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OPTIONS FOR SOFT SIZING OF MECHANICAL PAPERS Paul Rankin Technology Development Manager Raisio Chemicals Canada, Inc.

Suite 1550, 1200 West 73rd. Avenue Vancouver, BC, Canada V6P 6G5 Phone: 604 264 9799 Fax: 604 264 0252 Kari Luukkonen Global Product Manager Raisio Chemicals Oy PO Box 101, SF 21201, Raisio, Finland Phone: 011 358 2 434 2724 Fax: 011 358 2 434 2816 Mari Lindstrom Senior Research Chemist Raisio Chemicals Oy PO Box 101, SF 21201, Raisio, Finland Phone: 011 358 2 434 2691 Fax: 011 358 2 434 2787

Paper Presented at 2000 TAPPI Papermakers Conference, Vancouver, BC, Canada, Apr 16 19th 2000. ABSTRACT A degree of soft sizing has historically been desired in certain mechanical papers to optimize performance. By controlling the rate and extent of water uptake during printing and converting processes, hydrophobic sizing technology minimises problems of sheet cockle, waviness, hygroexpansitity and low rewetted paper strength that can give rise to poor efficiency and quality in several coating and printing operations. Current industry trends to multicolour offset printing of all mechanical papers, including newsprint and directory grades, have resulted in more water contacting the paper during printing. This increases the potential for paper dimensional stability and strength loss problems. Increasing use of water based inks and hydrophilic fillers add to the concern. For these reasons, there is increasing interest from manufacturers of mechanical grades on effective hydrophobic sizing technologies for all mechanical grades, from Newsprint to LWC. This paper reviews traditional hydrophobic sizing technologies available for mechanical grades and experience to date in applying these technologies. It also introduces Raisafob 30S technology, a newly developed unique hydrophobic low molecular weight cationic starch (HLWCS) soft sizing technology specifically developed by Raisio Chemicals for water uptake control and printability enhancement in mechanical papers. 1. INTRODUCTION Paper fibres are naturally hydrophilic. Paper sizing involves the ability to control the uptake rate and amount of water penetration into the pores and onto the fibre surfaces of a paper web by introducing a chemistry capable of imparting a degree of hydrophobicity to the paper web. These so-called hydrophobic size chemistries are typically organic compounds containing non-polar and polar functional groups, with the polar groups attaching to fibers and the non-polar groups sticking out from the fibre surfaces. The common hydrophobic sizing agents are typically non-ionic or anionic. In order to retain the size onto negatively charged fibres, it is usually necessary to add a cationic agent to maximise retention. In free sheet applications, where anionic trash levels and dissolved solids are generally low, sizing efficiencies onto sheet fibres and fines are good. However in mechanical grade systems where typically anionic dissolved and colloidal material levels are higher, these materials compete for cationic size adhesion, making size retention more difficult. The challenge for effective hydrophobic sizing of mechanical grades is to maximise hydrophobic size retention in the sheet, while minimising paper strength loss and machine runnability deterioration due to poor hydrophobic size retention and subsequent hydrolysis and/or deposition. It is necessary to maintain sufficient sheet dry strength for runnability. Mechanical furnishes contain products of wood pulping such as fatty and resin acids that can act as natural sizing agents. The extent of natural sizing is dependent, among other things, on the wood species and pulping and bleaching processes used (Ref. 1). Redistribution of these compounds in the sheet during and after manufacture can result in increase in sheet hydrophobicity by a self sizing mechanism. Mechanical papermakers cannot generally

rely on natural self sizing to produce required sizing levels consistently, so must resort to external chemical addition programs. The literature abounds with good descriptions of sizing technology (Refs. 2, 3, 4 ) 2. MEASUREMENT OF SIZE The more common methods for quantifying size in paper sheets are summarised in Fig. 1

Fig 1 Water Drop Cobb Hercules Dynamic Water Absorption Contact Angle

Size Testing in Papers

Absorbance time of water drop into paper Amount of water absorbed into paper at a given time Time for dye to reduce underside paper reflectance to a given value Rate of uptake of water into sheet, as measured by ultrasound Measure of water bead/sheet geometry

In mechanical grades, water drop is the most common and straightforward test used, since most of the applications require at most a soft sizing of the sheet, as for example would apply to an application for improvement in heatset offset printing performance. Some grades, i.e. food and fast food wraps, and non archaival desktop publishing papers can require higher sizing levels that are better characterised by HST and Cobb tests. Increasing emphasis is now being placed on dynamic water penetration measurements, since both the rate, as well as the amount of water penetration is key to performance in many end use applications. 3. HYDROPHOBIC SIZING APPLICATIONS Hydrophobic sizing technology is increasingly being applied on wood-containing papermachines for all grades from Newsprint to LWC. A summary of the main applications is shown in Fig. 2.

Fig 2 Grade Typical Sizing Levels (water drop) 35 - 200 70 - 250 50 150

Sizing in Mechanical Grades Objectives

Newsprint SC LWC

linting, web growth, strength, printability strength, offset printability coating holdout

The key issues in application of sizing technology in these grades are as follows. Non Image Linting In some multicolor offset printing applications, fine dusting or linting has been observed on the printing press which is more predominant in the non image areas of the printed sheet (as evidenced from plate and blanket tape pulls). Such lint generally arises from excessive lowering of sheet surface strength upon rewetting by the fountain solution during printing. Web Growth & Fan Out Some mechanical papers, particularly lighter weight papers such as directory, can experience excessive web growth in the cross direction during offset printing. This expansion can be uniform or non-uniform, and generate print misregister problems in multicolor offset or water based ink printing. Although sheet structure considerations play a

major role in this effect, it is also known that sizing technology can reduce sheet hygroexpansivity by reducing water absorption into the fibre structure. (see fig. 10). Rewetted Web Strength In offset printing, some mechanical papers lose more x-y strength, notably tensile, than others as the web picks up moisture through the various printing units. This may be severe enough to cause frequent web breaks in the later printing units. Printability Enhancement Printing processes involving water, such as offset, flexo and water based gravure, can suffer from excessive dot gain and ink penetration into the paper if the water uptake of the paper is excessive. This can occur, for example, in highly filled sheets or lightweight papers. Sizing can help reduce dot gain and improve ink holdout and image vividity by minimising ink penetration into the paper. Coating Holdout It is generally agreed that coating effectiveness is reduced if the applied coating is absorbed appreciably into the basepaper. Since the coating can be a significant cost in product manufacture, any technology that can reduce the basepaper uptake of a coating is desirable. Sizing technology is used to impart some hydrophobicity in basepapers for LWC and surface sized newsprint to minimise coating costs. Preservation of basesheet strength by reduced rewetting can also improve web runnability through the coater. Non Printing Uses Mechanical grades are finding increasing use in food, fast food, and stationary papers where some degree of hydrophobicity is required to suppress water penetration for a short but finite time. 4. TRADITIONAL SIZING TECHNOLOGIES Surface sizing describes the process of external application of chemical(s) to the paper web to enhance surface strength and printability. Traditional chemistries employ modified hydrophilic starches, either alone or in combination with minor amounts of other products. This technology generally requires capital equipment such as a puddle size press, gate roll size press, or film press, coupled with a chemical preparation plant. Newsprint surface sizing with gate roll coaters is practiced extensively in Japan to improve surface strength and print quality of high recycle newsprint. Internal sizing describes the process of adding a hydrophobic chemistry to the papermachine wet-end in order to improve paper performance in subsequent coating, printing or converting operations. In contrast to surface sizing, internal sizing technologies do not generally enhance sheet strength. In seeking paper quality enhancement, North American mechanical paper producers have not had, to date, the stomach for the capital costs of external sizing, preferring to concentrate on internal sizing opportunities. Accordingly, this review will only henceforth deal with internal sizing technologies. 4.1 SIZING CHEMISTRIES Sizing chemistries available for mechanical grades are summarised in Fig. 3. Traditional chemistries include rosin, ASA and AKD with polymeric sizing chemistry representing an emerging technology. Excellent reviews of the traditional technologies are available in the literature (Refs. 1,2,3).

Fig 3

Sizing Chemistries Rosin / Alum AKD ASA Combisize Polymerics Starches CMC

4.1.1 ROSIN Chemistry Rosin originates from resin acids in the sticky material that trees exude to seal bark wounds. Rosin can be extracted from pine tree sap or from kraft tall oil. Free rosin size has nowadays been superceded by a variety of chemical modifications to increase its sizing efficiency. These include both anionic and cationic dispersed rosin size, saponified or so-called soap sizes, and fortified rosin sizes. In papermaking systems, rosin needs aluminium ions in order to form the alunimium rosinate that can then attach the size to fibres, and also to form sintered sizing complexes. The aluminium rosinate must then be sintered on the fibre surface to provide effective sizing. It is necessary for papermakers to add a source of aluminium ions i.e alum or sodium aluminate to achieve paper sizing with rosin. Sintering needs at least 70 degrees Celsius for efficient sizing with dispersed rosin sizes. Rosin sizing is most effective in the pH 4.5 5.5 range, and requires good wet end chemistry control to develop acceptable sizing efficiency and minimise size reversion due to unbonded rosin complexes. Rosin sizing is ineffective at higher pH, as under these conditions the aluminium ion only exists in a hydrolysed form that does not generate the sizing development upon sintering. Application in Mechanical Grades Rosin size has been used in mechanical grades produced at acid pHs to impart desired hydrophobicity. Typically dispersed rosin sizes are used. They are supplied as 35% solids milky emulsions, and are diluted to about 2-5% with clean water prior to thick stock or fan pump addition. Alum is usually added just prior to, or together with rosin addition. Typical rosin dosages in the range of 1-2 kg/t are common with dispersed sizes for mechanical grades, depending on the level of size required. Historically, application in mechanical grades has been to improve converting and/or printing performance, for example in stationary papers. 4.1.2 ALKYL KETENE DIMER (AKD) Chemistry AKD is a non-ionic synthetic polymer produced by dimerizing fatty acid chlorides. Stearic acid is the common starting material, although other fatty acids can be used. The final product is a water-insoluble waxy bead at room temperature. For papermaking use, the solid must be emulsified prior to use. This is commonly done offsite using cationic starch, synthetic cationic polymers and/or other stabilizing additives. The resultant white emulsion is typically 6-15% solids, of which 30% are AKD solids. In contrast to rosin, the functional groups of the AKD molecule that bond to fibres also have the ability to react progressively with water to hydrolyse. The AKD hydrolysate does not contribute to sizing and so reduces sizing efficiency. AKD emulsions typically have a one month shelf life at normal temperature. AKD sizing is a slow development. Sizing development can be enhanced by increasing alkalinity, temperature, and paper drying rate. Alum use can hurt AKD sizing. AKD sizing development is slow, generally continuing in the stored paper rolls. Sizing with AKD works best in the 6 9 pH range.

Application in Mechanical Grades Emulsified AKD is used in relatively low dosages (up to 2 kg/t) in some newsprint applications with both virgin and recycle furnishes to provide some degree of slack sizing ( 35 130 second water drop) for certain end use applications where printability and sheet rewetted strength enhancements are desired. AKD use in PCC containing papers is complicated by loss of sizing due to PCC adsorption of the size. Maintenance of consistent AKD sizing levels in the final paper is more complicated in mechanical versus free sheet applications, with predictive cure tests being less reliable. AKD size can also make the paper more slippery, so loss of surface friction at the sizing levels needed for pressroom printability benefits may be excessive. 4.1.3 ALKENYL SUCCINIC ANHYDRIDE (ASA) Chemistry ASA is a highly reactive synthetic size produced by reacting an olefin with an organic anhydride, typically maleic anhydride. The resultant product is an amber colored stable non-ionic liquid which also needs to be emulsified with a starch based or synthetic cationic polymer prior to use. In contrast to AKD, sizing response with ASA is more rapid. The highly reactive functional groups of the ASA molecule form strong covalent bonds with fibres, generating high and stable sizing efficiency. Sintering is still required to maximise sizing performance. These same reactive functional groups will readily hydrolyse with water, severely reducing sizing efficiency. For this reason, ASA emulsions must be prepared on-site and used as soon as possible after preparation. ASA does not suffer the curing or reversion issues often encountered with AKD, but has greater potential to cause machine runnability problems, particularly if first pass size retention is low. Sizing with ASA works best in the pH 5 10 range. Application in mechanical grades In contrast to rosin and AKD, on-site chemical preparation equipment needs for ASA are greater, with on-site emulsifiers a necessity. High first pass retention in mechanical papers is essential to minimise hydrolysate formation and subsequent reaction in the white water with anionic materials, and calcium and magnesium ions. These reactions will produce tacky compounds that can cause press roll picking and troublesome deposits in the press and dryer section, and spots in the paper. ASA is typically added to the thin or thick stock to improve heatset offset pressroom runnability in specific applications. Because of its high sizing efficiency, only low dosages (0.2 1 kg/t) are normally required to produce the typical target 35 150 water drop target. While alum addition is not necessary, it can enhance ASA sizing efficiency. 4.1.4 POLYMERIC SIZE Chemistry Other organic polymers have been found to have some sizing potential. While not capable of effectively developing the hard sizing typically demanded for many free sheet and liquid packaging applications, these products can nonetheless develop sufficient soft sizing for mechanical grade applications. Like ASA and AKD, these products are generally non ionic, requiring a cationic polymer for emulsification. Raisio Chemicals has recently developed a unique polymeric size technology for internal soft sizing of mechanical papers. The product chemistry involves enhancement of patented low molecular weight cationic starch technology (ref 5 ) with an organic polymer to produce a cationic starch-based product with a hydrophobic component. The chemistry allows for variations in the degree of hydrophobic enhancement. The resulting unique product, which will be referred to as a hydrophobic low molecular weight cationic starch (HLWCS) in this article, is produced as a milky brown water emulsion. Sizing is achieved by charge attraction to the negatively charged fibres, and subsequent retention in the web during the papermaking process. The product appears to perform at all pHs in the 4 9 range, does not appear to require curing to attain sizing levels, and does not require sintering to fully develop sizing characteristics. Application in mechanical grades Laboratory Studies Initial lab results with a typical mechanical pulp furnish (fig. 4) indicate that the development of hydrophobicity increases with dosage, and degree of polymeric size enhancement in the product chemistry.

Fig 4 Hydrophobicity Development with HLWCS Polymeric Size

Mechanical Grade - 30% SBK / 70% TMP

HLWCS 1 - low polym eric size enhancem ent HLWCS 2 - high polym eric size enhancem ent

Water Drop, seconds

300 250 200 150 100 50 0 0 1 2 3 4 5 6 7

HLWCS Dosage, kg/T

A further lab study looked at the performance of different sizing products (and other chemistries) on the hydrophobicity, strength preservation, and hygroexpansivity of a filled lightweight mechanical paper furnish. At the dosages applied, ASA size was seen to be the most effective at developing hydrophobicity (fig. 5) but this was accompanied by some slight strength deterioration (fig 6.). Cationic wet end starch showed the best strength preservation, but hydrophobicity increase was minimal (fig 7). HLWCS technology (fig 8) appears to represent a good compromise between soft sizing and strength development in mechanical grades. The overall relationship between strength and hydrophobicity is shown schematically in fig. 9.

Fig 5 Sizing and Strength Response with Different Sizing Chemistries

Filled Lightweight Mechanical Paper

100 90 80 Water Drop, seconds 70 60 50 40 30 20 10 0
Fibre Blank Fibre & Filler Low M W Wet End Wet HLWCS 1 HLWCS 2 Starch Starch Strength 8# /t 8# /t 8# /t 20# /T Resin 30# /T Rosin 30# /T AKD 4# /T ASA 4# /T

60 50 40 30 20 10 0 MD Internal Bond and Breaking Length

Water Drop

MD Breaking Length /100

MD Internal Bond

Fig 6 ASA Performance in Mechanical Paper

Filled Lightweight Mechanical Paper

80 70 60 50 40 30 20 1 0 0 Water Drop MD TEA CD TEA MD B.L./1 00 CD B.L./1 00 ASA 2#/t MD I.B. CD I.B.

Fibre Blank

Fibre +Filler Blank

ASA 4#/t

Fig 7 Starch Performance in Mechanical Paper

F illed L ig htw eig h t M ec ha n ica l P ap er

1 00 90 80 70 60 50 40 30 20 1 0 0 Water Drop M D TEA CD TEA MD B.L./1 00 CD B.L./1 00 M D I.B. CD I.B.

Fibre Blank

Fibre + Filler Blank

W .E. Starc h 1 0#/t

W .E. Starc h 2 0#/t

Legend TEA = B.L. = I.B. =

Total Energy Absorbed Breaking Length Internal Bond

Fig 8 HLWCS Polymeric Size Performance in Mechanical Paper

Filled Lightw eight Mechanical Paper

80 70 60 50 40 30 20 1 0 0 W ater Drop MD TEA CD TEA MD B.L./1 00 CD B.L./1 00 MD I.B. CD I.B.

F ib re B la n k

F ib re + F ille r B la n k

H LW C S 1 4#/t

H LW C S 2 8#/t

Fig 9 Strength/Hydrophobicity Relationships Strength Wet End Starch Low MW Cationic Starch HLWCS AKD, Rosin and ASA Slack sizing = printability Hard sized =Cobb sizing Hydrophobicity

The effect on hygroexpansivity was also studied. The results can be seen in fig 10. ASA had the lowest impact on web growth. Wet end starch addition produced the highest web hygroexpansion, presumably due to its hydrophilic attributes. HLWCS displays fairly low impact on hygroexpansion (fig 10). However when considering the combination of minimum hygroexpansivity increase and maximum strength preservation, ref fig 11, HLWCS technology represents a good opportunity.

Fig 10

Sizing Chemistry Impact on Hygroexpansion

Filled Lightweight Mechanical Paper

80 70 Water Drop, seconds 60 50 40 30 20 10 0
Fibre Blank Fibre + Low M W Filler Starch 8# /t W.E. Starch 20# /t Wet HLWCS1 HLWCS2 Strength 8# /t 8# /t Resin 30# /t Rosin 30# /t AKD 4# /t ASA 4# /t

0.14 0.135 0.13 0.125 0.12 0.115 0.11 0.105 0.1 Hygroexpansion Coefficient

Water Drop

Hygroexpansion Coefficient

Fig 11

Hygroexpansion vs.
TEA, J/m2


W e t E n d S t a r c h 10 # / t

W e t E n d S t a rc h 20# /t

L o w M W C a t .S t a r c h 8# /t

H LW C S 1

8# /t

W e t S t r e n g t h R e s in H LW C S 2 8# /t

F ib r e + F ille r C o n t r o l H LW C S 2 4 # / t

- 0 .0 1 5

- 0 .0 1

A SA 4# /t

H y g r o e xp a n si o n
A SA 2# /t

- 0 .0 0 5


0 .0 0 5

0 .0 1

0 .0 1 5

R o s in


Lab studies concluded that HLWCS technology is a viable soft sizing technology for development of required hydrophobicity and minimisation of hygroexpansivity in unfilled and filled mechanical grades without significantly compromising sheet strength.

Commercial Applications To date three separate commercial trials have been run in two applications. The applications were in newsprint and SC. System pHs were acid and neutral. Fillers were both clay and carbonate. Our agreements with these clients do not permit public disclosure of any detailed trial results. However, there are some things we can say in general about the performance of our soft sizing technology in these applications. 1. 2. 3. 4. 5. 6. 7. HLWCS was supplied as product in totes, and pre-diluted with mill water prior to addition to the thick stock. There were no operating problems with HLWCS technology in two trials. In one trial, some foaming, deaeration issues surfaced at higher dosages. In all three trials, addition of HLWCS technology generated improved first pass retention. Retention aid dosage was reduced to bring retention back to normal. In all trials, there was a noticeable increase in paper hydrophobicity to soft sizing levels, as measured by water drop. Paper strength changes were observed in two trials. One trial showed a significant increase in sheet dry and rewetted tensile strength. Another trial showed increase in internal bond. Other noticeable improvements in paper quality in one or more of these trials include slower water penetration rate, higher water drop contact angle, and improved wet pick resistance Initial commercial printing results indicate an observable improvement in print quality.

Further commercial trials will shortly be underway, and it is hoped specific data from these applications will be available in the near future. 5. SUMMARY Soft sizing of mechanical grades give papermakers an opportunity to improve paper quality to meet the demands of today's printers and printing presses, specifically in the areas of linting, paper strength and printability. Coating costs are also driving basepaper sizing technology as a means to improve coating holdout. Traditional hydrophobic sizes such as rosin, AKD and ASA are accepted technology for hard sizing of freesheet, board and liquid packaging grades. These products have found limited applications for soft sizing in mechanical grades. The wet end chemistry situation in mechanical grades taxes the effectiveness of these products due to issues of on site equipment, sizing efficiency, sizing consistency and predictability, size retention, hydrolysis/deposition, and compatibility with high filler levels. Polymeric sizing chemistry represents an emerging technology for mechanical grade soft sizing. A unique hydrophobic low molecular weight starch technology developed by Raisio Chemicals has demonstrated in both laboratory studies and commercial trials the ability to effectively soft size mechanical grades. The soft sized papers so far produced using this technology have displayed at least comparable strength, and improved wet pick resistance and printed quality, compared to the unsized paper. References 1. The Effects of peroxide bleaching on thermo-mechanical pulp self-sizing. J. Ness & K. Hodgson, Nordic Pulp and Paper Research Journal Vol 14 no. 2 1999 Principles of Wet End Chemistry W. Scott, TAPPI Press, 1996 Paper Chemistry second edition J. Roberts, Blackie Academic and Professional, 1996 Applications of Wet End Paper Chemistry C. Au and I. Thorn, Blackie Academic and Professional, 1995 Raibond A Novel Technology for Lint Suppression P. Rankin, Paper presented at PAPTAC Annual Conference, Montreal, Canada, Jan 1999.