CN104781469A - Filler suspension and its use in the manufacture of paper - Google Patents

Filler suspension and its use in the manufacture of paper Download PDF

Info

Publication number
CN104781469A
CN104781469A CN201380052234.4A CN201380052234A CN104781469A CN 104781469 A CN104781469 A CN 104781469A CN 201380052234 A CN201380052234 A CN 201380052234A CN 104781469 A CN104781469 A CN 104781469A
Authority
CN
China
Prior art keywords
starch
filler
suspension according
filler suspension
paper
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
CN201380052234.4A
Other languages
Chinese (zh)
Inventor
L·K·希尔维科斯基
A-P·J·拉克索
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Special Minerals (michigan) Co Ltd
Specialty Minerals Michigan Inc
Original Assignee
Special Minerals (michigan) Co Ltd
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.)
Filing date
Publication date
Application filed by Special Minerals (michigan) Co Ltd filed Critical Special Minerals (michigan) Co Ltd
Publication of CN104781469A publication Critical patent/CN104781469A/en
Pending legal-status Critical Current

Links

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
    • 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
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • 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
    • D21H17/25—Cellulose
    • 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
    • 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
    • D21H17/33—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
    • 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
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Paper (AREA)

Abstract

Provided herein are filler suspensions comprising an ionic starch, a complementary ionic co-additive 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

Filler suspension and the application in papermaking thereof
Technical field
The present invention relates to a kind of filler suspension being total to additive containing filler particles, ionic starch and complementary ion.Additionally provide and use described suspension to prepare the method for paper batching and the method by described batching papermaking.
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 to be formed " batching " alleged in field of papermaking, 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, adds 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 glidant 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 improves one, the two or three component chemical additive of filler and fines retention typically 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 shear rate in paper-making process and the contact time between retention agent and furnish component.
Existing industrial trend is the filer content that increases in paper thus reduces costs further.But owing to instead of fiber with filler, paper strength is lowered, 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 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), winnofil (PCC), chalk, talcum, titanium dioxide, grinding calcium sulfate (GCS) and sulfate precipitate calcium (PCS).The filler 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 and narrow size distribution, 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 permeable or porous.When in preparing burden, filer content 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/hydrophobicity.This is because a part of out-of-proportion sizing chemicals is attracted on filler particles.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.But, in the paper of these grades, use the main misgivings of calcium carbonate to be still in (especially) retention, paper strength and printing.
Another 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 is a kind of filler suspension for papermaking, and it comprises filler particles, ionic starch and complementary ion additive altogether.
In one aspect of the invention, described filler particles is selected from by the following group formed: clay, talcum, synthetic silicate, sodium silicoaluminate magnesium, sodium silicoaluminate, grinding calcium carbonate (GCC), chalk, winnofil (PCC), grinding calcium sulfate (GCS), sulfate precipitate calcium (PCS), titanium dioxide and their combination.
In one aspect of the invention, described ionic starch is uncooked amylum.
In one aspect of the invention, described ionic starch is swelling ionic starch.
In one aspect of the invention, described ionic starch is the ionic starch of slaking.
In one aspect of the invention, described ionic starch is cationic.
In one aspect of the invention, described ionic starch is anion.
In one aspect of the invention, described ionic starch is both sexes.
In one aspect of the invention, described ionic starch is selected from by the following group formed: cornstarch, rice fecula, farina, wooden sweet potato starch (cassava starch), tapioca (tapiocastarch), waxy corn starch, wheaten starch, sorghum starch and wax sorghum starch.
In one aspect of the invention, described swelling ionic starch is formed by heating farinose waterborne suspension at farinose gel point temperature ± 10 DEG C.
In one aspect of the invention, described swelling ionic starch is formed by heating farinose waterborne suspension in the gel point temperature of described starch to the temperature range of the gel point temperature+10 DEG C of described starch.
In one aspect of the invention, described complementary ion is total to additive is Flokal B.
In one aspect of the invention, described Flokal B comprises the copolymer of acrylamide and sodium acrylate.
In one aspect of the invention, described complementary ion altogether additive be selected from by the following group formed: NALCO 61815, Nalco 61816, Nalco 61830,
In one aspect of the invention, described complementary ion is total to additive is anionic inorganic microparticles.
In one aspect of the invention, described anionic inorganic particles is selected from by the following group formed: bentonite, cataloid, borsal, aluminium hydroxide or their combination.
In one aspect of the invention, described complementary ion is total to additive is nano-cellulose.
In one aspect of the invention, described complementary ion is total to additive is polyvinyl alcohol.
In one aspect of the invention, described complementary ion is total to additive is anion PVAm or both sexes PVAm.
In one aspect of the invention, described complementary ion is total to additive is biopolymer.
In one aspect of the invention, described biopolymer is based on starch.
In one aspect of the invention, described starch-based bio polymer is adhesive.
In one aspect of the invention, described complementary ion is total to additive is anion pp acid or polyacrylic sodium salt.
In one aspect of the invention, described complementary ion is total to additive is natural polymer.
In one aspect of the invention, described natural polymer is selected from by the following group formed: carboxymethyl cellulose, sky heat natural gum, soy polymers or their combination.
In one aspect of the invention, described filler particles is winnofil.
One aspect of the present invention is a kind of intermittent pulp proportioning, and it comprises paper pulp fiber and filler suspension of the present invention.
In one aspect of the invention, above-mentioned intermittent pulp proportioning also comprises the additive be selected from by the following group formed: sizing agent, dry strength agent, wet strength agent, retention agent and other functionalized chemical material such as Optical Bleaching Agent, dyestuff, defoaming agent, bioside and their combination.
One aspect of the present invention is a kind of paper products, and it comprises above-mentioned intermittent pulp proportioning.
Accompanying drawing explanation
Fig. 1 is a kind of schematic diagram of papermaking process, and wherein additive and filler particles are added in aqueous medium substantially simultaneously altogether for ionic starch, complementary ion.
Fig. 2 is a kind of schematic diagram of papermaking process, wherein before interpolation filler particles, by complementary ion additive and ionic starch premixed in an aqueous medium altogether.
Fig. 3 is a kind of schematic diagram of papermaking process, wherein before interpolation ionic starch, by complementary ion additive and filler particles premixed in an aqueous medium altogether.
Fig. 4 is a kind of schematic diagram of papermaking process, wherein before interpolation complementary ion altogether additive, by ionic starch and filler particles premixed in an aqueous medium.
Fig. 5 is when being heated to gelling temp and the gelling temp higher than farina of farina, the curve map of the viscosity reaction of farina.
Fig. 6 comprises micro-image when farina grain heats in the water of different temperatures.
Fig. 7 is the curve map of the TENSILE STRENGTH providing the paper using the multiple fill composition comprising those fill compositions of the present invention to make.
Fig. 8 is the curve map providing the paper hardness using the multiple fill composition comprising those fill compositions of the present invention to make.
Detailed description of the invention
Form explanation
Table 1 shows and uses the paper made of fill composition that comprises swelling cationic starch and the contrast using the paper performance comprising the paper that fill composition that swelling cationic starch adds anionic micropolymers additive is altogether made.
Table 2 shows the contrast of the paper performance of the paper using the fill composition adding each component of composition with different order of addition to make.
Table 3 shows with the paper be only made up of the PCC filler of swelling cationic starch process and the contrast improved by the TENSILE STRENGTH of the paper be made up with the PCC filler being total to additive treating of swelling cationic starch.
Table 4 illustrates and depends on that paper tensile index/breaking length that swollen starches and multiple altogether additive add the order of PCC to improves the contrast of percentage.
The contrast that the paper that table 5 shows multiple PCC process improves relative to the TENSILE STRENGTH of the paper of non-PCC process baseline.
Table 6 shows the contrast used containing by swelling cationic starch or the cationic starch of slaking or the cationic starch of slaking and the multiple paper performance of the fill composition of the PCC of additive treating altogether.
Discuss
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 filler particles, ionic starch and the complementary ion additive altogether in liquid media (normally water).
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 being added into paper pulp fiber raw material and forming intermittent pulp proportioning and then by described batching papermaking by filler suspension of the present invention.Other reagents for anion and cation reagent can be added into batching to strengthen retention and to improve dehydration rate.As previously mentioned, described batching also can comprise other known papermaking reagent of those skilled in the art.
Present invention also offers the method forming filler suspension for the production of the compositions of additives of starch/altogether and their combination and filler particles.
Starch herein can be uncooked amylum, swollen starches, ripe starch or their combination.
As used herein, " life " starch refers to without being enough to make its swelling or slaking to be the hereinafter described hot water of state or the starch of steam treatment.
As used herein, " swelling " starch refers to and absorbs water and expand (preferred at this) does not break to wherein said swelling particle, can not absorb the uncooked amylum grain of the state of water again.The exemplary swollen starches be suitable in filler suspension herein includes but not limited at United States Patent (USP) the 7th, 074, No. 845, the 7th, 625, No. 962 and the 8th, 354, disclosed in No. 004, those, be here incorporated to the full content that they are set forth herein by way of reference.
Usually, swollen starches requirement is prepared: carry out swelling under the condition of the temperature and time controlled carefully.Other interested parameter comprises slurry pH, compatibility and mixing.Controling 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.General procedure is suspended in cold water by life ionic starch, and then heated suspension liquid is until starch is swelling.By swelling starch, additive and filler particles mix with the order needed arbitrarily altogether with complementary ion subsequently, namely, substantially can add all components simultaneously, or, can any two kinds and to add remaining component afterwards to form filler suspension of premixed component.Such as, in FIG, the common additive 8a of swelling ionic starch 1, complementary ion 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 ionic starch 1 and complementary ion altogether additive 8a are pre-mixed, 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, complementary ion altogether additive 8a and filler particles 2 is pre-mixed, and then this combination mixes in mixer 4 with ionic starch 1, and the filler suspension of formation is transferred to mixer 5, and here it mixes with paper pulp fiber 3 and forms batching.In the diagram, ionic starch 1 and fiber grain 2 premixed in mixer 4, and pre-composition is transferred to mixer 5, in the transport substantially between mixer 4 and mixer 5, complementary ion is total to additive 8a and is added into pre-composition.In each case, the batching comprising filler suspension is transferred to paper machine 6 subsequently to form paper 9 together with optional additives 7.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.
As used herein, " ripe " starch refers to the temperature that is heated above its gel point and keeps until the swelling and starch that broken of all swellable particles substantially of amylum body.
The combination of ionic starch, ionic additive 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 the intensity of paper.Common additive/filler particles the composition of ionic starch/ion is used to be tending towards obtaining than using the intensity that independent starch or common additive and filler particles are larger.
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, grinding calcium sulfate (GCS) and sulfate precipitate calcium (PCS), titanium dioxide, synthetic silicate, sodium silicoaluminate magnesium, sodium silicoaluminate and their blend.The pulp adding filler suspension can be made up of mechanical pulp, chemical pulp, recovery paper pulp and their mixture.
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.Starch can be cationic, anion or both sexes; Each in these forms is all well known in the art, and normally business can be bought.Pass through limiting examples, starch can be made in starch to present cationic state by comprising quaternary ammonium cation, by comprising carboxyl or sulfate group makes starch present the state of anion in starch, and comprise the starch of aforesaid combination by preparation and make starch present the state of both sexes.Technical staff due to field of papermaking knows all these ionic starch forms, therefore, is not described further herein.
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 reach the critical-temperature being called as " gelatinization " temperature, " gelation " temperature or being called " gel " temperature simply, now 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.Swollen starches grain is different from ripe starch.Ripe starch produces when swollen starches grain breaks at higher than the temperature of gelling temp and discharges amylose and amylopectin (they are dissolved in aqueous medium) thus.
By carefully controlling the process of concrete starch, its swelling or slaking can be made.For swollen starches, depend on 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.
Additive altogether
Additive is included in the effect of the performance being improved ionic starch strengthening loaded sheet among filler suspension by modified filler suspension altogether.Altogether additive can be cationic, anion or both sexes.Select to be total to additive thus the net charge making it have the net charge complementation to ionic starch." complementary " refer to if starch is cationic, then preferably additive is anion altogether, and vice versa.If starch is both sexes, then altogether additive can be cationic, anion or itself be both sexes.Anion altogether additive includes but not limited to carboxymethyl cellulose, nano-cellulose, polyacrylic acid, alginates, cataloid, bentonite, polyacrylamide, natural gum and soluble soap.CATION altogether additive includes but not limited to polymine, shitosan, polyvinylamine, PDDA, polyacrylamide, alum, Tricationic and quadrivalent cation.Soy polymers also can be used as additive altogether.More than one common additive can be used together with filler with concrete starch.
The limiting examples be suitable as the common additive of both sexes of the common additive in filler suspension of the present invention is
Other material be suitable as the common additive in filler suspension of the present invention is anionic colloidal silica nano particle, such as but not limited to with they are all from AkzoNobel; From Kemira's and from Nalco's
Nalco Ultra 8693, BD420 and TR420 is also suitable as the common additive in filler suspension of the present invention, and they are borsal nano particle (general size are 1-100nm).
From S & B Industrial Minerals's from Kemira's lF5 and from BASF's be suitable as the bentonite for the common additive in filler suspension of the present invention.
Anion hydrogen alumina particulate is also considered to be suitable as the common additive in filler suspension of the present invention.
are anionic acrylamide copolymers from Hercules Incorporated (being Ashland-Hercules now) with 9232, they are also be suitable as the common additive in filler suspension of the present invention. be described in MSDS 9,991,060 1076, in the 3rd edition (being issued on February 12nd, 2007).
As described in the MSDS of distribution on March 23rd, 2006, from Ciba SpecialtyChemicals Corporation (being BASF now) be the copolymer being dispersed in sodium acrylate in mineral oil and acrylamide, be suitable as equally for the common additive in filler suspension of the present invention.Other composition such as but not limited to m100, M135, M200, M300, S10, M100A, M8A and SC22 also can be suitable as the common additive in filler suspension of the present invention.
the additive of family comprises such as (the two is all based on acrylamide/acrylic acid copolymer) and anionic form; And such as the cationic form of (comprising the preparation of acrylamide/p-amine), E128 (comprising the preparation of polyacrylamide/PDDA (DADMAC) copolymer), ES-325 (comprising the preparation of polyacrylamide/salt) and E-126 (acrylamide/p-amine) is also suitable as the common additive in filler suspension of the present invention.
Nano-cellulose (such as but not limited to described in WO 2007/091942 and WO 2009/126106, the two is all incorporated to herein all by way of reference) is also suitable as the common additive in filler suspension of the present invention.
Being considered to the other material be suitable as the common additive in filler suspension of the present invention is cellulosic-based material and derivative, such as, from the EngineeeredCellulose Additive (ECA) of AkzoNobel; By way of reference the full content that it is set forth is incorporated to the noil fubril described in No. the 6th, 156,118, United States Patent (USP) herein; Material containing hemicellulose and the material containing high hemicellulose.
Carboxymethyl cellulose (CMC) is also suitable as the common additive in filler suspension of the present invention.
Natural gum such as guar gum and xanthans are also suitable as the common additive in filler suspension of the present invention.
Think that other material be suitable as the common additive in filler suspension of the present invention is that (they are Flokal Bs to NALCO 64110,64114 and 64170 (they are glyoxalated DADMAC/ acrylamide copolymer compositions) and NALCO 61815,61816 and 61830 at present, described Flokal B by way of reference the full content that it is set forth is incorporated to United States Patent (USP) 8 herein, 088, the acrylamide of general description and the copolymer of sodium acrylate in 213).
The other material be suitable as the common additive in filler suspension of the present invention is Ashland-Hercules hA5305and SP7200and Eka PL8660.
Polyvinyl alcohol (PVA) is suitable as equally for the common additive in filler suspension of the present invention.
Also be suitable as the common additive in filler suspension of the present invention be the polyvinylamine of anion polyvinylamine (PVAm) and both sexes such as but not limited to vinyl formamide, vinyl amine and acrylic acid both sexes trimer, its limiting examples is from BASF f3000.
Biopolymer also can be used as the common additive in filler suspension of the present invention.Suitable biopolymer as filler additive includes but not limited to starch-based bio polymer.Described biopolymer can be microparticle or nano particle.Biopolymer includes but not limited to the Ecosynthetix from Ontario, Canada Burlinton 2202 adhesives.
If altogether additive is polymer, then it can not be crosslinked, lightly crosslinked or highly cross-linked.
Additive can be water-soluble or water-fast altogether.The limiting examples of water-soluble common additive is polyacrylamide base anionic polymer.
Polymer altogether additive can be micro-polymer.As used herein, " micro-polymer " refers to and is polymerized by emulsion polymerisation, dispersin polymerization and water-water the polymer beads obtained, under the existence of coagulant, wherein carry out the reaction of water-soluble monomer, described coagulant is such as but not limited to polyamines such as DADMAC or DIMAPA.Described micro-polymer can be " structurized ", and that is, the independent polymer chain of polymer particles intragranular can present stable three-dimensional structure.
" lightly crosslinked " refers to that cross-linked polymer keeps water-soluble substantially.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.
" highly cross-linked " although it is solvable for referring to simply when uncrosslinked or lightly crosslinked, no longer water-soluble polymer due to the degree of cross linking.
Filler/ionic starch/ion is additive suspension altogether
Usually, suspension comprise based on filler, ionic starch and complementary ion altogether additive altogether 100% the total solids content ionic starch of filler, the by weight 35-0.499% of 60-99.5% and the complementary ion additive altogether of 5.0-0.001% by weight by weight.
Understand: suspension will be total to the compound of additive containing ionic starch and complementary ion, but also can comprise free ionic starch and free ion additive altogether.
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 dry 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 microgel particle (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 shearing force produced in the character of the ionic charge of handled filler slurry, paper making stock furnish and paper-making process.
Usually, filler suspension herein uses as solid body with the amount of the dry weight based on paper pulp in batching using 5% to 70%.
As passed through measured by Scott combination technology (Scott bond technique), the paper be made up of filler suspension of the present invention can show the internal bond strength larger than the contrast paper without filler process.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 only 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 and printability, and/or reduce and use expensive enhancing chemical paper fiber.
Under certain condition, the combination of ionic starch and the common additive of ion may be used for strengthening the paper grades not containing filler of such as sack kraft paper and board product.
Embodiment
Embodiment provided below is only intended to help to understand many aspects of the present invention.These embodiments are not intended to or are interpreted as limiting the scope of the invention by any way.
General introduction
In the following embodiments, laboratory scale technology is used to obtain result.
If starch to be used is uncooked amylum, then it can suspend in water or it can suspend in water, and is heated to enough lower than the temperature of its gel point, thus neither to a great extent swelling described starch do not make its slaking yet.
On the other hand, if need swollen starches, then the uncooked amylum solid of usual 0.5-20% (at room temperature in water paste) can carry out in batch steamer, jet cooker at the temperature of approximate starch gel point swelling or 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 denseness of the initial starch slurry in cold water, the final goal temperature of swollen starches, cold starch size, pH and the time of staying.Temperature and the reaction time of preparing swollen starches 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
Make it swelling by the temperature raw ionic starch dispersion in cold water being heated to the gel point of this specific starch approximate.When starch by swelling time, add complementary additive altogether, and mixture added in the filler suspension of stirring.
Embodiment 2
First make starch dispersions swelling, then added in the filler suspension of stirring, then introduce additive altogether.In this method, starch powder is scattered in cold water, then mixes or be heated to the temperature of gel point of this starch approximate with hot water.Then swelling starch is promptly mixed with filler suspension at the temperature lower than starch gel point, then add additive altogether.
Embodiment 3
First make starch dispersions swelling, then added in the common additive/filler suspension of stirring.In this method, starch powder is scattered in cold water, then mixes or be heated to the temperature of gelling temp of this specific starch approximate with hot water.Then swelling starch is promptly mixed with filler suspension.
The composition of swelling starch, altogether additive and filler is operated under good mixing condition.Other additive can be added to form compound with filler in the process preparing starch/common additive/filler suspension before adding swelling starch and common additive.
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.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, the consumption of the retention agent of such as anionic microparticles (cataloid, bentonite, Organic micropolymers), anionic polymer (anionic polyacrylamide), cationic polymer (cationic polyacrylamide, cationic starch) can be increased.
Embodiment 4
By inner cationic starch is mixed with intermittent pulp proportioning, then mix with pretreated 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 50% relative humidity (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 precipitation of Specialty Minerals Inc. calcium carbonate ( lOPCC), 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.Mix with the PCC of 20% solid the preliminary treatment swelling cationic starch being used for PCC by the swelling cationic starch of the paper 5kg by per metric ton (ton, tn).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 consumption of simultaneously swelling cationic starch is fixed as 5kg/ ton paper, the consumption 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 and water are mixed into 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 5
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 consumption of anionic micropolymers is 0.05-0.1% sample material/dry PCC (weight).Compared with the PCC of independent swollen starches process, in PCC preliminary treatment, the paper of anionic micropolymers is used to show reasonable strength character-stretching, inner combination, bending hardness.Best strength character is obtained with the consumption of 0.1% 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 6
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 is the geometrical mean of vertical and horizontal.
Embodiment 7
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 potato starch 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 refers to following state: 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 can be used to determine the opportunity of fully swelling starch 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.The temperature range of available useful swollen starches grain is in the scope from Tu5Feng district extension +/-10 DEG C.Preferably, heating uncooked amylum grain suspension adds between 10 DEG C with the temperature producing swollen starches at the peak temperature of peak temperature and Fig. 5, and here, all amylum bodies are all swelling, and all not swelling particles are all eliminated.
Embodiment 8
The preparation method of handmade paper is with described similar above.
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 Specialty Minerals Inc. winnofil ( lOPCC), average grain diameter 2.1 μm.In paper, PCC content changes by weight between 20.4% and 25.5%.PCC uses as follows: 1) do not do any preliminary treatment, 2) only use swollen starches preliminary treatment and 3) use anionic micropolymers and uncooked amylum preliminary treatment.
for the pretreated starch of PCC: cationic maize starch, it uses with following two kinds of methods:
1. by dry cationic starch powder and water are mixed and made into 3% slurry of solids to prepare, and additive uses so together, and described starch is particle form.
2. by first dried starch powder and water being mixed and made into 3% starch size, then this slurry being heated to 77 DEG C under mixing, using as swollen starches.By the swollen starches of 5kg/ ton paper has been mixed with the PCC of 20% solid with the preliminary treatment of swollen starches to PCC.
for being total to additive with uncooked amylum grain to PCC is pretreated:
Anionic polymer (the trade mark of BASF sell as " micro-polymer ").
By first will mix with PCC and then add cold uncooked amylum slurry to carry out the process of PCC. consumption be 0.04kg/tn paper.The consumption of raw cationic starch is 5kg/tn paper.
internal starch: cationic maize 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 as internal starch by it being mixed with intermittent pulp proportioning with 8kg/ ton paper.
retention agent: use the cationic polyacrylamide (CPAM) of 0.15kg/ ton paper and the silica of 1.5kg/ ton paper to be used for keeping extraly.
As shown in Figure 7, with compared with this pretreated paper, with swollen starches, preliminary treatment is carried out to PCC and improve paper strength.
Further improvement can be realized by the interaction using anionic micropolymers to strengthen between cationic starch and CATION PCC.Cationic starch can be even the uncooked amylum shown in embodiment.Hardness in fig. 8 can see similar characteristic.
Embodiment 9
By being mixed with intermittent pulp proportioning by inner cationic starch, then with pretreated PCC (or for baseline criteria, without any pretreated PCC) mixing, prepare the material of 0.3% concentration.Before formation paper, retention agent is added in material.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 precipitation of Specialty Minerals Inc. calcium carbonate ( lOPCC), average grain diameter 2.3 μm.The amount of Fillers in Paper is adjusted to two levels: by weight 20% and 25%.
for the pretreated swollen starches of PCC: cationic maize 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 75 DEG C to prepare swollen starches under mixing.By the swollen starches of 5kg/ ton paper is mixed with the PCC of 20% solid the preliminary treatment swelling cationic starch being used for PCC.Some packing samples only use swollen starches preliminary treatment, some packing samples swelling starch and additive preliminary treatment altogether.
the pretreated additive altogether of PCC for utilizing swollen starches to carry out: by by swollen starches and altogether additive to have mixed the process of PCC with PCC.The amount using different orders of addition and add altogether.The amount of swollen starches remains fixed in 5kg/ ton paper.The incorporation time of often kind of component is 1min.Tested common additive is: carboxymethyl cellulose (CMC), polyacrylic acid, soy polymers and nano-cellulose.
internal starch: cationic maize 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 as internal starch by it being mixed with intermittent pulp proportioning with 8kg/ ton paper.
retention agent: use the cationic polyacrylamide (CPAM) of 0.2kg/ ton paper for keeping extraly.
Table 3 give with not with compared with the baseline case of any PCC process, with the improvement of the TENSILE STRENGTH acquired by PCC filler pre-treatment.PCC filler or only use swollen starches preliminary treatment, or with swollen starches and extra common additive preliminary treatment.Tensile strength is compared under equal grey classification.
Use aforesaid technology, and not with compared with the baseline of any PCC process, the TENSILE STRENGTH that only swollen starches process gives 7.4% is improved.By using such as carboxymethyl cellulose or polyacrylic extra common additive and swollen starches, tensile strength can as shown in table 3ly be improved like that a little again.Nano-cellulose is used as additive altogether in swollen starches PCC process and as shown in table 3ly can improves strength character significantly like that.
Table 3
PCC: winnofil, SST: CATION swollen starches, AMP: anionic micropolymers.
Tensile index values is the geometrical mean of vertical and horizontal.
Embodiment 10
By being mixed with intermittent pulp proportioning by inner cationic starch, then with pretreated PCC (or for baseline criteria, without any pretreated PCC) mixing, prepare the material of 0.5% concentration.Before formation paper, retention agent is added in material.Use Formax paper forming machine, then carry out dynamic paper compacting and at 120 DEG C drying to manufacture 80g/m 2without wooden handmade paper.Before paper test, controlled condition at 50%RH and 23 DEG C, and by paper first with 180psi dual lustre surfaces, then with 220psi dual lustre surfaces.
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 precipitation of Specialty Minerals Inc. calcium carbonate ( lOPCC), average grain diameter 2.3 μm.The amount of Fillers in Paper is adjusted to two levels: by weight 20% and 25%.
for the pretreated swollen starches of PCC: cationic maize starch.By dry cationic starch powder and water are mixed and made into 1% slurry of solids, subsequently this 1% slurry of solids is heated to 75 DEG C to prepare swollen starches under slight mixing in starch cooker.By the swollen starches of 5kg/ ton paper is mixed with the PCC of 20% solid the preliminary treatment swelling cationic starch being used for PCC.Some packing samples only use swollen starches preliminary treatment, some packing samples swelling starch and additive preliminary treatment altogether.
the pretreated additive altogether of PCC for utilizing swollen starches to carry out: by the temperature of 55 DEG C by swollen starches and altogether additive to have mixed the process of PCC with PCC.The amount using different orders of addition and add altogether.The incorporation time of often kind of component is 1min.After all components all mixes with PCC, under the mixing of constant low sheraing, heat blended object height to 70 DEG C.
the common additive of test: anion hydrogen aluminium oxide, natural gum, silica, bentonite, polyvinyl alcohol (PVA), PVAm, biopolymer and several anionic polymer.
internal starch: cationic maize starch.Dried starch powder is mixed with water and obtains 0.5% slurry of solids, subsequently by the slaking at 95 DEG C under low mixing in starch cooker of this 0.5% slurry of solids.Ripe cationic starch is used as internal starch by it being mixed with intermittent pulp proportioning with 8kg/ ton paper.In one embodiment, the ripe cationic starch of 8kg/ ton is used to substitute swollen starches for PCC preliminary treatment.Use common additive and do not use common additive to process ripe starch.
retention agent: use the cationic polyacrylamide (CPAM) of 0.2kg/ ton paper for keeping extraly.
Embodiment 11
Use the method for embodiment 10.
Test PCC, swollen starches with laboratory scale and be total to the different orders of addition of additive.Carry out PCC process in the following sequence: first mixed with PCC by swollen starches, then additive mixing together; Or, first will be total to additive and mix with PCC, then mix with swollen starches.
The laboratory scale result provided in table 4 shows: when using identical common additive with identical chemical dose, can obtain similar strength enhancing, has nothing to do with order of addition.Visible, first still first as broad as long with being total to additive treating PCC with swollen starches process PCC.
Table 4
PCC: winnofil, SST: CATION swollen starches
Embodiment 12
Use the method for embodiment 10.
Table 5 gives compared with the baseline case without any PCC process, with the improvement of the TENSILE STRENGTH acquired by PCC filler pre-treatment.PCC filler or only use swollen starches preliminary treatment, or with swollen starches and extra common additive preliminary treatment.Compare under equal grey classification.
When using the method for previous embodiment 10, compared with the baseline without filler pre-treatment, the improvement giving the TENSILE STRENGTH of average 9.2% of only swollen starches process.By in the filler pre-treatment of being carried out by common additive introducing swollen starches, as shown in table 5, strength character is improved to be promoted to from limit and is exceeded twice.
Table 5
PCC: winnofil, SST: CATION swollen starches
Embodiment 13
Use the method for embodiment 10.
Also ripe starch can be used to replace swelling starch to carry out the preliminary treatment of PCC, but use the strength character of ripe starch to be starkly lower than the strength character using swollen starches.Table 6 shows only with swelling starch process PCC with only by the result of ripe starch process PCC.The starch of 5kg/tn is all used in both of these case.Under identical grey classification, swollen starches process provides the improvement of the TENSILE STRENGTH of 13%, and ripe starch process provides the improvement of the TENSILE STRENGTH of 3%.
Similar with swollen starches process, ripe starch fillers process also can by using common additive to improve, as shown in table 6.According to dosage, and only with compared with ripe starch process, performance can be double.
Table 6
PCC: winnofil
The all patents quoted in 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 (29)

1., for a filler suspension for papermaking, it comprises filler particles, ionic starch and complementary ion additive altogether.
2. filler suspension according to claim 1, wherein said filler particles is selected from by the following group formed: clay, talcum, synthetic silicate, sodium silicoaluminate magnesium, sodium silicoaluminate, grinding calcium carbonate (GCC), chalk, winnofil (PCC), grinding calcium sulfate (GCS), sulfate precipitate calcium (PCS), titanium dioxide and their combination.
3. filler suspension according to claim 1, wherein said ionic starch is uncooked amylum.
4. filler suspension according to claim 1, wherein said ionic starch is swelling ionic starch.
5. filler suspension according to claim 1, wherein said ionic starch is the ionic starch of slaking.
6. filler suspension according to claim 1, wherein said ionic starch is cationic.
7. filler suspension according to claim 1, wherein said ionic starch is anion.
8. filler suspension according to claim 1, wherein said ionic starch is both sexes.
9. the filler suspension according to any one of claim 1-8, wherein said ionic starch is selected from by the following group formed: cornstarch, rice fecula, farina, wooden sweet potato starch, tapioca, waxy corn starch, wheaten starch, sorghum starch and wax sorghum starch.
10. filler suspension according to claim 4, wherein forms described swelling ionic starch by heating farinose waterborne suspension at farinose gel point temperature ± 10 DEG C.
11. filler suspension according to claim 4, wherein heat farinose waterborne suspension form described swelling ionic starch by adding in the temperature range of 10 DEG C in gel point temperature to the gel point temperature of described starch of described starch.
Filler suspension according to any one of 12. claim 1-6 and 8-11, wherein said complementary ion altogether additive is Flokal B.
13. filler suspension according to claim 12, wherein said Flokal B comprises the copolymer of acrylamide and sodium acrylate.
14. filler suspension according to claim 13, wherein said complementary ion altogether additive be selected from by the following group formed: NALCO 61815, Nalco 61816, Nalco 61830, eS210, eS211, m305.
Filler suspension according to any one of 15. claim 1-6 and 8-11, wherein said complementary ion altogether additive is anionic inorganic microparticles.
16. filler suspension according to claim 15, wherein said anionic inorganic particles is selected from by the following group formed: bentonite, cataloid, borsal, aluminium hydroxide or their combination.
Filler suspension according to any one of 17. claim 1-11, wherein said complementary ion altogether additive is nano-cellulose.
Filler suspension according to any one of 18. claim 1-6 and 8-11, wherein said complementary ion altogether additive is polyvinyl alcohol.
Filler suspension according to any one of 19. claim 1-11, wherein said complementary ion altogether additive is anion PVAm or both sexes PVAm.
Filler suspension according to any one of 20. claim 1-11, wherein said complementation altogether additive is biopolymer.
21. filler suspension according to claim 20, wherein said biopolymer is based on starch.
22. filler suspension according to claim 21, wherein said starch-based bio polymer is 2202 adhesives.
Filler suspension according to any one of 23. claim 1-6 and 8-11, wherein said complementary ion altogether additive is anion pp acid or polyacrylic sodium salt.
Filler suspension according to any one of 24. claim 1-11, wherein said complementary ion altogether additive is natural polymer.
25. filler suspension according to claim 24, wherein said natural polymer is selected from by the following group formed: carboxymethyl cellulose, sky heat natural gum, soy polymers or their combination.
Filler suspension according to any one of 26. claim 1-25, wherein said filler particles is winnofil.
27. 1 kinds of intermittent pulp proportionings, it comprises the filler suspension according to any one of paper pulp fiber and claim 1-26.
28. intermittent pulp proportionings according to claim 27, it also comprises the additive be selected from by the following group formed: sizing agent, dry strength agent, wet strength agent, retention agent and other functionalized chemical material such as Optical Bleaching Agent, dyestuff, defoaming agent, bioside and their combination.
29. 1 kinds of paper products, it comprises claim 27 or intermittent pulp proportioning according to claim 28.
CN201380052234.4A 2012-10-05 2013-10-03 Filler suspension and its use in the manufacture of paper Pending CN104781469A (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US201261710624P 2012-10-05 2012-10-05
US61/710,624 2012-10-05
US201261718137P 2012-10-24 2012-10-24
US61/718,137 2012-10-24
US201361857600P 2013-07-23 2013-07-23
US61/857,600 2013-07-23
PCT/US2013/063310 WO2014055787A1 (en) 2012-10-05 2013-10-03 Filler suspension and its use in the manufacture of paper

Publications (1)

Publication Number Publication Date
CN104781469A true CN104781469A (en) 2015-07-15

Family

ID=49447820

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380052234.4A Pending CN104781469A (en) 2012-10-05 2013-10-03 Filler suspension and its use in the manufacture of paper

Country Status (12)

Country Link
US (1) US20150197892A1 (en)
EP (1) EP2904147A1 (en)
JP (1) JP2015533954A (en)
KR (1) KR20150063561A (en)
CN (1) CN104781469A (en)
BR (1) BR112015007620A2 (en)
CA (1) CA2886671A1 (en)
IN (1) IN2015DN02852A (en)
MX (1) MX2015004176A (en)
RU (1) RU2015116429A (en)
WO (2) WO2014055780A1 (en)
ZA (1) ZA201502047B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017177349A1 (en) * 2016-04-15 2017-10-19 合肥信拓高分子技术有限公司 Ternary filler system for paper/paperboard production and preparation method therefor
JP2018523764A (en) * 2015-08-06 2018-08-23 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Paper manufacturing method
CN109440533A (en) * 2018-11-21 2019-03-08 福建省青山纸业股份有限公司 A method of high stretched paper bag thoroughly is produced using bamboo pulp
CN112796152A (en) * 2020-12-30 2021-05-14 冠宏化工（扬州）有限公司 Organically modified filler, preparation method thereof and papermaking process using filler
CN114561833A (en) * 2022-02-28 2022-05-31 山东博汇纸业股份有限公司 Production method of single-layer white pulp fine dried noodle white-surface kraft liner board

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN104846685B (en) * 2015-04-27 2016-09-14 浙江华川实业集团有限公司 A kind of disinfecting armaticity tissue and preparation method thereof
CN105088857A (en) * 2015-08-18 2015-11-25 浙江华川实业集团有限公司 High-quality paper and preparation method thereof
BR112018007308B1 (en) * 2015-10-12 2023-03-07 Solenis Technologies, L.P. METHOD TO INCREASE THE DRAINAGE PERFORMANCE OF A PULP AND PAPER PRODUCT
RU2753445C2 (en) * 2016-09-16 2021-08-16 Соленис Текнолоджиз, Л.П. Improved dehydration efficiency in paper-making systems using micro-fibrillated cellulose
SE541110C2 (en) * 2016-12-01 2019-04-09 Stora Enso Oyj Pre-mix useful in the manufacture of a fiber based product
SE540387C2 (en) 2016-12-21 2018-09-04 Stora Enso Oyj A process for surface sizing using a jet cooked dispersion comprising microfibrillated cellulose, starch and pigment and / or filler
CN110409215A (en) * 2019-06-20 2019-11-05 浙江金龙纸业有限公司 A kind of mechanical pulp page and preparation method thereof being filled with nano material
CN111851136B (en) * 2020-07-25 2022-07-08 吉特利环保科技（厦门）有限公司 Starch-based biological fluorine-free oil-proof agent, emulsification system for preparing oil-proof agent and production process of emulsification system

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1269855A (en) * 1997-09-12 2000-10-11 西巴特殊化学水处理有限公司 Paper-making method
CN1295637A (en) * 1997-11-24 2001-05-16 纳尔科化学公司 Selective retention of filling components and improved control of sheet properties by enhancing additive pretreatment
US20030188738A1 (en) * 2002-04-09 2003-10-09 Makhlouf Laleg Swollen starch-latex compositions for use in papermaking
US20100181037A1 (en) * 2007-07-05 2010-07-22 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

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1347071A (en) * 1971-07-01 1974-02-13 Starch Products Ltd Paper fillers
JPS60119299A (en) * 1983-11-25 1985-06-26 神崎製紙株式会社 Papermaking method
SE8403062L (en) * 1984-06-07 1985-12-08 Eka Ab PAPER MANUFACTURING PROCEDURES
JPH0672394B2 (en) * 1987-05-28 1994-09-14 三菱製紙株式会社 Manufacturing method of paper with internal filler
GB9410965D0 (en) * 1994-06-01 1994-07-20 Allied Colloids Ltd Manufacture of paper
US5827398A (en) * 1996-02-13 1998-10-27 Allied Colloids Limited Production of filled paper
ES2221631T3 (en) 1996-12-31 2005-01-01 Ciba Specialty Chemicals Water Treatments Limited MATERIALS FOR USE IN THE MANUFACTURE OF PAPER.
FI106140B (en) 1997-11-21 2000-11-30 Metsae Serla Oyj Filler used in papermaking and process for its manufacture
TW524910B (en) 1999-11-08 2003-03-21 Ciba Spec Chem Water Treat Ltd Manufacture of paper and paperboard
TW483970B (en) 1999-11-08 2002-04-21 Ciba Spec Chem Water Treat Ltd A process for making paper and paperboard
TW527457B (en) 1999-11-08 2003-04-11 Ciba Spec Chem Water Treat Ltd Manufacture of paper and paperboard
TW550325B (en) 1999-11-08 2003-09-01 Ciba Spec Chem Water Treat Ltd Manufacture of paper and paperboard
FR2849441B1 (en) * 2002-12-30 2006-07-28 Rhodia Chimie Sa PROCESS FOR PREPARING A SUSPENSION OF SILICA IN A SILICONE SUBSTANCE POSSIBLY CROSSLINKABLE
JP2007138305A (en) * 2005-11-14 2007-06-07 Nippon Paper Industries Co Ltd Coated paper for printing
DE07709298T1 (en) 2006-02-08 2014-01-30 Stfi-Packforsk Ab Process for the preparation of microfibrillated cellulose
GB0702249D0 (en) * 2007-02-05 2007-03-14 Ciba Sc Holding Ag Manufacture of paper or paperboard
WO2009004079A1 (en) * 2007-07-05 2009-01-08 Basf Se Method for producing aqueous suspensions of fine particulate fillers and use thereof for producing papers having a high filler content and a high dry strength
US8088213B2 (en) 2007-09-12 2012-01-03 Nalco Company Controllable filler prefloculation using a dual polymer system
JP2009120967A (en) * 2007-11-12 2009-06-04 Nippon Shokuhin Kako Co Ltd Natural paper strengthening agent, and method for producing paperboard using the same
SE0800807L (en) 2008-04-10 2009-10-11 Stfi Packforsk Ab New procedure
FI124464B (en) * 2009-04-29 2014-09-15 Upm Kymmene Corp Process for the preparation of pulp slurry, pulp slurry and paper
US8449665B2 (en) * 2010-01-08 2013-05-28 Hewlett-Packard Development Company, L.P. Coating compositions including starch nanoparticles

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1269855A (en) * 1997-09-12 2000-10-11 西巴特殊化学水处理有限公司 Paper-making method
CN1295637A (en) * 1997-11-24 2001-05-16 纳尔科化学公司 Selective retention of filling components and improved control of sheet properties by enhancing additive pretreatment
US20030188738A1 (en) * 2002-04-09 2003-10-09 Makhlouf Laleg Swollen starch-latex compositions for use in papermaking
US20100181037A1 (en) * 2007-07-05 2010-07-22 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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018523764A (en) * 2015-08-06 2018-08-23 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Paper manufacturing method
WO2017177349A1 (en) * 2016-04-15 2017-10-19 合肥信拓高分子技术有限公司 Ternary filler system for paper/paperboard production and preparation method therefor
CN109440533A (en) * 2018-11-21 2019-03-08 福建省青山纸业股份有限公司 A method of high stretched paper bag thoroughly is produced using bamboo pulp
CN109440533B (en) * 2018-11-21 2021-06-04 福建省青山纸业股份有限公司 Method for producing high-transparency paper bag paper by using bamboo pulp
CN112796152A (en) * 2020-12-30 2021-05-14 冠宏化工（扬州）有限公司 Organically modified filler, preparation method thereof and papermaking process using filler
CN114561833A (en) * 2022-02-28 2022-05-31 山东博汇纸业股份有限公司 Production method of single-layer white pulp fine dried noodle white-surface kraft liner board

Also Published As

Publication number Publication date
BR112015007620A2 (en) 2017-07-04
JP2015533954A (en) 2015-11-26
KR20150063561A (en) 2015-06-09
WO2014055780A1 (en) 2014-04-10
CA2886671A1 (en) 2014-04-10
WO2014055787A1 (en) 2014-04-10
ZA201502047B (en) 2016-01-27
IN2015DN02852A (en) 2015-09-11
RU2015116429A (en) 2016-11-27
MX2015004176A (en) 2015-09-25
EP2904147A1 (en) 2015-08-12
US20150197892A1 (en) 2015-07-16

Similar Documents

Publication Publication Date Title
CN104781469A (en) Filler suspension and its use in the manufacture of paper
AU2003218571B2 (en) Swollen starch-latex compositions for use in papermaking
TWI515348B (en) Filler composition
CN104746388B (en) A kind of method of the sizing efficiency for the ASA lotions for improving macromolecule emulsifier emulsification
CN103547734B (en) The method manufacturing paper and cardboard
CA2868621A1 (en) Manufacture and use of a composite structure containing precipitated carbonate
JP2001510251A (en) Paper products containing filling materials
US20150197890A1 (en) Filler suspension and its use in the manufacture of paper
CN104812958A (en) Filler suspension and its use in the manufacture of paper
CN104755673A (en) Preflocculation of fillers used in papermaking
AU2004255246A1 (en) Gelled starch compositions and methods of making gelled starch compositions
AU2006201187B2 (en) Swollen starch compositions for use in papermaking

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20150715