WO1996024721A1 - Compositions a base de matiere de remplissage pigmentaire et leurs procedes de preparation et d'utilisation - Google Patents

Compositions a base de matiere de remplissage pigmentaire et leurs procedes de preparation et d'utilisation Download PDF

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Publication number
WO1996024721A1
WO1996024721A1 PCT/US1996/001549 US9601549W WO9624721A1 WO 1996024721 A1 WO1996024721 A1 WO 1996024721A1 US 9601549 W US9601549 W US 9601549W WO 9624721 A1 WO9624721 A1 WO 9624721A1
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WIPO (PCT)
Prior art keywords
pigment
polymer
water
composition
mixture
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Application number
PCT/US1996/001549
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English (en)
Inventor
Leo E. Nagan
Original Assignee
Diatec Environmental Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Diatec Environmental Company filed Critical Diatec Environmental Company
Priority to AU49152/96A priority Critical patent/AU4915296A/en
Publication of WO1996024721A1 publication Critical patent/WO1996024721A1/fr

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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
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper

Definitions

  • the invention relates to methods of paper manufacture and, more particularly, the invention relates to pigment compositions and methods of making and using such compositions.
  • Calcium carbonate pigment is usually the filler of choice in the manufacture of alkaline papers. Calcium carbonate pigment provides whiteness, brightness, and opacity to the paper. Because calcium carbonate is cheaper than the cellulose fiber used to make paper, it is to the economic advantage of the papermaker to use as much calcium carbonate as possible, consistent with maintaining standards with respect to, for example, tensile strength, internal bond strength, and fold strength.
  • Papermakers have been constrained from using inexpensive forms of calcium carbonate, which can be made at the plant site, in amounts over twelve to fourteen weight percent because of the unacceptable loss of strength of the paper at calcium carbonate addition over this range.
  • any paper as it is currently made has been acknowledged to be derived from hydrogen bonding between the hydroxyl sites on adjacent fiber surfaces and can be enhanced in some cases by additives mixed with the fiber/filler slurry, such as starches and gums, which can reinforce fiber-to-fiber bonding.
  • additives mixed with the fiber/filler slurry such as starches and gums, which can reinforce fiber-to-fiber bonding.
  • the problem with high levels of fillers, such as calcium carbonate, is that the pigment particles can prevent too many of the hydrogen bonding sites on adjacent fibers from touching, and the consequent loss of strength leads to commercially unacceptable paper.
  • Starches and gums have been used for many years to improve the strength of paper.
  • the standard procedure has been to add the gum or starch to a slurry of fiber and pigment filler.
  • the literature indicates that such addition is for the most part successful at filler levels of about eleven to thirteen weight percent.
  • the tolerable level of clay pigment in paper may be increased by flocculation of the clay with a cationic starch prior to adding the clay to a fiber slurry.
  • a cationic starch prior to adding the clay to a fiber slurry.
  • a theory that may be advanced for the success of such a procedure is that the pre-flocculation or agglomeration of the clay with the starch allows the fibers to contact fewer clay surfaces than with dispersed clay, and consequently, the clay is less likely to interfere with the fiber-to-fiber hydrogen bonding that gives paper its strength.
  • the Mather et al. article emphasizes the need for mixing the clay and the cationic starch at a low shear level to maximize agglomeration and, accordingly, to minimize the clay surface to fiber contact.
  • a calcium carbonate-cationic starch binder system for use as a retention aid in papermaking.
  • a highly dispersible, high specific area precipitated calcium carbonate is prepared by introducing carbon dioxide into an aqueous slurry of calcium hydroxide.
  • the slurry is heat aged at a pH from 9-11 to reduce surface area and increase dispersibility and then treated with an anionic dispersant, preferably an inorganic polyelectrolyte and more preferably sodium tripolyphosphate or sodium hexametaphosphate to result in a colloidal anionic PCC.
  • an anionic dispersant preferably an inorganic polyelectrolyte and more preferably sodium tripolyphosphate or sodium hexametaphosphate to result in a colloidal anionic PCC.
  • the Gill et al. patent discloses that in the papermaking operation, the filler, PCC, and a cationic starch are individually introduced to a fiber slurry.
  • the filler is added to a fiber slurry at a blend chest, the colloidal anionic PCC at a stuff box, and the cationic starch before the fan pump.
  • U.S. Patent No. 4,174,998 discloses a flocculated filler composition for use in papermaking comprising a pigment, a starch phosphate, and an organic polymeric retention aid, such as polyacryla ide.
  • the Shiel patent states that the filler composition components are brought together as a mixture, preferably as a dispersion in water, before being introduced into a medium containing paper fibers with the objective of increasing pigment and starch retention.
  • the Shiel patent is silent concerning the pH of such a filler composition prior to addition to the paper fiber medium.
  • the invention concerns a method of preparing a filler composition for use in a papermaking process including the step of providing a composition for blending with a fiber slurry.
  • the composition is a mixture of a pigment, a water soluble or dispersible polymer, and water.
  • the pH of the pigment, the polymer, the water, or the mixture thereof is adjusted to result in the composition having a pH of at least about 9.
  • the invention also comprehends a composition produced according to such a method.
  • a pigment slurry for example, a slurry of calcium carbonate and water, is adjusted to a pH of at least about 9 (preferably between pH 9 and pH 12, and most preferably at about pH 11).
  • the pigment slurry is then mixed with an aqueous solution or dispersion of at least one water soluble or dispersible polymer, which may be either synthetic or natural.
  • the pigment slurry/polymer mixture is then added to a fiber-containing slurry or composition in a papermaking machine.
  • the invention also comprehends adjusting the pH of the water or polymer components of the mixture prior to mixing with a pigment to result in a mixture having a pH of at least about 9.
  • a pigment/water slurry and a polymer may be mixed and then the pH of the resulting mixture adjusted to at least about pH 9.
  • mixing of the water, pigment, and polymer, and any pH adjustment are performed under high shear mixing conditions.
  • Polymers according to the invention include, for example, acrylamide polymers, such as acrylamide homopolymers, methacrylamide homopolymers or copolymers of acrylamide and methacrylamide, aerylate, or metal salts of acrylic acid.
  • the acrylamide polymer may be partially hydrolyzed.
  • Polymers according to the invention also include polyvinyl alcohols, colloidal or polymerized silica, starches, and gums.
  • the polymer addition preferably ranges between about 0.5 wt.% and about 15 wt.%, based upon the dry pigment weight.
  • a preferred pigment for use in the invention is calcium carbonate.
  • a particularly preferred pigment for use in the invention is a high specific area precipitated calcium carbonate (PCC) .
  • PCC precipitated calcium carbonate
  • the invention also comprehends the use of clay and titanium pigments.
  • an elevated pH creates hydrogen bonding sites on the pigment surface.
  • the polymer also has hydrogen bonding sites.
  • the elevated pH confers substantivity (i.e. the ability to be fixed or associated) of polymer to pigment.
  • a pigment such as calcium carbonate in a manner that will affix the polymer or polymer mixture to the surfaces of the calcium carbonate particles
  • the pH level of the calcium carbonate slurry is elevated substantially above its natural equilibrium level to a pH ranging between about 9 and about 12.
  • a benefit to the inventive method is that upon the drying of paper made with cellulose fiber and a high pH pigment/polymer composition according to the invention, the pigment particles can bond to one another and to the fiber surface via the bridging of the polymer from surface to surface through hydrogen bonding.
  • the net result is paper that has a higher tensile strength and internal bonding strength, for example, than paper made which is not treated with a pigment/polymer composition according to the invention.
  • the invention also comprehends the use of alkalies such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, calcium hydroxide, calcium oxide, and any combination thereof, to increase the pH and alkalinity of a pigment slurry to a level between about pH 9 and about pH 12.
  • alkalies such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, calcium hydroxide, calcium oxide, and any combination thereof.
  • the polymers utilized according to the invention identified herein may be used in their unmodified form, or they may be modified in various ways that may improve their handling characteristics, their bonding capabilities, and their substantivity (i.e., ability to be fixed or associated) to the pigment particles.
  • polyacry1amides are utilized in a method and composition of the invention, they may be modified through copolymerization which inserts other active units in the polymer chain such as carboxyl units, amine units, and quaternary amine units. Or they may be hydrolyzed with caustic soda to convert some of the amide units to carboxyl units.
  • the polyacrylamides may also be converted to a polyacrylamide-phosphonate construction as shown in Nagan U.S. Patent No. 5,342,539.
  • a natural polymer i.e., starch
  • it may be modified, for example by hydroxyethylation, methoxymethylation, acid treatment, oxidation, the addition of tertiary or quaternary amine sites, chemical bonding with a latex copolymer, and phosphatizing.
  • Gums such as guar gum, locust bean gum, and tamarind kernel may also be utilized in a method of the invention. The most common modification of guar gum is the addition of tertiary or quaternary amine sites.
  • a preferred polymer for use in the invention is potato starch. This is most likely because it has phosphate radicals inherent in its molecular structure as well as having hydroxyl radicals.
  • the choice of polymer in any given situation may depend on characteristics such as retention aid flocculant choice and the ionic characteristics of other system additives.
  • the preferred addition level of polymer to pigment solids is in the range of between about 0.5 wt.% and about 15 wt.% depending, for example, upon needs for the type of paper being made, ash levels, and fiber strength characteristics.
  • a filler pigment composition according to the invention such as a calcium carbonate slurry adjusted to a pH of about 11 and mixed with a polymer, such as potato starch, is that the calcium carbonate pigment surface enters into hydrogen bonding with the polymer and as a result the polymer becomes firmly attached to it.
  • the polymers then further enhance strength through bridging from pigment particle to pigment particle, and pigment particle to fiber during and after drying.
  • Significantly increased levels of pigment in a finished paper are thus possible without dropping the paper strength below commercially acceptable levels. Instead of blocking bonding sites, the pigment can enter into bonding.
  • the benefits to the papermaker in being able to substantially increase calcium carbonate levels further include increased opacity and brightness and reduced furnish costs.
  • a screening was performed wherein dry films of calcium carbonate pigment slurries were formed on flat bottomed Petri dishes using precipitated calcium carbonate (PCC) having a scalenohedral crystalline structure.
  • PCC precipitated calcium carbonate
  • the papermaking industry acknowledges that the scalenohedral form interferes with the strength development in paper much more than a rhombohedral form that is typically found in ground calcium carbonate (GCC) . Because of their irregular shapes, the scalenohedral crystals cannot pack together as efficiently as the rhombohedral crystals. However, the use of scalenohedral crystals provides significantly more opacifying power, a very desirable attribute in papermaking.
  • the strength enhancement effects derived from a process according to the invention applies to all crystal forms of calcium carbonate.
  • Glass was chosen as the film substrate for its known ability to enter into hydrogen bonding because of the hydroxyl radicals attached to the silicon atoms in the glass.
  • the dried films were prepared from PCC slurries treated with both natural and synthetic polymers listed in Table I below. Such polymers are known to enter into hydrogen bonding and in so doing provide a strength reinforcing mechanism when mixed with solids that are also known to enter into hydrogen bonding. For example, paper made from cellulose fiber only can be strengthened with these materials. Dried films on glass were also prepared from untreated PCC to provide baseline data. Films were made at a pH of 8.2 (which is generally the upper limit target at which PCC slurries enter a paper machine system) as well as at elevated pH levels of up to 12.
  • a preferred element believed to aid in the performance of the inventive method disclosed herein is the thorough mixing of the treatment polymer and PCC particles under high shear conditions to achieve a maximum possible dispersion.
  • the polymer/pigment mixture was mixed vigorously with a large quantity of water before it was allowed to settle. If the polymer wasn't substantive to the PCC particles, it would remain, for the most part, in the water phase and, accordingly, not be available to bind the pigment particles to one another in the film.
  • PCC PCC
  • 10 wt.% and 1 wt.% sodium hydroxide solutions pH indicator strips by E.M. Science (pH 0- 14 and pH 6.5-10) ; flat bottomed glass Petri dishes 95 X 22 mm;
  • the dried films were allowed to stand at room temperature and pressure for at least 12 hours in order for them to come to a stable moisture equilibrium before testing.
  • each film was assessed by rubbing the film with firm pressure using the underside of a full top joint of the index finger (area about 2.6 cm 2 ) in the case of the untreated PCC film, or the top partial area (about 1.1 cm 2 ) for the other tests recorded in Table I. The number of rubs were counted until the film broke through to the glass surface. During early screening, the number of rubs were not recorded. However, the following was recognized:
  • a 64/40 mix (by weight) of hardwood bleached Kraft fiber and softwood Bleached Kraft fiber was refined (each separately) to a Canadian Standard Freeness (CSF) of 400 in a Valley beater.
  • CSF Canadian Standard Freeness
  • Six ten liter aliquots of 0.3 wt.% fiber were placed in six stainless steel buckets.
  • About two grams of calcium chloride was dissolved in each bucket in an effort to replicate calcium pickup by fibers in a papermaking system making alkaline paper using calcium carbonate as a filler.
  • the pH in each bucket was adjusted to 8.2 with a sodium hydroxide solution to replicate equilibrium conditions in an alkaline papermaking system.
  • a scalenohedral precipitated calcium carbonate (PCC) pigment was used at a pH of 8.2 for a series of handsheets made with untreated PCC. This pH is a common upper limit target for PCC slurries used in alkaline papermaking. PCC slurries adjusted to pH 11 with sodium hydroxide were used for the handsheets made with treated pigment. The solids content of each PCC slurry was 24 wt.%.
  • a solution/dispersion of 1 wt.% acid modified potato starch was made by slurrying the raw starch in distilled water and cooking it for 15 minutes at 190°F. In making the treated sheets, the starch was added to the pigment at a dosage of 2 wt.% based on the dry pigment weight.
  • a cationic polyacrlyamide (IV 13; 5 mole) was utilized as a retention aid. It was used at the rate of 0.7 lbs/ton based on the dry weight of the fiber/PCC mix.
  • the target weight of each handsheet was 1.2 gm which equates to an oven dry basis weight of 60 gm/m 2 .
  • the target PCC levels were 14 wt.%, 20 wt.%, and 25 wt.%.
  • a series of six handsheets were made for each of these levels, both for treated PCC and untreated PCC.
  • test sheets were run to confirm basis weight and ash levels.
  • Quick ash level determinations were made using a Weyerhaeuser developed apparatus that utilizes an oxygen gas atmosphere to develop an instant, intense heat.
  • six aliquots were taken from the bucket designated for that series and placed in one liter beakers. The aliquot volume was based on the target fiber content for that series.
  • the beakers were set upon a six place magnetic stirring table which provided the required agitation.
  • the PCC slurry dosage was added to the beaker containing the fiber slurry under agitation.
  • the pigment was treated in a Waring blender mini-container of 35 cc capacity. The procedure was to add about 20 cc of pH 11 distilled water to the blender, begin agitation, add the appropriate dosage of pH 11 pigment, add the appropriate dosage of potato starch, continue agitation for ten seconds, and add the treated pigment to the fiber aliquot under agitation in the one liter beaker.
  • the retention aid dosage was added to the one liter beaker immediately after the addition of the PCC. Agitation was then continued in the beaker for twelve seconds, and the beaker was handed to the lab manager for sheet formation.
  • Deionized water was used throughout, including the British sheet mold.
  • the sheet mold was filled to the halfway level and the pH adjusted to 8.2 with caustic soda.
  • TAPPI standard methods were used for sheet formation, pressing, and drying. The sheets were air dried and tested in a standard constant temperature and constant humidity room. All of the dry lab testing for strength, basis weight, and ash, etc, were performed under TAPPI/ISO standards. A typical moisture level for sheets dried and tested under these conditions is reported to be about 7 wt.%. The following Table II provides a summary of the results of the handsheet tests. TABLE II HANDSHEET STUDIES
  • both Series 1 and Series 4 had the same fiber weight (1.05 grams).
  • the increased basis weight of the sheets made from PCC treated according to the invention is from an increased amount of pigment only. This indicates that PCC may be increased by 2 wt.% without strength loss. At the treatment level used, this was done with only 6 lbs. starch/ton of paper level of treatment. Better results may occur with higher treatment levels of starch.
  • tensile strength is believed to be the most meaningful test.
  • the tensile index (TI) , tensile energy absorption (TEA) , and tensile breaking length (BL) results that are often calculated in this type of testing are methods meant to even out basis weight variations based on fiber content. The higher the fiber content, the higher the tensile strength. For example, the breaking length number for a 67 gm sheet would be lowered by calculation in the TI, TEA and BL results when compared to a 65 gm sheet by what amounts to a gram difference ratio. However, when the mass increase is because of increased PCC only, this penalizing adjustment obviously would not be justified.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)

Abstract

On prépare une composition contenant une matière de remplissage destinée à un processus de fabrication du papier en mélangeant un pigment, un polymère soluble ou dispersible dans l'eau, et de l'eau, le pH du mélange obtenu étant d'au moins environ 9.
PCT/US1996/001549 1995-02-08 1996-02-06 Compositions a base de matiere de remplissage pigmentaire et leurs procedes de preparation et d'utilisation WO1996024721A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU49152/96A AU4915296A (en) 1995-02-08 1996-02-06 Pigment filler compositions and methods of preparation and use thereof

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US38544595A 1995-02-08 1995-02-08
US08/385,445 1995-02-08

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WO1996024721A1 true WO1996024721A1 (fr) 1996-08-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1303667B2 (fr) † 2000-07-24 2018-08-22 Ecosynthetix Ltd. Utilisation de dispersions d'amidon cationique reticule dans la fabrication de papier

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804656A (en) * 1972-02-22 1974-04-16 Engelhard Min & Chem Pigment dispersions and use thereof
GB1425114A (en) * 1973-03-09 1976-02-18 Ass Portland Cement Acid resistant whitings for use in the manufacture of paper
US4045235A (en) * 1973-04-12 1977-08-30 English Clavs Lovering Pochin & Company, Limited Treatment of clay minerals
US4174998A (en) * 1974-11-15 1979-11-20 The Associated Portland Cement Manufacturers Limited Preflocculated filler compositions for use in the manufacture of paper
US4450013A (en) * 1981-06-15 1984-05-22 Basf Aktiengesellschaft Grinding or dispersing agents for pigments
US4892590A (en) * 1988-06-03 1990-01-09 Pfizer Inc. Precipitated calcium carbonate-cationic starch binder as retention aid system for papermaking
EP0355521A2 (fr) * 1988-08-05 1990-02-28 J.M. Huber Corporation Pigments en matières de charge composites et procédé de fabrication
EP0445953A1 (fr) * 1990-03-08 1991-09-11 Minerals Technologies Inc. Matériau de remplissage modifié par un polymère cationique, son procédé de préparation et son utilisation pour la fabrication
US5106420A (en) * 1989-10-27 1992-04-21 J. M. Huber Corporation Mineral based coloring pigments
EP0491346A1 (fr) * 1990-12-17 1992-06-24 Hercules Incorporated Dispersion cationique et procédé de cationisation de matière particulaire finement divisée
WO1992014881A1 (fr) * 1991-02-26 1992-09-03 Basf Aktiengesellschaft Boues aqueuses de matieres de charge finement pulverisees et leur utilisation pour produire du papier contenant des charges

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804656A (en) * 1972-02-22 1974-04-16 Engelhard Min & Chem Pigment dispersions and use thereof
GB1425114A (en) * 1973-03-09 1976-02-18 Ass Portland Cement Acid resistant whitings for use in the manufacture of paper
US4045235A (en) * 1973-04-12 1977-08-30 English Clavs Lovering Pochin & Company, Limited Treatment of clay minerals
US4174998A (en) * 1974-11-15 1979-11-20 The Associated Portland Cement Manufacturers Limited Preflocculated filler compositions for use in the manufacture of paper
US4450013A (en) * 1981-06-15 1984-05-22 Basf Aktiengesellschaft Grinding or dispersing agents for pigments
US4892590A (en) * 1988-06-03 1990-01-09 Pfizer Inc. Precipitated calcium carbonate-cationic starch binder as retention aid system for papermaking
EP0355521A2 (fr) * 1988-08-05 1990-02-28 J.M. Huber Corporation Pigments en matières de charge composites et procédé de fabrication
US5106420A (en) * 1989-10-27 1992-04-21 J. M. Huber Corporation Mineral based coloring pigments
EP0445953A1 (fr) * 1990-03-08 1991-09-11 Minerals Technologies Inc. Matériau de remplissage modifié par un polymère cationique, son procédé de préparation et son utilisation pour la fabrication
EP0491346A1 (fr) * 1990-12-17 1992-06-24 Hercules Incorporated Dispersion cationique et procédé de cationisation de matière particulaire finement divisée
WO1992014881A1 (fr) * 1991-02-26 1992-09-03 Basf Aktiengesellschaft Boues aqueuses de matieres de charge finement pulverisees et leur utilisation pour produire du papier contenant des charges

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1303667B2 (fr) † 2000-07-24 2018-08-22 Ecosynthetix Ltd. Utilisation de dispersions d'amidon cationique reticule dans la fabrication de papier

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