CN1082132A

CN1082132A - The papermaking process of acid-to-alkaline

Info

Publication number: CN1082132A
Application number: CN 93106423
Authority: CN
Inventors: 亚当·F·凯利斯基
Original assignee: Industrial Progress Inc
Current assignee: Industrial Progress Inc
Priority date: 1992-08-20
Filing date: 1993-05-29
Publication date: 1994-02-16
Also published as: AR246992A1; AU3472893A; EP0658229A1; EP0658229A4; TW283178B; CA2142367A1; WO1994004752A1; AU666168B2

Abstract

The present invention relates to a kind of papermaking process of basic novelty, be used on papermaking machine, preparing paper, cardboard and other wet laid product are created conditions to acidity arrives alkalescence, and used aqueous formulations usefulness (in situ) synthetic little glue of composite functional is then and there handled.

Description

The papermaking process of acid-to-alkaline

The present invention relates to a kind of novel basically papermaking process, it is to be essentially novel flocculation mechanism, and is different with charging neutrality well known in the prior art (charge-neutra lization) or polymer bridging (polymer-bridging) technology.

Specifically, the present invention relates to a kind of be used to prepare novel and method improved paper, cardboard and other wet laid product (wet-laid product), its preparation batching (fur nishes) comprises cellulosic and/or synthetic fiber, also optionally comprise inorganic and organic filler pigment, water-soluble and aqueous dispersion polymers adhesive, illuminating colour and other auxiliary agent of handling with little viscose binder of composite functional (complex functional microgel cement).

The little viscose binder of composite functional is by with crosslinked and (in situ) synthetic (in the batching) then and there of transition (transient), chemical reactivity idiozome sodium silicoaluminate or the similar hydrosol and two valencys and/or polyvalent mineral salt, also optionally uses each molecule to have organic, the cation activity chemical compound of two reactive groups at least as auxiliary (additionally) crosslinking agent.

Paper, as a kind of cellulosic web of fiber (web), mainly partly the moisture content and the dry final screen cloth residue of the aqueous suspension of (making with extra care) cellulosic fiber of crushing are made by removing on the net at fixing or diaphragm for they.

Quality also improper major part purposes now obviously according to the prepared paper products of aforesaid way; Therefore, the modern paper batching generally includes the mixture of following material: the selected multiple cellulosic fiber that is refined into accurate definition standard, mineral and/or plastic cement filler pigments, dyestuff, cementing agent, strengthened polymer or the like, final paper web is through suitable processing and sorting.For the modern paper machine forming screen in fast moving and vibrations obtains making the satisfied solid retention of people on the net from this type of compounding ingredient, these batchings must under a controlled manner and suitable colloid chemistry mechanism is auxiliary be flocculated down.Flocculation-control mechanism depends on particular chemical agent (" wet-end chemicals " (wetend ch the emical)) system of employed papermaking process.

As those skilled in the art institute is intelligible, as long as how many main different substantially papermaking process are arranged, just have how many main different basically flocculation mechanisms, the flocculation mechanism of two kinds of unique these type of prior aries is charging neutrality and polymer bridging.According to the above, on whole modern paper industry basis, two main papermaking process are decided according to the colloid-chemism (wet end chemistry) of two kinds of main differences of batching flocculation, are " acidity " method of just knowing ancient times and " alkalescence " method that just occurs in recent decades.

The flocculation of batching composition is induced under papermaking aluminium (aluminum sulfate) auxiliary in the acid papermaking method, and the pH value during it need be prepared burden remains on below 5.3.Only in the pH value that is lower than 5.3, aluminium just can resolve into Tricationic, Al ^{+ 3}, it can suppress the negative electrical charge on the batching particle effectively and cause its flocculation.In order in batching, to keep accurate pH control level, mix mutually with sulfuric acid with aluminium usually.Usually consumption is that the aluminium of the about 10-15 kilogram of furnish solids per ton is enough to that the latter is flocculated and obtains the solid retention on the shaping papermaking wire-cloth that the people is satisfied with.The high molecular organic cationic polymer is used as auxiliary flocculant usually, and its consumption is that furnish solids per ton is 0.5 to 2 kilogram, to increase the efficient that solid keeps.

In order to overcome the distinctive shortcoming of acid papermaking method, a kind of alkaline paper-making method many decades in the past is developed, and the trend that replaces acid process is gradually arranged at present.To be that traditional acid papermaking process is verified have low mechanical strength and bad aging paper products characteristic to significant disadvantages, and the serious environmental side effect.Alkaline paper-making method, its wet end chemistry rely on and use specific functionality heavy polymer (maintenance auxiliary agent) is to carry out in about 7 to 8 o'clock at batching pH usually, yet high slightly or low slightly pH value is also very common.The used basic colloid chemistry mechanism of latter's method batching flocculation is based on " polymer bridging ", and above-mentioned heavy polymer keeps the quite long nasolabial groove subchain of auxiliary agent to be directly connected to the bonding station on cellulosic fiber and/or filler particles surface.The effect of polymer bridging, such as " knot " (" tying ") of adjacency particle and polymer chain proof, the agglutinating matter of whole formation can effectively be remained on the forming net on the paper machine.

Though the alkaline paper-making method does not have the shortcoming of acid process, some critical defect of itself is arranged still.Wherein important disadvantages is technological trend and the progress that the former can't adapt to day by day increases.These new trends and progressive target be for rolling up paper machine speed, be about 1800-2400 rice/minute; Form paper web with the batching that significantly more is higher than at present used concentration; The industrial water stream of the totally-enclosed on the paper machine; Preparation " ash-rich " printing paper, wherein the loading capacity of filler is 25% to more than 50%(weight); Prepare high-quality machine coated paper; And the preparation two sides is with super opacity paper (opacity at least 98%), fine definition computer printout paper and office's copy paper.Therefore, with regard to its technology growth potentiality, say alkaline paper-making method of the prior art prematurely senile be rather just and sound, though for its new hand really of paper-making industry.

Papermaking process of the present invention is to rely on immediately (to all actual purpose), the indiscriminate and flocculation completely that is present in any and all particles in the papermaking batching, this flocculation is to carry out by means of synthetic then and there many compositions, functional compound little glue, described little glue is disclosed in common unexamined patent application case 07/919,831(" Functional Complex Microgels with Rapid Formation Kinetics "), application on July 27th, 1992, it is a reference of the present invention.Described compound little glue mainly carries out crosslinked and synthetic obtaining by that form, transition, chemical reactivity sodium silicoaluminate and the similar idiozome hydrosol then and there under two valencys and/or polyvalent mineral salt auxiliary.

More than be used for implementing (papermaking batching) then and there of the present invention synthetic little glue of composite functional and it is believed that the most effective and the widest colloid chemistry system of purposes in existing colloid science and the technology that represented.In the past in 150 years, though having thousands of kinds, to seem similar colloid system revealed and/or obtain patent, the applicant does not find any and Chemical composition that, supper-fast formation dynamics, though the multipurpose of colloid chemistry character or application relevant the trickle similar little glue of described composite functional only arranged.

All paper products of manufacturing all have an inevitable shortcoming in existing acidity and the alkaline paper-making method, lack the real even distribution of highly diversified particulate matter exactly in the papermaking batching that is used for manufacturing a product.As is known to the person skilled in the art, the paper products of homogeneous texture (on the statistics of all particle compositions homogeneous space distribute) only just may obtain having satisfied following condition:

(a) all particle compositions (fiber, fine fibre, filler) in the papermaking batching are carried out the best (for all actual purpose) and disperse, before flocculation, intactly keep the even distribution on the statistics of particle;

(b) immediately (for all actual purpose), the papermaking of optimum dispersion batching particle composition in the flocculation step (a) indiscriminately and fully is to keep the even distribution on the suitable statistics of batching particle in final flocculate; With

(c) make final flocculate possess a kind of sufficient mechanical integrity, make the latter effectively bear flocculation batching and be transported to flow box (headbox) or imposing on shearing force on the paper machine forming net.

Described mechanical integrity can reach by being produced flocculate by sufficient intrinsic toughness or giving these flocculates can recombinate (reconfiguring) after temporary transient division ability.What should further emphasize is the batching of using fine dispersion (saying nothing of optimum dispersion) in existing acidity and alkaline paper-making method hereinbefore, (a) is needed as condition, for all actual purpose is technical feasible, can't overcome the strong effect of modern dispersant because the flocculation mechanism basis of above-mentioned two kinds of methods is too weak.Moreover the wet end chemistry of " ideal " papermaking process should provide, and except flocculation, a kind of mechanism of inherence to be strengthening the mechanical strength of final paper product, even gives desirable functional character.So ' and, as well known to the skilled person, the wet end chemistry of existing acid and alkaline paper-making method is for all actual purpose, do not have above-mentioned any " ideal " characteristic and occur, and the multiduty papermaking process of the present invention can provide multiple rich attraction and important advantage.

Though known to this case applicant, the technology or the patent documentation of any indirect correlation do not have the direct prior art relevant at present, even but all can be considered the reference that helps to understand flesh and blood of the present invention with the papermaking process of acid to alkaline of the present invention.

Based on context, main purpose of the present invention is to provide a kind of novel basically acidity to the alkaline paper-making method, it is with novel basically, a unprecedented flocculation mechanism, with paper, cardboard and the wet-laying adhesive-bonded fabric for preparing improved or complete novelty, used batching uses the little glue of composite functional that is synthetic, that have intrinsic caking property and surface chemical modification performance to handle then and there.

More particularly, the wet end chemistry that the purpose of this invention is to provide a kind of papermaking process, it depends on and is disclosed in common unexamined patent application case 07/919,831(" Functional Complex Microgels with Rapid Formation Ki netics "), the use of the little glue of composite functional in (application on July 27th, 1991), this little glue is applicable to each field work, is fabricated into the most complete production operation of paper machine from the laboratory scale handmade paper.

Further purpose of the present invention provides a kind of paper of making on paper machine, the method of cardboard and wet-laying adhesive-bonded fabric, this method is used 100% particulate matter basically, as is present in fiber or filler in the initial batching, therefore obtains not having the effluent of particle contamination.

Another purpose of the present invention provides a kind of with the method than acidity of the prior art and the more uniform paper web of alkaline method paper machine speed manufacturing faster.

Another purpose of the present invention provides a kind of the use than the denseer batching manufacturing of the concentration that adopts in the prior art acidity and alkaline paper-making method paper web very uniformly on paper machine, therefore significantly reduce the needed huge water yield of latter's method.

Another purpose of the present invention provides a kind of method of wishing the target reached on the environment of the industrial water stream that obtains totally-enclosed on the paper machine most.

Another purpose of the present invention provides a kind of method of making good aging-resistant cellulosic paper web.

Another purpose of the present invention provides the method for a kind of manufacturing high temperature resistance wet-laying (nonwoven) product.

Another purpose of the present invention provides " characteristic " glue applying method of a kind of cellulosic paper web.Another purpose of the present invention provides a kind of method that reaches the maintenance efficient that surpasses existing at present acidity and alkaline paper-making method filler.

Another purpose of the present invention provides the method for a kind of manufacturing " good ash-rich " paper, its filler loading capacity in addition surpass 50%(weight).

Another purpose of the present invention provides a kind of manufacturing coloured fiber matter and wet-laying nonwoven paper web, and uses 100% illuminating colour basically.

Another purpose of the present invention provides the method for the paper web of acceptance (dissipation) water that a kind of manufacturing can be very fast and organic liquid.

Another purpose of the present invention provides a kind of the manufacturing and does wet strength and surpass method with the cellulosic paper web of the resulting similar paper web of existing acid and alkaline paper-making method.

Another purpose of the present invention provides a kind of method of making superhigh intensity cellulosic and other wet laid product, used batching optionally comprises (except cellulosic and/or synthetic fiber) one or more additional ingredients, as synthetic microfibril, Zhi Bei new cellulosic microfiber, new ultra-fine polymer emulsion binder and new moisture rubber adhesive in addition.

Another purpose of the present invention provides a kind of woody paper product of making under alkali condition, comprise newsprint, and its quality can't obtain by existing papermaking process.

Another purpose of the present invention provides the method for a kind of manufacturing as the super opacity paper (opacity at least 98%) of fine definition, two-sided computer printout paper and office's copy paper.

Another purpose of the present invention provides a kind of general blueprint that supplies conventional design to use, be used for the various paper of preparation on paper machine, cardboard and other wet laid product, this product possesses preferable quality and/or uses than existing acidity and alkaline paper-making method and made sooner and more with having an economic benefit, provide simultaneously make with prior art and material the complete novel paper that can't obtain, the method for cardboard and other wet laid product.

The present invention relates to prepare in a kind of scope (being preferred for pH scope of the present invention) method of paper, cardboard and other wet laid product for alkalescence with near alkalescent at pH4.5-12.0, used aqueous formulations comprises at least a cellulose fibre that is selected from, the fiber of synthetic organic fibre and inorfil, this batching is handled through the little viscose binder of synthetic then and there compound merit, the ratio in this product of being retained in is 0.4% to 10.0%(weight), recorded by ashing method, this method may further comprise the steps:

(a) mix the little glue colloidal sol of the chemical reactivity for preparing a transition then and there with two kinds of independent solution by preparing burden, wherein a kind of solution comprises at least a reagent that is selected from alkali silicate and quaternary ammonium silicate, consumption accounts for 0.2% of furnish solids and arrives 5.0%(weight), another kind of solution comprises at least a reagent that is selected from alkali metal aluminate and alkali metal zincate, its consumption account for furnish solids 0.2% to 5.0%(weight), wherein this silicate to the ratio of aluminate, zincate or its mixture be 1: 10 to 10: 1(weight);

(b) with a kind of aqueous solution with from the batch mixes of step (a), this aqueous solution comprises at least a first group the crosslinking agent of being made up of two valencys and polyvalent mineral salt that is selected from, its consumption accounts for 0.4% of furnish solids and arrives 10.0%(weight), this aqueous solution comprises that optionally one or more are selected from second group the additional crosslinking agent that has at least the organic cation activity chemistry compound of two reactive groups to form by each molecule, its consumption accounts for furnish solids and reaches 0.5%(weight), with the little glue colloidal sol of chemical reactivity of crosslinked synthetic transition then and there and the synthetic then and there little viscose binder of composite functional, should prepare burden immediately after mixing, flocculate indiscriminately He fully;

(c) optionally clean from step (b) dissolved pollutant, the flocculation batching; With

(d) retrieve from step (b) and the batching of flocculation (c), on a papermaking machine, to form paper, cardboard or other wet laid product.

Batching comprises that optionally one or more have the material of following special ratios (% weight) in aforesaid method, in furnish solids weight:

(a) filler pigments, content is higher than 50%;

(b) illuminating colour, content reaches 5.0%;

(c) carbon black goes cohesionization with masterbatch (master-batch) method, and content reaches 0.1%;

(d) emulsion binder, average particulate diameter are greater than 70nm, and content reaches 5.0%;

(e) ultra-fine acrylate polymer emulsion adhesive, average particulate diameter are less than 55nm, and vitrification point is-60 ℃ to+20 ℃, and content reaches 5.0%;

(f) moisture acrylic rubber adhesive, content reaches 5.0%;

(g) contain the water dispersible thermoplastic adhesives, content 20.0%;

(h) the water-soluble wet end binding agent of commodity, content reaches 2.0%;

(i) synthetic microfibril reaches 2.0%;

(j) cellulosic microfiber, 10 microns to 200 microns of length, from external stepwise microfiber method preparation, content reaches 2.0%(weight);

(k) ultra-fine electrical conductance and/or magnetic ceramics and/or metal dust, particle diameter are less than 0.2 micron, and content reaches 20.0%(weight).

In aforesaid method, the aqueous solution of organic cation activity chemistry compound that each molecule is had at least two reactive groups mixes the batching of the little viscose binder flocculation of the described aqueous solution and the composite functional that has been synthesized then and there as a kind of post processing mutually.

In aforesaid method, at least a concentration of reagent in batching that is selected from sodium metasilicate and potassium silicate and quaternary ammonium silicate is 0.01% to 2.0%(weight).

In aforesaid method, at least a concentration of reagent in batching that is selected from sodium aluminate and potassium aluminate and sodium zincate and potassium zincate is 0.01% to 2.0%(weight).

In aforesaid method, in batching, use at least a pair of valency or the crosslinked salt of polyvalent mineral, it is selected from water miscible, colourless calcium basically, magnesium, barium, aluminium, zinc and zirconates, concentration is 0.02% to 4.0%(weight).

In aforesaid method, in batching, use at least a each molecule to contain the organic cation activity chemistry compound of two reactive groups at least, it is selected from cationic surfactant, organic metal Louis Vernet (Werner) compound and cationic polyelectrolyte, its concentration reaches 0.15%(weight).

In aforesaid method, length is that the cellulosic microfiber of 10 microns to 200 microns extra preparation utilizes stepwise microfiber method to make from cellulose fibre, and this method may further comprise the steps:

(a) fiber is prescinded prevent the follow-up length that the waterpower spinning takes place during refining, the purification apparatus that final length adopts according to furnish solids and subsequent operation and deciding;

(b) at the aqueous dispersion of solid concentration high chopped fibres of purification step (a) during to 35% weight;

(c) the fiber water dispersion of extra purification step (b) under the effect of cintrifugal disintegrator; With

(d) finish stepwise microfiber method with homogenizer, wherein the resulting refined fiber aqueous dispersion of step (c) is being compressed under the high pressure very much, remove pressure by a nozzle apace then, be separated into single microfiber with causing residual microfiber bundle explosion type.

The invention provides a kind of preparation paper, the method for cardboard and other wet laid product, used aqueous formulations as previously mentioned, this method is to carry out with continuous mode, comprising:

Step (a) is the logistics of the reagent of two bursts of independent idiozome hydrosols formation to be injected the stirring logistics of the pipeline of this batching respectively, to form the chemical reaction idiozome hydrosol of transition, wherein a logistics comprises at least a reagent that is selected from alkali silicate and quaternary ammonium silicate, and another kind of logistics comprises at least a reagent that is selected from alkali metal aluminate and alkali metal zincate;

Step (b) is to stir the aqueous solution that injects at least a crosslinking agent in the logistics on the pipeline of step (a) batching, this crosslinking agent is to be selected from first group that two valencys and polyvalent mineral salt are constituted, this aqueous solution comprises at least a or multiple extra crosslinking agent, this crosslinking agent is to be selected from second group that organic cation activity chemistry compound that each molecule has two reactive groups at least is constituted, with crosslinked this idiozome hydrosol and the synthetic then and there little viscose binder of this composite functional, this batching immediately, and is indiscriminate and flocculate completely;

Optionally step (c) is to clean the batching of having dissolved the flocculation of pollutant from step (b); With

Step (d) is to retrieve from step (b) and the batching of flocculation (c), to form paper on a papermaking machine, cardboard or other wet laid product.

The invention provides a kind of method for preparing paper, cardboard and other wet laid product, it is to be 4.5 to 12.0 scope at pH, be selected from cellulose fibre from comprising, the aqueous formulations of synthetic organic fibre and inorfil is prepared from, the little viscose binder of the compound merit that this batching is synthesized is then and there handled, the ratio in this product of being retained in is 0.4% to 10.0%(weight), be to record by ashing method, this method may further comprise the steps:

(a) with a kind of aqueous solution to the batching in, this aqueous solution comprises at least one crosslinking agent of first group that is made of two valencys and polyvalent mineral salt that is selected from, its consumption accounts for 0.4% of furnish solids and arrives 10.0%(weight), this aqueous solution comprises that optionally each molecule by one or more has second group the additional cross linking agent that organic cation activity chemistry compound is constituted that is selected from of two reactive groups at least, and its consumption accounts for furnish solids to 0.5%(weight);

(b) prepare the chemical reactivity idiozome hydrosol of a transition separately, promptly mix two kinds of solution, wherein a kind ofly comprise at least a reagent that is selected from alkali silicate and quaternary ammonium silicate, consumption accounts for 0.2% of furnish solids and arrives 5.0%(weight), another kind comprises at least a reagent that is selected from alkali metal aluminate and alkali metal zincate, its consumption accounts for 0.2% of furnish solids and arrives 5.0%(weight), wherein this silicate is 1: 10 to 10: 1 to the ratio of aluminate, zincate or its mixture;

(c) batching of step (a) is mixed with the chemical reaction idiozome hydrosol of the transition of step (b), with the synthetic little viscose binder of composite functional then and there, this is prepared burden immediately, and is indiscriminate and fully flocculate;

(d) optionally clean the batching of having dissolved the flocculation of pollutant from step (c); With

(e) retrieve from step (c) and the batching of flocculation (d), on a papermaking machine, to form paper, cardboard or other wet laid product.

The present invention relates to a kind of novel basically acidity to alkaline method on paper machine, to prepare paper, cardboard and other wet laid product, its be with pH4.5 to the 12(the invention process be preferably alkalescence and intimate alkalescent pH scope) aqueous formulations prepared, this method may further comprise the steps:

(a) with a kind of alkali metal or the quaternary ammonium silicate aqueous solution, the aqueous solution with second kind of alkali metal aluminate and/or alkali metal zincate, with paper, cardboard or wet-laying nonwoven batch mixes, in the chemical reactivity idiozome hydrosol that forms a transition then and there, wherein the concentration of every kind of solution in batching is 0.01% to 2.0%(weight);

(b) with a kind of aqueous solution of at least a crosslinking agent and batch mixes that step (a) obtains of containing, this crosslinking agent is to be selected from two and/or polyvalent mineral salt, this aqueous solution optionally comprises at least a extra (assisting) crosslinking agent, this crosslinking agent is to be selected from the organic cation activity chemistry compound that each molecule has two reactive groups at least, the consumption of this crosslinking agent in batching is 0.02% to 4.0%(weight), the chemical reactivity idiozome hydrosol with crosslinked described transition, and the synthetic then and there little viscose binder of a composite functional, all particle compositions that make this batching immediately, non-selectivity ground and flocculation fully;

(c) optionally clean the batching that the step (b) dissolved pollutant obtains, for example by the method for filtering and cleaning; And

(d) recycling step (b) and/or the batching that (c) obtains are to prepare paper, cardboard or other wet-laying (nonwoven) product on paper machine.

Used generic term in this specification and claims, little glue that step (b) is synthetic then and there, no matter its particular chemical composition, as the little glue of composite functional or little viscose binder, consumption is 0.4% to 10%(weight), measure as ashing method, with final paper, the weight of cardboard or wet-laying adhesive-bonded fabric is proportional, wherein consisting of of little viscose binder:

(a) the chemical reaction idiozome hydrosol of the transition of 0.4% to 10% weight, with paper, the gross weight of cardboard or wet-laying nonwoven furnish solids is proportional, and this hydrosol is formed at

(1) at least a reagent that is selected from alkali silicate and quaternary ammonium silicate; With

(2) at least a reagent that is selected from alkali metal aluminate and alkali metal zincate, the ratio of reagent (1) and reagent (2) be 1: 10 to 10: 1(weight);

Crosslinked by following composition

(b) at least a first group the crosslinking agent of forming by two valencys and polyvalent mineral salt that is selected from, its consumption is a paper, 0.4% to 10.0% of cardboard or other wet laid product gross weight, and (optionally) at least aly is selected from second group the auxiliary crosslinking agent that organic cation activity chemistry compound that each molecule has two reactive groups at least is formed, its consumption is up to paper, 0.5% of cardboard or other wet laid product gross weight, crosslinking agent is 1: 10 to 10: 1 to the ratio of the chemical reaction idiozome hydrosol.

Except cellulosic and/or synthetic fiber and be used for the habitual dispersion and/or water-soluble functional auxiliary agent of papermaking, above-mentionedly be used for papermaking, the batching of cardboard or other wet laid product optionally comprises at least a following material (proportional with furnish solids):

(a) filler pigments, content is more than 50% weight;

(b) illuminating colour, content is 5.0% weight nearly;

(c) carbon black is gone cohesionization by the masterbatch method, and content is 0.1% weight nearly;

(d) commodity emulsion binder, average grain diameter are greater than 70nm, and content is 5.0% weight nearly;

(e) novel ultra-fine acrylate polymer emulsion binding agent, average grain diameter are less than 55nm, and vitrification point is-60 ℃ to+20 ℃, and content is 5.0% weight nearly;

(f) novel moisture propylene is a rubber adhesive, and content is 5.0% weight nearly;

(g) contain the aqueous dispersion thermoplastic adhesives, content 20.0% weight;

(h) the water-soluble wet end adhesive of commodity, content is 2.0% weight nearly;

(i) synthetic microfibril, nearly 2.0% weight;

(j) cellulosic microfiber, 10 microns to 200 microns of length, from external stepwise microfiber method preparation, content is 2.0% weight nearly;

(k) ultra-fine electrical conductance and/or magnetic ceramics and/or metal dust, particle diameter are less than 0.2 micron, and content is 20.0% weight nearly.

Embodiment

In implementing better model of the present invention, novel and be improved paper, cardboard or other wet laid product are to be made by aqueous formulations on paper machine, this batching comprises cellulosic and/or synthetic fiber, also optionally comprise at least a functional component such as inorganic and organic pigment, organic polymer binder, illuminating colour and other can be used for the auxiliary agent of papermaking, its dispersion and/or be dissolved in the batching, its method for making be make all batching particle compositions under the above-mentioned synthetic then and there little glue of composite functional is auxiliary immediately, non-selectivity ground and flocculation fully, this little glue, (its bond property of mat) also can make contributions to the dried wet strength of final cellulose or wet-laying nonwoven paper web with regard to second function.Described little glue (little viscose binder) is disclosed in the common unexamined patent application case of before being mentioned 07/919, and 831(1992 applied for July 27), be to be formed at two kinds of distinct methods steps, mechanisms of polymerization different in each step is all effective.

In first method step, two kinds of independent reagent solutions are introduced in the aqueous formulations, this batching comprises cellulosic and/or synthetic fiber, also optionally comprise filler pigments, aqueous dispersion and/or water-soluble binder, dyestuff and other aqueous dispersion and/or water-soluble additive (miscellaneous function material).Wherein a kind of reagent solution contains alkali metal or quaternary ammonium silicate, preferred sodium metasilicate.Another kind of reagent solution contains an alkali metal aluminate and/or alkali metal zincate, preferred sodium aluminate.The polyaddition that above-mentioned " mainly " idiozome hydrosol that begins immediately forms reagent can cause forming aluminosilicate (zincate) sodium dimer, tripolymer and senior oligomer.The precursor of the chemical reaction anionic polymer of these transitions can maintain a very specific solution state in one section finite time, therefore adopt objective suitable " the idiozome hydrosol " herein.

In the second method step, one aqueous solution that contains at least one crosslinking agent is introduced into the above-mentioned batching that contains the idiozome hydrosol that is formed at first method step, described crosslinking agent comprises mainly colourless, the calcium salt of two valencys and/or multivalence, magnesium salts, barium salt, aluminium salt, zinc salt and zirconates, preferably calcium chloride or nitrate.Betide transition, polycondensation reaction meeting between chemical reactivity idiozome sodium silicoaluminate (zincate) hydrosol and the inorganic crosslinking salt causes the supper-fast formation of compound (many components) calcium aluminate silicon (zincate) or similar little viscose binder, produces the giant molecule network of polymer condensation polymer kenel.

Be used in implement in the present invention's batching the colloid result of synthetic compound little glue then and there for any and all be present in that particle in the batching takes place immediately, indiscriminate and flocculation (co-coagulation effect) completely.The flocculate intensity that is developed into can often be reinforced, and is forming online maintenance efficient to improve, its be add small scale cationic polyelectrolyte in above-mentioned inorganic pair of valency and/or multivalence crosslinking agent salt and reach.

Should emphasize before the crosslinked idiozome hydrosol and two valencys or polyvalent mineral salt are with synthetic (in second method step) any compound little glue, be used for first method step and form compound little glue, the necessary first interreaction of the main agents of sodium metasilicate and sodium aluminate (zincate) just is to form chemical reactivity idiozome sodium silicoaluminate (zincate) hydrosol of transition.Therefore, little glue sodium silicoaluminate (zincate) hydrosol (is that certain little glue forms agent with inorganic crosslinking salt) must be regarded as initial more rudimentary reagent, i.e. sodium metasilicate and sodium aluminate (zincate)) synthetic then and there " more senior " reagent.If the indivedual reagent of the latter are (own) and a crosslinked salt directly, as reacting with calcium chloride, then the product of this kind reaction will only be the suspension or the precipitation of solid, two component calcium silicates more or less and calcium aluminate (zincate) crystallinity particle, but not little glue, let alone be compound little glue, with regard to definition, this compound little glue must contain at least three different chemical constitution unit (building block) in its structure.

Be used to implement the little glue formation of complex function of the present invention speed and be exceedingly fast, the polycondensation reaction between the above-mentioned low molecular weight idiozome hydrosol and two valency and the polyvalent mineral salt takes place within 1 microsecond according to estimates.It is as follows that the result of this polycondensation reaction further is proved to be, and between ca aluminosilicate (polymer-condensed polymer) giant molecule, association extremely fast takes place within the number microsecond, produces useful molecular weight thus and may reach billions of colloid formation.

It is important, this kind molecular weight growth overrun continuously and healthily, " extend to " (" sweeping ") entire reaction space, this kind phenomenon is regarded as immediately, the indiscriminate and reason of flocculation completely of most heterodispersity well known in the prior art and polydispersity colloid system, no matter the physics of these systems, why are chemistry or colloform texture.

Consider the organic polymer flocculate effectiveness (as be used for acidity of the prior art and alkaline paper-making method) along with molecular weight increases and significant the raising, just understand the quantitative aspect that the uniqueness flocculation of synthetic compound little glue is then and there renderd a service easily.Yet, know as those skilled in the art, it is about 15,000 to use molecular weight to be higher than, also very difficult usually even 000 polymerization flocculate is not impossible, because its solubility in water is low.Moreover, the molecular weight distribution of all organic polymer flocculates is rather narrow, therefore can't satisfy the flocculation requirement of " widely distributed " difference in height, this requirement is the heterodispersity of batching of modern paper and other wet-laying product and the peculiar demand of polydispersity system.On the other hand, described compound little glue possesses so widely distributed flocculation ability, because synthetic then and there and lasting from very small size growth, molecular weight distribution is very extensive.It is apparent that and similar external high molecular polymerization flocculate can not be introduced in paper (nonwoven) batching, because can't dissolve event.

It is unknown fully being used to implement compound (many compositions) of the present invention little glue former, be used for synthetic this slightly the chemical reactivity idiozome hydrosol of the transition of glue need take a little power could with the similar system difference of prior art.Because can obscure and lack the standard of present colloid chemistry term, be necessary subject matter of the present invention is done an arrangement substantially, and a short review is made in the development over the years of relevant this subject matter.

Above content points out that the very important point is that the whole world mainly is inchoate after following discovery to interest natural and synthetic silica and aluminic acid silicon;

(1) water-soluble metasilicate (waterglass), by Johann Nepomuk von Fuchs(1774-1856) invent, he advises the application of multiple relevant this kind chemicals, for example, is applied to adhesive, dyestuff, the fire retardant of paint, cleaning agent, soapmaking agent, color additive, metal fusing agent and fertilizer;

(2) metallic aluminium was invented by Oerstedt and Woehler in 1825, and most inorganic chemical compound of known this kind element is disclosed in the technical literature by the many decades of countless scientists after then at present; With

(3) soil (natural aluminium silicate) intermediate ion exchange phenomenon is invented in 1850 by J.T.Way.

Below various other business-like silica and alumina silicate mineral (be applied to dry gas, purify water, remove the foreign pigment of edible oil and mineral oil, perhaps prepare pigment and catalyst etc.) useful quality cause silica and alumina silicate field extensive studies.The guiding of these achievements improves the functional character of natural generation material and makes similar or still unknown so far and possess improvement more or even the synthetic of novel character.

Because Si ^{+ 4}And Al ^{+ 3}Similar (being respectively 0.41 dust and 0.50 dust) of ionic radius size, and these two kinds of elements contain abundantly at the earth's crust, a large amount of alumina silicate mineral are synthetic by the natural method of geochemistry (geochemical).Opposite, compound (comprising three kinds or the more composition) mineral that are relevant to alumina silicate the more, the just previous calcium silicates aluminium of mentioning, rarer in nature.Seldom produce alumina silicate mineral (three clinohedrites for example, Ca[Al ₂SiO ₈], perhaps emerylite, CaAl ₂[Al ₂Si ₂O ₁₀] [OH] ₂) reason after considering following factor, just known better because Ca ^{+ 2}Ionic radius be that 0.99 dust be difficult to form the alumina silicate matrix, so, be difficult to form this complex mineral with slow especially geochemical method.

Because the application that the calcium silicates aluminium mineral is never significantly practical, be difficult to the discussion of the degree of depth or synthetic with science or industrial research viewpoint.With regard on the other hand, in the past since 150 years because highly diversified commercial the application arranged, had a large amount of alumina silicate prepared products to be synthesized out.This kind be characterized as the diversified chemical compound that possesses different physics and colloid chemistry character can only use one or below two kind four kinds simply and the sample of conveniently obtaining be synthesized, four kinds of samples are sodium metasilicate, silicic acid, sodium aluminate and aluminum sulfate never have its precursor to occur at inorganic chemistry circle.The bulletin about synthetic silica and alumina silicate product under mentioned reagent is auxiliary that almost can't estimate over 150 years in the past is main only relevant with three kinds of main colloid systems, just continuous glue and discontinuous solution and precipitation.

Under identical few sample reagent is auxiliary, can synthesize the fabulous various product form of people and character can be possessed under the hypothesis of lowermost level system of " memory " and obtain explanation in that to accept colloid be that the Nature is known, also with regard to because so just make colloid " remember " that it derives historical in detail and react according to this, as its final physical property and behaviour performance and obtain proof.Therefore, any premeditated or unexpected, just depart from synthetic method or the reaction condition set up, will on final colloid system foundation and/or functional character, produce inevitable certain species diversity, the difference major part aspect quantitative, but but be long-drawn-out difference of closing qualitative aspect sometimes.Really, basically all are similar, or even identical patent synthetic silica and alumina silicate product only quite in a small amount composition part, the degree bar changes (for example about speed, interpolation order and reagent concentration, pH scope, and heat and aging method) upward variant, perhaps variant on end product improvement physics and physicochemical properties and new Application Areas.

Even the detailed content of a little trickle methods, how the serviceability to synthetic aluminium silicate produces decisive influence, can be with reference to United States Patent (USP) the 2nd, 757, No. 085 (Paquin).As described in this article, only take the lead in being added at the synthetic then and there satisfied colour response alumina silicate pigment of people that makes of papermaking batching, and just can obtain when adding sodium metasilicate at sodium aluminate, on the contrary quite different.Similarly, United States Patent (USP) the 4th, 213, No. 874 (Williams et al) have disclosed and only kept the exchange material that proper procedure and reagent interpolation speed just might be synthesized the unsetting sodium aluminium silicate that makes people's satisfaction in intermediate processings.

The important relations of dependence when keeping strict difinition method parameter and condition with the preparation colloid system of success are 269 pages of the 2nd section (Mir Publishers in the middle of S.Voyutasky " COLLOID CHEMISTRY " book perhaps, Moscow) announcement is arranged, this book point out " colloid system can be by various chemical reactions as exchange; reduction; oxidation; hydrolysis etc. and obtaining, but colloid system does not always form the reaction that can make the aqueous solution (sol); Their only (suggestion of applicant) in the initial substance specific concentrations, specific blend order and temperature and just formation under some other condition cooperates ".

Being used to implement the preferred transition chemical reactivity idiozome hydrosol of the present invention is soluble sodium silicoaluminate, when sodium metasilicate and sodium aluminate solution were mixed in the water slurry for preparing cellulosic or the particulate material that the wet-laying adhesive-bonded fabric is used with described papermaking process, sodium silicoaluminate had just spontaneously formed.When beginning polyaddition reaction immediately, dimer, tripolymer and senior oligomerization compound (polymer precursor) continue and the sodium silicoaluminate giant molecule that is segregated into the anionic polyelectrolyte kenel of low-down molecular weight continuously.Owing to use the reagent of suitable low concentration, but major part is because very fast crosslinked (the stopping the further growth of its molecular weight) of the transition idiozome hydrosol, emanate and the sodium aluminium silicate giant molecule that comes is very little, it estimates that size maximum only is slightly larger than the 1nm(10 dust).

Border (borderline) solution that the representative of this kind high degree of dispersion system is special, it is classified as dimensionally and is higher than crystalloid solution (simple molecules or ion), but is lower than colloidal solution, as starch, protein or polyacrylamide.A kind of " the idiozome hydrosol " noun very suitable on science is in this systematic said system that means, should with the aquasols(hydrosol of prior art) difference to some extent, it is the solid particle suspension of the about 5nm of diameter to 100-200nm.

In the past, the used term of colloid science and technology was with to carry out the instrument that colloid research institute can obtain relevant, just conventional optical microscope and ultramicroscope.Diameter almost can't be resolved with the old-fashioned light microscope that is equipped with low hole objective lens less than the colloidal particle of 200nm; Therefore, it is called " submicroscopic ".On the other hand, utilize the ultramicroscope of Tyndall effect can see little particle, though still can't resolve it to the 5nm diameter.As a result, colloid system is in the main field that is becoming ultramicroscope research traditionally, and it is categorized as " ultramicroscopic view ", particle diameter be 5nm to 200nm, most practical application is still had quite big use.Make the people regrettably, some not rigorous colloid textbook still according to toward example classify the colloid size as 1nm to 500nm, even arrive 1000nm.

The modern scientific research system is rather perfect really, yet, " colloid " and " non-colloid " (crystal, crystalloid) between the system traditionally record be fully based on decentralized photo in particle size, and just rules of thumb of this respect.Therefore, modern theory is refuted over relevant " colloid " and " crystal " the quite sure idea of setting up, accept meet relevant on the contrary and set up with disperse system " colloid seemingly " behavioral standard specific " colloidal attitude ".This kind reason can very clearly in the aqueous solution, show typical crystal behavior with sodium chloride and in benzole soln the example of performance colloid behavior find out that multiple other this type systematic also is proved.

Many experiments in research high degree of dispersion system find, very clearly confirm particle size interval at 1nm to the 5nm(10-50 dust) singularity, wherein colloid and crystal attitude particle diameter overlap each other, and the incomplete disappearance of the name of colloid chemistry is the most obvious.Therefore, the above-mentioned decentralized system of ambiguous general processing make with basic term defined become fully injunctive, as handling many considerable media such as surfactant, dyestuff, toxin is the same with antitoxic situation.For example, partly the individual molecule size of above-mentioned substance is greater than the 1nm(10 dust), this is regarded as the conventional crystal particle upper limit, but less than the 5nm(50 dust), this is regarded as the lower limit of actual typical colloidal particle.Because the field of this kind system action and crystal and colloid is overlapping, partly the author quotes the quite noun of artificialization " hemicolloid " handle these rare solution.Still have the author to point out that this kind high degree of dispersion system particle size distribution in 1nm to 5nm is " amicron " (amicron), it is to build on particle diameter greater than 5nm's " sub-micron " (submicron).

Perhaps in traditional colloid chemistry term the most unfortunately " aquasol " with and appositive " hydrosol " (hydrosol), wherein prefix " sol " representative " aqueous solution " refers to ultramicroscopic view solid particle formed suspension in water.Though the aquasol(hydrosol, hydrosol) under no aid, appear as translucent solution really, when the science disclosure around the boundary system that covers behavior emphatically spin in (for example crystal/idiozome or idiozome/colloid) or when surpassing professional domain, this term makes more shape complexity of whole event.Yet, should be noted that correct term " suspension " refers to the aquasol(hydrosol of the prior art on many rigorous very systematic use science of colloid science man).

The above-mentioned problem relevant with name is when handling novel subject matter even become more complicated, for example is used for synthesizing the compound idiozome sodium silicoaluminate or the similar hydrosol on basis of the present invention.The hydrosol of idiozome constitutes the border solution of transition chemical reaction polyanionic molecule.As for solution, its outward appearance is limpid fully, does not have solids fully, can't show Tynd all effects.

These transient characteristics that continue the idiozome sodium silicoaluminate hydrosol of variation can't defined following oligomerization compound and giant molecule basically with correct physical size or chemical composition.The close examination polyaddition reaction can be understood this situation, and this reaction is at the beginning sodium metasilicate and sodium aluminate solution to be added reactor (batching), and proceeds.Therefore, even might determine giant molecule size at any time, molecular weight, or chemical composition, this kind data the ensuing moment also with out-of-date and unavailable.

Yet the philosophy of science standard that may take to be used for the regulation scientific definition objectively defines above-mentioned unique system.According to these standards, this continuous variation transition idiozome hydrosol can't be classified as " material " with traditional concept, because it does not narrate or be defined in specific in the material science textbook (fixing) shape, quality or character as tradition.Otherwise, represent this idiozome system of one very specific " state of matter " to be defined as

(a) a kind of begin synthetic little glue colloidal sol be described in detail reaction media and condition, just in time of t=0; With

(b) a kind of fixed point of follow-up time arbitrarily (t=0), if the synthetic then and there of the expression one random transition idiozome hydrosol is to begin at time t=0, it is to use identical reagent, ratio of reagents and concentration, reagent interpolation order and speed, temperature, pH and all other effective reaction condition and method parameters, then, have only so, the final transition idiozome hydrosol just can pass through follow-up time t=x(t=c each time) all identical when putting.

Though above-mentioned continuous segregation (generating moment) idiozome system, the transition idiozome sodium silicoaluminate hydrosol for example, can't be defined with the traditional material scientific words, also can completely specifiedly be that it is with the existing natural of any identical name chemical composition thing or synthetic is different.Opposite, all traditional water solution are classified as phase colloid (phaseal colloid), show that decentralized photo and exists the class patibhaga-nimitta of huge scale identical, in principle, and can be in mechanical crushing or the auxiliary acquisition down of other preparation method.

Must lay special stress on be used to implement the transition aspect of the idiozome sodium silicoaluminate hydrosol of the present invention, because the addition polymerization method between sodium metasilicate and the sodium aluminate belongs to continous mode, therefore, at some advanced polymerization stage (wearing out), above-mentioned idiozome hydrosol particle needs sufficiently high molecular weight to surpass the restriction of solubility, the idiozome hydrosol changes into tradition (prior art) hydrosol, just solids soliquid.Start the needed ageing time of this a kind of conversion can from 1 second to a couple of days, perhaps even several weeks or several months, decide according to (batching) sodium metasilicate and sodium aluminate (zincate) concentration in the reaction media, can obtain proof by the Tydndall effect occurring.

Know as those skilled in the art, described transition idiozome hydrosol chemical reactivity, just assist the ability that forms compound little glue down by chemical crosslinking and in two valencys (multivalence) inorganic salts on basis of the present invention, this ability can and fail along with polymerisation degree raising (wearing out).When above-mentioned little glue colloidal sol is aggregated to the solubility that surpasses the solid colloid particle transform into traditional water solution, reactivity is almost completely lost.Therefore, it is important that the synthetic second stage of compound little glue carried out then and there before the Tyndall effect occurring, the wherein above-mentioned idiozome sodium silicoaluminate or the similar hydrosol carry out crosslinked under two valencys and/or polyvalent mineral salt are auxiliary.

In device with the typical paper mill of continuation method mode operation, above-mentioned crosslinked can carrying out between several branches in the several seconds, the time is added into batching with preparation paper from sodium metasilicate and sodium aluminate solution, counts when cardboard and other wet laid product.

The synthetic then and there little glue main purpose of composite functional is to induce all to be present in paper, in cardboard or the wet-laying nonwoven batching raw material dispersion immediately, do not have select and flocculation (co-coagulation effect) completely.The flocculation phenomenon is played the part of very basic role at preparation cellulosic and wet-laying adhesive-bonded fabric; Yet it is slow to be used for prior art flucculation process speed acid and the alkaline paper-making method, harmful selectivity (not being indiscriminate ground) and incomplete.According to the above, these methods not too are appropriate to prepare the first paper feed that does not need to cause with separating according to kind and the size selectivity flocculation of batching composition bad result, cardboard and wet method adhesive-bonded fabric (particularly on high speed paper machine), this more or less can be proved by the final products insufficiency of function.In fact, many potential useful ultra-fine colloidal materials based on all practical uses can't be in the prior art the acid and employed inefficient flucculation process of alkaline paper-making method and reagent flocculate under assisting (precipitation), therefore can effectively get rid of it as making above-mentioned first paper feed, the feasibility of cardboard and wet-laying adhesive-bonded fabric raw material.

Typical modern paper batching is height heterodispersity and polydispersity aqueous system, this system's fibre-bearing matter fiber and fine fibre, inorganic and organic filler, water-soluble binder, cementing agent, dyestuff and other auxiliary agent.All above-mentioned batching compositions co-coagulation are uniformly made people's paper web of satisfied (evenly) effectively to maintain on the papermaking machine forming net and to produce.Yet there is different surface chemical properties in each heterodispersity system, and charge density is disperseed stability or the like, therefore, different deflocculation character is arranged also.Moreover, in fact, the particle type of the paper that is useful on batching itself more or less be polydispersity, the flucculation process of the different component ratios of this class is controlled by different colloid chemistry and other mechanism.Particularly the flocculation this as about 0.1 micron to the 20 microns suitable sphere diameter of e.s.d(of particle diameter) the polydispersion mineral filler time can meet with sizable difficulty especially.Therefore, coarse grain footpath filler, for example quite sphere diameter has suitable anticol body chemical flocculation greater than 2 microns, and its situation about remaining on the paper web mainly is subjected to mechanical factor such as turbulent flow, the influence of gravitational settling or filtration.On the other hand, medium size flocculation partly mainly is the influence that is subjected to charging neutrality and polymer bridging on the filler.The ultra-fine filling material part, just quite sphere diameter is less than 0.1 micron, and it is subjected to prior art to use the influence of the flocculation mechanism of acid and alkaline paper-making method hardly.Similar, many ultrafine particles, for example illuminating colour or polymer emulsified binding agent, major part is by aluminum sulfate or organic polymer flocculation.

In the existing acid and alkaline paper-making method speed of heterodispersity and polydispersity batching composition slow with the another kind of side effect of selective flocculation be form separating of not wishing to take place [... fibre/fibre ...] or [... filler/filler ...] aggregation of kenel.Separate to form just and keep the reason that filler grain reduces and remaines in filler grain optical property efficient reduction on the papermaking wire-cloth on the papermaking wire-cloth.Speed and selective flocculation have special side effect to the optical property of expensive TiO 2 pigment slowly, and titanium dioxide in fact always uses with the more cheap index increment agent pigment of price, with as physical separation agent (spacer).The reason that titanium dioxide optics performance reduces is because the flucculation process of prior art efficient poor (the slow and selectivity of speed), the main filler grain aggregation that forms be optical difference [... titanium dioxide/titanium dioxide ...] and [... extender/extender ...] kenel, rather than desirable optical efficiency better [... extender/titanium dioxide/extender ...] kenel.

It should be noted, the batching composition that is distributed to shape essence ratio into the net from flow box for the first time by the time can not be retained, and must after papermaking process period time, just can be retained.Because tradition (prior art) is acid and the flocculation of alkaline paper-making method batching composition is also incomplete, the ill effect of the isolation and selection gathering (flocculation) of the composition of preparing burden individually is in the continuous deterioration of above-mentioned cycle period.

The little glue of composite functional immediately to be used to implement the present invention's synthetic (in batching) then and there, do not select to have eliminated general use height heterodispersity and polydispersity paper fully with complete flocculation, the shortcoming of cardboard and wet-laying nonwoven batching, therefore, even can be from the most novel, the paper of extreme heterodispersity and polydispersity batching preparation novelty and outstanding kenel, cardboard and wet-laying adhesive-bonded fabric, and even can not cause a little selectivity (separation) or not exclusively flocculation.Know as existing those skilled in the art, above-mentioned kenel batching has no idea to be used to papermaking process of the prior art not causing to make under unacceptable material unaccounted-for (MUF) of people and the operational situation of difficult, let alone probably can cause the consequence on harmful ecology.

Novel batching can comprise cellulose fibre, synthetic organic fibre, inorfil, the cellulosic microfiber of reinforcing fiber microfiber and external preparation, magnetic and electrical conductance metal dust, about 0.1 micron the plastic cement filler pigments of mineral and particle diameter to 20 microns e.s.d, particle diameter is little of (the non-fusion of the non-film forming of 30nm, or only at high-temperature digestion) Emulgating polymers, particle diameter is-60 ℃ to+20 ℃ a novel ultra-fine polymer emulsification binding agent less than 55nm and vitrification point, novel water-based rubber adhesive, commercial water dissolubility paper binding agent, the particulate thermoplastic adhesive, coloured pigment and particle diameter are less than the carbon black of 10nm.Moreover the relative density of above-mentioned particle is approximately from the high 4.2 gram/cubic centimetres to titanium dioxide of 1 gram/cubic centimetre of organic polymer, the perhaps metal dust of higher particle diameter, and its surface chemical property can be extremely hydrophily to hydrophobicity extremely.

Foreseeablely be to use papermaking process of the present invention can cause any restriction to potential batching hardly, also so not can have influence on final paper, the variability of cardboard and wet-laying adhesive-bonded fabric and versatility, because no matter how thin find after applicant's broad research, complicated or difficult, can resist the synthetic little glue of composite functional then and there immediately, indiscriminate and complete flocculation from finding no water-based dispersiveness or colloid system.

Because its distinctive adhesive properties, second purpose of the little glue of composite functional provides a kind of the inventive method prepared paper, cardboard and wet-laying adhesive-bonded fabric of possessing mechanical strength acquisition reinforcement of adopting.This slightly glue bond property can with usage quantity and painstakingly the composition of optimization controlled, with to make the modern industry inorganic bond reach the mode of optimization traditionally similar.With the cellulosic paper web, main mechanical strength is to be derived from formed hydrogen bond between the functional group who is exposed to fibrillation (refining) cellulose fibre surface, and the sphere of action of this kind key only extends to several dusts.Using the second prepared reinforcing fiber matter paper web of existing papermaking process is being to obtain under water-soluble polymer (mainly being starch) auxiliary at present, and it is directly added in the papermaking batching.

Though to implement synthetic organic and idea inorfil of the little glue bond of composite functional used herein is quite simple and clear, a kind of cellulose fibre similar bonding is very unique and needs further effort really.As consider it is significantly from the elementary analysis aspect, (in batching) then and there synthetic compound little glue of ca aluminosilicate or similar kenel can stay the inorganic residue of inserting wherein in final cellulosic paper web structure after drying.Yet, according to prior art instruction and experience, any and all place inorganic particulate between the cellulose fibre by the physics mode defibre, can suppress to form hydrogen bond among a small circle all the time, therefore weaken final paper web.

For effectively making between the cellulose fibre under little glue auxiliary " gummed " mutually, must meet three kinds of tangible conditions.At first, little (ultra-fine) that protomere must be very for example used at paper really, and synthetic then and there this obtains under glue high shear force auxiliary slightly in cardboard and the wet-laying nonwoven batching.The second, superfine micelle must " strategic ground " be placed between two adjacent fibres.The 3rd, protomere must possess peculiar deformability so that can extend between the fiber of two adjacency with discontinuous superthin layer.It goes without saying that to have only real protomere, but be not solid water colloidal sol (aquasol) particle or precipitation that for example pigment has the ability to do this distortion.Causing in the cellulosic paper web some will do further to inquire in following example about the quantitative aspect discussion of compound little viscose binder cementation.

Bond can be directly with compound little glue between a kind of extra fiber not seen before, and novel ultra-fine polymer emulsification binding agent adds in the papermaking batching, obtains by flocculation.This type of target of using specifically developed novel binding agent for little binding agent by the applicant is disclosed in the patent application case 07/958 of common examination, 283(Ultrafine Polymer-Emulsio n Adhesives for Mircoadhesion), applying on October 9th, 1992, is reference of the present invention in the lump.Above-mentioned binding agent mainly comprises acrylic polymer and co-polymer, and its mean particle diameter is less than 55nm, and vitrification point (Tg) is-60 ℃ to+20 ℃.Relatively, in the thinnest mean particle diameter, known commodity be in the traditional polymer binding agent (commercialization) " latex " (latexes) particle diameter is quite thick, for example above about 70nm.

Till above should be noted that order, polymer emulsified binding agent still be not found the batching that is applied directly to and alkaline paper-making method acid as prior art because its can't with can received mode by art methods flocculate (being retained) with the furnish solids form.Moreover even the thinnest traditional latex, as wet end additive the time, its particle diameter also too slightly can't provide bond between any measurable fiber, and the relative weight content of latex surpasses about 15% in paper web.As a result, commercial latex only is used to saturated used paper or wet-laying nonwoven paper web.

By a kind of novel basically discovery of bond representative between the fiber of the cellulosic paper web of above-mentioned ultra-fine polymer emulsification binding agent combination, in all actual purpose, only being applied to papermaking process of the present invention, and can't be applied to the acidity or the alkaline paper-making method of prior art.Yet, should be emphasized that bond between fiber only the mean particle diameter of above-mentioned ultra-fine polymer emulsification binding agent less than 55nm and its cellulosic paper web in content when being no more than 2% paper web weight (between the latter's fiber bonding interaction clearly surpass 2% after just stop to increase, binder content in reaching higher in fact paper web reaches 10-20% approximately) just can see.

Three kinds of functions of the synthetic then and there little glue of composite functional are that desirable functional character is passed to final paper, cardboard and wet-laying adhesive-bonded fabric, and it is considerable using from the latter's end.These functional characteristics are derived from highly diversified physics of little glue itself and surface chemical property, as long as the chemical composition of the little glue of autotelic improvement is used to be fit to desired end, just can control its characteristic very easily.For example, peculiar sized paper can be prepared according to the present invention, and it is that each molecule that adds a small amount of ratio contains the organic of at least two reactive groups, cation activity chemical compound and two valencys and the crosslinked salt of polyvalent mineral.Form final compound little glue is dispersed in merging in well-proportioned mode on the statistics cellulosic paper web by the mixing giant molecule of inorganic/organic polymer polycondensation kenel, provide a kind of space of discontinuous hydrophobic position to arrange matrix, therefore a kind of peculiar gluing characteristic that obtains to control also is provided.

The surface chemical property of final paper web also can be improved under the little glue of the composite functional that comes into question is auxiliary indirectly, it is prepared burden by other due to composition co-coagulation, the composition surface chemistry modifying agent that for example function is strong is with as polymer emulsified binding agent (possessing dual organic hydrophilic/hydrophobic property), organic hydrophilic or even hydrophobic organic dyestuff, polar mineral pigment, or polarity obtains the organic polymer of control.

Being mainly used in synthetic compound (many compositions) the of the invention process functional little glue commercial reagents that supplies comprises:

(1) alkali silicate and quaternary ammonium silicate are good with potassium silicate or sodium metasilicate:

(2) alkali metal aluminate, the mixture of alkali metal zincate and its any ratio is good with sodium aluminate or sodium aluminate and/or sodium zincate or potassium zincate;

(3) water-soluble, mainly colourless, the calcium salt of two valencys and/or multivalence, magnesium salts, barium salt, aluminium salt, zinc salt and zirconates, preferable with calcium chloride or nitrate.

When hot weather when the paper mill runs into serious germ contamination and sludge growth question, with independent use calcium nitrate or use more favourable with calcium chloride.

It is about 8 to 12 that the paper of little glue flocculating, the pH of cardboard and wet-laying nonwoven batching are distributed in usually, and the water quality of this and institute's using method has very big relation.Wish to reduce flocculation paper batching at those, when particularly containing fine grinding xylon batching, using aluminum sulfate separately or use together with calcium chloride and/or other corresponding crosslinked salt may be more favourable.In addition, perhaps desirable thiosulfuric acid aluminium also can use for above-mentioned purposes with other common acidulant by sulfuric acid.Need to reduce batching pH and must be assessed in advance, for example by (alkalescence) free from foreign meter compound little glue a part of furnish samples of flocculating, then with the acidulant solution titration that the is about to use batching of finally flocculating to the acidulant ratio of desired level.

Be subjected to paper because be used for implementing the major function of the little glue of composite functional of the present invention, the flocculation of cardboard and wet-laying nonwoven batching particle composition, the restriction of adhesive effect and surface chemistry improvement, according to toward example, it is required to use little glue amount of these quantity to be merely able to finish desired work.Generally speaking, about 0.4% to the 10%(weight of little glue content range) (being measured by ash) is found sufficient paper supply, cardboard and the use of wet-laying adhesive-bonded fabric.To most commercial paper of use, the best little glue content of cardboard and wet-laying adhesive-bonded fabric is about 4% to arrive 10%(weight), it is to rinse out the electrolyte byproduct such as the sodium chloride of cross-linking reaction, after sodium nitrate or the sodium sulphate, again with ash purification determining it.

Mainly comprise cellulose fibre in the used papermaking batching of laboratory and pilot plant test, conventional inorganic fillers, and/or novel aggregation filler pigments (hereinafter will be described in more detail) are used the little glue reagent of formation of two kinds of varying numbers.The solids content of batching surpasses 5%(weight), its reagent dosage comprises the dried batching of per 100 grams and contains 2 gram sodium metasilicate, 2 gram sodium aluminates and 4 gram calcium chloride.The solids content of batching is less than 5%(weight) time, its reagent dosage is that the dried batching of per 100 grams contains 3 gram sodium metasilicate, 3 gram sodium aluminates and 6 gram calcium chloride.From reducing reagent demand and the viewpoint that reaches better final result, so that more beneficial with the highest as far as possible furnish solids concentration.Solid concentration is a little less than 2%(weight) batching may need the little glue quantity more higher than above suggestion amount.

With regard on the one hand, relevant for (intermediate) transition, quantitative and the qualitative composition of the sodium silicoaluminate of chemical reactivity idiozome or similar water colloidal sol and on the other hand (finally) be used to implement compound little glue of the present invention very big selection space arranged, and can not destroy its desired function of reaching.For example, the sodium metasilicate that is used to form above-mentioned little glue colloidal sol is to sodium aluminate, sodium metasilicate to sodium zincate or sodium metasilicate to the ratio of sodium aluminate and sodium zincate can be from 1: 10 to 10: 1 weight.At relevant manufacturing paper, in many tests that cardboard and wet-laying adhesive-bonded fabric have been set up, its preferable ratio was as 1: 1.

Batching mesosilicic acid sodium preferred concentration is 0.01% to 2.0%(weight), same preferred concentration also is fit to sodium aluminate, sodium zincate or its mixture.Reagent concentration in above-mentioned batching surpasses 2%(weight), can quicken sodium silicoaluminate (zincate) giant molecule molecular weight and grow up, reduce the chemical reactivity of the latter to inorganic crosslinking salt.In order to keep the chemical reactivity that to synthesize enough levels of the little glue of composite functional that possess enough flocculations and cementing property, from this type of concentrated reagent solution the isolated transition idiozome hydrosol should be in the several seconds crosslinked finishing, use (in line) blender/reactor on the line of special additional efficiency then.

The ratio that the corresponding inorganic crosslinking salt pair of calcium chloride or its mixes is about to be crosslinked the little glue colloidal sol of transition chemical reaction can be 1: 10 to 10: 1 weight, can synthesize the little glue of composite functional then and there that makes the people the most satisfied but 1: 1 simple ratio is found, this functional little glue possesses sufficient flocculation efficiency and the dry type and the wet type intensity of significant final paper web can subsequently be provided.When furnish solids inorganic crosslinking salt can use content is 0.4% to 10%(weight), calcium or its be corresponding be present in two valencys of reaction media and multivalent ion should be the most suitable above at least by 50% quantity of this ion of above-mentioned transition idiozome hydrosol chemical bonded refractory.As from synthesizing in shown in the filtrate chemical analysis of compound little glue of light water, above-mentioned excessive cross-linking ion reduces the residual concentration of unreacted silicon hydrochlorate and aluminate (zincate) molecule to number ppm.For most actual purpose, working concentration is for accounting for paper, cardboard and wet-laying nonwoven batching 0.02% to 4.0%(weight) two valencys (multivalence) inorganic crosslinking salt has been just enough.

Though many each molecules contain at least two reactive groups organic cation activity chemistry compound itself can crosslinked transition chemical reactivity idiozome sodium silicoaluminate and the similar hydrosol, for major part purpose in fact, do not advise only using a kind of crosslinking agent.Otherwise, be selected from cationic surfactant, the organic compound of organic metal Louis Vernet compound and cationic polyelectrolyte should be to be added in the inorganic crosslinking salting liquid on a small quantity, the desired surface chemistry improvement property that reaches is passed to synthetic compound little glue then and there, therefore also pass to final paper, cardboard and wet-laying adhesive-bonded fabric indirectly.Yet the mixing that it is important to control segregation is inorganic/adhesion efficiency of organic little glue, because the former can reduce apparently along with the increase that enters the macromolecular organic cation compound of forming little glue.

The specific functionality purpose, as paper through surface chemical modification, cardboard and wet-laying nonwoven paper web, need quantity levels that each molecule contains the active cross-linking reagent of organic cation of at least two reactive groups must determine the application of indivedual reagent dosages and desired final products by experiment, for example measuring contact angle, carrying out under gluing test or the like is auxiliary.According to the present invention, when the quantity of organic crosslinking agent accounts for paper, 0.0003% of cardboard and wet-laying nonwoven batching arrives 0.15%(weight) time, will find under compound little glue of inorganic/organic kenel is auxiliary, can access the modification of the surface chemical property of fiber product.The particularly useful ratio of these reagent in final cellulosic or wet-laying nonwoven paper web is about 0.001% to 0.5%(weight).

Should be emphasized that, form two kinds and be used to implement the present invention's (intermediate) transition chemical reactivity idiozome sodium silicoaluminate or similar water colloidal sol and the little viscose binder of (finally) composite functional is not to determine in the stoichiometry mode.Yet, in building-up process, use same composition, concentration, ratio, quantity and add reagent speed and when order and special reaction condition, will obtain the identical transition idiozome hydrosol and final compound little viscose binder at every turn.

Owing to be the ultrafast chemical reaction in the typical aqueous medium, it is in fact irrelevant with the temperature of reaction medium to form the little glue of enforcement composite functional of the present invention then and there.Therefore, in principle, above-mentioned little glue can still form for during the whole temperature of fluid at water, supposes stability impregnable words under high reaction temperature of reagent.Should consider the limited heat endurance of sodium aluminate solution especially.

Above-mentioned synthetic method and heat condition and method are irrelevant fully, be the exclusive characteristic of above-mentioned compound little glue, if (for example the preparation method of the hydrosol (colloidal suspension liquid of solid particle) known of silica and aluminosilicagel or prior art by comparison can be clearer with using simpler single composition or two composition colloid system.For example, many patents have disclosed various different useful in preparing drug formulations, ion-exchanger, catalyst and other are with colloid external or that prepare then and there, the hydrosol or sediment, sometimes be identical Chemical composition that method, seemingly small (although be harsh to the synthetic of success of product) difference is only arranged in heat treatment method usually for the product on basis.

The concentration of reagent and chemical composition or tolerable have very wide scope in the reaction condition of the synthetic little glue of composite functional, and this is to mean to be used to implement of the present inventionly generally with the colloid chemistry system very big potentiality are arranged.It should be noted that similar vast scope never hears in similar approach of the prior art, even the simplest single composition of silica or alumina silicate and two composition colloid system also must be kept strict difinition concentration in program and heat treatment and the anti-media in strictness in the prior art, and be synthetic under ratio and types of agents and the pH condition.

More going through of the little glue subject matter of above-mentioned composite functional is found in the common unexamined patent application case 07/919,831 that this paper once carried.

The alkaline scheme of papermaking process of the present invention is illustrated in the following example.

The example I

To consist of gloss be that the chemical pulp of 50: 50 corks/hardwood mixture of 86% prepares a collection of handmade paper by handling one, adopts aforementioned (in the batching) then and there synthetic little glue of ca aluminosilicate as papermaking (wet end) chemical raw material.Be of a size of 20cmx20cm, Substance be 60 grams/square metre handmade paper under a paperboard form is auxiliary, use to be in particular the program that laboratory applications papermaking of the present invention develops out and to be prepared.

According to the program that above-mentioned special development is come out, " small lot " paper pulp (denseness is 3%) capacity that is introduced into that a quantity is enough to prepare a slice hand papermaking is 500 cubic centimetres Wei Lin Shi (Waring) blender.5% solid aqueous solution of sodium metasilicate and sodium aluminate is injected into the batching of high degree of agitation simultaneously with being arranged in the toss about plastic cement injection tube of position of blender diameter, to avoid directly contact between the reagent solution injected current.After about 20 seconds, 5% calcium chloride solid aqueous solution is injected in the batching of identical high degree of agitation.The ratio of the active agent that uses is the sodium metasilicate that 100 gram paper pulp have 3 grams, the calcium chloride of the sodium aluminate of 3 grams and 6 grams.

Small lot flocculation batching moves into from blender in the flask of 2 liters of capacity, and after several minutes arrived between about 2 hours aging period, it is full up to flask that water is diluted (stirring down), pours into then in the paper matrix to form handmade paper.It is about 35% that wet handmade paper at first is extruded into solids content, covers on the rotation heating drum of felt one then and give drying.Remain in inorganic residue (the little glue deposit of the calcium aluminate silicon of dispersion) relative weight content on the hand papermaking (being also referred to as " main handmade paper ") and equal about 7%, measure with the standard weights method.

Similarly handmade paper is also referred to as " contrast handmade paper ", uses aluminum sulfate and Perc ol 292(high molecular weight cation polyacrylamide flocculate) a typical acid papermaking method, its consumption is respectively 10 kilograms of paper pulp per ton and 0.5 kilogram.Partly contrasting handmade paper is to be prepared in a fibrous batching, and partly extra contrast handmade paper is to be prepared in identical batching, and wherein the starch composition increases.

The feature of main handmade paper is the preferable formation quality of similar contrast handmade paper that obtains than not using the preparation of paper web intensity reinforcement starch, the dried wet strength and the hardness that significantly improve, more sound sound and high glaze and opacity slightly.Because the optical property of regular comparison criticism paper need be by the identical mechanical strength of the system held of criticism, the starch reinforcement contrast handmade paper that main handmade paper is more suitably mated by other criticism.Because wet end starch can reduce the gloss and the opacity of hand papermaking significantly, main handmade paper (no starch) has more about percentage point of 1.5 to 2 at the amyloid contrast handmade paper than corresponding same mechanical intensity aspect gloss and the opacity under final balance.

It is important in the main handmade paper quite a small amount of (promptly about 7%(weight)) the solvent of little glue residue only can increase the latter's gloss and opacity a little, very undersized protomere of this demonstration clearly (deposit) can be stayed on the cardboard.Generally speaking, the particle diameter below the dimensions is called as ultra-fine or little pigment less than the pigment of about 0.1e.s.d in the present technique field, and it is called as pigment in tradition (commerce) viewpoint because its astigmatic efficient is not enough.Yet the little glue residue that places the dispersion on the handmade paper is dimensionally much smaller than typical little pigment particles.As well known to the skilled person, if little glue residue is by equal proportion (being 7%(weight) in the cardboard) external synthetic filling pigment replace, as be disclosed in United States Patent (USP) the 2nd, 757, the precipitated silicate calcium or one of No. 085 (Paquin) is the alumina silicate filler kenel of (in the batching) precipitation then and there, then the gloss of main handmade paper can exceed 3-4%, and opacity more exceeds about 8-10%.

It should be noted that when by sodium zincate partly or whole replacements, perhaps when during by calcium nitrate part or whole replacement, also obtaining result same as described above as the calcium chloride of crosslinking agent as the sodium aluminate of transition idiozome hydrosol composition.

When the discovery that the above-mentioned example of analysis is discussed, should emphasize to be used to implement unique cardboard strengthening action of synthetic compound little glue then and there of the present invention.Except many advantages of compound little glue and peculiar property, obtain unheard-of cardboard strengthening action through inserting inorganic particulate and can have no the above-mentioned little glue of making of deviation and distinguished with the inorganic colloid chemical system that as if all these relevant skills known.

Another great discovery when criticism is prepared in the pattern product of example I is by the height of ca aluminosilicate main handmade paper that little glue is given " wet type intensity ".Concerning the very common above-mentioned functions character of compound little glue attractive especially from commercial point of view, because it is quite limited to increase the practical approach of wet type intensity of the paper that this skill knows.Therefore, be found approximately according to the wet type intensity of the handmade paper of the described program drying of example I and exceed 100% than similar control sample.Yet after 204 ℃ (400 °F) additionally heated 30 seconds, the wet type intensity of handmade paper was found than corresponding control sample and exceeds 600%.

Above-mentionedly contain little glue handmade paper outstanding especially wet type intensity is arranged, this phenomenon little glue of available silicon calcium aluminate in principle is heated at about 218 ℃, makes major part become to harden fully thereby the fact that becomes WATER RESISTANCE is explained.As what the crowd understood, high wet type intensity property can be passed to the cellulosic paper web via synthesizing compound little glue then and there, be ultra-thin shape only because be scattered in discontinuous little glue deposit of fibre structure fully, can not cause interference, and strategically be positioned at closely fiber the fiber contact area to the formation of the tight arrangement hydrogen bond between cellulose fibre.Relatively go up, the unique feasible method that increases cellulosic paper web dry type known in the state of the art or wet type intensity is via adding organic water-soluble " glue " in fiber furnish.

An outstanding characteristic is that all batching composition particles become co-coagulation in the most uniform mode on the statistics in the papermaking process of the present invention, no matter the size of these particles, form, relative density, surface chemistry or colloid property, this characteristic and the present invention are immediately distinctive, and be indiscriminate with flocculation mechanism is relevant completely.The result, contained bad separation the in heterodispersity and the polydispersity papermaking batching, assemble and the particle composition of selective aggregation (flocculation), for example in existing papermaking process can't avoid, based on all actual purpose, in papermaking process of the present invention, can not occur.

The distinctive flocculation mechanism of some the present invention derive out immediately and potential advantage under the explanation of following example, can become more obvious.

The example II

Three kinds of laboratory same ingredients batch, every kind contains 80%(weight) 50: 50 hardwood/softwood mixtures and 20%(weight) remove the stratification clay filler, be 3%(weight from initial denseness) time preparation.

The main part batch that is named as " mainly " batch according to the described program of example I under the little glue of synthetic aluminosilicate calcium then and there is auxiliary by flocculating, be diluted to 0.7% used denseness of general business-like machine operation then.It is 0.7% that first control batch that is named as " AC " (acidity) is diluted to denseness at once, then according to typical prior art acid papermaking method by flocculating, it is to use furnish solids per ton to contain the aluminum sulfate and the Percol 292 of 10 kilograms and 0.5 kilogram respectively.Similar, second control batch that is named as " ALK " (alkalescence) is diluted to 0.7% denseness, then according to prior art neutral and alkali papermaking process by flocculating, it is to use one group of organic polymer to keep auxiliary agent (Calgon Polymer H-7392 and Calgon Polymer H-7736 EZ), and each consumption is 1 kilogram of a solid ingredient per ton.The pH of batching is adjusted to 8 level by NaOH.

Each above-mentioned flocculating furnish samples is transferred to independent sealed glass bottle for further observation.The feature of two control batch " AC " and " ALK " clearly is uneven, and coarse grained flocculate structure is not at the bottom of a large amount of solid matters are deposited to bottle at once in the carrier (water) and remain muddiness.Different with two control batch is, at the bottom of being deposited to bottle with single flocculate (single flocculate) form main batch, its outer appearnce be similar to a limpid topper of the brilliant firefly of quilt around large-scale fine hair shape cotton balls, the feature of single flocculate is a micrograined texture very uniformly.

Through after certain period aging, above-mentioned each bottle is inverted fast, and the adhesive residue of denseization of one deck appears in two bottles that contain control batch, mainly comprises the filler grain at the bottom of firm stick to bottle.The separation of above-mentioned batching composition provides tangible proof to confirm that prior art acidity and the distinctive flocculation mechanism of alkaline paper-making method are that speed is slow certainly, selective and incomplete, cause that main formation do not wish to obtain separating [... filler/filler ...] and [... fibre/fibre ...] aggregation of kenel, rather than desirable [... fiber/filler ...] heteromers of kenel.Opposite, the bottom that contains main batch of invert bottle is clarification fully, the whole amount of filler and the cellulose fibre that mean batching carry out firm and close co-coagulationization.

As well known to the skilled person, the practical potentiality of above-mentioned discovery are quite big, and according to prior art, for example, paper and cardboard are prepared in and only contain about 0.5-0.7%(weight) solid matter.It is indispensable needing the trouble dilution operation of big water gaging, because form the deterioration along with solid concentration increase in the batching that the quality of paper web can be very fast.Opposite, the auxiliary peculiar very even ingredient particles structure down of synthetic compound little glue might be with the batching that is significantly higher than the feasible solids content of prior art papermaking process then and there, and can not damage the quality of final formation paper web.Find the meaning of representative according to this, as long as revise present flow box design a little, solid concentration in the batching (furnish consistency) can be added to 2 or 3 times that are higher than traditional level.Yet higher furnish consistency for example exceeds 4 or 5 times than present employee, also can reach via revising the flow box design by a larger margin.

Paper web formed in order to increase papermaking machine speed that to cause unavoidable quality badness also be well-known to those skilled in the art to surpass the present actual speed upper limit.Moreover, because by the peculiar micrograined texture of the fibre/fibre flocculate that effect produced of synthetic batching (in containing the filler batching) is very even then and there, might increases the speed of papermaking machine greatly at present and can not diminish the shaping quality of final paper web.Furnish consistency that also might comprehensively increase and higher papermaking machine speed prepare be shaped good paper, cardboard and wet-laying non-woven fleece with papermaking process of the present invention simultaneously.

The cellulose fibre of finishing by synthetic compound little glue then and there and whole co-coagulation effects of mineral filler particle are another the great discoveries of example II.Know as existing those skilled in the art, the sheet forming uniformity of acidity and alkaline paper-making method is along with filler load level is brought up to 20%(weight in the prior art) and increase.Yet, when filler load level further increases, papermaking batching must excessive flocculation obtaining first by pigment particles is kept on paper web fully, this kind inevitably " overflocculation " result frequent visible be that the sheet forming quality excessively worsens.Under the sharp contrast, with the ash-rich of the synthetic compound little glue flocculation then and there peculiar micrograined texture of preparing burden, and the shaping quality of final paper web, can improve and be improved along with filler load level) even the latter surpasses 50%(weight.Hereinafter will discuss the latter in more detail and heavily cover the discovery of variation and may prepare high part of ash paper product with the sheet forming quality, this institute under the prior art papermaking process is auxiliary is beyond one's reach.

As known to those skilled in the art, significantly the effectiveness batching composition that has of ratio is flowed by waste water with expendable when using prior art acidity or alkaline paper-making method methodically, causes most material to run off and serious ecological problem.On the other hand, total (100% is complete) flocculation of the particle batching composition that is reached under papermaking process of the present invention auxiliary is able to the particle of recovery 100% from used batching before the latter is by waste water stream.Use and filter, cyclonic separation and other straightforward procedure from the fluid separation applications solid are removed contaminant particles fully from waste water stream, and a kind of advantage that more meets economy and ecological benefits than prior art papermaking process is provided.

The fiber that the synthetic then and there little glue of composite functional of mat carries out and total flocculation of filler grain provide reach a kind of on paper machine the attracting possibility of true " autocide " (self-extinguishi ng) method circle (process loop).This a kind of autocide circle can be easier to understand after following explanation: with particle (polymer emulsified) binding agent replace the water soluble starch binding agent of traditional papermaking and under little dose of synthetic composite functional then and there is auxiliary these very highly filled batchings of flocculation, for example up to 10-30%(weight).Clean final system and other solute pollutant that little glue forms the salt byproduct, for example use vacuum filtration and spray cleaning, can not had solute and electrolytical papermaking batching haply.Above contamination-free batching is diluted to after the desired flow box denseness by water, can be back on the papermaking machine, uses up fully up to its solid, is retained in the pure batching continuous supplementation of the furnish solids quilt new (former) on the shaping papermaking wire-cloth.Therefore, traditional heavily contaminated waste water stream of papermaking machine can be removed fully, and its other advantage is to save a large amount of water.Unique waste stream of planting airtight circle papermaking process since then is a small size, the quite dense clear filtrate that contains sodium and calcium salt, dispersant (for example coming self filler and binding agent) and the similar solute that the papermaking of extraction autoflocculation high-consistency is prepared burden before using on the papermaking machine.

The traditional experiment program that should emphasize to make hand papermaking is to rely on the similar papermaking batching of concentration ratio to exceed 25-50 batching doubly, can always not show that the correct filler of commercial operation keeps efficient.For example, when the laboratory handmade paper is prepared in this type of high dilution batching at auxiliary all inorganic (calcium aluminate silicon) the little glue that use down of papermaking process of the present invention, can obtain keeping efficient than the filler that similar hand papermaking is acid in prior art and the auxiliary end of alkaline making method is low.Yet, when similar large-scale papermaking test uses the typical commercial ingredients concentration to be 0.5-0.7%(weight in a guide paper mill) under when carrying out, final filler keeps the papermaking process that uses prior art acid and alkaline that is higher than of efficient unanimity.

The reason that above-mentioned filler keeps the reverse (being shown to the actual result of scale fully from the laboratory paper machine) of trend is more to excel at leveraging the fine fibre that is produced during the refined fiber matter wood oar.The refining discontinuous fibre matter fine fibre that is produced " the life-span weak point ", what meeting was very fast quite lacks in the ageing time at one section, perhaps, during the slow speed and inefficient batching flocculation mechanism of particularly acid in the prior art and alkaline paper-making method, be connected to and relatively go up on the bigger complete fiber.As a result, latter's fine fibre is not contributed very less or at all to the reservation of reinforcement final fiber networking or convenient filler grain.Yet, when just (still being contained freely and float by refining fiber furnish, the fine fibre of Lian Jieing not) when synthetic compound little glue is handled then and there, induce the flocculation immediately of all particles in the batching, numerous fine fibre and complete fiber carry out complicated co-coagulation effect, and the reinforcement to final fiber networking significantly has contribution.

Yet, the most important thing is that the fine fibre of Lian Jieing is not mainly with filler grain how carries out the co-coagulation effect according to the statistics law in order to count still in the batching.The fine fibre of load filler is explained with its physical dimension and is shown overweight, and its buoyancy is little.Therefore, must remember that it is that (fibre mat forms on the shaping papermaking wire-cloth earlier in filtration that filler grain is retained in the dominant mechanism that forms on the papermaking wire-cloth, filter the filler grain of flocculation then), readily understand that the fine fibre of load filler is difficult to be retained in the shaping screen cloth when when paper is copied by hand in high dilution feed preparation laboratory.On the other hand, when using solids content to prepare burden as the typical commercial of 0.5-0.7%, the efficient fact that is retained on the papermaking machine of load filler fine fibre is very clearly pointed out an additionally and so far still unknown filler retention mechanism, and this mechanism is with the fine fibre of load filler and strong fiber networking generation " tangling ".

As shown in many tests of having carried out, when the many electrolyte of organic cation of suitable small scale are added in the inorganic crosslinking salting liquid in advance, can as one man obtain in the prior art the acid and alkaline paper-making method of typical case incomparable very high filler keep efficient, no matter it is diluted or concentrated to prepare burden.For example, in furnish solids per ton, directly add 0.25 to 0.37 kilogram of Percol 292 or Hydraid 777 in crosslinked salt (calcium chloride) solution, final filler keeps efficient compared to acid and the alkaline paper-making method is resultant in prior art under conditions of similarity, increases several percentage points.Yet, what deserves to be mentioned is that above-mentioned or similar polymerizer generally is used in traditional papermaking process with significant proportion, generally the consumption of furnish solids per ton approximately is 1 kilogram to 2 kilograms.Moreover, above-mentioned mixing inorganic/the auxiliary down resulting cardboard of the little glue of organic composite functional forms quality and is better than best business standard items known to the applicant all the time greatly.

Papermaking one of most important work that industry faces is the frontier of the high-quality printing paper of exploitation at present, and main fiber is partly replaced by mineral filler in this field.The paper product of latter's kenel, for example filer content surpasses 25%(weight relatively), in the industry cycle be called as " ash-rich " paper.Yet,, carry out customary mass-produced actual techniques progress and still be in the initial stage no matter how obvious the ecology and the economic benefit of ash-rich paper product be.So far the most important reason that obtains obviously success not yet is that paper board strength is in the excessive deterioration of high level of filler, the abrasion performance that conventional filler pigment is quite high, and the cardboard forming quality badness of measuring generation by the colloid chemistry of harshness, must carry out this measurement to guarantee effective flocculation, the filler in the ash-rich paper of reservation and level altitude ratio.In the measurement of these harshnesses most important for the polymerization flocculate that uses big quantity obtaining the fully flocculation of filler grain in the ash-rich batching, and use a high proportion of water-soluble binder to break away from bond with the excess fibre of replenishing the high capacity level of filler and being caused.As well known to the skilled person, the increase level of flocculate relevant with ash-rich batching and binding agent makes the delicate balance complexity of acid and alkaline paper-making method wet end chemistry in the prior art to having surmounted these method purpose performance limitations.As a result, the optical property efficient of the paper web of ash-rich paper product formation quality and filler pigments and cellulose fibre is adversely affected.

Remember that potentiality and peculiar restriction acid and the alkaline paper-making method were inquired into completely in the relevant prior art, extremely can not in a foreseeable future solve many difficulties of producing ash-rich paper with material well known in the prior art and technology.

Yet, be applicable to the novelty of producing the ash-rich paper product and scheme likely is disclosed by papermaking process of the present invention.This a kind of scheme is applicable to produces medium ash-rich paper, and it is to contain nearly 25%(weight) traditional mineral filler pigment and the novel ultra-fine polymer emulsification binding agent of before having discussed.Be scattered in flocculation batching composition inside, final filler paper web drying and hot rolling, the ultra-fine polymer particle is forming little bonding joint (joint) between the filler grain and between indivedual filler grain or the filler aggregation, on the other hand with cellulose fibre.Use papermaking process of the present invention may obtain making the satisfied mechanical strength of people really, it is to contain nearly 25%(weight) go stratification clay, 1-2%(weight) novel ultra-fine polymer emulsification binding agent.

It is 25% to 50%(weight that papermaking process of the present invention also is fit to preparation filler load level) the paper of very ash-rich.Yet the paper for preparing above-mentioned grade need use aforementioned novel functionality filler pigments and ultra-fine polymer emulsification binding agent simultaneously.The filler load is on close level or is surpassed 50%(weight), synthetic microfibril and/or novel cellulosic microfiber (hereinafter will be described in a more detailed discussion) should be used in the papermaking batching.

Above-mentioned novel aggregation filler pigments is by the detailed U.S. patent application case number 07/811 that is disclosed in, and 623(Kaliski) (Low-Refractive-Index Aggregate Pi gment Products) applied for the U.S. on December 23rd, 1991.Patent the 5th, 116,4 No. 18 (" Process for Making Structural Aggregate Pigments ") is reference of the present invention in the lump.Filler pigments mainly be prepared in control polymerization very the fine particle size kaolinic (being commonly referred to the high glaze clay in this skill) and mix other functional component, for example novel ultra-fine polymerization emulsification binding agent, send fiber with minimizing in the paper wadding application facet and take off the bond phenomenon, and/or mixes with synthetic and/or cellulosic microfiber, take off bond and reinforcer reservation efficient to reduce fiber.Filler pigments is very unique qualified on the ash-rich applying filler, even because the optical property efficient of these pigment still can not decay and its rare low abrasion performance characteristic in the highest filler load level, at the Einlehner exerciser seldom near 0.5 milligram.

Novel ultra-fine polymer emulsification binding agent is being considered its mean particle diameter in the unique stability of preparation ash-rich paper and will had gained some understanding after less than 55nm.On the contrary, overwhelming majority's mean particle diameter of being used for the polymer emulsified binding agent (latex) of papermaking industry is about 150 to 200nm.Therefore, under the situation of any bonding amount, adopt the formed little bonding joint of novel ultra-fine polymer emulsification binding agent (relevant) than using traditional latex and have more 60 times at least with single bonding particle.Moreover, as well known to the skilled person, " tree lace " (two s' joint between binding agent) size should be much smaller than the size of joint itself, and as a rule, traditional latex particle size is too big and can't form suitable little binding agent joint of fiber/filler or filler/filler kenel.As finding that in many tests through increasing novel ultra-fine polymer emulsification binding agent to accounting for 2% of paper web weight, paper web intensity is understood remarkable and stable increase, traditional latex then can not obtain the increase of corresponding paper web intensity.

Be worth being two kinds of traditional latexes and novel ultra-fine polymer emulsification binding agent in all actual purpose and being not suitable as the wet end additive of acid and alkaline paper-making method in the prior art proposed above.Because the flocculation mechanism poor efficiency on prior art papermaking process basis, so flocculation that can't any polymer emulsified binding agent is whole in addition, use will cause serious problems in many runnings as wet end additive, the for example obstruction of papermaking machine felt, paper falls the pollution of hair and waste water stream during spreading or the printing.On the contrary, two kinds of commercial latexes and novel ultra-fine polymer emulsification binding agent are implemented the synthetic little glue 100% of composite functional of the present invention then and there and flocculate completely, use this kind binding agent the bad problem of above-mentioned running can not occur as wet end additive.

Use contains previous described aggregation filler pigments, the paper batching of organic look dyestuff and novel ultra-fine polymer emulsification binding agent prepares very ash-rich, super opaque colour coding paper will be confirmed at following example for two-sided high the print table or distinguish public chamber autotype paper of computer of resolving.The opacity of the super opaque paper of prining herein is at least 98.0%, need remove the puzzlement of prining and can penetrate from the high optical density (OD) laser of opposite side.

To obtain an opacity be the significant difficulties that 98% conventional machines spreading cardboard is met with on actual job in order to understand, as long as think about it (xerox) paper of folded three whites " electrostatic printing " that typically are made for office's copy paper or computerized print paper, or folded two colour coding computerized print paper, can always not obtain 98% opacity and just can understand.

The example III

Super opaque, the colour coding handmade paper is to use described program of example I and fiber furnish composition to be prepared, except a Hydraid 777(commercialization polyelectrolyte keeps auxiliary agent) ratio be 0.37 kilogram of furnish solids consumption per ton, it is in the calcium chloride solution that is introduced directly into as crosslinked salt.

Except cellulose fibre, it is that per 100 gram furnish solids have 1.5 gram ultra-fine polymer emulsification binding agents that the batching that is used to prepare handmade paper also contains aforementioned quantity, blue dyes (Vic toria blue), consumption is that per 10 gram furnish solids have 0.075 gram (be equivalent to furnish solids per ton 1 kilogram of dyestuff is arranged), with above-mentioned aggregation filler pigments, its consumption is at least 35% for can obtain a filler load level in final handmade paper.

All mixing that comprise that the batching composition of polymer emulsified burl agent and dyestuff synthesized then and there are inorganic/all even co-coagulation fully of organic compound little glue, and upper strata liquid (filtrate) is clarification and colourless fully.The basis weight of handmade paper be 84.5 the gram/square metre, filler load level is a 35.0%(weight), opacity is 98.0%, brightness is 82.3%, luminosity is 85.0%.This handmade paper possesses the intensity that makes the people satisfied, operability and sound, and the very shallow cyanic colours and the utmost point resemble the most attracting appearance of coated paper.

The superelevation opacity of the handmade paper of above-mentioned very ash-rich makes it may use the laser printing machine at the image of the high optical density (OD) of two-face printing and can not see through another side from tossing about.Moreover, because high brightness and high luminosity, also find the most suitable needs fine definition of handmade paper, high fax, the duplicating of the meticulous halftoning yardstick of high-contrast.

The Hydraid 777 that also uses consumption to equal 0.75 kilogram of furnish solids per ton as the handmade paper of the described similar very ash-rich of above-mentioned example is prepared, and it is that it is added in the batching of the little glue flocculation of all inorganic calcium aluminate silicon that synthesized then and there.Though handmade paper contains identical filer content and optical property with the handmade paper of example III, it is significantly very poor that its cardboard forms quality.The reason that cardboard forms inferior quality is that the polymerization reservation auxiliary agent that adds the batching of flocculating to induces secondary thick flocculation kenel on original very uniform little flocculation kenel.Total result, keep as filler, the optical property of above-mentioned handmade paper (with Hydraid 777 as post processing) or color even still are better than using the acid and resulting similar handmade paper of alkaline method in the prior art, better progress is to utilize papermaking process of the present invention, and wherein auxiliary organic reservation auxiliary agent was introduced directly into calcium chloride solution or corresponding crosslinked salt before the batching flocculation.

Following example is relevant preparation fine grinding wood handmade paper, and its clearer enumerating directly will assist organic polymer reservation auxiliary agent to be added to enforcement inorganic crosslinking salt used in the present invention.

The example IV

A kind of typical fine grinding wood batching of producing newsprint additionally contains a typical low-level mineral filler (mechanical system is removed a layer clay), its by aging a few hours with prepare burden the thus formation quality of handmade paper of preparation of the deterioration of having a mind to.

A batch of news paper handmade paper (being also referred to as main handmade paper) is pressed the program preparation of example I, and except the Percol 292 that uses 0.25 kilogram of furnish solids per ton, it is directly added in the solution of calcium chloride.Two groups of similar contrast handmade papers that use-case I acid papermaking method is prepared from identical aging batching, Percol 2 92 consumptions of first group of contrast handmade paper are 0.5 kilogram of furnish solids per ton, and Percol 292 consumptions of second group of contrast handmade paper are 1 kilogram of furnish solids per ton.

Except the batching of having a mind to wears out, form the deterioration of quality as causing the prepared handmade paper paper web of any existing papermaking process all the time, the feature of main newsprint handmade paper is almost ideal sheet forming quality.In fact, according to applicant's knowledge in one's power, be the sheet forming quality that impossible obtain with preparation experiment chamber in any prior art or commercial method with newsprint.On the contrary, the coarse flocculate that the sheet forming quality of two groups of control group newsprint handmade papers is very poor, loosen collagen fibre block and other be in the clear shortcoming that can see in handmade paper surface, and one penetrate the light sight also in cardboard inside.

As expected, the brightness ratio of the main fine grinding wood cardboard of making at alkali condition (pH about 9.5) is by the made control group cardboard of prior art acid papermaking method brightness low 3%.The reverse of above-mentioned brightness can be by aluminum sulfate in addition partly or all replace and/or add that a pre-stoichiometric acid is reduced to cross linking agent solution or even elimination.

Yet from the standard of total result, still preference is used alkaline paper-making method of the present invention, cooperate directly add fine grinding wood bleach the hydrogen peroxide of habitual ratio prepare burden to newsprint.Through before adding sodium metasilicate and sodium aluminate or simultaneously, add hydrogen peroxide to the newsprint batching, can eliminate the brightness reverse of fine grinding xylon fully.

Can obtain to prove by the brightness of the main newsprint cardboard of example IV even the fact that after aging, still remains unchanged in some potential advantage of the paper of framing news under the alkali condition through segment length's time.On the contrary, the original brighter contrast newsprint cardboard prepared by the acid papermaking method becomes more yellow gradually, and its fragility also increases along with aging carrying out.Should be emphasized that the whole world attempting preparing newsprint under alkali condition always, understand, up to the present do not obtain real success always as yet according to the applicant.

Another kind in previous examples is observed and is revealed out when the consumption of Percol 292 and be increased to 1.0 kilograms from 0.5 kilogram of furnish solids per ton, and control group newsprint cardboard filler keeps efficient and can obtain to improve.Yet, it is to derive from from being synthesized then and there to mix the prepared main newsprint cardboard of batching that the little glue of inorganic/organic composite functional is handled that the highest filler keeps efficient, the consumption of its Percol 292 is that furnish solids per ton has 0.25 kilogram, is directly added in the calcium chloride solution.

Paper, in cardboard and the wet-laying nonwoven batching all particles immediately, but another benefit witness indiscriminate and flocculation fully is block in forming, the fact that the astigmatic efficient of the filler grain aggregation of the three-dimensional configuration of even dispersion is improved greatly.As well known to the skilled person, if can in paper web structure, not form a lot of favourable aggregation configurations on the optics, can not only contain the low-refraction filler and obtain opacity from the example III be 98.0%, weight be 84.5 the gram/square metre cardboard.

Another important benefit of described papermaking process is organic dyestuff and paper, and the particle composition of cardboard and wet-laying nonwoven batching carries out fully and very uniform co-coagulation effect.The cardboard that derives from the example III has high-caliber especially opacity (high opacity be low-refraction filler can not reach), most be the result of peculiar interactional astigmatism and light absorption between all even close inner dispersion filler and the dyestuff.Should be emphasized that also the used entire quantity that quite hangs down colourity Victoria Blue dyestuff of example III is equivalent to batching per ton and has 1 kilogram.Under acid in the prior art and alkaline paper-making method is auxiliary, in order to obtain high-caliber colourity, dye strength is according to exceeding 10 times than example III at least toward example in the batching, and this is not good because of the retention difference of organic dyestuff nearly all in above-mentioned two kinds of methods and flocculation feature.

Rich shade degree paper also can obtain under papermaking process of the present invention is auxiliary, and it is only to increase the ratio of adding dyestuff in the batching to.Can't not cause serious dyestuff loss and incident inevitable serious waste water to flow the similar rich shade degree paper of preparation under the situation about polluting with acidity in the prior art or alkaline paper-making method.Moreover, adopt papermaking process of the present invention to alleviate or even the rich shade degree paper eliminated by the preparation of prior art papermaking process serious strength loss situation takes place, it is high efficiency novel ultra-fine polymer emulsification binding agent and/or novel water-based rubber adhesive to be added in the initial batching reach.

Up to the present, most attracting coloured paper is to derive from the dyestuff that interpolation is filled by ash-rich.The surface of resulting coloured paper particularly after handling through height a kind of jade ray machine (supercale ndering), possesses a unique and very pleasing silk quality outward appearance, can't be duplicated by existing method in any this skill fully.Moreover the uniformity of chromaticity of final products is very perfect, as the uniformity of coloured glass or ceramic tile very much.On the contrary, can very fast being found out by more or less inhomogeneous and two-sided form and aspect of colourity in the main institute of the typical case Colored Paper of papermaking process preparation in the prior art by common people.

Cellulose fibre and filler grain that papermaking process of the present invention also is particularly suitable in carbon black and the paper batching carry out co-coagulation completely.Papermaking at present is more and more ardent to the demand of carbon black, because use very a spot of carbon black just can most economical mode essence increase opacity.Must sacrifice some cardboard brightness to obtain more valuable and the expensive cardboard opacity of cost, the transaction that best brightness exchanges opacity for is to utilize United States Patent (USP) the 5th, the prepared carbon black dispersion of 116, No. 418 (Kal iski) (" Process for Making Structure Aggregate Pigments ") obtains.Said method all is referred to as with " masterbatch " method hereinafter with among claims, thereby might increase the opaque effectiveness of existing goods carbon black dispersion greatly.According to industry experience of the present invention, get the opaque effectiveness of carbon black of planting the dispersion thing since then and exceed 100-150 doubly than the opaque effectiveness of titanium dioxide approximately.The mode that under the masterbatch method is auxiliary another operated commercial carbon black dispersion still can increase above-mentioned opaque effectiveness and reach 20 to 50 times.

For keep whole carbon blacks be fixed in final paper or wet-laying adhesive-bonded fabric (even disengage micro-carbon black in full ppb also can't be accepted by industry), carbon black must with latex or ultra-fine polymer emulsification binding agent, perhaps mix use with the novel water-based rubber adhesive of polymerization superfine emulsification binding agent gained.On the contrary, as well known to the skilled person, the prior art papermaking process can't be reached the flocculation fully and the fixation of carbon black or polymer emulsified binding agent.

Papermaking process of the present invention also can be used to preparation near or even surpass 50%(weight) the printing paper of very ash-rich of filler load level, significantly reduce the basis weight of these paper simultaneously and keep the necessary intensity of cardboard.Keep paper and must plate intensity be the novel ultra-fine polymer emulsification binding agent that adds about 10 microns to the 200 microns synthetic microfibril of 2% weight nearly, length and 1 to 5% weight and/or water-based rubber adhesive in the batching for preparing above-mentioned very ash-rich paper product.

Novel (external) cellulosic microfiber should be distinguished to some extent with the common fine fibre that results from machine finish cellulosic wood oar, fine fibre is the little fiber type that is defined as by 200 meshes (mesh), its draw ratio (aspect ratio) (length diameter group) exceeds 10 to 1000 times than fine fibre, can only be by hereinafter and " effect of stepwise fibrillation " method of following claims indication preparation.According to above-mentioned, preferable derived from cottonizing or the cellulose fibre of fibrillation cellulosic water slurry carry out following continuation method step:

(a) with dry type or wet type mode fiber is prescinded and prevent that follow-up wet type from during refining the length that waterpower is spun (hydraulic spinning) taking place, final length adopts purification apparatus according to furnish solids and subsequent operation and decides;

(b) at the highest practicable solid concentration, for example 30 to 35% weight are carried out the chopped fibres of primary purification from step (a), and are preferable in sodium metasilicate, carry out under Congo red and/or other is inorganic and organic fibrillation potentiator exists the condition;

(c) fiber of extra purification step (c), it is in cintrifugal disintegrator (by the demonstration of existing colloidal grinding factory); With

(d) the fibrillation effect of usefulness Gmolin homogenizer or corresponding equipment completing steps (c), wherein fiber furnish is being compressed under the high pressure very much, the very fast then nozzle that passes through is removed pressure, causes other microfibril that is separated into of residual fibrillation bundle " outburst " formula.

Also the most suitable being used for of the present invention made the advanced wet-laying adhesive-bonded fabric of preparation on the machine one.This modern non-woven fleece as a kind of material of classifying is produced in two continuous program steps, and first step is to adopt wet-laying scheme or the main at present dry type formation scheme of using to come preform not adhere to the fibrous web (seat (mats)) of (unbound).The preform paper web is mainly to be made of synthetic fiber, thereby does not have adhesion strength, must second program step add the binding agent that is fit in the paper web to set up the adhesive joint (joint) between the adjacent fibres.

The main method that desired adhesion strength degree is passed to the preform paper web is to be that latex makes it saturated to reach the nearly binder content of 20% weight with propylene, and is in addition dry then.Another kind method is that quite coarse thermoplastic adhesive powder " is blown into " the preform seat with static in the air with being suspended in, and then will be deposited on the binders between fibers heating and melting.

Know as those skilled in the art, the scheme of above-mentioned preparation adhesive-bonded fabric has many potential shortcomings.At first, wet-laying and the dry type preform velocity ratio that forms non-woven fleece prepare several times slowly of the like fibrous matter paper webs of similar basis weight on paper machine.The second, the fibrage of coarse (not adhering to) nonwoven paper web is quite difficult at the beginning, still can continue deterioration when paper web is handled by reinforced cementitious dose of following one program step.The 3rd, the batching composition owner that preparation wet-laying and dry type form non-woven fleece will be restricted to fiber, has not used useful functional additive in many papermaking batchings.The 4th, be used for adhesion strength is passed to the latex and the thermoplastic powder binding agent of non-woven fleece product, use rather waste.For example, content of latex reaches about 15 to 20%(weight in seat), at first obtain by the sufficient mechanical strength of the saturated non-woven fleece of latex, the effect of powder adhesive is not good.

Above-mentioned use binding agent is rather wasted situation, incorporates adhesive powder into and all binding agent effectively can't be imported strategic locations and make and enter or near the fibre/fibre contact area considering that with the latex wet type saturated and static is assisted, will very fast understanding.As a result, the latex of quite a lot of quantity is being passed through fiber itself under the situation about being used, and similar, the adhesive powder particle of main ratio too far can't form binding agent apart from the fibre/fibre contact area and engage.Some unique problem is also relevant with use dry binder powder, because nearly all very thin powder all is easy to assemble (adhesion) together, its flowing property variation.Moreover according to toward example, very thin particle can be very not fast by electrostatic precipitation.Therefore, the adhesive powder particle diameter must engage needed bigger (for example 20 to 25 microns e.s.d) than set up individual adhesive between quite thin synthetic fiber, and its diameter is typically between 10 and 15 microns.

On the contrary, the method for papermaking of the present invention may prepare the novelty that possesses unique function character and material property and the wet-laying adhesive-bonded fabric of improvement, this be in the prior art preparation non-woven fleece technology can't reach.The related substance feature can be prepared burden with many compositions nonwoven of the particular design of the little glue flocculation of synthetic composite functional then and there, and forms the wet-laying non-woven fleece on a papermaking machine.Above-mentioned many composition batchings may be more diversified and more complicated than the feed that is used for prior art for preparing non-woven fleece technology, it comprises synthetic fiber, synthetic reinforcement microfiber, polymerization emulsification binding agent, the novel propylene that particularly first prerequisite is crossed are ultra-fine polymer emulsification binding agent, novel water-based rubber adhesive, the aqueous liquid dispersion of the fine grain thermoplastic adhesive that preferable particle diameter is about 0.5 micron, organic dyestuff, bioactivator, the above-mentioned functions additive has more detailed description hereinafter.

Though, as understood by the skilled person, can only from finely disseminated fiber furnish, prepare uniform seat, the inefficient flocculation mechanism of prior art papermaking process can't overcome the virtuous modern effect that disperses thing.Therefore, by nonpolar synthetic fiber more or less, it is more inhomogeneous than the paper web (paper) that has remarkable pole filter matter fiber to make that rough (mechanical type) is scattered in the wet-laying non-woven fleece of water-based batching.Moreover existing wet-laying non-woven fleece shaping sheet quality is originally just very poor, makes to be difficult to improve very slow machine speed at present, perhaps uses longer fiber (producing stronger paper web), prepares non-woven fleece.

On the contrary, make us can use good dispersion, highly variation batching constituent, all can in the flocculating batching, produce very uniform micrograined texture based on the strong flocculation mechanism of papermaking process of the present invention.Therefore, can be under using than long fiber and the papermaking machine velocity conditions that significantly improves compared to existing prior art for preparing non-woven fleece technology, the very even wet-laying nonwoven of preform paper web.

The preparation convenience of rough wet-laying non-woven fleece accounts for furnish solids 5%(weight in interpolation) novel ultra-fine polymer breast binding agent and/or declare possess under the novel water-based rubber adhesive of wet sticking (wet-tack) character and obtain to improve greatly.Binding agent and the synthetic then and there little viscose binder of composite functional can be given rough non-woven fleece intensity immediately to a certain degree, protect originally uniform fiber at follow-up latex saturated or be blown into thermoplastic adhesive during do not suffer damage.

Because the main discontinuous deposition that is placed in the little glue of composite functional between the adjacent fibres with tactic of polymer emulsified binding agent and water-based rubber adhesive is by co-coagulation and keep, total binding agent quantity of the binding agent of the saturated or interpolation of follow-up latex has substantial minimizing.Yet, no matter the flocculation fully of all particles, it is unpractical will adding in the batching more than the novel polymeric emulsification binding agent of 5% weight and/or novel water-based rubber adhesive, because excessive viscosity aggregation may cause the pollution of papermaking machine felt in the vehement thing of the non-volume of rough wet-laying.More than Xu Shu logical consequence is, in the tradition second road program step of preparation wet-laying non-woven fleece, as long as the saturated main matchmaker of carrying who provides paper web intensity of latex.

The second road program step of preparation wet-laying non-woven fleece can be omitted when using papermaking process of the present invention fully, and it is that the thermoplastic adhesive powder is directly added in the nonwoven batching.Identical mode is retained in the online rough wet-laying nonwoven paper web of forming screen, uncontaminated papermaking machine felt to the adhesive powder that is used with the aqueous liquid dispersion form of fine particle size on the paper paper web to be retained in common fillers pigment.

Except omitting second program step, the main advantage of such scheme is to obtain preferable comprehensive material and method economic benefit and strategy to go up the preferable fibre/fibre contact area that is placed in of binding agent particle.Relevant economic benefit, as long as consider about 0.5% micron about 125,000 particles of diameter (125,000 little adhesive joint of its potential formation) as long as the adhesive powder particle of 25 microns of diameters just can obtain, with regard to clearly.Moreover, use that quite thin binding agent particle can excessive corase particles is easier to form adhesive joint between quite thin synthetic fiber than using.

Why above-mentioned tactic can take place settle bonding particle and protomere to produce the copolymerization collection, be that minimizing moisture content moves during (drying) because aggregation dewaters with rough wet-laying non-woven fleece.Last water bag (pocket) is restricted in the capillary that forms the fibre/fibre junction in the paper web because dewater, and adhesive joint can form after the paper web that dewaters is heat-treated automatically.

Using another advantage that papermaking process of the present invention prepares the wet-laying non-woven fleece, is organic dyestuff directly to be added in the wet-laying nonwoven batching can meet the non-woven fleece product that economized form obtains color even.Yet, it is important simultaneously novelty ultra-fine acrylic polymer emulsification binding agent and/or water-based rubber adhesive to be added in the batching effectively the fixing of dye is retained in the non-woven fleece.On the other hand, as understood by the skilled person, for making wet-laying non-woven fleece product in the prior art, it is very unpractical flocculating and remaining with organic dye.

Under papermaking process of the present invention auxiliary, from containing finely disseminated synthetic fiber, the reinforcement synthetic microfibril, ultra-fine acrylic polymer emulsification binding agent and/or water-based rubber adhesive and the batching of before having addressed the aqueous liquid dispersion of fine particle size thermoplastic adhesive powder, can prepare attractive, novel and very strong adhesive-bonded fabric.Just allocated according to aforesaid way and to have formed (rough) non-woven fleece (unlike the rough non-woven fleece of prior art) and possess quite high " giving birth to embryo " intensity and (take from the ceramic technology term, refer to not adhere to as yet or have only the rough seat that partly adheres to), can be very fast at the auxiliary lamination down of roller plate (cylinder-board) machine or multiple Fourdrinier machine, produce stronger, the more new non-woven fleece product of purposes is enough to compile paper web one than length with tradition.The wet-laying non-woven fleece is made into before the multilayer materials, and the thermoplastic adhesive powder is sprayed onto on the indivedual rough wet-laying non-woven fleece of the firm formation surface, and the lamination method can be convenient more thus.

Know as those skilled in the art, what be used for wishing most to possess with the non-woven fleece product of Body contact is hydrophobic property, and peculiar biological static(al) or bactericidal property also are many hospitals that are used for, and the used adhesive-bonded fabric of biology laboratory and related application field wishes to possess.According to the prepared the said goods of prior art the time, must be by special, the post processing that separates is passed to adhesive-bonded fabric with above functional character.On the contrary, polarity by little glue, certain peculiar hydrophobic property is by automatically the prepared wet-laying adhesive-bonded fabric under synthetic compound little glue then and there is auxiliary of passing to, and higher hydrophobicity then can directly be added hydrophily anion or non-ionic polymers to wet-laying non-woven fleece batching or be added the hydrophily cationic polymer to calcium chloride or corresponding crosslinked salting liquid and reach.Biological static(al) and/or biological antibiotic character can be added suitable biological static(al) and/or biological antibiotic material in the wet-laying non-woven fleece batching under similar manner, and are passed to the wet-laying adhesive-bonded fabric.

Papermaking process of the present invention also is appropriate to prepare with the batching that comprises the heat resistance inorfil wet-laying non-woven fleece of high temperature resistance especially.In preparation during the said goods, adopt in the time of often favourable polymer emulsified binding agent in batching to improve the living embryo intensity of the non-volume paper web of final rough wet-laying, burn binding agent with sintering processing then.

Papermaking process of the present invention novel electrical conductance of also suitable especially preparation and/or magnetized paper, cardboard and wet-laying adhesive-bonded fabric, it is that metal or ceramic electrical are led the superfine powder (0.2 micron e.s.d is thin for size ratio) of material or pottery or metal (alloy) magnetisable material (aqueous liquid dispersion of super-permalloy (supermalloy) or permalloy (permalloy) for example, to account for furnish solids 0.1% to 20%(activity) weight adds paper to, in cardboard and the wet-laying non-woven fleece.For example, paper is particularly suitable for the antiforge divine force that created the universe with the wet-laying non-woven fleece that contains peculiar deposition Magnaglo, tears not bad banknote (being made by non-woven fleece), and the magnetic reaction of this kind banknote can be detected with cheap desktop detector very fast and very easily.

Papermaking of the present invention (non-woven fleece) method can be used for many-sided actual rolling in the paper operation.In a preferable application scheme, in going to big case way and after entering big case or leaving big case, paper, cardboard or wet-laying nonwoven batching are by synthetic compound little glue flocculation then and there.In order to prepare the paper that contains fine grinding wood, preferable before the strong base solution that adds sodium metasilicate and sodium aluminate (zincate) or simultaneously, hydrogen peroxide is added in the batching.

Best scheme is to use the flocculation that mixing reactor is prepared burden on the line in the continuous mode fully, is undertaken by following consecutive steps:

(a) in the first road program step, continuously indivedual sodium metasilicate and sodium aluminate (sodium zincate or sodium aluminate and sodium zincate mixture) aqueous solution logistics are injected the paper that stirs on the line, cardboard or wet-laying non-woven fleece batching are learned the reaction idiozome hydrosol to form to change a flash then and there;

(b) the continuous aqueous solution in the second road program step with calcium chloride or equal two valencys or multivalence interlinkage salt, selectivity comprises the organic cation reactive compound that has two reactive groups as each molecule of crosslinked salt assitant at least, be added into the batching logistics of step (a), with the crosslinked idiozome hydrosol and the synthetic then and there little viscose binder of composite functional, and paper, cardboard or wet-laying non-woven fleece batching immediately, and is indiscriminate and completely by flocculating;

(c) optionally continuous wash is prepared burden from the flocculation of dissolved contaminants step (b); With

(d) retrieve continuously from step (b) and the batching of flocculation (c), on paper machine, to prepare paper, cardboard or other wet laid product.

In the another kind of scheme of above-mentioned continuation method pattern, the batching logistics at first is divided into two half logistics that separate, and sodium silicate solution is injected into wherein half logistics, sodium aluminate, and the solution of sodium zincate or its mixture is injected into second half logistics.Two and half logistics are mixed in follow-up step station (blender reactor on the line), to form the transition chemical reaction idiozome hydrosol then and there, at the down-stream work station cross-linking agent solution is injected mixing half logistics, to form the little viscose binder of composite functional then and there.

As known to those skilled in the art, the order of the individual programs step of conventional method of the present invention can change as follows: two valencys of step (a) interpolation and/or the crosslinked salt of polyvalent mineral are in feed; Prepare the transient reaction idiozome sodium silicoaluminate or the similar hydrosol in the step (b) respectively; Mix system from step (a) and (b) in the step (c) to form a composite functional calcium aluminate silicon or similar little viscose binder then and there, and will prepare burden immediately, indiscriminate and completely the flocculation, therefore obtaining one is adapted at preparing on the paper machine paper, the media of cardboard or other wet-laying non-woven fleece batching.Yet, this kind program step reversed order is only at paper, the colloidal stability of cardboard or wet-laying non-woven fleece batching add aforementioned prepare respectively the transition chemical reaction idiozome hydrosol before the batching during, can do not damage under the situation of unaffordable stage, just can advise using by the effect of two valencys and/or the crosslinked salt of polyvalent mineral.Though resulting all results of above scheme can be better than in the prior art acid and the alkaline paper-making method is resulting, the idiozome hydrosol in the major programme of the inventive method is to form (in batching) then and there first road step is crosslinked in the second road step then, the obvious prior art that is better than.

Claims

1, a kind of method for preparing paper, cardboard and other wet laid product, it at pH 4.5 to 12.0 scope, by comprising at least a cellulose fibre that is selected from, the aqueous formulations of synthetic organic fibre and inorfil is prepared from, this batching is to handle with the little viscose binder of synthetic then and there compound merit, the ratio that is retained in this product is 0.4% to 10.0% (weight), is to be recorded by ashing method, and this method may further comprise the steps:

(a) mix the chemical reactivity idiozome hydrosol for preparing a transition then and there with two kinds of independent solution by preparing burden, wherein a kind of solution comprises at least a reagent that is selected from alkali silicate and quaternary ammonium silicate, consumption accounts for 0.2% to 5.0% (weight) of furnish solids, another kind of solution comprises at least a alkali metal aluminate and the alkali metal zincate of being selected from, its consumption accounts for 0.2% to 5.0% (weight) of furnish solids, wherein this silicate is to aluminate, and the ratio of zincate or its mixture is 1: 10 to 10: 1 (weight);

(b) mix a kind of aqueous solution and batching from step (a), this aqueous solution comprises and at least aly is selected from two valencys and polyvalent mineral salt constitutes first group crosslinking agent, its consumption accounts for 0.4% to 10.0% (weight) of furnish solids, this aqueous solution comprises that optionally one or more are selected from second group the additive-crosslinking agent that organic cation activity chemistry compound that each molecule has two reactive groups at least is constituted, its consumption accounts for nearly 0.5% (weight) of furnish solids, with the crosslinked transition chemical reactivity idiozome hydrosol of occasion one-tenth and the synthetic then and there little viscose binder of this composite functional of deserving, should prepare burden immediately after mixing, indiscriminate and fully flocculate;

(c) optionally clean the batching of having dissolved this flocculation of pollutant from step (b); With

2, according to the process of claim 1 wherein that described batching comprises that optionally one or more have the material of following special ratios, in furnish solids weight:

(a) filler pigments, content is more than 50%(weight);

(b) illuminating colour, content reach 5.0%(weight);

(c) carbon black is gone cohesionization by the masterbatch method, and content reaches 0.1%(weight);

(d) emulsion binder, mean particle diameter are greater than 70nm, and content reaches 5.0%(weight);

(e) ultra-fine acrylate polymer emulsion binding agent, mean particle diameter are less than 55nm, and vitrification point is-60 ℃ to+20 ℃, and content reaches 5.0%(weight);

(f) moisture acrylic rubber adhesive, content reaches 5.0%(weight);

(g) contain the aqueous dispersion thermoplastic adhesives, content 20.0%(weight);

(h) water-soluble binder, content reach 2.0%(weight);

(i) synthetic microfibril, nearly 2.0%(weight);

(j) cellulosic microfiber, 10 microns to 200 microns of length, from external stepwise fibrillation method preparation, content reaches 2.0%(weight);

3, according to the method for claim 1, the aqueous solution of organic cation activity chemistry compound that wherein each molecule is had at least two reactive groups is as a kind of post processing, makes the described aqueous solution and mixed mutually by the batching of the little viscose binder flocculation of synthetic composite functional then and there.

4, according to the process of claim 1 wherein that at least a concentration of reagent in batching that is selected from sodium metasilicate and potassium silicate and quaternary ammonium silicate is 0.01% to 2.0%(weight).

5, according to the process of claim 1 wherein that at least a concentration of reagent in batching that is selected from sodium aluminate and potassium aluminate and sodium zincate and potassium zincate is 0.01% to 2.0%(weight).

6, use at least a pair of valency or the crosslinked salt of polyvalent mineral according to the process of claim 1 wherein in batching, it is to be selected from water miscible, colourless calcium basically, magnesium, and barium, aluminium, zinc and zirconates, its concentration is 0.02% to 4.0%(weight).

7, according to the method for claim 1, wherein in batching, use at least a each molecule to contain the organic cation activity chemistry compound of two reactive groups at least, it is selected from cationic surfactant, organic metal Louis Vernet compound and cationic polyelectrolyte, its concentration reaches 0.15%(weight).

8, according to the method for claim 2, wherein length is that 10 microns to 200 microns outer system cellulosic microfiber utilizes stepwise microfiber method to be made by cellulose fibre, and this method may further comprise the steps:

(a) fiber is prescinded prevent the follow-up length that the waterpower spinning takes place during refining, final length adopts purification apparatus according to furnish solids and subsequent operation and decides;

(b) high at solid concentration to 35%(weight) time purification step (a) the aqueous solution of chopped fibres;

9, a kind of preparation paper, the method for cardboard and other wet laid product adopts the described aqueous formulations of claim 1, and this method is carried out with continuous mode, comprising:

Step (a) is the logistics of the reagent of two bursts of independent idiozome hydrosols formation to be injected the stirring logistics of the pipeline of this batching respectively, to form the chemical reactivity idiozome hydrosol of transition, wherein a logistics comprises at least a reagent that is selected from alkali silicate and quaternary ammonium silicate, and another kind of logistics comprises at least a reagent that is selected from alkali metal aluminate and alkali metal zincate;

Step (b) is to inject at least a aqueous solution that is selected from first group the crosslinking agent that two valencys and polyvalent mineral salt constituted in the stirring logistics on the pipeline of step (a) batching, this aqueous solution optionally comprises one or more, this crosslinking agent is selected from second group the extra crosslinking agent that organic cation activity chemistry compound that each molecule has two reactive groups at least is constituted, with crosslinked this idiozome hydrosol and the synthetic then and there little viscose binder of this composite functional, this batching immediately, indiscriminate and fully flocculate;

Optionally step (c) is to clean the batching of having dissolved this flocculation of pollutant from step (b); With

Step (d) is to retrieve from step (b) and the batching of flocculation (c), to form paper, cardboard or other wet laid product on a papermaking machine.

10, a kind of method for preparing paper, cardboard and other wet laid product, it is to be 4.5 to 12.0 scope at pH, be selected from cellulose fibre from comprising, the aqueous formulations of synthetic organic fibre and inorfil is prepared from, the little viscose binder of the compound merit that this batching is synthesized is then and there handled, the ratio that is retained in this product is 0.4% to 10.0%(weight), be to record by ashing method, this method may further comprise the steps:

(a) mix a kind of aqueous solution in batching, this aqueous solution comprises at least one crosslinking agent of first group that two valencys and polyvalent mineral salt are constituted that is selected from, its consumption accounts for 0.4% of furnish solids and arrives 10.0%(weight), this aqueous solution optionally comprises at least a second group the extra crosslinking agent that organic cation activity chemistry compound that each molecule has two reactive groups at least is constituted that is selected from, and its consumption accounts for furnish solids to 0.5%(weight);

(b) prepare the chemical reactivity idiozome hydrosol of a transition separately, promptly mix two kinds of solution, wherein a kind ofly comprise at least a reagent that is selected from alkali silicate and quaternary ammonium silicate, consumption accounts for 0.2% of furnish solids and arrives 5.0%(weight), another kind comprises at least a alkali metal aluminate and the alkali metal zincate of being selected from, its consumption accounts for 0.2% of furnish solids and arrives 5.0%(weight), wherein this silicate is to aluminate, and the ratio of zincate or its mixture is 1: 10 to 10: 1;

(c) with the chemical reactivity idiozome hydrosol of the transition of the batching of step (a) and step (b), with the synthetic little viscose binder of composite functional then and there, this is prepared burden immediately, and is indiscriminate and flocculate completely;

(d) optionally clean the batching of having dissolved this flocculation of pollutant from step (c); With