CA2037525C - Cationic polymer-modified filler material, process for its preparation and method for its use in papermaking - Google Patents
Cationic polymer-modified filler material, process for its preparation and method for its use in papermakingInfo
- Publication number
- CA2037525C CA2037525C CA002037525A CA2037525A CA2037525C CA 2037525 C CA2037525 C CA 2037525C CA 002037525 A CA002037525 A CA 002037525A CA 2037525 A CA2037525 A CA 2037525A CA 2037525 C CA2037525 C CA 2037525C
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- Prior art keywords
- filler
- filler material
- dimer
- acid
- cationic polymer
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/17—Ketenes, e.g. ketene dimers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Paper (AREA)
Abstract
Material, such as natural ground and precipitated calcium carbonate, when modified by surface-treatment with a cationic polymer, has been discovered to be highly effective as a filler material in the making of paper.
Utilization of this type of filler material greatly improves the papermaking process by reducing the usage of wet end sizing agent, improving opacity, improving filler retention in the furnish, and causing better drainage on the papermachine, all of which result in the production of a high quality paper having excellent opacity and tensile strength characteristics. The nature of the polymer-modified filler material, the process for its preparation and the method of its use in papermaking are disclosed.
Utilization of this type of filler material greatly improves the papermaking process by reducing the usage of wet end sizing agent, improving opacity, improving filler retention in the furnish, and causing better drainage on the papermachine, all of which result in the production of a high quality paper having excellent opacity and tensile strength characteristics. The nature of the polymer-modified filler material, the process for its preparation and the method of its use in papermaking are disclosed.
Description
~ o~ ~52~ PC7749 CATIONIC POLYMER-MODIFIED FILLER MATERIAL, PROCESS FOR ITS PREPARATION AND
METHOD OF ITS USE IN PAPERMAKING
This invention broadly relates to the field of surface treated inorganic compounds. More particularly, the invention relates to the provision of compositions suitable for use as a papermaking filler material wherein an inorganic base filler material is surface treated with a substance which enhances the performance of the filler in the papermaking process. The invention also relates to a method for improving the papermaking process, especially by reducing the requirement for sizing material and for improving the characteristics of paper produced according to the process.
Adequate internal sizing of alkaline papers is an important issue for most papermakers. Early development of cellulose reactive sizing agents resulted in poor control of sizing with excessive amounts of sizing agent used, resulting in increased wet-end deposits, press picking, and in coefficient of friction problems with the paper surface.
Problems still occur, mainly due to the overuse of sizing materials. The problems are caused by high surface area materials (e.g., filler and fines) found in the wet-end, which adsorb the size and render it ineffective.
The purpose of internal sizing is to impart resistance to liquid penetration to the sheet. Internal sizing, along with sheet porosity (which is controlled at the size press), controls ink penetration in printing and writing papers, along with binder migration in coating basestock. The sizing of alkaline papers with cellulose reactive sizing agents or "synthetic sizes" has been established for more than 30 years. Two synthetic sizes presently in commercial use, alkyl ketene dimer tAKD) and alkenyl succinic anhydride (ASA), impart sizing to the sheet by means of a chemical reaction (covalent bonding) with the hydroxyl groups of cellulose fiber.
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METHOD OF ITS USE IN PAPERMAKING
This invention broadly relates to the field of surface treated inorganic compounds. More particularly, the invention relates to the provision of compositions suitable for use as a papermaking filler material wherein an inorganic base filler material is surface treated with a substance which enhances the performance of the filler in the papermaking process. The invention also relates to a method for improving the papermaking process, especially by reducing the requirement for sizing material and for improving the characteristics of paper produced according to the process.
Adequate internal sizing of alkaline papers is an important issue for most papermakers. Early development of cellulose reactive sizing agents resulted in poor control of sizing with excessive amounts of sizing agent used, resulting in increased wet-end deposits, press picking, and in coefficient of friction problems with the paper surface.
Problems still occur, mainly due to the overuse of sizing materials. The problems are caused by high surface area materials (e.g., filler and fines) found in the wet-end, which adsorb the size and render it ineffective.
The purpose of internal sizing is to impart resistance to liquid penetration to the sheet. Internal sizing, along with sheet porosity (which is controlled at the size press), controls ink penetration in printing and writing papers, along with binder migration in coating basestock. The sizing of alkaline papers with cellulose reactive sizing agents or "synthetic sizes" has been established for more than 30 years. Two synthetic sizes presently in commercial use, alkyl ketene dimer tAKD) and alkenyl succinic anhydride (ASA), impart sizing to the sheet by means of a chemical reaction (covalent bonding) with the hydroxyl groups of cellulose fiber.
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All commonly used untreated fillers (e.g., clay, titanium dioxide, calcium carbonate) are known to have a detrimental effect on sizing. Studies of alkaline papers filled with various types of calcium carbonate have revealed strong inverse correlations between filler specific surface area and internal sizing values in the sheet measured by the Hercules size test (HST). In circumstances where increasing the filler content would be advantageous, associated sizing problems have occurred affecting sheet quality, machine performance, and runnability.
Specially modified precipitated calcium carbonate (PCC) fillers, which can be synthesized at an on-site PCC plant, have been developed to make the sizing of filled sheets more economical and efficient. Laboratory results have shown that by using a chemically modified PCC filler, which has been surface treated with a cationic polymer, the amount of sizing agent can be reduced by one-half while improving other properties as well.
It has been discovered that the addition of certain cationic resin materials to papermaking filler materials such as calcium carbonate, either ground natural calcium carbonate from limestone, or precipitated, greatly enhances the performance of the filler material and results in a paper requiring the addition of substantially less wet end sizing agent, and having excellent opacity and tensile strength properties.
Fig. 1 is a plot of Hercules size measurement versus filler content for handsheets containing modified and unmodified fillers.
Fig. 2 is a plot of water pick-up as measured by the Cobb size test versus filler content for handsheets containing modified and unmodified fillers.
Fig. 3 is a plot of Hercules size measurement versus filler content for handsheets containing modified filler at 35 ~various levels of polymer treatment.
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Fig. 4 is a plot of Hercules size measurement versus filler content for handsheets containing modified and unmodified fillers at different sizing levels.
Fig. 5 is a plot of sheet opacity versus filler content for handsheets containing modified and unmodified fillers.
Fig. 6 is a plot of sheet opacity versus sheet tensile strength for handsheets containing modified and unmodified fillers.
Fig. 7 is a plot of sheet brightness versus filler content for handsheets containing modified and unmodified fillers.
Fig. 8 is a plot of Hercules size measurement versus filler content for sheets containing modified and unmodified fillers made on a pilot papermachine.
Fig. 9 is a plot of water pick-up as measured by the Cobb size test versus filler content for sheets containing modified and unmodified fillers made on a pilot papermachine.
Fig. 10 is a plot of corrected sheet opacity versus filler content for sheets containing modified and ummodified fillers made on a pilot papermachine.
Fig. 11 shows comparative microscopic photographs illustrating distribution of filler material for sheets containing modified and unmodified fillers made on a pilot papermachine.
Fig. 12 represents a three-dimensional plot of Hercules size measurement versus treatment temperature and percent cationic polymer treatment level at an 8% filler level in the handsheets.
Fig. 13 represents a three-dimensional plot of Hercules size measurement versus treatment temperature and percent cationic polymer treatment level at an 16% filler level in the handsheets.
Fig. 14 represents a three-dimensional plot of Hercules size measurement versus treatment temperature and percent cationic polymer treatment level at an 24% filler level in the handsheets.
The cationic ~polymers found to be most effective for surface treating the papermaking filler materials are dimers of the general formula:
R - CH = C - fH - R
o - C = O
where R is a hydrocarbon group selected from the group consisting of alkyl with at least 8 carbon atoms, cycloalkyl with at least 6 carbon atoms, aryl, aralkyl and alkaryl.
Specific dimers are octyl-, decyl-, dodecyl-, tetradecyl-, hexadecyl-, octadecyl-, eikosyl-, dokosyl-, tetrakosyl-, phenyl-, benzyl-beta-naphthyl-, and cyclohexyl- dimer.
Other utilizable dimers are dimers produced from mining acids, naphthenic acid, delta-9,10-decylenic acid, delta-9,10 dodecylenic acid, palmitoline acid, olein acid, ricine olein acid, linoleate, linoleic acid, and olestearic acid, as well as dimers manufactured from natural fatty acid mixtures, such as are obtained from cocoanut oil, babassu oil, palm seed oil, palm oil, olive oil, peanut oil, rape seed oil, beef suet and lard, and mixtures of the above.
The polymer is made cationic as a result of treating the dimer with a polyamino-amide and/or polyamine polymer reacted with an epoxidized halohydrin compound, such as epichlorohydrin, thereby forming tertiary and quaternary amine groups on the dimer surface. It is preferred that the cationic charge on the dimer be derived primarily from quaternary amine groups. A polymer material of this type is manufactured by and is commercially available from Hercules, Inc., Wilmington, DE, under the tradename Hercon.
It has been discovered that the use of from about 0.1%
to about 10.0% by weight of the cationic polymer material on a filler significantly enhances filler performance in terms of a reduction in the requirement for the addition of wet end sizing agent and an improvement in the optical and physical properties, particularly opacity, Z-directional filler distribution and tensile strength, of the resulting paper in which the filler is utilized.
*Trademark 2~3~52~
For the case of utilizing clay as a filler material, it has been discovered that surface treatment of the filler with from about 1.0 to about 2.0 weight percent of a cationic polymer material of the aforesaid type is effective in producing a filler clay having a substantially reduced sizing demand.
It has also been discovered that surface treatment of a PCC filler material with from about 0.25 to about 2.0 weight percent of a cationic polymer material of the aforesaid type is effective in producing a filler having a substantially reduced sizing demand.
Other filler materials, such as titanium dioxide, talc and silica/silicate pigments, which if used untreated have a detrimental effect on sizing, are utilizable when treated with a cationic polymer material of the aforesaid type according to the present invention.
For all types of fillers, it has been discovered that the amount of cationic polymer required to be added to the filler material-containing slurry is directly correlated with the surface area of the filler material.
It has further been discovered that the temperature at which the filler material is treated with the cationic polymer is also a significant parameter in determining the extent to which the sizing demand of the polymer-treated filler is reduced.
Generally, treatment of the aqueous slurry containing the filler material with the cationic polymer is done at a temperature of from about 5 to 70C. The preferred treatment temperature range is from about 20 to 30C, and the most preferred treatment temperature is at about 25OC.
It has still further been discovered that the pH of the aqueous slurry containing the filler material has an effect on treatment. The slurry should not be at a pH greater than 10 at the time of the treatment. The filler material treated with the cationic polymer should also subsequently be stored at a pH not greater than 10 to prevent decomposition of the cationic polymer coating which occurs at pH's greater than about 10.
The nature and scope of the present invention may be more fully understood in view of the following non-limiting examples, which demonstrate the effectiveness of cationic polymer modified filler materials.
ExamPle 1 Preparation and ComParative Testing of Handsheets Containing Modified and Unmodified Fillers Comparative Formax (Noble and Wood) handsheets (60 g/m2 or 40 lbs./3300 ft2) were prepared from a furnish consisting of 75% bleached hardwood and 25% bleached softwood Kraft pulps beaten to 400 Canadian Standard Freeness (CSF) at pH
7.0 in distilled water. A high molecular weight, medium charge density, cationic polyacrylamide (PAM) retention aid was used at 0.05%. Synthetic sizing agents (AKD or ASA) were added at levels from 0.10% to 0.30%. Several fillers were used, including various polymer-modified PCC fillers to test the effect of the polymer treatment against unmodified PCC and fine ground limestone (FGL). The fillers were added to the furnish at 20% solids to achieve 8%, 16%, 24% and 40%
filler in the finished sheets. In addition, a blank, containing no filler was prepared and tested. Distilled water was used throughout the handsheet process. The sheets were conditioned at 50% RH and 23C and tested for grammage, percent filler, HST, Cobb size, opacity, brightness, caliper, tensile, and porosity. Scattering coefficients were determined using the appropriate reflectance values and Kubelka-Munk equations. Elemental mapping of the filler distribution in the sheet, both in the XY plane and in the Z-directional plane, was performed using a scanning electron microscope (SEM) with elemental analysis capabilities.
Sizing values (HST and Cobb) for sheets filled with the modified PCC fillers were significantly improved, with higher levels of polymer on the PCC providing significantly better sizing at all loading levels greatér than 10% versus a low sizing demand filler (e.g., FGL) (Figs. 1, 2, and 3).
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Comparable sheets can be made using one-third less sizing agent when a 0.5 percent by weight cationic polymer-treated PCC filler was used (Fig.4), and as the graph reveals, even less sizing agent was needed using a 1.0 percent by weight cationic polymer-treated PCC filler. Table I also shows the efficiency of polymer treatment of the filler.
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TAB~E I
Improvements in Paper ProPerties by Surface Treatment of Filler with ARD Resin (16% filler in sheet) % AKD* % AKD* Sheet added added Opacity Brightness HST
to pulp to filler (%) (%) (seconds) 0.4~ 0 87.7 84.3 158 0 0.4% 88.5 85.7 335 0.6% 0 87.9 83.9 361 0 0.6% 88.9 84.9 434 * Percentage based on total furnish.
A secondary benefit derived from the modified fillers was an increase of one-half point in opacity without a subsequent loss in tensile strength or sheet brightness (Figs. 5, 6, and 7). The increased opacity without loss of strength or brightness appears to be predominately due to the substantial increase in the cationic charge of the modified filler particles. Increasing the cationic charge on the particles makes them adsorb more uniformly on the fiber surface and less between fiber crossings. Scanning electron micrographs revealed better distribution of the filler in the sheet for the modified PCC fillers which supports improved optical performance. Table II shows the relationship between the filler's specific surface area and polymer treatment level on sizing values.
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TAB~E II
Effect of Surface Area and PolYmer Treatment Level on Sizinq 5Specific SurfacePolymer HST (sec) Area of CaC03 Treatment(filler in sheet) Fillers (m2/q) Level (%) 8% 16% 24%
5.9 0.0 322 246 38 0.5 354 440 626 1.0 413 542 807 7.2 0.0 219 114 6 0.5 287 411 556 1.0 316 484 779 8.7 0.0 147 5 0.5 234 226 44 1.0 301 473 871 10.8 0.0 117 8 0.5 214 215 36 1.0 259 430 442 22.7 0.0 101 4 0.5 184 33 2 1.0 239 140 11 Blanks (no filler) = 1876 seconds 0.25% AKD added to furnish At higher surface area, more polymer is needed to cover the surface and provide improved sizing. Unexpectedly, as the filler level is increased in the sheet, the sizing values continue to rise for all but the highest surface area filler. This indicates that by the method of treatment of this invention, increased sizing is maintainable through the use of higher filler levels in the sheet. This condition cannot be achieved by the use of untreated fillers.
-lo- 2Q37525 Example 2 Evaluation of Modified PCC Fillers for Retention and Drainaqe.
A vacuum drainage jar apparatus was used to measure the retention and drainage characteristics of the fillers under conditions similar to an actual high-speed paper-machine.
The furnish was the same as used in Example 1 with the retention aid level evaluated at 0.05%. The fillers were added so that a content of 16% +/- 1.0~ would be retained in the final pad. The stock (0.5% consistency) was agitated in a three vane jar at 750 rpm. Automatic control placed the contents of the jar under a vacuum of 10 kPa during initial drainage followed by 5 seconds of high vacuum (50 kPa). The pad which formed was weighed and then dried and reweighed to yield percent sheet dryness values (these numbers predict the ease at which water is removed from the sheet). Percent filler retention was calculated from the amount of calcium carbonate in the fiber pad via X-ray fluorescence and the known amount added to the stock.
Improved papermachine runnability can be measured in many ways. Improved drainage on the wire along with increased sheet dryness off the couch provides the paper-maker with the opportunity to increase machine speed (increase production rate) and/or decrease steam consumption at the dryers (increased profitability). Improved filler retention without the need to use excessive amounts of retention aid enhances sheet quality which includes formation. This also leads to better runnability and economics from a cleaner wet end system. Retention and drainage results, shown in Table III, using a vacuum drainage jar revealed improved first pass filler retention for the modified PCC fillers.
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TAB~E III
~rain~e/Retention Data on Polymer Treated CaCO~
16% Filler In Pad Drainage Rate First Pass (cc/sec)~/Sheet Filler Retention Dryness (%) b Unfilled Sheet112/19.8 PCC 87/22.2 72.0 PCC-modified with 0.5% polymer 91/22.5 77.4 PCC-modified with 1.0% polymer 94/22.7 76.4 ' Confidence Level (C.L.) @ +/- 3 cc/sec b C.L. Q +/- 0.2 Sheet dryness values were also improved over the untreated PCC filler, indicating better drainage. The experiments were conducted under precise and well-controlled conditions in the laboratory, however these results are transferable to a papermachine leading to better wet end control with improved runnability, as is shown in Examples 3 and 4, following.
Example 3 Comparative Testinq of Furnishes Incorporatinq Both Modified and Unmodified Fillers on Actual Pilot Papermachine.
A pilot machine run was conducted utilizing a pilot scale papermachine. A 60 g/m2 (40 lbs./3300 ft2) sheet was produced using the same furnish composition as in Examples 1 and 2. The same cationic retention aid was utilized at 0.0125% and an AKD sizing agent was added at 0.15%. Various calcium carbonate fillers (i.e., untreated commercial PCC, untreated commercial FGL, 0.5 and 1.0 percent by weight ~ 12- 2037525 cationic polymer-modified PCC's) were added to achieve levels of 8%, 16%, and 24% filler in the sheet.
The paper was tested for the same properties as in Example 1.
The fillers were characterized with respect to particle size by gravity sedimentation analysis using a Micromeritics *
Sedigraph 5000D. Specific surface area was determined by the use of BET nitrogen adsorption analysis. Dry brightness was measured using a Hunter LabScan. Particle charge (zeta potential) was determined using doppler laser light scattering technique from a Coulter DELSA 440. Filler properties are listed in Table IV.
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Results from the pilot papermachine corroborated the results from the handsheet work. Sizing values shown in Figs. 8 and 9 reveal the improved sizing performance for the modified PCC fillers. Since the Hercules size test (HST) was not sensitive enough to distinguish between sizing differences at the low end, the Cobb test was used to better ascertain their performance. The Cobb sizing test results show the characteristic increase in water pick-up for the commercial fillers (i.e., FGL and PCC) with increasing filler loading. This increase is virtually eliminated when utilizing the modified PCC fillers. In addition, l.0 percent by weight cationic polymer-modified PCC filler provides essentially the same resistance to water pick-up at all filler loading levels as the unfilled sheet using the equivalent amount of sizing agent. Print quality evaluated through microscopic analysis of half-tone dots shows a marked improvement in ink hold-out in sheets using the modified PCC fillers.
There was a one-half point improvement in opacity, corroborating laboratory results (Fig. 10). Calcium elemental mapping of the filler distribution in the sheet (Fig. 11) revealed better distribution, especially in the Z-directional plane, for the modified PCC fillers.
Example 4 Comparative Testinq of Furnishes IncorPoratinq Both Modified and Unmodified Fillers on a Production Papermachine.
A mill trial was conducted utilizing a Fourdrinier papermachine running at 2000 fpm. A 60 g/m (40 lbs/-3300 ft) high opacity sheet was run with and without a modified PCC filler as part of the furnish composition. The modified PCC filler was treated with 1.5 percent by weight of cationic polymer. An anionic retention aid was utilized along with an ASA sizing agent. Both additives were held constant throughout the trial. Handbox and white-water tray samples were obtained throughout the trial and analyzed for first pass filler retention and total retention. These results are shown in Table V.
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TABLB V
Retention Results from Mill Trial Untreated 1.5 Wt~% Cationic Commercial Polymer-Modified PCC PCC
Total Retention (%) 78.3 80.7 First-Pass Filler Retention (%) 50.0 56.1 % Filler (felt side) 22.7 18.6 ~ Filler (wire side) 19.4 17.7 Significant improvement in both filler retention and total retention were realized. Z-directional distribution of the modified filler through the sheet was also greatly improved. Better distribution of the filler means less two-sidedness, better dimensional stability and better printability of the paper with less associated whitening and dusting (Table V). Paper samples were tested and revealed a 263% improvement in sizing (i.e. 40 sec. vs. 11 sec.) and equivalent opacity with 4.5% less PCC (i.e. 15.0% vs. 15.7%) and 25% less Tio2 (0.6% vs 0.8%). A 9% improvement in tensile strength was also realized. These results are shown in Table VI.
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TABLE VI
Physical Properties from Mill Trial Untreated 1.5 Wt.~ Cationic Commercial Polymer-Modified PCC PCC
Basis Weight (lb/3300 ft) 39,0 40.1 PCC (%) 15.7 15.0 TiO2 (%) 0.8 0.6 Total Filler (%) 16.5 15.6 Corrected Opacity (%) 88.3 88.2 Machine Direction Breaking Length (km) 7.77 8.50 Hercules Size Test (sec.) 11 40 Loss of sizing, referred to as "fugitive sizing", was evaluated after 5 weeks (35 days). The results are shown in Table VII.
TAB~E VII
Fugitive 8izinq Results from Mill Trial (Reel No. 6 and 10) 1.5'Wt.%
Cationic Untreated Polymer-Commercial Modified PCC PCC
Hercules Size Test (sec) 9 37 (initial testing) Hercules Size Test (sec) 7 36 (35 days later) Percent Change in Sizing (%)-22 -3 ~37~25 The samples showed a minimum loss of sizing compared to typical commercially filled sheets. The surface coefficient of friction of the sheets was also evaluated. The surface coefficient of friction of the sheets is an important measure of the runnability of the paper through high-speed reprographic equipment. The results of this evaluation are shown in Table VIII.
Table VIII
Coefficient of Friction (COF) on Surfaoe of Paper from Mill Trial Untreated1.5 Wt.% Cationic CommercialPolymer-Modified PCC PCC
COF* (static) .308 .385 COF* (dynamic) .214 .281 * results reported as qrams force sled weight (grams) Contact: felt-to-wire side The polymer-modified PCC-filled sheets showed a better coefficient of friction of the sheet surface than the unmodified sheets.
Example 5 Effect of Filler Treatment TemPerature on Sizing Demand Reduction at Various Levels of Cationic PolYmer Treatment and Filler Loadinq A handsheet study was performed to evaluate the effect of filler treatment temperature, that is, the temperature at which the cationic polymer is applied to the filler material, on reduction in the sizing demand in the handsheets utilizing the cationic polymer-treated filler.
Treatment was at temperatures in the range of from 25-650C.
Treatment was performed at levels of from 0 to 1.25 weight percent of cationic polymer. The cationic polymer used was an alkyl ketene dimer, Hercon-85 ~(Hercules, Inc., Wilmington, DE). The filler was a precipitated calcium carbonate (PCC) (Albacar H0, Pfizer, Inc., New York).
Filler loading in the handsheets was at several levels, of from 8 to 24 weight percent of treated filler.
Twenty separate surface treatments were performed using four treatment levels (0.5, 0.75, 1.0 and 1.25 wt %) and five treatment temperatures (25, 35, 45, 55 and 65C), along with an untreated control sample, as shown in Table IX.
TABLE IX
Bample Filler Level and Treatment TemPerature Cationic Polymer Treatment Treatment Level Temperature 20Sample # (Wt. ~) (C) Control None 25 1 0.5 25 2 0.75 25 25 3 1.0 25 4 1.25 25 0.5 35 6 0.75 35 7 1.0 35 30 8 1.25 35 9 0.5 45 0.75 45 11 1.0 45 12 1.25 45 3513 0.5 55 14 0.75 55 1.0 55 16 1.25 55 17 0.5 65 4018 0.75 65 19 1.0 65 1.25 65 All treatments were performed using 10 minutes of low-shear mixing time per sample. Elevated temperatures were *Trademark . -;, 2037~25 maintained for approximately 4 hours before samples were allowed to cool.
Comparative Formax (Noble and Wood) handsheets (60 g/m2 or 40 lbs./3300 ft2) were prepared from a furnish blend consisting of 75% bleached hardwood and 25% bleached softwood Kraft pulps beaten to a consistency of 0.3125% and a Canadian Standard Freeness (CSF) of 400 +25 at pH 7.0 in distilled water. Additional wet end additives included an alkyl ketene dimer size (Hercon-75, Hercules, Inc., Wilmington, DE) in an amount of 0.25 wt. % (5 lb/ton of paper) and a cationic polycacrylamide retention aid (Percol-175) in an amount of 0.05 at ~ (1 lb/ton of paper). All sheets were conditioned and tested at standard TAPPI
conditions of 50% relative humidity and 23C.
Paper properties tested include size, opacity, pigment scattering coefficient and sheet brightness~ Size was tested by the Hercules Size Test. Reported values are in seconds. Opacity was tested by the TAPPI test. Reported values are Corrected opacity, %. Sheet brightness was tested by the TAPPI test. Reported values are Brightness, ~. The results are reported in Table X.
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rq The results show that HST values are directly proportional to filler treatment level, that is, the higher the treatment level, the higher the HST response, and inversely proportional to treatment temperature, that is, the higher the slurry treatment temperature, the lower the HST response. Thus, the highest sizing values (greatest sizing demand reduction) occurred at high treatment level and low treatment temperature, while low treatment level and high treatment temperature resulted in poorer size reduction performance. The magnitude of the effect varied considerably, however, with filler level in the handsheets.
This is shown in Figures 12, 13 and 14. In Fig. 12, at an 8% filler level, the effect of both treatment level and treatment temperature on HST is minimal, with HST values ranging from a low of 193 seconds to a high of 237 seconds.
In Fig. 13, at a 16~ filler level, the effect is more noticeable, with HST values ranging from 35 seconds to 392 seconds. Finally, as is seen in Fig. 14, at a 24% filler level, a significant effect is seen, with HST values ranging from 2 to 313 seconds and a very steep transition occurring from lower to higher treatment levels and higher to lower treatment temperature. Treatment level is, however, a more sensitive variable than treatment temperature since a small change in treatment level produces a more drastic HST shift than does a small change in temperature.
Specially modified precipitated calcium carbonate (PCC) fillers, which can be synthesized at an on-site PCC plant, have been developed to make the sizing of filled sheets more economical and efficient. Laboratory results have shown that by using a chemically modified PCC filler, which has been surface treated with a cationic polymer, the amount of sizing agent can be reduced by one-half while improving other properties as well.
It has been discovered that the addition of certain cationic resin materials to papermaking filler materials such as calcium carbonate, either ground natural calcium carbonate from limestone, or precipitated, greatly enhances the performance of the filler material and results in a paper requiring the addition of substantially less wet end sizing agent, and having excellent opacity and tensile strength properties.
Fig. 1 is a plot of Hercules size measurement versus filler content for handsheets containing modified and unmodified fillers.
Fig. 2 is a plot of water pick-up as measured by the Cobb size test versus filler content for handsheets containing modified and unmodified fillers.
Fig. 3 is a plot of Hercules size measurement versus filler content for handsheets containing modified filler at 35 ~various levels of polymer treatment.
-%037~
Fig. 4 is a plot of Hercules size measurement versus filler content for handsheets containing modified and unmodified fillers at different sizing levels.
Fig. 5 is a plot of sheet opacity versus filler content for handsheets containing modified and unmodified fillers.
Fig. 6 is a plot of sheet opacity versus sheet tensile strength for handsheets containing modified and unmodified fillers.
Fig. 7 is a plot of sheet brightness versus filler content for handsheets containing modified and unmodified fillers.
Fig. 8 is a plot of Hercules size measurement versus filler content for sheets containing modified and unmodified fillers made on a pilot papermachine.
Fig. 9 is a plot of water pick-up as measured by the Cobb size test versus filler content for sheets containing modified and unmodified fillers made on a pilot papermachine.
Fig. 10 is a plot of corrected sheet opacity versus filler content for sheets containing modified and ummodified fillers made on a pilot papermachine.
Fig. 11 shows comparative microscopic photographs illustrating distribution of filler material for sheets containing modified and unmodified fillers made on a pilot papermachine.
Fig. 12 represents a three-dimensional plot of Hercules size measurement versus treatment temperature and percent cationic polymer treatment level at an 8% filler level in the handsheets.
Fig. 13 represents a three-dimensional plot of Hercules size measurement versus treatment temperature and percent cationic polymer treatment level at an 16% filler level in the handsheets.
Fig. 14 represents a three-dimensional plot of Hercules size measurement versus treatment temperature and percent cationic polymer treatment level at an 24% filler level in the handsheets.
The cationic ~polymers found to be most effective for surface treating the papermaking filler materials are dimers of the general formula:
R - CH = C - fH - R
o - C = O
where R is a hydrocarbon group selected from the group consisting of alkyl with at least 8 carbon atoms, cycloalkyl with at least 6 carbon atoms, aryl, aralkyl and alkaryl.
Specific dimers are octyl-, decyl-, dodecyl-, tetradecyl-, hexadecyl-, octadecyl-, eikosyl-, dokosyl-, tetrakosyl-, phenyl-, benzyl-beta-naphthyl-, and cyclohexyl- dimer.
Other utilizable dimers are dimers produced from mining acids, naphthenic acid, delta-9,10-decylenic acid, delta-9,10 dodecylenic acid, palmitoline acid, olein acid, ricine olein acid, linoleate, linoleic acid, and olestearic acid, as well as dimers manufactured from natural fatty acid mixtures, such as are obtained from cocoanut oil, babassu oil, palm seed oil, palm oil, olive oil, peanut oil, rape seed oil, beef suet and lard, and mixtures of the above.
The polymer is made cationic as a result of treating the dimer with a polyamino-amide and/or polyamine polymer reacted with an epoxidized halohydrin compound, such as epichlorohydrin, thereby forming tertiary and quaternary amine groups on the dimer surface. It is preferred that the cationic charge on the dimer be derived primarily from quaternary amine groups. A polymer material of this type is manufactured by and is commercially available from Hercules, Inc., Wilmington, DE, under the tradename Hercon.
It has been discovered that the use of from about 0.1%
to about 10.0% by weight of the cationic polymer material on a filler significantly enhances filler performance in terms of a reduction in the requirement for the addition of wet end sizing agent and an improvement in the optical and physical properties, particularly opacity, Z-directional filler distribution and tensile strength, of the resulting paper in which the filler is utilized.
*Trademark 2~3~52~
For the case of utilizing clay as a filler material, it has been discovered that surface treatment of the filler with from about 1.0 to about 2.0 weight percent of a cationic polymer material of the aforesaid type is effective in producing a filler clay having a substantially reduced sizing demand.
It has also been discovered that surface treatment of a PCC filler material with from about 0.25 to about 2.0 weight percent of a cationic polymer material of the aforesaid type is effective in producing a filler having a substantially reduced sizing demand.
Other filler materials, such as titanium dioxide, talc and silica/silicate pigments, which if used untreated have a detrimental effect on sizing, are utilizable when treated with a cationic polymer material of the aforesaid type according to the present invention.
For all types of fillers, it has been discovered that the amount of cationic polymer required to be added to the filler material-containing slurry is directly correlated with the surface area of the filler material.
It has further been discovered that the temperature at which the filler material is treated with the cationic polymer is also a significant parameter in determining the extent to which the sizing demand of the polymer-treated filler is reduced.
Generally, treatment of the aqueous slurry containing the filler material with the cationic polymer is done at a temperature of from about 5 to 70C. The preferred treatment temperature range is from about 20 to 30C, and the most preferred treatment temperature is at about 25OC.
It has still further been discovered that the pH of the aqueous slurry containing the filler material has an effect on treatment. The slurry should not be at a pH greater than 10 at the time of the treatment. The filler material treated with the cationic polymer should also subsequently be stored at a pH not greater than 10 to prevent decomposition of the cationic polymer coating which occurs at pH's greater than about 10.
The nature and scope of the present invention may be more fully understood in view of the following non-limiting examples, which demonstrate the effectiveness of cationic polymer modified filler materials.
ExamPle 1 Preparation and ComParative Testing of Handsheets Containing Modified and Unmodified Fillers Comparative Formax (Noble and Wood) handsheets (60 g/m2 or 40 lbs./3300 ft2) were prepared from a furnish consisting of 75% bleached hardwood and 25% bleached softwood Kraft pulps beaten to 400 Canadian Standard Freeness (CSF) at pH
7.0 in distilled water. A high molecular weight, medium charge density, cationic polyacrylamide (PAM) retention aid was used at 0.05%. Synthetic sizing agents (AKD or ASA) were added at levels from 0.10% to 0.30%. Several fillers were used, including various polymer-modified PCC fillers to test the effect of the polymer treatment against unmodified PCC and fine ground limestone (FGL). The fillers were added to the furnish at 20% solids to achieve 8%, 16%, 24% and 40%
filler in the finished sheets. In addition, a blank, containing no filler was prepared and tested. Distilled water was used throughout the handsheet process. The sheets were conditioned at 50% RH and 23C and tested for grammage, percent filler, HST, Cobb size, opacity, brightness, caliper, tensile, and porosity. Scattering coefficients were determined using the appropriate reflectance values and Kubelka-Munk equations. Elemental mapping of the filler distribution in the sheet, both in the XY plane and in the Z-directional plane, was performed using a scanning electron microscope (SEM) with elemental analysis capabilities.
Sizing values (HST and Cobb) for sheets filled with the modified PCC fillers were significantly improved, with higher levels of polymer on the PCC providing significantly better sizing at all loading levels greatér than 10% versus a low sizing demand filler (e.g., FGL) (Figs. 1, 2, and 3).
~Trademark ~ J ~
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Comparable sheets can be made using one-third less sizing agent when a 0.5 percent by weight cationic polymer-treated PCC filler was used (Fig.4), and as the graph reveals, even less sizing agent was needed using a 1.0 percent by weight cationic polymer-treated PCC filler. Table I also shows the efficiency of polymer treatment of the filler.
2~37~2~
TAB~E I
Improvements in Paper ProPerties by Surface Treatment of Filler with ARD Resin (16% filler in sheet) % AKD* % AKD* Sheet added added Opacity Brightness HST
to pulp to filler (%) (%) (seconds) 0.4~ 0 87.7 84.3 158 0 0.4% 88.5 85.7 335 0.6% 0 87.9 83.9 361 0 0.6% 88.9 84.9 434 * Percentage based on total furnish.
A secondary benefit derived from the modified fillers was an increase of one-half point in opacity without a subsequent loss in tensile strength or sheet brightness (Figs. 5, 6, and 7). The increased opacity without loss of strength or brightness appears to be predominately due to the substantial increase in the cationic charge of the modified filler particles. Increasing the cationic charge on the particles makes them adsorb more uniformly on the fiber surface and less between fiber crossings. Scanning electron micrographs revealed better distribution of the filler in the sheet for the modified PCC fillers which supports improved optical performance. Table II shows the relationship between the filler's specific surface area and polymer treatment level on sizing values.
-9- 2~37~2~
TAB~E II
Effect of Surface Area and PolYmer Treatment Level on Sizinq 5Specific SurfacePolymer HST (sec) Area of CaC03 Treatment(filler in sheet) Fillers (m2/q) Level (%) 8% 16% 24%
5.9 0.0 322 246 38 0.5 354 440 626 1.0 413 542 807 7.2 0.0 219 114 6 0.5 287 411 556 1.0 316 484 779 8.7 0.0 147 5 0.5 234 226 44 1.0 301 473 871 10.8 0.0 117 8 0.5 214 215 36 1.0 259 430 442 22.7 0.0 101 4 0.5 184 33 2 1.0 239 140 11 Blanks (no filler) = 1876 seconds 0.25% AKD added to furnish At higher surface area, more polymer is needed to cover the surface and provide improved sizing. Unexpectedly, as the filler level is increased in the sheet, the sizing values continue to rise for all but the highest surface area filler. This indicates that by the method of treatment of this invention, increased sizing is maintainable through the use of higher filler levels in the sheet. This condition cannot be achieved by the use of untreated fillers.
-lo- 2Q37525 Example 2 Evaluation of Modified PCC Fillers for Retention and Drainaqe.
A vacuum drainage jar apparatus was used to measure the retention and drainage characteristics of the fillers under conditions similar to an actual high-speed paper-machine.
The furnish was the same as used in Example 1 with the retention aid level evaluated at 0.05%. The fillers were added so that a content of 16% +/- 1.0~ would be retained in the final pad. The stock (0.5% consistency) was agitated in a three vane jar at 750 rpm. Automatic control placed the contents of the jar under a vacuum of 10 kPa during initial drainage followed by 5 seconds of high vacuum (50 kPa). The pad which formed was weighed and then dried and reweighed to yield percent sheet dryness values (these numbers predict the ease at which water is removed from the sheet). Percent filler retention was calculated from the amount of calcium carbonate in the fiber pad via X-ray fluorescence and the known amount added to the stock.
Improved papermachine runnability can be measured in many ways. Improved drainage on the wire along with increased sheet dryness off the couch provides the paper-maker with the opportunity to increase machine speed (increase production rate) and/or decrease steam consumption at the dryers (increased profitability). Improved filler retention without the need to use excessive amounts of retention aid enhances sheet quality which includes formation. This also leads to better runnability and economics from a cleaner wet end system. Retention and drainage results, shown in Table III, using a vacuum drainage jar revealed improved first pass filler retention for the modified PCC fillers.
- -11- 203752~
TAB~E III
~rain~e/Retention Data on Polymer Treated CaCO~
16% Filler In Pad Drainage Rate First Pass (cc/sec)~/Sheet Filler Retention Dryness (%) b Unfilled Sheet112/19.8 PCC 87/22.2 72.0 PCC-modified with 0.5% polymer 91/22.5 77.4 PCC-modified with 1.0% polymer 94/22.7 76.4 ' Confidence Level (C.L.) @ +/- 3 cc/sec b C.L. Q +/- 0.2 Sheet dryness values were also improved over the untreated PCC filler, indicating better drainage. The experiments were conducted under precise and well-controlled conditions in the laboratory, however these results are transferable to a papermachine leading to better wet end control with improved runnability, as is shown in Examples 3 and 4, following.
Example 3 Comparative Testinq of Furnishes Incorporatinq Both Modified and Unmodified Fillers on Actual Pilot Papermachine.
A pilot machine run was conducted utilizing a pilot scale papermachine. A 60 g/m2 (40 lbs./3300 ft2) sheet was produced using the same furnish composition as in Examples 1 and 2. The same cationic retention aid was utilized at 0.0125% and an AKD sizing agent was added at 0.15%. Various calcium carbonate fillers (i.e., untreated commercial PCC, untreated commercial FGL, 0.5 and 1.0 percent by weight ~ 12- 2037525 cationic polymer-modified PCC's) were added to achieve levels of 8%, 16%, and 24% filler in the sheet.
The paper was tested for the same properties as in Example 1.
The fillers were characterized with respect to particle size by gravity sedimentation analysis using a Micromeritics *
Sedigraph 5000D. Specific surface area was determined by the use of BET nitrogen adsorption analysis. Dry brightness was measured using a Hunter LabScan. Particle charge (zeta potential) was determined using doppler laser light scattering technique from a Coulter DELSA 440. Filler properties are listed in Table IV.
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Results from the pilot papermachine corroborated the results from the handsheet work. Sizing values shown in Figs. 8 and 9 reveal the improved sizing performance for the modified PCC fillers. Since the Hercules size test (HST) was not sensitive enough to distinguish between sizing differences at the low end, the Cobb test was used to better ascertain their performance. The Cobb sizing test results show the characteristic increase in water pick-up for the commercial fillers (i.e., FGL and PCC) with increasing filler loading. This increase is virtually eliminated when utilizing the modified PCC fillers. In addition, l.0 percent by weight cationic polymer-modified PCC filler provides essentially the same resistance to water pick-up at all filler loading levels as the unfilled sheet using the equivalent amount of sizing agent. Print quality evaluated through microscopic analysis of half-tone dots shows a marked improvement in ink hold-out in sheets using the modified PCC fillers.
There was a one-half point improvement in opacity, corroborating laboratory results (Fig. 10). Calcium elemental mapping of the filler distribution in the sheet (Fig. 11) revealed better distribution, especially in the Z-directional plane, for the modified PCC fillers.
Example 4 Comparative Testinq of Furnishes IncorPoratinq Both Modified and Unmodified Fillers on a Production Papermachine.
A mill trial was conducted utilizing a Fourdrinier papermachine running at 2000 fpm. A 60 g/m (40 lbs/-3300 ft) high opacity sheet was run with and without a modified PCC filler as part of the furnish composition. The modified PCC filler was treated with 1.5 percent by weight of cationic polymer. An anionic retention aid was utilized along with an ASA sizing agent. Both additives were held constant throughout the trial. Handbox and white-water tray samples were obtained throughout the trial and analyzed for first pass filler retention and total retention. These results are shown in Table V.
~ 2~37~2~ .
TABLB V
Retention Results from Mill Trial Untreated 1.5 Wt~% Cationic Commercial Polymer-Modified PCC PCC
Total Retention (%) 78.3 80.7 First-Pass Filler Retention (%) 50.0 56.1 % Filler (felt side) 22.7 18.6 ~ Filler (wire side) 19.4 17.7 Significant improvement in both filler retention and total retention were realized. Z-directional distribution of the modified filler through the sheet was also greatly improved. Better distribution of the filler means less two-sidedness, better dimensional stability and better printability of the paper with less associated whitening and dusting (Table V). Paper samples were tested and revealed a 263% improvement in sizing (i.e. 40 sec. vs. 11 sec.) and equivalent opacity with 4.5% less PCC (i.e. 15.0% vs. 15.7%) and 25% less Tio2 (0.6% vs 0.8%). A 9% improvement in tensile strength was also realized. These results are shown in Table VI.
~ _ _ _ _ _ _ - ~ 2~37~
TABLE VI
Physical Properties from Mill Trial Untreated 1.5 Wt.~ Cationic Commercial Polymer-Modified PCC PCC
Basis Weight (lb/3300 ft) 39,0 40.1 PCC (%) 15.7 15.0 TiO2 (%) 0.8 0.6 Total Filler (%) 16.5 15.6 Corrected Opacity (%) 88.3 88.2 Machine Direction Breaking Length (km) 7.77 8.50 Hercules Size Test (sec.) 11 40 Loss of sizing, referred to as "fugitive sizing", was evaluated after 5 weeks (35 days). The results are shown in Table VII.
TAB~E VII
Fugitive 8izinq Results from Mill Trial (Reel No. 6 and 10) 1.5'Wt.%
Cationic Untreated Polymer-Commercial Modified PCC PCC
Hercules Size Test (sec) 9 37 (initial testing) Hercules Size Test (sec) 7 36 (35 days later) Percent Change in Sizing (%)-22 -3 ~37~25 The samples showed a minimum loss of sizing compared to typical commercially filled sheets. The surface coefficient of friction of the sheets was also evaluated. The surface coefficient of friction of the sheets is an important measure of the runnability of the paper through high-speed reprographic equipment. The results of this evaluation are shown in Table VIII.
Table VIII
Coefficient of Friction (COF) on Surfaoe of Paper from Mill Trial Untreated1.5 Wt.% Cationic CommercialPolymer-Modified PCC PCC
COF* (static) .308 .385 COF* (dynamic) .214 .281 * results reported as qrams force sled weight (grams) Contact: felt-to-wire side The polymer-modified PCC-filled sheets showed a better coefficient of friction of the sheet surface than the unmodified sheets.
Example 5 Effect of Filler Treatment TemPerature on Sizing Demand Reduction at Various Levels of Cationic PolYmer Treatment and Filler Loadinq A handsheet study was performed to evaluate the effect of filler treatment temperature, that is, the temperature at which the cationic polymer is applied to the filler material, on reduction in the sizing demand in the handsheets utilizing the cationic polymer-treated filler.
Treatment was at temperatures in the range of from 25-650C.
Treatment was performed at levels of from 0 to 1.25 weight percent of cationic polymer. The cationic polymer used was an alkyl ketene dimer, Hercon-85 ~(Hercules, Inc., Wilmington, DE). The filler was a precipitated calcium carbonate (PCC) (Albacar H0, Pfizer, Inc., New York).
Filler loading in the handsheets was at several levels, of from 8 to 24 weight percent of treated filler.
Twenty separate surface treatments were performed using four treatment levels (0.5, 0.75, 1.0 and 1.25 wt %) and five treatment temperatures (25, 35, 45, 55 and 65C), along with an untreated control sample, as shown in Table IX.
TABLE IX
Bample Filler Level and Treatment TemPerature Cationic Polymer Treatment Treatment Level Temperature 20Sample # (Wt. ~) (C) Control None 25 1 0.5 25 2 0.75 25 25 3 1.0 25 4 1.25 25 0.5 35 6 0.75 35 7 1.0 35 30 8 1.25 35 9 0.5 45 0.75 45 11 1.0 45 12 1.25 45 3513 0.5 55 14 0.75 55 1.0 55 16 1.25 55 17 0.5 65 4018 0.75 65 19 1.0 65 1.25 65 All treatments were performed using 10 minutes of low-shear mixing time per sample. Elevated temperatures were *Trademark . -;, 2037~25 maintained for approximately 4 hours before samples were allowed to cool.
Comparative Formax (Noble and Wood) handsheets (60 g/m2 or 40 lbs./3300 ft2) were prepared from a furnish blend consisting of 75% bleached hardwood and 25% bleached softwood Kraft pulps beaten to a consistency of 0.3125% and a Canadian Standard Freeness (CSF) of 400 +25 at pH 7.0 in distilled water. Additional wet end additives included an alkyl ketene dimer size (Hercon-75, Hercules, Inc., Wilmington, DE) in an amount of 0.25 wt. % (5 lb/ton of paper) and a cationic polycacrylamide retention aid (Percol-175) in an amount of 0.05 at ~ (1 lb/ton of paper). All sheets were conditioned and tested at standard TAPPI
conditions of 50% relative humidity and 23C.
Paper properties tested include size, opacity, pigment scattering coefficient and sheet brightness~ Size was tested by the Hercules Size Test. Reported values are in seconds. Opacity was tested by the TAPPI test. Reported values are Corrected opacity, %. Sheet brightness was tested by the TAPPI test. Reported values are Brightness, ~. The results are reported in Table X.
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rq The results show that HST values are directly proportional to filler treatment level, that is, the higher the treatment level, the higher the HST response, and inversely proportional to treatment temperature, that is, the higher the slurry treatment temperature, the lower the HST response. Thus, the highest sizing values (greatest sizing demand reduction) occurred at high treatment level and low treatment temperature, while low treatment level and high treatment temperature resulted in poorer size reduction performance. The magnitude of the effect varied considerably, however, with filler level in the handsheets.
This is shown in Figures 12, 13 and 14. In Fig. 12, at an 8% filler level, the effect of both treatment level and treatment temperature on HST is minimal, with HST values ranging from a low of 193 seconds to a high of 237 seconds.
In Fig. 13, at a 16~ filler level, the effect is more noticeable, with HST values ranging from 35 seconds to 392 seconds. Finally, as is seen in Fig. 14, at a 24% filler level, a significant effect is seen, with HST values ranging from 2 to 313 seconds and a very steep transition occurring from lower to higher treatment levels and higher to lower treatment temperature. Treatment level is, however, a more sensitive variable than treatment temperature since a small change in treatment level produces a more drastic HST shift than does a small change in temperature.
Claims (6)
1. A composition characterized by a papermaking filler material, selected from the group consisting of finely ground natural calcium carbonate from limestone, precipitated calcium carbonate, clay, titanium dioxide, talc, silica/silicate pigments, and combinations of the above, which has been surface treated with from about 0.1 to about 10.0 weight percent of a cationic polymer, based on the dry weight of filler material, wherein the cationic polymer is a dimer of the general formula where R is a hydrocarbon group selected from the group consisting of alkyl with from 8 to 20 carbon atoms, cycloalkyl with at least 6 carbon atoms, aryl, aralkyl and alkaryl, the dimer having been made cationic by treatment with at least one of a polyamino-amide and a polyamine polymer reacted with an epoxidized halohydrin compound to form tertiary and quaternary amine groups on the dimer surface.
2. The composition according to claim 1 further characterized by the dimer being selected from the group consisting of octyl-, decyl-, dodecyl-, tetradecyl-, hexadecyl-, octadecyl-, eikosyl-, dokosyl-, tetrakosyl-, phenyl-, benzyl-beta-naphthyl-, and cyclohexyl- dimers, dimers produced from mining acids, naphthenic acid, delta-9,10-decylenic acid, delta-9,10-dodecylenic acid, palmitoline acid, olein acid, ricine olein acid, linoleate, linoleic acid, and olestearic acid, and dimers manufactured from natural fatty acid mixtures, such as are obtained from cocoanut oil, babassu oil, palm seed oil, palm oil, olive oil, peanut oil, rape seed oil, beef suet and lard, and mixtures of the above.
3. The composition according to claim 1 further characterized by the epoxidized halohydrin being epichlorohydrin.
4. A process for the preparation of a papermaking filler material surface treated with a cationic polymer, said process being characterized by adding from about 0.1 to about 10.0 weight percent of a cationic polymer, which is a dimer of the general formula where R is a hydrocarbon group selected from the group consisting of alkyl with a least 8 carbons atoms, cycloalkyl with at least 6 carbon atoms, aryl, aralkyl and alkaryl, which has been made cationic by treatment with at least one of a polyamino-amide and a polyamine polymer reacted with an epoxidized halohydrin compound to form tertiary and quaternary amine groups on the dimer surface, to a filler slurry containing from about 1% to about 76% solids, while maintaining the slurry under agitation at a temperature of from about 5°C to about 70°C, and at a pH less than about 10, in order to improve filler performance.
5. The process according to claim 4 wherein the amount of polymer added to the slurry is directly correlated with the surface area of the filler material.
6. A method for improving papermaking by accomplishing at least one of the results of reducing the amount of sizing required, maintaining the sizing content over time, improving the handling properties of a formed paper web, including water release, improving the physical properties of the resulting paper, including filler retention, filler distribution, tensile strength, and surface coefficient of friction, and improving the optical properties of the resulting paper, including brightness, opacity, and pigment scattering coefficient, the method being characterized by adding from about 5 to about 50 weight percent of a filler material which has been surface-treated with from about 0.1 to about 10.0 weight percent, based on the dry weight of filler material, of a cationic polymer, which is a dimer of the general formula where R is a hydrocarbon group selected from the group consisting of alkyl with at least 8 carbon atoms, cycloalkyl with at least 6 carbon atoms, aryl, aralkyl and alkaryl, which has been made cationic by treatment with at least one of a polyamino-amide and a polyamine polymer reacted with an epoxidized halohydrin compound to form tertiary and quaternary amine groups on the dimer surface to a papermaking furnish.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49090990A | 1990-03-08 | 1990-03-08 | |
| US490,909 | 1990-03-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2037525A1 CA2037525A1 (en) | 1991-09-09 |
| CA2037525C true CA2037525C (en) | 1995-10-31 |
Family
ID=23950014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002037525A Expired - Fee Related CA2037525C (en) | 1990-03-08 | 1991-03-04 | Cationic polymer-modified filler material, process for its preparation and method for its use in papermaking |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0445953B1 (en) |
| JP (1) | JP2528557B2 (en) |
| KR (1) | KR940001536B1 (en) |
| AU (1) | AU632403B2 (en) |
| BR (1) | BR9100933A (en) |
| CA (1) | CA2037525C (en) |
| DE (1) | DE69112239T2 (en) |
| ES (1) | ES2078436T3 (en) |
| FI (1) | FI102198B (en) |
| HK (1) | HK1007778A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660150A (en) * | 2012-04-28 | 2012-09-12 | 华南理工大学 | Modified calcium carbonate filler and preparation method and application thereof in wet-strength paper |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR244372A1 (en) * | 1990-04-11 | 1993-10-20 | Hercules Inc | Pretreatment of filler with cationic ketene dimer |
| US5152835A (en) * | 1991-05-08 | 1992-10-06 | Engelhard Corporation | Composite titania-calcined kaolin opacifying pigments and method for making and using same |
| CA2092955C (en) * | 1992-04-06 | 1999-01-12 | Sunil P. Dasgupta | Stable blend of ketene dimer size and colloidal silica |
| IL113721A (en) * | 1994-05-20 | 1999-04-11 | Minerals Tech Inc | Dual surface treated filler material method for its preparation and use in papermaking |
| SE9404201D0 (en) * | 1994-12-02 | 1994-12-02 | Eka Nobel Ab | Sizing dispersions |
| WO1996024721A1 (en) * | 1995-02-08 | 1996-08-15 | Diatec Environmental Company | Pigment filler compositions and methods of preparation and use thereof |
| CA2180371A1 (en) * | 1996-02-13 | 1997-08-14 | Brian Frederic Satterfield | Production of filled paper and compositions for use in this |
| DE19719899A1 (en) | 1997-05-12 | 1998-11-19 | Clariant Gmbh | Largely water-insoluble cationized solids as well as their production and use |
| DE10209448A1 (en) * | 2002-03-05 | 2003-09-18 | Basf Ag | Aqueous slurries of finely divided fillers, processes for their production and their use for the production of filler-containing papers |
| JP2006124885A (en) * | 2004-10-29 | 2006-05-18 | Daio Paper Corp | Neutral newsprint and method for producing the same |
| JP2007113155A (en) * | 2005-10-24 | 2007-05-10 | Nippon Paper Industries Co Ltd | Clear coated paper for printing |
| EP1943313A1 (en) * | 2005-11-04 | 2008-07-16 | Alpha Calcit Füllstoff Gesellschaft mbH | Surface-modified inorganic fillers and pigments (ii) |
| US7964063B2 (en) | 2006-08-11 | 2011-06-21 | Georgia Tech Research Corporation | Methods and compositions for papermaking |
| CN101611196B (en) | 2007-01-26 | 2011-08-31 | 播磨化成株式会社 | Additive for papermaking and paper containing filler |
| PL2662416T3 (en) | 2012-05-11 | 2015-12-31 | Omya Int Ag | Treatment of calcium carbonate containing materials for increased filler load in paper |
| PL2662419T3 (en) | 2012-05-11 | 2015-11-30 | Omya Int Ag | Charge controlled PHCH |
| FR3001236B1 (en) | 2013-01-22 | 2015-06-26 | Emin Leydier | AQUEOUS COMPOSITION FOR THE PRODUCTION OF FIBROUS SHEET CARRIERS WITH IMPROVED MECHANICAL STRENGTH PROPERTIES, PROCESS, USE, FIBROUS CARRIERS AND MANUFACTURED ARTICLES THEREOF |
| ES2672735T3 (en) | 2014-11-07 | 2018-06-15 | Omya International Ag | A process for the preparation of flocculated filler particles |
| SI3018175T1 (en) | 2014-11-07 | 2019-05-31 | Omya International Ag | A process for the preparation of flocculated filler particles |
| KR102608657B1 (en) * | 2021-06-07 | 2023-12-05 | 태경산업 주식회사 | Paper-making filler or coating material containing talc and manufacturing method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2865743A (en) * | 1957-03-11 | 1958-12-23 | Hercules Powder Co Ltd | Ketene dimer sizing composition and process for sizing paper therewith |
| US4240935A (en) * | 1978-12-22 | 1980-12-23 | Hercules Incorporated | Ketene dimer paper sizing compositions |
| JPS5926595A (en) * | 1982-07-29 | 1984-02-10 | 花王株式会社 | Internal sized paper |
| JPS61204034A (en) * | 1985-03-08 | 1986-09-10 | Kao Corp | Aqueous dispersion liquid |
| GB8701491D0 (en) * | 1987-01-23 | 1987-02-25 | Ecc Int Ltd | Aqueous suspensions of calcium |
| JPH074963B2 (en) * | 1987-11-05 | 1995-01-25 | 新王子製紙株式会社 | Inkjet recording paper |
| US4892590A (en) * | 1988-06-03 | 1990-01-09 | Pfizer Inc. | Precipitated calcium carbonate-cationic starch binder as retention aid system for papermaking |
| GB8815515D0 (en) * | 1988-06-29 | 1988-08-03 | Ecc Int Ltd | Pitch control |
-
1991
- 1991-02-27 EP EP91301574A patent/EP0445953B1/en not_active Expired - Lifetime
- 1991-02-27 ES ES91301574T patent/ES2078436T3/en not_active Expired - Lifetime
- 1991-02-27 DE DE69112239T patent/DE69112239T2/en not_active Expired - Fee Related
- 1991-03-04 CA CA002037525A patent/CA2037525C/en not_active Expired - Fee Related
- 1991-03-07 AU AU72727/91A patent/AU632403B2/en not_active Ceased
- 1991-03-07 FI FI911147A patent/FI102198B/en not_active IP Right Cessation
- 1991-03-07 KR KR1019910003634A patent/KR940001536B1/en not_active IP Right Cessation
- 1991-03-07 BR BR919100933A patent/BR9100933A/en not_active IP Right Cessation
- 1991-03-08 JP JP3043833A patent/JP2528557B2/en not_active Expired - Fee Related
-
1998
- 1998-06-26 HK HK98106946A patent/HK1007778A1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660150A (en) * | 2012-04-28 | 2012-09-12 | 华南理工大学 | Modified calcium carbonate filler and preparation method and application thereof in wet-strength paper |
| CN102660150B (en) * | 2012-04-28 | 2014-02-26 | 华南理工大学 | Modified calcium carbonate filler and preparation method and application thereof in wet-strength paper |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05247886A (en) | 1993-09-24 |
| BR9100933A (en) | 1991-11-05 |
| EP0445953B1 (en) | 1995-08-23 |
| AU632403B2 (en) | 1992-12-24 |
| FI911147A0 (en) | 1991-03-07 |
| CA2037525A1 (en) | 1991-09-09 |
| EP0445953A1 (en) | 1991-09-11 |
| DE69112239D1 (en) | 1995-09-28 |
| JP2528557B2 (en) | 1996-08-28 |
| HK1007778A1 (en) | 1999-04-23 |
| FI102198B1 (en) | 1998-10-30 |
| DE69112239T2 (en) | 1996-05-02 |
| ES2078436T3 (en) | 1995-12-16 |
| FI102198B (en) | 1998-10-30 |
| KR910017026A (en) | 1991-11-05 |
| KR940001536B1 (en) | 1994-02-23 |
| FI911147A (en) | 1991-09-09 |
| AU7272791A (en) | 1991-10-31 |
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| EEER | Examination request | ||
| MKLA | Lapsed |