CN104812958A - Filler suspension and its use in the manufacture of paper - Google Patents
Filler suspension and its use in the manufacture of paper Download PDFInfo
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- CN104812958A CN104812958A CN201280076267.8A CN201280076267A CN104812958A CN 104812958 A CN104812958 A CN 104812958A CN 201280076267 A CN201280076267 A CN 201280076267A CN 104812958 A CN104812958 A CN 104812958A
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- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- 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
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
-
- 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
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
- D21H17/29—Starch cationic
-
- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
-
- 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
-
- 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
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Paper (AREA)
Abstract
Provided herein are filler suspensions comprising swollen cationic starch, anionic, water-soluble polymer and filler particles. Pulp furnishes comprising the filler suspensions and paper comprising the pulp furnish are also provided. Processes for making the filler suspensions and processes for their use in manufacturing paper are also provided.
Description
Technical field
There is provided herein a kind of filler suspension containing the water-soluble polymer of swelling cationic starch and anion, it is for the method for papermaking, and contains paper and the paper products of described suspension.
Background technology
In the manufacture of loaded sheet, before forming section filler slurry being transferred to paper machine, added to routinely in pulp suspension.Usually add retention agent or the retention system containing several component to paper pulp/filler suspension (also referred to as batching), thus filler is kept in obtained paper.
Adding filler to paper can make paper performance obtain many improvement, comprises the opacity of improvement, brightness, texture and print distinctness.In addition, when filler is more cheap than paper pulp, because filler instead of paper pulp fiber, therefore add filler and make cost savings to paper.When using low-cost filler (such as winnofil (PCC)) to substitute expensive chemical paper fiber, this saving can be very large.In addition, loaded sheet can be easier to be drier than the paper not containing filler, and result is that paper machine can run faster, consumes less steam, and this can reduce costs further and improve productivity.
But, for a given paper weight, there is multiple restriction to addible amount of filler.The intensity of the paper obtained is principal element, adds the efficiency of paper machine, limits filer content together, although also will other factors be considered, and such as retention, dehydration rate (drainage) and applying glue.
Manufacture the paper with high filler content and need an effective Microparticle Retention System.There is provided good filler retention under the high shear that retention agent should occur in paper-making process and turbulent flow, and should dehydration rate be improved and not damage formation.The porch of the head box usually before the entrance of the head box of paper machine or at paper machine, adds to retention agent chemical substance in batching.Described retention agent is the one, the two or three component chemical additive that are improved filler and fines retention by bridge joint and/or flocculation mechanism.Described chemical substance contributes to filler particles and fiber fines (fubril fragment) being attached to long fiber or causing them to be gathered into the larger coagulated particles more easily kept in net.In order to produce described attachment and flocculation, described chemical substance must be adsorbed on the surface of filler, fiber fines and fiber.The adsoptivity of described chemical substance and adhesive force by being permitted multifactor impact, comprise batching cleannes and batching chemical feature, add the character of chemical substance, the level of shear in paper-making process and the contact time between retention agent and furnish component.
Filler alternative fiber inevitably reduces paper strength, and this is not only because have less fiber in paper thus reduce the number that Fiber-Fiber combines, also because the existence of described filler reduces the contact between remaining fiber.Do not combine between filler particles itself, and their positions in Fiber-Fiber calmodulin binding domain CaM prevent between paper pulp fiber and produce Hydrogenbond.Consequently, the filler of a large amount of reservation can produce the more weak paper that may more easily rupture on paper machine, sizing applicator (size press), coating machine, bobbin winder and printing machine.More weak Fiber-Fiber combines the surface strength also reducing paper, causes the increase that the reduction of anti-stripping and paper hair come off.The bad combination of the filler particles in fibre structure also may increase the dust in machine room.
Generally speaking, the known all inorganic fillers being generally used for papermaking all can damage the intensity also demand of increase to chemical substance of paper such as but not limited to clay, grinding calcium carbonate (GCC), PCC, chalk, talcum, titanium dioxide and sulfate precipitate calcium (PCS).The filler such as little scalenohedron PCC with high surface has substantial negative effect to intensity, and increases for intensity, applying glue and the chemical requirements of additive kept.Due to its shape, narrow particle size distribution and high surface, PCC has following trend: reduce the combination in paper more than other common papermaking filler (such as chalk, GCC and clay), and gives paper and make its open architecture that is too permeable or porous.When in preparing burden, the content of PCC increases, to the increase in demand of sizing chemicals such as alkyl ketene dimer (AKD) and alkenyl succinic anhydrides (ASA) to keep required degree of sizing or hydrophobicity.This is because a part of out-of-proportion sizing chemicals is attracted on high surface PCC.The sizing efficiency of difference and As time goes on and the hydrophobicity (applying glue reverse) of losing be with AKD and ASA applying glue highly-filled without wooden paper in use PCC adjoint FAQs.In recent years, many manufactures change Neutral Papermaking into containing the paper mill of wooden paper grade paper using, such as, to allow to use bright pearl filler, GCC and PCC; In the paper of these grades, use the main misgivings of calcium carbonate to be still in retention, paper strength and printing.
Existing industrial trend reduces paper grammes per square metre thus reduces costs.Regrettably, along with grammes per square metre declines, nearly all paper performance all can worsen, and comprises the limiting factor of opacity, bending rigidity and permeability.Reduce grammes per square metre and also may reduce the retention of filler in paper-making process, and increase paper on a papermaking machine and changing and the frequency of breakage in printing process.For overcoming the loss of paper opacity, papermaker can add the high filler of more opacity, but this may cause paper strength to worsen further.Industry needs cost-benefit technology to produce the lightweight grade paper using with good filler retention and dehydration rate and acceptable intensity, formation, optical property and printing performance.
Summary of the invention
Therefore, one aspect of the present invention relates to a kind of filler suspension for papermaking, and it comprises the water-soluble polymer of filler particles, swelling cationic starch and anion.
In one aspect of the invention, the water-soluble polymer of described anion is lightly crosslinked.
In one aspect of the invention, described anion, tan δ that is lightly crosslinked, water-soluble polymer flow become vibration values under 0.005Hz in the aqueous solution of 1.5% at least 0.5.
In one aspect of the invention, described anion, lightly crosslinked, water-soluble polymer comprises sodium acrylate, acrylamide and methylene-bisacrylamide.
In one aspect of the invention, the water-soluble polymer of described anion is
m305.
In one aspect of the invention, described filler particles is selected from by the following group formed: clay, talcum, grinding calcium carbonate, chalk, winnofil, sulfate precipitate calcium and their combination.
In one aspect of the invention, at gel point temperature ± 10 of cationic starch DEG C, described cationic starch slaking (cooking) is not made with the swelling described cationic starch grain of hot water.
In one aspect of the invention, the temperature of swelling described cationic starch grain is gel point temperature+10 DEG C.
In one aspect of the invention, described filler particles is of a size of 1-10 micron.
In one aspect of the invention, described swelling cationic starch grain is of a size of 25-100 micron.
In one aspect of the invention, based on the total solids content of described filler suspension, described filler particles exists with the amount of 60% to 99.5% by weight, described swelling cationic starch exists with the amount of 35% to 0.499% by weight, and the water-soluble polymer of described anion exists with the amount of 5.0% to 0.001% by weight.
One aspect of the present invention is a kind of intermittent pulp proportioning, and it comprises paper pulp fiber and filler suspension herein.
In one aspect of the invention, described intermittent pulp proportioning also comprises the common additive be selected from by the following group formed: sizing agent, wet strength agent, retention agent and their combination.
One aspect of the present invention is a kind of paper, and it comprises above-mentioned intermittent pulp proportioning.
One aspect of the present invention is the method for a kind of production for the filler suspension of papermaking, and it comprises makes filler particles contact with the water-soluble polymer of anion with swelling cationic starch.
In one aspect of the invention, in the above-mentioned methods, the water-soluble polymer of described anion is lightly crosslinked.
One aspect of the present invention is a kind of method manufacturing paper, and it comprises: make paper pulp fiber contact to form a kind of intermittent pulp proportioning with filler suspension herein; Described intermittent pulp proportioning is discharged to form paper by circuit; And dry described paper.
In one aspect of the invention, in the above-mentioned methods, described intermittent pulp proportioning also comprises and is a kind ofly selected from by the common additive of the following group formed: sizing agent, wet strength agent, dry strength agent, retention agent and their combination.
Accompanying drawing explanation
Fig. 1 is a kind of schematic diagram of papermaking process, and wherein the water-soluble polymer of anion, cationic swelling starch and filler are mixed substantially simultaneously.
Fig. 2 is a kind of schematic diagram of papermaking process, and wherein the water-soluble polymer of anion was pre-mixed before mixing with filler with swelling cationic starch.
Fig. 3 is a kind of schematic diagram of papermaking process, and wherein the water-soluble polymer of anion was pre-mixed before mixing with swelling cationic starch with filler.
Fig. 4 is a kind of schematic diagram of papermaking process, and wherein swelling cationic starch was pre-mixed before mixing with the water-soluble polymer of anion with filler.
Fig. 5 is when being heated to gelling temp and the gelling temp higher than cornstarch of cornstarch, the curve map of the viscosity reaction of cornstarch.
Fig. 6 comprises cornstarch grain micro-image at different temperatures when water heats.
Detailed description of the invention
General introduction
Unless expressly stated otherwise, otherwise odd number used herein comprises plural number, and vice versa.That is, " one " and " described " refers to the thing that one or more this word is modified.Such as, " a kind of lightly crosslinked polymer " comprises a kind of such polymer, two kinds of such polymer, or in appropriate circumstances, even more such polymer.Again, obviously draw unless expressly stated otherwise, or from context and do not mean like this, otherwise for the same reason, multiple such reagent can be referred to such as but not limited to the word that " sizing agent " is such or only refer to a kind of such reagent.
Such as but not limited to " about ", " substantially ", " substantially " and " approx ", the word of approximation represents that the feature of modifying does not need accurately clearly to describe, and can be different from written description to a certain extent.This degree being different from description will depend on may produce great change, and those of ordinary skill in the art is recognized, and modified feature still has characteristic needed for the feature of unmodified and function.Usually, be limited by discussion above, herein by the word of approximation modify clearly represent or hint value can differ with setting value ± 15%.
Composition
In an embodiment in this article, provide a kind of filler suspension for papermaking, it comprises the water-soluble polymer of the filler particles in liquid media (normally water), swelling cationic starch and anion.
In another embodiment, provide a kind of intermittent pulp proportioning, it comprises filler suspension as described herein in aqueous media and paper pulp fiber.Described batching also can comprise other papermaking reagent.
In still another embodiment, provide a kind of method of producing paper, it is by adding filler suspension of the present invention to paper pulp fiber raw material and form intermittent pulp proportioning and then by described batching papermaking.Reagents for anion and cation reagent can be added into comprise described filler suspension batching to strengthen retention and to improve dehydration rate.As previously mentioned, described batching also can comprise other papermaking reagent.
Present invention also offers the method forming filler suspension for the production of swelling starch/polymer composition and their combination and filler particles.
As used herein, the uncooked amylum grain that " swelling " starch refers to wherein absorbed water and expand (preferred at this) to wherein absorbing the starch that water just may make the state of described swelling breakage of particles again.For realizing this aspect, under the temperature controlled carefully, pH value, mixing and the condition of time, carry out starch swelling.These parameters will be different with starch type difference, and before the paper production for plant layout, usually empirically determine these parameters of every type starch.Uncooked amylum is just suspended in cold water by general procedure, and then heated suspension liquid is until starch is swelling.Subsequently the water-soluble polymer of swelling starch and anion and filler particles are mixed with the order needed arbitrarily and form filler suspension.Such as, in FIG, swelling cationic starch 1, anionic polymer 8a and filler particles 2 mix and form filler suspension in mixer 4, and it is transferred to mixer 5 subsequently, and here it and paper pulp fiber 3 are mixed to form batching.In fig. 2, swelling cationic starch 1 and the water-soluble polymer 8a of anion are by premix, and then this combination mixes in mixer 4 with filler particles 2, and after this, the filler suspension of formation mixes in mixer 5 with paper pulp fiber 3.In figure 3, the water-soluble polymer 8a of anion and filler particles 2 are by premix, then this combination mixes in mixer 4 with swelling cationic starch 1, and the filler suspension of formation is transferred to mixer 5, and here it and paper pulp fiber 3 are mixed to form batching.In the diagram, swelling cationic starch 1 and fiber grain 2 premix in mixer 4, and pre-composition is transferred to mixer 5, in the transport substantially between mixer 4 and mixer 5, anionic polymer 8a is added into pre-composition.In each case, the batching comprising filler suspension is transferred to paper machine 6 subsequently to form paper 9.Can selectively add common additive.In paper drying process, the swollen starches grain kept will break, and discharge the large molecule of amylopectin and the large molecule of amylose, they play the effect of the solid constituent in conjunction with paper.
The combination of swelling cationic starch, anionic polymer and filler particles may be used for papermaking under acid, neutrality or alkali condition.Composition is mainly used to ensure that filler and starch are kept in good condition in paper in paper-making process, simultaneously minimum to the negative effect of paper strength.The composition of swelling cationic starch/anionic water-soluble polymer/filler particles is used to be tending towards obtaining than using the retention and intensity that independent swelling cationic starch or anionic polymer and filler particles are larger.
When filler mixes with swelling cationic starch/anionic water-soluble polymer and adds pulp to, filler particles lumps and is adsorbed onto on the surface of slurry fiber fines and fiber, causes the rapid flocculation of preparing burden.Even if do not add retention agent, so also can obtain the retention of good filler and fiber fines and improve mesh dehydration (web drainage).But, under high shear level, turbulent flow and vacuum, due to filler from fiber surface solution flocculation and be separated, filler retention may reduce.Before the head box place of paper machine or its, and at this preferably before the pressurized screen of paper machine, anion microparticle (such as colloid silicic acid) is added to the paper making stock furnish comprising filler suspension and can improve retention and dehydration rate further.
Filler
Filler particles can be any filler well known by persons skilled in the art, and filler suspension can comprise a kind of single filler or more than a kind of filler.Filler particles normally average particle size range is 0.5 μm to 30 μm, is more typically the inorganic material of 1 μm to 10 μm, such as, but not limited to clay, grinding calcium carbonate (GCC), chalk, winnofil (PCC), talcum and sulfate precipitate calcium (PCS) and their blend.At present, PCC is preferred filler.The pulp adding filler suspension to it can be made up of mechanical pulp, chemical pulp, recovery paper pulp and their mixture.
Cationic starch
Be applicable to starch of the present invention include but not limited to be derived from corn, waxy corn, potato, wheat, cassava, Chinese sorghum, wax Chinese sorghum and rice those.Usually in starch, starch is made to present cationic state by comprising quaternary ammonium cation.Cationic starch is that business can be bought, and their preparation is known by the technical staff of field of papermaking, and does not therefore need herein to further describe.The average specific dimensions of most of uncooked amylum grain is approximately 5 μm to 45 μm.
Amylum body is insoluble to cold water.For dispersion or " slaking " starch, heating starch in waterborne suspension.Along with the carrying out of heating, amylum body is first through slight, a reversible swelling period, until be called as " gelatinization " temperature, " gelation " temperature or be called the critical-temperature of " gel " temperature simply, extensive swelling generation, causes viscosity significantly to increase.If remain on time enough on gelling temp, then because swellable particles breaks, viscosity can be returned to reduced levels.Often kind of starch has its oneself gelling temp.The gelling temp of much starch can be found in existing document, or, also can by heat given starch suspension simultaneously monitoring viscosity come easily empirically to determine gelling temp.Swelling amylum body is different from ripe starch.Ripe starch produces when swelling amylum body breaks at higher than the temperature of gelling temp and discharges amylose and amylopectin (they are dissolved in aqueous medium) thus.
For object of the present invention, carefully control the swelling of amylum body thus form the swollen starches minimum swellable particles wherein occurring and breaks.According to starch source, the ultimate size scope of swollen starches grain is about 25 μm to about 100 μm.The representativeness but nonrestrictive example of preparing swollen starches is given in embodiment.
The water-soluble polymer of anion
The water-soluble polymer of anion can be linear or lightly crosslinked.It is lightly crosslinked that to mean that crosslinked polymer is still water miscible.That is, the completely crosslinked polymers exhibit that lightly crosslinked polymeric thing cede territory weave in thus show more inseparable than polymer chain is insoluble in water obtains more as " branching " polymer.As used herein, alternately can use lightly crosslinked being cross-linked but still water-soluble polymer with referring to of branching.At United States Patent (USP) the 5th, 958, No. 188, the 6th, 391,156 No. B1, the 6th, 395,134 No. B1, the 6th, 406,593 No. B1 and the 6th, describe in 454,902 No. B1 anion, branching, the example of water-soluble polymer, here by way of reference the full content that their are set forth is incorporated to herein.
In certain embodiments, described anion, branching, water-soluble polymer:
A () is prepared to monomer feed by interpolation crosslinking agent or branching agent;
B () has the inherent viscosity higher than about 3dl/g; And
C () tan δ under 0.005Hz flows and becomes vibration values at least 0.5, or its deionization SLV viscosity number is at least three times of the salted SLV viscosity number of the polymer prepared by identical monomer feed when not adding branching agent under the same conditions.
Under polymerizing condition (such as inverse emulsion polymerization), monomer or grams of monomer blend and the crosslinking agent be contained among monomer feed or branching agent can be reacted by traditional approach and make polymer.The amount of branching agent and polymerizing condition is selected to obtain water-soluble polymer instead of water-fast cross-linked polymer to make polymerisation.
For object of the present invention, there is no need appointment one and will obtain the crosslinked digital scope (i.e. percentage) of available water-soluble branched polymer.But, monitor the character of the polymer obtained until obtain some scope of those character.The instruction that branched polymer shows as solution polymer instead of microparticle polymer is tan δ value.Although without any specific theories integration, it is believed that the speed of deformation of polymer samples under low frequency (such as 0.005Hz) is enough slow, thus enable linear winding chain or branching winding chain untie winding, obtain high tan δ value.On the other hand, network polymers or highly cross-linked polymer are for good and all wound around, and show low tan δ value in a wide frequency range.Therefore, by determining the tan δ under low frequency (namely 0.005), the measurement of the degree of branching can be determined.For the purposes of the present invention, tan δ value higher than 0.5, preferably higher than 0.7, even more preferably higher than 0.9,1.3 or even higher.Tan δ value ordinary representation lower than 0.5 is too highly cross-linked to such an extent as to as the polymer of real solution polymer, and preferably cannot avoid.
Can to by weight 1.5% polymer solution in deionized water use proof stress flow graph to obtain the tan δ value under 0.005Hz in oscillation mode.The value of tan δ is loss (viscosity) modulus G " with store the ratio of (elasticity) modulus G '.
The tan δ value of preferred branched polymer herein under 0.005Hz is suitably close to the value of the non-branched polymer of correspondence; That is, do not add polymer prepared by branching agent under the same conditions and obtain higher inherent viscosity.Such as, at least 50% of the tan δ of the non-branched polymer that the tan δ of branched polymer is preferably corresponding, and usually at least 80%, such as, up to 120% or more.
Polymer is in the form of a solution instead of at least three times of another instruction of particulate form to be the deionization SLV viscosity number of branched polymer be salted SLV viscosity number of the polymer prepared by making identical monomer feed react when not adding branching agent under same polymeric condition.This is called as " corresponding non-branched polymer ".
Described " same monomer charging " and described " same polymeric condition " represents the constant charging and condition that can reasonably obtain in the commodity production except deliberately the changing of amount of branching agent and optional chain-transferring agent.
Branching agent can be any can with the crosslinked entity of the reaction of pendant group on main polymer chain such as but not limited to acrylic acid hydroxy-acid group, but preferred described branching agent is poly-ethylenically unsaturated monomer (polyethylenically unsaturated monomer).It can be dual functional material, such as methylene-bisacrylamide that described polyene belongs to branching agent, or it can be trifunctional, four senses or the branching agent of higher functional, such as, tetra-alkyl ammonium chloride.The water soluble of preferred described branching agent own.
The amount that polyene belongs to branching agent is usually less than 10ppm (mole), preferably lower than 5ppm (mole).Use 0.5ppm (mole) useful result can be obtained to 3.8ppm (mole), but 4.1ppm (mole) also can be used in some cases to as high as 7ppm (mole) the even amount of 10ppm (mole).In fact, sometimes also can use up to 20ppm (mole) or even up to the amount (usually under the existence of chain-transferring agent) of 30ppm (mole) or 40ppm (mole), but for meeting the restriction of tan δ, usually need lower amount.Title " ppm (mole) " refers to the molal quantity (i.e. ppm (mole)) of branching agent in the monomer of every 1,000,000 moles.
Branched polymer can be prepared under polymerization conditions, wherein be intended to deliberately there is not chain-transferring agent in course of reaction.When not adding chain-transferring agent, the amount of branching agent given above, particularly 1ppm (mole) to 10ppm (mole) and preferred 0.5ppm (mole) to 3.8ppm (mole) especially applicable.But, may need to add some chain-transferring agents, under these circumstances, the amount that can increase branching agent, up to 20ppm (mole) or 30ppm (mole) or even 40ppm (mole), still keeps characteristic and the performance of polymer simultaneously.Used concrete material and amount, the monomer feed of branching agent are depended in the selection of the amount of chain-transferring agent, and polymerizing condition.
Although quite a large amount of branching agents can be used, preferably a small amount of, because observe: a small amount of chain-transferring agent can obtain best result.Preferred chain-transferring agent is sodium hypophosphite.Although can use in a large number, best result requires usually (based on monomer weight by weight) lower than the amount of 50ppm, preferably lower than the amount of 20ppm.Usual use can not obtain best result higher than 10ppm.But, if described amount is too low, such as, lower than about 2ppm, then may not be fully benefited from usage chain transfer agent.
Chain-transferring agent (such as but not limited to isopropyl alcohol or the compound containing sulfydryl) the substituting as hypophosphites of any suitable polymerizable aqueous in water soluble propene's acid monomers can be used.If use the material of non-hypophosphites, then it should with produce with it the amount of the identical chain tra nsfer effect of the chain tra nsfer effect cardinal principle that produces of the amount of hypophosphites that substitutes use.
Although preferably use a small amount of chain-transferring agent, if the combination of material and polymerizing condition makes polymer have required physical property, also can use greater amount such as 100ppm or more, it obtains not good enough result usually.
One of required physical property is the inherent viscosity of polymer.This inherent viscosity uses outstanding face viscosity meter in the 1M NaCl being buffered to pH 7.5 at 25 DEG C.This value normally at least 3dl/g or 4dl/g, preferably at least 6dl/g.It up to such as 18dl/g, but can be usually less than 12dl/g, and often lower than 10dl/g.
Also suitable branched polymer can be characterized by comparing with corresponding nonbranched polymer.The inherent viscosity of described nonbranched polymer normally at least 6dl/g, and preferred at least 8dl/g.Frequently, it is 16dl/g to 30dl/g.The amount of branching agent normally make inherent viscosity reduce the value of nonbranched polymer at least 10%, usually at least 25% or 40%, up to 70% or sometimes up to 90% amount.
Alternative feature viscosity or except inherent viscosity, can also carry out characterize polymers with its salt solution Brookfield viscosity.Salt solution Brookfield viscosity is measured by being prepared at 25 DEG C the solution of polymer in the 1M NaCl aqueous solution of 0.1% by weight.The Brookfield viscosimeter that UL adaptation is housed of 60rpm can be used.Therefore, powder polymer is added in the 1M NaCl aqueous solution, or inverse emulsion polymer is added in this solution.The viscosity of saline solution usually at more than 2.0mPa.s., and is at least 2.2 usually, is preferably at least 2.5mPa.s.Usually, this viscosity number is not more than 5mPa.s, and often this value preferred is 3 to 4.
Substitute tan δ value or except tan δ value, the ratio between deionization SLV viscosity number and salted SLV viscosity number can also be used as the non-existent instruction of insoluble crosslinked fine particles.
Hang face viscosimeter by using glass at 25 DEG C and determine SLV viscosity number, select described viscosimeter according to the viscosity of solution.Viscosity number is η-η
0/ η
0, wherein η and η
0be respectively the viscosity results of aqueous polymer solution and the viscosity results of blank solvent.Described viscosity number also can be called as specific viscosity.The viscosity number that the polymer solution in deionized water that deionization SLV viscosity number is 0.05% obtains.The viscosity number that the aqueous solution of the 1M sodium chloride of the polymer that salted SLV viscosity number is 0.05% obtains.
Deionization SLV viscosity number is preferably at least 3, is generally at least 4.When deionization SLV viscosity number obtains optimum time (such as 7 or 8) more than 5.Preferably, this value is higher than the deionization SLV viscosity number of non-branched polymer.If described deionization SLV viscosity number is not more than the deionization SLV viscosity number of last branched polymer, then preferably this value is at least 50% of last branched polymer deionization SLV viscosity number, is generally at least 75%.Salted SLV viscosity number is usually less than 1.Deionization SLV viscosity number is generally at least five times of salted SLV viscosity number, preferably at least octuple.
Described polymer can be obtained from commercial source, also described polymer be can be obtained by the polymerization that any routine is suitable, described the polymerization such as bead polymerization or gel polymerization process of preparing water-soluble acrylic polymer and other addition polymers become known for.The polymerization of preferred type is inverse emulsion polymerization, to form the reversed-phase emulsion of water-soluble polymer particles in anhydrous liquid.Typically there is the initial particle of this product of by weight at least 95% lower than 10 μm, preferably have the initial particle of this product of by weight at least 90% lower than 2 μm, such as, be low to moderate 0.1 μm or 0.5 μm.Thus, it can be conventional reversed-phase emulsion or microemulsion, and can be prepared by any already known processes for the preparation of such material.If needed, the number average bead diameter of microemulsion typically can such as be low to moderate 0.05 μm or 0.1 μm.
Described emulsion can provide using the form (emulsion as the waterborne polymeric drop in oil or other water immiscible liquid) made by emulsion, if or need, it can be dewatered substantially to be formed substantially anhydrous polymer drop and be scattered in stabilising dispersions in oil.Conventional surfactant and optional polymer both sexes stabilizing agent can be included to stable emulsion in known manner.
To usually in aqueous needed for the charging of monomer or grams of monomer blend carry out reversed-phase polymerization or other polymerization.
Usual preferred anionic branched polymer is 5-97% acrylamide or other is water-soluble, the copolymer of nonionic, ethylenically unsaturated monomer and 95-3% ethylenically unsaturated carboxylic acids monomer, sulfonic acid monomer or other anionic monomer by weight by weight.Water-soluble carboxylic monomer and the sulfonic acid monomer of any routine can be used, such as but not limited to acrylic acid, methacrylic acid, butenoic acid, vinyl sulfonates and AMPS.Preferred anionic monomer is acrylic acid now, usually used as sodium acrylate or other water soluble salt.Preferred copolymer comprises the acrylic acid of 20-80%, usually 40-75% by weight, and surplus is acrylamide.
In special embodiment, the waterborne polymeric of described anion is
m305 (BASF, business can be bought).
Swelling cationic starch/anionic polymer/filler particles suspension
Usually, suspension comprise based on filler, cationic starch and anionic polymer altogether 100% the total solids content swelling cationic starch of filler, the by weight 35-0.499% of 60-99.5% and the anionic polymer of 5.0-0.001% by weight by weight.Understand: suspension contains the compound of the anionic polymer be attached on swelling cationic starch, but also can comprise free swelling cationic starch and free anionic polymer particles.
Swelling cationic starch and anionic polymer are applicable to using using the amount of the 0.5-10% by weight of the weight based on filler particles as solid body.
Papermaking agent
Composition, suspension and batching additionally can comprise conventional papermaking agent such as but not limited to sizing agent such as alkyl ketene dimer, alkenyl succinic anhydride and rosin herein; Wet strength agent, and cationic polymer retention or anionic polymer retention agent.It can be the retention agent of single chemicals that described composition can comprise, such as cationic microparticles (colloid silicic acid, bentonite), anionic polyacrylamide, cationic polymer (cationic polyacrylamide, cationic starch), two chemical system (cationic polymer/anionic microparticles, cationic polymer/anionic polymer) or three compositions system (cationic polymer/anionic microparticles/anionic polymer, cationic polymer/anionic micropolymers/anionic polymer).The selection of retention agent chemicals and the addition point in paper forming process thereof depend on the character of the ionic charge of handled filler slurry and paper making stock furnish.
Usually, the filler suspension of this paper is to use as solid body based on the amount of the dry weight 5% to 60% of paper pulp in batching.
As passed through measured by Scott combination technology (Scott bond technique), the Packed paper of the tool made can show than not having the internal bond strength that Packed contrast paper is larger.Under equal filer content, the paper that the wet strength performance of the paper using filler suspension described herein to make and dry strength performance can be made with filler than those is stronger.
Use filler suspension of the present invention to allow to produce the loaded sheet with minimum intensity loss and good optical properties to be such as coated with and uncoated fine paper, supercalendered paper and newsprint.Therefore, filler suspension of the present invention is used to allow papermaker to produce the loaded sheet had in paper compared with high filler content.In general, use the potential benefit of the filler suspension processed of the present invention to comprise the applying glue of improvement, wet strength, dry strength, opacity and print quality, and reduce and use expensive enhancing chemical paper fiber.
Under certain condition, the combination of swelling cationic starch and anionic polymer may be used for reinforcing other grade paper using not containing filler of such as sack kraft paper and board product.
Embodiment
General introduction
Can be described by following illustrative embodiment and understand suspension of the present invention and method.In the described embodiment, laboratory scale technology is used to obtain result.But these embodiments are not intended to or are interpreted as limiting by any way.
The starch solid of 2-20% (at room temperature in slurry) can carry out in batch steamer, jet cooker at the temperature of approximate starch gel point swelling or by mix with hot water carry out swelling.Preferred method is by the starch size prepared in cold water is mixed to come swellable particles with hot water.Use the temperature of hot water to depend on the temperature of the final goal temperature of the denseness of the initial starch slurry in cold water, swollen starches, cold water, pH and the time of staying.Temperature and the reaction time of preparing swollen starches/polymer composition depend on the type of used starch, the pH of starch size and heat time heating time.Here is the example of the preparation method of swollen starches for the object of the invention.
Embodiment 1
By swelling with the uncooked amylum dispersion of mixed with polymers in cold water, and swelling starch/polymer composition is added in the filler suspension of stirring.In this method, first starch powder is scattered in cold water, then under shear polymer is incorporated in dispersion.Mix starch/anionic polymer mixture with hot water or be heated to the temperature of approximate starch gel point.Then swelling starch/anionic polymer compositions is promptly mixed at the temperature lower than starch gel temperature with filler suspension.
Embodiment 2
First cationic star dispersions is swelling, then added in the filler suspension of stirring, introduced anionic polymer afterwards.In this method, starch powder is scattered in cold water, then mixes or be heated to the temperature of approximate starch gel point with hot water.Then swelling starch is promptly mixed with filler suspension at the temperature lower than starch gel point, then add anionic polymer.
The combination of swelling cationic starch, anionic water-soluble polymer and filler is carried out under good mixing condition.Other reagents for anion or cation reagent can be added to form compound before adding filler in the process of composition preparing swelling cationic starch/anionic water-soluble polymer, or they can be added in the filler suspension of shear treatment to form bridge joint filler particles.These processing policies can produce during prolonged storage stable uniform filler suspension.
Can the filler suspension of process be introduced directly in pulp, if or need, also can such as in the porch of blending chest, paper machine stock tank or fan pump, the filler suspension of process be diluted before paper forming process and add paper machine paper pulp raw material to.The filler of process is introduced into pulp suspension causes pulp to flocculate.But level of shear and the time of staying can affect the degree of flocculation.In general, the filler suspension of process is tended to when adding in paper making pulp slip along with the time keeps its flocculating properties.For reinforcer retention, anionic microparticles preferably head box or pressurized screen before or at head box or pressurized screen place can be added into batching such as but not limited to CMC or traditional polymer glidant such as but not limited to polyacrylamide such as but not limited to silica, anionic polymer.Once silica or CMC are added in the paper pulp raw material containing the filler processed, retention and dehydration rate are improved greatly.
Embodiment 3
By inner cationic starch is mixed with intermittent pulp proportioning, then mix with pre-prepared PCC, finally mix the material preparing 0.3% concentration with retention agent.Use dynamic paper forming machine (DSF) then to carry out dynamic paper compacting and at 120 DEG C drying to manufacture 80g/m
2without wooden handmade paper.Before paper test, by paper press polish at identical conditions, then controlled condition is at 50%RH and 22 DEG C.
Raw material in manufacturing for paper are as follows:
Fiber: the Eucalyptus of 100% is used as paper pulp, uses Valley Beater laboratory refiner to be refined to SR 30 (at 20 DEG C).
Filler: from the winnofil (Albacar LO PCC) of Specialty Minerals Inc., average grain diameter 2.3 μm.In paper, PCC content changes by weight between 19.3% and 25.9%.
For the pretreated swelling cationic starch of PCC: cationic potato starch.By dry cationic starch powder and water are mixed and made into 3% slurry of solids, subsequently this 3% slurry of solids is heated to 63 DEG C prepare swelling cationic starch under mixing.By the swelling cationic starch of 5kg/ metric ton (ton) paper is mixed with the PCC of 20% solid the preliminary treatment swelling cationic starch being used for PCC.Some packing samples are only with swelling cationic starch preliminary treatment, and some packing samples swelling starch and anion are total to additive preliminary treatment.
The pretreated additive altogether of PCC for utilizing swelling cationic starch to carry out: the anionic micropolymers (trade mark of BASF
).By swelling cationic starch and anionic micropolymers to have been mixed the process of PCC with PCC.Use different orders of addition, and the dosage of simultaneously swelling cationic starch is fixed as 5kg/ ton paper, the dosage of anionic micropolymers is 0.05% sample material/dry PCC (weight) and 0.1% sample material/dry PCC (weight).
Internal starch: cationic potato starch.Dried starch powder is mixed with water and obtains 1% slurry of solids, subsequently by the slaking at 97 DEG C under mixing of this 1% slurry of solids.Ripe cationic starch is used by it being mixed with intermittent pulp proportioning with 8kg/ ton paper.
Retention agent: the cationic polyacrylamide (CPAM) of 0.2kg/ ton paper is used to keep.
Embodiment 4
Table 1 gives only by the PCC of swollen starches process and the performance of paper then made with the PCC of anionic micropolymers process with swelling starch.The agent of anionic micropolymers is 0.05-0.1% sample material/dry PCC (weight).Comparing with the paper of swelling starch with only using the PCC processed, in PCC preliminary treatment, using the paper of anionic micropolymers to show reasonable strength character-stretching, inner combination, bending hardness.Best strength character is obtained with the dosage of the highest 0.1%/PCC anionic micropolymers.This can obtain 6% unit filler increases and does not lose strength character.
Table 1
PCC: winnofil, SST: CATION swollen starches, AMP: anionic micropolymers.
Tension values and hardness number are the geometrical mean of vertical and horizontal.
Embodiment 5
Table 2 gives by the PCC of only swollen starches process and PCC (the different order of addition: with swollen starches then with the PCC of anionic micropolymers process by swelling starch and anionic micropolymers process; And the PCC of anionic micropolymers process then swollen starches process) performance of paper prepared.The existence of anionic micropolymers improves the strength character of the paper prepared by the PCC of swollen starches process, and has nothing to do with order of addition.
Table 2
PCC: winnofil, SST: CATION swollen starches, AMP: anionic micropolymers.
Tension values and hardness number are the geometrical mean of vertical and horizontal.
Embodiment 6
How these MIcrosope images in Fig. 6 increases if describing the how swelling and viscosity of amylum body, until cause it to start to decline because swollen starches grain breaks.Image table is shown in the cornstarch sample at 25 DEG C, 56 DEG C, 60 DEG C, 66 DEG C and 95 DEG C.
For object of the present invention, swollen starches is characterized as being: as in 56 DEG C of images, most of particle has started swelling until swellable particles large as in 66 DEG C of images is still visible.Therefore, viscograph can be used to determine starch swelling opportunity for the preparation of filler suspension of the present invention in conjunction with micro-image.The region of the peak viscosity in Fig. 5 be most starches grain swelling but uncracked time.Can obtain the temperature range of useful swollen starches grain in the +/-10 DEG CFeng district of Fig. 5, here, most starches grain is swelling but break completely not yet.Preferably, the temperature of heating uncooked amylum grain suspension is+10 DEG C, peak, and here, all amylum bodies are all swelling, and all not swelling particles are all eliminated.
The all patents quoted in this description and patent application are incorporated to all by reference, also independently fully set forth each independently patent and patent application as concrete herein.Although just multiple embodiment describes claimed theme, understanding can be carried out multiple amendment, replacement, deletion and change and not depart from spirit of the present invention by technical staff.Therefore, the scope of the theme only limited by the scope of claim is below intended to comprise its equivalency range.
Claims (19)
1., for a filler suspension for papermaking, it comprises:
Filler particles;
Swelling cationic starch; With
The water-soluble polymer of anion.
2. filler suspension according to claim 1, the water-soluble polymer of wherein said anion is lightly crosslinked.
3. filler suspension according to claim 2, tan δ that is wherein said anion, lightly crosslinked, water-soluble polymer flow become vibration values under 0.005Hz in the aqueous solution of 1.5% at least 0.5.
4. the filler suspension according to any one of claim 1-3, wherein said anion, lightly crosslinked, water-soluble polymer comprises sodium acrylate, acrylamide and methylene-bisacrylamide.
5. filler suspension according to claim 1, the water-soluble polymer of wherein said anion is
m305.
6. filler suspension according to claim 2, the water-soluble polymer of wherein said anion is
m305.
7. filler suspension according to claim 1, wherein said filler particles is selected from by the following group formed: clay, talcum, grinding calcium carbonate, chalk, winnofil, sulfate precipitate calcium and their combination.
8. filler suspension according to claim 1, wherein at gel point temperature ± 10 of cationic starch DEG C, does not make described cationic starch slaking with the swelling described cationic starch grain of hot water.
9. filler suspension according to claim 8, wherein the temperature of swelling described cationic starch grain is gel point temperature+10 DEG C.
10. filler suspension according to claim 1, wherein said filler particles is of a size of 1-10 micron.
11. filler suspension according to claim 1, wherein said swelling cationic starch grain is of a size of 25-100 micron.
12. filler suspension according to claim 1, wherein based on the total solids content of described filler suspension, described filler particles exists with the amount of 60% to 99.5% by weight, described swelling cationic starch exists with the amount of 35% to 0.499% by weight, and the water-soluble polymer of described anion exists with the amount of 5.0% to 0.001% by weight.
13. 1 kinds of intermittent pulp proportionings, it comprises paper pulp fiber and filler suspension according to claim 1.
14. intermittent pulp proportionings according to claim 12, it also comprises the common additive be selected from by the following group formed: sizing agent, wet strength agent, retention agent and their combination.
15. 1 kinds of paper, it comprises the intermittent pulp proportioning described in any one of claim 13 or 14.
16. 1 kinds of productions are used for the method for the filler suspension of papermaking, and it comprises makes filler particles contact with the water-soluble polymer of anion with swelling cationic starch.
17. methods according to claim 16, the water-soluble polymer of wherein said anion is lightly crosslinked.
The method of 18. 1 kinds of papermaking, it comprises: make paper pulp fiber contact to form a kind of intermittent pulp proportioning with filler suspension according to claim 1; Described intermittent pulp proportioning is discharged to form paper by circuit; And dry described paper.
19. methods according to claim 18, wherein said intermittent pulp proportioning also comprises the common additive be selected from by the following group formed: sizing agent, wet strength agent, dry strength agent, retention agent and their combination.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2012/059117 WO2014055092A1 (en) | 2012-10-05 | 2012-10-05 | Filler suspension and its use in the manufacture of paper |
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| CN104812958A true CN104812958A (en) | 2015-07-29 |
Family
ID=50435291
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| CN201280076267.8A Pending CN104812958A (en) | 2012-10-05 | 2012-10-05 | Filler suspension and its use in the manufacture of paper |
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| EP (1) | EP2904145A4 (en) |
| JP (1) | JP2015533953A (en) |
| KR (1) | KR20150064193A (en) |
| CN (1) | CN104812958A (en) |
| BR (1) | BR112015007495A2 (en) |
| CA (1) | CA2886369A1 (en) |
| MX (1) | MX2015004170A (en) |
| RU (1) | RU2015115882A (en) |
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| ZA (1) | ZA201502046B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106758499A (en) * | 2017-03-23 | 2017-05-31 | 长沙理工大学 | A kind of method for improving hot-pressing type bedding paper heat resistance |
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| FI126543B (en) * | 2013-05-17 | 2017-02-15 | Fp-Pigments Oy | A process for the preparation of an aqueous pigment-containing cationic high solids dispersion, an aqueous pigment dispersion and its use |
| CN106320066B (en) * | 2015-07-01 | 2018-04-03 | 金东纸业（江苏）股份有限公司 | A kind of preparation method of fill composition, fill composition and paper |
| EP3704568A1 (en) | 2017-10-30 | 2020-09-09 | Nanoga SA | Device for a digital writing instrument |
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| TW524910B (en) | 1999-11-08 | 2003-03-21 | Ciba Spec Chem Water Treat Ltd | Manufacture of paper and paperboard |
| MY140287A (en) * | 2000-10-16 | 2009-12-31 | Ciba Spec Chem Water Treat Ltd | Manufacture of paper and paperboard |
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| US8227529B2 (en) | 2007-07-05 | 2012-07-24 | Basf Se | Aqueous slurries of finely divided fillers, a process for their preparation and their use for the production of papers having a high filler content and high dry strength |
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| EP2246472A1 (en) * | 2009-03-24 | 2010-11-03 | Mondi Limited South Africa | Process for preparing polysaccharide gel particles and pulp furnish for use in paper making |
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- 2012-10-05 RU RU2015115882A patent/RU2015115882A/en not_active Application Discontinuation
- 2012-10-05 MX MX2015004170A patent/MX2015004170A/en not_active Application Discontinuation
- 2012-10-05 KR KR1020157011715A patent/KR20150064193A/en not_active Application Discontinuation
- 2012-10-05 CN CN201280076267.8A patent/CN104812958A/en active Pending
- 2012-10-05 JP JP2015535641A patent/JP2015533953A/en active Pending
- 2012-10-05 BR BR112015007495A patent/BR112015007495A2/en not_active IP Right Cessation
- 2012-10-05 WO PCT/US2012/059117 patent/WO2014055092A1/en active Application Filing
- 2012-10-05 CA CA2886369A patent/CA2886369A1/en not_active Abandoned
- 2012-10-05 EP EP12885948.5A patent/EP2904145A4/en not_active Withdrawn
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- 2015-03-24 ZA ZA2015/02046A patent/ZA201502046B/en unknown
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| EP1167392A1 (en) * | 1996-12-31 | 2002-01-02 | Ciba Specialty Chemicals Water Treatments Limited | Materials for use in making paper |
| US20030188738A1 (en) * | 2002-04-09 | 2003-10-09 | Makhlouf Laleg | Swollen starch-latex compositions for use in papermaking |
| CN101680189A (en) * | 2007-02-05 | 2010-03-24 | 巴斯夫欧洲公司 | Manufacture of filled paper |
| US20110233124A1 (en) * | 2008-10-15 | 2011-09-29 | Pentti Virtanen | Acidic water and its use for drainage or separation of solids |
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| CN106758499B (en) * | 2017-03-23 | 2019-01-22 | 长沙理工大学 | A method of improving hot-pressing type bedding paper heat resistance |
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| Publication number | Publication date |
|---|---|
| CA2886369A1 (en) | 2014-04-10 |
| EP2904145A4 (en) | 2016-04-20 |
| MX2015004170A (en) | 2015-10-22 |
| KR20150064193A (en) | 2015-06-10 |
| RU2015115882A (en) | 2016-11-27 |
| BR112015007495A2 (en) | 2017-07-04 |
| EP2904145A1 (en) | 2015-08-12 |
| ZA201502046B (en) | 2016-01-27 |
| WO2014055092A1 (en) | 2014-04-10 |
| JP2015533953A (en) | 2015-11-26 |
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