprenant une bande de papier préparée par un procédé selon l'une quelconque des revendications 2, 6 à 12 et 14.
 






Cited references

REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description