CN1791722A - Method for the treatment of paper surfaces - Google Patents

Abstract

The invention relates to a method for the treatment of paper surfaces.

Description

The method of treatment of paper surfaces

The present invention relates to a kind of method of treatment of paper surfaces, wherein adopt particle (compound particle) the coated paper surface that constitutes by polymer and inoganic solids particulate, the average particle size≤100nm of inoganic solids particulate.

The invention still further relates to a kind of method of treatment of paper surfaces, wherein adopt the aqueous dispersion treatment of paper surfaces, described aqueous dispersion is by mixing acquisition with aqueous polymer dispersion with the dispersion inoganic solids particulate of at least a weight average particle diameter≤100nm.

Paper has extensive use.According to its final use, paper must be able to be easy to write or print (for example write paper, news printing with paper, be used for periodical, catalogue, books or the like), must easily absorb (cotton paper for example, napkin paper, kitchen crepe paper and sanitary paper) or must be very firm, for example under seal paper money paper, the situation of the Holy Bible with paper, brown paper, electric capacity paper or printing paper.

Particularly under the situation of the paper that can write and print and under the situation of very firm paper, often paper surface is carried out extra process thereon to obtain desired properties.Especially, paper surface is adopted paper coating lubrication prescription coating or employing paper sizing material handle.

Paper coating lubrication prescription mainly comprises polymer adhesive, one or more pigment and various other auxiliary agent.By adopting the coating of paper coating lubrication prescription, body paper has obtained to have firm, the level and smooth white surface of improved impressionability.

Adhesive commonly used is generally acrylate or styrene/butadiene copolymers in the paper coating lubrication prescription.Corresponding paper coating lubrication prescription is described in, for example WO97/00776, EP-A1101425 or EP-A1132521.

The paper sizing material is generally unpigmented adhesive, for example starch, protein, rosin size and aqueous polymer dispersion, and particularly be described in, for example the aqueous polymer dispersion that contains starch among EP-A307816, EP-A735065, DE-A3627494 and the DE-A10039388.Because applying glue makes fibre structure be consolidated especially, and therefore resistance to water and writing property and impressionability have been improved.In addition, fixedly pigment and filler better.

The new method that the purpose of this invention is to provide a kind of paper surface modification.

We have found that above-mentioned purpose can reach by the method for when beginning definition.

In this article, paper can be regarded as a kind of material, described material according to DIN 6730 (in August, 1985) for laminar and to comprise basically mainly be the fiber of plant origin and by making the fibrous suspension that contains various auxiliary agents go up draining at net (wire), the fibrofelt compacting that will so obtain then also makes its drying.Used auxiliary agent is filler for example well known by persons skilled in the art, dyestuff, pigment, adhesive, fluorescent whitening agent, retention agent, wetting agent, defoamer, preservative agent, stick-slip controlling agent, plasticizer, antitack agent, antistatic additive, water-repelling agent or the like.For the lamellar material that obtains,, also use term body paper (Substance≤225g/m according to the Substance that is reached ²) or rough cardboard (Substance＞225g/m ²).Another kind of generic term is a cardboard, and its Substance is about 150-600g/m ², comprise body paper and rough cardboard.In order to simplify, following term body paper comprises body paper, rough cardboard and cardboard.

Usually, the form that can use is immediately handled or be translated into to body paper also by coating.The coating paper is interpreted as adopting the moisture coating lubrication prescription single or double coating that mainly comprises pigment and adhesive.Type according to the coating lubrication prescription, the coating layer thickness that obtains or the paper rank of production, for above-mentioned purpose has been used various coating processes, roller coat for example well known by persons skilled in the art, blade coating, air-brush or curtain coating coating process, all there is drying steps the back under each situation.So the paper of handling is called the coating paper.

The another kind of method of handling of paper comprises employing sizing material treatment of paper surfaces.So the paper of handling is called sized paper.

Essential feature is that new method not only is applicable to body paper but also be applicable to coating and sized paper.

In one embodiment, with compound particle with on the form paint paper surface of compound particle aqueous dispersion (method 1).

The aqueous dispersion of compound particle is normally known.They are fluid systems, and described fluid system comprises the polymer drops that is made of the polymer chain that tangles a plurality of, i.e. the particle conduct of polymeric matrix and inoganic solids particulate formation exists with dispersed and distributed and the decentralized photo in aqueous dispersion media.Compound particle typically have a diameter from 30-5000nm.

Compound particle that is compound particle aqueous dispersion form and preparation method thereof is known to those skilled in the art and is disclosed in, US-A3 for example, 544,500, US-A4,421,660, US-A4,608,401, US-A4,981,882, EP-A104498, EP-A505230, EP-A572128, GB-A2227739, WO0118081, WO0129106 and Long etc., University Of Tianjin's journal 4(1991), 10-14, Bourgeat-Lami etc., Die Angewandte MakromolekulareChemie 242(1996), 105-122, Paulke etc., Synthesis Studies of ParamagneticPolystyrene Latex Particles in Scientific and Clinical Applications ofMagnetic Carriers, the 69-76 page or leaf, Plenum Press, New York, 1997, Armes etc., Advanced Materials 11The 5th phase (1995) is among the 408-410.

For example, according to the present invention, also be fit to according to the compound particle aqueous dispersion that is disclosed in the method preparation among the WO03000760.Said method comprise at least a ethylenically unsaturated monomer is dispersed in the aqueous medium and by moisture free-radical emulsion polymerization method make its in the presence of the inoganic solids particulate of at least a dispersion and at least a anion, CATION and non-ionic dispersing agent by means of at least a radical polymerization initiator polymerization.

A) stable aqueous dispersions of at least a inoganic solids of use, the initial solid concentration of described aqueous dispersion is 〉=1 weight %, aqueous dispersion based at least a inoganic solids, the script dispersed solids that is discrete form that after its preparation, still comprised more than 90 weight % in 1 hour, and the diameter that its dispersed solids particle has is≤100nm

B) solids of at least a inoganic solids of Fen Saning have the electrophoretic mobility of non-zero in the standard potassium chloride solution under the pH of its water-containing reacting medium before pH is equivalent to begin to add dispersant,

C) before beginning to add at least a ethylenically unsaturated monomer, at least a anion, CATION and non-ionic dispersing agent are added in the solids aqueous dispersion,

D) add at least a monomer of the 0.01-3 weight % of total amount in the solids aqueous dispersion thereafter and make its be polymerized to conversion ratio at least 90% and

E) then at least a monomer of surplus is added continuously with its wear rate under polymerizing condition.

What be applicable to said method is the inoganic solids particulate that all that forms stable aqueous dispersion, the initial solid concentration that described particulate has is 〉=1 weight %, aqueous dispersion based at least a inoganic solids, in the script dispersed solids that is discrete form that after its preparation, still comprised more than 90 weight % in 1 hour under the situation that does not stir or shake, and diameter≤100nm that the dispersing solid particle of described particulate has, and has in addition the electrophoretic mobility of non-zero under the pH of the water-containing reacting medium before being equivalent to begin to add dispersant.

The quantitative assay of initial solid concentration and the solid concentration after 1 hour and the mensuration of particle diameter realize (about this on the one hand by analytical ultracentrifugation, referring to S.E.Harding etc., AnalyticalUltracentrifugation in Biochemistry and Polymer Science, Royal Society ofChemistry, Cambridge, Great Britain 1992, the 10th chapter, Analysis of PolymerDispersions with an Eight-Cell-AUC-Multiplexer:High Resolution ParticleSize Distribution and Density Gradient Techniques, W.M  chtle, the 147-175 page or leaf).The value of defined is equivalent to d under the situation of particle diameter ₅₀Value.

The method of measuring electrophoretic mobility be to those skilled in the art known (referring to, R.J.Hunter for example, Introduction to Modern Colloid Science, the 8.4th part, the 241-248 page or leaf, Oxford University Press, Oxford, 1993 and K.Oka and K.Furusawa, Electrical Phenomena at Interfaces, Surfactant Science Series, the 76th volume, the 8th part, the 151-232 page or leaf, Marcel Dekker, New York, 1998).The electrophoretic mobility that is dispersed in the solids in the water-containing reacting medium is by the commodity electrophoresis apparatus, and for example the Zetasizer 3000 available from MalvernInstruments Ltd. clings to (definitely) mensuration down at 20 ℃ and 1.For this reason, employing pH is that the potassium chloride solution (standard Klorvess Liquid) of 10 mM volumetric concentrations (mM) of neutrality is about 50-100mg/l with the dilution of solids aqueous dispersion until solid particle concentration.Specimen is adjusted to begins to add the pH that water-containing reacting medium has before the dispersant, use herein by conventional inorganic acid, for example watery hydrochloric acid or nitric acid, or alkali, for example diluted sodium hydroxide solution or potassium hydroxide solution are realized.The migration of dispersed solids particle in electric field by electrophoretic light scattering detect (referring to, for example B.R.Ware and W.H.Flygare, Chem.Phys.Lett. 12(1971), 81-85 page or leaf).The symbol of electrophoretic mobility is by the definition of the migratory direction of dispersed solids particle, if promptly they move to negative electrode, then the electrophoretic mobility of dispersed solids particle is for just, and on the other hand, if they move to anode, then it is for bearing.

The parameter that is suitable for influencing under certain external condition or regulates the electrophoretic mobility of dispersed solids particle is the pH of water-containing reacting medium.By the protonated of dispersed solids particle or remove protonatedly, electrophoretic mobility changed forward, and in alkaline pH scope (pH＞7), electrophoretic mobility is changed on negative sense.The pH scope that is applicable to disclosed method among the WO03000760 is the scope that can carry out the polymerization of free radical aqueous emulsion.Described pH scope is generally pH1-12, is generally pH1.5-11, often is pH2-10.

The pH of water-containing reacting medium can pass through commercial acid, for example watery hydrochloric acid, nitric acid or sulfuric acid, or alkali, and for example dilute sodium hydroxide or potassium hydroxide solution are regulated.Usually advantageously, the part or the total amount that will be used for the consumption of the acid of pH regulator or alkali before at least a inoganic solids particulate joins water-containing reacting medium.

Want part to be for overstating according to the WO033000760 disclosed method, under above-mentioned pH condition, the dispersed solids particle

-have an electrophoretic mobility that has negative sign, at least a ethylenically unsaturated monomer of per 100 weight portions uses 0.01-10, preferred 0.05-5, preferred especially at least a cation dispersing agent of 0.1-3 weight portion, 0.01-100, preferred 0.05-50, preferred especially at least a non-ionic dispersing agent of 0.1-20 weight portion and at least a anionic dispersing agents, the consumption of anionic dispersing agents makes the quantity ratio of equivalent and the equivalent of cation dispersing agent of anionic dispersing agents be higher than 1, or

-have an electrophoretic mobility that has positive sign, at least a ethylenically unsaturated monomer of per 100 weight portions uses 0.01-10, preferred 0.05-5, preferred especially at least a anionic dispersing agents of 0.1-3 weight portion, 0.01-100, preferred 0.05-50, preferred especially at least a non-ionic dispersing agent of 0.01-20 weight portion and at least a anionic dispersing agents, the consumption of cation dispersing agent make the quantity ratio of equivalent and the equivalent of anionic dispersing agents of cation dispersing agent be higher than 1.

The quantity of the equivalent of anionic dispersing agents and the equivalent of cation dispersing agent is that the molal quantity of anionic dispersing agents is than the quantity that multiply by the anionic group that every mole of anionic dispersing agents comprises than being interpreted as looking like, divided by the molal quantity of employed cation dispersing agent, multiply by the quantity of the cation group that every mole of cation dispersing agent comprises.This also is applicable to the equivalent of cation dispersing agent and the quantity ratio of the equivalent of anionic dispersing agents.

The total amount of at least a anion, CATION and the non-ionic dispersing agent that uses according to WO03000760 can at first be put into the solid water dispersion.But, can also at first in the solid water dispersion, only adopt the described dispersant of part and in the process of free-radical emulsion polymerization, add remaining consumption continuously or in batches.But, necessaryly for this method is, according to the electrophoresis symbol of solia particle, before the free-radical emulsion polymerization or during, keep the equivalent of anionic dispersing agents and the quantity ratio of the equivalent of cation dispersing agent.If use the inorganic solid particle have the electrophoretic mobility that has negative sign under above-mentioned pH condition, then the quantity ratio of the equivalent of anionic dispersing agents and the equivalent of cation dispersing agent must be higher than 1 in whole emulsion polymerization process.Adopt corresponding mode, under the situation of the inorganic solid particle with the electrophoretic mobility that has positive sign, the equivalent of cation dispersing agent must be higher than 1 with the quantity ratio of the equivalent of anionic dispersing agents in whole emulsion polymerization process.Advantageously the quantity of above-mentioned equivalent than for 〉=2, 〉=3, 〉=4, 〉=5, 〉=6, 〉=7 or 〉=10, the number of bits of above-mentioned equivalent is 2-5 not advantageously.

The another kind of method of treatment of paper surfaces comprises employing aqueous dispersion treatment of paper surfaces, and described aqueous dispersion is by mixing acquisition (method 2) with aqueous polymer dispersion with the organic solid particulate of the dispersion of at least a weight average particle diameter＜100nm.

Aqueous polymer dispersion is normally known.They are fluid system, and described fluid system comprises the polymer drops that the polymer chain by a plurality of entanglement constitutes, i.e. polymeric matrix or polymer particle are as the decentralized photo that is dispersed in the aqueous dispersion media.Polymer particle typically have a diameter from 10-5000nm.

The preparation example of aqueous polymer dispersion is as realizing by the polymerization of free radical aqueous emulsion.The method of the free radical aqueous emulsion polymerization of ethylenically unsaturated monomer extensively describe and therefore be to those skilled in the art fully known [referring to, Encyclopedia of Polymer Science andEngineering for example, the 8th volume, the 659-677 page or leaf, John Wiley ﹠amp; Sons, Inc., 1987; D.C.Blackley, Emulsion Polymerisation, 155-465 page or leaf, Applied SciencePublishers, Ltd., Essex, 1975; D.C.Blackley, Polymer Latices, the 2nd edition, the 1st volume, 33-415 page or leaf, Chapman ﹠amp; Hall, 1997; H.Warson, The Applications ofSynthetic Resin Emulsions, 49-244 page or leaf, Ernest Benn, Ltd., London, 1972; D.Diederich, Chemie in unserer Zeit 24(1990), 135-142 page or leaf, Verlag Chemie, Weinheim; J.Piirma, Emulsion Polymerisation, 1-287 page or leaf, Academic Press, 1982; E.H lscher, Dispersionensynthetischer Hochpolymerer, the 1-160 page or leaf, Springer-Verlag, Berlin, 1969 and DE-A4003422].It makes their polymerizations by in the presence of dispersant ethylenically unsaturated monomer being dispersed in the aqueous medium and by means of at least a radical polymerization initiator usually.Disclosed method is different from and only is there is at least a inoganic solids particulate in addition outside the said method and uses specific dispersant combination that in polymerization process described inoganic solids particulate has the electrophoretic mobility of non-zero among the WO03000760.

Metal, metallic compound, for example metal oxide and slaine, and semimetal and nonmetallic compound are the inoganic solids particulates that is fit to, described inoganic solids particulate can be used for two kinds of said new method.Precious metal colloid, for example palladium, silver, ruthenium, platinum, gold and rhodium and the alloy that contains them can be used as the metal fine-powder.The example of metal oxide is that the titanium dioxide that is amorphous and/or is its various crystal modification forms is (for example as Hombitec ^Series of products are commercially available from SachtlebenChemie GmbH), zirconia (IV), tin oxide (II), tin oxide (IV) be (for example, as Nyacol ^The SN series of products are commercially available from Akzo-Nobel), aluminium oxide is (for example, as Nyacol ^The AL series of products are commercially available from Akzo-Nobel), barium monoxide, magnesia, various ferriferous oxide, for example iron oxide (II) (wustite), iron oxide (III) (bloodstone) and iron oxide (II/III) (magnetic iron ore), chromium oxide (III), antimony oxide (III), bismuth oxide (III), zinc oxide are (for example, as Sachtotec ^Series of products are commercially available from Sachtleben Chemie GmbH), nickel oxide (II), nickel oxide (III), cobalt oxide (II), cobalt oxide (III), cupric oxide (II), yittrium oxide (III) be (for example, as Nyacol ^The YTTRIA series of products are commercially available from Akzo-Nobel), cerium oxide (IV) is (for example, as Nyacol ^The CEO2 series of products are commercially available from Akzo-Nobel), it is amorphous and/or is its different crystal modified form, with and hydrous oxide, for example hydrous titanium oxide (IV), hydrous zirconium oxide(HZO) (IV), hydrated alumina are (for example, as Disperal ^Series of products are commercially available from Condea-Chemie GmbH) and hydrated ferric oxide (III).The slaine that can in new method, use following amorphous metal salt and exist in principle: sulfide with its different crystal structure, as iron sulfide (II), iron sulfide (III), ferrous disulfide (II) (pyrite), artificial gold (II), artificial gold (IV), mercuric sulphide (II), cadmium sulfide (II), zinc sulphide, copper sulfide (II), silver sulfide, nickel sulfide (II), cobalt sulfide (II), cobalt sulfide (III), manganese sulfide (II), chromic sulfide (III), titanium sulfide (II), titanium sulfide (III), titanium sulfide (IV), sulfuration zirconium (IV), antimony trisulfide (III) and bismuth sulfide (II), hydroxide, as stannic hydroxide (II), aluminium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, iron hydroxide (II) and iron hydroxide (III), sulfate, as calcium sulfate, strontium sulfate, barium sulfate and lead sulfate (IV), carbonate, as lithium carbonate, magnesium carbonate, calcium carbonate, zinc carbonate, zirconium carbonate (IV), ferric carbonate (II) and ferric carbonate (III), orthophosphates, as the orthophosphoric acid lithium, tricalcium orthophosphate, zinc orthophosphate, magnesium orthophosphate, aluminum orthophoshpate, orthophosphoric acid tin (III), ferric orthophosphate (II) and ferric orthophosphate (III), metaphosphate, as lithium metaphosphate, calcium metaphosphate and aluminium metaphosphate, pyrophosphate, as magnesium pyrophosphate, calcium pyrophosphate, zinc pyrophosphate, ferric pyrophosphate (III) and stannous pyrophosphate (II), ammonium phosphate, as ammonium magnesium phosphate and zinc ammonium phosphate, phosphate rock [Ca ₅{ (PO ₄) ₃OH}], orthosilicate, as positive lithium metasilicate, calcium orthosilicate/magnesium, positive alumina silicate, fayalite (II), fayalite (III) and positive magnesium silicate, positive zinc silicate, positive zirconium silicate (III) and positive zirconium silicate (IV), metasilicate, as lithium metasilicate, calcium metasilicate/magnesium, calcium metasilicate, metasilicic acid magnesium and zinc metasilicate, phyllosilicate is as sodium aluminium silicate and sodium metasilicate magnesium, particularly be from the delamination form, for example Optigel ^SH (available from the series of products of Sudchemie AG), Saponit ^SKS-20 and Hektorit ^SKS21 (available from the series of products of Hoeschst AG) and Laponite ^RD and Laponite ^GS (available from the series of products of Laporte Industries Ltd.), aluminate is as lithium aluminate, calcium aluminate and zinc aluminate, borate, as magnesium metaborate and magnesium orthoborate, oxalates is as calcium oxalate, oxalic acid zirconium (IV), magnesium oxalate, zinc oxalate and oxalic acid aluminium, tartrate, as calcium tartrate, acetylacetonate is as acetylacetonate aluminium and acetylacetonate iron (III), salicylate, as salumin, citrate is as calcium citrate, ironic citrate (II) and zinc citrate, palmitate, as aluminum palmitate, calcium palmitate and magnesium palmitate, stearate is as aluminum stearate, calcium stearate, dolomol and zinc stearate, laruate, as calcium laurate, linoleate is as calcium linoleate, oleate is as calcium oleate, iron oleate (II) or zinc oleate.

As important semi metallic compound that can be used according to the invention, what can mention is amorphous silica and/or the silica that exists with different crystal version.

The silica that is fit to according to the present invention is commercially available and can be for example as Aerosil ^(available from the series of products of Degussa AG), Levasil ^(available from the series of products of Bayer AG) Ludox ^(available from the series of products of DuPont), Nyacol ^And Bindzil ^(available from the series of products of Akzo-Nobel) and Snowtex ^(available from Nissan Chemical industries, the series of products of Ltd.) obtain.The nonmetallic compound that is fit to according to the present invention is for example aquadag or diamond.

Particularly suitable inoganic solids particulate be under 20 ℃ and 1 crust (definitely) in water its solubility≤1, preferably≤0.1, particularly≤those of 0.01g/l.Be preferably selected from the compound of silica, aluminium oxide, tin oxide (IV), yittrium oxide (III), cerium oxide (IV), hydrated alumina, calcium carbonate, magnesium carbonate, tricalcium orthophosphate, magnesium orthophosphate, calcium metaphosphate, magnesium metaphosphorate, calcium pyrophosphate, magnesium pyrophosphate, iron oxide (II), iron oxide (III), iron oxide (II/III), titanium dioxide, phosphate rock, zinc oxide and zinc sulphide especially.The silicon dioxide gel that especially preferably has the electrophoretic mobility that has negative sign.

In new method, can also advantageously use commercially available compd A erosil ^, Levasil ^, Ludox ^, Nyacol ^And Bindzil ^Series of products (silica), Disperal ^Series of products (hydrated alumina), Nyacol ^AL series of products (aluminium oxide), Hombitec ^Series of products (titanium dioxide), Nyacol ^SN series of products (tin oxide (IV)), Nyacol ^YTTRIA series of products (yittrium oxide (III)), Nyacol ^CEO2 series of products (cerium oxide (IV)) and Sachtotec ^Series of products (zinc oxide).

Operable inoganic solids particulate makes and is dispersed in particle diameter≤100nm that the solids in the water-containing reacting medium have in new method.Can successfully use particle diameter that its dispersed particle has for 〉=0nm but≤90nm ,≤80nm ,≤70nm ,≤60nm ,≤50nm ,≤40nm ,≤30nm ,≤20nm or≤those inoganic solids particulates of 10nm and all medians thereof.Advantageously use the inoganic solids particulate of particle diameter≤50nm.Particle diameter operational analysis supercentrifugation is measured.

Solia particle in principle by method known to those skilled in the art and for example the precipitation reaction by in gas phase or chemical reaction obtain (referring to E.Matijevic, Chem.Mater.5 (1993), 412-426 page or leaf; Ullmann ' s Encyclopedia of Industrial Chemistry, A23 volume, 583-660 page or leaf, Verlag Chemie, Weinheim, 1992; D.E.Evans, H.Wennerstr m, The Colloidal Domain, 363-405 page or leaf, Verlag Chemie, Weinheim, 1994 and R.J.Hunter, Foundations of Colloid Science, the 1st volume, the 10-17 page or leaf, Clarendon Press, Oxford, 1991).

The directly preparation or in the process of synthesizing inorganic solia particle in aqueous medium usually of stable solid dispersions by the inoganic solids microparticulate is prepared in aqueous medium.According to the method for preparing the inoganic solids particulate, said method or directly, for example under the situation of precipitation or pyrogenic silica, aluminium oxide etc., or by means of suitable additional device, for example disperser or sonotrode are realized.

But, what be fit to according to the present invention only is those inoganic solids particulates, described inoganic solids particulate its preparation after 1 hour or since the stirring or shake settle solids after, under the situation that does not further stir or shake, aqueous dispersion based on the inoganic solids particulate, solid water dispersion with initial solid concentration 〉=1 weight % still contains the script dispersed solids that is discrete form more than 90 weight %, and the diameter that its dispersing solid particle has is≤100nm.It is initial that solid concentration≤60 weight % are common.But, advantageously can also use initial solid concentration≤55 ,≤50 ,≤45 ,≤40 ,≤35 ,≤30 ,≤25 ,≤20 ,≤15 or≤10 weight % and 〉=2, 〉=3, 〉=4 or 〉=5 weight % and all medians thereof, under each situation all based on the aqueous dispersion of inoganic solids particulate.According to the present invention, at least a ethylenically unsaturated monomer of per 100 weight portions (method 1) or 100 weight portion polymer dispersions (method 2) use 1-1000 in the preparation of compound particle aqueous dispersion, general 5-300, at least a inoganic solids particulate of 10-200 weight portion usually.

In the process of preparation compound particle aqueous dispersion and in the process of preparation aqueous polymer dispersion and with its with process that inoganic solids mixes in, have dispersant, described dispersant makes the mixture of the compound particle of inoganic solids particulate and monomer droplet and formation or polymer particle and inoganic solids be dispersed in aqueous phase and the stability of the aqueous dispersion therefore having guaranteed to be produced.The dispersion of a great deal of is protecting colloid and the emulsifying agent that is generally used for carrying out the polymerization of free radical aqueous emulsion.

The detailed description of the protecting colloid that is fit to is published in Houben-Weyl, Mothoden derorganischen Chemie, and the XIV/1 volume, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart is in 1961, the 411-420 pages or leaves.

The neutral protecting colloid that is fit to is, for example polyvinyl alcohol, poly alkylene glycol, cellulose derivative, starch derivatives and gelatine derivative.

The anion protecting colloid that is fit to; it is the protecting colloid that its dispersing component has at least one negative electrical charge; be; for example polyacrylic acid and polymethylacrylic acid and alkali metal salt thereof, contain copolymer and the alkali metal salt and the high-molecular weight compounds of acrylic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid, 4-benzene sulfonic acid and/or maleic anhydride; as polystyrene, the alkali metal salt of sulfonic acid.

The CATION protecting colloid that is fit to; be that the protecting colloid that its dispersing component has at least one positive charge is, for example contain N-vinyl pyrrolidone, N-caprolactam, N-vinylcarbazole, 1-vinyl imidazole, 2-vinyl imidazole, 2-vinylpyridine, 4-vinylpridine, acrylamide, Methacrylamide, protonated and/or alkylating homopolymers and the copolymer that has the derivative of amino acrylate, methacrylate, acrylamide and/or Methacrylamide on nitrogen.

Certainly, can also use the mixture of emulsifying agent and/or protecting colloid.Usually, use on the contrary with protecting colloid, relative molecular weight is usually less than 1500 emulsifier special as dispersant.Certainly, under the situation of the mixture that uses surface-active property, each component must be compatible with each other, and it can detect by several preliminary tests under uncertain situation.The summary of the emulsifying agent that is fit to is published in Houben-Weyl, Mothoden der organischen Chemie, and the XIV/1 volume, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart is in 1961, the 192-208 pages or leaves.

Conventional nonionic emulsifier is, for example ethoxylation monoalkyl, dialkyl group and trialkyl phenol (degree of ethoxylation: 3-50, alkyl: C ₄-C ₁₂) and ethoxylized fatty alcohol (ethoxylation degree degree: 3-80; Alkyl: C ₈-C ₃₆).The example is the Lutensol available from BASF AG ^A series of products (C ₁₂C ₁₄-alcohol ethoxylate, degree of ethoxylation: 3-8), Lutensol ^AO series of products (C ₁₃C ₁₅-oxo alcohol ethoxylate, degree of ethoxylation: 3-30), Lutensol ^AT series of products (C ₁₆C ₁₈-alcohol ethoxylate, degree of ethoxylation: 11-80), Lutenso ^ON series of products (C ₁₀-oxo alcohol ethoxylate, degree of ethoxylation: 3-11) and Lutensol ^TO series of products (C ₁₃-oxo alcohol ethoxylate, degree of ethoxylation: 3-20).

Conventional anion emulsifier is, for example the alkali metal of alkyl sulfonic acid and ammonium salt (alkyl: C ₈-C ₁₂), ethoxylation alkanol (degree of ethoxylation: 4-30, alkyl: C ₁₂-C ₁₈) and ethoxylated alkylphenol (degree of ethoxylation: 3-50, alkyl: C ₄-C ₁₂) the alkali metal of sulfuric acid monoester and ammonium salt, alkyl sulfonic acid (alkyl: C ₁₂-C ₁₈) and alkarylsulphonic acid (alkyl: C ₉-C ₁₈).

The compound that has also proved following formula I is another kind of anion emulsifier,

R wherein ¹And R ²Be H or C ₄--C ₂₄-alkyl and be not H simultaneously, and A and B can be alkali metal ion and/or ammonium ion.In formula I, R ¹And R ²Be preferably 6-18, the particularly alkyl of the straight chain of 6,12 or 16 carbon atoms or branching or H, R ¹And R ²Be not H simultaneously.A and B are preferably sodium, potassium or ammonium, preferred especially sodium.Particularly advantageous is that wherein A and B are sodium, R ¹Be branched-alkyl and R with 12 carbon atoms ²For-H or R ¹Compound I.Usually use and contain 50-90 weight % monoalkylation product, as Dowfax ^The cuts of 2A1 (brand of Dow ChemicalCompany).Compound I is for example known from US-A 4269749 usually and is commercially available.

The cationic emulsifier that is fit to is generally has C ₆--C ₁₈-alkyl, C ₆--C ₁₈-aralkyl or heterocyclic group primary, secondary, uncle or quaternary ammonium salt, alkanol ammonium salt, pyridiniujm, imidazoline salt, oh salt, quinolinium, isoquinolin salt, salt, sulfonium salt and the phosphonium salt of azoles quinoline salt, alkylbenzyldimethylasaltsum saltsum, thiazoline salt and amine oxide.Example is acetic acid dodecyl ammonium or corresponding hydrochloride, multiple 2-(N, N, the N-trimethyl ammonium) chloride of ethyl alkanoate or acetate, N-cetyl pyridinium chloride, N-lauryl pyridine sulfate and N-cetyl-N, N, N-trimethyl ammonium bromide, N-dodecyl-N, N, N-trimethyl ammonium bromide, N-octyl group-N, N, N-trimethyl ammonium bromide, N, N-distearyl-N, N-alkyl dimethyl ammonium chloride bromide and Gemini surfactant N, N '-(lauryl dimethyl) ethylenediamine dibromide.Many other examples are published in H.Stache, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981 and McCutcheon ' s, Emulsifiers﹠amp; Detergents, MC Publishing Company, Glen Rock is in 1989.

Operable aqueous dispersion generally contains 0.1-10 according to the present invention in method 1 and 2, common 0.5-7.0, the frequent dispersant of 1.0-5.0 weight %, under each situation all based on aqueous dispersion.The preferred emulsifying agent that uses.

Wherein, the suitable ethylenically unsaturated monomer that is used for preparation operable compound particle (method 1) and polymer dispersion (method 2) used according to the invention according to the present invention is, especially, can adopt straightforward procedure to carry out the monomer of radical polymerization, as ethene, vi-ny l aromatic monomers, as styrene, α-Jia Jibenyixi, chloro styrene or vinyltoluene, the monocarboxylic acid of 1-18 carbon atom and the ester of vinyl alcohol, as vinylacetate, propionate, vinyl propionate, vinyl laurate and stearic acid vinyl ester, the α that preferably has 3-6 carbon atom, β-monoene belongs to unsaturated monoacid and binary acid, acrylic acid particularly, methacrylic acid, maleic acid, fumaric acid and itaconic acid and 1-12 normally, preferred 1-8, the ester of the alkanol of 1-4 carbon atom particularly, the methyl esters of acrylic acid and methacrylic acid particularly, ethyl ester, positive butyl ester, isobutyl ester and 2-ethylhexyl, dimethyl maleate or n-butyl maleate, α, the nitrile of β-monoethylenically unsaturated carboxylic acid, as acrylonitrile, with conjugation C4-8-diene, as 1,3-butadiene and isoprene.Above-mentioned monomer be generally the amount that often accounts for together based on the total amount for the treatment of the monomer of polymerization by new method for 〉=50, 〉=80 or 〉=principal monomer of 90 weight %.Generally speaking, above-mentioned monomer only has moderate in low solubility under standard conditions [20 ℃, 1 crust (definitely)] in water.

Usually the monomer of the internal intensity of the film of raising polymeric matrix often has at least one epoxy radicals, hydroxyl, N-methylol or carbonyl, or at least two non-conjugated ethylenical unsaturated double bonds.The example is monomer with two vinyl, have the monomer of two ethenylidenes and have the monomer of two alkenyls.Particularly advantageous is dihydroxylic alcohols and α, and β-monoene belongs to the diester of unsaturated monoacid (wherein preferred acrylic acid and methacrylic acid).Example with above-mentioned monomer of two non-conjugated ethylenical unsaturated double bonds is aklylene glycol diacrylate and dimethylacrylate, as glycol diacrylate, 1, the 2-propylene glycol diacrylate, 1, the ammediol diacrylate, 1, the 3-butanediol diacrylate, 1,4-butanediol diacrylate and ethylene glycol dimethacrylate, 1,2-propylene glycol dimethylacrylate, 1, the ammediol dimethylacrylate, 1,3-butanediol dimethylacrylate or 1,4-butanediol dimethylacrylate, and divinylbenzene, the metering system vinyl acetate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, methylene diacrylamine, acrylic acid cyclopentadienyl group ester, triallyl cyanurate or triallyl isocyanurate.C particularly importantly also in this ₁-C ₈-hydroxyalkyl methacrylates and acrylate are as the positive hydroxyethyl ester of acrylic acid and methacrylic acid, positive hydroxypropyl ester or positive hydroxyl butyl ester and compound such as diacetone acrylamide and acetoacetoxy groups ethyl propylene acid esters or methacrylate.According to the present invention, above-mentioned monomer is with based on the monomer total amount for the treatment of polymerization, and consumption is up to the form of the polymerized unit of 5 weight % to be introduced.

Can also choose wantonly and use the monomer that contains siloxane group, as vinyl trialkyl oxysilane such as vinyltrimethoxy silane, alkyl vinyl dialkoxy silicane, acryloxyalkyl trialkoxy silane or methacryloxy alkyltrialkoxysilaneand are as acryloxy ethyl trimethoxy silane, methacryloxyethyl trimethoxy silane, acryloxy propyl trimethoxy silicane or methacryloxypropyl trimethoxy silane.Above-mentioned monomer with under each situation all based on the monomer total amount, being up to 2,0.01-1 usually, often the amount of 0.05-0.5 weight % is used.

Can use in addition the ethylenically unsaturated monomer B that contains at least one acidic group and/or its corresponding anionic ethylenically unsaturated monomer A or contain at least one amino, amide groups, urea groups or N-heterocyclic radical and/or its on nitrogen protonated or alkylating ammonium derivative as monomer.The consumption of monomer A or monomers B is up to 10, common 0.1-7, and frequent 0.2-5 weight % is based on the monomer total amount.

The ethylenically unsaturated monomer that will have at least one acidic group is as monomer A.Acidic group can be, for example carboxyl, sulfo group, sulfuric acid, phosphoric acid and/or phosphonyl group.The example of monomer A is the phosphate monoester of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 4-styrene sulfonic acid, 2-methacryloxy ethyl sulfonic acid, vinyl sulfonic acid and vinyl phosphonate and positive hydroxy alkyl ester of acrylic acid and the positive hydroxy alkyl ester of methacrylic acid, as the phosphate monoester of hydroxyethyl acrylate, the positive hydroxypropyl ester of acrylic acid, the positive hydroxyl butyl ester of acrylic acid and methacrylic acid hydroxyethyl ester, the positive hydroxypropyl ester of methacrylic acid and the positive hydroxyl butyl ester of methacrylic acid.But,, can also use the ammonium and the alkali metal salt of above-mentioned ethylenically unsaturated monomer with at least one acidic group according to the present invention.Sodium and potassium are particularly preferred as alkali metal.Herein, example is an ammonium and two ammoniums, a sodium and disodium and the potassium and the di-potassium of the phosphate monoester of ammonium, sodium and the sylvite of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 4-styrene sulfonic acid, 2-methacryloxy ethyl sulfonic acid, vinyl sulfonic acid and vinyl phosphonate and hydroxyethyl acrylate, the positive hydroxypropyl ester of acrylic acid, the positive hydroxyl butyl ester of acrylic acid and methacrylic acid hydroxyethyl ester, the positive hydroxypropyl ester of methacrylic acid or the positive hydroxyl butyl ester of methacrylic acid.

Preferred acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 4-styrene sulfonic acid, 2-methacryloxy ethyl sulfonic acid, vinyl sulfonic acid and the vinyl phosphonate of using.

To contain the ethylenically unsaturated monomer of at least one amino, amide groups, urea groups or N-heterocyclic radical and/or its on nitrogen protonated or alkylating ammonium derivative as monomers B.

The example that contains at least one amino monomers B is an acrylic acid 2-amino-ethyl ester, methacrylic acid 2-amino-ethyl ester, acrylic acid 3-aminopropyl ester, methacrylic acid 3-aminopropyl ester, the amino n-butyl of acrylic acid 4-, the amino n-butyl of methacrylic acid 4-, acrylic acid 2-(N-methylamino) ethyl ester, methacrylic acid 2-(N-methylamino) ethyl ester, acrylic acid 2-(N-ethylamino) ethyl ester, methacrylic acid 2-(N-ethylamino) ethyl ester, acrylic acid 2-(N-n-pro-pyl amino) ethyl ester, methacrylic acid 2-(N-n-pro-pyl amino) ethyl ester, acrylic acid 2-(N-isopropyl amino) ethyl ester, methacrylic acid 2-(N-isopropyl amino) ethyl ester, acrylic acid 2-(N-tert-butyl group amino) ethyl ester, methacrylic acid 2-(N-tert-butyl group amino) ethyl ester is (for example, as Norsocryl ^TBAEMA is commercially available from Elf Atochem), acrylic acid 2-(N, N-dimethylamino) ethyl ester is (for example, as Norsocryl ^ADAME is commercially available from Elf Atochem), methacrylic acid 2-(N, N-dimethylamino) ethyl ester is (for example, as Norsocryl ^MADAME is commercially available from Elf Atochem), acrylic acid 2-(N, the N-diethylamino) ethyl ester, methacrylic acid 2-(N, the N-diethylamino) ethyl ester, acrylic acid 2-(N, N-di amino) ethyl ester, methacrylic acid 2-(N, N-di amino) ethyl ester, acrylic acid 2-(N, the N-diisopropylaminoethyl) ethyl ester, methacrylic acid 2-(N, the N-diisopropylaminoethyl) ethyl ester, acrylic acid 3-(N-methylamino) propyl diester, 3-(N-methylamino) propyl diester, acrylic acid 3-(N-ethylamino) propyl diester, methacrylic acid 3-(N-ethylamino) propyl diester, acrylic acid 3-(N-n-pro-pyl amino) propyl diester, methacrylic acid 3-(N-n-pro-pyl amino) propyl diester, acrylic acid 3-(N-isopropyl amino) propyl diester, methacrylic acid 3-(N-isopropyl amino) propyl diester, acrylic acid 3-(N-tert-butyl group amino) propyl diester, methacrylic acid 3-(N-tert-butyl group amino) propyl diester, acrylic acid 3-(N, the N-dimethylamino) propyl diester, methacrylic acid 3-(N, the N-dimethylamino) propyl diester, acrylic acid 3-(N, the N-diethylamino) propyl diester, methacrylic acid 3-(N, the N-diethylamino) propyl diester, acrylic acid 3-(N, N-di amino) propyl diester, methacrylic acid 3-(N, N-di amino) propyl diester, acrylic acid 3-(N, the N-diisopropylaminoethyl) propyl diester and methacrylic acid 3-(N, N-isopropyl amino) propyl diester.

The example that contains the monomers B of at least one amide groups is an acrylamide, Methacrylamide, N methacrylamide, N-methyl acrylamide, the N-ethyl acrylamide, N-ethyl-methyl acrylamide, N-n-pro-pyl acrylamide, N-n-pro-pyl Methacrylamide, the N-N-isopropylacrylamide, N-isopropyl methyl acrylamide, N tert butyl acrylamide, N-tert-butyl group Methacrylamide, N, the N-DMAA, N, the N-dimethylmethacryl amide, N, N-diethyl acrylamide, N, N-diethylmethyl acrylamide, N, N-di acrylamide, N, N-di Methacrylamide, N, N-diisopropyl acrylamide, N, N-diisopropyl Methacrylamide, N, N-di-n-butyl acrylamide, N, N-di-n-butyl Methacrylamide, N-(3-N ', N '-dimethylaminopropyl) Methacrylamide, diacetone acrylamide, N, N '-methylene diacrylamine, N-(diphenyl methyl) acrylamide, N-cyclohexyl acrylamide and N-vinyl pyrrolidone and N-caprolactam.

The example that contains the monomers B of at least one urea groups is N, and N '-divinyl ethylidene-urea and methacrylic acid 2-(1-imidazoline-2-ketone group) ethyl ester is (for example, as Norsocryl ^100 is commercially available from Elf Atochem).

The example that contains the monomers B of at least one N-heterocyclic radical is 2-vinylpyridine, 4-vinylpridine, 1-vinyl imidazole, 2-vinyl imidazole and N-vinylcarbazole.

The following compound of preferred use: 2-vinylpyridine, 4-vinylpridine, 2-vinyl imidazole, acrylic acid 2-(N, the N-dimethylamino) ethyl ester, methacrylic acid 2-(N, the N-dimethylamino) ethyl ester, ethylacrylic acid 2-(N, the N-diethylamino) ester, methacrylic acid 2-(N, the N-diethylamino) ethyl ester, methacrylic acid 2-(N-tert-butyl group amino) ethyl ester, N-(3-N ', N '-dimethylaminopropyl) Methacrylamide and methacrylic acid 2-(1-imidazoline-2-ketone group) ethyl ester.

According to the pH of water-containing reacting medium, part or all of above-mentioned nitrogen containing monomer B can exist with quaternary ammonium form protonated on nitrogen.

The example that has the monomers B of season alkylammonium structure on nitrogen is that 2-(N, N, N-trimethyl ammonium) ethyl propylene acid esters chloride is (for example, as Norsocryl ^ADAMQUAT MC 80 is commercially available from Elf Atochem), methacrylic acid 2-(N, N, N-trimethyl ammonium) ethyl ester chloride is (for example, as Norsocryl ^MADQUAT MC 75 is commercially available from Elf Atochem), acrylic acid 2-(N-methyl-N, the N-diethyl ammonium) ethyl ester chloride, methacrylic acid 2-(N-methyl-N, the N-diethyl ammonium) ethyl ester chloride, acrylic acid 2-(N-methyl-N, the N-dipropylammonium) ethyl ester chloride, methacrylic acid 2-(N-methyl-N, the N-dipropylammonium) ethyl ester chloride, acrylic acid 2-(N-benzyl-N, the N-Dimethyl Ammonium) the ethyl ester chloride is (for example, as Norsocryl ^ADAMQUAT BZ 80 is commercially available from ElfAtochem), methacrylic acid 2-(N-benzyl-N, N-diethyl ammonium) ethyl ester chloride is (for example, as Norsocryl ^MADQUAT BZ 75 is commercially available from ElfAtochem), acrylic acid 2-(N-benzyl-N, the N-diethyl ammonium) ethyl ester chloride, methacrylic acid 2-(N-benzyl-N, the N-diethyl ammonium) ethyl ester chloride, acrylic acid 2-(N-benzyl-N, the N-dipropylammonium) ethyl ester chloride, methacrylic acid 2-(N-benzyl-N, the N-dipropylammonium) ethyl ester chloride, acrylic acid 3-(N, N, the N-trimethyl ammonium) propyl diester chloride, methacrylic acid 3-(N, N, the N-trimethyl ammonium) propyl diester chloride, acrylic acid 3-(N-methyl-N, the N-diethyl ammonium) propyl diester chloride, methacrylic acid 3-(N-methyl-N, the N-diethyl ammonium) propyl diester chloride, acrylic acid 3-(N-methyl-N, the N-dipropylammonium) propyl diester chloride, methacrylic acid 3-(N-methyl-N, the N-dipropylammonium) propyl diester chloride, acrylic acid 3-(N-benzyl-N, the N-Dimethyl Ammonium) propyl diester chloride, methacrylic acid 3-(N-benzyl-N, the N-Dimethyl Ammonium) propyl diester chloride, acrylic acid 3-(N-benzyl-N, the N-diethyl ammonium) propyl diester chloride, methacrylic acid 3-(N-benzyl-N, the N-diethyl ammonium) propyl diester chloride, acrylic acid 3-(N-benzyl-N, the N-dipropylammonium) propyl diester chloride and methacrylic acid 3-(N-benzyl-N, N-dipropylammonium) propyl diester chloride.Certainly, can also use corresponding bromide and sulfate to replace above-mentioned chloride.

The preferred acrylic acid 2-(N that uses, N, the N-trimethyl ammonium) ethyl ester chloride, methacrylic acid 2-(N, N, the N-trimethyl ammonium) ethyl ester chloride, acrylic acid 2-(N-benzyl-N, the N-Dimethyl Ammonium) ethyl ester chloride and methacrylic acid 2-(N-benzyl-N, N-Dimethyl Ammonium) ethyl ester chloride.

Certainly can also use the mixture of above-mentioned ethylenically unsaturated monomer.

All radical polymerization initiators that can cause the polymerization of free radical aqueous emulsion all are suitable for preparing compound particle aqueous dispersion and aqueous polymer dispersion by radical polymerization.In principle, they can be peroxide and azo-compound.Certainly, the redox initiator system also is fit to.Operable in principle peroxide is an inorganic peroxide, as hydrogen peroxide or peroxidating pyrosulfate, an alkali metal or two alkali metal or ammonium salt as the peroxidating pyrosulfuric acid, as a sodium and disodium or a potassium and dipotassium or ammonium salt, or organic peroxide, as alkyl hydroperoxide, as the tert-butyl group, to menthyl or cumyl hydroperoxides, with dialkyl group or diaryl peroxide, as di-t-butyl or dicumyl peroxide.The azo-compound that uses mainly is 2,2 '-azodiisobutyronitrile, 2,2 ,-azo two (2, the 4-methyl pentane nitrile) and 2,2 '-azo two (amidino groups propyl group) dihydrochloride (AIBA is equivalent to the V-50 available from WakoChemicals).The oxidant that is suitable for the redox initiator system is above-mentioned peroxide basically.Can use sulphur compound with low-oxidation-state, as alkali metal sulfite, as potassium sulfite and/or sodium sulfite, the alkali metal bisulfites, as potassium bisulfite and/or sodium hydrogensulfite, the alkali metal bisulfites, as inclined to one side potassium bisulfite and/or sodium metabisulfite, formaldehyde sulfoxylate salt, as formaldehyde sulfoxylate potassium and/or sodium sulfoxylate formaldehyde, the alkali metal salt of aliphatic sulfinic acid, particularly sylvite and/or sodium salt and alkali metal sulfuration hydrogen salt, as potassium hydrogen sulfide and/or sodium bisulfide, multivalent metal salt is as ferric sulfate (II), ferric sulfate (II) ammonium or ferric phosphate (II), enediol is as dihydroxymaleic acid, benzoin and/or ascorbic acid, and reducing sugar, as sorbose, glucose, fructose and/or dihydroxyacetone (DHA) are as corresponding reductant.Generally speaking, the consumption of the radical polymerization initiator that uses is as 0.1-5 weight %, based on the total amount of monomer mixture.

Gamut 0-170 ℃ is suitable as the reaction temperature that is used for the reaction of free radical aqueous polymerization under the existence of inoganic solids particulate or non-existent situation.Generally speaking, use 50-120 ℃, 60-110 ℃ usually, frequent 〉=70-100 ℃ temperature.The polymerization of free radical aqueous emulsion can be less than, be equal to or higher than under 1 crust (definitely) at pressure to be carried out, and it can and be up to 170 ℃ above 100 ℃ for polymerization temperature.Volatile monomer is as the preferably polymerization under super-atmospheric pressure of ethene, butadiene or vinyl chloride.Pressure can be 1.2,1.5,2,5,10 or 15 crust or can also adopt higher value.If emulsion polymerisation is under reduced pressure carried out, the pressure of determining is 950, and is common 900, often 850 millibars (definitely).Advantageously the free radical aqueous emulsion is aggregated under the inert gas atmosphere, as carrying out under 1 crust (definitely) under nitrogen or the argon gas.

Water-containing reacting medium also can comprise water-soluble organic solvent in principle, as methyl alcohol, ethanol, isopropyl alcohol, butanols, amylalcohol, acetone etc.But, polymerisation preferably do not exist described solvent situation under realize.

Except above-mentioned component, in the method for preparing compound particle aqueous dispersion or aqueous polymer dispersion, can also choose wantonly and use the free radical chain transfer compounds, so that reduce or control the molecular weight of the polymer that obtains by polymerization.What use is to be essentially aliphatic series and/or araliphatic halogen compounds, as n-butyl chloride, n-butyl bromide, n-butyl iodide, carrene, dichloroethanes, chloroform, bromofom, the monobromo chloroform, two bromodichloromethanes, carbon tetrachloride, carbon tetrabromide, benzyl chloride or benzyl bromide a-bromotoluene, organic thio-compounds, as primary, the second month in a season or uncle's aliphatic mercaptan, as ethyl mercaptan, n-propyl mercaptan, the 2-propanethiol, n-butyl mercaptan, the 2-butyl mercaptan, 2-methyl-2-propanethiol, n-amyl mercaptan, the 2-amyl hydrosulfide, the 3-amyl hydrosulfide, 2-methyl-2-butyl mercaptan, 3-methyl-2-butyl mercaptan, positive hexyl mercaptan, the 2-hexyl mercaptan, the 3-hexyl mercaptan, 2-methyl-2-amyl hydrosulfide, 3-methyl-2-amyl hydrosulfide, 4-methyl-2-amyl hydrosulfide, 2-methyl-3-amyl hydrosulfide, 3-methyl-3-amyl hydrosulfide, 2-ethyl butyl mercaptan, 2-ethyl-2-butyl mercaptan, n-heptanthiol and isocompound thereof, n-octyl mercaptan and isocompound thereof, positive ninth of the ten Heavenly Stems mercaptan and isocompound thereof, positive decyl mercaptan and isocompound thereof, positive undecyl mercaptan and isocompound thereof, positive lauryl mercaptan and isocompound thereof, positive 13 mercaptan and isocompound thereof, replace mercaptan, as 2-hydroxyl ethyl mercaptan, aromatic mercaptans, as benzenethiol, adjacent, between or to the methylbenzene thiophenol, with all in addition Polymerhandbook the 3rd edition, 1989, J.Brandrup and E.H.Immergut, John Wiley ﹠amp; Sons, part ii, sulphur compound described in the 133-141, and aliphatic series and/or aromatic aldehyde are as acetaldehyde, propionic aldehyde and/or benzaldehyde, unrighted acid, as oleic acid, has the diene of unconjugated double bond, as divinyl methane or vinyl cyclohexane, or have the hydrocarbon of the hydrogen atom of easy extraction, as toluene.But, can also use the mixture of the above-mentioned free radical chain transfer compounds of not disturbing.The total amount of the optional use of free radical chain transfer compounds generally≤5, and is frequent≤1 weight % usually≤3, based on the monomer total amount for the treatment of polymerization.

Compound particle aqueous dispersion used according to the invention is 1-70 with the total solids content that the aqueous dispersion that comprises aqueous polymer dispersion and inoganic solids particulate has usually, usually 5-65, often 10-60 weight %.

The particle diameter that compound particle used according to the invention or polymer dispersion generally have for 〉=0 and≤1000nm, usually≤500nm, often≤250nm.The mensuration of above-mentioned particle diameter also realizes by analytical ultracentrifugation.Described value is equivalent to d ₅₀Value.

Operable compound particle can have different structure according to the present invention.Compound particle can contain one or more solia particles.Solia particle can be wrapped up by polymeric matrix fully.But, the part solia particle is wrapped up by polymeric matrix, simultaneously an other part is arranged on the surface of polymeric matrix.Certainly, most of solia particle can also be attached on the polymer-matrix surface.

Should illustrate that also the compound particle aqueous dispersion can adopt the straightforward procedure drying to produce redispersible compound particle powder (for example by freeze drying or spray drying).When the glass transition temperature of the polymeric matrix of the compound particle that obtains according to the present invention be 〉=50 ℃, preferred 〉=60 ℃, preferred especially 〉=70 ℃, more preferred 〉=80 ℃, especially preferably 〉=90 ℃ or 〉=especially true 100 ℃ the time.The compound particle powder also is applicable to the new processing of paper surface.

The mixture of aqueous polymer dispersion and inoganic solids particulate for example is stirred in the aqueous polymer dispersion that 20-25 ℃ (room temperature) stirs down by the inoganic solids particulate that will or be powder type or be the respective amount of solid water dispersion form and it is evenly mixed and obtains.

In the new processing of paper surface, with the mixture of compound particle or polymer dispersion and inoganic solids particulate with 0.1-100,0.2-20, often 0.5-10g/m usually ²On the consumption paint paper surface of paper.Also it is contemplated that bigger consumption, but be disadvantageous generally from considering economically.If on the form paint paper surface of mixture with aqueous polymer dispersion with compound particle or polymer dispersion and inoganic solids particulate, above-mentioned consumption is based on the amount of the mixture of the compound particle that is comprised in the aqueous dispersion or polymer dispersion and inoganic solids particulate.After applying aqueous dispersion, generally carry out drying steps well-known to those skilled in the art.

Especially, compound particle or polymer dispersion are used for new method, its polymer can form film and minimum film-forming temperature≤150 ℃, and is preferred≤100 ℃, preferred especially≤50 ℃.Because minimum film-forming temperature is being lower than under 0 ℃ and can not surveying, thereby only can determine the lower limit of minimum film-forming temperature by glass transition temperature.Glass transition temperature should not be lower than-60 ℃, preferred-30 ℃.The mensuration of minimum film-forming temperature is according to DIN 53787 or ISO 2115 realizes and the mensuration of glass transition temperature realizes according to DIN 53765 (difference formula scanning calorimetric, 20K/min, middle point measurement).

Maybe advantageously, if be coated with paper with compound particle, particularly when coating realizes with the form of its aqueous dispersion, after coating process, the paper that is coated with compound particle exerted pressure and/or temperature so that the polymer film forming that in compound particle (method 1), is comprised.If make paper surface be coated with the aqueous dispersion of the mixture of polymer and inoganic solids particulate according to method 2, this is suitable for too.No matter whether select drying condition (temperature/pressure), or all be unessential no matter whether in down-stream, realize film forming, separating step so that under the situation of for example using aqueous dispersion, make polymer film forming.When using corresponding aqueous dispersion, the film forming step is carried out in dry run usually.

The coating paper that obtains by new method is with a wide range of applications, for example as write paper, news printing with paper, be used for periodical, catalogue, books or the like, as seal paper money paper, Holy Bible paper, brown paper, electric capacity paper or printing paper.

Advantageously, new paper can be write and for example by offset printing, aniline printing (Flexo-Druckverfahren) and the printing of photogravure method.Especially, the new paper of the printing that can obtain by adherography has the advantage of dry tenacity, moisture-resistant profit adhesiveness and anti-absorbency and good blackening aspect of performance thereof.

Embodiment

I. prepare the compound particle aqueous dispersion

Under nitrogen atmosphere and stirring (200 rev/mins), under 20-25 ℃ (room temperature) and 1 crust (definitely) in 5 minutes time with the Nyacol 2040 of 416.6g, be then the mixture of the sodium hydrate aqueous solution of 2.5g methacrylic acid and 12g10 weight % concentration join 2 liters be equipped with reflux condenser, thermometer, mechanical agitator and metering device four-hole boiling flask in.Then with the non-ionic surface active agent Lutensol of 10.4g20 weight % concentration ^(trade name of BASF AG on average has the C of 18 ethylene oxide units to AT 18 ₁₆C ₁₈The mixture of the aqueous solution-alcohol ethoxylate) and 61.4g demineralized water joins in the reactant mixture of stirring in 15 minutes process.In 60 minutes process, will be dissolved in the 0.83gN-cetyl-N in the 200g demineralized water then, N, N-trimethyl ammonium bromide (CTAB) is metered in the reactant mixture.Then reactant mixture is heated to 80 ℃ of reaction temperatures.

Simultaneously, the monomer mixture formed of preparation 117.5g methyl methacrylate, 130g n-butyl acrylate and 0.5g methacryloxypropyl trimethoxy silane comprises the initiator solution of the sodium hydroxide solution of 2.5g peroxidating sodium pyrosulfate, 11.5g10 weight % concentration and 100g demineralized water as charging 2 as charging 1 and preparation.

Then in 5 minutes process with 21.1g charging 1 and 57.1g charging 2 by two independently feeding line join in the reaction solution that under reaction temperature, stirs.Reactant mixture stirred 1 hour under reaction temperature then.Then with the Dowfax of 0.92g45 weight % concentration ^The 2A1 aqueous solution joins in the reactant mixture.Then, in 2 hours the process that begins at the same time, the charging 1 and charging 2 continuous meterings of surplus are joined in the reactant mixture.

, reactant mixture under reaction temperature stirred other 1 hour, then it is cooled to room temperature thereafter.

The solid content that the compound particle aqueous dispersion that obtains like this has is 40.1 weight %, based on the total amount of compound particle aqueous dispersion.

By adopting the demineralized water dilution, under agitation at room temperature make the solid content of compound particle aqueous dispersion reach 10 weight %.

II. test performance feature

In order to study, under 30 ℃ and normal pressure, make no wooden body paper (Substance 70g/m available from German Scheufelen by DT laboratory coating machine (having the rigid blade that thickness is 0.3mm) available from Finland DT Paper Science Oy Ab ²) coating 10g/m ²Coating lubrication prescription (calculating) as solid, described coating lubrication prescription comprises:

70 weight portion Hydrocarb ^90 (available from the calcium carbonate of Switzerland Omya AG),

30 weight portion Amazon Plus ^(available from the kaolin of Brazilian CADAM S.A),

0.15 weight portion Polysalz ^S (available from the aqueous solution of the polyacrylic acid sodium salt of the 45 weight % concentration of German BASFAG),

10 weight portion Styronal ^PR 8736 (available from the phenylethylene/butadiene aqueous dispersion of the 50 weight % concentration of German BASFAG),

0.3 weight portion Sterocoll ^FD (available from BASF AG, the ethyl acrylate/acrylic acid/methacrylic acid aqueous dispersion of 25 weight % concentration of Germany) and

34 weight portion demineralized waters.

Paper web carries out drying by IR drier and air drying (8 IR lamps that are respectively 650 watts, output speed 30m/min).

The test-strips that to measure to 35cm * 20cm cuts down and makes its evenly compound particle aqueous dispersion of coating dilution from paper web.The consumption of described dispersion makes that the consumption of compound particle is 1.0g/m ²Paper surface.Be that 50% (DIN 50014-23/50-2) down store 15 hour at 23 ℃ with relative humidity with test-strips then.At room temperature test-strips is gone up laboratory calender K8/2 press polish by the table available from German KleinewefersAnlagen GmbH then.Nip pressure between the roller is that 200kN/cm paper width and speed are 10m/min.Said method carries out four times altogether.

Comparative example

Compare example according to the foregoing description, except not adopting compound particle aqueous dispersion treatment surface.

Use IGT print trial machine to measure resist drying adhesiveness (IGT drying)

Use standard ink (available from the printing-ink 3808 of Lorilleux-Lefranc) under quickening in printing equipment (IGT impressionability test machine AC2/AIC2) with the test-strips printing.Maximum print speed is 200cm/s.At nip pressure is to apply printing ink under the 350N/cm.

Speed (cm/sec) when having 10 places from the adhesion (sticking point) of paper coating lubrication prescription after beginning to print is defined as that resist drying is adhering to be measured.Described print speed printing speed is high more when the tenth stain, assert that the result is good more.

Moisture-resistant profit adhesiveness

As under test resist drying adhering situation, produce and prepare test-strips.

Adopt following manner that printing equipment (IGT impressionability test machine AC2/AIC2) is set: before print process, to adopt water that test-strips is wetting.

In constant speed is to print under the 0.6cm/s.

From the adhesion of paper as seen as printing zone not.In order to measure moisture-resistant profit adhesiveness, use color densitometer to measure the ink density (in %) of comparing with pure hue.Described ink density is high more, and moisture-resistant profit adhesiveness is good more.

Anti-stick plate under the situation of multiple printing (offset printing test)

The printing of test-strips (referring to, the adhering test of resist drying) is under the 1m/s with at nip pressure to be to carry out under the 200N/cm in constant speed.

Repeat print after 30 seconds.Number of pass times when haftplatte takes place is defined as anti-stick plate.Print pass is big more when the generation haftplatte first time, assert that the result is better.

Table 1: the results list

	Anti-stick plate is in cm/s	Moisture-resistant profit adhesiveness %	Offset printing test number
				Embodiment	71	57	6
Comparative example	63	51	4

Claims (15)

1. the method for treatment of paper surfaces wherein makes paper surface be coated with particle (compound particle), and described particle is made of polymer and inoganic solids particulate, the average particle size≤100nm of inoganic solids particulate.

2. the process of claim 1 wherein the form of compound particle with the compound particle aqueous dispersion imposed on the paper.

3. the method for claim 2, wherein the compound particle aqueous dispersion is by such method preparation, promptly wherein at least a ethylenically unsaturated monomer is dispersed in the water-bearing media and by moisture free-radical emulsion polymerization method make its in the presence of the inoganic solids particulate of at least a dispersion and at least a dispersant by means of at least a radical polymerization initiator polymerization

A) stable aqueous dispersions of at least a inoganic solids of use, aqueous dispersion based at least a inoganic solids, the initial solid concentration of described aqueous dispersion is 〉=1 weight %, the script dispersed solids that is discrete form that after its preparation, still comprised more than 90 weight % in 1 hour, and weight-average diameter≤100nm that its dispersed solids particle has

B) in the standard potassium chloride solution, have the electrophoretic mobility of non-zero under the pH of the water-containing reacting medium of the dispersing solid particle of described at least a inoganic solids before pH is equivalent to begin to add dispersant,

C) before beginning to add at least a ethylenically unsaturated monomer, at least a anion, CATION and non-ionic dispersing agent are added in the solids aqueous dispersion,

D) thereafter at least a monomer of the 0.01-30 weight % of total amount is added in the solids aqueous dispersion and makes it be polymerized to conversion ratio and be at least 90%

With

E) then at least a monomer of surplus is added continuously with its wear rate under polymerizing condition.

4. the method for treatment of paper surfaces; wherein adopt the aqueous dispersion treatment of paper surfaces; described aqueous dispersion can be by mixing acquisition with aqueous polymer dispersion with the inoganic solids particulate of at least a dispersion, weight average particle diameter≤100nm that described inoganic solids particulate has.

5. each method among the claim 1-4, wherein the consumption of the mixture of compound particle or polymer dispersion and inoganic solids particulate is 0.1-100g/m ²Paper.

6. each method among the claim 1-5, wherein polymer can form film.

7. each method among the claim 1-6, wherein used paper is a body paper.

8. each method among the claim 1-6, wherein used paper is coated paper or sized paper.

9. each method among the claim 1-8, wherein the inoganic solids particulate is selected from silica, aluminium oxide, hydrated alumina, calcium carbonate, magnesium carbonate, tricalcium orthophosphate, magnesium orthophosphate, iron oxide (II), iron oxide (III), iron oxide (II/III), tin oxide, cerium oxide, yittrium oxide (III), titanium dioxide, phosphate rock, zinc oxide and zinc sulphide.

10. each method among the claim 1-9, wherein the paper of handling is exerted pressure and/or temperature so that make polymer form film.

11. can be by the paper of each method acquisition among the claim 1-10.

12. the purposes of the paper of claim 11 in offset printing, aniline printing and photogravure method.

13. the paper of the printing that can obtain by the purposes of claim 12.

14. the aqueous dispersion of particle is used to be coated with the purposes of paper, described particle is made of polymer and inoganic solids particulate, the average particle size≤100nm of inoganic solids particulate.

15. aqueous dispersion is used to be coated with the purposes of paper, described aqueous dispersion is by mixing acquisition with aqueous polymer dispersion with the inoganic solids particulate of at least a dispersion, weight average particle diameter≤100nm that described inoganic solids particulate has.