CN1051826C - Paper coating - Google Patents
Paper coating Download PDFInfo
- Publication number
- CN1051826C CN1051826C CN90110340A CN90110340A CN1051826C CN 1051826 C CN1051826 C CN 1051826C CN 90110340 A CN90110340 A CN 90110340A CN 90110340 A CN90110340 A CN 90110340A CN 1051826 C CN1051826 C CN 1051826C
- Authority
- CN
- China
- Prior art keywords
- cationic
- pigment
- paper coating
- paper
- polyelectrolyte
- 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.)
- Expired - Fee Related
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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
There is disclosed an aqueous paper coating composition which comprises at least 45% by weight of a particulate pigment dispersed with a dispersing agent, and an adhesive; characterized in that said dispersing agent comprises an anionic polyelectrolyte and a cationic polyelectrolyte, the cationic polyelectrolyte being present in an amount sufficient to render the particles cationic, in that said adhesive is a cationic or non-ionic adhesive and in that said particulate pigment is one which is not capable of being dispersed in water at high solids, and following vigorous mixing, in the sole presence of said cationic polyelectrolyte. Also disclosed is a method for making the paper coating composition, a method for coating a paper with a paper coating composition and the resulting coated paper.
Description
The present invention relates to a kind of paper coating mixture, a kind of method for preparing the paper coating mixture, a kind of with the paper coating mixture give paper and coating method and thus obtained coated paper.The invention still further relates to a kind of method of recycling of paper, in this method, coated paper of the present invention is taken as " waste paper " in the paper technology." waste paper " is a term that is used to represent paper, cardboard or its analog that those are recycled in this area.
Calcium carbonate is a kind of known paper coating pigment, and, because it generally carries positive charge, therefore, disperse it with a kind of anionic dispersing agent usually.Other paper coating pigment that carries neutral charge or positive charge also has: gypsum, talcum, baked kaolin etc., these face grains also must disperse with a kind of anionic dispersing agent.(these mineral matters also are considered to have hole, negative position).
Title that James P.Casey writes for the second edition of " paper pulp and paper: chemistry and technology " book, III volume, XIX chapter in, expounded the component of paper coating mixture adequately and these mixtures be applied to method on the paper." the aquifer coating operator guide of paper and cardboard " (Britain's paper and paperboard industry association, London, 1979) book that T.W.R.Dean writes has been done further argumentation to this.
A kind of cationic pigment dispersion method is disclosed among DE-3707221 and the EP-0307795.Earlier give pigment a protective colloid cover layer, then, disperse with cation type polymer under certain condition with cationic polymer.
A.J.Sharpe, Jr. etc. are at " improved cationic conducting polymer shows significant film performance " literary composition (TAPPI, Vol, 65, no.4, April nineteen eighty-two, 123-125 page or leaf, Atlanta, Geor9ia, U.S.A.) in, described a kind of by strong cation type polymer, as poly-(diallyldimethylammonium chloride) and weak anionic type polymer, as the polyacrylic acid formed polysalt that interacts.So the polysalt that forms adds in a kind of graining paste pre-dispersed, low solid content with fundamental quantity (be about pigment weight 50%), so that form a kind of conductive coating color, prepares the paper with conductive surface with this.
According to a first aspect of the invention, provide a kind of moisture paper coating mixture, this mixture contains: (I) weight percent is at least 45% usefulness dispersant dispersed particles inorganic pigment; (II) a kind of adhesive; It is characterized in that said dispersant comprises a kind of anionic polyelectrolyte and a kind of cationic polyelectrolyte, the consumption of cationic polyelectrolyte is enough to make granules of pigments to have cationic; Said adhesive is a kind of CATION or nonionic adhesive; Said granular pigment is when the cationic polyelectrolyte individualism, can not in water, disperse with high solid content, and the pigment that still can not disperse along with violent mixing.
According to a second aspect of the invention, provide a kind of method to the paper coating, this method comprises with the step of the said paper coating mixture in first aspect of the present invention to paper coating.
According to a third aspect of the present invention, provide a kind of coated paper of producing by the said method in second aspect of the present invention.
Be used for graininess pigment of the present invention, be a kind of when the cationic polyelectrolyte individualism, can not in water, disperse with highly filled (as greater than 60% (weight)), and the pigment that still can not disperse along with violent mixing (consuming 10 kJ (kilojoule) energy at least as per kilogram pigment).This means that the surface of pigment should have neutral charge or positive charge generally.For example, it is desirable resembling calcium carbonate, calcium sulfate, talcum and the such inorganic pigment of baked kaolin.Optimal pigment is calcium carbonate, any type of one natural or synthetic all can.Optimal pigment is marble that grind or crushing, and but, chalk or winnofil (PCC) also can use.In this respect, although should be pointed out that the chalk of giving birth in that just not have under the violent situation of mixing can enough cationic polyelectrolyte dispersions, if it is just undesirable that chalk is acutely mixed situation.It is believed that this is because violent the mixing removed the cause that is present in the anion silicon aluminium lamination on the living chalk usually.Under the situation of acutely not mixing, sial can form negative electrical charge on the surface of chalk particle, and like this, it just can be disperseed by a kind of cationic polyelectrolyte.
Comparatively it is desirable to, the pigment that grinds has such particle size distribution: promptly the particle of at least 50% (weight) has the suitable sphere diameter less than 2 microns.Even more ideal is that the particle of at least 60% (weight) has the suitable sphere diameter less than 2 microns.
Be used for the marble particle that grinds of the present invention preferably by at moisture suspension, do not having under the situation of chemical dispersant, make with a kind of graininess abrasive media batch grinding marble.Any agglomerate that forms can be by sloughing the water in the marble suspension that grinds, for example, by filtering under the situation of flocculant not having, dried pigment then, and the method that on a conventional grinder desciccate is ground is pulverized.
Graininess pigment disperses with the mixture of anionic polyelectrolyte and cationic polyelectrolyte.More satisfactory anionic polyelectrolyte is water miscible polyvinyl, its alkali metal salt or ammonium salt, perhaps the alkali metal salt or the ammonium salt of poly-silicic acid.Optimal anionic polyelectrolyte is a polyacrylic acid, polyisobutene acid, any alkali metal salt or the ammonium salt of the polyacrylic acid of replacement or the acid of the polyisobutene of replacement or above-mentioned these acid.The polyacrylic acid that replaces can be partly sulfonated polymer.A kind of anionic polyelectrolyte of special efficacy is the alkali metal salt or the ammonium salt of the copolymer of acrylic acid and acrylic acid sulfonic derivative, and wherein, the ratio of sulfonic derivative monomer preferably accounts for the 5%-20% of monomeric unit sum.
The number-average molecular weight of anionic polyelectrolyte is advisable but be no more than 100,000 to be at least 500.Its amount ranges is the 0.01%-0.5% of dry colour weight normally, preferably in the scope of 0.1%-0.2%.
Cationic polyelectrolyte can be water miscible, as to contain quaternary ammonium group replacement polyolefin.Quaternary ammonium group can be positioned on the linear polymer chain or be positioned on the side chain of polymer chain.Replace polyolefinic number-average molecular weight with at least 1,500, be advisable but be not more than 1000,000,50,000-500, best in 000 the scope.Its requirement is the 0.01%-1.5% of dry colour weight normally.When replace polyolefin be poly-(diallyl two (hydrogen or low alkyl group) ammonium salt] time, can obtain desirable effect.Low alkyl group can be same or different, can reach 4 carbon atoms, and still, each low alkyl group is methyl preferably.Ammonium salt can be ammonium chloride, ammonium bromide, ammonium iodide, ammonium hydrogen sulfate, methanesulfonic acid ammonium or ammonium nilrite.Comparatively ideal salt is ammonium chloride.Optimal cationic polyelectrolyte is poly-(diallyldimethylammonium chloride).But the another kind selection scheme is, water miscible replacement polyolefin can be the copolymerization product of epichlorohydrine and aliphatic secondary amine, and this product has following structural:
In the formula: R can be identical with R ', also can be different, they each hydrogen or have low alkyl group, particularly methyl or the ethyl of 1-4 carbon atom naturally; X is cl-, Br-, I-, Hso
4-, CH
3So
4-or nitrite ion.The number-average molecular weight of this epichlorohydrine product is preferably 50, and 000-300 is in 000 the scope.
Another kind of selectable scheme is: cationic polyelectrolyte can be a water-soluble organic compounds, and this compound has a plurality of basic groups and number-average molecular weight to be not less than 10,000, is good but be not more than 1,000,000.Ideal is that number-average molecular weight is at least 50,000.This water-soluble organic compounds can be known as polyacid valency organic base, preferably only be carbon, hydrogen or nitrogen compound, and, there is not other functional group-as hydroxyl or carboxyl, because this will increase their solubility in water and therefore increase them by the possibility of disengaging the clay in aqueous suspension.This organic compound preferably number-average molecular weight 50,000-1, the polymine (PEI) in 000,000 scope.The example of the water-soluble organic compounds that another can use is the polyethylene diamines, and it can be the copolymer of ethylene diamine with ethylene dihalide or formaldehyde.
The consumption of cationic polyelectrolyte should be enough to make mineral grain have cationic.Test shows, treated after, the zeta potential of particle is at least+20mv usually, generally in+30mv-+40mv scope, and, generally be not more than+50mv-+60mv.These electromotive forces are with " Pen Kem Laser z " measuring instrument, are sample measurement with a kind of low solid concentration (0.02% (weight)) suspension, and this suspension has used potassium chloride supporting electrolyte (10
-4M).
When calcium carbonate was the marble of pulverizing, the used cationic polyelectrolyte and the weight ratio of anionic polyelectrolyte were preferably 2: 1-20: in 1 the scope.
According to a fourth aspect of the present invention, provide a kind of method for preparing the paper coating mixture, it may further comprise the steps:
(I) granular pigment is distributed in the moisture suspension;
(II) dispersed aqueous suspension is mixed with a kind of adhesive, and, if desired, adjust dilution factor, make that the content of granular materials is at least 45% (weight) in the mixture;
It is characterized in that said pigment is to use the dispersant of the mixture that contains anionic polyelectrolyte and cationic polyelectrolyte to disperse: the consumption of said cationic polyelectrolyte should be enough to make face grain particle to have cationic; Said adhesive is CATION or nonionic adhesive; Said granular pigment material is a kind of when the cationic polyelectrolyte individualism, can not in water, disperse with high solid content, and the pigment that still can not disperse along with violent mixing.
In the method for the invention, normally this situation-is promptly given birth to pigment and is used to admit in advance with the form of filter cake with relative higher solids granule content.In this gives birth to pigment filter cake, add dispersant,, subsequently, this slurry is carried out violent mixing so that produce a kind of dispersed, slurry (solid particle that contains 45-80% (weight)) with high solid granule content.Then, by CATION or nonionic adhesive and other paper coating mixture assistant commonly used of dilution and interpolation aequum, this slurry is made the paper coating mixture.
Pigment preferably mixed with anionic polyelectrolyte earlier before mixing with cationic polyelectrolyte.Do so as if can obtain concentration of solid particles higher, the better suspension of fluidity.
The aqueous dispersion of pigment also can comprise the paper coating mixture auxiliary agent that other is commonly used, such as solvent not (for example, melamino-formaldehyde resin), lubricant (for example, calcium stearate) and be used for the catalyst of the crosslinked action of catalysed cationic latex (if present).A kind of this proper class catalyst is a sodium bicarbonate.The consumption that requires of these auxiliary agents is known to those skilled in the art.
Being used for adhesive of the present invention should be nonionic or cationic adhesive.This class adhesive is different from the anionic adhesive that is generally used in the paper coating mixture that pigment is anionic.Therefore, cationic guar gum and cationic starch adhesive and CATION or nonionic latex can both use.This cationoid or nonionic adhesive are easy to buy from the market.Concrete CATION that is adopted or nonionic adhesive for example will depend on one, used typography, and for example lithographic printing just needs water insoluble adhesive.For the paper of using in lithography technique, adhesive consumption is the 7-25% of pigment weight preferably, and for intaglio printing paper, adhesive consumption is the 4-15% of pigment weight preferably.The accurate consumption of required adhesive will depend on adhesive and want the character of coated material that still, this consumption those skilled in the art be easy to determine.
The pigment suspension of mixing in the paper coating mixture of the present invention preferably carries out violent mixing before disperseing or after disperseing.In general, violent mixing should be abundant, consumes 10 kJ (kilojoule) energy at least with per kilogram pigment, is good but be no more than 50 kJ (kilojoule) energy.Usually, the energy of input is in the scope of per kilogram pigment 18-36 joule.
The paper coating mixture can be applied on the paper under the paper coating condition of routine with the paper coating machine of routine.Have found that, be coated with the paper of cationic mixture of the present invention and paper that traditional anion method is obtained and have roughly the same result.
When being used as " waste paper " in the paper technology or recycling paper, coated paper of the present invention benefits.Usually, for some reason or other, with regard to the production meaning, a large amount of paper will be recycled, and the advantage that paper of the present invention is had aspect recycling is most important for paper production producer.Therefore, according to a fourth aspect of the present invention, provide a kind of method of recycling paper, this method comprises the paper of gained according to a third aspect of the present invention reverted to the fiber condition that can recycle, and this fiber is sneaked into step in the papermaking mixture.
Can comprise traditional paper pulp in this papermaking mixture, such as bleached sulfite pulp, usually, used waste paper fibre with the ratio of paper pulp 10: 90-60: in 40 scopes.
Can also comprise filler in the papermaking mixture, for example pearl filler also can comprise retention agent.Owing to had the calcium carbonate of a part in the waste paper fibre, therefore, added some pearl fillers less and just can make the filler total amount account for the 5-20% of papermaking amount of the mixture (weight) from coating.Add dried waste paper (fiber+filler) weight preferably be about the 5-30% of total weight of fiber.
Have found that, when used waste paper fibre be from coated paper of the present invention produce the time, the amount of used retention agent can reduce in the papermaking mixture.
Now will the present invention will be described by following example:
Example 1
The living marble of pulverizing is not contained containing 30% (weight) dried solid particle in three batches in the aqueous suspension of chemical dispersant and grind with a kind of graininess abrasive media.The grinding duration difference of each batch, so that obtain three kinds of different grinding products, these three kinds of grinding products have respectively that following particle size distribution-promptly the particle of 50%, 68% and 87% (weight) has the suitable sphere diameter less than 2 microns.In each case, the marble suspension that ground all will dewater by the mode of filtering in a tubulose pressure filter not having under the prerequisite of flocculant, and the filter cake that obtains will give drying and grind on hammer-mill in the laboratory.
With following two kinds of distinct methods with three kinds of marble dust sample Tong Shui that grind and two kinds of different dispersant.These two kinds of dispersants are:
(E) a kind of anionic polyelectrolyte, it is the Sodium Polyacrylate with 4,000 number-average molecular weights;
(F) a kind of cationic polyelectrolyte, it is poly-(diallyldimethylammonium chloride) with 50,000 number-average molecular weights.
In each case, (F) be 4: 1, still, determine the dispersant total amount an of the best, and find that in each case, this total amount is different for each marble dust that grinds with (E) weight ratio.
Two kinds of methods of the aqueous suspension of preparation marble dust are:
(I) water of said powder with (E) that contain required amount is mixed, after fully mixing, add (F) of required amount, then further mix;
(II) said powder is mixed with (E) that contain required amount simultaneously and water (F).
In each case, all to measure the viscosity of suspension with 100 rev/mins axle speed with a Brookfield viscosimeter, and the suspension by the finish-drying known weight is also determined the weight percent of dried solids to the method that the residue of drying is weighed.Then, suspension is diluted with a spot of water, and measure the weight percent of its viscosity and the solids of doing once more.Provide the curve map of viscosity, and determine the solid concentration that viscosity is the suspension of 500mPa.S by interpolation to the weight percent of dried solids.
The gained result lists in the following Table I:
Account for the suspension that marble viscosity is 500Pa.s with diameter in the marble of method (I), (II) preparation less than (E), (F)
The weight percent of the powder of 2 microns particle
In the weight percent of dried solids
Weight percent (%) is rate (%) (%)
(E) (F) (I) (II)50 0.02 0.083 72.0 71.368 0.075 0.289 71.4 65.687 0.166 0.65 64.6 60.3
These results show, with method (I) (earlier powder is mixed with anionic polyelectrolyte, and then mix) with cationic polyelectrolyte than obtaining the higher fluid suspension of concentration of solid particles with method (II) (powder is mixed simultaneously with two kinds of dispersants).It is more obvious that the marble dust of fine gtinding and thicker product are compared this phenomenon.
Example 2
Method described in the use-case 1 prepares the marble dust of other a collection of fine gtinding, and grinding product has that such particle size distribution-promptly the particle of 87% (weight) has the suitable sphere diameter less than 2 microns.
With the sample mixed of this marble dust in paper coating mixture according to following formulation:
Component weight portion mixture (a) marble dust 100
Tetravalence cationic
Acrylic based emulsion 12
Cationic guar gum 0.5
Component weight portion mixture (b) marble dust 100
Tetravalence cationic
Acrylic based emulsion 8
Cationic starch 4
Prepared three kinds of different (b) type mixtures that contain following three kinds of different cationic starch respectively:
(I) cationic starch of low degree of substitution;
(II) cationic starch of another kind of low degree of substitution;
(III) cationic starch of high substituted degree.
With these three kinds of mixtures be marked with respectively mixture (b) (I), (b) (II) and (b) (III).
Component weight portion mixture (c) marble dust 100
Butadiene-styrene rubber latex 12
Sodium carboxymethylcellulose 0.75
Component weight portion mixture (d) marble dust 100
Butadiene-styrene rubber latex 8
Oxidized starch 4
Under cationic mixture (a) and situation (b), the aqueous suspension that will at first prepare a kind of marmorean powder with top example 1 described method, wherein, anionic dispersing agent (E) as dispersant is 0.16% of a dried marble weight, and cationic dispersing agent (F) is 0.65% of a dried marble weight.
Under anionic mixture (c) and situation (d), marble dust is only handled with the dispersant (E) that accounts for dried marble weight 0.30% and is got final product.
In addition, also to every kind of mixture (a) and (b), (c) and the melamino-formaldehyde resin that adds 0.8 weight portion (d) as solvent not, and respectively add the calcium stearate of 0.5 weight portion.Also add the sodium bicarbonate of 0.2 weight portion to cationic mixture (a) and (b), in order to the cross-linking reaction of catalysed cationic type latex.
If possible, each paper coating mixture dilute with water, producing one ought be with " Ferranti-shirley " viscosimeter with 12,800S
-1Shear rate when measuring, have the high shear force viscosity in the 60-70mPa.S scope.The weight percent of dried solids is listed in the following Table II in high shear force viscosity and the mixture that diluted.
Laboratory paper coating machine with a type described in british patent specification No.1032536 is applied to individual layer to each mixture and weighs 48 gram/rice
2Lightweight lithographic plate base paper on.Then, at 1000 pounds/inch
2Under (6.89 MPa) pressure and the 65C temperature, the roll gap that the coated paper sample is passed the calender roller for 10 times with 36 meters/minute speed carries out supercalendering processing.
Each sample of coated paper after the press polish carries out the gloss test with the TAPPI standard method and carries out the smoothness test with Parker PrintSurf with 10kgf; And be that reflection of light percentage and the opacity percentage of 457nm test to wavelength.In all cases, gloss, smoothness, reflection percentage and opacity are percentile to be determined to finish through the following steps: with different coating weights the paper sample is carried out coating, these parameters when measuring each coating weight, draw the curve map of these parameters with respect to coating weight, finding out coating weight with interpolation is 8 gram/rice
2The time parameter value.The result lists in the following Table II:
Table II
The heavy high shear force gloss wavelength 457nm of dried solids
Opacity mixture amount percentage (%) viscosity (TAPPI smoothness reflection of light (%)
(mPa.s) (a) (I) (II) (III) 59.4 72 38 0.71 78.4 90.1 (c) 65.8 73 46 0.67 78.1 90.1 (d) 64.9 104 39 0.76 77.8 89.7 of 61.2 70 43 0.68 78.4 89.8 (b) of 60.6 66 45 1.05 78.4 90.4 (b) of 62.0 62 45 0.72 78.1 90.1 (b) of rate (%) unit)
When the result of cationic mixture (a) and the result of corresponding anionic mixture (c) are compared, when the result of the result of cationic mixture (b) and corresponding anionic mixture (d) is compared, we will find that the coated paper that the coated paper that CATION method according to the present invention is produced and traditional anion method are obtained has roughly the same parameter.
Be used as in paper technology with the pattern product of above-mentioned coating mix coating and recycle paper or " waste paper ".According to TAPPI standard T200, to break into beating degree be 45SR or break into 270 canadian standard freeness with bleached sulfite pulp, and, prepare the papermaking mixture of forming by the aqueous suspension of following component:
The component weight portion
The sulfite pulp 70 of bleaching
Waste paper fibre 30
Pearl filler 50
Polyacrylamide retention agent 0.03
Pearl filler has that such particle size distribution-promptly the particle of 43% (weight) has the suitable sphere diameter less than 2 microns.Because contained the inorganic filler of 20% (weight) in the waste paper, therefore, should add some new pearl fillers less so that the filler total amount is 50 weight portions.Equally, the weight of the dried waste paper (fiber+filler) of interpolation should be able to make fiber reach 30 weight portions.
By keeping bottle and agitator, stirred for 30 seconds with the 5th grade speed (1050rpm), use above-mentioned coating mix (a) to measure respectively by containing, and b ((II), (c) and (d) be coated with the reservation amount of the pearl filler in the paper that the regenerated papermaking mixture of layer makes.As a kind of comparison, the reservation amount of the same pearl filler of the existence in the papermaking mixture that does not contain waste paper is also measured.The result lists in the following Table III:
Table III
The reservation amount (weight %) that contains the waste paper calcium carbonate of coating mix
Do not contain 73.4
(a) 83.9
(b)(II) 79.2
(c) 49.8
(d) 46.2
These results show, although compare with the papermaking mixture that does not contain waste paper, in the papermaking mixture, sneak into and scribble anionic mixture (c) and waste paper (d), can reduce the reservation amount of pearl filler, scribble the anionic mixture waste paper mix the reservation amount that has in fact improved filler.
Example 3
Use-case 1 described method is ground a collection of rough crushed marble, a kind ofly has the particle of 60% (weight) of such material size distribution-promptly and has grinding product less than 2 microns suitable sphere diameter so that produce.With a desk centrifuge the marmorean suspension that ground is dewatered, the centrifugation cake that contains the dried solids of 68% (weight) is used to following experiment.
The marble centrifugation cake sample that will grind earlier mixes with anionic dispersing agent, mixes with cationic dispersing agent after fully mixing again.In each case, all to use the anionic dispersing agent of scheduled volume, still, for cationic dispersing agent, should add sub-fraction earlier, violent mixing suspension one minute, and with the viscosity of a Brookfield viscosimeter with a tachometric survey suspension of 100 rev/mins.The consumption and the viscosity of record dispersant add the sub-fraction dispersant again, and repeat said process.The dispersant that adds another little increment again, till the viscosity of suspension reached minimum, at this moment, the total amount of the cationic dispersing agent that is added was considered to optimum amount.
Dispersant is as follows:
(G) a kind of anionic polyelectrolyte, it is have 70,000 number-average molecular weights poly-
Sodium acrylate;
(H) sodium metasilicate, it is the sodium salt of poly-silicic acid, can play anionic dispersing agent;
(I) a kind of cationic polyelectrolyte, it is have 50,000 number-average molecular weights poly-
(diallyldimethylammonium chloride);
(J) a kind of cationic polyelectrolyte, it is a polymine.
When using dispersant (J), also must add the sulfuric acid of capacity, to adjust PH to 7.8 because polymine is very responsive to PH, and, when pH value greater than 8 the time, can not play dispersant effectively.
As a kind of comparison, a sample of centrifugation cake only uses dispersant (J) to handle PH7.8, anionic dispersing agent of no use.
For each combination of dispersant, all to write down and do marmorean weight percent in the suspension, the consumption of the minimal viscosity of suspension and anionic dispersing agent and cationic dispersing agent, the result lists in the following Table IV:
The Table IV anionic divides minimal viscosity powder (% by weight) powder (% by weight) weight percent (%) of the cationic minute dried solids of consumption of consumption (mPa.s) to add-J 0.37 67.1＞10,000 at G 0.10 I 0.48 67.2 3000 G 0.10 J 0.40 67.5 252 H 0.16 J 0.39 65.4 224 end
These results show, in general, can obtain still, before cationic dispersing agent uses, must earlier anionic dispersing agent being added as cationic dispersing agent with polymine than with gathering (diallyldimethylammonium chloride) as the lower suspension of cationic dispersing agent viscosity.
Example 4
A collection of have marble powder that such particle size distribution-promptly all basically particles can both pass No.300 order B.S.screens (53 microns of nominal mesh diameters) a kind of dense place, grind containing in the aqueous suspension Huaihe River of deflocculation, the amount of marble, water and abrasive sand is as follows:
Marble powder 615 grams
Water+anion and cationic dispersing agent 330 grams
Sand 1500 grams
(nominal mesh diameter is 0.850 millimeter to the size of sand grains, but greater than No.30 purpose B.S.screens (nominal mesh diameter is 0.500 millimeter) less than No.18 purpose B.S.screens.Used anionic dispersing agent is (E), cationic dispersing agent is (F), and the two is all as described in the example 1.With (E) of different total amounts with (F) every batch of marble powder is ground, still, in each case, weight ratio (F) (F) and (E): (E) all be 4: 1.In each case, grinding all will continue one section is enough to make the dried marble of per kilogram to consume the time of 396 kJ (kilojoule) energy in suspension, and, in each case, grinding product should have all that such particle size distribution-promptly the particle of 50% (weight) has the suitable sphere diameter less than 2 microns.After having ground, the marble suspension that ground is separated in sand, and with the viscosity of Brook field viscosimeter with 100 rev/mins axle tachometric survey suspension.Then, suspension is diluted with a spot of water, and measure viscosity once more.Determine that by the suspension of dry sub-fraction known weight and to the way that the residue of drying is weighed dried marmorean weight percent also is fine in the suspension.Dilute with water, measurement viscosity and definite three steps of marmorean weight percent of doing repeat several times.Draw the curve map of viscosity, and find out dried marmorean weight percent in the suspension with 500mPa.s viscosity by interpolation to dried marmorean weight percent.The result lists in the following Table V:
Do marmorean heavy when the gross weight viscosity of the weight percent powder of the weight (F) of Table V (E) is 500mPa.s percentage (%) branch rate (%) amount percentage (%)
Amount percentage (%) 0.05 0.20 0.25 63.9 0.06 0.24 0.30 64.5 0.07 0.28 0.35 65.0
Example 5
The described methods of use-case 4 grind in addition several with example 4 in used identical marble powder, the amount that is used as (E) of anionic dispersing agent is to do 0.07% of a large amount of stone weight, and be 0.28% of dried marble weight as the amount of cationic dispersing agent, cationic dispersing agent is selected from a kind of in poly-(diallyldimethylammonium chloride) polyelectrolyte of different molecular weight.In each case, all will resemble example 4 and measure described and do marmorean weight percent in the suspension that viscosity is 500mPa.s, the result lists in the following Table VI:
The viscosity of Table VI cationic dispersing agent is done the weight percent (%) 9 of Dali number-average molecular weight stone during for 500mPa.s, 500 58.4 26,000 61.8 50,000 65.0 71,500 64.9
These results show that if expect the marble suspension of satisfied mobility, then poly-(diallyldimethylammonium chloride) should have at least 50,000 number-average molecular weight.
Example 6
Use-case 1 described method is ground a collection of rough crushed marble, produces a kind ofly to have the particle of 60% (weight) of such particle size distribution-promptly and have grinding product less than 2 microns suitable sphere diameter.The marmorean suspension centrifuge dewatering that grinds, the centrifugation cake of the dried solids that contains 73% (weight) of gained is used in the following experiment:
Is that 0.1% anionic dispersing agent G of dried marble weight (is that number-average molecular weight is 70 with the marble centrifugation cake sample that grinds and example 3 described such elder generations with consumption, 000 Sodium Polyacrylate) mixes, after fully mixing, in each sample of the marble aqueous suspension that grinds that is disperseed by anionic dispersing agent, add a certain amount of one of following four kinds cationic dispersing agent.
(I) a kind of cationic electrolyte, it is that number-average molecular weight is 50,000-100,000 poly-(diallyldimethylammonium chloride);
(J) a kind of cationic polyelectrolyte, it is a polymine;
(K) a kind of number-average molecular weight is than the low polymine of (J);
(L) a kind of number-average molecular weight polymine lower than (K);
By experiment, find out the consumption of every kind of cationic dispersing agent, make suspension have MV minium viscosity with specified solids content.For dispersant (I), find that this consumption is 0.45% of a dried marble weight, for dispersant (J), (K) and (L), find that this consumption is 0.40% of a dried marble weight.
Using under polymine dispersant (J), (K) and the situation (L), also must add the sulfuric acid of q.s, to adjust PH to 7.8.In each case, all to measure the viscosity of suspension with 100 rev/mins axle rotating speed with a Brook field viscosimeter, and suspension that also will be by a known weight of finish-drying is also determined the weight percent of dried solids in the suspension to the method that dried residue is weighed.Then, with a spot of water diluted suspension, and the weight percent of further definite viscosity and dried solids.The process of the weight percent of diluted suspension and measurement viscosity and solids repeats 2-3 time, draws the curve map of viscosity to dried solids weight percent.The concentration of solids when determining that by interpolation the viscosity of suspension is 300mPa.s.The result lists in the following Table VII;
Table VII
Dried marble when cationic viscosity is 300mPa.s
The weight face of dispersant divides rate (%)
I 61.0
J 68.5
K 71.8
L 73.0
Example 7
A collection of rough crushed marble is not contained at the dried solids that contains 30% (weight) in the aqueous suspension of chemical dispersant and grind with the graininess abrasive media, so that produce the calcium carbonate product that grinds that a kind of paper coating is used, this grinding product has that such particle size distribution-promptly the particle of 90% (weight) has the suitable sphere diameter less than 2 microns.The marble suspension that grinds is not having under the situation of flocculant by filtering means dehydration, wears into powder with the gained filtration cakes torrefaction and in a laboratory on hammer-mill.
The marble powder sample that fine gtinding is crossed mixes with water, form a kind of dried solids and the anion of different amounts and the suspension of cationic dispersing agent that contains 60% (weight), anionic dispersing agent is that number-average molecular weight is 4,000 Sodium Polyacrylate, and cationic dispersing agent to be number-average molecular weight be about 50,000 poly-(diallyldimethylammonium chloride).
In each experiment, all will anionic dispersing agent add grind marble powder suspension in, and mixture stirs 9,400 circles in order to the impeller-agitator of 1,420 rev/min of rotational speed.Then, add cationic dispersing agent, the compound of laying equal stress on closes process.After the second time, mixed process finished, measure viscosity with Brook field viscosimeter immediately.
The gained result lists in the following Table VIII:
The dispersant anionic dispersible cationic type dispersant that Table VIII is sneaked into is cationic and cloudy from the weight ratio (mPa.S) of weight percent (%) dispersant of weight percent of viscosity total amount (weight %) agent
(％)0.416 0.053 0.363 6.9 10,0000.642 0.082 0.560 6.9 4,6000.850 0.108 0.742 6.9 1061.03 0.131 0.899 6.9 821.29 0.164 1.13 6.9 782.07 0.263 1.81 6.9 4800.348 0.070 0.278 4.0 9,4000.504 0.101 0.403 4.0 3,6000.616 0.123 0.493 4.0 600.800 0.160 0.640 4.0 741.02 0.204 0.816 4.0 5761.28 0.256 1.02 4.0 2,4000.364 0.102 0.262 2.6 3,6000.570 0.159 0.411 2.6 1,8000.732 0.205 0.527 2.6 3,4000.910 0.254 0.656 2.6 4,3501.05 0.294 0.756 2.6 4,6501.60 0.447 .15 2.6 4,1500.145 0.053 0.092 1.7 10,00000.273 0.100 0.173 1.7 6,1500.351 0.129 0.222 1.7 3,3600.434 0.160 0.274 1.7 7,6000.541 0.199 0.342 1.7 7,9000.790 0.291 0.499 1.7 5,9001.26 0.464 0.796 1.7 6,000
These results show, when the weight ratio of cationic dispersing agent and anionic dispersing agent is about 4: 1, can obtain best dispersion effect.Still may obtain the extraordinary suspension of fluidity when ratio is increased to 6.9: 1, still, its cost is that the consumption of the dispersant of sneaking into is higher slightly.
Example 8
A collection of rough crushed marble is not contained in the aqueous suspension of chemical dispersant containing 30% dried solids, grind with the graininess abrasive media, a kind ofly have the particle of 78% (weight) of such particle size distribution-promptly and have grinding product less than 2 microns suitable sphere diameter so that produce.Under the prerequisite that does not add flocculant, the marble suspension that grinds is dewatered to dried solid contents on rotary drum vacuum filter be 64% (weight).The method drying of some filter cakes that so form, and add to get back in the moistening filter cake and go, with the mixture that to form a kind of dried solid contents be 70% (weight) with heating.
This mixture is divided into three parts to be handled with three kinds of poly-(diallyldimethylammonium chloride) dispersants of CATION with different number-average molecular weights respectively, each part in these three parts is subdivided into less three parts, uses the anionic dispersing agent (E) described in the example 1 of various dose to handle respectively.
In each case, all want earlier anionic dispersing agent to be added in the marble cake that grinds, and fully mix, add cationic dispersing agent then and also mix.The dosage of used cationic dispersing agent all is approximately 3.5 times of anionic dispersing agent dosage in each case.
In each case, all will be with the viscosity of Brook field viscosimeter with 100 rev/mins axle tachometric survey gained suspension, suspension that also will be by a known weight of finish-drying is also determined the weight percent of dried solids to the way that dried residue is weighed.Then, suspension is diluted with a spot of water, and further determine the weight percent of viscosity and dried solids.Draw the curve map of viscosity, determine that by interpolation viscosity is the content of dried solids in the suspension of 300mpa.s dried solids weight percent.
The gained result lists among the following Table I X:
Weight percent (%) dried solid particle of the weight percent (%) of the molecular weight of agent was heavy when the cationic dispersion anionic dispersing agent of Table I X cationic dispersing agent viscosity was 300mpa.s
Amount percentage (%) 100,000 0.080 0.265 64.1100,000 0.108 0.370 65.4100,000 0.124 0.450 64.7200,000 0.074 0.260 64.7200,000 0.100 0.360 68.1200,000 0.125 0.450 67.1500,000 0.075 0.260 67.9500,000 0.100 0.360 68.4500,000 0.125 0.450 67.6
These results show, for a specific solid content, when the use number-average molecular weight is 500,000 cationic dispersing agent, can access the more better slightly suspension of mobility.
Claims (17)
1, a kind of moisture paper coating mixture comprises that (I) weight percent is at least 45% usefulness dispersant dispersed particles inorganic pigment; (II) a kind of adhesive; It is characterized in that dispersant comprises a kind of anionic polyelectrolyte and a kind of cationic polyelectrolyte, the consumption of cationic polyelectrolyte is enough to make face grain particle to have cationic; Adhesive is cationic or the nonionic adhesive; Graininess pigment is a kind of when the cationic polyelectrolyte individualism, can not in water, disperse with highly filled, and the pigment that still can not disperse along with violent mixing.
2, paper coating mixture according to claim 1 is characterized in that, pigment is selected from calcium carbonate, calcium sulfate, talcum or baked kaolin.
3, paper coating mixture according to claim 1 is characterized in that, said pigment is calcium carbonate pigment.
4, paper coating mixture according to claim 1 is characterized in that, the number-average molecular weight of anionic polyelectrolyte is at 500-100, in 000 scope.
5, paper coating mixture according to claim 4 is characterized in that, the consumption of anionic polyelectrolyte is the 0.01-0.5% that does weight of calcium carbonate
6, paper coating mixture according to claim 4 is characterized in that, cationic poly voltolisation electrolyte is a kind of water-soluble replacement polyolefin that contains quaternary ammonium group.
7, paper coating mixture according to claim 6 is characterized in that, replaces polyolefinic number-average molecular weight 1, and 500-1 is in 000,000 scope.
8, paper coating mixture according to claim 7 is characterized in that, the consumption of cationic polyelectrolyte is the 0.01%-1.5% of dried calcium carbonate pigment weight.
9, paper coating mixture according to claim 5 is characterized in that, cationic polyelectrolyte is to have a plurality of basic groups and number-average molecular weight 10,000-1000, the water-soluble organic compounds in 000 scope.
10, paper coating mixture according to claim 9 is characterized in that, said organic compound is that number-average molecular weight is 50,000-1,000,000 polymine.
11, according to each described paper coating mixture in the preceding claim, it is characterized in that, cationic polyelectrolyte with the weight ratio of anionic polyelectrolyte 2: 1-20: in 1 scope.
12, a kind of method for preparing the paper coating mixture may further comprise the steps:
(I) discrete particles pigment in aqueous suspension;
(II) dispersed aqueous suspension is mixed with a kind of adhesive, and, if necessary, can adjust dilution factor, make that the weight percent of means of particulate material is at least 45% in the mixture;
It is characterized in that said pigment disperses with the mixture dispersant that contains anionic polyelectrolyte and cationic polyelectrolyte; The consumption of cationic polyelectrolyte should be enough to make face grain particle to have cationic; Said adhesive is cationic or the nonionic adhesive; Said graininess pigment is a kind of when the cationic polyelectrolyte individualism, can not in water, disperse with highly filled, and the pigment that still can not disperse along with violent mixing.
13, method according to claim 12 is characterized in that, pigment is selected from calcium carbonate, calcium sulfate, talcum or baked kaolin.
14, method according to claim 13 is characterized in that, pigment is calcium carbonate pigment.
According to claim 12,13 or 14 described methods, it is characterized in that 15, pigment is elder generation and anionic polyelectrolyte mixing before mixing with cationic polyelectrolyte.
16, each described paper coating mixture is used for the coating paper among the claim 1-11.
17, use any coated paper of each described paper coating mixture coating paper gained among the claim 1-11.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8927536.6 | 1989-12-06 | ||
| GB898927536A GB8927536D0 (en) | 1989-12-06 | 1989-12-06 | Paper coating |
| US61344790A | 1990-11-13 | 1990-11-13 | |
| PCT/GB1990/001883 WO1991008341A1 (en) | 1989-12-06 | 1990-12-04 | Paper coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1052912A CN1052912A (en) | 1991-07-10 |
| CN1051826C true CN1051826C (en) | 2000-04-26 |
Family
ID=26296317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90110340A Expired - Fee Related CN1051826C (en) | 1989-12-06 | 1990-12-06 | Paper coating |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0504245B1 (en) |
| JP (1) | JPH05502484A (en) |
| CN (1) | CN1051826C (en) |
| AT (1) | ATE121149T1 (en) |
| AU (1) | AU647762B2 (en) |
| BR (1) | BR9007899A (en) |
| CA (1) | CA2072641A1 (en) |
| DE (1) | DE69018648T2 (en) |
| DK (1) | DK0504245T3 (en) |
| ES (1) | ES2070484T3 (en) |
| FI (1) | FI101091B (en) |
| GB (2) | GB8927536D0 (en) |
| NO (1) | NO180598C (en) |
| NZ (1) | NZ236353A (en) |
| WO (1) | WO1991008341A1 (en) |
| ZA (1) | ZA909749B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103827229A (en) * | 2011-08-31 | 2014-05-28 | Omya国际股份公司 | Self-binding pigment hybrid |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9200683D0 (en) * | 1992-01-14 | 1992-03-11 | Univ Manchester | Improvements relating to materials |
| US5387826A (en) * | 1993-02-10 | 1995-02-07 | National Semiconductor Corporation | Overvoltage protection against charge leakage in an output driver |
| US5406140A (en) * | 1993-06-07 | 1995-04-11 | National Semiconductor Corporation | Voltage translation and overvoltage protection |
| US5653795A (en) * | 1995-11-16 | 1997-08-05 | Columbia River Carbonates | Bulking and opacifying fillers for cellulosic products |
| AU5324796A (en) * | 1995-04-11 | 1996-10-30 | Columbia River Carbonates | Bulking and opacifying fillers for paper and paper board |
| US5676748A (en) * | 1995-12-29 | 1997-10-14 | Columbia River Carbonates | Bulking and opacifying fillers for paper and paper board |
| US5676747A (en) * | 1995-12-29 | 1997-10-14 | Columbia River Carbonates | Calcium carbonate pigments for coating paper and paper board |
| WO1996032448A1 (en) * | 1995-04-11 | 1996-10-17 | Columbia River Carbonates | Calcium carbonate pigments for coating paper and paper board |
| AU5376396A (en) * | 1995-04-11 | 1996-10-30 | Columbia River Carbonates | Bulking and opacifying fillers for cellulosic products |
| EP0790135A3 (en) * | 1996-01-16 | 1998-12-09 | Haindl Papier Gmbh | Method of preparing a print-support for contactless ink-jet printing process, paper prepared by this process and use thereof |
| DE102005057836B3 (en) * | 2005-12-03 | 2007-03-08 | Corvus Beschichtungssysteme Gmbh | Adhesion-improving material, useful for paper and copying paper, comprises fixing agent and polycarboxylic acid as dispersant, also microcapsule coating mass containing it |
| JP2007163955A (en) * | 2005-12-15 | 2007-06-28 | Nippon Paper Industries Co Ltd | Transfer paper for electrophotography |
| JP5264661B2 (en) * | 2009-09-14 | 2013-08-14 | 北越紀州製紙株式会社 | Manufacturing method of coated paper for offset and gravure printing |
| DK2447328T3 (en) * | 2010-10-29 | 2015-03-09 | Omya Int Ag | A method for improving håndterligheden of calcium carbonate-containing materials |
| PT2565237E (en) * | 2011-08-31 | 2015-07-02 | Omya Int Ag | Process for preparing self-binding pigment particle suspensions |
| PL2662416T3 (en) * | 2012-05-11 | 2015-12-31 | Omya Int Ag | Treatment of calcium carbonate containing materials for increased filler load in paper |
| SI2662419T1 (en) * | 2012-05-11 | 2015-09-30 | Omya International Ag | Charge controlled PHCH |
| 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 |
| SE1651136A1 (en) | 2016-08-24 | 2018-02-25 | Organoclick Ab | Bio-based pec compositions as binders for fiber based materials, textiles, woven and nonwoven materials |
| JP7131832B2 (en) | 2016-08-24 | 2022-09-06 | オルガノクリック アーベー | Bio-based polyelectrolyte complex compositions containing water-insoluble particles |
| ES2866893T3 (en) | 2016-08-24 | 2021-10-20 | Organoclick Ab | Bio-derived polyelectrolyte complex compositions with high hydrophobicity comprising fatty compounds |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0278603A1 (en) * | 1987-01-21 | 1988-08-17 | FARMITALIA CARLO ERBA S.r.l. | Condensed pyrazole derivatives and process for their preparation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8701491D0 (en) * | 1987-01-23 | 1987-02-25 | Ecc Int Ltd | Aqueous suspensions of calcium |
-
1989
- 1989-12-06 GB GB898927536A patent/GB8927536D0/en active Pending
-
1990
- 1990-12-04 ES ES91900880T patent/ES2070484T3/en not_active Expired - Lifetime
- 1990-12-04 DK DK91900880.5T patent/DK0504245T3/en active
- 1990-12-04 JP JP3501306A patent/JPH05502484A/en not_active Expired - Lifetime
- 1990-12-04 DE DE69018648T patent/DE69018648T2/en not_active Expired - Fee Related
- 1990-12-04 AU AU69584/91A patent/AU647762B2/en not_active Ceased
- 1990-12-04 AT AT91900880T patent/ATE121149T1/en not_active IP Right Cessation
- 1990-12-04 CA CA002072641A patent/CA2072641A1/en not_active Abandoned
- 1990-12-04 BR BR909007899A patent/BR9007899A/en not_active IP Right Cessation
- 1990-12-04 WO PCT/GB1990/001883 patent/WO1991008341A1/en active IP Right Grant
- 1990-12-04 ZA ZA909749A patent/ZA909749B/en unknown
- 1990-12-04 EP EP91900880A patent/EP0504245B1/en not_active Expired - Lifetime
- 1990-12-05 NZ NZ236353A patent/NZ236353A/en unknown
- 1990-12-06 CN CN90110340A patent/CN1051826C/en not_active Expired - Fee Related
-
1992
- 1992-04-07 GB GB9207583A patent/GB2253857B/en not_active Expired - Fee Related
- 1992-06-03 FI FI922555A patent/FI101091B/en active
- 1992-06-04 NO NO922206A patent/NO180598C/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0278603A1 (en) * | 1987-01-21 | 1988-08-17 | FARMITALIA CARLO ERBA S.r.l. | Condensed pyrazole derivatives and process for their preparation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103827229A (en) * | 2011-08-31 | 2014-05-28 | Omya国际股份公司 | Self-binding pigment hybrid |
| US10723886B2 (en) | 2011-08-31 | 2020-07-28 | Omya International Ag | Self-binding pigment hybrid |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0504245A1 (en) | 1992-09-23 |
| NO180598C (en) | 1997-05-14 |
| JPH05502484A (en) | 1993-04-28 |
| GB9207583D0 (en) | 1992-06-03 |
| ES2070484T3 (en) | 1995-06-01 |
| FI922555A (en) | 1992-06-03 |
| NO922206D0 (en) | 1992-06-04 |
| FI101091B (en) | 1998-04-15 |
| DE69018648D1 (en) | 1995-05-18 |
| FI922555A0 (en) | 1992-06-03 |
| DK0504245T3 (en) | 1995-09-04 |
| CN1052912A (en) | 1991-07-10 |
| CA2072641A1 (en) | 1991-06-07 |
| BR9007899A (en) | 1992-09-15 |
| ATE121149T1 (en) | 1995-04-15 |
| NO922206L (en) | 1992-06-30 |
| GB2253857A (en) | 1992-09-23 |
| AU647762B2 (en) | 1994-03-31 |
| NO180598B (en) | 1997-02-03 |
| AU6958491A (en) | 1991-06-26 |
| WO1991008341A1 (en) | 1991-06-13 |
| EP0504245B1 (en) | 1995-04-12 |
| GB2253857B (en) | 1993-08-04 |
| NZ236353A (en) | 1993-01-27 |
| GB8927536D0 (en) | 1990-02-07 |
| DE69018648T2 (en) | 1995-08-10 |
| ZA909749B (en) | 1991-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1051826C (en) | Paper coating | |
| CN1020914C (en) | Process for preparation of heat stabilizing water base kaolins pigment slurry and its usage | |
| CN1120262C (en) | Method of reusing fillers and coating pigments used in paper, paperboard and cardboard manufacture | |
| CN1274380A (en) | Pigment materials and their prepn. and use | |
| CN1301909C (en) | Titanium dioxide-calcium carbonate composite particles | |
| CN101184894B (en) | Polymer-pigment hybrids for use in papermaking | |
| CN1088777C (en) | Production of filled paper and compositions for use in this | |
| US5384013A (en) | Cationic pigment-containing paper coating composition | |
| CN86105012A (en) | Use treatment of clays with cationic polymers to prepare high bulking pigments | |
| CN1189458A (en) | Aqueous slurry of precipitated calcium carbonate and ground calcium carbonate in combination | |
| KR20070007364A (en) | Surface-modified inorganic fillers and pigments | |
| EP0278602B1 (en) | Aqueous suspensions of calcium-containing fillers | |
| CN1726262A (en) | Fine platy kaolin composition | |
| CN1238600C (en) | Method for recycling pulp rejects | |
| CN101031686A (en) | Method to manufacture paper | |
| CN1009015B (en) | Electrically conductive carbon coated fibers | |
| KR101721284B1 (en) | Coarse pigment addition and high solids slurries for higher coating colour cocentrations | |
| JP5449824B2 (en) | Paper filler made from incinerated ash | |
| CN1675319A (en) | Kaolin pigment products | |
| JP5419620B2 (en) | Heatset offset printing paper | |
| JP5484002B2 (en) | Printed coated paper containing papermaking filler | |
| JP5346235B2 (en) | Cold offset printing paper containing papermaking filler | |
| CN116752374A (en) | Paper product, papermaking filler and coating pre-flocculation modification method thereof | |
| CN116145474A (en) | Corrugated paper filling material and preparation method of modified fly ash material | |
| KR20190112970A (en) | Recycling method of scrap paper using liquid phase process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |