CN1231639C - Silica-acid colloid blend in a microparticle system used in papermaking - Google Patents

Abstract

A micro-particle system for use as a retention and drainage aid in the production of alkaline and acid paper products comprises a high molecular weight flocculant polymer (6) and a silica-acid colloid blend (7), and optionally a cationic coagulant or a medium molecular weight flocculant (5). The high molecular weight flocculant polymer (6) may be added to the furnish after the fan pump (1) and prior to the pressure screen (2); the silica-acid colloid blend (7) may be added to the furnish after the pressure screen (2), and optionally, the coagulant or medium molecular weight flocculant (5) may be added prior to the fan pump (1). Addition of the micro-particle system to the paper furnish improves retention and drainage during the papermaking process and sheet formation. The acid colloid of the silica-acid colloid blend (7) is a polymer or a copolymer of a melamine aldehyde acid colloid.

Description

Silica-acid colloid blend in the microparticle system that in paper-making process, uses

Background of invention

Invention field

The present invention relates to a kind of be used as in the preparation process of paper product such as paper or cardboard auxiliary agent, improved microparticle system, described system is at retention, drainability, and the paper formation aspect has the performance of improvement.More particularly, the present invention relates to: be included in the microparticle system microparticle system as the silica-acid colloid of inorganic particulate pellet.

The background technology explanation

In the production process of paper or cardboard, rare Aquo-composition that will be referred to as " batching " or " slurry " is sprayed onto on the mesh of the motion that is referred to as " fourdrinier wire ".Make the solid composition of said composition such as cellulose fiber peacekeeping inorganic particles packing carry out drainage or filtration by this fourdrinier wire, thereby form page." passing through retention first " that the percentage of keeping the solid material on fourdrinier wire is referred to as paper-making process (FPR).Use filter aid, retention agent and shaping additive (D/R/F) at paper-making process.

It is believed that retention changes with different mechanism, the filtration of described mechanism such as mechanical entrapment thing, electrostatic attraction, and the bridging between fiber and the filler in the batching.Because the many fillers commonly used of cellulose fiber peacekeeping are all electronegative, therefore, they repel mutually.In general, unique factor that can strengthen retention is the mechanical entrapment thing.Therefore, use retention agent to improve fiber and the retention of filler on fourdrinier wire usually.The retention of fiber fines and filler is crucial for paper machine, so that guarantee to hold back the particle of colloid applying glue in the page.Measure the ability that this keeps program by retention (FPR) first.Cataloid was used as the particulate in the filter aid of alkaline fine paper in the past always.When correct use, hold back the microfloc of colloidal materials by formation, silica can strengthen the retention of fiber fines and filler, and paper pulp is dewatered rapidly.

The speed that drainage is removed from batching when forming page is relevant.Drainage is commonly referred to as: the dehydration that is taken place before the squeezing to page after forming page.Therefore, filter aid is used for improving dewatering efficiency total when producing paper or cardboard.

Shaping relates to the paper or the cardboard evenness of producing in paper-making process.Evenness is assessed by page iuuminting rate variance usually.The printing opacity rate variance shows the evenness of " poor " greatly, and the little words of light transmittance show the evenness of " well ".In general, retention increases, and formation value will be reduced to poor evenness from good evenness usually.

It should be understood that for various reasons special what wish is that wherein of paramount importance reason is a productivity ratio aspect retention and drainage and in the improvement of paper or cardboard forming aspect of performance.Good retention and filtration rate make the paper function move quickly, and reduce paper machine fault.Good paper formation will reduce the waste paper amount.These improve by using retention agent and filter aid to realize.Thereby retention agent and filter aid normally are used for making the tiny solid material flocculation that is present in the batching to improve the additive of these parameters in the paper-making process.Use described additive the influence of paper formation is limited by flocculation.If add too many retention agent, the size of tiny solid material flocculate will increase, and this will change the density of page usually then, as mentioned above, and the paper formation that this may so-called with causing " poor ".Because overflocculation finally may form hole and lose vacuum pressure at the subsequent dewatering of paper-making process in the stage in page, therefore, overflocculation also will influence drainage.Usually, retention agent and filter aid are added in the batching, and they have three types usually, that is: at the wet end of paper machine

(a) single polymers;

(b) bi-component polymeric; Or

(c) microparticle system that can use with flocculant and/or coagulating agent.

As retention agent and filter aid, microparticle system can provide best result usually, and in the existing description widely of prior art.The example of microparticle system publication comprises: EP-B-235, and 893, wherein, the interpolation order with specific together with the HMW cationic polymer, is used as inorganic material with bentonite; WO-A-94/26972 has wherein disclosed vinyl amide polymer and various inorganic material such as silica, bentonite, and one of clay and organic material use together; Disclosed the kaolin that various cationic polymers use together among the WO-A-97/16598; And EPO805234, bentonite wherein, silica, or acrylate polymer uses with the cationic dispersion polymer.

US4,305,781 and 4,753,710 have disclosed HMW nonionic and ionomer have been used with bentonite, so that help the dehydration of paper-making process and keep effect.US4,388,150 and 4,385,961 have illustrated use cationic starch and cataloid.US4,643,801 and 4,750,974 have described and have used cationic starch in paper-making process, anion HMW polymer, and cataloid.US5,185,062 have described the anionic polymer that is equivalent to the particulate of HMW cationic flocculant.US5,167,766 have instructed in paper-making process charged organic polymer microballon as particulate.

In paper, use melamine one formaldehyde (MF) acidoid to know as wet strength agent.This can be with reference to " wet strength of paper and cardboard " (C.S.Maxwell, J.P.Weidner, editor) of the special number of the edition 29 of TAPPI.US2,345,543 have described the preparation method of stable melamine-formaldehyde acidoid, and US2, and 485,080 comprise urea are mixed in the condensation product.US2,559,220 and 2,986,489 have instructed the wet strength that increases paper with these colloids.US4,845,148 have described and use the amino-aldehydic acid colloid that has acrylamide to increase the dry strength of paper.US5,286,347 have described the pitch trouble control that use melamine-glutol body is used for paper-making process.US4,461,858 have described the polyvinyl alcohol-melamine formaldehyde (MF) colloid blend that is used for the paper wet strength.US4,009,006 has instructed use MF colloid and anion HMW polymer to make the raw sugar flocculation.US5,382,378 have described cataloid and the melamine aldehyde that is blended together, and the composition of urea aldehyde or melamine-urea aldehydic acid colloid is used for collecting paint, oil and lubricating grease, or colorant from industrial water.

Microparticle system comprises usually: with or without the polymer flocculants and the fine particle material of cationic coagulant.The fine particle material can be the inorganic particulate pellet, and can improve the efficient of flocculant and/or can produce littler, more uniform flocculate.

For obtaining better paper machine operation and/or obtaining the performance of specific final unusable paper, as be used for the paper formation of the improvement of better printability, or the surface strength of improving, although the microparticle system that has some kinds of paper supply factories to use, but really still need to improve the improved microparticle system of paper or cardboard, described paper or cardboard are by being improved to the improvement of drainage and retention with to the improvement of shaping paper sheet formation performance in the paper-making process.

Summary of the invention

The present invention has satisfied above-mentioned needs.The present invention relates to a kind of microparticle system that in paper-making process, is used as retention agent and filter aid, comprising:

A) weight average molecular weight is 100000 or bigger HMW polymer flocculants, and in solid dry weight in the described batching, the amount of HMW polymer flocculants is from 0.0025 weight % to 1.0 weight %, and b) silica-acid colloid formed by following material:

(1) acidoid of forming by melamine aldehyde or derivatives thereof, or comprise melamine aldehyde and be selected from the acidoid of copolymer of the condensation polymer of melamine-aldehyde, dicyano diamides aldehyde, urea-formaldehyde polyalkylene polyamine and polyamides urea, or amine-aldehyde type and be selected from the acidoid of copolymer of the ethylenically unsaturated monomer of acrylamide, dimethylaminoethyl acrylate, diallyldimethylammonium chloride and methacrylamidopropyltrimethyl trimethyl ammonium chloride; With

(2) cataloid, wherein in pH be 3.0 or lower sour environment under total solid, described acidoid and described cataloid be correspondingly with 99.5: 0.5 to 0.5: 99.5 ratio blending,

In the dry weight of solid in the described batching, the content of described silica-acid colloid blend is from 0.0005 weight % to 0.5 weight %.

According to a first aspect of the invention, a kind of production method of paper is provided, described method comprises the microparticle system as retention agent and/or filter aid is added in slurry or the intermittent pulp proportioning, described retention agent and/or filter aid comprise heavy polymer flocculant and inorganic particulate pellet, wherein the inorganic particle material package contains silica one acidoid blend, and this blend comprises cataloid and acidoid.

According to a second aspect of the invention, a kind of improved microparticle system that is added into as retention agent and/or filter aid in slurry or the batching is provided, and described microparticle system comprises heavy polymer flocculant and inorganic particulate pellet, wherein the inorganic particle material package contains silica one acidoid blend, and this blend comprises cataloid and acidoid.

According to a third aspect of the invention we, providing a kind of has at retention, the paper or the cardboard of performance improved in drainage and evenness aspect, wherein said paper or cardboard make by improved microparticle system being added in aqueous cellulosic slurry or the batching, wherein microparticle system comprises heavy polymer flocculant and inorganic particulate pellet, described inorganic particle material package contains silica-acidoid blend, and this blend comprises cataloid and acidoid.

A fourth aspect of the present invention relates to a kind of method, in the method, makes paper or cardboard by forming the aqueous cellulosic slurry, and this method comprises:

(a) after first shear stage, the heavy polymer flocculant is added in the underflow stream of paper furnish,

(b) after second shear stage, the inorganic particle grain that will comprise silica-acidoid blend is added in the paper furnish, and described blend comprises cataloid and acidoid;

(c) make the paper furnish dehydration form page; With

(d) page is carried out drying.

The method that a kind of usefulness microparticle system of the present invention is produced paper product comprises the steps:

(a) after the first high shear stage and before the second high shear stage, the heavy polymer flocculant is added in the paper furnish, in the dry weight of solid in the described batching, addition from 0.0025% to 1.0% weight; With

(b) before or after described second shear stage, silica-acidoid blend is added in the paper furnish, in the dry weight of solid in the described batching, addition from 0.0005% to 0.5% weight.

The method that a kind of usefulness microparticle system of the present invention is produced paper product comprises the steps:

(a) after the first high shear stage and before the second high shear stage, silica-acidoid blend is added in the paper furnish, in the dry weight of solid in the described batching, addition from 0.0005% to 0.5% weight; With

(b) before or after described second shear stage, the heavy polymer flocculant is added in the paper furnish, in the dry weight of solid in the described batching, addition from 0.0025% to 1.0% weight.

Described acidoid can be made up of the aqueous solution of water-soluble polymer, and described water-soluble polymer can be the melamine urea formaldehyde, urea urea formaldehyde, or melamine-urea urea formaldehyde, and described aldehyde has following structural formula:

R in the formula ₁Be selected from the C of straight or branched _1-4Alkyl.Preferably, described acidoid is the polymer of melamine formaldehyde (MF), but can be the copolymer of melamine-formaldehyde and urea-formaldehyde also, or comprises the copolymer of melamine aldehyde and the condensation product or the copolymer of amine-aldehydes and ethylenically unsaturated monomer.

In system of the present invention, melamine-formaldehyde is by the pure etherificate of linearity or side chain.The silica-acid colloid blend comprises the acidoid of cataloid and melamine-formaldehyde and urea-copolyoxymethylenes.The silica-acid colloid blend comprises the acidoid of a described cataloid and a copolymer, and described copolymer comprises described melamine aldehyde and is selected from the condensation polymer of following material: melamine-aldehyde, dicyano diamides aldehyde, urea-formaldehyde polyalkylene polyamine and polyamides urea.The silica-acid colloid blend comprises the acidoid of the copolymer of described cataloid and amine-aldehyde type and ethylenically unsaturated monomer, and described monomer is selected from acrylamide, dimethylaminoethyl acrylate, diallyldimethylammonium chloride and methacrylamidopropyltrimethyl trimethyl ammonium chloride.

In silica-acidoid blend, under pH3.0 or lower sour environment, at the total solid meter, the mixing ratio of acidoid and cataloid is correspondingly from about 99.5: 0.5 to about 0.5: 99.5.In the dry weight of solid in the batching, the content of silica-acidoid blend from about 0.0005% to about 0.5% weight.

In the dry weight of solid in the batching, the content of heavy polymer flocculant is from about 0.0025% to about 1.0% weight, and in the dry weight of solid in the batching, the content of silica-acid colloid blend is from about 0.0005% weight to about 0.5% weight.High charge density cationic coagulant or intermediate molecular weight flocculant can be added in the batching before first shear stage, and can add before or after adding the silica-acid colloid blend in some occasion.In some occasion, the order that changes chemical addition agent point of addition in the paper machine may be more useful.Be that silica-acidoid blend can be added into before first shear stage in slurry or the batching, and the flocculant of coagulating agent or intermediate molecular weight can second cut want the stage after or before add, high molecular weight flocculants second shear stage after or before interpolation.

Brief description of drawings

Accompanying drawing is an explanation common paper machine part and with the sketch of the microparticle system component point of addition of the present invention of preferred form.

Detailed Description Of The Invention

The present invention relates to the microparticle system as retention agent and/or filter aid, this microparticle system is especially for the wet end of paper machine in acid system and the alkaline process fine paper paper-making process.

The term " paper " that uses in the present invention comprises the product that comprises cellulosic sheet material, and these products comprise page, cardboard etc.

" microparticle system " of the present invention refers to: be used as at least a hydrophilic polymer of flocculant and in this system, be the inorganic particulate pellet of particulate, and the mixture of dispensable cationic coagulant or intermediate molecular weight flocculant. In the present invention, the inorganic particulate pellet is silica-acidoid blend. The each component of this mixture can be added in pending slurry or the batching together, but preferably adds individually and add by following described order.

The present invention can utilize conventional paper machine to implement. According to conventional practice, batching or " thin pulp " that drainage forms page usually prepare by the dilution underflow, described underflow is usually by blending pigment or filler, suitable fiber, the reinforcing agent of any hope and/or other additive, and can be that the water of recycle-water makes in mixer or stock tank. Can for example utilize the Vortex hydrocyclone to clean thin pulp with the mode of routine. Usually, by by screen centrifuge thin pulp being cleaned. Thin pulp send along the paper pump by the centrifugal pump that one or more is referred to as mixing pump usually. For example, can thin pulp be pumped to screen centrifuge by the first mixing pump. Underflow can be diluted by water, thereby is forming thin pulp before the position that enters the first mixing pump or before the first mixing pump, for example by by making underflow and dilution water pass through mixing pump. Thin pulp can further clean by passing through the second screen centrifuge or pressurized screen, and passes through flow box before the paper machine forms the page process.

Can use paper or the cardboard forming machine of any routine, smooth long mesh paper making machine for example, twin wire former, or any combination of cylinder former or these formers are implemented the forming process of page. The system for handling of paper machine can comprise the parts shown in the figure. These parts comprise: mixing pump 1, pressurized screen 2, and flow box 3. Underflow can be diluted by water, thereby by making underflow and dilution water by the mixing pump (not shown), forms thin pulp before underflow enters mixing pump 1. By the impurity that cleans out by pressurized screen 2 in the thin pulp, and before forming page, the thin pulp of staying on the pressurized screen 2 is delivered in the flow box 3.

In addition, described accompanying drawing has also illustrated the preferred point of addition of microparticle system each component of the present invention. Preferably, if use the flocculant of cationic coagulant or intermediate molecular weight (MMW), before thin pulp is by mixing pump 1, be added in the thin pulp so; Described mixing pump is pressed the operation of direction shown in the arrow 4, and adds by arrow 5 indications. As shown in arrow 6, when discharging mixing pump 1 such as thin pulp, HMW (HMW) flocculant polymer is added in the thin pulp, and, as shown in arrow 7, sieved 2 o'clock in the thin pulp discharge pressure, the silica-acid colloid blend is added in the thin pulp. Mixing pump 1 and pressurized screen 2 will form the high shear stage in the paper machine.

In the present invention, preferably before the final position of thin pulp arrival high shear, add the HMW flocculant polymer of microparticle system, and final thin pulp preference was preferably sheared before the silica-acid colloid blend that adds microparticle system of the present invention as at the place, final position of high shear. In the accompanying drawings, shown HMW flocculant added before pressurized screen 2 is passed through in the thin pulp operation; And shown in the silica-acid colloid blend at slurry by interpolation after the pressurized screen 2.

Preferably, the HMW flocculant polymer of microparticle system of the present invention is added in the thin pulp (be desirable solids content be not more than 2% or be at most 3% weight), and be not added in the underflow. Therefore, the HMW flocculant polymer can be added directly in the thin pulp, maybe can be added into underflow is changed in the dilution water of thin pulp.

The HMW flocculant polymer comprises for the solid that makes the papermaking batching, especially the preparation of fiber fines flocculation. The term " fiber fines " that uses in the present invention means the tiny solid particle and the fiber that define respectively in TAPPI method of testing T261 and T269.

The flocculation of fiber fines can itself be finished or be combined to finish with high charge density cationic coagulant or MMW flocculant by it by the HMW polymer in the batching. The flocculation of fiber fines will make that fiber fines has better retention, improved whereby dehydration or drainage in the fibre structure of shaping page.

The HMW flocculant is preferred by the polymer of flocculation is provided itself.

Being applicable to HMW flocculant polymer example of the present invention comprises: molecular weight about 100,000 or larger, especially 500,000 or those larger polymer. Preferably, described molecular weight is about more than 100 ten thousand, and usually about more than 500 ten thousand, the most frequently used is 10,000,000 to 3,000 ten thousand or larger. These polymer can be linear, side chain, cationic, anion, non-ionic, both sexes, or the polymer of acrylamide or other non-ionic monomer hydrophobically modified.

The amount of HMW flocculant that is added into the microparticle system in slurry of the present invention or the batching can be the flocculation solid, especially is enough to provide the amount of substantial role during fiber fines, and described solid is present in the batching. The total amount of the water-soluble polymer that adds can from about 0.0025% to about 1%, more preferably from about 0.01% weight to about 0.2% weight, most preferably from about 0.0125% to about 0.1% weight (based on the dry weight that is present in the polymer of solid dry weight the batching). Interpolation can be carried out at one or more point of additions by one or many, preferably, once is added into after the mixing pump that produces high shear forces in the thin pulp stream.

It is desirable for before the silica-acid colloid blend that adds microparticle system of the present invention, make the flocculate that is formed by the HMW polymer flocculants stand shear action. Preferably, described shear action is produced by the pressurized screen that produces high shear forces.

In preferred embodiments, granules of the present invention is comprised of silica-acidoid blend, and as at aforementioned US5, those compositions that disclose in 382,378 are incorporated herein by reference instruction at this. For example, melamine aldehyde, urea aldehyde, or the blend of melamine-urea aldehyde and cataloid comprises silica of the present invention-acidoid blend. As US5, described in 382,378, Ludox is that both sexes silica is discontinuous, the stabilising dispersions of colloid size particles in the aqueous solution. Ludox comprises 5-50% silica, and particle diameter is less than 1 micron. The stability of Ludox depends on the high electrostatic repulsion forces of maintenance between the silica dioxide granule. The pH value must be alkalescence, with the negative electrical charge on the maintenance silica dioxide granule, thereby prevents from assembling. Colloidal solution under low pH be less stable and tend to occur gelling.

Be used for suitable Ludox of the present invention, its particle diameter is preferably the 3-20 nanometer less than 1 micron, and solid content is 0.5% to 50% weight.

In preferred embodiments, with regard to the acidoid component of particulate, can use the polymer of any melamine aldehydes. By using the melamine of a) melamine or replacement; And b) aldehyde that has a following formula prepares described this polymer:

R in the formula₁Be selected from the C of straight or branched_1-4Alkyl. Also can use dialdehyde in addition. Described dialdehyde can be to comprise the straight chain of 2-8 carbon atom or the dialdehyde of ring-type, and it can be that C-replaces and comprise hetero atom. Preferred aldehyde is formaldehyde, acetaldehyde, propionic aldehyde, glyoxal, and glutaraldehyde. Most preferred aldehyde is formaldehyde.

Above-mentioned component a) with component b) mol ratio from about 1: 1 to about 1: 10, preferred mol ratio was from about 1: 3 to 1: 6. Most preferred mol ratio is that about 1 mole of melamine or derivatives thereof is to about 3 moles of aldehyde. Therefore, highly preferred polymer is by melamine and formaldehyde preparation, and the mol ratio of melamine PARA FORMALDEHYDE PRILLS(91,95) is about 1: 3.

Melamine aldehyde polymer of the present invention is water insoluble, but can remain in the soliquid of acid solution. Although preferred hydrochloric acid also can prepare with any acid or compatible acid blend the melamine aldehydic acid colloid of granules of the present invention. In acidic suspension or solution, the active quantities of melamine aldehyde type polymer should be from about 0.1% to about 20%, preferably from 1% to about 15%, and most preferably from about 4% to about 12%. PH should be enough low, namely makes it to remain between the 1.0-2.5 with aqueous inorganic acid or organic acid, in order to make melamine aldehyde type polymer be thin soliquid.

Being applicable to urea aldehyde type polymer solution of the present invention is: wherein aldehyde by previously defined those, urea-formalin most preferably. The urea element should be from 1: 1 to 1: 10 to the mol ratio of aldehyde, and most preferred mol ratio was from 1: 3 to 1: 6.

Melamine urea aldehyde copolymer solution also can be used for the present invention. These solution are according to aldehyde component as mentioned above, urea, and melamine or replace melamine and prepare. Melamine-urea-copolyoxymethylenes solution preferably. Be applicable to melamine-urea of the present invention-copolyoxymethylenes solution and comprise the urea of 1-70% mole, the melamine of 30-99% mole, and for the aldehyde of every mole of compound melamine in acidic aqueous media and the about 1-4% mole of urea. Be used for copolymer solution of the present invention, its solid content is from 0.1-20%, preferably from 1-12%.

Acidoid can be the copolymer that comprises melamine aldehyde, and includes ammeline-aldehyde, dicyano diamides aldehyde, two guanidines-aldehyde, urea-formaldehyde polyalkylene polyamine, and the condensation polymer of polyamides urea.

Prepare acidoid by specific aldehyde and amine being reacted and under the acid condition that usually uses hydrochloric acid, this solution being worn out. When wearing out, colloidal solid will grow to the size of 20-200 dust. Average degree of polymerization is from 10-20 methylolation melamine unit. Described particle band cationic charge, namely some secondary amine unit is by protonated. Colloidal solution is blue muddy shape in characteristic. Described solution stores with the concentration of 8-12% active matter. This solution can only be comprised of amine and aldehyde, maybe can be their derivative. This solution can be with pure, glycol, or the material of other hydroxyl carries out the part etherificate. This solution can be the co-condensation polymer of melamine-formaldehyde and other aminoplast, and then co-condensation polymer can carry out etherificate. This solution can be the mixture of described aminoplast, and then they be used for forming acidoid. The aminoplast that forms colloid also can be ethylenically unsaturated monomer such as acrylamide, dimethylaminoethyl acrylate, diallyldimethylammonium chloride (DADMAC), or the copolymer of methacryl amido oxypropyl trimethyl ammonium chloride etc.

In preferred embodiments, the component and the preparation method of particulate of the present invention are similar to US5, disclosed in 382,378, be introduced into as a reference at this.Utilize 10% hydrochloric acid, at first the pH with cataloid solution reduces to 1.3-2.0.Under agitation add acidoid solution then, for example melamine urea aldehyde copolymer.Its pH of resulting blend is preferably 1.5 approximately from 1.0-3.0.The total solid content of this blend is from 1.0-50%.In the present invention, with regard to preparation paper or cardboard, these silica-acidoid blend is as drainage, keeps and forms the part of the microparticle system that the page program uses and use.

In the microparticle system of the present invention, be added into the amount of silica one acidoid of the fine-grained particles material in paper or the batching, in the dry weight of solid in the batching, from about 0.0005% to about 0.5% dry weight, preferably from about 0.005% to about 0.25% dry weight.Interpolation can be carried out at one or more point of additions by one or many, preferably, adds after the pressurized screen 2 in the accompanying drawings, and adds between pressurized screen 2 and flow box 3 at least.

The silica-acid colloid blend of microparticle system of the present invention comprises cataloid and acidoid, preferably melamine formaldehyde (MF) acidoid and aforesaid derivative.

Add the HMW flocculant polymer and will in paper that adds polymer or batching, form the flocculate of big suspended solid usually.These big flocculates are broken in the prior art the very little flocculate that is referred to as " microfloc " immediately or subsequently by high shear force.Described " high shear force " can produce by the pressurized screen in the accompanying drawing 2 by the batching that makes flocculation.

Water-soluble coagulating agent, its molecular weight are usually less than the molecular weight that was added into the HMW flocculant in the slurry before pressurized screen 2, preferably,, by before accompanying drawing 1 mixing pump 1 coagulating agent are added in the slurry at slurry.Described coagulating agent is preferably the cationic polymer of high charge density.For example, if the coagulating agent polymer is the cationic nitrogenous polymer, its charge density can be about 0.2 in per kilogram polymer nitrogen gram equivalent, and preferably at least 0.35, most preferably be 0.4-2.5 or higher.When described polymer and when forming by the polymerization of CATION ethylenically unsaturated monomer and not essential other monomer, to be used to form the monomer total amount of polymer, about 2% mole usually of the amount of cationic monomer, usually about 5% mole, preferably at least about 10% mole.

Suitable cationic coagulant comprises: diallyl dimethyl ammoniumchloride (P-DADMAC), poly-alkylamine, the cationic polymer of chloropropylene oxide and dimethylamine and/or ammonia or other primary amine and secondary amine, polyamidoamines amine, non-ionic monomer, as acrylamide and cationic monomer, as the copolymer of DADMAC or acryloxy ethyl-trimethyl salmiac, the polymer of the urea/formaldehyde of cyanoguanidines modification/resin, melamine/yuban, urea/yuban, polymine, cationic starch, the monomer of cation aluminium salt and polymer, have the amphiphilic polymers of clean cationic charge and the blend of above-mentioned coagulating agent.

The amount that is added into the cationic coagulant polymer of the microparticle system of the present invention in slurry or the material can be to be enough to provide the amount of substantial role when condensing to being present in solid in paper or the batching.In the dry weight of solid in the batching, the total amount of water-soluble coagulating agent polymer can be from about 0.0025%-1.0% weight, more preferably from about 0.005%-0.50% weight.

If with MMW flocculant place of cation coagulating agent, so, described flocculant can be at slurry by adding before the mixing pump 1.The example that is applicable to MMW flocculant of the present invention is: those flocculants between the weight average molecular weight from 500,000 to about 500 ten thousand and 600 ten thousand.This chemical addition agent can be the copolymer of acrylamide or any unsaturated monomer.Suitable MMW flocculant can comprise: derive from Calgon Corporation, the ECCat of PA ^TM500 copolymers.

The amount of MMW flocculant can be to be enough to provide the amount of substantial role when condensing to being present in solid in paper or the batching.In the dry weight of solid in the batching, the total amount of MMW flocculant can be from about 0.0025%-1.0% weight.This dosage at polymer per ton in the scope of 0.01-5.0 pound.

As mentioned above, cationic coagulant or MMW flocculant can be added into before mixing pump in the underflow, the HMW flocculant polymer can be added in the thin pulp after slurry is by mixing pump 1, and silica-acid colloid blend of the present invention can be added in the thin pulp after the pressurized screen 2 of slurry by accompanying drawing.In addition, these chemical addition agents can also different orders be added in the slurry except that shown in the accompanying drawing.That is, can after mixing pump 1, add the silica-acid colloid blend, after pressurized screen 2, add the HMW flocculant, and before pressurized screen 2, add coagulating agent or MMW flocculant.For the chemical addition agent of paper machine, the order of other feed location can also be arranged.

Underflow at the beginning can prepare according to the paper making pulp of routine, described slurry such as traditional chemical pulp, for example bleaching and do not float sulfate pulp or sulfite pulp; Mechanical pulp is as ground wood pulp; Thermomechanical pulp; Or CTMP; Or reuse paper pulp, as the deinking waste material that obtains by gathering or circular treatment, fiberfill; And their mixture.

Be used for batching of the present invention or slurry, can not carry out a large amount of filling (for example in final paper, comprise be less than 10% and be less than the filler of 5% weight usually) with final paper, or fill with filler, described filler can provide 50% consumption at the most in solid dry weight in the batching, or provides 40% consumption at the most in the paper dry weight.When using filler, wherein can use any conventional white paint filler, as calcium carbonate, kaolin, calcined kaolin, titanium dioxide, or talcum, or its combination.If Packed words are preferably mixed in the batching with conventional mode and before adding microparticle system each component of the present invention.

Be used for the selective additives that batching of the present invention or slurry can comprise that other is known, as rosin, alum, neutral sizing agent or optical brightener.Batching can also include reinforcing agent or binding agent, and these materials for example can comprise starch, as cationic starch.The pH of batching is usually from about 4-9.

Fiber, filler and other additive are usual amounts as the consumption of reinforcing agent or alum.Usually, the solid content of thin pulp is from 0.1-3% weight, or fiber content is from 0.1-2% weight.The common solid content of thin pulp is from 0.1-2% weight.Described these percentages are all in solid dry weight in the batching.

As mentioned above, the silica one acidoid blend that is used as granules in microparticle system of the present invention comprises cataloid and acidoid or derivatives thereof.Preferably, acidoid is made up of the aqueous solution of water-soluble polymer, and described water-soluble polymer is melamine aldehyde preferably, preferably melamine-formaldehyde.In paper-making process, this particulate material is scattered in the water-containing pulp suspension easily, thereby strengthens the surface characteristic of final paper product.

The present inventor finds that silica-acidoid blend perhaps can increase water filtering performance and retention with coagulating agent or MMW flocculant with the HMW flocculant, and improves the paper formation in the paper-making process.

Embodiment

Following Example will illustrate the present invention in more detail, but and not mean that scope of the present invention is constituted qualification by any way.In these embodiments, use following product:

Polymer A: the active acrylamide of 25% weight-derive from Calgon Corporation (Pittsburgh, PA) acryloxy ethyl-trimethyl salmiac copolymer comprises about 90% mol propylene acid amides and about 10% mol propylene acyloxy ethyl-trimethyl salmiac.

Polymer B: Flokal B-(Pittsburgh, 28% weight active anion acrylamide and acrylic acid copolymer PA) comprise about 70% mol propylene acid amides and about 30% mol propylene acid to derive from Calgon Corporation.

Polymer C: derive from Calgon Corporation (Pittsburgh, PA), the intermediate molecular weight cation copolymer of acrylamide and diallyldimethylammonium chloride.

Polymer D: derive from Calgon Corporation (Pittsburgh, PA), acrylamide, diallyldimethylammonium chloride and acrylic acid intermediate molecular weight terpolymer.

Melamine-formaldehyde (MF) acidoid: derive from Calgon Corporation (Pittsburgh, the solution of 8% active matter PA).

Cataloid: derive from DuPont (Wilmington, DE), the solution of 15% active matter.

Carbital 60: derive from ECC International Inc. (Atlanta, anhydrous powdered whiting GA).

Stalok ^400 (U.S.'s trade mark of A.E.Staley) and Interbond C: the cationic starch that derives from A.E.Staley.

Hercon 70: derive from Hercules, the AKD of Inc. (alkyl ketene dimer) sizing agent.

Embodiment 1-16-alkalescence fine paper batching

Preparation of batch

The synthetic alkaline fine paper batching of preparation, and be used for drainage and keep test and make handmade paper.Described batching utilizes following component to be prepared:

Fiber: 50/50% (weight) bleaching leaf wood kraft pulp/bleaching needlebush kraft pulp.

Filler: 50/50% (weight) powdered whiting (Carbital 60)/preformed precipitate calcium carbonate.

Filler feeding quantity: in fibre solid 20% weight.

Starch: in fibre solid 0.5% weight (Interbond C).

Sizing agent: 0.25% weight Herxon 70 (AKD).

Dry pulp paperboard slurry is immersed in the water of low-grade fever for the time 10 minutes, be diluted with water to the concentration of 2% weight solid, and with laboratory scale Voith Allis Valley beater correct grinding or pull an oar to 590 milliliters Canadian Standard Freeness (CSF).In this program, with starch, sizing agent and filler are added in the refining slurries.The pH of slurries is generally 7.5 ± 0.3.With running water further with slurry dilution to the concentration of about 1.0% weight, thereby be formed for drainage and keep test and the thin pulp of the handmade paper that is used to manufacture paper with pulp.The commonly used alkaline fine paper batching of this batching for being used for preparing the printing level and writing grade paper.

The drainage testing procedure

1. will be that 200 milliliters of batchings (2 gram) of 1% weight concentration are poured in the square mixer and with running water and are diluted to 500 milliliters at the flow box place.

2. be simulation second mixing pump inlet, the mixing pump outlet, and the chemical agent interpolation of pressurized screen outlet, utilize standard Britt Jar type propeller mixer (1 inch diameter), under following incorporation time (second) and speed (rpm) condition, mix these components:

Time Speed (rpm) Additive Feed location

Before the t0 1200 coagulating agent mixing pumps

Before the t10 1200 flocculant pressurized screens

Behind the t20 600 D/R/F auxiliary agent pressurized screens

T30 stops

3. the inclusions in the mixer is transferred in 500 milliliters the band scale drainage test tube, 100 purpose screen clothes wherein are housed in the bottom.Test tube is reversed 5 times so that guarantee that slurry is even.The stopper of test tube bottom is removed and is measured the elution time of 100,200 and 300 milliliters of elution volumes.For the blank test of the slurry that is untreated, the elution time of 300 ml volumes preferably should be greater than 60 seconds.

4. for untreated blank sample, based on drainage time, by calculating as getting off by the improvement of the water filtering performance that is provided is provided:

The retention testing procedure (FPR, FPAR)

Tappi test method T269

1. the batching of 500 milliliters of flow box denseness (1.0%) is poured among the Britt Jar that has 70 mesh sieves, the speed with 1200rpm stirs slurry simultaneously.

2. used identical of incorporation time (second)/speed (rpm) order and top drainage testing procedure, so that simulation chemical agent point of addition, it is as follows to change part:

At t ₃₀The time, open bottom plug valve and collection 100 milliliters of eluents at the beginning.

3. this eluent is filtered by No. 4 Whatman filter paper and at 105 ℃ carry out drying.

4. filter cake is 600 ℃ of burnings 2 hours, so that determine ash retention.

Handmade paper preparation and test

Use Noble ﹠amp; The Wood handsheet mold, preparation quantitatively is 70 gram/rice ²Handmade paper.This device will be produced the square handmade paper of 20cm * 20cm.The used order of incorporation time/speed order of using during handmade paper in preparation and drainage testing procedure is identical.Pour the batching sample of handling into Noble ﹠amp; In the tentering case of Wood handmade paper paper machine, and the standard technology that utilizes those skilled in the art to know prepares handmade paper.

Page characteristic

Utilize MK Systems evenness tester (M/K 95OR type) that the evenness of handmade paper is tested.Utilize Technidyne Color Touch (ISO type) that brightness and opacity are measured.

The preparation of blend

Prepare cataloid-acidoid blend according to the following step:

1. in the ratio of table 1, calculate the amount of cataloid solid and acidoid solid, and add independently in the beaker with regard to the concrete weight of each solution weighing.

2. the pH probe that will connect pH meter is put into cataloid solution.By adding 10% hydrochloric acid and the pH of this solution is reduced to about 1.5.

3. when cataloid solution is stirred, acidoid solution is added into wherein.

4. by adding 10% hydrochloric acid, the pH of above-mentioned final blended thing (3) is transferred to 1.5.

Table 1 has summarized the ratio of silica-melamine formaldehyde (MF) (MF) blend each component that uses in embodiment 1-16.

Table 1

The blend general introduction

The solids ratios of silica in the blend: MF	Silica solid content (% total solid)	MF solid content (% total solid)	Total solid content (%)
				4∶1	80	20	14.3
1∶1	50	50	11.8
				1∶4	20	80	10.0
9∶1	90	10	15.0

Embodiment 1-7

Table 2 shows the drainage result of embodiment 1-7, and table 3 shows the retention result of embodiment 1-7. Embodiment 2 and 4 shows the efficient of utilizing 4: 1 silica-MF blends especially.

Drainability:

Dosage among the embodiment 1-7 is represented based on the active matter of pound/ton dry pulp.Data in the table 2 show the efficient of 4: 1 silica-MF blends aspect increase batching rate of water loss.Pointed as embodiment 2, utilize 1.0 pounds of/ton (0.45 gram/kilogram) blends of 4: 1 will increase drainability, promptly use the drainage speed of the embodiment 2 of 4: 1 silica-MF blends when comparing, to demonstrate value added with embodiment 1, promptly compare with embodiment 1 its drainage speed of 39%, the drainage speed of embodiment 2 is 57%.By embodiment in the table 23 and 4 as can be seen, when the dosage of 4: 1 silica-MF blends increases, drainability will further increase, promptly 63% of embodiment 3 and embodiment 4 68%.

At the dosage (embodiment 7) of the dosage (embodiment 4) of 4: 1 silica-MF blends and silica itself during with 2.0 pounds/ton (0.9 gram/kilogram) identical dosage, when being added in the batching in the mixing pump porch, embodiment 4 will demonstrate better performance; The starch that has less amount among the embodiment 4 is promptly compared with embodiment 7 15 pounds/ton (6.75 gram/kilograms), and embodiment 4 is 5 pounds/ton (2.25 gram/kilograms).Since by required starch consumption in the minimizing papermaking systems, the cost saving of paper producer energy, and therefore, this will be a far reaching.

Table 2

Blend-drainability improved in 4: 1

	Before the mixing pump		Before the pressurized screen		Behind the pressurized screen
								Embodiment number	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	600rpm (pound/ton)/(gram/kilogram)	300 milliliters of drainabilities improve (%)
1	Stalok400	5/2.25	Polymer A	0.5/0.225			39
								2	Stalok400	5/2.25	Polymer A	0.5/0.225	4: 1 blends	1.0/0.45	57
3	Stalok400	5/2.25	Polymer A	0.5/0.225	4: 1 blends	1.5/0.675	63
								4	Stalok400	5/2.25	Polymer A	0.5/0.225	4: 1 blends	2.0/0.9	68
5	Stalok400	15/6.75	Polymer A	0.5/0.225	Silica	0.8/0.36	47
								6	Stalok400	15/6.75	Polymer A	0.5/0.225	Silica	1.6/0.72	62
7	Stalok400	15/6.75	Polymer A	0.5/0.225	Silica	2.0/0.9	65

Retention:

Table 3 shows the ability that the present invention's silica-MF blend increase aspect drainage/retention/evenness program in 4: 1 is passed through retention (FPR) first and passed through ash retention (FPAR) first.Utilize above-mentioned order by merging, use Britt method (tappi test method T269) to measure retention.The embodiment 1 that does not have granules, its FPR are 85.2%.Shown in embodiment 4, when adding 2.0 pounds/ton (0.9 gram/kilograms) 4: 1 silica-MF blend, FPR will increase to 92.0%,, PAR will increase to 80.1% (embodiment 4) from 61% (embodiment 1).The increase of FPR and FPAR is crucial factor for the paper producer, and like this, it is more effective that paper-making process can become, and can reduce amount of filler, and the performance of page can improve.In addition, silica-MF blend can also use starch still less in 4: 1 of the present invention, meanwhile obtain the retention result identical, the embodiment 3 (4: 1 blends) that promptly compares with embodiment 6 (silica) with those embodiment that only use silica.

Table 3

4: 1 blend-retentions

	Before the mixing pump		Before the pressurized screen		Behind the pressurized screen
									Embodiment number	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	600rpm (pound/ton)/(gram/kilogram)	FPR (％)	FPAR (％)
1	Stalok400	5/2.25	Polymer A	0.5/0.225	-	-	85.2	61.0
									2	Stalok400	5/2.25	Polymer A	0.5/0.225	4: 1 blends	1.0/0.45	88.7	72.0
3	Stalok400	5/2.25	Polymer A	0.5/0.225	4: 1 blends	1.5/0.675	90.4	75.5
									4	Stalok400	5/2.25	Polymer A	0.5/0.225	4: 1 blends	2.0/0.9	92.0	80.1
5	Stalok400	15/6.75	Polymer A	0.5/0.225	Silica	0.8/0.36	88.3	63.5
									6	Stalok400	15/6.75	Polymer A	0.5/0.225	Silica	1.6/0.72	91.4	77.7
7	Stalok400	156.75	Polymer A	0.5/0.225	Silica	2.0/0.9	92.6	81.0

Embodiment 8-12,1: 1 blend

Table 4 shows the drainage result of embodiment 8-12, and table 5 shows the retention result of embodiment 8-12.These results show: when with the dosage of 1: the 1 silica-MF blend of table 1 when 1.0 pounds/ton (0.45 gram/kilograms) increase to 2.0 pounds/ton (0.9 gram/kilogram), in the enhancing efficient of drainability and retention.1: 1 blend, and 4: 1 silica-MF blends are similar with respect to its effect of silica, but the starch consumption is lower, promptly compares with 15 pounds/ton (6.75 gram/kilograms) of silica, is 5 pounds/ton (2.25 gram/kilograms).

Table 4

Blend-drainability improved in 1: 1

	Before the mixing pump		Before the pressurized screen		Behind the pressurized screen
								Embodiment number	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	600rpm (pound/ton)/(gram/kilogram)	300 milliliters of drainabilities improve (%)
8	Stalok400	5/2.25	Polymer B	0.5/0.225	-	-	27
								9	Stalok400	5/2.25	Polymer B	0.5/0.225	1: 1 blend	1.0/0.45	35
10	Stalok400	5/2.25	Polymer B	0.5/0.225	1: 1 blend	1.5/0.675	46
								11	Stalok400	5/2.25	Polymer B	0.5/0.225	1: 1 blend	2.0/0.9	52
12	Stalok400	15/6.75	Polymer B	0.5/0.225	Silica	1.0/0.45	48

Table 5

1: 1 blend-retention

	Before the mixing pump		Before the pressurized screen		Behind the pressurized screen
									Embodiment number	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	600rpm (pound/ton)/(gram/kilogram)	FPR (％)	FPAR (％)
8	Stalok400	5/2.25	Polymer B	0.5/0.225			87.0	63.6
									9	Stalok400	5/2.25	Polymer B	0.5/0.225	1: 1 blend	1.0/0.45	87.5	65.9
10	Stalok400	5/2.25	Polymer B	0.5/0.225	1: 1 blend	1.5/0.675	87.6	66.0
									11	Stalok400	5/2.25	Polymer B	0.5/0.225	1: 1 blend	2.0/0.9	88.6	69.9
12	Stalok400	15/6.75	Polymer B	0.5/0.225	Silica	1.0/0.45	89.4	70.1

Embodiment 13-16,1: 4 blend

Table 6 shows the drainage result of embodiment 13-16, and table 7 shows the retention result of embodiment 13-16.These results show: when with 1: 4 silica of table 1-when the MF blend is added into the DRF program, the improvement of drainability and retention.It can also be seen that from table 6 and 7 when using 1: 4 silica of the present invention-MF blend, drainability and retention will improve, i.e. the embodiment 14-16 that compares with the embodiment 13 that does not use blend.

Table 6

1: 4 blend-drainability

	Before the mixing pump		Before the pressurized screen		Behind the pressurized screen
								Embodiment number	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	600rpm (pound/ton)/(gram/kilogram)	300 milliliters of drainabilities improve (%)
13	Stalok400	5/2.25	Polymer B	0.5/0.225			11
								14	Stalok400	5/2.25	Polymer B	0.50.225	1: 4 blend	1.0/0.45	22
15	Stalok400	5/2.25	Polymer B	0.5/0.225	1: 4 blend	1.5/0.675	26
								16	Stalok400	5/2.25	Polymer B	0.5/0.225	1: 4 blend	2.0/0.9	40

Table 7

1: 4 blend-retention

	Before the mixing pump		Before the pressurized screen		Behind the pressurized screen
									Embodiment number	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	600rpm (pound/ton)/(gram/kilogram)	FPR (％)	FPAR (％)
13	Stalok400	15/6.75	Polymer B	0.5/0.225			83.8	42.6
									14	Stalok400	15/6.75	Polymer B	0.5/0.225	1: 4 blend	1.0/0.45	85.8	50.3
15	Stalok400	15/6.75	Polymer B	0.5/0.225	1: 4 blend	1.5/0.675	87.2	49.6
									16	Stalok400	15/6.75	Polymer B	0.5/0.225	1: 4 blend	2.0/0.9	89.5	58.9

(Stalok ^Be U.S.'s trade mark of A.E.Staley)

The stability of blend

Just as shown in table 8, when pH=2, depend on component, the blend of silica-MF different proportion has different stability.Carry out following observation.

Table 8

The stability of blend

Blend	Total solid content (%)	The fate of gelling takes place when pH=2
			Silica	15	90
MF	12	15
			4∶1	14.3	150
1∶1	11.8	＞180
			1∶4	10.0	＞180

Indicated as silica-MF blending in 1: 4, under acid pH, acidoid is many more in the blend, and blend is just stable more, promptly greater than 180 days.Make 12% MF by the solution concentration that makes 8% total solid content.Blend of the present invention, its stability is more far better than each independent component, and promptly 15 and 90 days to this 150 days or longer time with bright silica-acid colloid blend.

Embodiment 17-21: the low quantitatively batching of coating (LWC)

It is the silica-MF blend of 9: 1 (solid weight/solid weight) ratios of 15% that these embodiment use total solid content.Used silica is to derive from E.I.Du Pont Company (Wilmington, DE) silica of 30% solid.Blend is prepared as mentioned above.

Embodiment 17-21 among table 9-A and the 9-B has illustrated at the drainability that improves synthetic aqueous formulations, retention, and page characteristic aspect efficient of the present invention.This batching is for being used for preparing featherweight coated paper page or leaf batching commonly used.Before adding retention agent, handled 15 minutes with 400 pairs of batchings of 15 pounds of/ton (6.75 gram/kilogram) Stalok.

The batching preparation:

Utilize following component preparation to be used for the synthetic batching of drainage and retention test and preparation handmade paper:

Fiber: 45% weight bleaching needlebush kraft pulp (SWK);

Paper pulp (CTMP): 55% weight CTMP;

Filler: calcined clay;

Filling adding amount: in bone dry fiber weight 10% weight;

Alum: in bone dry fiber weight 0.5% weight.

In when batching preparation, with CTMP be dipped in the hot water for the time 15-20 minute, in water, be diluted to 1.5% weight solid, and utilize laboratory scale Voith Allis Valley beater correct grinding or making beating to 200 milliliters Canadian Standard Freeness (CSF).SWK is dipped in the water, is diluted to 1.5% solid, and correct grinding or making beating are to 550 milliliters CSF.Be added into above-mentioned fiber in the preparation of listing above then and add calcined clay.Utilize sulfuric acid that the pH of batching is transferred to 5.0, and utilize sodium sulphate that conductance is transferred to 2000 μ S/cm.

Table 9-A

The LWC batching

	Before the mixing pump		Before the pressurized screen		Behind the pressurized screen
										Embodiment number	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	600rpm (pound/ton)/(gram/kilogram)	300 milliliters drainage improves	FPR ash content %	FPR total amount %
Blank	Polymer C	0/0	Polymer A	0/0	9: 1 blends	0/0	0	8.7	79.4
										17	Polymer C	1/0.45	Polymer A	0.25/0.1125	9: 1 blends	0/0	39.0	43.8	84.9
18	Polymer C	1/0.45	Polymer A	0.25/0.1125	9: 1 blends	0.6/0.27	48.6	57.8	88.8
										19	Polymer C	1/0.45	Polymer A	0.25/0.1125	9: 1 blends	1.05/0.4725	50.2	59.6	89.8
20	Polymer C	1/0.45	Polymer A	0.25/0.1125	9: 1 blends	1.5/0.675	59.8	59.0	87.4
										21	Polymer C	1/0.45	Polymer A	0.25/0.1125	9: 1 blends	1.95/0.8775	60.6	70.2	91.6

Table 9-B

The LWC batching

	Before the mixing pump		Before the pressurized screen		Behind the pressurized screen
										Embodiment number	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	600rpm (pound/ton)/(gram/kilogram)	MK evenness	Brightness %	Opacity %
Blank	Polymer C	0/0	Polymer A	0/0	9: 1 blends	0/0	54.3	56.9	95.2
										17	Polymer C	1/0.45	Polymer A	0.25/0.1125	9: 1 blends	0/0	46.4	58.4	95.3
18	Polymer C	1/0.45	Polymer A	0.25/0.1125	9: 1 blends	0.6/0.27	29.0	58.4	95.3
										19	Polymer C	1/0.45	Polymer A	0.25/0.1125	9: 1 blends	1.05/0.4725	20.2	58.5	95.5
20	Polymer C	1/0.45	Polymer A	0.25/0.1125	9: 1 blends	1.5/0.675	15.1	58.2	95.2
										21	Polymer C	1/0.45	Polymer A	0.25/0.1125	9: 1 blends	1.95/0.8775	18.5	58.3	91.6

Embodiment 18-21 among table 9-A and the 9-B shows the pressurized screen position after and the particulate blend to be added into the effect of LWC in preparing burden.When the consumption of particulate blend increases, drainability, FPR, and FPAR will obviously increase.These benefits are crucial, wherein the paper producer can increase the speed of paper machine, compares with the page of handling without microparticle system of the present invention, and page can be dry quickly, meanwhile, the filler and the fiber fines of batching can be retained in the page more.In addition, the result of table 9-A and 9-B has also shown: when comparing with the page of handling without microparticle system of the present invention, by the present invention, reduced the evenness of page, brightness simultaneously keeps relative constant with opacity.

Embodiment 22-26: cardboard batching

The embodiment 22-26 of table 10-A and 10-B has illustrated the present invention at the drainability that improves synthetic aqueous formulations, retention, and the efficient of page characteristic aspect.This batching is for being used for preparing the batching commonly used of cardboard body paper.

The batching preparation:

Broken and be diluted to 23 liters and preparation batching in the warm water by 360 grams not being floated old corrugated board (OCC) with running water.Then, the laboratory scale beater by being similar to previous embodiment is with the CSF of paper pulp correct grinding to 300 milliliters.18 liters of these slurries are diluted to 0.5% concentration and add following salt, so that the chemical of water is regulated the condition of paper plant: 5.61 gram calcium chloride; 0.96 gram potassium chloride; 8.17 gram alum (50% weight); 15.96 gram sodium sulphate; 0.59 gram sodium bicarbonate and 0.97 gram sodium metasilicate.The conductance that records is about 2000 μ S/cm.With dilute sulfuric acid with pH regulator to 5.0.

Table 10-A

The cardboard batching

			Before the mixing pump		Before the pressurized screen		Behind the pressurized screen
											Embodiment number	Handled in 10 minutes	Pound/ton/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	600rpm (pound/ton)/(gram/kilogram)	300 milliliters drainage improves	FPR ash content %
Blank	Stalok 400	0/0	Polymer D	0/0	Polymer A	0/0	9: 1 blends	0/0	0.0	22.73
											22	Stalok 400	20/9	Polymer D	1/0.45	Polymer A	0.375/ 0.16875	9: 1 blends	0/0	52.1	42.73
23	Stalok 400	10/4.5	Polymer D	1/0.45	Polymer A	0.375/ 0.16875	9: 1 blends	0.5/0.225	53.7	46.36
											24	Stalok 400	10/4.5	Polymer D	1/0.45	Polymer A	0.375/ 0.16875	9: 1 blends	1.5/0.675	62.4	49.09
25	Stalok 400	20/9	Polymer D	1/0.45	Polymer A	0.375/ 0.16875	9: 1 blends	0.5/0.225	55.6	47.27
											26	Stalok 400	20/9	Polymer D	1/0.45	Polymer A	0.375/ 0.16875	9: 1 blends	1.5/0.675	60.8	50.91

Table 10-B

The cardboard batching

			Before the mixing pump		Before the pressurized screen		Behind the pressurized screen
											Embodiment number	Handled in 10 minutes	Pound/ton/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	600rpm (pound/ton)/(gram/kilogram)	The total % of FPR	MK evenness
Blank	Stalok 400	0/0	Polymer D	0/0	Polymer A	0/0	9: 1 blends	0/0	83.22	17.3
											22	Stalok 400	20/9	Polymer D	1/0.45	Polymer A	0.375/ 0.16875	9: 1 blends	0/0	88.39	13.3
23	Stalok 400	10/4.5	Polymer D	1/0.45	Polymer A	0.375/ 0.16875	9: 1 blends	0.5/0.225	88.84	14.4
											24	Stalok 400	10/4.5	Polymer D	1/0.45	Polymer A	0.375/ 0.16875	9: 1 blends	1.5/0.675	88.60	10.6
25	Stalok 400	20/9	Polymer D	1/0.45	Polymer A	0.375/ 0.16875	9: 1 blends	0.5/0.225	88.71	12.5
											26	Stalok 400	20/9	Polymer D	1/0.45	Polymer A	0.375/ 0.16875	9: 1 blends	1.5/0.675	89.06	11.6

In table 10-A and 10-B, embodiment 22,25 and 26 has illustrated: the effect of in the cardboard batching 20 pounds of starch being used with particulate blend of the present invention.In addition, table 10-A and 10-B also show: when the consumption of particulate blend of the present invention and starch increases, and drainability, FPR and FPAR will increase.These results also show: when using 10 pounds of starch in batching, particulate blend of the present invention also can play good effect.As if this shows: in order to work in some batching, the present invention can not need the starch of high consumption.Showed already that the traditional silicon dioxide degree needed the starch of high dose usually, so that work, and as if when using microparticle system of the present invention, situation is not such.

Embodiment 27-30: newsprint batching

Table 11-A, the embodiment 27-30 of 11-B and 11-C has illustrated the present invention and has improved drainability, retention, and the efficient of the page characteristic aspect of synthetic aqueous formulations.This batching is for being used for preparing newsprint body paper ground wood pulp batching commonly used.

The batching preparation:

Be used for drainage and keep test and the synthetic batching of preparation handmade paper by being prepared as follows:

Fiber: 80% weight CTMP

10% weight SWK

10% weight reuse newsprint

Filler: calcined clay

Filler feeding quantity: in bone dry fiber weight 4% weight

Alum: 50 pounds/ton (22.5 gram/kilogram).

In preparation this when batching, be soaked in CTMP in the hot water (140) and in the blending machine defibre 15-20 minute.With identical method independent process reuse newsprint.Be soaked in SWK in the warm water and in blender defibre 15-20 minute.

With CTMP, reuse newsprint and SWK are blended together and be refined to the CSF of 50-75 milliliter in the denseness of 1.5% weight by the laboratory scale beater that is similar to front embodiment.Add calcined clay and alum, so that final pH from 4.8 to 5.2.Utilize sodium chloride that the conductance of slurry is transferred to 2000 μ m/cm.

Table 11-A

The newsprint batching

			Before the mixing pump		Before the pressurized screen		Behind the pressurized screen
											Embodiment number	Handled in 15 minutes	Pound/ton/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	600rpm (pound/ton)/(gram/kilogram)	300 milliliters drainage improves	The total % of FPR
Blank	Stalok 400	0/0	Polymer D	0/0	Polymer A	0/0	9: 1 blends	0/0	0	74.3
											27	Stalok 400	0/0	Polymer D	1.5/0.675	Polymer A	0.375/ 0.16875	9: 1 blends	0.5/0.225	68.3	82.1
28	Stalok 400	0/0	Polymer D	1.5/0.675	Polymer A	0.375/ 0.16875	9: 1 blends	1.5/0.675	72.8	84.0
											29	Stalok 400	10/4.5	Polymer D	1.5/0.675	Polymer A	0.375/ 0.16875	9: 1 blends	0.5/0.225	65.0	82.9
30	Stalok 400	10/4.5	Polymer D	1.5/0.675	Polymer A	0.375/ 0.16875	9: 1 blends	1.5/0.675	69.9	80.9

Table 11-B

The newsprint batching

			Before the mixing pump		Before the pressurized screen		Behind the pressurized screen
											Embodiment number	Handled in 15 minutes	Pound/ton/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	600rpm (pound/ton)/(gram/kilogram)	FPR ash content %	MK evenness
Blank	Stalok 400	0/0	Polymer D	0/0	Polymer A	0	9: 1 blends	0/0	34.5	21.1
											27	Stalok 400	0/0	Polymer D	1.5/0.675	Polymer A	0.375/ 0.16875	9: 1 blends	0.5/0.225	53.1	12.6
28	Stalok 400	0/0	Polymer D	1.5/0.675	Polymer A	0.375/ 0.16875	9: 1 blends	1.5/0.675	56.5	7.2
											29	Stalok 400	10/4.5	Polymer D	1.5/0.675	Polymer A	0.375/ 0.16875	9: 1 blends	0.5/0.225	55.3	9.6
30	Stalok 400	10/4.5	Polymer D	1.5/0.675	Polymer A	0.375/ 0.16875	9: 1 blends	1.5/0.675	50.6	9.6

Table 11-C

The newsprint batching

			Before the mixing pump		Before the pressurized screen		Behind the pressurized screen
											Embodiment number	15 divisional processing	Pound/ton/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	1200rpm (pound/ton)/(gram/kilogram)	Handled in 10 seconds	600rpm (pound/ton)/(gram/kilogram)	Brightness %	Opacity %
Blank	Stalok 400	0/0	Polymer D	0/0	Polymer A	0	9: 1 blends	0/0	49.11	98.56
											27	Stalok 400	0/0	Polymer D	1.5/0.675	Polymer A	0.375/ 0.16875	9: 1 blends	0.5/0.225	49.32	99.17
28	Stalok 400	0/0	Polymer D	1.5/0.675	Polymer A	0.375/ 0.16875	9: 1 blends	1.5/0.675	49.19	99.19
											29	Stalok 400	10/4.5	Polymer D	1.5/0.675	Polymer A	0.375/ 0.16875	9: 1 blends	0.5/0.225	48.35	99.35
30	Stalok 400	10/4.5	Polymer D	1.5/0.675	Polymer A	0.375/ 0.16875	9: 1 blends	1.5/0.675	48.31	99.45

In table 11-A to 11-C, embodiment 27 and 28 has illustrated: drainability when particulate blend of the present invention is added in the newsprint batching after pressurized screen, the increase of FPR and FPAR.In the High-Speed Newsprint machine, drainability, the increase of FPR and FPAR may be crucial item.Embodiment 27 and these results of 28 also show: even when not having starch, microparticle system of the present invention also is effective.These factors make the paper producer to reduce cost, and whereby, have reduced the totle drilling cost of producing paper per ton.

The application of industry Paper dissolving machine

Alkali spare fine paper

On industrialization alkalescence fine paper paper machine, performance of the present invention is assessed.Particulate blend program of the present invention and original program are compared.Add before pressurized screen in polymer B (0.15 pound of/ton active matter), polymer C is added into the original degree of operation on the paper machine of (1.0 pounds of/ton (0.45 gram/kilogram) active matters) in the batching behind pressurized screen.For particulate degree of the present invention, the stage before pressurized screen is added into polymer C in the batching, and the stage of particulate blend after pressurized screen added (1.0 pounds of/ton (0.45 gram/kilogram) active matters).Be to be noted that described dosage is approximation and will changes according to the grade of different basis weights and paper.In addition, also program of the present invention and the silica program of using always are compared, in the described silica program, polyamine is added into (1.5 pounds of/ton (/ 0.675 gram/kilogram) active matters) in the dish, the stage of HMW anionic polyacrylamide before pressurized screen added (1.0 pounds of/ton (0.45 gram/kilogram) active matters), and the stage of cataloid after pressurized screen added (1.5 pounds of/ton (/ 0.675 gram/kilogram) active matters).What compared the results are shown in table 12 and 13.

Table 12

-80 pounds of paper machine contrasts are quantitative

	Original mean value	Mean value of the present invention	Silica mean value
				The paper motor speed	2247	2250	2251
The contrast of evenness paper machine	32.6	29.1	29.8
				Backbone steam	31.8	25.5	29.8
Total retention	84.6	82.8	86.0
				Denseness in the dish	0.092	0.102	0.105
The squeezing solid that calculates	41.3	44.4	43.7
				The steam consumption that calculates, pound/ton (gram/kilogram)	1150/517.5	1012/455.4	1042/468.9
The tonnage that produces during identical steam	19.0	21.6	21.0
				The speed of estimation increases	Can not get	13.6％	10.5％

Table 13

-100 pounds of paper machine contrasts are quantitative

	Original mean value	Mean value of the present invention	Silica mean value
				The paper motor speed	1860	1919	1958
The contrast of evenness paper machine	32.6	28.6	30.9
				Backbone steam	40.3	36.1	37.2
Total retention	89.6	87.3	86.9
				Denseness in the dish	0.075	0.092	0.098
The squeezing solid that calculates	41.51	44.45	43.55
				The steam consumption that calculates, pound/ton (gram/kilogram)	1140/513	1009/454.05	1047/471.15
The tonnage that produces during identical steam	20.9	23.6	22.7
				The speed of estimation increases	Can not get	12.9％	9.7％

As can be seen, compared with other program by table 12 (80 pounds quantitatively), particulate blend of the present invention has improved the evenness (numerical value is low more good more) of page, reduces steam consumption, and higher squeezing solids.When equating steam consumption, machine speed of the present invention will increase by 13.6% than original program, and increase by 3.1% than traditional silica program.This factor makes the paper producer can increase the speed of paper machine, produces more paper and/or produces steam with still less energy.When making particulate blend of the present invention, these results also show better paper formation.This factor is more even for producing, and higher-quality page is crucial.

Table 13 (100 pounds quantitatively) has shown the contrast of using particulate blend of the present invention and using 100 pounds of quantitative paper sheets between other program.For heavier paper, dehydration is crucial, needs more energy to carry out drying in thicker page.When contrasting with original program or with the silica program, shownly the invention provides better paper formation, more squeeze solid, and lower steam consumption.These factors make papermaker to produce higher-quality page with higher paper motor speed.

Described particular of the present invention is illustrative, not breaking away under the present invention who is limited by appended claims, the present invention is made various improvement and change, is conspicuous for those skilled in the art.

Claims (19)

1. microparticle system that is used as retention agent and filter aid in paper furnish comprises:

A) weight average molecular weight is 100000 or bigger HMW polymer flocculants, and in solid dry weight in the described batching, the amount of HMW polymer flocculants is from 0.0025 weight % to 1.0 weight %, and b) silica-acid colloid formed by following material:

(1) acidoid of forming by melamine aldehyde or derivatives thereof, or comprise melamine aldehyde and be selected from the acidoid of copolymer of the condensation polymer of melamine-aldehyde, dicyano diamides aldehyde, urea-formaldehyde polyalkylene polyamine and polyamides urea, or amine-aldehyde type and be selected from the acidoid of copolymer of the ethylenically unsaturated monomer of acrylamide, dimethylaminoethyl acrylate, diallyldimethylammonium chloride and methacrylamidopropyltrimethyl trimethyl ammonium chloride; With

(2) cataloid, wherein in pH be 3.0 or lower sour environment under total solid, described acidoid and described cataloid be correspondingly with 99.5: 0.5 to 0.5: 99.5 ratio blending,

In the dry weight of solid in the described batching, the content of described silica-acid colloid blend is from 0.0005 weight % to 0.5 weight %.

2. the microparticle system of claim 1, wherein said melamine aldehyde, melamine is for replacing or unsubstituted; And aldehyde is:

R in the formula ₁Be selected from the C of straight or branched _1-4Alkyl.

3. the system of claim 2, wherein said aldehyde is selected from formaldehyde, acetaldehyde, propionic aldehyde, glyoxal and glutaraldehyde.

4. the system of claim 3, wherein said aldehyde is formaldehyde.

5. the system of claim 4, wherein said melamine aldehyde is melamine-formaldehyde.

6. the system of claim 5, wherein melamine-formaldehyde is by the pure etherificate of linearity or side chain.

7. the system of claim 1, wherein said silica-acid colloid blend comprises the acidoid of cataloid and melamine-formaldehyde and urea-copolyoxymethylenes.

8. the system of claim 1 also comprises the cationic coagulant of high charge density, in the dry weight of solid in the described batching, and its consumption from 0.005% to 0.5% weight.

9. the system of claim 1 also comprises the flocculant of intermediate molecular weight, in the dry weight of solid in the described batching, and its consumption from 0.0025% to 1.0% weight.

10. paper product that the microparticle system that utilizes claim 1 makes.

11. paper product that the microparticle system that utilizes claim 2 makes.

12. a method of producing paper product with the described microparticle system of claim 1 comprises the steps:

(a) after the first high shear stage and before the second high shear stage, the heavy polymer flocculant is added in the paper furnish, in the dry weight of solid in the described batching, addition from 0.0025% to 1.0% weight; With

(b) before or after described second shear stage, silica-acidoid blend is added in the paper furnish, in the dry weight of solid in the described batching, addition from 0.0005% to 0.5% weight.

13. the method for claim 12 also comprises the steps:

(c) before the described first high shear stage, the cationic coagulant of high charge density is added in the described paper furnish, in the dry weight of solid in the described batching, addition from 0.005% to 0.5% weight.

14. the method for claim 12, wherein said silica-acid colloid blend is made up of melamine-formaldehyde acidoid.

15. the method for claim 12 also comprises the steps:

C) before the described first high shear stage, the polymer of intermediate molecular weight is added in the described batching, in the dry weight of solid in the described batching, addition from 0.0025% to 1.0% weight.

16. a method of producing paper product with the described microparticle system of claim 1 comprises the steps:

(a) after the first high shear stage and before the second high shear stage, silica-acidoid blend is added in the paper furnish, in the dry weight of solid in the described batching, addition from 0.0005% to 0.5% weight; With

(b) before or after described second shear stage, the heavy polymer flocculant is added in the paper furnish, in the dry weight of solid in the described batching, addition from 0.0025% to 1.0% weight.

17. the method for claim 16 also comprises the steps:

(c) before the described first high shear stage, the cationic coagulant of high charge density is added in the described paper furnish, in the dry weight of solid in the described batching, addition from 0.005% to 0.5% weight.

18. the method for claim 16, wherein said silica-acid colloid blend is made up of melamine-formaldehyde acidoid.

19. the method for claim 16 also comprises the steps:

C) before the described first high shear stage, the polymer of intermediate molecular weight is added in the described batching, in the dry weight of solid in the described batching, addition from 0.0025% to 1.0% weight.

Images