CN1161724A - Improvement in or relating to application of material to a substrate - Google Patents

Abstract

The invention relates to a process of applying a polyhydroxy high molecular weight polymer or like material to a substrate, comprising adding to a solution of such material in anionic form a flocculent of oppositely charged form in order to insolubilise such material, and thereafter applying such insolubilised material to said substrate. The invention has particular application in respect of production of paper by adding to the slurry supplied in paper production of an anionic starch and a cationic flocculent in predetermined amounts. The cationic polymer is preferably added prior to addition of the anionic starch. The cationic polymer preferably has a molecular weight of 150,000 or more and the anionic starch is preferably added in an amount of from 75% to 125% of the reaction ratio amount. Preferably, the cationic polymer flocculent is added in an amount of 0.5 kg or more per 1,000 kg of paper substrate and the anionic starch showing an amount of 2 kg or more per 1,000 kg of paper substrate.

Description

Material is applied to improving one's methods on a kind of base material

It is the priority of the application of UK 9416520.6 and UK 9419323.2 that the present invention requires application number.Technical field

The present invention relates to a kind of material is applied to improving one's methods and material is not dissolved on the base material.Specifically, the present invention relates to a kind of by apply the method for material improvement substrate property to it.The present invention will describe especially by preferred scheme, in these preferred versions, the invention describes in the production process of paper material is added on the paper to improve the intensity of the paper of being produced.Background technology

In the preparation process of various base materials, developed by insoluble material being applied on the base material strengthening base material, thereby improved the technology of substrate intensity.An example of this base material is exactly a paper.In the production process of paper, cellulose is made into paper pulp, slurry is applied to makes fiber alignment and discharge liquor body on the net.Normal conditions are to squeeze between roller with further minimizing moisture content from online paper again, have suitably just produced a piece of paper after the drying.The intensity of the paper of being produced depends on the character of paper pulp.For example, in general, the new paper pulp of given quality (virgin pulp) and the paper of the same quality paper pulp that obtains of pulling an oar is once more compared, and can produce the much higher paper of intensity.In addition, reduce with each recycling by the obtainable intensity of paper pulp.Therefore, often interested in the additive that can improve paper intensity.Paper intensity is by using size press operation (size press operation) or adding (wet end addition) by wet end and improve before this.Mainly be to eliminate applying glue to add, because from producing and the viewpoint of energy content, its efficient all is extremely low.Usually, it is by with the finished paper on the wetting overflow roller of starch solution (flooded rollers) that size press adds, and starch is infiltrated in the paper, next dry again to improve the intensity of paper.This method has several shortcomings, and one of them is that the amount of starch of being added in this mode is limited, has therefore limited the possibility that intensity improves, because paper can only absorb the solution of fixed amount.In addition, size press is a kind of big project of investing, and needs extra drier to come dry paper again, so need a large amount of spaces.

The consumption of paper increases in worldwide, and estimates and can further increase.The most of solid waste that is produced is paper and paper product.Many countries make an effort and reduce the various waste products that comprise paper and bury the place with saving.Therefore, interest and the demand to the circulation paper product improved.Before this, the shortcoming of paper circulation and restriction are that all or part of paper with the circulation pulp production can not reach required intensity.When attempting to make when having circulated the paper recirculation of one or many, the difficulty that reaches sufficient intensity will be exaggerated.For example, than U.S. height, produce certain other paper of level with recycled fibre in Europe circulation degree fully, the paper of special box board level is very general.

With circulation carton and mixed waste, and need not a certain rank of any new fiber production, product as corrugation (fluting) paper level, can not satisfy QUALITY STANDARD, measured deflection (stiffness) parameter can not be greatly improved in concorra dielectric testing (CMT) or the test of STIF afterwards.As necessary, realize this improvement, factory must add starch by size press, and with respect to fiber, its amount changes between 3%-10%.So far, generally accept such notion, promptly under the state of various charge density and charge species, add conventional reinforcing agent by wet end, as starch, carboxymethyl cellulose, polyvinyl alcohol etc., can not obtain being equivalent to the resulting quality improvement of starch that size press adds about 4-10%, its reason has several, they are: 1. compare with the totle drilling cost that size press adds thick starch, the cost of wet end additive is too high.2. see technically that wet end adds can not add enough reinforcing agents to keep under the suitable form and desired intensity is provided in paper pulp.

Therefore, when using circulation to replace original new paper pulp from generation to generation, paper manufacturer trends towards adopting wet end to add (being about to chemical substance is applied in the paper pulp), can improve the intensity of other paper of a specific order relatively.Use wet end additive,, also have many technical restrictions to obtain intensity as cationic starch, polyvinyl alcohol, xanthans (xanthan gum) etc.In general.Having the exogenous impurity (tramp material) that is referred to as " anionic trash (anionic trashi) " usually, suppressed the performance of these additives, is infeasible so that the intensity that obtains is improved (if any improved words are arranged) economically.Select as another kind, the size press technology is sought help to obtain the bigger raising of intensity by paper manufacturer, and intake is quantitative, depends on that finished paper sucks the saturation degree of concentration known reinforcing agent solution.Be better than wet end in the industrial result who has recognized that this technology obtains and add, particularly improve deflection and the box board of a lot of grades-particularly-in many valuable character.

Yet, recognize that it is that dry end adds that size press adds, and pay a large amount of costs economically.Therefore, if can obtain identical quality improvement, still have and eliminate the requirement of applying glue operation to raise the efficiency and to reduce cost by the wet end interpolation.

Existing paper technology is by adding polyhydroxylated polymer, improves intensity by hydrogen bonding in the natural or synthetic binder of base material as starch, polyvinyl alcohol, carboxymethyl cellulose, xanthans, guar gum and other.Yet, in existent method, can not be from solution the polymer of these neutral charge forms being fixed in the paper that wet method forms, they stay in the solution and the paper through producing and emitting simply.As the method that these polymer is fixed on the base material, existing several method has been awarded patent and has been described.Common acceptable method is:

(a) polymeric cationic is to improve the replacement performance to the anion point on the base material, as cationic starch;

(b) some anionic species that makes with polyvalent metal ion such as aluminium, iron, zirconium does not dissolve, as carboxymethyl cellulose.

These methods can be introduced additive to the wet end of paper-making process, have therefore avoided using expensive extra applying glue adding method, applying glue adding method to comprise once more the necessary extra dry of wetting paper.Yet based on quality of fiber, anionic trash, pH etc., these methods are subjected to some restrictions, have limited the raising of paper intensity, have particularly limited the raising of deflection.The inventive method particularly under neutral pH, can be improved performance widely in " dirty system (dirty system) " operation, compared with prior art, add suitable material (entities) by wet end from process to paper that make and can improve intensity widely.In many application, the present invention can eliminate size press, causes saving cost widely and process is simplified.Advantage of the present invention comprises: (a) compare with existing method, significantly improve the ability of intensity, (b) saved applying glue equipment, (c) reduced refining (refining), (d) choice reaction reagent and reaction condition are to realize necessary strength and improve or to obtain ability corresponding to other desirable character of used paper pulp feature, and (e) improved drainage performance, quite or be better than the particulate technology of common acceptance.

Because in the component reaction of this method, can quantitatively produce gelatinous precipitate basically, (its physical property is with raw materials variations).

The present invention is applied in the following field: i) enhancing of paper also can be added and applying glue by the wet end at paper machine with the character that higher-strength is provided.Bonding system with high wet strength ii) is provided.Iii) soil adjusting (earth conditioning)-in the material of any similar dust, the production of glue produces and does not contain dust

Wet solid, it can keep moisture content and may then, be used for such occasion as the medium that continues growth,

Must stablize the sufficiently long time can make soil covering vegetables living as sand and/or any other light dust earth that rises

Long soil improves (land remediation).Product also can be used for having stoped dirt.Iv) because can produce different glue, product can be extruded into fiber or other shape, it is tool under drying regime

Very good tensile property is arranged.Under the situation of fiber, matrix is spinnable, has good absorbent properties,

Can be used for commodity, on diaper etc.Fiber production after the intensive drying can be exposed to as formaldehyde or second

Produce fabric fibre behind the crosslinking agent of dialdehyde, this also becomes possibility.V) corresponding to (iv) above-mentioned, because it has good absorbent properties, the another kind of application is to be used to produce bandage.Vi) with regard to fiber,, can see as medium with the material of the stone cardboard/timber sample of high-level glue production

The conventional phenolic resins of usefulness of density fiber board, hardboard or any other kind etc. are sticking as adhesive

The knot matrix substrate can replace with this system.Its advantage is that economy, no solvent flashing, product can be used wet method

Form and do not produce the effluent of pollution.Compare with existing production technology, available advantage is obvious.Vii) we find, have few system to the 1-3% binding agent to produce the extruding of the sand that can bond/can in sand

The resin that solidifies waters on the mould of casting sand so sand can be used on as casting.After the use, dry sand can be in water

Disperse, can not produce the toxic pollutant relevant with phenolic resins.Do not have VOC in this external forming step

Exist, all are reflected under the wet condition carries out, and mould is dry getting final product in baker.Viii) handle and so on as red soil, coal dust or any its itself is used for equipment that dirt/dust handles be useful on

Dust suppresses.The cake that produces with the glue reaction is a waterproof, therefore can be exposed in rain and the wind.Ix) on another kind, during stratification, can form the extremely thin glued membrane of one deck when a kind of solution.It may have semi permeability

Matter can be used on some professional isolation technics of using infiltration.X) can or use the mixture of high percentage starch paper pulp fibres to make ceiling/wall with glue and aluminosilicate

Plate.These products may have high thermal resistance, can replace traditional insulation material.In addition, this system can

Produce insulation material as binding agent.Xi) modified starch also can be used for producing different still foreseeable effects, is included in and produces hydrophobe on the skeleton.

A kind of such application is to remove in paper manufacturing systems and the passivation stickum.If we find the viscosity of dispersion

Material as ethyl vinyl acetate (ethyl vinyl acetate), is dispersed in and has formed the cloud form dispersion in the water,

After the acetylated starch with anionic functional group contacts, if in mixture, add flocculant

(flocculent), will produce the flocculate (flocculation) that to remove the turbidity relevant with stickum.Use phase

Flocculant does not together produce clarifying reaction with identical dosage than handling original emulsification stickum.We trust mutually

The hydrophobic substituted starch what has the anion binding site can both react similarly to remove stickum, as making

In raw material, add flocculant in the paper process and can cause that to keep (retention) the same.Xii) plate of any other type, as be equivalent to be used in lamination as on the goods of door or any other ornamental covering with paint

Plate.Xiii) use wet method injection moulding (shot wet molding) technology can not form paper and make box.

Except that being used for above-mentioned special Application Areas, also can consider to use the high electric charge starch material of the CATION with long-chain skeleton, mix to cause required deposition with anionic starch.Can believe that these are applied in third world countries is particularly advantageous, the Starch Production that can mix two kinds of assimilations (identified) can be used for forming products such as sheet material.

As can be seen, the inventive method has many application, and the mixing of two kinds of complete body (integers) produces high-intensity product, can be used for many Application Areass.

The strength characteristic of paper can be assessed with many diverse ways.At machine direction, transverse machine and thickness direction measurable intensity is arranged.Various ionization meters are pop strength, tearing strength, TENSILE STRENGTH, deflection, taber deflection, ring type crushing (ring crush) intensity, folding resistance, the experiment of concorra medium (CMT) and STIFI.These physical propertys (with other character) can use paper industry technological associations (Technical Association of Paperprocessing Industry (TAPPI)) standard to measure.The present invention has by the amount that changes reaction reagent can cause the supplementary features that the effect of dissimilar intensity changes, and therefore, the present invention has the advantage that selectively influences all kinds intensity.Summary of the invention

On the one hand, the present invention relates to a kind of by using flocculant (flocculents) and starch to improve method as the substrate intensity of paper pulp with the intensity of improvement ethene base material.In preferred embodiments, the present invention adds to make the insoluble cationic polymer of starch in the slurry that contains paper pulp, the required amount of anionic charge during its amount is equal to or less than and in the pulp components.This method also comprises the starch that adds scheduled volume in slurry, and the amount of adding starch is the 75%-125% of the reactive ratio between starch and the CATION to the amount of adding cationic polymer, or surpasses this reactive ratio.After this, reactant mixture needs the shearing of suitable degree with the observed flocculate of fragmentation.Lf dose is very big under extreme case, needs input to be equivalent to the shearing displacement of slight refining (refining), perhaps under the most weak situation, can be observed slight shearing in the clarifier (cleaner) of pre-head box (pre-headbox) system.

In a preferred embodiment of the invention, before adding starch ingredients, in the slurry that contains base material, add cationic polymer and fully stirring.Useful in the present invention cationic polymer is that molecular weight surpasses 150,000 polyhydroxylated polymer or acrylamide polymer.The preferred cation polymer has 1,000,000 or higher molecular weight.Other useful polymer is knownly can surpass 150,000, preferred 1,000,000 or higher polymer as the molecular weight of flocculant.

In preferred embodiments, the cationic polymer that the present invention relates to add q.s with in and in the slurry 10% or more electric charge, but the required amount of electric charge in being less than or equal to fully and in the slurry.At the starch that in slurry is bathed, adds scheduled volume after the suitable shearing.Describe in detail

Therefore, one aspect of the present invention provides a kind of method, and this method is to contain functionalized natural or synthetic polyhydroxy or the polyamide polymer of being derived from paper, and the interpolation of polymer occurs in the wet end of paper machine.The present invention will be described in detail according to papermaking, but those skilled in the art will be appreciated that it also can be applied to other base material.

The present invention can use with the base material with charged feature.Base material can have positive charge or negative electrical charge.In common paper-making process, base material is a paper pulp, and at the wet end of process, the paper pulp of pulp has negative electric charge.The inventive method is described by the base material that has negative electric charge, but when the opposite charge of different component, also can use principle of the present invention.

In preferred embodiments, the present invention a kind ofly makes the insoluble method of starch having on the base material of cationic polymer.By selecting base material, cationic polymer and starch, the character of final paper products is changed on demand.

For in and base material on anion can determine how many cationic polymers the base material of per unit weight needs.This can be put into by the base material with known quantity in the container and to form the such experiment of slurry and finish.Then, use charge monitoring device (particle charging analyzer) to monitor electric charge, progressively add the electric charge of polymer on base material and be neutralized.

In some industrial operation, slurry may be dirtier, wherein also may contain the charged particle of non-base material, and CATION wherein also is neutralized.Therefore owing to have other material in the slurry, for the base material of identical weight, in and in the base material amount of the required cationic polymer of electric charge possible different.The cationic amount of adding preferably can be fully in and in the base material slurry 10% or more electric charge, and in being equal to or less than fully and electric charge is required and measure.

Outside the decationize polymer, also will in the base material slurry, add starch, and preferred fully shearing is with the contingent flocculate of fragmentation.The addition of starch should enough guarantee not dissolve in base material and associated polymer.Preferably, the amount of starch of interpolation is no more than 125% of reactive ratio amount.The reactive ratio amount of starch is the amount of starch of per unit weight polymer, and starch equals reactive ratio to the amount of polymer.For example, if starch: the reactive ratio of polymer is 4: 1, and the reactive ratio amount is per 1 gram polymer, 4 gram starch.Therefore in this example, 125% reacting dose is 5 gram starch.

Reactive ratio can add polymer so that starch sedimentation is determined then gradually by starch is put in the aqueous solution.Behind the polymer of an increment of every interpolation, and after sedimentation a few minutes, measure COD level (COD), the COD ppm that descends, insoluble corresponding to the starch of a ppm., COD just reached maximum COD decline on this point but further not descending at the further polymer that adds.Reduction by measuring COD has just been determined reactive ratio divided by the ppm of the polymer that is added.Have been found that if add polymer continuously finally to make starch insoluble, shown in Fig. 4,4A, 5,6 and 7.

Fig. 4 represents the decline of COD when using the potato starch of the cationic polymer precipitation boiling of selling as FLOEGER 4698 with trade mark.The polymer that adds 4/1000000ths parts can obtain about 955 maximum COD reduction.Per hundred very much a COD descend and to equal to precipitate the starch of a ppm.Therefore, reactive ratio is 955/4 or 238.

The entire curve of this reaction is shown in Fig. 4 A, shows to use excessive polymer is how to make starch fully insoluble.

The measurement result of the precipitation reaction of starch phosphate (phosphate starch) Retabond AP (a kind of cold-water-soluble starch phosphate that is provided by Avebe starches) has been provided Fig. 5.Use with Fig. 4 in identical polymer cation, for this specific starch, be 800 by the resulting maximum COD decline of representing with a few millionths of the polymer of interpolation 150ppm with polymer reaction, promptly reactive ratio is 5.3.

The measurement result of reactive ratio of the starch Quicksolan CMS of the carboxylic acidization that is provided by Avebe Starches has been provided Fig. 6, and used cationic polymer is FLOEGER F04550BPM.For these two kinds of components, the maximum COD that the polymer of use 250ppm obtains drops to 1,005, and reactive ratio is 4: 1.

Fig. 7 shown oxidation boiling the measurement result of reactive ratio of (ccok-up) potato starch Avebe Perfectamil A2177, used cationic polymer F04550BPM.As shown in the figure, be 580 by the resulting maximum COD that represents with ppm of polymer that adds 175ppm, promptly reactive ratio is 3.3.

Should be noted that destruction reverse carry out of insoluble degree meeting, or excessive polymer can make sediment composite dissolving more easily owing to paper stock structure (oxidation).

Fig. 5-7 shows, adds the starch that substantially exceeds the reactive ratio amount and can not cause insoluble obvious increase.Can use starch less than the reactive ratio amount.The specified quantitative that adds starch depends on the type of the improved intensity of wanting.

The specified quantitative of cationic polymer and starch depends on the fixed ratio of starch, starch and the polymer that will add.By selective polymer and starch advisably, a large amount of possible combining forms can be provided, the selection by special combining form can determine cost, necessary final character and the restriction of process.

Carry out an experiment, the natural potato starch of the different amounts of boiling, with different potato starch levels different amounts is added in OCC and the pulp (2%) from the mixed waste of the cardboard manufactory (flurring board manufacturer) of confusion, it contains previously described charge density is 60% cationic polymer.Pop strength (burst strength) and the influence of concorra are reflected among Fig. 8.During the amount of the polymer that exists is enough to and the electric charge in the base material slurry.Believe that pop strength decline 2% may be experimental error in the drawings, usually, TENSILE STRENGTH can have rising slightly.

Experiment above repeating only is to use the natural potato starch of 8% boiling, and its reactive ratio to polymer is 200: 1, and polymer has lower charge density (10%), and making has relatively large polymer on the fiber.

Sample	The polymer that adds *Amount (kg/ton base material)	Starch **Percentage by weight to base material	The raising percentage of the pop strength of untreated relatively paper pulp	The concorrar of untreated relatively paper pulp improves percentage
					????4	?????4	?????8	????25.9	????50.8
????5	?????8	?????8	????25.9	????52.6
					????6	?????12	?????8	????38.2	????51.9

Carried out a series of experiment to compare the present invention's may improve to intensity.At first use the central layer (coreboard) of pulping to make original ingredient (OCC and mixing waste) is produced one 100 gram on the testing machine of University of Manchester benchmark paper.Mensuration does not have the anti-broken and concorra intensity of the paper of additive.This intensity is equivalent to the sample 0 of Fig. 3 as baseline.Next continue on testing machine, to produce paper, and use 10% starch solution to add the natural potato starch of relative fibre weight 6% by applying glue.Concorra and anti-broken increase percentage are shown in the sample 1 of Fig. 3.It is 60% the polymer and the starch phosphate Retabond AP (is benchmark with paper pulp weight) of 2% weight that service-test machine adds 5 kg/ton charge density by wet end.Resulting paper is operated without applying glue.The anti-broken and concorra intensity improvement value that paper showed of but, being produced is 0 with respect to benchmark.The manufacturing of this paper is difficult, because pulp quality has several obvious variation, has seriously influenced the operation of machine.Its influence is successively: a) quality of the precipitation of Chan Shenging is gluey and is viscosity, and wet paper is adhered on the first granite backer roll securely, can not produce paper in the time of any suitable length.Use the flocculant of this amount, when this specific starch phosphate of adding 1%, the trend of this influence is bigger.When this machine is testing machine, finish required dehydration on second backer roll that can raise colored hilllock roller and use rubber to cover.Final paper also can and carry out character and measure by drier.B) a large amount of flocculant with high charge density serious undue flocculation of formation thing of inducing must be broken this formation thing with shearing before the head box that enters before copying gauze.

This is by adding in thick paper stock and the material that highly flocculates being finished to break flocculation through a small-sized refining device.Even like this, paper stock also still too flocculates.C) discharging is subjected to positive influences, finds that paper stock discharges very fast, and is fast more about 50% than the material that is untreated, and handles obviously fast than traditional particulate (microparticular).D) stretching is subjected to positive influences, and residual COD value significantly descends.

On testing machine, make another kind of paper, wherein attempt to stop or alleviation observed pressurization first time in aforementioned operation.Breadboard test shows that other swelling particle cationic starch of a specific order can be caught by the compound of anionic starch/cationic polymer, thereby improves the intensity (particularly corrugation level circulation paper) of paper widely.In addition, find that this method can also reduce the bonding of granite roller to improve the speed of service.

Can obtain following synergy can inferring after a large amount of experiments: a) in thick paper stock, add polymer and make its mixing with about 1-2kg ton; B) in thick paper stock, add the swelling cationic starch and make its mixing with about 2.5%; C) starch phosphate of interpolation appropriate amount can cause thick and considerable flocculation; D) all mixtures are delivered to the refining device (light low refiner) of slight low water-mark to break flocculate; E) before being discharged on the net, before clarifier, add the final paper that adds, as the 1-2kg ton.

So just produced the paper with excellent in shape and improved mechanical performance, it has the concorra value that is equivalent to size press-treated paper and a little improved pop strength is arranged.

Only can obtain identical improvement with polymer to insoluble further work announcement with the starch of high reactive ratio.In addition, recognize when it is modified, tensile property and stiffness properties needn't pro rataly improve, as being added anti-broken improvement percentage that (size press addition) obtained by size press and adding anti-broken improvement percentage at wet end and compare the same with respect to the concorra value.

Therefore, if higher amount is added in discovery, as 8%, natural potato starch (height ratio reaction starch) can reach with the size press potato starch and similarly measure.

Because on testing machine, finished original experiment,, compare with interpolation 8% natural potato starch with blank so the identical device fabrication and the handmade paper (handsheet) of testing machine same basic weight are used in decision.Its result shown in sample 4, shown with size press to concorra and anti-broken improvement similar forms.Use this method, use the repeated experiments of natural potato starch to show constant improvement, about 30-35% on TENSILE STRENGTH, concorra are 50-70%.These two sample explanation the inventive method are improved on intensity significantly, and do not need the applying glue operation.

At last, use old presspaper container of circulation and mixed waste as raw material, on industrial machine, produce corrugation level paper with 1.5 tons/hour speed.

Machine is with the operation of 115 meters/minute speed, and 2% carboxymethylated starch that adds that the front described and 0.5% charge density are 60% acrylamide.

Product is added in the thick paper stock together and is sent into the refining device.

Its result is as follows:

	Blank	The average treatment sample	The % that parameter increases
				Substance	???110gsm	????109gsm	??????-
???concorra(N)	????144	????214.33	????48.84
				The ring type crushing	????123	?????159	????29.27
Anti-broken	????180	?????215	????43.33

This is a typical dirty system, handles the back and demonstrate tangible purification in returning water system.Holding back has increased 60%-77%.

Aforementioned part has shown the thing that uses the reaction technology those skilled in that art to realize by applying starch.Yet, use anionic polyvinyl alcohol or carboxymethyl cellulose, and no matter its structure and component are carried out other operation, the main difference part is the molecular weight and the charge density of two kinds of polymer, also observes similar result.

Use prior art experiment that the dirty recycled fibre of returning in the water system carries out to show that they have seriously limited the raising of the intensity of final paper products.

Utilize the polymer poly vinyl alcohol to carry out different experiments in conjunction with traditional coagulant product again with anionic starch.Used following material: 1. 3. aluminium salt 3. molysite 5. zirconates, 6. wet-strength resins (MF) of polyamine (low arrive high molecular) 2.polydadmacs (hang down arrive high molecular).

In all experiments of carrying out, even under the polymer of unusual high dose ratio, can not obtain the raising of any intensity of paper.Yet, use anionic polymer, dried filter paper saturated certain produced very large intensity and improved.The product of anionic polymer and coagulant is insoluble or is unsuitable for being used for improving intensity may be one or Another reason.So, in paper machine, polymer can not be fixed on the fibrous material that is used for papermaking.The inventive method has overcome this deficiency.

In a preferred embodiment of the invention, preferably before adding anionic starch, cationic polymer is added in the base material.Cationic polymer and base material associate, and provide starch can be fixed to the position that base material and cationic polymer get on.As seen from Figure 2, make anionic starch insoluble linear basically with raising intensity.The required concentration of negative electric charge in the concentration of cationic polymer is equal to or less than and in the paper pulp, this relation all remains unchanged.

In and in the paper pulp amount of the required cationic polymer of negative electric charge can come theoretically to determine or come by experiment easily to determine.If come by experiment to determine, then the paper pulp of known quantity is put into the aqueous solution, the cationic polymer that brings Selection In is monitored the electric charge in the solution simultaneously.Electric charge in the solution is easily by monitoring as conventional particle charge analyzer.In case determined this value, the suitable fixed ratio of polymer that can be by starch and selection is determined the amount of used starch, and this is because the amount of the starch that can deposit can be multiply by starch by the weight of used cationic polymer the fixed ratio of polymer to be estimated.

Carry out an experiment, new kraft pulp is put in the flask.Use the cation polypropylene imide polymer, sold by SNF Floerge, commodity are called F04698, and positive charge density is 60%.In this polymer and the amount of charge density in the paper pulp be defined as 2.5-3.5 kg/ton (1000kg).For the insoluble of starch is described, carried out a series of experiment, wherein in new kraft pulp mixture, add centesimal carboxylic acid starch, particularly Quicksolan CMF with variable concentrations cationic polymer.Produce paper with various samples then, and test its pop strength.Fig. 1 and 2 has illustrated that the amount of starch of maintenance interpolation is constant, improves by the intensity that amount reached that improves cationic polymer.

The required amount of discovery electric charge in the cation concn that adds surpasses and in the paper pulp also can descend even the amount of starch is gained in strength.Although be not bound by any theory, can believe in the amount of cationic polymer is equal to or less than and base material in during the required amount of electric charge, polymer will associate with base material, help the starch on the base material insoluble.Yet during the required amount of electric charge in the amount of polymer surpasses and on the base material, with paper pulp polymer that associates and the polymer competition of having associated to paper pulp.

For specific base material, for making it insoluble, the amount of employed polymer may be owing to selecting the low cationic polymer of charge density to raise.Charge density is to learn from the specification of manufacturer.

In this mode, if the reactor ratio between starch and the lower cationic polymer of charge density is with identical with the reactive ratio of the higher polymer of charge density, then the addition of starch will increase.

Can believe, use the lower polymer of charge density, need more polymer to combine with base material.Make that consequently starch is more insoluble.Use identical paper pulp, can use charge density is 10 polymer, and its amount is six times of 60 percent cationic polymer up to surpassing charge density.Experimentize, wherein prepare kraft pulp, and to add charge density in sample be 10 cationic polymer, FLOEGER CW711.Add starch afterwards, Retabond AP, with respect to untreated paper pulp, sample has obtained following raising on pop strength.

Sample	The polymer that adds *Amount (kg/ton base material)	The starch that adds **Percentage by weight to base material	The raising percentage of the pop strength of untreated relatively paper pulp	The percentage that the concorra of untreated relatively paper pulp improves
					????1	?????4	????2	?????18.5	?????27.5
????2	?????8	????2	?????33.2	?????46.3
					????3	?????12	????2	?????53.7	?????37.6

^*Polymer is FLOEGER CW711 ^*Starch is starch phosphate Retabond AP

Cationic polymer is useful in the present invention, comprises the homopolymers or the copolymer of side chain cationic polyacrylamide polymer, straight chain acrylamide.Its molecular weight should be 150,000, or higher, and preferred 1000000 or higher.

In the present invention, starch is useful, comprises that molecular weight is enough high so that insoluble any anionic functional starch.Furtherly, can use polyvinyl alcohol and carboxymethyl cellulose or any other conventional anionic retention aids of accepting.

On the other hand, the present invention relates to use by the functionalized anionic polymer of cationic flocculant material.Can replace starch with these polymer, as functionalised into anionic polyvinyl alcohol.Yet because they are expensive more many than starch, and their reactive ratio is higher usually, needs extra polymer, so be undesirable.

Be surprisingly found out that by further experiment, when the anionic polymer solution with same anionic functionalization is exposed to the cationic flocculant material, the moment reaction can take place, cause that polymer is almost insoluble quantitatively, with a kind of suitable form, the moment flocculation provides the improvement of intensity after suitably shearing.In another embodiment, the present invention is a kind of like this method: anion polyhydroxy macromolecular material mixes with apparent flocculant, the mixture of polyhydroxy high molecular weight material and flocculant mixes with base material, and a kind of like this paper pulp makes the polyhydroxy material be insoluble to base material.

Further experiment shows that polyhydroxy is the reaction of high order activity not only under this form, and the material that contains a large amount of hydrophobicity bases also can react in this way.Therefore found through experiments by using cationic flocculant,, can make any type of complete hydroxylating or partial esterification, etherificate or any other functionalized group precipitation as flocculant as fixed polymer.

Therefore, found a kind of method, can polyhydroxylated polymer be incorporated in the paper of just in paper machine, producing at wet end, add like this polyalcohols can to paper provide add by size press polyalcohols resulting in intensity and/or wet strength or applying glue or any other character; As folding resistance, tear resistance, glossiness etc.If provide same ion, this method of then being found can be used for any polyhydroxy high molecular polymer or similar material.

By another embodiment of the present invention, a kind of method that applies polyhydroxy heavy polymer or similar material to base material is provided, comprising that solution to the ionic species of this material adds has the flocculant of opposite charges so that this material is insoluble, adds this insoluble material to described base material then.

Have been found that, if any polyhydroxy heavy polymer, can or there be other base material of similarity to produce any material of a large amount of hydrogen bonds with cellulose as polyvinyl alcohol, starch, carboxymethyl cellulose, xanthans, glucan glue or any similar structures, utilize suitable technique, as reaction, can have ionizable group to described polymer introducing, as sulfonate radical, carboxylate radical, phosphate radical.Preferred molecular weight should be 120,000 or higher.Then, resulting polymer dissolve again and with the suitable material reaction with opposite charges, so polymer is just insoluble after being applied on the base material, and keeps thereon or wherein.

Above-mentioned when having the polymer of hydroxy-acid group on it when utilizing, use the cationic flocculant that has fully stable cationic charge.In this combination, the water treatment in paper industry, can use polyacrylamide, but be not limited to pure polyacrylamide amine structure, can use other utility, have the relative high-molecular cationic polymer or the copolymer of permanent quaternary nitrogen as the acrylamide/diallyldimethylammonium chloride of copolymerization or Manny phase acrylamide or other, comprise cationic starch, polyvinyl alcohol or other similar substance.

In the experiment of carrying out with anionic polyvinyl alcohol, can expect that the lower molecular weight limits that insoluble polymer does not take place of adding is 150,000-250,000.In the Study of Interaction between low-molecular-weight, anionic polyvinyl alcohol and the cation acrylamide, find that insoluble degree is not only relevant with the concentration of cationic form in the solution, but also relevant with the charge density of the concentration of polyvinyl alcohol and acrylamide.

Experimentize with high molecular and the low-molecular-weight material that contains 30% hydrophobic grouping of having an appointment.Be surprisingly found out that the anionic polyvinyl alcohol that is used for the low molecular weight fraction of this experiment also can obtain significant intensity and improve.Utilize high molecular weight material and complete hydrolysis level anionic polyvinyl alcohol further to test.Find to use high molecular weight material that stronger combination can be provided, the effect of complete hydrolysis level and partial hydrolysis level is similar.

In addition, also find to use the inventive method can in paper, introduce than before possible much more polyvinyl alcohol.Use in the past in dried paper and add polyvinyl alcohol, believe that the maximum that can introduce polyvinyl alcohol is 2%, the inventive method also provides a kind of advantage of adding polyvinyl alcohol at the paper machine wet end.Therefore, the inventive method allows to introduce to the wet end of paper machine the polyvinyl alcohol of various molecular weight.In addition,, the particulate technology of having used can be believed, therefore draining can be improved because insoluble process has taken place.Because the paper stock of only handling with cationic flocculant before observing has experienced wonderful flocculation after adding the ion polyvinyl alcohol, so this is an importance of technology.

Therefore, the good effect that has liked Flokal B of material itself, but when by aforementioned make it with cationic materials insoluble after, can strengthen draining.

When the polyvinyl alcohol of in the paper that paper machine is produced, introducing 5%, these polyvinyl alcohol are handled by the inventive method, and the wet end of introducing paper machine, discovery is compared with the paper that the dry paper interpolation polyvinyl alcohol of having produced with forward direction is produced, and the pop strength of the paper of Sheng Chaning has improved about 90% like this.In paper, add the advantage of getting polyvinyl alcohol so not only provide, avoided the additional step after paper is produced, and can in paper, add the more polyvinyl alcohol of volume with comparing in the past, therefore improved the intensity of paper at the paper machine wet end.

Can see that the inventive method can improve the paper that will produce.For example, by using the anionic polyvinyl alcohol that adds partial hydrolysis, coarse paper can improve intensity.In addition, because utilized the thickness of paper to improve the intensity of paper in the past, so can reduce the thickness of paper.In addition, believe that the improvement paper that utilizes the inventive method can be used for as special dimensions such as medicine.In addition, utilize the inventive method,, can also can produce paper to produce high-quality paper than low in the past cost as plastics by introducing the polyvinyl alcohol of appropriate amount.

Although said method also can use other ionic compound form by using anionic polyvinyl alcohol to describe, as long as it has identical polyhydroxy skeleton.

In preferred scheme, the present invention is that the wet end at paper-making process adds 0.5% (weight) or higher flocculant in paper pulp base material slurry, 2% (weight) or higher polyhydroxy high molecular weight material (percentage is that weight with the paper pulp base material is benchmark).

The corresponding situation of anionic starch is as follows.

Experiment is to use the cold-water-soluble carboxymethyl starch that is purchased:

Starch chain=R-OH+CICH ₂-CO ₂Na-R-CH ₂-CO ₂H

This product is anionic starch or institute of cellulose manufacturer common used in industry method by using alkaline monochloro sodium acetate and native starch prepared in reaction.

Adopt this product and following substance reaction:

Aluminium ion

polydadmacs

Wet-strength resins (MF)

Polyamine

CATION dry strength agent (Cationic Dry Strength Agents)

In all situations, when using the method for being found under neutral pH, to prepare handmade paper, do not observe intensity and improve.Yet, when cationic flocculant product and various straight chains or the structuring skeleton reacts, formed the gel precipitation, when introducing pump, the intensity of the handmade paper that obtains has had improvement.

Test with single starch phosphate shows with cationic polymer to have similar reactivity.

Studied various character, the product sample and the gained result of gained will list below in detail.

This does not provide as restrictive embodiment, but as a kind of guidance by the obtainable possibility of this method effect.(1) utilizes the insoluble desizing and relevant COD of from waste water, removing

The sample solution that contains 1000ppm all carries out COD and measures with cationic flocculant titration gradually, the filtrate in each step.The result shows that original COD is 1074ppm, and linearity drops to 70ppm behind the interpolation flocculant.When adding excessive flocculant, the inversion point that on complete post precipitation curve, has a COD to rise.This point has shown uses this to add excessive COD is removed in strong method from the sewage in paper mill adaptability.(2) dry strength is improved

Use spectrophotometer to measure owing in starch test solution, adding the test that the flocculant turbidity raises.Maximum insoluble appearing under the ratio of about 4 parts of starch to 1 part of flocculant.This changes with concrete starch and flocculant.The test of carrying out is with new and contain the circulation of the filler handmade paper that is equipped with made of paper, under all scenario, has all observed the intensity improvement.Except that influencing paper forms, the interpolation of reaction reagent is unessential in proper order.

Use cork typical operation in, kraft pulp, a kind of common paper stock are used with respect to 1% starch of fibre weight and are handled.Under stirring condition, add sedimentum flocculant gradually.In this case, flocculant is added in the paper stock, can before paper stock adds with starch reaction.The gained result is as follows:

The handmade paper of about 0.65 gram of preparation in papermaking device (sheet maker), 4 of each tests, every paper carries out 4 anti-broken tests, and the result is the mean value of 0.65 gram paper.All tests are that carry out on the basis with this method all.Cork bleached kraft pulp (newly)

The test of 1% starch is arranged in the paper stock	Anti-broken kpa
		Blank	????59.8
27mls flocculant 0.05%	????80.8

37mls flocculant 0.05%	????87.3
		47mls flocculant 0.05%	????107.3

The extra flocculant that increases can not make intensity improve again, and promptly all available starch have all precipitated with useful form.

Use deinking paper stock to experimentize from the circulation news printing of local manufacturer.The result

Use the starch and the theoretical insoluble maximum of various amounts.

The test of 1% starch is arranged in the paper stock	Anti-broken kpa
		Blank	????39.7
1% starch	????44.4
		1.5% starch	????45.8
2% starch	????46.9

Use other circulation waste paper to carry out same experiment from high-quality blank sheet of paper factory (quiality whites mills).Paper contains 15% the ash of having an appointment:

Test	Anti-broken kpa	Ash
			Blank	????17.4	????16％
1% starch	????25.3	????14％
			2% starch	????30.2	????14％

Equally, the raising of intensity is very big and can reproduce.

The result who is obtained is so wondrous, seem that traditional cationic coagulant (coagulant) material can not precipitate these polymer with suitable form with the generation dry strength, and cationic flocculant (flocculent) can.

Economic Importance of the present invention be thick starch can be in makers' workshop or in the paper mill anionization at an easy rate simply, be easy to be applied in the paper machine as fluid product with crude reaction product.That is to say, can the low-down strength additive of use cost, can not only give intensity, and the suitable modification of skeleton can produce applying glue or any by adding other character that modified starch obtained, as resistance to soiling (pick resisrtance), oil resistivity and ABRASION RESISTANCE etc.In addition, this product can be dry, and sell with preparation on the spot as cold-water-soluble starch or as cooking starch.

As can be seen, found a kind of method, can make by the functionalized material of additional ions side chain thereon to be applied on the base material and to be retained in wherein or on it that material reaction by making these materials and oppositely charged also makes it insoluble.When the inventive method is applied to papermaking especially, and when using anionic polyvinyl alcohol or having the anionic starch of carboxyl attached to it, it and cationic flocculant react, and it is insoluble in order to being applied to the appropriate ions material on the base material to should be appreciated that this method can be used any needs.Especially, this method can be used the functional polyethylene alcohol of the different molecular weight of partially or completely hydrolysis in field of papermaking, can also be used for the polymeric material that other has the polyhydroxy skeleton, as starch.

Other applying method comprises: A) anionic polymer weight polymers, as starch or other suitable material, mix with the base material that will strengthen.Add suitable cationic materials then, and stir to keep fully mixing and precipitation.Afterwards, discharge excessive water, it is dry again that product forms certain shape.According to the character of the addition and the base material of material, by changing the interpolation percentage of gel, can obtain following heterogeneity at product, that is, the intensity of raising, pop strength, Z-are to intensity, wet strength and applying glue (sizing).These character can obtain by paper fiber or mineral fibres.B) two kinds of reaction solutions are admixed together to produce gel, soak suitable matrix with gel then.This method can be finished by component is independent or mixed atomizing.Therefore, this method can be used for coating resin on material processed.C) a kind of solution soaking of matrix is soaked with another kind of reaction reagent then.Such method imitation fixing resin section bar material, it can be operable to double-deck epoxy resin (to two pack epoxy resins) with similar material.

Should be appreciated that according to above-mentioned material and can carry out changes and improvements,, therefore the material of insoluble form can be added on the base material, can use non-woven material, mineral fibres and ceiling as base material to obtain identical result.

In addition, be also noted that the wet strength that is produced surpasses dry strength 10% in the paper that adds the processing of 4% anionization starch.Dry strength under this dosage is quite high.Can also believe that the gel of reaction precipitation can or extrude and remove by centrifugal (spinning), obtain the sorbent material of high-quality, it has very high water (liquid) hold facility.Can be used on as on diaper, personal hygiene article or the bandage.

Also can under suitable pH, use Amphoteric Materials in addition, as amphoteric starch.These materials must ionization.

On the other hand, the present invention relates to a kind of passing through and add component to improve the method for paper intensity to the wet end of paper-making process.In this embodiment of the present invention, the addition of cationic starch is lower than the point of neutralization of base material slurry.Afterwards, add anionic starch swelling rather than boiling.Swollen starches is through the insoluble starch of boiling.For example, when by accepting water swelling taking place in about neutral starch of heating below 65 ℃ that can make starch dissolution.The starch that adds swelling is better than adding the anionic starch of boiling, and this is because when the online l Water Paper that forms of slurry process, if used the starch of boiling, starch can not be viscosity as the starch of boiling.When l Water Paper reaches treatment tub, discharge excessive water by heating and pressurization, paper can not stick on the roller.The starch that pressure on the roller and heat can cause swelling cooks and is anti-broken, thereby strengthens paper, and can not become sticky and be bonded on the roller.

The swollen starches that adds should have anionic property to a certain degree.The starch that is added should have certain Pka, greater than the pH of base material slurry.

After adding swollen starches, add above-mentioned cationic polymer, its amount should be able in and the negative electric charge in the base material slurry.This makes the starch flocculation of aforementioned interpolation on the base material slurry, and its amount was greater than known in the past.The amount of the cationic polymer that is added should be must in and the amount of 0% electric charge in the slurry, and the amount of electric charge in the slurry in being equal to or less than.

Claims (18)

1. one kind is applied to method on the base material with polyhydroxy heavy polymer or similar material, comprise the flocculant that in the solution of the material of this charged form, adds the oppositely charged form, so that this material is insoluble, then this insoluble material is applied on the described base material.

2. according to the method for claim 1, wherein said polyhydroxy heavy polymer is selected from polyvinyl alcohol, starch, carboxymethyl cellulose, xanthans, glucan glue or any other and has the material that can produce the similar structures of the hydrogen bond that acts on cellulose or other base material in a large number, and described polymer has been introduced can strong Ionized group.

3. according to the method for claim 2, wherein ionogen is sulfate radical, carboxylate radical or phosphate radical.

4. according to claim 1,2 or 3 method, wherein flocculant is the acrylamide/diallyldimethylammonium chloride or the Manny phase acrylamide of polyacrylamide cationic polymer, copolymerization, or other high-molecular cationic polymer or copolymer, it for good and all has quaternary nitrogen, comprises cationic starch or polyvinyl alcohol.

5. the method for the intensity of the paper in paper machine, produced of an improvement, wherein, the wet end of this paper-making process in paper machine contains pulp, adds anionic starch and cationic polymer flocculent, and wherein, starch can be not molten to described paper aborning.

6. according to the method for claim 5, comprise in pulp, adding to make the insoluble cationic polymer of anionic starch the needed amount of negative electric charge during its amount is equal to or less than and in the pulp components.

7. according to the method for claim 6, wherein add the starch of scheduled volume in slurry, the amount of the cationic polymer of feasible amount of starch of adding and interpolation equals the reactive ratio between starch and the cationic polymer, or surpasses this reactive ratio.

8. according to any one method in the claim 5,6 or 7, wherein before adding anionic starch, in slurry, add cationic polymer, and fully mix.

9. according to any one method among the claim 5-8, wherein used cationic polymer is polyhydroxylated polymer or acrylamide polymer.

10. according to any one method among the claim 5-9, wherein the molecular weight of cationic polymer surpasses 150,000, is preferably 1,000,000 or higher.

11. according to any one method among the claim 5-10, wherein the addition of cationic polymer should be able in and in the slurry 10% or more electric charge, but the required amount of electric charge in being less than or equal to fully and in the slurry.

12. according to the method for claim 10, wherein the addition of anionic starch is less than 125% of the reactive ratio amount, described reactive ratio is the amount of starch of the polymer of per unit weight, and the amount of starch and polymer equals its reactive ratio under this amount.

13. according to any one method among the claim 5-12, wherein anionic starch is oxidized starch, starch phosphate or carboxymethylated starch.

14. a papermaking process wherein prepares the slurry of paper base material, base material forms l Water Paper on the net, wherein in the slurry of paper base material, add 0.5kg/1,000kg paper base material or more cationic polymer flocculent, 2kg/1,000kg paper base material or more anionic starch.

15. according to the method for claim 14, wherein said anionic starch adds after described cationic starch.

16. the method for a papermaking, comprise the slurry that forms the paper pulp base material earlier, in slurry, add cationic polymer, the molecular weight of described polymer is 150,000 or higher, 10% electric charge in the described at least slurry that presents in an amount at least sufficient to neutralize, but be no more than and slurry in the required amount of electric charge, then, add anionic starch, its amount is the 75%-125% of reactive ratio amount.

17. a method of improving the intensity of the paper of producing with following slurry comprises: a) slurry of formation paper base material; B) add cationic polymer, its amount less than in and the required amount of electric charge in the slurry; C) cationic starch of interpolation swelling; D) add anionic starch to cause flocculation, its amount is the 1-20kg/ ton; E) preferably adding cationic polymer; And f) preferably make slurry stand shearing force with the resulting flocculate of fragmentation.

18. method of in paper machine, producing paper with slurry with improvement intensity, wherein the cationic flocculant of the anionic starch of mix predetermined quantities and scheduled volume make starch be used in the slurry of papermaking insoluble, the nature parameters of these materials is depended in the selection of the amount of starch and flocculant, to produce the maximum insoluble of starch.

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