Microspheres

FIELD: technological processes.

SUBSTANCE: invention relates to thermoplastic thermally expanding microspheres and their application. Microspheres contain a polymer shell made of monomers with ethylene unsaturation that encapsulates a propellant. Monomers with ethylene unsaturation contain from 20 to 80 wt % of acrylonitrile, from 20 to 80 wt % of monomers selected from the group that consists of acrylic acid ethers, from 0 to 10 wt % of methacrylonitrile, from 0 to 40 wt % of monomers selected from the group that consists of methacrylic acid ethers. The total quantity of acrylonitrile and acrylic acid ethers makes from 50 to 100 wt % as monomers with ethylene unsaturation. The propellant contains at least one representative selected from the group of methane, ethane, propane, isobutane, n-butane and isopentane.

EFFECT: microspheres have high ability of foaming, low Tstart without high quantities of halogen-containing monomers, resistance to chemicals and high transparency.

22 cl, 8 tbl, 28 ex

 

The present invention relates to a thermally expanding 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 of 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 microspheres and their receipt m which can be found for example, in U.S. patents№3615972, 3945956, 4287308, 5536756, 6235800 (meets EP 1067151), 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 received, as described, for example, in U.S. patent No. 3556934 and 4133688, JPP 2689787, lined with Japanese application No. 2003-105693, WO 2004/113613, in International patent applications 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 & Paper 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, for example, 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 yet R is sewed these problems satisfactorily.

Even in the microspheres without halogenated monomers there may be a problem of unsatisfactory yield of the polymerization, in particular, if initiators are used, giving a high reaction rate. This leads to the presence of residual monomers in the microspheres, and even though the monomers such as Acrylonitrile, can be removed by suitable paleobotany, this represents an additional step in the production method, and the residual monomers are also the loss of the source material.

The aim of the present invention is to provide an expanding microspheres with high capacity for expansion and low Tstartwithout 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, which can be obtained with high yield in the polymerization method.

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 one is th the aim of the present invention is to provide aqueous suspensions containing an expanding microspheres used in obtaining paper.

Was unexpectedly discovered 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 20 to 80 wt.% of Acrylonitrile, from 20 to 80 wt.% monomers selected from the group consisting of esters of acrylic acid, from 0 to 10 wt.% Methacrylonitrile, from 0 to 40 wt.% monomers selected from the group consisting of esters of methacrylic acid, the total amount of Acrylonitrile and esters of acrylic acid is from 50 to 100 wt.% these monomers with ethylene unsaturation, and the specified propellant contains at least one representative from methane, ethane, propane, isobutane, n-butane and isopentane.

Monomers with ethylene unsaturation, preferably, contain from 30 to 70 wt.%, most preferably, from 35 to 65 wt.% Acrylonitrile. Monomers with ethylene unsaturation, in addition, preferably contain from 20 to 70 wt.%, most preferably 25-60 wt.% monomer is, selected from the group consisting of esters of acrylic acid.

Esters of acrylic acid, preferably, have only one double bond in the carbon-carbon bonds. Possible esters of acrylic acid include, for example, methyl acrylate, acrylate and mixtures thereof, among which particularly preferred is methyl acrylate. Monomers with ethylene unsaturation, thus, preferably, contain from 20 to 80 wt.%, most preferably, from 30 to 70 wt.%, in particular, most preferably from 35 to 65 wt.%, monomers selected from the group consisting of methyl acrylate, ethyl acrylate and mixtures thereof, of which the methyl acrylate is particularly preferred.

The total amount of Acrylonitrile and esters of acrylic acid, preferably, ranges from 65 to 100 wt.%, most preferably, from 75 to 100 wt.%, in particular, most preferably, from 90 to 100 wt.%, monomers with ethylene unsaturation.

Monomers with ethylene unsaturation can essentially do not contain Methacrylonitrile, but if it is contained, its amount is preferably from 0 to 5 wt.%, most preferably, from 0 to 2 wt.%.

Monomers with ethylene unsaturation can essentially not contain esters of methacrylic acid, but if they are, their amount is preferably from 0 to 30 wt.%, most preferably, from 0 to 25 wt.%, in particular, most preferably, from 0 to 10 wt.% or even from 0 to 5 wt.% monomers with ethylene unsaturation. A number of esters of methacrylic acid may also comprise from 0 to 5 wt.% or even from 0 to 2 wt.% monomers with ethylene unsaturation. Examples of esters of methacrylic acid include one or more representatives from methyl methacrylate, isobutylacetate, ethyl methacrylate, butyl methacrylate or hydroxyethylmethacrylate, of which the methyl methacrylate is most preferred.

Preferably the monomers with ethylene unsaturation does not inherently contain vinylidenechloride. If it is contained, its amount is preferably less than 10 wt.%, most preferably less than 5 wt.% or even less than 1 wt.% 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 wt.% or even less than 1 wt.% 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 pre the representatives of 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, criticalpoint(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 which 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 wt.% monomers with ethylene unsaturation, and particularly preferred is 0.1 to 1 wt.% when one or more multifunctional monomers are the I, at least trifunctional, and particularly preferred is 1-3 wt.% when one or more multifunctional monomers are bifunctionality.

If contains monomers with ethylene unsaturation other than Acrylonitrile monomers selected from the group consisting of esters of acrylic acid and one or more crosslinking multifunctional monomers, their amount is preferably from 0 to 10 wt.%, most preferably, from 0 to 5 wt.%. Examples of such other monomers that can be included are nitrosobenzene monomers, such as α-ethoxyacrylate, fumaronitrile or crotonates, vinylpyridine, complex, vinyl esters such as 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, and other unsaturated compounds, for example, acrylamide, methacrylamide or N-substituted maleimide.

In the embodiment of the present invention the monomers with ethylene unsaturation essentially consist of Acrylonitrile 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 school is that 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 80°C.

The propellant is a hydrocarbon or mixture of hydrocarbons, preferably having a boiling point of not higher than the softening temperature of thermoplastic 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 isopentane, 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, neopentane, 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 simple EPE is s, etc. Preferred propellants include 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 wt.%.

Tstartexpanding the microspheres is preferably from 50 to 100°C, most preferably from 80 to 95°C. Tmaxexpanding the microspheres is preferably from 90 to 170°C, most preferably from 110 to 150°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 wt.%. 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 like Al, Ca, Mg, Ba, Fe, Zn, Ni and Mn, for example, one or more representatives of the following: calcium phosphate, calcium carbonate, magnesium hydroxide, barium sulfate, calcium oxalates and hydroxides of aluminum, iron, zinc, nikasil 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 an 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 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, 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 propelle is so 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 1288272, WO 2004/072160 and lined with Japanese application No. 1987-286534.

In the embodiment of the present invention microspheres receive periodic way, and the polymerization can be carried out, as described below, in the reaction vessel. On 100 parts by weight of Monomeric 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 hours, the aqueous phase is preferably in the range from 100 to 800 hours and one or more, preferably, solid colloidal suspendida agents, preferably in an amount of from 1 to 20 hours, the droplet Size of the Monomeric 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 fitting the th pH depends on a 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, magnesium oxide, barium sulfate, calcium oxalates 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 starch, methylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, DIN 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 the data of 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 wt.%. 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 products condense the tion amine, 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 gelatin, glue, 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 organic peroxides, such 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-methylp opional), 2,2'-azobis-[2-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 or be dehydrated by any conventional method, 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 of the technologies 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, the R 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 exact composition of the polymer shell and a propellant. 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 obtaining the paper, printing inks 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) such various materials, such as paper, cardboard, plastics, metals and fabric, explosives cable insulation, thermoplastics such as polyethylene, polyvinyl chloride and ethylene-vinylacetat is) or thermoplastic elastomers such as a styrene-ethylene-butylene-styrene, copolymer of styrene-butadiene-styrene, thermoplastic polyurethanes and thermoplastic polyolefins), the best choice rubber, natural rubber, vulcanized rubber, silicone rubber, thermotherapies polymers such as epoxies, 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, 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, from 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 vodorastvorimami, 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 salt (preferably up to 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, okra, 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) (ethylhydroxylamine ulose) 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, sulfates, 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 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, Garga, 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 number is the number, 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 achieved by introducing 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 wt.%.

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 raw material containing cellulose fiber is, in 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 more binders and one or more thickeners. Other components may include, for example, pigments, antirassistische 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 the microspheres are expanded by heating 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 other type of structure. Artificial leather can be obtained by any standard method such as a method of release b the sorcerers, direct application of a 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 to expand the microspheres.

In obtaining paper expanding microspheres, preferably, are 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, containing 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 p is edocfile, from 0.2 to 10 wt.% dry microspheres dry matter content in the feedstock. You can use any type of papermaking machine known in the technique.

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 obtaining the plates, cardboard, 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 preferably contains from 50 to 100 wt.%, most preferably, from 70 to 100 wt.% 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, for example, mineral fillers such as kaolin, China clay, titanium dioxide, gypsum, talc, chalk, ground marble or precipitated calcium carbonate, and, optionally, other customary what about the additives used, such as additive 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 organic polymers, such as 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 does not interact with the 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, so the x as the origin of the 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 extension agent. Can be used any conventional method of drying, including heat transfer paper, such as contact drying (e.g., 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 of wood, such as hard 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.

Us is Aasee the invention, in addition, as 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 degree of conversion of monomers determined by gas chromatography (GC). Approximately 0.2 g of dispersion are taken directly from the reactor and dissolved in 10 g of N,N-dimethylacetamide, containing THF as an internal standard. The conversion of monomers are calculated according to the results of GC relative to the original Monomeric power.

The expansion properties of the microspheres is determined on the installation Mettler TMA 40 processor TSTA and a personal computer with software STAReusing a heating rate of 20°C/min and load (net.) 0,06 N. Tstartrepresents the temperature at which the expansion, 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) on the device of the E. 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 4,4 including Mg(OH)2, 0,009 including bis(2-ethylhexyl) matriculating and 279 including water. Organic drops contain 0,6 including di-(4-tert-butylcyclohexyl) peroxide-carbonate of 27.9 including isobutane, 100,0 hours of methyl acrylate and 0.3 g trimethylolpropane. The polymerization is carried out at 56°C in a sealed reactor under stirring. After cooling to room temperature, the samples obtained suspension of the microspheres are removed to determine the monomer conversion and distribution of particle size. The rest of the material is filtered, washed and dried and then TMA-analysis. Dry particles contain about 2 wt.% propellant. The particles are fused together, and in the process of heating expansion does not occur.

Examples 2-14

Microspheres receive many experiments on the polymerization carried out as in example 1, except for monomers and propellants are injected in accordance with table 1. The amount of water and Mg(OH)2in the examples vary in the range of 220-280 hours and 3.6 and 4.4 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 11, 12 and 14 before processing the particles out of the reactor reduces the amount of residual monomer processing of 2.6 hours NaHSO3for 4 h at 70°C, after which the temperature is reduced to room temperature, and the particles are separated and analyzed. In the case of examples 2, 4, 5, 7, 9, 10 and 14 after cooling to room temperature a sample of the resulting suspension of the microspheres are removed to determine the conversion of the monomers (see table 2). The obtained particles have a particle size in the range of from about 13 μm to 33 μm and contain 12 to 27 wt.% propellant. The results of the analysis are presented in table 1. Example 2 particles partially fused together, as in examples 9 and 10 particles show a bad extension or lack of it. The degree of conversion of monomers for examples 2, 4, 5, 7, 9, 10 and 14 shown in table 2.

Examples 15-17

Experiments on the polymerization carried out as in example 1 except for using monomers and propellants in accordance with table 1 and dilapilated as an initiator and implementation of polymerization overnight at 62°C. the amount of water and Mg(OH) 2were 280, 350 and 270 hours and 4.8, and 3.4 and 4.8 hours, respectively. In the case of example 18 after cooling to room temperature a sample of the resulting suspension of the microspheres are removed to determine the monomer conversion (see table 2). To the rest of the reaction mixture of 0.2 PM NaHSO3and then 11 o'clock water. After stirring for 1 h at 40°C carry out a second addition of NaHSO3and water, and the temperature rises to 70°C for another 4 hours

25
Table 1
Analytical results for examples 1-17 and the number of chemicals used, expressed in parts by weight
ExampleANMAMMAIBIPSize (µm)Propellant (wt.%)Tstart
(°C)
Tmax(°C)TMA-density (g/l)
10100-27,9--2- --
21090-27,9-30107479129,5
32080-27,9-3315828922,1
43070-27,9-2616579313,7
54060-27,9-25197097of 17.5
65050-26,9-14127311520,5
75842-23,1-19118212319,7
87030-26,9-13208712027,9
98020-25,8-151987139400
10 9010-25,8-1419---
115050-33,0-14277412115,7
126040-33,0-15248112615,2
135842--31,714249012132,5
14453028,2-1419901218,7
156530533,0-8269513211,4
165050-33,3-10248911512,8
1752202834,3-3225831318,4
AN - Acrylonitrile, MA - MMA, MMA is methyl methacrylate, IB - isobutane, IP - isopentane.

the reamers 18-20

Microspheres are given as in example 1 except that the monomers introduced in accordance with table 2 and that as a propellant using n-pentane.

Table 2

Analytical results for examples 18-20 and the number of chemicals used, expressed in parts by weight of

ExampleANMAMMANBSize (µm)Propellant (wt.%)Tstart
(°C)
Tmax (°C)TMA-density (g/l)
186040-27,911249512329,2
195050-27,9122684116102
45302527,91219147149115
AN - Acrylonitrile, MA - MMA, MMA is methyl methacrylate, NB - n-pentane.

Examples 21-22

Microspheres are given as in example 1 except that the monomers introduced in accordance with table 3. The obtained particles have a particle size of 15 microns and 14 microns and contain 18 and 22 wt.% propellant respectively. Method on GC of the reaction mixture to determine the degree of conversion of the monomers, and the results are presented in table 3.

Table 3
Monomer conversion and the content of residual monomers in the reaction mixture
ExampleComposition (wt.%)Conversion (%)The number of suspensions (h/m)
ANMAMMAANMAMMA ANMAMMA
21090-99,699,8-84437-
43070-99,399,6-478617-
54060-of 99.199,2-8241060-
165050-99,899,8-265216-
758 42-99,699,6-625453-
98020-99,499,4-1190300-
109010-98,0the 98.9-4300273-
1445302599,098,7N.d.1100918N.d.
2150133797,396,7N.d. 35701130N.d.
2258-42for 91.3-99,911100-72
AN - Acrylonitrile, MA - MMA, MMA is methyl methacrylate, N.d. - not defined.

Because of the difficulty of sampling, for example, due to agglomeration, some inaccuracies of the data presented in table 3 cannot be excluded. But the trends are clear and show that the copolymerization of Acrylonitrile with methyl acrylate gives extremely high monomer conversion compared to copolymerization with methyl methacrylate. You can also see that at very high relations Acrylonitrile/methyl acrylate conversion of Acrylonitrile is below.

Transparency of dry microspheres of examples 6, 7 and 16 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 is to be measured only through a glass disk, that gives the decrease in reflectance of approximately 11% (units of percent). Thus, the figures obtained with lower refractive index, mean that true transparency values are approximately 11% of the units above. 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 4.

Table 4
The transparent microspheres
Transparency (%)
Example 684,0
Example 782,3
Example 1680,8
The placeholder60,1

Examples 23-26

Microspheres receive many experiments on the polymerization as in example 1 except that the monomers introduced in accordance with table 5. The obtained particles have a size 22-34 μm. Examples 23 and 25 contain about 20 wt.% isobutane, while the example 24 and example 26 containing about 9 wt.% isobutane and do not actually contain isobutane COO is responsible. The levels of residual monomer is low and comparable with the corresponding polymerization of methyl acrylate. Table 5 presents the extension properties, showing that the particles of examples 25 and 26 extension is missing.

Table 5
Analytical results for examples 23 to 26 and the number of monomers, expressed in parts by weight
ExampleANEABATstart
(°C)
Tmax
(°C)
TMA-density (g/l)
237030-8412452.8
245050-5510227.4
2570-30---
50-50---
AN - Acrylonitrile, EA - acrylate, VA - butyl acrylate, IB - isobutane.

Example 27

A single layer of thick paper with a base weight of approximately 80 g/m2get on a pilot paper machine with a machine speed of 4 m/min, without return process water. The pulp contains to 42.5 wt.% solid wood, to 42.5 wt.% soft wood and 15.0 wt.% 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 wt.% dry microspheres of dry matter in the feedstock. As an additive retention use Compozil® (Eka Chemicals) and as a sizing agent used AKD. In the drying section of a paper canvas heated rolls having a temperature profile of from 65 to 122°C. are Experiencing expanding microspheres of examples 11, 12 and 17. For stabilization against flotation or sedimentation in suspensions of microspheres injected Gohseran L-3266™ (polyvinyl alcohol, modified, sulfoxylate is) (see example 11 and example 12 in table 6 below). Starch (Solvitose C5™ from the company Avebe Starches North Europe) enters as a thickener in part to the suspension of microspheres from example 12 (example 12b). 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. This is performed by determining the amount of isobutane present in the paper a method GC, and, based on the data, calculate the quantity of microspheres. 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 6.

In the same way get a single layer of thick paper with a base weight of approximately 300 g/m2. The microspheres of examples 11, 12 and 16 (Gohseran L-3266™ as a thickener) experience with microspheres-prototypes. The results are shown in table 7.

Table 6
The base is ACCA about 80 g/m 2
AN/MAM/MA in the polymer shell (wt.%)The amount of propellant (wt.%)Particle size (µm)Retention (%)Increased volume (% percentage held microspheres)
50/50/0 (Example 11)27142511
60/40/0 (Example 12a)24152331
60/40/0 (Example 12b)24158112
52/20/28 (Example 17)25323759
Prototype 1 VDC/AN/MMA1414779
Prototype 2 VDC/AN/MMA17207023
AN - Acrylonitrile, MA - MMA, VDC - vinylidenechloride, MMA - methyl methacrylate

Table 7
The base weight of approximately 300 g/m2
AN/MAM/MA in the polymer shell (wt.%)The amount of propellant (wt.%)Particle size (µm)Retention (%)Increased volume (% percentage held microspheres)
50/50/0 (Example 16)24102113
50/50/0 (Example 11)27143210
60/40/0 (Example 12)24153617
52/20/28 (Example 17)25324146
Prototype 1 VDC/AN/MMA141478 16
Prototype 2 VDC/AN/MMA17207023
AN - Acrylonitrile, MA - MMA, VDC - vinylidenechloride, MMA is methyl methacrylate.

The results show that 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 28

Microspheres from example 16 experience in printing ink in obtaining a homogeneous dispersion of a mixture of 16.1 hours of raw microspheres (74.4% of dry mass), 73,9 including dispersion of copolymer of vinyl acetate-ethylene as a binder (Mowilith DM-107 from Celanese, 60% of dry mass), 66,3 including emulsion copolymer of a methyl methacrylate-acrylate as a binder (Primal ECO-16 from Rohm and Has, 45.5% of dry mass), 10,0 including glycerol and 0.8 g defoamer based on mineral oil (Nopco ENA-515 from Cognis) and 29.9 hours water using a mixer Silverson. Then add 3,0 including acrylic polymer dispersion as a thickener (Alcoprint PT-XN from Ciba), and then further mixing the solvent mixer to full zag is tion and homogeneous mixture. This gives the paint containing 12% by dry weight of the microspheres. Put the stencil paint that is dried overnight at room temperature. Then the thickness newspronet paint, which was installed is 40 μm, measured with a device for determining the thickness of the coating (Elcometer 355 Standard). Paint churn within 60 s at 90-150°C in a heating Cabinet hot air laboratory ovens Mathis. Determine the thickness of the foam paints and expansion coefficients calculated by dividing the thickness newspronet paint. In the same way, feel the printing ink obtained with commercially available microspheres having a polymer shell of 73% vinylidenechloride, 24% Acrylonitrile and 3% of methyl methacrylate and having isobutane as propellant. The expansion coefficients are presented in table 8.

Table 8
The coefficients of expansion of the microspheres in the printing ink
Temperature (°C)Example 16The placeholder
901,02,3
1003,03,0
1104,3 3,3
1205,33,5
1305,03,5
1403,02,8
1501,82,3

The results show that the coefficients of expansion of the paint with the microspheres of the present invention, does not contain chlorine, are higher than the coefficients of expansion of the microspheres containing chlorine, especially in the range of 100-140°C.

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 20 to 80 wt.% of Acrylonitrile, from 20 to 80 wt.% monomers selected from the group consisting of esters of acrylic acid, from 0 to 10 wt.% Methacrylonitrile, from 0 to 40 wt.% monomers selected from the group consisting of esters of methacrylic acid, the total amount of Acrylonitrile and esters of acrylic acid is from 50 to 100 wt.% these monomers with ethylene unsaturation, and the specified propellant contains at least one will represent the ü from methane, ethane, propane, isobutane, n-butane and isopentane.

2. Microspheres according to claim 1, in which the aforementioned esters of acrylic acid have only one double bond in the carbon-carbon bonds.

3. Microspheres according to any one of claims 1 and 2, in which the aforementioned monomers with ethylene unsaturation containing from 30 to 70 wt.% Acrylonitrile and 20 to 70 wt.% monomers selected from the group consisting of esters of acrylic acid.

4. Microspheres according to any one of claims 1 and 2, in which the aforementioned monomers with ethylene unsaturation containing from 35 to 65 wt.% Acrylonitrile and from 25 to 60 wt.% monomers selected from the group consisting of esters of acrylic acid.

5. Microspheres according to any one of claims 1 and 2, in which the quantity of Acrylonitrile and esters of acrylic acid comprises from 75 to 100 wt.% these monomers with ethylene unsaturation.

6. Microspheres according to any one of claims 1 and 2, in which the aforementioned monomers with ethylene unsaturation containing from 20 to 80 wt.% monomers selected from the group consisting of methyl acrylate, ethyl acrylate and mixtures thereof.

7. Microspheres according to claim 6, in which the aforementioned monomers with ethylene unsaturation containing from 20 to 80 wt.% of methyl acrylate.

8. Microspheres according to any one of claims 1, 2 or 7, in which the aforementioned monomers with ethylene unsaturation containing one or more crosslinking multifunctional monomers.

9. Microspheres of claim 8, in which the above monomers with ethylene unsaturation containing one or more crosslinking monomers, which are at least trifunctional.

10. Microspheres according to any one of claims 1, 2, 7, or 9, in which the aforementioned monomers with ethylene unsaturation essentially do not contain or contain less than 10 wt.% halogenated monomers.

11. Microspheres according to any one of claims 1, 2, 7, or 9, in which said propellant contains isobutane.

12. Microspheres according to claim 11, in which said propellant contains from 50 to 100 wt.% isobutane.

13. A method of obtaining a thermally expanding microspheres according to any one of claims 1 to 12, 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 20 to 80 wt.% of Acrylonitrile, from 20 to 80 wt.% monomers selected from the group consisting of esters of acrylic acid, from 0 to 10 wt.% Methacrylonitrile, from 0 to 40 wt.% monomers selected from the group consisting of esters of methacrylic acid, the total amount of Acrylonitrile and esters of acrylic acid is from 50 to 100 wt.% these monomers with ethylene unsaturation, and the specified propellant contains at least one representative from methane, ethane, propane, isobutane, n-butane and isopentane.

14. Water suspension containing thermally races is arausiaca microspheres according to any one of claims 1 to 12.

15. Aqueous suspension for 14 additionally contains at least one thickener, which is at least partially water-soluble polymer 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, 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.

16. Advanced microspheres obtained by the expansion of the expanding microspheres according to any one of claims 1 to 12.

17. The use of thermally expanding microspheres according to any one of claims 1 to 12 in receiving papers from the source of raw materials containing cellulose fibers.

18. The use of thermally expanding microspheres according to any one of claims 1 to 12 in printing inks.

19. The use of thermally expanding microspheres according to any one of claims 1 to 12 in obtaining artificial leather.

20. The use of thermally expands nausicca microspheres according to any one of claims 1 to 12 in obtaining a non-woven material.

21. The method of obtaining the paper, including the introduction phase thermally expanding microspheres according to any one of claims 1 to 12 in the original 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 the temperature of the microspheres enough to expand and increase the volume of paper.

22. The method according to item 21, in which thermally expanding microspheres injected in the form of an aqueous suspension according to any one of p and 15.



 

Same patents:
Microspheres // 2432202

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

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

Microspheres // 2432202

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

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

Microspheres // 2432202

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

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