WO1995026441A1

WO1995026441A1 - Multi-ply cellulosic products using high-bulk cellulosic fibers

Info

Publication number: WO1995026441A1
Application number: PCT/US1995/003524
Authority: WO
Inventors: Hugh West; Amar N. Neogi; Dwight Albert Ii Dudley; Dwayne M. Shearer
Original assignee: Weyerhaeuser Company
Priority date: 1994-03-25
Filing date: 1995-03-20
Publication date: 1995-10-05
Also published as: US6736933B2; JP3558638B2; JPH09511030A; US6582553B2; US20030205342A1; US20020096287A1; US6306251B1; EP0752029A1; US20030051835A1; US6716306B2

Abstract

A multi-ply paparboard comprising at least one ply of conventional cellulose fibers and from about 0.1 to about 6 weight percent of a water-borne binding agent; and at least one ply of chemically intra-fiber crosslinked cellulosic high-bulk fibers and from about 0.1 to about 6 weight percent of a water-borne binding agent. The water-borne binding agent may be a starch, a modified starch, a polyvinyl alcohol, a polyvinyl acetate, a polyethylene/acrylic acid copolymer, an acrylic acid polymer, a polyacrylate, a polyacrylamide, a polyamine, guar gum, an oxidized polyethylene, a polyvinyl chloride, a polyvinyl chloride/acrylic acid copolymer, an acrylonitrile/styrene copolymer or polyacrylonitrile. A method for making the paperboard.

Description

MULTI-PLY CELLULOSIC PRODUCTS USING HIGH-BULK CELLULOSIC FIBERS

FIELD OF THE INVENTION

This invention concerns multi-ply cellulosic products and a method for making such products using a composition comprising chemically crosslinked cellulosic fiber and water-borne binding agents.

BACKGROUND OF THE INVENTION Products made from cellulosic fibers are desirable because they are biodegradable, are made from a renewable resource and can be recycled. The main drawback is that the typical cellulosic product has a relatively high density or low bulk. Bulk is the reciprocal of density and is the volume occupied by a specific weight of material and is designated in cm³/g. The amount of cellulosic material required to provide the requisite strength creates a heavy product. It has poor heat insulating qualities.

A 1990 brochure from Weyerhaeuser Company describes a chemically crosslinked cellulosic fiber known as High Bulk Additive or HBA and indicates the HBA fibers may be incorporated into paperboard at levels of 5% and 15%. The brochure also indicates that HBA can be used in the center ply of a three-ply paperboard. The board was compared with a conventional three-ply board. The basis weight was reduced 25%; the Taber Stiδhess remained constant; but the breaking load was reduced from 25 kN/m to 16 kN/m in the machine direction and from 9 kN/m to 6 kN/m in the cross direction. Knudsen et al U. S. Patent No. 4,913,773 describe a product that has increased stiffriess without an increase in basis weight. It is a three-ply paperboard mat. The middle ply is of anfractuous fibers. The two exterior plies are of conventional fibers. This structure, containing a middle ply of all anfractuous fibers, is compared with single ply mats of conventional and anfractuous fibers and double and triple ply constructions of different conventional fibers. Although in the comparison the middle ply is all anfractuous fibers, Knudsen et al also propose constructions in which the middle ply combines conventional and anfractuous fibers. In this latter construction Knudsen et al requires at least 10 % by weight of anfractuous fibers in the center ply in order to obtain the necessary stiffness.

Knudsen et al obtain the anfractuous fibers by mechanical treatment, by chemical treatment with ammonia or caustic or by a combination of mechanical and chemical treatment. The treatment proposed by Knudsen et al does not provide intra-fiber crosslinking. Knudsen et al may use bonding agents with certain multi-ply constructions, using 1 weight percent starch to obtain adequate bonding of the plies.

Kokko European Patent No. 0 440 472 discusses high-bulk fibers. The fibers are made by chemically crosslinking wood pulp using polycarboxylic acids. Kokko is directed to an individualized crosslinked fiber, and single ply absorbent and high-bulk paper products made from this fiber.

Kokko used a blend of 75% untreated fibers and 25% treated fibers. The maximum dry bulk achieved by Kokko was 5.2 cm³/g using 25% citric acid treated fibers and 5.5 cm³/g using 25% citric acid/monosodium phosphate treated fibers. Kokko also states that polycarboxylic acid crosslinked fibers should be more receptive to cationic additives important to papermaking and that the strength of sheets made from the crosslinked fibers should be recoverable without compromising the bulk enhancement by incorporation of a cationic wet strength resin. There is no indication that Kokko actually tried cationic strength additives, or any strength additives, with the crosslinked fibers. Consequently, Kokko did not describe the amount of cationic additive that might be used or the result of using the additive. Treating anionic fibers, such as Kokko describes, with a cationic additive substantially completely coats the entire surface of the fiber with additive. This is noted by Kokko in the experiment with methylene blue dye. The cationic additive is attracted to the entire surface of the anionic fiber. More additive is used than is needed to provide binder at the fiber-to-fiber contact points because the entire fiber is coated.

Young et al U. S. Patent No. 5,217,445 discloses an acquisition distribution zone of a diaper. It comprises 50 to 100 % by weight of chemically stiffened cellulosic fibers and 0 to 50 % by weight of a binding means. The binding means may be other nonstiffened cellulosic material, synthetic fibers, chemical additives and thermoplastic fibers. The material has a dry density less than about 0.30 g/cm³, a bulk of 3.33 cm³/g. SUMMARY OF THE INVENTION

The addition of suitable water-borne binding agents to intra-fiber crosslinked cellulosic fiber and incorporating this material into one or more plies of a multi- ply structure produces a material that has a relatively high bulk and relatively high physical strength. It also produces a material that requires less fiber (i.e., lower basis weight product), compared to conventional fiber, to produce the desired strength. One of the plies of a two-ply paperboard construction, the center ply of a three ply paperboard construction, or the middle plies of a multiply paperboard construction having more than three plies, uses a high-bulk fiber/water-borne binding agent composition.

The high-bulk fiber is an intra-fiber chemically crosslinked cellulosic material that may be formed into a mat having a bulk of from about 1 cm³/g to about 50 cm³/g. The bulk of mats formed from such fibers typically is greater than about 5 cm³/g. Suitable crosslinking agents are generally of the bifunctional type which are capable of bonding with the hydroxyl groups to create covalently bonded bridges between hydroxyl groups on the cellulose molecules within the fiber. The use of a polycarboxylic acid crosslinking agent, such as citric acid, produces a product that is especially suitable for food packaging.

Adding certain weight percents of water-borne binding agents, such as starch and polyvinyl alcohol, to chemically crosslinked high-bulk fiber produces a composition having physical characteristics superior to high-bulk fibers alone, conventional fibers alone or mixtures of high-bulk fibers and conventional fibers without such binding agents.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram showing a process for making high-bulk chemically crosslinked fibers.

FIG. 2 is a scanning electron micrograph (SEM) of a High Bulk Additive (HBA) fiber/water-bome binding agent composition made according to this invention.

FIG. 3 is a block diagram showing how the mid-ply fraction containing HBA is produced according to the present invention. FIG. 4 is a graph of solids vs. loading pressure and shows the increase in basis weight when high bulk fibers are included in the furnish.

FIG. 5 is a graph of edge wicking vs. density and shows the decrease in absorbency when high bulk fibers are included in the furnish.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention provides a composition comprising chemically crosslinked cellulosic fiber and water-borne binding agents. When incorporated into a ply of a multi-ply paperboard construction it is combined with conventional papermaking fiber furnish. Conventional papermaking fiber furnish refers to papermaking fibers made from any species, including hardwoods and softwoods, and to fibers that may have had a debonder applied to them but that are not otherwise chemically treated following the pulping process. They include chemical wood pulp fibers.

The cellulose fiber may be obtained from any source, including cotton, hemp, grasses, cane, husks, cornstalks or other suitable source. Chemical wood pulp is the preferred cellulose fiber.

The high-bulk chemically crosslinked cellulosic fibers is an intra-fiber crosslinked cellulosic fiber which may be crosslinked using a variety of suitable crosslinking agents. The individual fibers are each comprised of multiple cellulose molecules and at least a portion of the hydroxyl groups on the cellulose molecules have been bonded to other hydroxyl groups on cellulose molecules in the same fiber by crosslinking reactions with the crosslinking agents. The crosslinked fiber may be formed into a mat having a bulk of from about 1 cm³/g to about 50 cm³/g, typically from about 10 cm³/g to about 30 cm³/g, and usually from about 15 cm³/g to about 25 cm³/g. The crosslinking agent is a liquid solution of any of a variety of crosslinking solutes known in the art. Suitable crosslinking agents are generally of the bifiinctional type which are capable of bonding with the hydroxyl groups and create covalently bonded bridges between hydroxyl groups on the cellulose molecules within the fiber. Preferred types of crosslinking agents are polycarboxylic acids or selected from urea derivatives such as metholylated urea, methylolated cyclic ureas, methylolated lower alkyl substituted cyclic ureas, methylolated dihydroxy cyclic ureas. Preferred urea derivative crosslinking agents would be dimethylol-dihydroxyethylene urea (DMDHEU), dimethyldihdroxyethylene urea. Mixtures of the urea derivatives may also be used. Preferred polycarboxylic acid crosslinking agents are citric acid, tartaric acid, malic acid, succinic acid, glutaric acid or citraconic acid. These polycarboxylic acids are particularly useful when the proposed use of the paperboard is food packaging. Other polycarboxylic crosslinking agents that may be used are poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(methylvinylether-co-maleate) copolymer, poly(methylvinylether-co-itaconate) copolymer, maleic acid, itaconic acid, and tartrate monosuccinic acid. Mixtures of the polycarboxylic acids may also be used. Other crosslinking agents are described in Chung U. S. Patent No.

3,440,135, Lash et al U. S. Patent No. 4,935,022, Herron et al U. S. Patent No. 4,889,595, Shaw et al U. S. Patent No. 3,819,470, Steijer et al U. S. Patent No. 3,658,613, Dean et al U. S. Patent No. 4,822,453, and Graef et al U. S. Patent No. 4,853,086, all of which are in their entirety incorporated herein by reference. The crosslinking agent can include a catalyst to accelerate the bonding reaction between the crosslinking agent and the cellulose molecule, but most crosslinking agents do not require a catalyst. Suitable catalysts include acidic salts which can be useful when urea-based crosslinking substances are used. Such salts include ammonium chloride, ammonium sulfate, aluminum chloride, magnesium chloride, or mixtures of these or other similar compounds. Alkali metal salts of phosphorus containing acids may also be used.

The crosslinking agent typically is applied in an amount ranging from about 2 kg to about 200 kg chemical per ton of cellulose fiber and preferably about 20 kg to about 100 kg chemical per ton of cellulose fiber.

The cellulosic fibers may have been treated with a debonding agent prior to treatment with the crosslinking agent. Debonding agents tend to minimize interfiber bonds and allow the fibers to separated from each other more easily. The debonding agent may be cationic, non-ionic or anionic. Cationic debonding agents appear to be superior to non- ionic or anionic debonding agents. The debonding agent typically is added to cellulose fiber stock. Suitable cationic debonding agents include quaternary ammonium salts.

These salts typically have one or two lower alkyl substituents and one or two substituents that are or contain fatty, relatively long chain hydrocarbon. Non-ionic debonding agents typically comprise reaction products of fatty-aliphatic alcohols, fatty-alkyl phenols and fatty-aromatic and aliphatic acids that are reacted with ethylene oxide, propylene oxide or mixtures of these two materials. Examples of debonding agents may be found in Hervey et al U. S. Patent

Nos. 3,395,708 and 3,544,862, Emanuelsson et al U. S. Patent No. 4,144,122, Forssblad et al U. S. Patent No. 3,677,886, Osborne in U. S. Patent No. 4,351,699, Hellston et al U. S. Patent No. 4,476,323 and Laursen U. S. Patent No. 4,303,471 all of which are in their entirety incorporated herein by reference. A suitable debonding agent is Berocell 584 from Berol Chemicals, Incorporated of Metairie, Louisiana. It may be used at a level of 0.25% weight of debonder to weight of fiber. Again, a debonding agent may not be required.

A high-bulk fiber is available from Weyerhaeuser Company. It is HBA fiber and is available in a number of grades. The suitability of any of the grades will depend upon the end product being manufactured. Some may be more suitable for food grade applications than others. U. S. Patent Application Nos. 07/395,208 and 07/607,268 describe a method and apparatus for manufacturing HBA fibers. These applications are in their entirety incorporated herein by reference.

In essence, a conveyor 12 (Fig. 1) transports a cellulose fiber mat 14 through a fiber treatment zone 16 where an applicator 18 applies a crosslinking agent onto the mat 14. Typically, chemicals are applied uniformly to both sides of the mat. The mat 14 is separated into substantially unbroken individual fibers by a fiberizer 20. Hammermills and disc refiners may be used for fiberization. The fibers are then dried and the crosslinking agent cured in a drying apparatus 22.

The high bulk fibers produce cellulosic products having poor fiber-to-fiber bond strength. One of the ways of measuring fiber-to-fiber bond strength is tensile index. Tensile index is a measure of a sheet's tensile strength normalized with respect to the basis weight of the sheet and provides a measure of the inherent tensile strength of the material. A wet laid sheet made from the unmodified and unbeaten cellulose fibers from which the HBA is subsequently made has a tensile index of about 1.1 Nm/g whereas a similar wet-laid sheet made from the chemically crosslinked high-bulk fibers has a tensile index of only about 0.008 Nm/g, a 140 fold decrease. Fibers can readily be removed from pads of the high-bulk material simply by blowing air across the pad.

The composition of the present invention requires a water-borne binding agent. This produces a product that has increased bulk, decreased density, and strength that is substantially the same as products made without high bulk fiber. The term water- borne means any binding agent capable of being carried in water and includes binding agents that are soluble in, dispersible in or form a suspension in water. Suitable water- borne binding agents include starch, modified starch, polyvinyl alcohol, polyvinyl acetate, polyethylene/acrylic acid copolymer, acrylic acid polymers, polyacrylate, polyacrylamide, polyamine, guar gum, oxidized polyethylene, polyvinyl chloride, polyvinyl chloride/acrylic acid copolymers, acrylonitrile/butadiene/ styrene copolymers and polyacrylonitrile. Many of these will be formed into latex polymers for dispersion or suspension in water. Particularly suitable binding agents include starch, polyvinyl alcohol and polyvinyl acetate. The purpose of the binding agent is to increase the overall binding of the high-bulk fiber within the sheet. Various amounts of the water-borne binding agent may be used. The amount of binding agent may be expressed as a loading level. This is the amount of binding agent relative to the dry weight of the fiber and binding agent. Suitable binding agent loading levels are from about 0.1 weight percent to about 6 weight percent, preferably from about 0.25 weight percent to about 5.0 weight percent and most preferably from about 0.5 weight percent to about 4.5 weight percent.

The binding agent may be applied to the high-bulk fiber pad and sucked through the sheet by vacuum. The excess binding agent is removed, as by blotting. The sheets are further dried by drawing 140°C air through the pads. The treated pads have low density and good stiffness. The pads can be cut easily using a sharp knife. The material strongly resembles expanded polystyrene in appearance and feel.

The material, either alone or mixed with conventional fiber may be used to form multiply paperboard having good thermal resistance.

The amount of high bulk additive fiber used in one of the plies of a two-ply paperboard sheet or the center ply or plies of a multi ply paperboard sheet can be up to 20%) by weight. It is preferred to use about 5% by weight. 10% by weight can be used. No high bulk additive fiber need be used in the outer plies of a multiply sheet but the use of around 5% high bulk additive fibers in the outer plies may be beneficial. The use of the HBA fiber in any of the plies can speed up the forming, pressing and drying process and improve calendering in the manufacture of the paperboard, depending on what the limiting steps in the process are. Examples of multi-ply paperboards are shown in Figures 4 and 5. Figure 4 shows a two-ply paperboard in which one of the plies 40 is of conventional pulp fibers or a combination of conventional fibers and up to 5% by weight of high bulk additive fibers, and the other ply 42 is of high bulk additive fibers or a combination of high bulk additive fibers and from about 5% by weight to 99.5% by weight of conventional pulp fibers. There would be more high bulk fiber in ply 42 than in ply 40. Both plies would include a binding agent.

Figure 5 shows a three-ply paperboard in which the outer plies 44 and 46 are of conventional fibers and the center ply 48 is of high bulk fibers. Again there may be up to 5% by weight of high bulk fibers in the outer plies and from 5% by weight to 99.5% by weight of conventional fibers in the center ply. There is a greater weight percent of high bulk fiber in the center ply than in the outer plies. All plies include binding agent.

Example 1 Twenty grams of commercially available HBA fiber were dispersed in 9.5 liters of water to form an HBA/water slurry having a consistency of 0.21%. Consistency is the weight of air-dry pulp as a percentage of the pulp/water slurry weight. The slurry was placed in an 8" x 8" laboratory hand-sheet mold. The slurry was dewatered to form a pad, first by suction, then by hand pressing between blotting papers, and finally by drying in an oven at a temperature of 105°C. The resulting cellulosic pad had a density of 0.02 g/cm³, a bulk of 50 cmVg. The density of commercially available paper typically is in the range of from about 0.5 g/cm³ to about 1 g/cm³, a bulk of from about 2 cm³/g to 1 cm³/g. The density of wet-laid HBA fiber pads is about 25 to 50 times lower than the densities of typical paper sheets, and the bulk is about 50 to 100 times greater than the bulk of typical paper sheets. Fibers could be removed from the HBA fiber pad by blowing air across the sheet. Example 2 6.5 grams of HBA fiber were dispersed in eight liters of water to provide a cellulose-water slurry having a consistency of about 0.08%. The slurry was formed into pads in a six-inch diameter laboratory hand sheet mold. The slurry was dewatered as in Example 1. The resulting pad had a density of 0.025 g/cm³, a bulk of 40 cmVg.

Tensile indexes for this pad were determined. Tensile indexes for the HBA fiber pad and for a control pad made from NB316, a starting pulp for a commercially available HBA. The results are in Table I.

Table I

Pulp Type Tensile Index (Nm/g)

HBA fiber 0.0081

NB316 control 1.15

Pads of HBA fiber made by air-laying have a similar low tensile index.

High-bulk additive sheets were prepared as in Example 1. Aqueous solutions of water borne binding agents were applied to the sheets. The solution typically is vacuum-sucked through the sheet. Excess binding-agent solution is removed from the sheets first by blotting. The sheets are further dried by drawing air through the pads. The air is at a temperature of about 140°C.

Dry pads made using this process have low density and good stiffness. The strength of the sheets was markedly increased relative to high-bulk additive sheets made without the binding agents. The products could be cut easily with a knife. The material strongly resembles expanded polystyrene in appearance and feel.

Example 3 Six-inch diameter pads were formed from high-bulk additive fibers using either an air-laid or a wet-laid process. Either process forms essentially unbonded high-bulk additive pads. The pads were weighed and placed in a six-inch diameter Buchner funnel. The pads were saturated with aqueous solutions of either starch or polyvinyl alcohol. The starch was HAMACO 277 starch from A. E. Staley Manufacturing

Company. The polyvinyl alcohol was ELVANOL HV from DuPont Chemical Company.

The amounts of binding agent in the solutions ranged from about 0.5 weight % to 5 weight % of the total weight of the solution.

The pads were removed from the Buchner funnel and supported between sheets of synthetic nonwoven. A suitable nonwoven is James River 0.5 oz yd² Cerex 23 nonwoven. The supported pad was squeezed between blotting papers to remove excess liquid from the saturated sheets. The pads were then dried by passing hot air, at about 140°C, through the pads using a laboratory thermobonder. Binder loading levels of from about 2.5 to about 5 % of the weight of the fiber in the pad have been obtained using this process. Binder loading levels typically are about 3 to about 4.5 % of the weight of the fiber in the pad.

Pulp densities and tensile indexes were determined as in Example 2. NB316 pulp with and without binder and HBA fibers without binder were used as controls. The samples and results are given in Table II. It will be noted that most of the binder treated HBA fiber pads have a tensile index equal to or greater than the 1.15 Nm/g tensile index of NB316 without binder even though the densities of the HBA pads were less than one-half the 0.220 g/cm³ density of the NB316 pad. It was noted that polyvinyl alcohol greatly increased the tensile index of HBA fiber pads. Polyvinyl alcohol bonded HBA fiber pads had a density of one-third that of starch bonded NB316 fibers but had a tensile index that almost equaled that of the starch bonded NB316. The density of another sample of polyvinyl alcohol bonded HBA fiber pads was less than one-half the density of the starch bonded NB316 but its tensile index was more than twice that of the starch bonded NB316.

Table II

Solution Loading

Strength Level Pad Density Pad Bulk Tensile Index

Fiber Type Bonding Agent

% of % of Pulp g/cm³ cm³/g Nm/g

Solution Weight Weight

NB316 wet laid None N/A N/A 0.220 4.55 1.15

NB316 wet laid Starch HAMACO 277 2 7.5 0.240 4.17 1.92

HBA wet laid None N/A N/A 0.025 40 0.0081

HBA air laid Starch HAMACO 277 5 4.1 0.108 9.26 1.504

HBA air laid Starch HAMACO 277 2 3.8 0.073 13.7 1.127

HBA air laid Starch HAMACO 277 0.5 3.2 0.043 23.26 0.413

HBA air laid Polyvinyl alcohol 5 2.9 0.077 12.99 1.82 Elvanol 52-22

HBA air laid Polyvinyl alcohol 5 3.8 0.100 10 4.71 Elvanol HV

25% HBA/75% Starch HAMACO 277 2 4.4 0.106 9.43 1.189 NB316 blend by weight - air laid

It can also be seen in Table II that a starch bonded blend of HBA fibers and conventional pulp fibers can provide a product that has a low density and a tensile index that is almost the same as conventional pulp fiber alone.

FIG. 2 is an electron-microscope micrograph of an HBA/water borne binding agent composition produced according to Example 4. FIG.2 shows that the water- borne binding agent substantially completely collects at the crossover or contact points between fibers. Without limiting the invention to one theory of operation, it is believed that the polymer collects or concentrates at the crossover or contact points primarily by capillary action. The majority of the binding agent is located where it is needed.

Example 4 Six-inch diameter air-laid HBA fiber pads were weighed and placed in a six- inch diameter Buchner funnel. Aqueous solutions of polyvinyl acetate latex polymer, Reichold PVAc latex 40-800, at concentrations of polymer of 2% and 5% of the total weight of the solution. The solutions were passed through the pads in the funnels. The pads were dried in the same manner as the pads in Example 4. The loading levels of the polymeric binder were from about 2% by weight to about 4% by weight. The resultant pads were well bonded.

Example 5

9.95 grams of a 10/90 weight ratio blend of chemically crosslinked high- bulk fiber and NB316 conventional pulp were dispersed in 9.5 liters of water. The water contained 0.8 weight % water-soluble cationic potato starch, D.S. 0.3 "ACCOSIZE 80" starch. The cellulosic dispersion was placed in an 8" x 8" hand-sheet mold to produce a pad having a basis-weight of about 240 g/m². Excess moisture was removed from the pad by pressing between blotter papers, and the pad was dried in a fan oven at 105°C.

The dry pad was tested for density, taber stiffness and thermal resistance. The same values were obtained for expanded polystyrene from the lid of a clam-shell packaging box used by McDonald's Corporation. The cost of material per unit area in the cellulosic pad and in the polystyrene lid were substantially equal. The results of the tests are given in Table 1H. Table III

Basis Starch Loading, Taber Thermal Weight, Caliper, Density, Bulk, % Weight Stiffness, Resistance,

Material mm g/cm³ cm³/g g on Fiber (sd) mK W

Blend, 10% HBA/ 240 1.5 0.16 6.25 3.2 123 (10) 0.049 90% NB316 by weight

Styrofoam 120 1.0 0.12 8.33 N/A 88-128* 0.035

* stiffness of styrofoam varies with the direction relative to the forming process.

The fiber blend compared favorably with the styrofoam material.

Example 6 The HBA fiber was substituted for 10% by weight of the conventional mid- ply fijrnish in a three-ply paperboard structure. The process is shown schematically in Fig. 3. The manufacture of 100 parts by weight of mid-ply fiber at high consistency is illustrated. High consistency is, in this process, a consistency above 2% by weight fiber in the furnish. In the present example the furnish is 3% by weight.

Eighty parts by weight of conventional fiber, here Douglas Fir (DF) is combined with water in hydropulper 30 to form a 3% by weight consistency furnish. The furnish is passed from hydropulper 30 to refiner 32 where it is refined or beaten to fibrillate the fiber surface and enhance fiber-to-fiber bonding in the dry sheet. The fiber leaving the refiner was at a Canadian Standard Freeness (CSF) of about 560. The refined fiber was carried to mid-ply stock chest 34.

HBA fibers tend to flocculate in an aqueous suspension, forming loose fiber clumps and agglomerations. The HBA may also contain nits or knots. The nits and knots, as well as the clumps and agglomerations, can cause lumps in the paperboard. The clumps and agglomerations can be reduced by combining the HBA fibers with conventional fibers and dispersing the mixture in water. The amount of conventional fiber may be from 10% by weight to 90% by weight. In the example, 10 parts by weight of HBA fiber is combined with 10 parts by weight of conventional DF fiber and added to water in a hydropulper 36 to form a 3% by weight consistency furnish. The conventional fiber may be either refined or unrefined fiber.

Any knits or knots, and remaining clumps or agglomerations are removed by passing the slurry from hydropulper 36 through a deflaker 38. HBA fiber should not be refined because refining fractures the fiber, reducing its length and its ability to provide bulk in a product. The 20 parts by weight HBA fiber/conventional fiber combination from hydropulper 36 is combined with the 80 parts by weight conventional fiber furnish from hydropulper 30 after the refiner 32 as shown schematically in Fig. 3. It is shown being combined at the stock-chest 34. Example 7 The fiber furnish of Example 6 was used to prepare the midply of a three ply paperboard. The mid-ply was formed using a high-consistency forming headbox. The purpose of the experiment was to determine whether chemically modified high bulk fiber could be used in a high consistency system, whether it would provide bulk in the final product when used in a high consistency system, and whether the paperboard would be formed and would have acceptable internal bond strength.

The water-borne binding agent is added to each of the plies either at the stockchest or between the stockchest and the headbox. Three conditions were studied. A control three-ply paperboard had no

HBA fibers and used a conventional starch loading of 15 pounds starch / Air Dry Ton (ADT) of pulp. The HBA fibers were studied at two starch levels. The first was at a starch loading of 15 pounds starch / Air Dry Ton (ADT) of pulp; the second was at a starch loading of 30 pounds starch / Air Dry Ton (ADT) of pulp. The starch loading was the same in all three plies. In each case the starch was a cold-water soluble cationic starch, ROQUETTE High Cat. CSW 042 cationic potato starch (DS 0.37-0.38). The paperboard was formed, dried on a conventional can-dryer and thereafter calendered to obtain a constant smoothness. The results are shown in Table IV.

Table IV

3-ply 3-ply 3-ply

Property Paperboard Paperboard Paperboard

HBA in center ply % by 0 10 10 weight of total pulp fiber in center ply

Starch loading level lbs/air 15 15 30 dry ton pulp

Overall Basis Weight 316.2 (1.077) 295.0 (1.400) 285.0 (1.861) (g m²)

% reduction in basis weight N/A 6.7 9.9 vs. control

Caliper (mm) 0.452 (0.002) 0.457 (0.002) 0.441 (0.003)

Density kg/m³ 699.0 (33.3) 645.4 (9.6) 645.7 (18.8)

Parker Print Surface 5.478 (0.575) 5.446 (0.269) 5.796 (0.311) 20s Microns

Scott Bond J/m² 285.9 (44.8) 262.4 (21.1) 323.7 (15.6)

Mullen kPa 985.7 (154) 964.5 (69.8) 980.7 (72.5)

Tensile kN/m 22.1 (0.83) 21.3 (1.03) 22.5 (1.52)

The numbers in parenthesis are the standard deviation.

As can be seen, the basis weight of the board can be significantly reduced without impacting the board's physical properties such as caliper, internal bond strength, printability, mullen and tensile.

Example 8

The edge wicking of sheets of conventional fibers and sheets of a mixture of conventional fibers and high bulk additive fibers were compared. Tappi hand sheets were prepared. They contained 10 pounds of starch per air dry ton of fiber and 5 pounds of Kymene per air dry ton of fiber. Two fiber furnishes were used. The first furnish contained conventional pulp fiber. The second contained 90% by weight conventional pulp fiber and 10% by weight high bulk additive fiber. The wet hand sheets were pressed to different densities and compared for edge wicking. The sheets were weighed and the edges of the sheets placed in a liquid for a specified period of time. The sheets were weighed again. Wicking is expressed as grams of liquid absorbed per 100 inches of edge. The results are shown in Figure 6. At a given density the conventional fiber absorbed more liquid than the conventional fiber/high bulk additive fiber mixture. The conventional fiber is shown in a bold line and the conventional fiber/high bulk additive mixture is shown in dotted lines.

Example 9

The solids level of sheets of conventional fibers and a mixture of conventional fibers and high bulk additive fibers after wet pressing were compared. Two pulp furnishes were used. The first furnish contained conventional pulp fiber. The second contained 90% by weight conventional pulp fiber and 10% by weight high bulk additive fiber. Wet hand sheets were roll pressed at different loading pressures and the solids level in the sheets after pressing were determined on a weight percent. The results are shown in Figure 7. The sheets of a mixture of conventional fibers and high bulk additive fibers had a higher solids level, i.e., they were drier after pressing than the conventional fiber sheets.

It will be apparent to those skilled in the art that the specification and examples are exemplary only and the scope of the invention is embodied in the following claims.

Claims

Claims:

1. A multi-ply paperboard comprising:

(A) at least one first ply comprising (i) conventional cellulose fibers and (ii) from about 0.1 to about 6 percent by weight of a water-borne binding agent; (B) at least one second ply comprising (i) chemically intra-fiber crosslinked cellulosic high-bulk fibers and (ii) from about 0.1 to about 6 percent by weight of a water-borne binding agent.

2. The paperboard according to claim 1 wherein said paperboard has two outer plies and at least one middle ply, and said outer plies are comprised of said first ply and said at least one middle ply is comprised of said second ply.

3. The paperboard according to claims 1 or 2 wherein the water-borne binding agent is anionic or nonionic.

4. The paperboard according to claims 1 or 2 wherein the water-borne binding agent is selected from the group consisting of a starch, a modified starch, a polyvinyl alcohol, a polyvinyl acetate, a polyethylene/acrylic acid copolymer, an acrylic acid polymer, a polyacrylate, a polyacrylamide, a polyamine, guar gum, an oxidized polyethylene, a polyvinyl chloride, a polyvinyl chloride/acrylic acid copolymer, an acrylonitrile/butadiene/styrene copolymer and polyacrylonitrile.

5. The paperboard according to claims 1 or 2 wherein the binding agent is selected from the group consisting of starch and modified starch.

6. The paperboard according to claims 1 or 2 wherein the binding agent is polyvinyl alcohol.

7. The paperboard according to claims 1 or 2 wherein the composition comprises from about 0.25 weight percent to about 5 weight percent water-borne binding agent.

8. The paperboard according to claims 1 or 2 wherein the crosslinking agent is selected from the group of urea derivatives consisting of methylated urea, methylated cyclic ureas, methylated lower alkyl substituted ureas, dihydroxy cyclic ureas, and methylated dihydroxy cyclic ureas, and mixtures thereof

9. The paperboard according to claims 1 or 2 wherein the crosslinking agent is selected from the group consisting of dimethylol urea, dimethyloldihydroxyethylene urea, dihydroxyethylene urea, dimethylolethylene urea and 4,5-dihydroxy-l,3-dimethyl-2- imidazolidinone.

10. The paperboard according to claims 1 or 2 wherein the crosslinking agent is a polycarboxylic acid.

11. The paperboard according to claims 1 or 2 wherein the crosslinking agent is selected from the group consisting of citric acid, tartaric acid, malic acid, glutaric acid, citraconic acid and mixtures thereof.

12. The paperboard according to claims 1 or 2 wherein the crosslinking agent is selected from the group consisting of poly(arcylic acid), poly(methacrylic acid), poly(maleic acid), poly(methylvinylether-co-maleate) copolymer, po_y(methylvinylether-co- itaconate) copolymer, maleic acid, itaconic acid, and tartrate monosuccinic acid

13. The paperboard according to claims 1 or 2 wherein said second ply further comprises from about 5 weight percent to about 99.5 weight percent conventional fiber furnish.

14. The paperboard according to claims 1 or 2 wherein said second ply further comprises at least about 80 weight percent conventional fiber furnish.

15. The paperboard according to claims 1 or 2 wherein said second ply further comprises at least about 90 weight percent conventional fiber furnish.

16. The paperboard according to claims 1 or 2 wherein adjacent fibers are in contact and form plural fiber crossover points, the majority of said water-borne binding agent being located at the fiber-fiber crossover points.

17. The paperboard according to claims 1 or 2 wherein said second ply has a bulk of from 1 cm³/g to about 50 c Vg.

18. The paperboard according to claims 1 or 2 wherein said second ply has a bulk less than about 3 cm³/g.

19. The paperboard according to claims 1 or 2 wherein said high-bulk fibers have been derived from pulp treated with a debonding agent.

20. The paperboard according to claims 1 or 2 wherein said high bulk fibers are individualized.

21. The paperboard according to claims 1 or 2 wherein said first ply comprises up to 5% by weight of said high-bulk fibers.

22. The paperboard according to claim 21 wherein said crosslinking agent in said first ply is the same as in said second ply.

23. A method for producing a multi-ply paperboard comprising forming a first ply; forming a second ply; said plies being combined into a multi-ply structure; one of said plies comprising conventional cellulosic fibers; the other of said plies comprising chemically intra-fiber crosslinked cellulosic high-bulk fibers; said plies further having from about 0.1 to 6 weight percent of a water- borne binding agent incorporated therein; and drying said combined plies to form a multi-ply paperboard.

24. The method of claim 23 further comprising forming a third ply; one of said plies in said multi-ply structure being between the other two plies; said one ply comprising said high bulk fibers; said other two plies comprising conventional pulp fiber.

25. The method according to claims 23 or 24 wherein the water-borne binding agent is anionic or nonionic.

26. The method according to claims 23 or 24 wherein the water-borne binding agent is selected from the group consisting of a starch, a modified starch, a polyvinyl alcohol, a polyvinyl acetate, a polyethylene/acrylic acid copolymer, an acrylic acid polymer, a polyacrylate, a polyacrylamide, a polyamine, guar gum, an oxidized polyethylene, a polyvinyl chloride, a polyvinyl chloride/acrylic acid copolymer, an acrylonitrile/butadiene/styrene copolymer and polyacrylonitrile.

27. The method according to claims 23 or 24 wherein the binding agent is selected from the group consisting of starch and modified starch.

28. The method according to claims 23 or 24 wherein the binding agent is polyvinyl alcohol.

29. The method according to claims 23 or 24 wherein the water-borne binding agent is added in an amount sufficient to incorporate from about 0.25 weight percent to about 5 weight percent of the fiber.

30. The method according to claims 23 or 24 wherein the crosslinking agent is selected from the group of urea derivatives consisting of methylated urea, methylated cyclic ureas, methylated lower alkyl substituted ureas, dihydroxy cyclic ureas, and methylated dihydroxy cyclic ureas, and mixtures thereof

31. The method according to claims 23 or 24 wherein the crosslinking agent is selected from the group consisting of dimethylol urea, dimethyloldihydroxyethylene urea, dihydroxyethylene urea, dimethylolethylene urea, 4,5-dihydroxy-l,3-dimethyl-2- imidazolidinone and mixtures thereof.

32. The method according to claims 23 or 24 wherein the crosslinking agent is a polycarboxylic acid.

33. The method according to claims 23 or 24 wherein the crosslinking agent is selected from the group consisting of citric acid, tartaric acid, malic acid, succinic acid, glutaric acid, citraconic acid and mixtures thereof.

34. The method according to claims 23 or 24 wherein the crosslinking agent is selected from the group consisting of poly(arcylic acid), poIy(methacrylic acid), poly(maleic acid), poly(methylvinylether-co-maleate) copolymer, poly(methylvinylether-co- itaconate) copolymer, maleic acid, itaconic acid, tartrate monosuccinic acid and mixtures thereof.

35. The method according to claims 23 or 24 wherein said high-bulk fiber ply comprises from about 5 weight percent to about 99.5 weight percent conventional fiber furnish.

36. The method according to claims 23 or 24 wherein said high bulk fiber ply comprises at least about 80 weight percent conventional fiber furnish.

37. The method according to claims 23 or 24 wherein said high bulk fiber ply comprises at least about 90 weight percent conventional fiber furnish.

38. The method according to claims 23 or 24 wherein adjacent fibers are in contact and form plural fiber crossover points, the majority of said water-borne binding agent being located at the fiber-fiber crossover points.

39. The method according to claims 23 or 24 wherein said high bulk fiber ply has a bulk from about 1 cm³/g to about 50 cm³/g.

40. The method according to claims 23 or 24 wherein said high bulk fiber ply has a bulk less than about 3 cm³/g.

41. The method according to claims 23 or 24 wherein said high-bulk fibers have been derived from pulp treated with a debonding agent.

42. The method according to claims 23 or 24 wherein said high bulk fibers are individualized.

43. The method according to claims 23 or 24 wherein said conventional fiber plies comprise up to 5% by weight of said high-bulk fibers.

44. The method according to claims 23 or 24 wherein said crosslinking agent in said conventional fiber ply or plies is the same as in said high bulk fiber ply.