Micro spheres

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

 

The present invention relates to a thermally expanding thermoplastic microspheres, to their preparation and application to the water suspension containing microspheres.

Thermoplastic expanding microspheres containing a shell of thermoplastic polymer, kapsulirujushchej propellant, are commercially available under the trademark EXPANCEL® and are used as foaming agent in many different applications.

In such microspheres by the propellant is typically a liquid, having a boiling point of not higher than the softening temperature of the shell of thermoplastic polymer. When heated propellant evaporates with the increase of the internal pressure at the same time, when the shell softens, giving, as a result, a significant expansion of the microspheres. The temperature at which the expansion is called the Tstartwhile the temperature at which maximum expansion, called the Tmax. Expanding microspheres are supplied in various forms, for example, as a dry free current particles as a suspension in water or partially dewatered raw sludge.

Expanding microspheres can be obtained by polymerization of monomers with ethylene unsaturation in the presence of the propellant. A detailed description of the various expanding micrope and receiving them can be found, for example, in U.S. patents 3615972, 3945956, 4287308, 5536756, 6235800, 6235394 and 6509384, in EP 486080, EP 1054034, EP 1288272 and EP 1408097, WO 2004/072160 and lined with Japanese application No. 1987-286534.

One important application of the expanding microspheres paper is obtained, as described, for example, in U.S. patents 3556934 and 4133688, JPP 2689787, lined with Japanese application No. 2003-105693, WO 2004/113613, WO 2006/068573 and WO 2006/068574 and in the work of O. Söderberg, “World Pulp & Paper Technology, 1995/96, The International Review for the Pulp & rereg Industry”, p. 143-145.

Other important applications of the expanding microspheres are printing inks, vinyl foams (e.g., plastisol), non-woven fabrics and artificial leather.

In some applications it is desirable that the microspheres had a relatively low Tstart. However, the polymer shell in commercially available microspheres with low Tstartusually made from Monomeric mixtures containing halogenated monomers, such as vinylidenechloride. Such microspheres are typically suffer from high amounts of residual monomers, discoloration and poor resistance to chemicals, such as solvents and plasticizers used in artificial leather and plastisols. Attempts to obtain microspheres with low Tstartand high ability to expand without halogenated monomers have not yet decided these problems satisfactorily.

The purpose of this is th invention is to provide an expanding microspheres with high capacity for foaming and low T startwithout high amounts of halogenated monomers.

Another objective of the present invention is to provide an expanding microspheres with low Tstarthigh resistance to chemicals and high transparency.

Another objective of the present invention is to provide an expanding microspheres used in the manufacture of paper or printing inks, for example, as a blowing agent.

Another objective of the present invention is to provide a method of producing paper.

Another objective of the present invention is to provide a water suspension containing the expanding microspheres used in obtaining paper.

Unexpectedly opened the possibility of achieving these goals by combining some Monomeric composition for a polymer shell with a group of propellants.

One aspect of this invention relates to thermoplastic expanding microspheres containing a polymer shell made from monomers with ethylene unsaturation, kapsulirujushchej propellant, and these monomers with ethylene unsaturation containing from 40 to 70% of the mass. of Acrylonitrile, from 5 to 40% wt. Methacrylonitrile, from above 10 to 50 wt%. monomers selected from the group consisting of esters of acrylic acid, esters of methacrylic acid and their mixture is th, and the specified propellant contains at least one representative from methane, ethane, propane, isobutane, n-butane and neopentane.

Monomers with ethylene unsaturation, preferably, contain from 45 to 65% of the mass. Acrylonitrile. If the target is low Tstartthe content of Acrylonitrile is, most preferably, from 45 to 55 wt. -%, and if the goal is high resistance to chemicals, the content of Acrylonitrile is, most preferably, from 55 to 65% of the mass. Monomers with ethylene unsaturation, in addition, preferably, contain from 10 to 35 wt. -%, most preferably 15 to 30 wt. -%, Methacrylonitrile. Monomers with ethylene unsaturation, in addition, preferably, contain from 15 to 50 wt. -%, most preferably 20 to 40 wt. -%, monomers selected from the group consisting of esters of acrylic acid, esters of methacrylic acid, and mixtures thereof.

It was found that, if the monomers with ethylene unsaturation contain more than 10% of the mass. esters of acrylic or methacrylic acid or their mixtures, it is possible to obtain microspheres with high capacity for expansion and relatively low Tstart.

Esters of acrylic and methacrylic acids, preferably, have only one double bond in the carbon-carbon bonds. It was found that particularly preferred as the monomers are esters of acrylic acid, such as methyl acrylate, acrylate and butyl acrylate, in particular methyl acrylate and acrylate. Monomers with ethylene unsaturation, thus, preferably, contain from more than 10 to 50 wt. -%, most preferably 15 to 50 wt. -%, in particular, most preferably from 20 to 40 wt. -%, monomers selected from the group consisting of esters of acrylic acid. Preferably, if the monomers with ethylene unsaturation containing from more than 10 to 50 wt. -%, most preferably 15 to 50 wt. -%, in particular, most preferably from 20 to 40 wt. -%, monomers selected from the group consisting of methyl acrylate, ethyl acrylate and mixtures thereof. Particularly preferably, if the monomers with ethylene unsaturation containing from more than 10 to 50 wt. -%, most preferably 15 to 50 wt. -%, in particular, most preferably from 20 to 40 wt. -%, of methyl acrylate.

If you are esters of methacrylic acid can be, for example, one or more representatives from methyl methacrylate, isobutylacetate, ethyl methacrylate, butyl methacrylate or hydroxyethylmethacrylate, of which the methyl methacrylate is particularly preferred.

Preferably the monomers with ethylene unsaturation does not inherently contain vinylidenechloride. If it is contained, its amount is preferably less than 10 wt. -%, Nai is more preferably less than 5% of the mass. or even less than 1% of the mass. monomers with ethylene unsaturation. Also preferably the monomers with ethylene unsaturation does not contain any halogenated monomers. If they are, their number is preferably less than 10 wt. -%, most preferably less than 5% of the mass. or even less than 1% of the mass. monomers with ethylene unsaturation.

Preferably the monomers with ethylene unsaturation contain small amounts of one or more crosslinking multifunctional monomers, such as one or more representatives from the following: divinylbenzene, etilenglikoli(meth)acrylate, diethyleneglycol(meth)acrylate, triethyleneglycol(meth)acrylate, propilenglikole(meth)acrylate, 1,4-butanediol(meth)acrylate, 1,6-hexanediol(meth)acrylate, glycerine(meth)acrylate, 1,3-butane-cioldi(meth)acrylate, neopentylglycol(meth)acrylate, 1,10-decandiol(meth)acrylate, PENTAERYTHRITE(meth)acrylate, pentaerythrityl(meth)acrylate, dipentaerythritol(meth)acrylate, cialisforsale(meth)acrylate, alismataceae, trimethylolpropane(meth)acrylate, tripotential(meth)acrylate, PEG-200 di(meth)acrylate, PEG-400 di(meth)acrylate, PEG-600 di(meth)acrylate, 3-acryloyloxyhexyloxy, triarylamine, triallylisocyanurate, triallylisocyanurate etc. Especially preferred are crosslinking monomers, the cat who they are, at least trifunctional, examples of which include PENTAERYTHRITE(meth)acrylate, pentaerythrityl(meth)acrylate, dipentaerythritol(meth)acrylate, cialisforsale(meth)acrylate, trimethylolpropane(meth)acrylate, triarylamine, triallylisocyanurate, triallylisocyanurate. The number of crosslinking functional monomers can be, for example, from 0.1 to 10 wt. -%, or from 0.1 to 1 wt. -%, or from 1 to 3% of the mass. monomers with ethylene unsaturation, and particularly preferred is 0.1-1% of the mass. when one or more multifunctional monomers are at least trifunctional, and particularly preferred is 1-3% of the mass. when one or more multifunctional monomers are bifunctionality.

If contains monomers with ethylene unsaturation other than Acrylonitrile, Methacrylonitrile, monomers selected from the group consisting of esters of acrylic acid, esters of methacrylic acid, and mixtures thereof, and one or more crosslinking multifunctional monomers, their amount is preferably from 0 to 10 wt. -%, most preferably from 0 to 5% of the mass. Examples of such other monomers that can be included are nitrosobenzene monomers, such as α-ethoxyacrylate, fumaronitrile or crotonates, vinylpyridin, the complex vinyl esters like vinyl acetate, styrene, such as styrene, halogenated styrene or α-methylsterols, diene, such as butadiene, isoprene and chloroprene, unsaturated carboxyl compounds, for example acrylic acid, methacrylic acid and their salts, or other unsaturated monomers, such as acrylamide, methacrylamide or N-substituted maleimide.

In the embodiment of the present invention the monomers with ethylene unsaturation essentially consist of Acrylonitrile, Methacrylonitrile, monomers selected from the group consisting of esters of acrylic acid, esters of methacrylic acid, and mixtures thereof, and one or more crosslinking multifunctional monomers. In his private version of the monomers with ethylene unsaturation essentially consist of Acrylonitrile, Methacrylonitrile, monomers selected from the group consisting of esters of acrylic acid, preferably one or more of methyl acrylate or ethyl acrylate, and one or more crosslinking multifunctional monomers.

The softening temperature of the polymer shell, usually corresponding to its glass transition temperature (Tarticle),(Tg)), is preferably in the range from 0 to 100°C, most preferably from 30 to 90°C.

The propellant is a hydrocarbon or mixture of hydrocarbons, preferably having a boiling point of not higher than the softening temperature is termoplastichny polymer shell. The boiling point at atmospheric pressure is preferably in the range from -50 to 100°C, most preferably from -20 to 50°C, in particular, most preferably from -20 to 30°C. the Propellant may consist essentially of at least one of methane, ethane, propane, isobutane, n-butane and neopentane, but may also optionally contain one or more other hydrocarbons, for example, in amounts of from 0 to 50 wt%. propellant. Examples of such hydrocarbons include n-pentane, isopentane, cyclopentane, hexane, isohexane, neohexane, cyclohexane, heptane, isoheptane, octane and isooctane. In addition they can also be used with other types of hydrocarbons such as petroleum ether, or chlorinated or fluorinated hydrocarbons such as methyl chloride, methylene chloride, dichloroethane, dichloroethylene, trichloroethane, trichloroethylene, Trichlorofluoromethane, perfluorinated hydrocarbons, fluorinated ethers, etc. Preferred propellants contain isobutane, individually or in a mixture with one or more other hydrocarbons. The amount of isobutane in the propellant is preferably from 50 to 100 wt. -%, most preferably from 75 to 100% of the mass.

Tstartexpanding the microspheres is preferably from 50 to 110°C, most preferably from 70 to 100°C. Tmaxexpanding microspheres composition is employed, preferably, from 100 to 200°C, most preferably from 120 to 170°C.

In addition to the polymer shell and a propellant microspheres may contain other substances introduced into their production process, usually in amounts of from 0 to 20 wt. -%, preferably from 1 to 10% of the mass. Examples of such substances are solid suspendresume substances, such as one or more representatives from the following: starch, crosslinked polymers, gum agar, cellulose derivatives, such as, for example, methylcellulose, hypromellose, hydroxyethyl cellulose and carboxymethyl cellulose, silicon dioxide, colloidal clay, such as, for example, limestone 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 representatives of the following: calcium phosphate, carbonate calcium, magnesium hydroxide, barium sulfate, calcium oxalates and hydroxides of aluminum, iron, zinc, Nickel or magnesium. If present, these solid suspendresume agents are usually located mainly on the outer surface of the polymeric shell. However, even if suspendisse agent was introduced in the process of obtaining microspheres, it can be washed at the last stage and, thus, can essentially be absent in the final product.

Expanding the microspheres preferably have the t average diameter of from 1 to 500 μm, more preferably from 5 to 50 μm, most preferably from 10 to 50 μm. The amount of propellant in expanding the microspheres is preferably from 5 to 40 wt. -%, more preferably from 10 to 40 wt. -%, most preferably 15 to 40 wt. -%, in particular, most preferably from 20 to 35% of the mass.

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, as described above. The method involves the polymerization of monomers with ethylene unsaturation, as described above, preferably, the aqueous suspension in the presence of the propellant, as described above, obtaining microspheres containing polymer membrane, kapsulirujushchej specified propellant. With regard to the types and amounts of monomers and propellant, they are listed in the above description, the expanding microspheres. May follow the same principles as described in the above U.S. patents№№ 3615972, 3945956, 4287308, 5536756, 6235800, 6235394 and 6509384, EP 486080, EP 1054034, EP 1288272 and EP 1408097, WO 2004/072160 and lined with Japanese application No. 1987-286534.

In the embodiment of the present invention microspheres receive periodic way is, the polymerization can be carried out, as described below, in the reaction vessel. 100 mass monomer phase (suitably comprising monomers and the propellant, the proportions of which determine the proportions of monomers in the polymeric shell and the amount of propellant in the final product) are mixed and homogenized one or more polymerization initiators, preferably in quantities of from 0.1 to 5 mass, the aqueous phase is preferably in the range from 100 to 800 mass and one or more, preferably, solid colloidal suspendida agents, preferably in an amount of from 1 to 20 mass the Size of the droplets of monomer phase determines the size of the finished expanding microspheres in accordance with the principles described in U.S. patent 3615972 that can be applicable for all such methods of obtaining various suspendresume agents. The temperature is suitably maintained in the range 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 the salts, oxides or hydroxides of metals like Ca, Mg, Ba, Zn, Ni and Mg, for example one or more representatives of the following: calcium phosphate, calcium carbonate, magnesium hydroxide, oxide mage is Oia, barium sulfate, calcium oxalates and hydroxides of zinc, Nickel or manganese. Low pH, preferably from 1 to 6, most preferably 3 to 5, is suitable if suspendisse agent selected from starch, methylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, gum agar, silicon dioxide, colloidal clays or oxides or hydroxides of aluminum or iron. Each of these agents has a different optimum pH depending on, for example, from solubility.

In order to improve the effect of suspending agent, you can also enter a small amount of one or more promoters, for example from 0.001 to 1% of the mass. Typically, these promoters are organic materials and can be selected, for example, one or more representatives from the following: water-soluble sulfonated polystyrenes, 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, materials, such gelatine, glue is, casein, albumin, glutino etc., non-ionic 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, the initiators suitably selected from one or more of these organic peroxides, as dialkylamide, diazepamonline, complex peroxidase, PEROXYDICARBONATE or azo compounds. Suitable initiators include dicetylperoxydicarbonate, di-(4-tert-butylcyclohexyl)PEROXYDICARBONATE, dictyospermi, Dibenzoyl peroxide, dilauroylperoxide, dodecanedioic, tert-butylmercaptan, tert-butylmalonate, tert-butylperbenzoate, tert-butylhydroperoxide, cumene hydroperoxide, AMYLPEROXY cumene, diisopropylperoxydicarbonate, 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 N-methyl-N-(2-hydroxy-ethyl)propionamide] etc. Polymerization can also be initiated by radiation, such as ionizing radiation high power.

When the polymerization is essentially ends microspheres are usually obtained as an aqueous suspension or dispersion, which can be used as such is or be dehydrated in any traditional way, such as filtration through a layer, filtration under pressure, filtration through a leaf filter, rotary filter, filtration through a belt filter or centrifugation, to obtain the so-called raw sludge. However, you can also be dried microspheres by any conventional method, such as spray drying, drying rack, drying, tunnel drying, rotary drying, drying in a rotary dryers, air drying, turborilla drying, drying in a disk-drying or drying in a fluidized bed.

If you microspheres at any stage can be treated to reduce the amount of residual unreacted monomers, for example, any technology described in the above WO 2004/072160 or US 4287308.

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

Expanding and expanded microspheres of the present invention are used in various applications, such as receipt paper, printing ink (such as water-based paints, paint solvents, plastisol, UV-cured inks, etc., for example, for fabric, Wallpaper, etc), mastics, sealants, toy clay, underwater coatings, adhesives, disconnect adhesives, synthetic leather, genuine leather, paint, non-woven materials, paper and cardboard, coating (e.g., coatings anti-slip etc) for various materials, such as paper, cardboard, plastics, metals and fabric, explosives, cable insulation, thermoplastics such as polyethylene, polyvinyl chloride 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), the best choice rubber, natural rubber, vulcanized rubber, silicone rubber, thermotherapies polymers (t is such as epoxides, polyurethanes and polyesters). In some of these applications expanded microspheres are particularly preferred, such as mastics, sealants, toy clay, leather, paint, explosives, cable insulation and thermotherapies polymers (for example, epoxies, polyurethanes and polyesters). In some cases, you can use a mixture of extended and expanding microspheres of the present invention, for example in underwater coatings, silicone rubber and lightweight foams.

Another aspect of this invention relates to aqueous suspensions containing thermoplastic expanding microspheres, as described above, preferably, in an amount of 5 to 55 wt. -%, most preferably 20 to 55 wt%. This suspension is used for various applications expanding microspheres, including, for example, paper. The suspension preferably contains at least one thickener, preferably compatible with the receiving paper. Examples of such thickeners include, at least partially water-soluble polymers selected from the group consisting of the following: starch, gums, cellulose, chitina, chitosans, glikana, galactanes, pectins, mannans, dextrins, copolymers derived from monomers containing acrylic acid or its salts (predpochtitel is about 50 mol%, most preferably up to 20 mol%, acrylic acid or its salts), Homo - and copolymers derived from monomers containing esters or amides of acrylic acid, Homo - and copolymers derived from monomers containing methacrylic acid, its esters or amides, latex rubbers, poly(vinyl chloride) and copolymers, poly(vinyl esters) and copolymers (e.g. ethylene), poly(vinyl alcohol), polyamine, polyethyleneimine, polyethylene/polypropyleneoxide, polyurethane and protondensity of aminoplast and phenoplast, such as urea/formaldehyde, urea/melamine/formaldehyde or phenol/formaldehyde and polymethylenepolyphenylene resin. Examples of suitable gums include gargani, tamarind-the gums, the gums beans false, gums wiki, gum karaya, gumey, acacia, xanthan gum-gums, etc. and their mixtures, of which particularly preferred are gargani. Examples of suitable cellulose derivatives include cellulose, such as optionally chemically modified CMC (CMC) (CMC) and ethers of cellulose, for example, EGEC (EHEC) (metilgidroxiatilzelllozu) and SCE (NES) (hydroxyethylcellulose), and mixtures thereof. Chemically modified derivatives of cellulose include, for example, cellulose, modified with different functional groups such as Quaternary amines, other amines, self is you, the sulfonates, phosphates, phosphonates, polyethylene oxide and propylene oxide.

At least partially water-soluble polymer may be unbranched, branched or crosslinked. The average molecular weight can vary within wide limits 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, guargum, polymethylenepolyphenylene resins, copolymers of acrylic acid with other monomers (for example, acrylamide) and Homo - or copolymers of polyacrylamides, polyamine, poly(vinyl alcohol) and polyethylene/polypropyleneoxide.

One or more at least partially water-soluble polymers, useful as a thickening agent, preferably present in a quantity sufficient to stabilize the suspension against significant sedimentation or flotation of the microspheres to such an extent that they cannot be re-dispersed. In many cases, this can be the achieved by incorporating a sufficient amount of polymer to obtain the preferred 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 (relates to the measurement of the viscometer Anton Paar DV-1P, equipped with a spindle L3). The quantity required for the stabilization of 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. -%, in particular, most preferably from about 0.5 to about 10% of the mass.

All thickeners and other additives discussed in any of the previously mentioned applications WO 2006/068573 and WO 2006/068574, can be used in aqueous suspensions of the invention in the preferred quantities are also discussed here.

Particular aspects of the present invention relate to the use of expanding microspheres, as described above, in printing inks and in obtaining paper from the source of raw materials containing cellulose fibers, artificial leather and non-woven materials.

When used in printing inks, in particular, in aqueous printing inks, expanding microspheres, preferably raw unexpanded microspheres are introduced in the standard formulation, is well known to specialists in this field of technology. Such formulations typically include one or bol is E. binder and one or more thickeners. Other components may include, for example, pigments, anti-foam agents, fillers, chemicals to prevent scaling or clogging, etc. Printing inks can also be based on acrylate dispersions or plastisols containing expanding microspheres. After printing microspheres foaming when heated before drying or after drying of the paint. Such printing inks are particularly suitable for printing on fabrics or Wallpaper.

When used in artificial leather expanding microspheres, preferably dry unexpanded microspheres are used in the standard formulations of the standard techniques known to experts in the art, for example, in the surface layer of the multilayer artificial leather, such as suede or any type of structure. Artificial leather can be obtained by any standard method such as a method of release paper, a direct application of woven or non-woven material or method of coagulation of any standard material such as polyurethane ((PU)(PU), polyvinyl chloride (PVC) (PVC)) and mixtures thereof. Usually artificial leather obtained by any of the methods above, covered with a paste PU or PVC containing expanding microspheres, and then heated for expansion of the microspheres.

In obtaining securities is expanding microspheres, preferably used to increase the amount of paper, but the alternative can serve other purposes. The microspheres are then preferably introduced into the raw materials containing cellulose fibers, which is then dehydrated and dried, which expanded microspheres. In most cases, the expansion increased the amount of paper.

A special aspect of this invention relates to a method for producing paper, including the introduction phase thermally expanding microspheres, as described above, in the raw material containing cellulose fibers, dewatering of raw materials on a wire grid with obtaining paper and drying of paper in the supply of energy and therefore also the temperature rise of the microspheres is sufficient for them to expand and increase the volume of paper.

The growing number of microspheres injected into the feedstock is preferably from 0.1 to 20 wt. -%, most preferably from 0.2 to 10 wt. -%, dry microspheres dry matter content in the feedstock. Can be used any known in the art, the type of paper machine.

The term "paper"as used here includes all types of cellulose-containing products in the form of a sheet or canvas, including, for example, a plate, cardboard and thick paper. Found that particularly useful to use the invention for which Holocene plate, cardboard and thick paper, in particular, with a base weight of 50 to 1000 g/m2preferably from 150 to 800 g/m2.

The paper can be obtained as a single-layer paper or laminated paper. If the paper contains three or more layers, expanding microspheres can be introduced into portions of the original raw material, forming one or more of these layers, for example, only part of the raw materials, do not form any of the two outer layers.

The feedstock contains from 50 to 100 wt. -%, most preferably from 70 to 100% of the mass. cellulose fibers with respect to the dry material. Before dehydration of 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 additives retention, sizing agents, aluminum compounds, dyes, resins, hardening in the wet state, optical brightening agents, etc. are Examples of aluminum compounds include alum, aluminates and semi-aluminum compounds, for example, polyaluminosilicate and sulfates. Examples of additives include retention of cationic polymers, anionic inorganic materials in combination with the PR is adicheskii polymers, for example, bentonite in combination with cationic polymers or silica sols in combination with cationic polymers or cationic and anionic polymers. Examples of sizing agents include interacting with cellulose sizing agent, such as alkylether and alchemistry anhydride, and noninteracting with cellulose sizing agent such as rosin, starch and other polymeric sizing agent, for example copolymers of styrene with vinyl monomers, such as maleic anhydride, acrylic acid and its alkalemia esters, acrylamide, etc.

When drying the paper, and therefore also of the microspheres is preferably heated at a temperature of from 50 to 150°C, most preferably from 60 to 110°C. This gives an expansion of the microspheres and therefore also the increase in the volume of paper. The value of the specified volume increase depends on various factors, such as the origin of cellulose fibers and other components in the feedstock, but in most cases is 5 to 70% or more of the mass percentage of the microspheres in the dried paper compared with the same kind of paper without the introduction of the expanding microspheres or any other foaming agent. Can be used any conventional method of drying, including heat transfer paper, such as pin the loops (for example, heated rollers), drying with forced convection (e.g., hot air), infrared technology, or combinations thereof. In case of contact drying temperature of the contact surfaces, for example, rollers, is preferably from 20 to 150°C, most preferably from 30 to 130°C. the Paper may pass through a series of one or more of the rolls, for example up to 20 or more, with the increase in temperature.

Cellulose fibers in the raw material can for example be derived from pulp obtained from any species, preferably, such wood as solid wood and soft wood. Cellulose fibers can also be partially or completely occur from recycled paper, and it was found that in this case, the invention provides unexpectedly good results.

Expanding microspheres can be entered in any form, although, from a practical point of view, most preferably, to introduce them in the form of an aqueous slurry, as described above.

The present invention is also described in connection with the following examples, which, however, should not be interpreted as limiting the scope of the invention. Unless otherwise specified, all parts and percentages are parts and percentages by weight.

The expansion properties of the microspheres is determined on the installation Mettler TMA 40 processor TSTA and personal to what computer software STAR eusing a heating rate of 20°C/min and the load (net.) 0,06 N. Tstartrepresents the temperature at which it starts foaming, Tmaxrepresents the temperature at which maximum expansion, and TMA-density represents the density of the microspheres at Tmax.

The particle size and distribution of particle size is determined by laser scanning device Malvern Mastersizer Hydro 2000 SM crude samples. The average particle size is presented as the average volume diameter d(0,5).

The amount of propellant is determined by thermogravimetric analysis (TGA) instrument Mettler Toledo TGA/SDTA851e. All samples prior to analysis is dried to remove as much moisture and, if present, also the residual monomers. Tests conducted in nitrogen atmosphere using a heating rate of 20°C/min-1starting from 30°C.

Example 1

The reaction mixture containing Mg(OH)2-the stable organic droplets in water is obtained by mixing phases and intense mixing to achieve a suitable droplet size. Aqueous dispersion contains 3.2 hours of Mg(OH)2and 331 including water. Organic drops contain 2,0 hours of dilapilated, 38 including isobutane, 52,0 including Acrylonitrile, 28,0 including Methacrylonitrile, 20,0 hours of methyl acrylate and 0.3 g trimethylolpropane. The polymerization is carried out at 6°C in a sealed reactor under stirring. After cooling to room temperature a sample of the resulting suspension of the microspheres are removed to determine the distribution of particle size. After filtering, washing and drying the particles to analyze the TMA. Dry particles contain approximately 23% of the mass. isobutane and have an average particle size of about 34 microns. TMA-the results are presented in table 1.

Examples 2-24

Microspheres receive many of the experiments conducted as in example 1, except for monomers and propellants, which are administered in accordance with table 1. The amount of water and Mg(OH)2the examples range from 235-365 including 2,2-4,8 hours, respectively. Due to the small differences in the formulations in different polymerization reactors has no influence on thermal properties of the polymerized particles. In examples 3, 4, 7 and 10 before processing the particles out of the reactor reduces the amount of residual monomers by treatment of 6 hours NaHSO3for 5 h at 70°C, after which the temperature is reduced to room temperature, and the particles are separated and analyzed. In example 2, the amount of residual monomer is reduced by the processing of 3.5 hours NaHSO3and in examples 18 and 22 - 1,4 including NaHSO3. In example 17, the amount of residual monomer is reduced by the processing of 8.6 hours 25% NH3and 30 o'clock water for 1 h at 70°C followed by the addition of 1.5 hours (NH4)2S2O8the solution is spent 17 PM water and continuing the reaction for 4 h at 70°C, after which the temperature is reduced to room temperature, and the particles are separated and analyzed. The results of the analysis are presented in table 1.

Table 1
Analytical results for examples 1-24 and the number of chemicals used, expressed in mass
ExampleANMANXIBIPSize (µm)Sang-tapes (% wt.)Tstart
(°C)
Tmax (°C)TMA-raft-ness (g/l)
1, X = MA52282038-3423901634,0
2, X = MA60301034- 34271041776,7
3, X = MA45253038-4022931515,2
4, X = MA60202038-3621971568,9
5, X = EA6233535-29171061858,5
6, X = EA59311035-25 22981765,1
7, X = EA52282038-3016941626,5
8, X = BA6233535-281910418413,2
9, X = BA59311035-28189717111,5
10, X=BA52282038-2822 9514923,0
11,X = MMA52282038-2520921575,3
12, X=EMA52282038-271190150the 9.7
13, X = BMA52282038-251294137to 45.4
146535--353225115 1855,2
15, X = MA522820-2334191211567,2
16, X = MMA522820-3527261121517,9
176535-34-44251131868,4
18, X = MA52282033-1221100141 9,1
19, X = MMA52282034-15189914014,6
20, X = MA52282035-2823921584,5
21,X = MA65152035-3019931609,9
22, X = MA45253033-1220951359,0
23, X = MA52282038-2320941595,1
24, X = MA553015383926981804,3
AN - Acrylonitrile, MAN - Methacrylonitrile, MA - MMA, EA - acrylate, VA - butyl acrylate, MMA is methyl methacrylate, EMA - methacrylate, MMA - butylmethacrylate, IB - isobutane, IP - isopentane.

Transparency of dry microspheres of examples 18 and 19 analyzed in accordance with ISO 2470 using a reflectometer Zeiss Elrepho, measurement of the diffusion index of reflection of blue light with a wavelength of 457 nm, and using a paper prototype 59,65. However, due to the necessity of the sample holder for powders, the refractive index of the microspheres can be measured only through a glass disk, which gives the decrease in reflectance of approximately 11% (units m is TA). Thus, the figures obtained with lower refractive index, mean that true transparency values are about 11 percent higher. As a prototype using a commercial product microspheres having a polymer shell of 58% vinylidenechloride, 33% Acrylonitrile and 9% of methyl methacrylate and isobutane as propellant. The results are shown in table 2.

Table 2
The transparent microspheres
Transparency (%)
Example 1875,9
Example 1978,6
The placeholder60,1

Dry microspheres of examples 20 and 21 are tested for resistance to solvents. Each sample is mixed with a mixture of solvents consisting of 2-butanone and DMF (90/10 wt./mass.), and incubated for 7 days at room temperature. After this processing microspheres is filtered and dried and again analyze the TMA to determine changes in the characteristics of the foaming. As a prototype commercial product microspheres having a polymer shell of 22% vinylidenechloride, 60% of Acrylonitrile and 18 of methyl methacrylate, and isobutane as propellant is treated in the same way. The results are shown in table 3.

Table 3
Resistance to a mixture of 2-butanone/DMF 90/10
MicrospheresThe extension before exposure to the solventExpansion after soaking in solvent for 1 weekNote
Tstart(°C)Tmax(°C)TMA-density (g/l)Tstart(°C)Tmax(°C)TMA-density (g/l)
Example 20921584,57316144,9
Example 21931609,99716113,6
The placeholder 9915012,3107148106,2Destroyed

It is seen that the microspheres of the invention are significantly less exposed to solvent mixtures than microspheres of the prototype, derived from high quantities vinylidenechloride monomers. You can also see that the microspheres of example 21, obtained with a high content of Acrylonitrile monomers, have better resistance to solvents.

Example 25

A single layer of thick paper with a base weight of approximately 300 g/m2get on a pilot paper machine with a machine speed of 4 m/min, without return process water. The pulp contains 42.5% of the mass. solid wood, 42,5% of the mass. soft wood and 15.0% of the mass. filler ICC, GCC (ground calcium carbonate) and is ground to a Shopper-Riegler values 25°SR, and then dispersed with obtaining pulp suspension/feedstock. Aqueous suspension of expanding microspheres before mixing chamber is introduced into the feedstock in an amount of about 2.0 percent of the mass. dry microspheres of dry matter in the feedstock.

As an additive retention use Compozil® and as a sizing agent used AKD. In the drying section of a paper sheet on Renaut rollers, with the temperature profile from 65 to 122°C. are Experiencing expanding microspheres of examples 3, 4, 18 and 22. For stabilization against flotation or sedimentation in suspensions of microspheres injected Gohseran L-3266™ (polyvinyl alcohol modified with acid). As microspheres prototype experience a commercially available suspension of microspheres with microspheres having a polymer shell of 73% of vinylidenechloride, 24% Acrylonitrile and 3% of methyl methacrylate and having isobutane as propellant, and with Solvitose C5™ (starch) from the company Avebe Starches North Europe as a thickener. In order to determine the retention of microspheres, samples of paper are selected before pressing section to determine the number of microspheres (using GC). Retention is calculated by the introduction of the microspheres and the microspheres content of the paper. In addition, samples of the dried paper selected for determination of volume and thickness. The results are shown in table 4.

In the same way get a single layer of thick paper with a base weight of approximately 80 g/m2. The microspheres of examples 3 and 4 have together with microspheres-prototypes. The results are shown in table 5.

Table 4
The base weight of approximately 300 g/m2
AN/MAN/MA in the polymer oblock is (% wt.) The amount of propellant (% wt.)Particle size (µm)Keep-tion (%)Increased volume (% percentage held microspheres)
45/25/30 (Example 22)20122820
52/28/20 (Example 18)21122110
45/25/30 (Example 3)22403971
60/20/20 (Example 4)21365054
Prototype 1 VDC/AN/MMA14147816
Prototype 2 VDC/AN/MMA17207023
AN - Acrylonitrile, MAN - Methacrylonitrile, MA - MMA, VDC - in Mildenhall, MMA - methyl methacrylate

Table 5
The base weight of about 80 g/m2
AN/MAN/MA in the polymer shell (% wt.)The amount of propellant (% wt.)Particle size (µm)Retention (%)Increased volume (% percentage held microspheres)
45/25/30 (Example 3)22404759
60/20/20 (Example 4)21364472
Prototype 1 VDC/AN/MMA1414779
Prototype 2 VDC/AN/MMA17205721
AN - Acrylonitrile, MAN - Methacrylonitrile, MA - MMA, VDC - vinylidenechloride, MMA - methyl methacrylate

The results show the, what the General trend is that the increase in the volume of paper from microspheres not containing chlorine, in the present invention is comparable to the increase in the volume of paper from microspheres containing chlorine. It also shows that particles with a large diameter to give a very high increase.

Example 2

The microspheres of examples 11 and 23 experience in PVC-plastisol by mixing 4% of the mass. dry microspheres using disk solvent with a pre-mixed formulation of plastisol comprising 100 including PVC (Pevikon P682 from Hydro), 57 CH diisononylphthalate, 3 hours epoxidizing soybean oil (Edenol D81 from Cognis), 1 h barium-zinc stabilizer (Mark BZ 505 from Crompton) and 3 hours of butylbenzylphthalate. A film applicator with a gap of 250 μm doing the drawing. One of the hoods heliroute at 100°C for 45 s, and the thickness newspronet hood is 160 μm, measured by a device for determining the thickness of the coating Elcometer 355 Standard. Other extrusion-foamed for 60 s at 140-200°C, determine the thickness of the same and the coefficients of expansion is calculated by dividing the thickness newspring layer. As for gelling and foaming use heat chamber hot air laboratory ovens Mathis. In the same way, feel the commercially available grade of microspheres having a polymer shell of 58% of Acrylonitrile and 42% metalmetal the TA and with isobutane as propellant. The expansion coefficients are presented in table 6.

Table 6
The coefficients of expansion of the microspheres in PVC-plastisol
Temperature (°C)Example 11Example 23The placeholder
1402,33,71,8
1503,44,82,3
1604,15,32,6
1704,35,62,5
1804,35,92,4
1904,65,92,3
200the 4.75,62,1

The results show that the coefficients of expansion of the plastisol with microspheres present Adamu invention are higher than the coefficients of expansion with microspheres-prototypes.

1. Thermoplastic thermally expanding microspheres containing a polymer shell made from monomers with ethylene unsaturation, kapsulirujushchej propellant, and these monomers with ethylene unsaturation containing from 40 to 70 wt.% of Acrylonitrile, from 5 to 40 wt.% Methacrylonitrile, from more than 10 to 50 wt.% monomers selected from the group consisting of esters of acrylic acid, esters of methacrylic acid, and mixtures thereof, and the specified propellant contains at least one representative from methane, ethane, propane, isobutane, n-butane and neopentane.

2. Microspheres according to claim 1, in which the aforementioned monomers with ethylene unsaturation containing from 45 to 65 wt.% Acrylonitrile.

3. Microspheres according to any one of claims 1 and 2, in which the aforementioned monomers with ethylene unsaturation containing from 10 to 35 wt.% Methacrylonitrile.

4. Microspheres according to any one of claims 1 and 2, in which the aforementioned monomers with ethylene unsaturation containing from 15 to 50 wt.%, at least one ester of acrylic acid or methacrylic acid.

5. Microspheres according to any one of claims 1 and 2, in which the aforementioned monomers with ethylene unsaturation containing from more than 10 to 50 wt.%, monomers selected from the group consisting of esters of acrylic acid.

6. Microspheres according to any one of claims 1 and 2, in which the aforementioned monomers with ethylene unsaturation with the keep from over 10 to 50 wt.% monomers, selected from the group consisting of methyl acrylate, ethyl acrylate and mixtures thereof.

7. Microspheres according to any one of claims 1 and 2, in which the aforementioned monomers with ethylene unsaturation containing from more than 10 to 50 wt.% of methyl acrylate.

8. Microspheres according to any one of claims 1 and 2, in which the aforementioned monomers with ethylene unsaturation, essentially, do not contain or contain less than 10 wt.% halogenated monomers.

9. Microspheres according to any one of claims 1 and 2, where the propellant contains isobutane.

10. Microspheres according to claim 9, in which said propellant contains from 50 to 100 wt.% isobutane.

11. Microspheres according to any one of claims 1 and 2, or 10, in which Tstartranges from 50 to 110°C.

12. A method of obtaining a thermally expanding microspheres according to any one of claims 1 to 11, comprising the polymerization of monomers with ethylene unsaturation in the presence of the propellant with obtaining microspheres containing polymer membrane, kapsulirujushchej specified propellant, and these monomers with ethylene unsaturation containing from 40 to 70 wt.% of Acrylonitrile, from 5 to 40 wt.% Methacrylonitrile, from more than 10 to 50 wt.% monomers selected from the group consisting of esters of acrylic acid, esters of methacrylic acid, and mixtures thereof, and the specified propellant contains at least one representative from methane, ethane, propane, isobutane, n-butane and neopentane is.

13. Water suspension containing thermally expanding microspheres according to any one of claims 1 to 11.

14. Aqueous suspension according to item 13, which additionally contains at least one thickener, which is at least partially water-soluble polymer selected from the group consisting of the following: starch, Gama, cellulose, chitina, chitosans, glikana, galactanes, pectins, mannans, dextrins, copolymers derived from monomers containing acrylic acid or its salts, Homo - and copolymers derived from monomers containing esters or amides of acrylic acid, Homo - and copolymers derived from monomers containing methacrylic acid, its esters or amides rubber latexes, poly(vinyl chloride) and copolymers, poly(vinyl esters) and copolymers, poly(vinyl alcohol), polyamine, polyethyleneimine, polyethylene/polypropyleneoxide, polyurethane and protondensity of aminoplast and phenoplast and polymethylenepolyphenylene resin.

15. The expanded beads obtained by foaming and 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 receiving paper from the source of raw materials containing cellulose fibers.

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

18. The use of thermally expanding mi is roster according to any one of claims 1 to 11 in obtaining artificial leather.

19. The use of thermally expanding microspheres according to any one of claims 1 to 11 in receipt of non-woven material.

20. A method of obtaining a paper, containing the introduction phase thermally expanding microspheres according to any one of claims 1 to 11 in the raw material containing cellulose fiber, dehydration of raw materials in wire mesh with getting the paper and drying the paper at the end of heat, and therefore also increasing the temperature of the microspheres enough for their foaming and increase the volume of paper.

21. The method according to claim 20, in which thermally expanding microspheres injected in the form of an aqueous suspension according to any one of p and 14.



 

Same patents:

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
The invention relates to the production of paper containing various means of protection against counterfeiting and unauthorized manufacture, and more particularly to securities with protective means, the action of which is based on the phenomenon of thermal sensitivity, t

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

FIELD: chemistry.

SUBSTANCE: invention relates to floor coating and can be used individually or industrially for floor coating in apartments and manufacturing facilities. The floor coating is polyvinyl chloride foam. Cost-effectiveness lies in use of available agents for cooling to technologically feasible temperature, creation of conditions for hardening of the surface layer of the fabric, possibility of turning the fabric by 180 degrees when there is need to use dyeing and lacquer coatings at rate of movement of the fabric of up to 25 m/min.

EFFECT: effect of sensory and organoleptic perception of natural species of wood and/or stones.

FIELD: technological processes.

SUBSTANCE: invention may be used for development of new nano-structured thin-film materials applied in systems of controlled transport and delivery of micron, submicron and molecular objects in liquid phase, in technologies of bioengineering, in nano-metrical assembly technologies, in analytic, sensor, biomedical, cosmetic, catalytic, membrane technologies. Thin-film material is made in the form of free thin film in liquid phase that includes colloidal particles, which are chemically connected between each other in the film plane, at that components of material separately are able to form solutions in liquid phase. Material is formed by the method on the basis of self-assembly and self-organisation effects of low-dimensional structures directly in the volume of liquid phase. Initial solutions of material individual components are prepared, and liquid phase that contains prepared thin-film material is formed. Processes of binding and creation of chemical links are carried out between colloidal particles by means of single or multiple addition of solution that contains one or several reagents or components into solution of another component or other components of prepared thin-film material. Formation of material thin-film structure is performed in the volume of liquid phase for the time sufficient for processes of material components binding and creation of free thin-film structure. Thin-film material is applied as a layer on the surface of extended articles - threads, wire, rods, etc.

EFFECT: method of thin-film material production is environmentally safe; provides higher material output and suggests possibility of technological process automation.

25 cl, 17 dwg, 1 ex

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