Microspheres

FIELD: process engineering.

SUBSTANCE: invention relates to thermally expanding thermoplastic microspheres and their application. Said microspheres comprise polymer shell made from ethylenically unsaturated monomers that encapsulate propellent. Ethylenically unsaturated monomers comprise up to 20-80 wt % of acrylonitrile and 1-70 wt % of poly(vinyl alcohol) with single carbon-carbon olefinic linkage. Total amount of acrylonitrile and poly(vinyl alcohol) makes up to 100 wt % of ethylenically unsaturated monomers.

EFFECT: higher expansivity and chemical resistance, absence of halogen-containing monomers.

23 cl, 5 tbl, 45 ex

 

The present invention relates to a thermally expanding thermoplastic microspheres, their production and use, to the water suspension comprising such microspheres, and also to advanced microspheres.

Expanding thermoplastic microspheres comprising a thermoplastic polymer shell enclosing the propellant, commercially available under the trademark EXPANCEL® and are used as a foaming agent in many different applications.

In such microspheres by the propellant is usually a liquid, having a boiling point of not higher than the softening temperature of thermoplastic polymer shell. After heating the propellant evaporates, increasing the internal pressure at the same time the shell softens, resulting in a significant expansion of the microspheres. The temperature at which the expansion, called TAC, while the temperature at which reaches maximum extension, referred to as Tmax. Expanding microspheres are sold in various forms, for example, as a dry free current particles as a suspension in water or as a partially dewatered wet paste.

Expanding microspheres can be obtained by polymerization Ethylenediamine monomers in the presence of the propellant. Detailed descriptions of the various expanding microspheres and their generation can be Nai and, for example, in U.S. patents 3615972, 3945956, 4287308, 5536756, 6235800, 6235394 and 6509384, in the patent applications U.S. 2004/0176486 and 2005/0079352, in the United Kingdom patent 1024195, in EP 486080 and EP 1288272, WO 2004/072160, and in the Japan patent, including published for General information 1987-286534, 2005-213379 and 2005-272633.

One important application of the expanding microspheres is the production of paper as described, for example, in U.S. patents 3556934 and 4133688, the Japan patent 2689787, the Japan patent published for General information 2003-105693, WO 2004/113613, 2006/068573, WO 2006/068574 and O. Soderberg, "World Pulp & Paper Technology 1995/96, The International Review for the Pulp & Paper Industry" p. 143-145.

Other important applications of the expanding microspheres are printing ink, vinyl foam (e.g., plastisol), non-woven and synthetic leather.

In some applications it is desirable that the microspheres had a relatively low TAC. However, the polymer shell in commercially available microspheres with low TAC is usually produced from a mixture of monomers comprising halogenated monomers, such as vinylidenechloride. Such microspheres have the disadvantage that is associated with a high content of residual monomers and insufficient resistance to chemicals such as solvents and plasticizers used in artificial leather and plastisols. Attempts to obtain microspheres with low TAC and high capacity for extended the Yu without halogenated monomers have not decided until the end of these tasks.

The aim of the invention is to provide an expanding microspheres with high capacity for expansion and low TAC, preferably having a high resistance to chemicals and do not contain high quantities of halogenated monomers.

Another aim of the invention is to provide an expanding microspheres useful in the manufacture of paper or inks, for example, as a foaming agent.

Another purpose is to provide a method of producing paper.

Another aim is to provide an aqueous suspension comprising expanding the microspheres useful in the manufacture of paper.

Found the opportunity to accomplish these goals, providing microspheres with a polymer shell, obtained from certain combinations of monomers.

One aspect of the invention relates to thermally expanding thermoplastic microspheres comprising a polymer shell, obtained from Ethylenediamine monomers encapsulating a propellant, and these Ethylenediamine monomers include from 20 to 80 weight. % of Acrylonitrile and from 1 to 70 weight. % simple vinyl ether having only one carbon-carbon double bond, with the total amount of Acrylonitrile and simple vinyl ether having only one carbon-carbon double bond, is from 30 to 100 weight. percent, suppose the equipment from 50 to 100 weight. %, or from 65 to 100 weight. % Ethylenediamine monomers.

Ethylenediamine monomers preferably comprise from 1 to 60 wt.%, most preferably, from 1 to 50 weight. % or 5-50 wt. % simple vinyl ether having only one carbon-carbon double bond. If not desirable very low TAC, the number from 5 to 30 weight. % is particularly preferable. Simple vinyl ether may be the only ether or a mixture of various vinyl ethers. Examples of vinyl ethers having only one carbon-carbon double bond include simple alkylvinyl esters, and alkyl group preferably has 1 to 10 carbon atoms, most preferably from 1 to 5 carbon atoms. Specific examples include the following simple vinyl ethers: metilidinovy ether, ethylenically ether, propylvinyl ether, isopropylaniline ether, butylvinyl ether, isobutylphenyl ether, tert-butylvinyl ether, sec-butylvinyl ether and mixtures thereof, of which especially preferred metilidinovy ether and ethylenically ether. One or more hydrogen atoms on the alkyl group may be substituted by a functional group such as hydroxyl, carboxylic acid, amine, ether, etc. One specific example is a simple vinyl ether of ethylene glycol.

Ethylenediamine monomers PR is doctitle include from 40 to 80 weight. %, most preferably from 50 to 70 weight. % of Acrylonitrile.

Ethylenediamine monomers preferably additionally include Methacrylonitrile, preferably in an amount of from 1 to 50 weight. %, most preferably from 5 to 40 weight. %.

Ethylenediamine monomers can optionally include one or more esters of acrylic acid, esters of methacrylic acid, and mixtures thereof. The number of such monomers may, for example, be from 1 to 50, preferably from 5 to 40 weight. %.

If enabled esters of methacrylic acid, one or more of them may be methyl methacrylate, isobornylacrylat, ethyl methacrylate, butylmethacrylate or hydroxyethylmethacrylate, of which the methyl methacrylate is particularly preferred.

If enabled esters of acrylic acid, one or more of them may be methyl acrylate, acrylate, propylacetate, butyl acrylate, 2-ethyl hexyl acrylate or hydroxyethylacrylate, of which the methyl acrylate is particularly preferred.

Preferably, Ethylenediamine monomers mainly not contain vinylidenechloride. If it is enabled, its amount is preferably less than 10 weight. %, most preferably less than 5 weight. % or even less than 1 weight. % Ethylenediamine monomers. It is also preferable to Ethylenediamine monomers generally not sod is neigh any halogen-containing monomers. If they are included, their number is preferably less than 10 weight. %, most preferably less than 5 weight. % or even less than 1 weight. % Ethylenediamine monomers.

Preferably, Ethylenediamine monomers include small amounts of one or more crosslinking multifunctional monomers, such as one or more of divinylbenzene, of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, dimethacrylate of 1,4-butanediol, dimethacrylate 1,6-hexanediol, glycerol dimethacrylate, dimethacrylate 1,3-butanediol, neopentyl glycol dimethacrylate, dimethacrylate 1,10-decandiol, trimethacrylate pentaerythritol, cerametallic pentaerythritol, hexametrical of dipentaerythritol, trimethacrylate of cialisforsale, alismataceae, trimethacrylate of trimethylolpropane, dimethacrylate tripotential, dimethacrylate PEG #200, PEG-dimethacrylate #400, PEG-dimethacrylate #600, monoacrylate 3-acryloyloxy, triarylamine, triallylisocyanurate, triallylisocyanurate, divinely ether, divinely ether of ethylene glycol, divinely ether of diethylene glycol, divinely ether of triethylene glycol, divinely broadcast tetraethyleneglycol, etc. are Particularly preferred cross-linked monomers, which, at least, are trifunctionally, examples of which include trimethacrylate pen is eritria, cerametallic pentaerythritol, hexametrical of dipentaerythritol, trimethacrylate of cialisforsale, trimethacrylate of trimethylolpropane, triarylamine, triallylisocyanurate, triallylisocyanurate. The number sewn functional monomers may, for example, be from 0.1 to 10 weight. % or from 0.1 to 1 weight. % or from 1 to 3 weight. % ethyleneimine monomer, and from 0.1 to 1 weight. % is particularly preferred if one or more multifunctional monomers are at least trifunctional and from 1 to 3 weight. % is particularly preferred if one or more multifunctional monomers are bifunctionality.

If enabled Ethylenediamine monomers in addition to Acrylonitrile, simple vinyl ether, Methacrylonitrile, esters of acrylic acid, esters of methacrylic acid and one or more crosslinking multifunctional monomers, the amount is preferably from 0 to 10 weight. %, most preferably from 0 to 5 weight. %. Examples of such other monomers that can be included are nitrosobenzene monomers, such as

α-ethoxyacrylate, fumaronitrile or crotonate; vinylpyridine; complex vinyl esters such as vinyl acetate; styrene, such as styrene, halogenated styrene or α-methylsterol; diene, such as butadiene, isoprene and x is orapred; unsaturated carboxyl compounds such as acrylic acid, methacrylic acid and their salts; or other unsaturated monomers, such as acrylamide, methacrylamide or N-substituted maleimide.

In a variant of the invention Ethylenediamine monomers consist mainly of Acrylonitrile, simple alkylvinyl ether, Methacrylonitrile, one or more esters of acrylic acid or methacrylic acid, and one or more crosslinking multifunctional monomers. In another embodiment, Ethylenediamine monomers consist mainly of Acrylonitrile, simple alkylvinyl ether, Methacrylonitrile and one or more crosslinking multifunctional monomers. In yet another embodiment, Ethylenediamine monomers consist mainly of Acrylonitrile, simple alkylvinyl ether, one or more esters of acrylic acid or methacrylic acid, and one or more crosslinking multifunctional monomers. In a further embodiment, Ethylenediamine monomers consist mainly of Acrylonitrile, simple alkylvinyl ether and one or more crosslinking multifunctional monomers.

The softening temperature of the polymer shell, usually coincides with its glass transition temperature (TC), is preferably in the range from 0 to 140°C, most preferably from 30 to 100°C.

The propellant is typically a liquid, having a boiling point of not higher than the softening temperature thermoplastic polymer shell and may include one or more hydrocarbons, such as methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, hexane, isohexane, neohexane, cyclohexane, heptane, isoheptane, octane and isooctane, isododecane. Besides them, other types of hydrocarbons may also be used, such as petroleum ether or chlorinated or fluorinated hydrocarbons, such as Harmattan, dichloromethane, dichloroethane, dichloroethylene, trichloroethane, trichloroethylene, Trichlorofluoromethane, perfluorinated hydrocarbons, fluorinated ethers, etc. Preferred propellants include at least one of propane, n-butane, isobutane or isopentane, single or in mixture, or in a mixture with one or more other hydrocarbons. The amount of n-butane and/or isobutane and/or isopentane in the propellant preferably from 50 to 100 wt.%, most preferably, from 75 to 100 wt.%. If propane is present, its amount in the propellant preferably from 10 to 50 wt.%. The boiling point of the propellant at atmospheric pressure is preferably in the range from -50 to 100°C, most preferably from -40 or -30 to 50°C or -30 or -20 to 30°C.

TAC for expanding microspheres p is impactfully from 40 to 140°C, the most preferred from 50 to 100°C. the Tmax for expanding microspheres are preferred from 80 to 200°C, most preferably from 100 to 170°C.

In addition to the polymer shell and a propellant microspheres can include other substances added during their production, usually in amounts of from 0 to 20 wt.%, preferably from 1 to 10 wt.%. Examples of such substances are solid suspendresume agents, such as one or more of starch, cross-linked polymers, agarwood resin, a derivative of cellulose, such as, for example, methylcellulose, hypromellose, hydroxyethylcellulose and carboxymethylcellulose, silicon oxide, colloidal clay, such as, for example, chalk and bentonite, and (or) one or more salts, oxides or hydroxides of metals such as Al, Ca, Mg, Ba, Fe, Zn, Ni and mn, for example, one or more of calcium phosphate, calcium carbonate, magnesium hydroxide, barium sulfate, calcium oxalate, and hydroxides of aluminum, iron, zinc, Nickel or manganese. If these solid suspendresume agents are present, they usually mainly located on the outer surface of the polymer shell. However, even if suspendisse agent was added during the production of the microspheres, it can be washed at a later stage and can thus largely be absent in the final product.

Expanding mikros is a career preferably have a diameter of from 1 to 500 μm, more preferably from 5 to 100 μm, most preferably from 10 to 50 μm. The amount of propellant in expanding the microspheres preferably from 5 to 50 wt.%, more preferably from 10 to 50 wt.%, most preferably, 15 to 40 wt.%, particularly most preferably from 20 to 35 wt.%.

The term "expanding microspheres", as used here, refers to the expanding microspheres that have not been previously extended, i.e. expanding unexpanded microspheres.

Another aspect of the present invention relates to a method for expanding thermoplastic microspheres described above. The method comprises the polymerization Ethylenediamine monomers described above, preferably, in aqueous suspension in the presence of the propellant with obtaining microspheres comprising a polymer shell encapsulating the specified propellant. As for the types and amounts of the monomers and of the propellant, it may include the above-mentioned description of the expanding microspheres. May follow the same rules as described in the previously mentioned U.S. patents№№ 3615972, 3945956, 4287308, 5536756, 6235800, 6235394 and 6509384, applications for U.S. patent 2004/0176486 and 2005/0079352, GB1024195, EP 486080, EP 1288272, WO 2004/072160 and applications JP published for General information 1987-286534, 2005-213379 and 2005-272633.

In a variant of the invention, the microspheres are obtained from on OSU periodic process, and the polymerization can be carried out in the reactor, as described below. With 100 parts of the phase monomer (respectively comprising the monomers and the propellant, the ratio being determined by the ratio of monomers in the polymeric shell and the amount of propellant in the final product) are mixed and homogenized one or more polymerization initiators, in the amount of preferably from 0.1 to 5 parts of an aqueous phase, in the amount of, preferably, from 100 to 800 parts, and one or more preferably a solid colloidal suspendisse agent, in amounts of, preferably, from 1 to 20 parts. The size of the droplets obtained phase monomer determines the size of the resulting expanding microspheres in accordance with the rules described, for example, in U.S. patent No. 3615972 that can be applied to manufacturing methods with different suspendresume agents. The temperature respectively support from 40 to 90°C, preferably from 50 to 80°C while the suitable pH dependent suspending agent. For example, high pH, preferably from 5 to 12, most preferably from 6 to 10, is suitable if suspendisse agent selected from salts, oxides or hydroxides of metals such as Ca, Mg, Ba, Zn, Ni and mn, for example, one or more of calcium phosphate, calcium carbonate, magnesium hydroxide, magnesium oxide, sulfate is Aria, calcium oxalate and hydroxides of zinc, Nickel or manganese.

Low pH, preferably from 1 to 6, most preferably, from 3 to 5, is suitable if suspendisse agent selected from a starch, methyl cellulose, hydroxypropylmethylcellulose, hydroxyethyl cellulose and carboxymethyl cellulose, agar resin, silicon oxide, colloidal clays or oxides or hydroxides of aluminum or iron. Each of the above means has a different optimum pH, depending on, for example, data on solubility.

To increase the effect of suspending agent, you can also add a small amount of one or more promoters, for example from 0.001 to 1 wt.%. Usually, such promoters are organic materials and may, for example, be selected from one or more of the water-soluble sulfonated polystyrene, alginates, carboxymethylcellulose, hydroxide or chloride of Tetramethylammonium or water-soluble complex resinous amine condensation products such as water-soluble condensation products diethanolamine and adipic acid, water-soluble condensation products of ethylene oxide, urea and formaldehyde, polyethylenimine, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylene, amphoteric materials such as protein materials such as gelatin, glue, casein, albumin, CH the tin, etc., nonionic materials such as methoxycinnamate, ionic materials, usually classified as emulsifying agents such as Soaps, alkyl sulphates and-sulfonates and long-chain Quaternary ammonium compound.

Can be used in conventional radical polymerization initiators respectively selected from one or more organic peroxides, such as dialkylamide, diazepamonline, peroxides, esters, peroxycarbonates or azo compounds. Suitable initiators include diacetylpyridine, di(4-tert-butylcyclohexyl)PEROXYDICARBONATE, dictyospermi, Dibenzoyl peroxide, dilauroylperoxide, dodecanedioic, tert-butylmercaptan, tert-butylmalonate, tert-butylperbenzoate, tert-butylhydroperoxide, cumonherface, semiliterate, diisopropylamide, in primary forms, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], etc. is Also possible to initiate the polymerization by radiation such as high energy ionization radiation.

When polymerization is substantially completed, the microspheres are usually obtained in the form of aqueous suspensions or dispersions, which can be used as such or dehydrated Liu is suspended by conventional means, such as a complex filter, release the filter press, plate filter, rotary filter, belt filter or centrifugation, to obtain a so-called wet paste. However, it is also possible to dry the microspheres by any conventional means such as spray drying, drying rack, channel drying, drying with rotation, drum drying, air drying, drying rack with turbo, disc drying or drying in a fluidized bed.

If necessary, the microspheres can be at any stage processed so as to reduce the amount of residual unreacted monomers, for example in accordance with any of the procedures described in the previously mentioned patents WO 2004/072160 or USA 4287308.

Another aspect of the present invention is an advanced microspheres obtained by expansion of the expandable microspheres as described above, for example, the diameter of the particles in the 2-5 times greater than the diameter of the unexpanded microspheres. The density of expanded microspheres may, for example, be 0.005 to 0.06 g/cm3. The extension is carried out by heating expandable microspheres to a temperature above Tnac. For the upper temperature limit, take the temperature, when the microspheres begin to collapse, and the temperature depends on the exact composition of the polymer shell and a propellant. In most cases, temperature is RA from 80°C to 150°C is suitable. The density of the expandable microspheres can be controlled by selecting the temperature and time of heating. The extension can be made by any appropriate means to heat in any suitable device, as described, for example, in EP 0348372, WO 004/056549 or WO 2006/009643.

Expanding and expanded microspheres according to the invention is useful in various applications such as paper manufacturing, printing ink such as water-soluble paint, solvent-based, plastisol, UV paint, etc., for example, for textiles, Wallpaper, paper, etc.), putty, sealants, toy clay, coatings for underwater part of the ship, adhesives, leavening agents adhesives, synthetic leather, genuine leather, paints, textiles, paper and paperboard, coatings (e.g., a non-slip coating, etc. for various materials, such as paper, cardboard, plastics, metals and textiles, explosives, cable insulation, thermoplastics such as polyethylene, PVC skin and ethylene-vinyl acetate) or thermoplastic elastomers such as a styrene-ethylene-butylene-styrene copolymer is a styrene-butadiene-styrene, thermoplastic polyurethanes and thermoplastic polyolefins), butadiene-styrene rubber, natural rubber, vulcanized rubber, silicone rubbers, thermoset polymers such as epoxy is s, polyurethanes and polyesters). In some of these applications are expanding microspheres are particularly preferred, for example, putties, sealants, clay, genuine leather, paint, explosives, cable insulation and thermosetting polymers such as epoxies, polyurethanes and polyesters). In some cases it is also possible to use a mixture of extended and expanding microspheres according to the invention, for example, in coatings for underwater part, silicone rubber and lightweight foams.

Another aspect of the present invention relates to aqueous suspensions comprising expanding thermoplastic microspheres described above, preferably in an amount of 5 to 55 wt.%, most preferably, from 20 to 55 wt.%. This suspension is useful for various applications expanding microspheres, including, for example, the production of paper. The suspension preferably also includes at least one thickener, preferably compatible with the production of paper. Examples of such thickeners include, at least partially water-soluble polymers selected from the group consisting of starches, gums, cellulose, chetinov, chitosans, glycans, galactanes, pectins, mannans, dextrins, copolymers made from monomers including acrylic acid or a salt thereof (preferably 50 mol.%, most pre is respectfully, up to 20 mol. % of acrylic acid or its salts), Homo - and copolymers made from monomers include esters or amides of acrylic acid, Homo - and copolymers made from monomers comprising methacrylic acid, its esters or amides, rubber latex, PVC skin and copolymers, poly(vinyl esters) and copolymers (e.g. ethylene), poly(vinyl alcohol), polyamine, polyethyleneimine, polyethylene-polypropyleneoxide, polyurethane, and precondensation of aminoplast and phenoplast, such as urea-formaldehyde, urea-melamine-formaldehyde or phenol-formaldehyde and polyamidoamine-epichlorhydrin resin. Examples of suitable gums include guar gum, tamarind gum, gum carob, gum wiki, karaya, okra, gum Arabic, xanthan gum, etc. and their mixtures, of which especially preferred guar gum. Examples of suitable cellulose derivatives include, such as optionally chemically modified CMC (carboxylmethylcellulose) and ethers of cellulose, such as EGEC (ethyl(hydroxyethyl)cellulose) and SCE (hydroxyethylcellulose), and mixtures thereof. Chemically modified derivatives of cellulose include, for example, cellulose derivatives, modified by various functional groups such as Quaternary amines, other amines, sulfates, with lithonate, phosphates, phosphonates, polyethylene oxide and polypropyleneoxide.

At least partially water-soluble polymer can be linear, branched or crosslinked. The average molecular weight can vary widely depending on the type of polymer. In most cases, the preferred average molecular weight is at least 500, more preferably at least 2000, and most preferably at least 5000. The upper limit is not critical, and in most cases, the average molecular weight is preferably up to 50000000, more preferably up to 10000000, most preferably, up to 1000000.

Particularly preferred polymers include starch, CMC, EGEC, guar gum, polyamidoamine-epichlorhydrin resins, copolymers of acrylic acid with other monomers (e.g., acrylamide), and Homo - or copolymers of polyacrylamide, polyamine, poly(vinyl alcohol)and polyethylene-polypropyleneoxide.

One or more at least partially water-soluble polymers useful as thickeners, preferably present in a quantity sufficient to stabilize the suspension against sedimentation or flotation of the microspheres to the extent that they cannot be re-dispersed again. In many cases this can be achieved by adding sufficient unto whom icesta polymer, to get the preferred suspension viscosity from about 150 to about 1000 MPa·s at 25°C, most preferably from about 200 to about 600 MPa·s at 25°C (reference measurement viscometer Anton Paar DV-1P, equipped with a spindle L3). The amount required to stabilize the suspension depends on the polymer and other circumstances, such as pH. In many cases, the preferred content of at least partially water-soluble polymer in the suspension is from about 0.1 to about 15 wt.%, most preferably, from about 0.1 to about 10 wt.%, particularly most preferably from about 0.5 to about 10 wt.%.

All thickeners and other additives disclosed in any of the previously mentioned patents WO 2006/068573 and WO 2006/068574 can be applied in aqueous suspension according to the invention in a preferred amounts are also disclosed in these patents.

The following aspects of the present invention relate to the use of expanding microspheres described above, in inks, artificial leather, nonwovens and paper production, especially from raw materials containing cellulose fibers. Another aspect of the present invention is the use of expanded microspheres described above, in the production of the Umaga.

When used in inks, especially in aqueous inks, and expanding microspheres, preferably wet unexpanded microspheres add to the standard compounds, known to specialists in this field. Such compositions typically include one or more binders and one or more thickeners. Other components may include, for example, pigments, defoamers, fillers, chemicals to prevent the formation of surface film or driving, etc. Printing ink can also be based on the dispersion of acrylate or plastisols, including expanding microspheres. After printing the microspheres are expanded by heating before, during or after drying of the paint. Such printing inks are particularly suitable for printing on textile or Wallpaper.

When used in artificial leather expanding microspheres, preferably dry unexpanded microspheres are used in standard formulations in the standard procedures, well known to the experts in this field, for example, in the surface layer of the multilayer artificial leather, such as suede or some other type of structure. Artificial leather can be made by any standard method, such as a Release paper, a method of Directly coating a woven or nonwoven silt shall way of Coagulation, from any standard material, such as polyurethane (PU), PVC skin (PVC) and their mixtures. Usually, artificial leather produced by any of the above methods, cover with paste PU or PVC containing expanding microspheres, and then heated to expand the microspheres.

The production of non-woven materials may include the stage of the formation of a web of fibers, adding to the specified fiber binder and expanding microspheres described above, the formation of non-woven material, and applying heat to raise the temperature to a temperature sufficient to expand the microspheres and, thus, to increase the volume of non-woven material. Expanding microspheres and a binder may be added separately or as a mixture. The amount added of the expanding microspheres is preferably from about 0.1 to about 30 wt.% dry goods, most preferably, from about 0.5 to about 15 wt.% dry products. The amount of the binder is preferably from about 10 to about 90 wt.% dry goods, most preferably, from about 20 to about 80 wt.% dry products. Details can be found in the previously mentioned patent WO 2004/113613.

In the manufacture of paper expanding the microspheres predpochtitel what about the use, to increase the amount of paper, but can also be used for other purposes. The microspheres are then preferably added to the raw material containing cellulose fibers, which is then dehydrated and dried, and in which the microspheres are expanded and contribute to an increase of paper.

Another aspect of the present invention relates to a method for producing paper, including the stage of adding thermally expanding microspheres described above, the raw material containing cellulose fibers, dewatering of raw materials on the net, to get the paper, and drying the paper with application of heat, namely with increasing temperature to a temperature sufficient to expand the microspheres and, thus, increase the amount of paper.

The growing number of microspheres added to the raw material, is preferably from 0.1 to 20 wt.%, most preferably, from 0.2 to 10 wt.% dry microspheres on the content of dry material in the raw material. Can be applied to any type of papermaking machine known in the technology.

The term "paper"as used here, refers to all types of products, based on the cellulose in sheet or mesh form, including, for example, the panel, cardboard and cardboard construction. It has been found that the invention is particularly useful for the production of panels, cardboard and cardboard construction, especially with the main weight of the t 50 to 1000 g/m 2preferably from 150 to 800 g/m2.

The paper can be obtained as a single-layer or multi-layer paper. If the paper includes three or more layers, expanding microspheres can be added to parts of the raw material, forming one or more of these layers, for example, only parts of raw materials, not forming any of the two outer layers.

Raw material preferably contains from 50 to 100 wt.%, most preferably, from 70 to 100 wt.% cellulose fibers, based on dry material. Before dehydration, raw materials, in addition to expanding the microspheres may also contain one or more fillers, such as mineral fillers, such as kaolin, China clay, titanium dioxide, gypsum, talc, chalk, ground marble or precipitated calcium carbonate, and optionally other commonly used additives, such as excipients retention of filler, adhesive, aluminum compounds, paint, wet-strength resins, optical brighteners, etc. Examples of aluminum compounds include alum, aluminates and semi-aluminum compounds, such as chlorides and sulfates of polyalanine. Examples of auxiliary substances retention of the filler include cationic polymers, anionic inorganic materials in combination with organic polymers, such as bentonite in combination with cationic polymers is or sols on the basis of silicon dioxide in combination with cationic polymers or cationic and anionic polymers. Examples of adhesives include adhesives, reactive with cellulose, such as dimers of alkylbetaine and alchemistry anhydride, and adhesives that do not react with cellulose, such as rosin, starch and other polymeric adhesives such as copolymers of styrene with vinyl monomers, such as maleic anhydride, acrylic acid and its alkyl esters, acrylamide, etc.

When drying the paper microspheres preferably heated to a temperature of from 50 to 150°C, most preferably from 60 to 110°C. This leads to the expansion of the microspheres and thereby also to increase the volume of paper. The magnitude of this increase depends on various factors such as the nature of cellulose fibers and other raw components, but is in most cases from 5 to 70 % or more weight percent of the microspheres contained in the dried paper, compared with the same kind of paper produced without the addition of the expanding microspheres or any other expanding means. Can be applied by any conventional means of drying, including the transfer of heat to the paper, such as contact drying (e.g., hot cylinders), forced convection drying (e.g., hot air), infrared techniques, or combinations thereof. In case of contact drying temperature of the contacting surfaces, for example, cylinders, PR is doctitle from 20 to 150°C, most preferably, from 30 to 130°C. the Paper can go through the ranks of several cylinders, for example up to 20 or more, with increasing temperature. The paper may then be subjected to any kind of normal processing, such as bonding surfaces, coating, calendering, etc.

Cellulose fibers in the raw material can, for example, be from the pulp made from any species, preferably of wood, such as solid hardwood, and soft wood of coniferous breeds. Cellulose fibers can also be partially or completely occur from recycled paper, in this case, a match is found, the invention gave unexpectedly good results.

Expanding microspheres can be added in any form, although from a practical point of view it is preferable to add them in the form of an aqueous suspension described above.

Another aspect of the present invention relates to a paper that includes enhanced microspheres obtained from the expanding microspheres described above. The paper may further include cellulose fibers, and other conventional components. The microspheres could be expanded in the method of production of paper, as described above, or were expanded separately and then added to the raw material containing cellulose fibers, which produce paper.

Hereinafter the invention is described with the following Example and, should not be interpreted as limiting the scope of the invention. Unless otherwise indicated, all parts and percentages relate to weight parts and percentages.

The expansion properties of the microspheres were evaluated on the instrument Mettler TMA 40 processor TC15 TA and computer software STAR6, using a heating rate of 20°C/min and the weight (net) 0,06 N. TAC is the temperature at which the expansion, Tmax is the temperature at which the maximum expansion, and TMA-density is the density of the microspheres at Tmax.

The particle size and size distribution were determined by laser light scattering instrument Malvern Mastersizer Hydro 2000 SM on wet samples. The average particle size is presented as the mean diameter of the volume d (0,5).

The amount of propellant was determined by thermogravimetric analysis (TGA) instrument Mettler Toledo TGA/SDTA851e. All samples were dried prior to analysis in order to exclude as far as possible humidity, as well as residual monomers, if present. Analyses were performed in nitrogen atmosphere using a heating rate of 20°C/min from 30°C.

Example 1. The reaction mixture containing the organic droplets, stabilized by Mg(OH)2in the water, created by the mixing of the phases and vigorous stirring until until a suitable size of the droplets was not achieved. Water dispersion of soda the sting of 2.2 parts of Mg(OH) 2and 332 parts of water. Organic droplets contained 2 parts of dilauroylperoxide, 38 parts of isobutane, 52 parts of Acrylonitrile, 28 parts of Methacrylonitrile, 20 parts of a simple etilenovogo ether and 0.3 part of trimethacrylate of trimethylolpropane. The polymerization was carried out at 62°C in a sealed reactor under stirring. After cooling to room temperature a sample of the resulting suspension of the microspheres was removed for determination of particle size distribution. After filtration, washing and drying the particles were analyzed by thermomechanical analysis (TMA). Dry particles contained approximately 23 wt.% isobutane and had an average particle size of about 25 microns. The TMA results are shown in Table 1.

Examples 2-30. Microspheres were obtained in many experiments according to the polymerization in Example 1, except for the used monomers and propellants, which are presented in Table 1. As a cross-linking monomer used 0.3 to 1 part trimethacrylate of trimethylolpropane (Examples 2-10 and 17-30) or diethylene glycol dimethacrylate (Examples 11-16) as initiator used 2.0 to 2.5 parts of dilauroylperoxide. In Examples 17 and 18 propellants were 38 parts of n-butane and propane and n-butane (14/86 by weight), respectively. The amount of water and Mg(OH)2in the examples was changed from 251 to 332 parts and from 2.2 to 4.8 parts is, respectively. This is due to small differences in composition in different polymerization reactors, but does not affect thermal properties of the polymerized particles. The polymerization was performed at 61-62°C, as described in Example 1. In Example 2, prior to processing the particles out of the reactor, the amount of residual monomers was reduced processing 2.1 parts NaHSO3for 4 hours at 73°C, after which the temperature was lowered to room temperature and the particles were isolated and analyzed. In Examples 22 and 23, the product contained a large amount of unreacted monomers and the samples were difficult to analyze. Dry particles from Example 30 contained a small amount of propellant, probably due to leakage during the drying of the particles. The results of the analysis can be found in Table 1.

Examples 31 and 32. Microspheres were obtained according to Example 1, except for monomers and propellants, which are presented in Table 1, and stabilization of organic droplets of water dispersion using silicon dioxide instead of Mg(OH)2. The aqueous dispersion was obtained by mixing 252 parts of water, 11 parts of 1M NaOH, 19 parts of 10% acetic acid, 0.3 part of Cr(NO3)310 parts of 40% colloidal silicon dioxide and 0.6 part of the condensation products of diethanolamine and adipic acid. After cooling to room temperature a sample of the resulting suspension of the microspheres was removed for defined who I distribution of particle size. After filtration, washing and drying the particles were analyzed by thermo-mechanical analysis. The results of the analysis are shown in Table 1.

Table 1
Analytical results of Examples 1-32 and the number of different compounds used, expressed in parts by weight
ExampleENAVEMANXIBFETime-measures (mcm)Sang-tapes (wt.%)TAC
(°C)
Tmax
(°C)
Density TMA
(g/l)
1522028-38-2523811426,2
2522028-33 -10259313010,0
3591031-38-4024841716,0
462533-38-2926961778,6
563334-38-35279718016,8
6553015 -38-42167514116,4
7453025-38-32357914414,3
865-35-38-29239819111,8
9522028--353228931518,1
1059 1031--3545261041668,4
1160-40--363627114197the 5.7
1260535--3640271101866,6
13601030--3635271041706,9
14602020--3639299315710,0
15603010--3648308214714.4V
166040---3638337211624,7
17522028---262290 1546,0
18522028---2817871527,4
197030--38-37167312177,4
205050--38-40315410123,8
215050---3529 346610450,4
223070---35the concentration is236082109
23-100---35the concentration isthe concentration isthe concentration isthe concentration isthe concentration is
24, X=MMA2010353530-23279412218,8
25, X=MMA30103525 30-20249412035,7

26, X=MMA3020302030-13168212116,3
27, X=MMA5220-28-3529268214023,6
28, X=MA5220-28-35302710912524,9
29, X=VDH5220-28-3530289011739,2
30, X=IBM5220-28-3526393110470
31, X=vác5220-28-239,2168811328,2
32522028--237,52413320,0
An = Acrylonitrile, AVE = ethylenically simple ether, MAN = Methacrylonitrile, MA = methyl acrylate, MMA = methyl methacrylate, VDH = vinylidenechloride, IBMA = isobutyronitrile, VAC = vinyl acetate, IB = isobutane, PI = isopentane, N.O. = not specified

Examples 33-38. Microspheres were obtained by polymerization according to Example 1, except for monomers and propellants, which are presented in Table 2. The amount of water in the samples was varied from 320 to 332 parts. This is due to a slight difference in the different reactors of the polymerization, but does not affect thermal properties of the polymerized particles. The results of the analysis are shown in Table 2.

Table 2
Analytical results of Examples 33 to 38 and the number of different compounds used, expressed in parts by weight
ExampleENBVAMANIBFESize (µm)Propellant (wt.%)TAC
(°C)
Tmax
(°C)
Density TMA
(g/l)
33522028-3543311091528,9
3452202838-4717971649,6
357030--35353110912579,3
367030-38-291470110246
375050--3537146682137
385050-38-242073105139
An = Acrylonitrile, BVA = simple butylvinyl ether, MAN = Methacrylonitrile, IB = isobutane, PI = isopentane, N.O. = not specified

Examples 39-43. Microspheres were obtained by polymerization according to Example 1, except for monomers and propellants, which are presented in Table 3. In Examples 39, 40 and 43 used 1 part of a crosslinking monomer diethylene glycol dimethacrylate, while in Examples 41 and 42 were not using a crosslinking monomer, different from RIVA. As an initiator was applied at 2.0-2.5 parts of dilauroylperoxide. The amount of water and Mg(OH)2in the examples was changed from 251 to 332 parts and from 2.1 to 4.8 parts, respectively. This is due to the small ethnicisation in different polymerization reactors, but does not affect thermal properties of the polymerized particles. The polymerization was carried out at 61-62°C, as described in Example 1. As can be seen from Table 3, when using deviceloop ether of 1,4-butanediol as a monomer, the particles show a bad extension or show no expansion in comparison with, for example, Examples 4 and 12 in Table 1.

Table 3
Analytical results of Examples 39-43 and the number of different compounds used, expressed in parts by weight
ExampleENRIVAMANIBFESize (µm)Propellant (wt.%)TAC
(°C)
Tmax
(°C)
Density TMA
(g/l)
3960238-35392511614452,3
60535-353327121122190
4160535-353427120121167
42601030-353035126127230
436253334_3818--No extensions
An = and elontril, BDA = divinely ether of 1,4-butanediol, MAN = Methacrylonitrile, IB = isobutane, PI = sapanta

Example 44. Microspheres of Example 2 was tested in printing inks, creating a homogeneous dispersion by mixing 16.1 parts of the wet microspheres (74.4% of dry weight), 73,9 parts of the binder dispersion of the vinyl acetate-ethylene copolymer (Mowilith DM-107 from Celanese, 60% of the dry weight), 66.3 parts of methyl methacrylate emulsion binder-ethylacrylate copolymer (ECO Primal-16 from Rohm and Haas, 45.5% of dry weight), 10.0 parts of glycerol, 0.8 part of a defoamer based on mineral oil (Nopco ENA-515 from Cognis) and 29.9 parts of water using a Silverson mixer. Then added to 3.0 parts of the dispersion of the thickener is an acrylic polymer (Alcoprint PT-XN from Ciba), and then further mixed in a mixing solvent to until thickening is not complete, with the formation of a homogeneous mixture. This leads to a stamp containing 12% (by dry weight) of the microspheres. Produced stamps for screen printing, which was dried overnight at room temperature. Then the thickness of the unexpanded stamps were measured coating thickness gauge (Elcometer 355 Standard) and was found equal to 40 microns. The stamps were extended for 60 s at 90-160°C in hot air oven Mathis labdryer. The thickness of the extended stamps were measured, and the expansion ratio was calculated by dividing by the thickness of the unexpanded stamp. Expand the iesa printing ink, created from commercially available microspheres with a polymer membranes from 58% vinylidenechloride, 33% Acrylonitrile and 9% of methyl methacrylate and isobutane as propellant was tested in the same way. The expansion coefficients are presented in Table 4.

Table 4
The coefficient of expansion of the microspheres in printing inks
Temperature (°C)Example 2Comparative example
901,01,0
1001,31,3
1103,02,5
1204,33,3
1305,3the 3.8
1406,0the 3.8
150the 3.83,5
1602,83,3

The results show is live, the expansion coefficient of the ink from the microspheres according to the invention, chlorine-free, higher than the coefficients of expansion of chlorine-containing microspheres, especially in the range of 110-150°C.

Example 45. Single layer construction cardboard with a weight basis approximately 300 g/m2produced on a pilot paper machine with a speed of approximately 4 m/min, which is not recirculated process water. The slurry consisting of 42,5% wt. pulp wood of firm breeds, to 42.5 wt.% pulp of softwood and 15.0 weight. % filler (GCC), crushed to a value shopper-Rigler (Schopper-Riegler) 28°SR and then dispersible obtaining pulp slurry raw material. Aqueous suspension of expanding microspheres were added to the raw material before the mixer in the amount of about 2.0 wt% dry microspheres in dry substance in raw materials. As an auxiliary substance for the retention of filler was used Compozil® (Eka Chemicals) and AKD was used as adhesive. In the drying section of a paper grid was heated rolls having a temperature profile of from 70 to 120°C. Were tested expanding microspheres of Example 2. Commercially available suspension of microspheres having a polymer shell of 73% vinylidenechloride, 24% Acrylonitrile and 3% of methyl methacrylate and isobutane as propellant tested as microspheres CPA is of high value. To a suspension of microspheres as a thickener were added starch (Solvitose C5™ from Avebe Starches North Europe)to stabilize against flotation or sedimentation. In order to determine the preservation of the microspheres, the paper samples were taken before the press section to determine the number of microspheres. It was made determination by gas chromatography quantity of isobutane present in the paper, and from this value, calculate the number of microspheres. The preservation of the microspheres was calculated from the additive microspheres and content of the microspheres in the paper. In addition, samples of the dried paper was selected for determination of volume and thickness. The results are shown in Table 5.

Table 5
The increase in paper
The sample microspheresThe amount of propellant
(wt.%)
Particle size
(µm)
Saving (%)Increased volume (%, percentage of retained microspheres)
Example 225106530
Comparative example1312 8025

The results show that the increase in the volume of paper from the microspheres according to the invention, chlorine-free, compared with the increase of chlorine-containing microspheres.

1. Thermally expanding thermoplastic microspheres comprising a polymer shell, obtained from Ethylenediamine monomers encapsulating a propellant, and Ethylenediamine monomers include from 20 to 80 wt.% Acrylonitrile and from 1 to 70 wt.% simple vinyl ether having only one carbon-carbon double bond, the total amount of Acrylonitrile and simple vinyl ether having only one carbon-carbon double bond, is from 30 to 100 wt.% Ethylenediamine monomers.

2. Microspheres according to claim 1, in which the aforementioned Ethylenediamine monomers include from 40 to 80 wt.% Acrylonitrile.

3. Microspheres according to any one of claims 1 and 2, in which the aforementioned unsaturated monomers comprise from 5 to 50 wt.% simple vinyl ether having only one carbon-carbon double bond.

4. Microspheres according to any one of claims 1 and 2, in which the total amount of Acrylonitrile and simple vinyl ether having only one carbon-carbon double bond, is from 50 to 100 wt.% Ethylenediamine monomers.

5. Microspheres on any and what claims 1 and 2, where the simple vinyl ether having only one carbon-carbon double bond, is a simple alkylvinyl ether.

6. Microspheres according to claim 5, in which the alkyl group has from 1 to 10 carbon atoms.

7. Microspheres according to claim 6, in which a simple alkylvinyl ether selected from the group consisting of methylvinylether ether, etilenovogo ether and mixtures thereof.

8. Microspheres according to any one of claims 1, 2, 6, or 7, in which the aforementioned Ethylenediamine monomers include Methacrylonitrile.

9. Microspheres according to any one of claims 1, 2, 6, or 7, in which the aforementioned Ethylenediamine monomers mainly not include or comprise less than 10 wt.% halogen-containing monomers.

10. Microspheres according to any one of claims 1, 2, 6, or 7, in which said propellant comprises at least one component of propane, n-butane, isobutane or isopentane.

11. Microspheres according to any one of claims 1, 2, 6, or 7, in which Tbegranging from 40 to 140°C.

12. A method of obtaining a thermally expanding microspheres according to any one of claims 1 to 11, comprising the polymerization Ethylenediamine monomers in the presence of the propellant with the formation of microspheres comprising a polymer shell encapsulating the specified propellant, and these Ethylenediamine monomers include from 20 to 80 wt.% Acrylonitrile and from 1 to 70 wt.% monomers selected from the gr is PPI, consisting of simple alkylvinyl esters having only one carbon-carbon double bond, the total amount of Acrylonitrile and monomers selected from the group consisting of alkylvinyl ethers having only one carbon-carbon double bond, is from 30 to 100 wt.% Ethylenediamine monomers.

13. Aqueous suspension comprising thermally expanding microspheres according to any one of claims 1 to 11.

14. Aqueous suspension according to item 13, further comprising at least one thickener, which is at least partially water-soluble polymer selected from the group consisting of starches, gums, cellulose, chetinov, chitosans, glycans, galactanes, pectins, mannans, dextrins, copolymers derived from monomers including acrylic acid or its salts, Homo - and copolymers obtained from monomers include esters or amides of acrylic acid, Homo - and copolymers obtained from monomers comprising methacrylic acid or its esters or amides, rubber latex, PVC skin and copolymers, complex polyvinyl ether copolymers, polyvinyl alcohol, polyamines, polyethyleneimine, polyethylene-polypropyleneoxide, polyurethane and precondensation of aminoplast and phenoplast and polyamidoamine-epichlorhydrin resin.

15. Advanced micro who very, obtained by expanding the expanding microspheres according to any one of claims 1 to 11.

16. The use of thermally expanding microspheres according to any one of claims 1 to 11 in the manufacture of paper.

17. The use of thermally expanding microspheres according to any one of claims 1 to 11 in inks.

18. The use of thermally expanding microspheres according to any one of claims 1 to 11 in the manufacture of artificial leather.

19. The use of thermally expanding microspheres according to any one of claims 1 to 11 in the manufacture of nonwoven materials.

20. The use of expanded microspheres according to § 15 in the manufacture of paper.

21. The method of obtaining the paper, including the stage of adding thermally expanding microspheres according to any one of claims 1 to 11 to raw materials containing cellulose fibers, dewatering of raw materials on the net to get the paper, and drying the paper by applying heat and thereby increasing the temperature of the microspheres to a temperature sufficient to expand and increase the volume of paper.

22. The method according to item 21, in which thermally expanding microspheres added to the aqueous suspension according to any one of p and 14.

23. Paper, including expanded microspheres obtained from the expanding microspheres according to any one of claims 1 to 11.



 

Same patents:
Micro spheres // 2432201

FIELD: process engineering.

SUBSTANCE: invention relates to thermally expanding thermoplastic microspheres and their application. Said microspheres comprise polymer shell made from ethylenically unsaturated monomers that encapsulate propellent. Ethylenically unsaturated monomers comprise up to 40-70 wt % of acrylonitrile and 5-40 wt % methylacrylonitrile, and 10-50 wt % of monomers selected from the group including acrylates, methacrylic esters and mixes thereof. Said propellent comprises at least one agent selected from the group including methane, ethane, propane, isobutene, n-butane and neopentane.

EFFECT: higher foaming capacity, expansivity and chemical resistance, absence of halogen-containing monomers.

21 cl, 6 tbl, 25 ex

FIELD: chemistry.

SUBSTANCE: composition contains at least one expandable microsphere and at least one ionic compound which is cationic. The composition also contains a certain set of cellulose fibres. The ionic compound is selected from a group comprising a polyamine, polyethyleneimine, colloid and sol. The colloid or sol contains at least one member from a group comprising silica, alumina, tin oxide, zirconium dioxide, antimony oxide, iron oxide and rare-earth metal oxides. The outer surface of the expandable microsphere, which is anionic, is not covalently bonded with an ionic compound. The composition has electrokinetic potential greater than or equal to 0 mV at pH of approximately 9.0 or less with ionic strength between 10-6 mol and 0.1 mol. The composition is prepared by bringing into contact at least one expandable microsphere and at least one ionic compound to form a mixture. The mixture is centrifuged to form a first phase containing at least one ionic compound and a second phase containing a particle. A solution containing a certain amount of cellulose fibre is also added. A low-density paper or cardboard base and article which is a cardboard container with good operational characteristics is obtained. The weight of the article is equal or less than 1 oz. The paper or cardboard base has Sheffield smoothness less than 250 units measured using a TARR1 T 538 om-1 technique, and colour speckling 2nd cyan not greater than 6. The base has Parker Print surface roughness from approximately 1.0 to 0.5, measured using a TARRI T 555 om-99 technique.

EFFECT: improved properties of the composition.

28 cl, 5 dwg, 4 tbl, 2 ex

FIELD: textile, paper.

SUBSTANCE: cellulose product comprises thermoplastic microspheres and a charged aromatic acrylamide polymer. The method to produce a cellulose product includes provision of an aqueous solution of suspension that contains cellulose fibres. Addition of thermoplastic microspheres and the charged aromatic acrylamide polymer into the suspension, and dehydration of the produced suspension. Thus made cellulose product may be used as a cardboard for liquid packing.

EFFECT: reduced porosity of a cellulose product as its volume increases and improved resistance of a wick edge to penetration of aqueous liquids for cellulose products.

25 cl, 3 tbl, 4 ex

FIELD: paper industry.

SUBSTANCE: paper with improved rigidity and bulk and method of its manufacturing may be used in pulp and paper industry and are intended for photocopier equipment. Paper comprises three-layer double-tee structure that forms a single web. It has central core layer manufactured mainly from cellulose, bulk of which is increased with the help of filler, such as hydrazine salt. Starch-based coating is applied on both sides of core layer, at the same time starch has high content of solid products. Coating forms three-layer paper having composite structure with outer layers of high strength that surround core of low density.

EFFECT: improved strength, rigidity and resistance to twisting of produced material.

32 cl, 2 dwg, 3 tbl, 3 ex

FIELD: textile; paper.

SUBSTANCE: method relates to production paper material and can be applied in paper-and-pulp industry when producing paper material with low-density. Method includes formation of aqueous suspension containing pulp. Addition of latex with agglomerated hollow particles in suspension. Formation of a wet sheet from the suspension and drying of the sheet. It also relates to paper material prepared by using the method.

EFFECT: production of paper material having good combination of optical, mechanical, tactile properties, evenness and volume including economical efficiency of the process.

10 cl, 6 dwg, 2 ex

FIELD: textile, paper.

SUBSTANCE: paper material and method of its production are designed for the production of paper products such as file folders and can be used in pulp and paper industry. The paper material contains cellulose fibers and expanded microspheres in the amount of approximately 0.1-0.4 wt % and 5.1-6.0 wt % of the web total dry weight; the paper web has the density equal to or exceeding about 6.0 pounds per 3000 square feet per mil. Method of manufacturing this material involves preparing composition for paper production containing cellulose fibers and expanded microspheres in the above amount, forming a fibrous web from this composition, web drying and calendering up to the above thickness.

EFFECT: preventing skin cuts, improving flexibility and stiffness of paper material.

29 cl, 25 dwg, 14 tbl, 8 ex

FIELD: pulp-and-paper industry, in particular, paper sheet having surface feeling hash to the finger, and method for applying coating onto paper sheet.

SUBSTANCE: paper sheet of such structure may be used for manufacture of paper or plastic medium for carrying of printed information, paper or plastic package, cover used in stitching and binding processes, or cardboard or plastic carton having surface feeling hash to the finger. At least one side of paper sheet is coated with layer containing non-compressible microscopic particles of non-gelatinized starch grains, or said particles are produced by grinding of plastic material. Method involves treating at least one side of paper sheet with water-based composition containing non-compressible microscopic particles which are made three-dimensional and rounded, binder, and filler; drying paper sheet after treatment. Particles are non-gelatinized starch grains, or particles are produced by grinding of plastic material. Method allows paper sheet to be produced, which has roughness coefficient Kd below 0.5.

EFFECT: simplified method and improved quality of paper sheet.

17 cl, 16 dwg, 1 tbl, 3 ex

FIELD: paper coated with composition for coating various kinds of paper, for offset printing of paper used for manufacture of books, magazines, annual reports, or packaging paper.

SUBSTANCE: composition comprises pigments and binder. Composition pigments are formed as microballs having sizes below 10 micrometers, preferably about 7 micrometers. Paper coated with such composition is silky by touch and has at least one surface coated with such composition, preferably both of its surfaces. This paper may be tracing paper.

EFFECT: improved quality of paper owing to preventing sliding thereof during separation of sheets in stacks, delamination of coating during printing process and, accordingly, elimination of paper dusting and formation of impure imprints.

7 cl, 2 dwg, 2 tbl, 13 ex

The invention relates to thermosensitive recording materials, in particular paper and taking into account the major area of application is the production of business and securities can be attributed to the means of their protection against forgery
Micro spheres // 2432201

FIELD: process engineering.

SUBSTANCE: invention relates to thermally expanding thermoplastic microspheres and their application. Said microspheres comprise polymer shell made from ethylenically unsaturated monomers that encapsulate propellent. Ethylenically unsaturated monomers comprise up to 40-70 wt % of acrylonitrile and 5-40 wt % methylacrylonitrile, and 10-50 wt % of monomers selected from the group including acrylates, methacrylic esters and mixes thereof. Said propellent comprises at least one agent selected from the group including methane, ethane, propane, isobutene, n-butane and neopentane.

EFFECT: higher foaming capacity, expansivity and chemical resistance, absence of halogen-containing monomers.

21 cl, 6 tbl, 25 ex

FIELD: personal use articles.

SUBSTANCE: invention relates to light industry and may be used to manufacture inner parts of shoes and prosthetic-orthopaedic items on the basis of non-woven needle-punching synthetic fibres and tanning wastes. Composite material for inner parts of shoes and prosthetic-orthopaedic items with thickness of 1.9-2.2 mm includes three layers impregnated with skin glue. At the same time outer layers of material represent needle-punching cloths made of mixture of synthetic bicomponent and polyester fibres. Inner layer consists of ground tanning chips with fibre size of 0.5-1.8 mm. Material has the following composition, wt % : synthetic fibres 61- 65; tanning chips 25-27; skin glue 10 -12. Produced material may be shaped as resistant in operation. Required hygienic properties are maintained both by presence of protein fibrous components - tanning chips and by using highly porous non-woven cloth made of synthetic fibres as the base. Composition of synthetic fibres producing cloth is selected so that as a result of their coupling and subsequent heat moulding, fibrous-porous structure of material is preserved.

EFFECT: new material, providing for required hygienic and strength properties, is suitable to make inner soles and various prosthetic-orthopaedic items.

1 tbl, 2 ex

FIELD: process engineering.

SUBSTANCE: invention relates to method of producing gas-permeable imitation multilayer leather, and imitation leather produced thereof. Said leather is made up of the layer of flat textile warp with, at least one foamed polyurethane-based intermediate layer applied there on that feature, at least, partially exposed porous structure, and face polyurethane-based layer applied on, at least, one intermediate layer. First stage of proposed method comprises applying face layer on peel-apart web. Then, at least one intermediate layer is applied onto face layer. Now, web layer is applied on, at least, one intermediate layer and web is separated from face layer. Note here that, to produce face layer, aqueous aliphatic polyurethane dispersion in liquid phase is applied onto web, and, immediately after applying said dispersion, water contained therein is evaporated by supplying heat thereto for 5 min, max., to facilitate drying of polyurethane dispersion on web without film formation and forming of face layer with micro pores.

EFFECT: small-sized pores, goo gas permeability.

39 cl, 4 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to method of producing gas-permeable imitation multilayer leather, and imitation leather produced thereof. Said leather is made up of the layer of flat textile warp with, at least one foamed polyurethane-based intermediate layer applied there on that feature, at least, partially exposed porous structure, and face polyurethane-based layer applied on, at least, one intermediate layer. First stage of proposed method comprises applying face layer on peel-apart web. Then, at least one intermediate layer is applied onto face layer. Now, web layer is applied on, at least, one intermediate layer and web is separated from face layer. Note here that, to produce face layer, aqueous aliphatic polyurethane dispersion in liquid phase is applied onto web, and, immediately after applying said dispersion, water contained therein is evaporated by supplying heat thereto for 5 min, max., to facilitate drying of polyurethane dispersion on web without film formation and forming of face layer with micro pores.

EFFECT: small-sized pores, goo gas permeability.

39 cl, 4 dwg

FIELD: construction industry.

SUBSTANCE: manufacturing method of floor covering involves preparation of glass-fibre mat roll, application of primer and front coatings, printing of patterns and application of transparent coating, application of PVC flakes, application of the second transparent coating, application of rear PVC coating, mechanical stamping of face coating and application of UV protection lacquer.

EFFECT: optimum speed choice of cloth supplied in automated line for manufacturing floor covering, choice of the most implemented patterns, chromaticity, shades of pictures, obtaining the appropriate cloth flexibility and consumer density of new material.

FIELD: process engineering.

SUBSTANCE: invention relates to floor coating shaping and can be used in production processes. Proposed method in consisting in using available production facilities cooling to technologically expedient temperatures in applying a number of techniques, as well as in creating conditions for solidification of coating surface layer, turning over the coating through 180° on using coat paint and lacquer layers, the coat being moved at 25 m/min rate.

EFFECT: expanded performances.

FIELD: chemistry.

SUBSTANCE: invention relates to multilayer, tent covering material. The material contains a polyester base and a double-sided polyvinyl chloride coating. The polyester base is flat knitted linen, made from polyester thread of 100-111 tex, with 200-400 filaments in the thread and 85-400 windings per metre. Mass ratio of layers front : intermediate : back equals 1.1:1:1.6 respectively. Mass ratio of layers of polyester base and polymer coating is 1:2.7. The polymer coating is obtained, based on suspended polyvinyl chloride and additionally contains a mixture of dioctylphthalate and dioctyl sebacate plasticizers, Vitur T thermoplastic polyurethane, synthetic butadiene-acrylo-nitric rubber BNKS -28, copolymer of methyl methacrylate, butadiene and styrene KANE ACE B-28A. The stabilisers used are barium-, cadmium-, zinc-containing Vigostab BKT complex stabilisers. The antipyretic additive is antimony trioxide and chloroparaffin CP-1100. The coating also contains a fungicide - salicylic acid alinide, processing additive - stearic acid and pigments.

EFFECT: good fatigue properties in static and dynamic conditions, high frost resistance (up to -60 °C), fire-resistance and resistance to action of microorganisms.

1 cl, 6 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to multilayer, tent covering material. The material contains a polyester base and a double-sided polyvinyl chloride coating. The polyester base is flat knitted linen, made from polyester thread of 100-111 tex, with 200-400 filaments in the thread and 85-400 windings per metre. Mass ratio of layers front : intermediate : back equals 1.1:1:1.6 respectively. Mass ratio of layers of polyester base and polymer coating is 1:2.7. The polymer coating is obtained, based on suspended polyvinyl chloride and additionally contains a mixture of dioctylphthalate and dioctyl sebacate plasticizers, Vitur T thermoplastic polyurethane, synthetic butadiene-acrylo-nitric rubber BNKS -28, copolymer of methyl methacrylate, butadiene and styrene KANE ACE B-28A. The stabilisers used are barium-, cadmium-, zinc-containing Vigostab BKT complex stabilisers. The antipyretic additive is antimony trioxide and chloroparaffin CP-1100. The coating also contains a fungicide - salicylic acid alinide, processing additive - stearic acid and pigments.

EFFECT: good fatigue properties in static and dynamic conditions, high frost resistance (up to -60 °C), fire-resistance and resistance to action of microorganisms.

1 cl, 6 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to multilayer, tent covering material. The material contains a polyester base and a double-sided polyvinyl chloride coating. The polyester base is flat knitted linen, made from polyester thread of 100-111 tex, with 200-400 filaments in the thread and 85-400 windings per metre. Mass ratio of layers front : intermediate : back equals 1.1:1:1.6 respectively. Mass ratio of layers of polyester base and polymer coating is 1:2.7. The polymer coating is obtained, based on suspended polyvinyl chloride and additionally contains a mixture of dioctylphthalate and dioctyl sebacate plasticizers, Vitur T thermoplastic polyurethane, synthetic butadiene-acrylo-nitric rubber BNKS -28, copolymer of methyl methacrylate, butadiene and styrene KANE ACE B-28A. The stabilisers used are barium-, cadmium-, zinc-containing Vigostab BKT complex stabilisers. The antipyretic additive is antimony trioxide and chloroparaffin CP-1100. The coating also contains a fungicide - salicylic acid alinide, processing additive - stearic acid and pigments.

EFFECT: good fatigue properties in static and dynamic conditions, high frost resistance (up to -60 °C), fire-resistance and resistance to action of microorganisms.

1 cl, 6 tbl, 9 ex

FIELD: personal demand items.

SUBSTANCE: colour match is provided for the items containing various materials of bases. Composition of the coating is chosen so that it can be applied to various materials of bases thus in general maintaining equal visual characteristics of the item. Bases can contain flexible materials such as natural leather, synthetic leather, vinyl, foam, cloth and the like. The item includes the first base having the first flexible material, the second base having the second material different from the first material, the coating with colour match, which is made on the basis of solvent or on the basis of water dispersion of polymeric material, which contains polyurethane, and covers at least the section of the first base and at least the section of the second base. Examples of the items are footwear, automobile upholstery and automobile interiors. Manufacturing method of the item including the first and the second flexible bases made from various materials includes the following: the coating of at least the section of the first flexible base by the composition of the coating with colour match as per item 1 of the formula; and the coating of at least the section of the second flexible base by the composition of the coating with colour match as per item 1 of the formula.

EFFECT: there shall preferably be provided the composition of the coating capable of covering various types of bases of the item, and at the same time excluding the necessity of levelling colours.

23 cl, 2 dwg, 12 tbl, 7 ex

Micro spheres // 2432201

FIELD: process engineering.

SUBSTANCE: invention relates to thermally expanding thermoplastic microspheres and their application. Said microspheres comprise polymer shell made from ethylenically unsaturated monomers that encapsulate propellent. Ethylenically unsaturated monomers comprise up to 40-70 wt % of acrylonitrile and 5-40 wt % methylacrylonitrile, and 10-50 wt % of monomers selected from the group including acrylates, methacrylic esters and mixes thereof. Said propellent comprises at least one agent selected from the group including methane, ethane, propane, isobutene, n-butane and neopentane.

EFFECT: higher foaming capacity, expansivity and chemical resistance, absence of halogen-containing monomers.

21 cl, 6 tbl, 25 ex

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