Aqueous dispersions of polymers containing fluorescent dye, preparation method thereof and use thereof in marking materials

FIELD: chemistry.

SUBSTANCE: aqueous dispersion of polymers has particle diameter of at least 1 mcm and contains a fluorescent dye, characterised by that it is obtained via radical polymerisation of a suspension of ethylene-unsaturated monomers in an "oil in water" emulsion, the dispersion phase of which contains at least one fluorescent dye dissolved in at least one ethylene-unsaturated monomer, and has average particle diameter of at least 1 mcm, in the presence of at least one surface-active compound and at least 0.5 wt %, in terms of the monomer, of at least one hydrophobic, non-polymerisable organic compound, a hydrophobic polymer composed of at least one olefin with 2-6 carbon atoms with molar weight Mw of up to 10000, siloxane with molar weight Mw of up to 5000 and/or polystyrene with molar weight Mw of up to 10000. The ethylene-unsaturated monomers used are hydrophobic monomers from a group of acrylic alkylesters with 1-8 carbon atoms, methacrylic alkylesters with 1-8 carbon atoms, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, chlorostyrene and/or α-methylstyrene, and the hydrophobic non-polymerisable organic compound used is aliphatic or aromatic hydrocarbons having 10-50 carbon atoms, alcohols having 10-24 carbon atoms, tetraalkyl silanes, olive oil, perfluoromethyl decalin and/or di-n-butyl dicarboxylic acid esters with 4-6 carbon atoms. The invention also relates to a method of preparing and using an aqueous polymer dispersion, power obtained from said polymer dispersion, binder, a spreading adhesive compound and a paper gluing agent based on said dispersion.

EFFECT: obtaining aqueous polymer dispersions with uniform distribution of particle size and powder based on said dispersions for marking materials.

19 cl, 14 ex, 1 tbl

 

The present invention relates to aqueous dispersions of polymers having a particle size of at least 1 μm, which contain a fluorescent dye, the method of production of such dispersions by free-radical polymerization slurry ethylene-unsaturated monomers in the emulsion oil-in-water", whose disperse phase comprises at least one fluorescent dye dissolved in at least one ethylene-unsaturated monomer, and is characterized by an average particle diameter of at least 1 μm, in the presence of at least one surface-active compound, and applying the thus obtained aqueous dispersions or derived from polymeric powders for marking materials.

From the international application WO-A-99/40123 known method for the production of aqueous dispersions of polymers, dispersed polymer particles which contain homogeneous, i.e. molecular-dispersed, distributed organic dye. Such aqueous dispersions are made by mini-emulsion polymerization, in which the ethylene-unsaturated monomers containing dissolved organic dye, polimerizuet in the form of an emulsion of oil-in-water" in the presence of forming radicals initiators of polymerization, and a disperse phase of the emulsion in the main form containing the dye droplets mono the EPA with a diameter of less than 500 nm. In an expedient form of execution of the invention used in the polymerization mixture of monomers containing monomers to effect cross-linking. Dispersion polymers are resistant to sedimentation. Dispersed particles have a mean diameter of from 100 to 400 nm. They can be distinguished from aqueous dispersions using conventional drying methods. Dispersions of polymers containing dye, used for example for coloring high molecular weight organic and inorganic materials, for pigmentation of printing inks and inks for inkjet printing.

Other containing the dye dispersion of polymer particles polymerizate which includes dye, have a diameter less than 1000 nm, is known from European patent application EP-A-1191041. In addition to organic dyes as coloring tools, use as absorbers of ultraviolet radiation and optical brighteners. They are produced by dissolving the coloring agent in at least one ethylene-unsaturated monomer emulsification of the solution in water with the formation of normal microemulsion, homogenization microemulsion with the formation of the mini-emulsion with an average droplet size not greater than 1000 nm, and polymerization, mini-emulsion in the presence of forming a radical polymerization initiator, 0.1 to 20 wt.% at least one neion the CSOs surfactants and 1-50 wt.%, in each case, the applied monomers, at least one amphiphilic polymerizate. The polymer particles contain from 0.5 to 50 wt.% at least one organic dye, optical Brightener or absorber of UV radiation, distributed homogeneous, that should be understood in such a way that organic coloring agents are present in the polymer matrix in dissolved form monomolecular or in the form of bimolecular or more high molecular weight aggregates.

From the international application WO-A-2004/037867 known aqueous dispersions of polymers containing acidimetry obtained by polymerization of a mini-emulsion of hydrophobic monoethylene-unsaturated monomers in the presence of acidication. These dispersions are used as tools for paper sizing agents of waterproofing leather, natural and/or synthetic fibers and textiles.

B.J.Battersby, G.A.Lawrie, A.P.R.Johnston and M.Trau reported in Chem. Commun., 2002, 1435-1441, "optical encoding" colloidal suspensions of fluorescent dyes, crystals and metals. So, for example, colloids with a diameter of from 3 to 6 μm is subjected to optical labeling by deposits in them fluorescent dyes or complex-associated lanthanides. Another way of marking colloids consists in the deposition of zinc sulfide, which contains Nanak Italy of cadmium selenide, or electrochemical deposition of metal ions in the cavities of the colloids. Colloids can be distinguished from each other, for example, using a fluorescent microscope or cytometer.

From the international application WO-A-99/52708 known method of marking a gaseous, liquid or solid materials, in which the gaseous, liquid or solid material, which must be specified later, add a sufficient number of colored microparticles and/or nanoparticles that are associated with particles-carriers". Used particles are, for example, from polystyrene cross stitching and have approx. diameter of 5.5 μm. Particles of paint or encode three different fluorescent dyes in eight different concentrations, thus obtaining the 512 different groups of encoded particles. Separate groups can be identified, for example, by using a cytometer. Coded particles used for marking substances, such as salt crystals, to install thus the manufacturer, the production lot and date of manufacture.

From German application DE-A 2004 027416 known method of marking material encoded microparticles, which are used coded microparticles produced by

(i) Polymerization of at least one water-soluble monoethylene unsaturated monomer in risotti at least one ethylene-unsaturated monomer with at least two double bonds in the molecule by reverse polymerization [?] suspension "water in oil" in the presence of labeled nanoparticles as a suspending agent,

(ii) Emulsion polymerization of water-insoluble monoethylene-unsaturated monomer, from 0 to 10 wt.%, from a mixture of monomers, of at least one ethylene-unsaturated monomer with at least two double bonds in the molecule, and as an emulsifier to stabilize the dispersed phase using labeled nanoparticles,

(iii) Polymerization of at least one ethylene-unsaturated monomer together with suitable for copolymerization with the dye having at least one ethylene-unsaturated double bond, and optionally - agglomeration of these particles,

(iv) adsorption of at least one dye on the polymer particle, practically insoluble in water, and if necessary agglomeration of these particles,

(v) Agglomeration of at least two different groups of microparticles, which differ in their performance of absorption, emission and/or scattering of electromagnetic radiation, in units with an average particle diameter of from 300 to 500 μm,

(vi) precipitation of at least one water-insoluble dye from a solution of at least one organic solvent, suitable for mixing with water, practically insoluble in water particle polymer or

(vii) the Precipitation of water-soluble dyes electrostatic attraction on oppositely charged polymer is a particle practically insoluble in water.

When polymerization according to (i) and (ii) use, for example, nanoparticles labeled with at least one dye or one compound from the group of rare earth elements of the periodic system or with radioactivity.

From European patent EP-B-0692517 known method for the production of fluorescent pigments in which the suspension will polimerizuet a mixture of

(A) from 69,9 to 99.8 wt.% the alkyl residue of acrylic or methacrylic acid with 1 to 8 carbon atoms,

(B) from 0 to 29.9 wt.% suitable for joint polymerization monoethylene-unsaturated monomer,

(C) from 0.1 to 30.0 wt.% suitable for joint polymerization of the polyfunctional monomer, with the effect of cross-linkage in the presence of

(D) from 0.1 to 15.0 wt.%, from the sum of (a) and (B)non-polar fluorescent dye of coumarin or perimenopause series.

The diameter dispersed in water of polymer particles containing a fluorescent dye is in the range from 0.1 to 3 mm, if the monomers in water emuleret with impeller stirrer, and from 1 to 100 μm, if the monomers emuleret in water having a significant effect of shift units, such as Ultra-Turrax®, a then polimerizuet emulsion. Aqueous dispersions of polymers obtained in this way, however, characterize the I wide distribution of particle sizes.

The task should be solved by the invention is to provide aqueous dispersions of polymers with particle diameters, comprising at least 1 μm, and containing a fluorescent dye, with possibly a more uniform distribution of particle sizes. Such dispersions of polymers are of special interest for analytical methods "single particle", because the particle size, for example, from 1 to 100 μm is particularly convenient to determine analytically.

According to the invention the task is solved by means of aqueous dispersions of polymers, which have a particle diameter of at least 1 μm and containing a fluorescent dye, obtained by radical polymerization slurry ethylene-unsaturated monomers in the emulsion oil-in-water", whose disperse phase comprises at least one fluorescent dye dissolved in at least one ethylene-unsaturated monomer, and is characterized by an average particle diameter of at least 1 μm, in the presence of at least one surface-active compound and at least 0.5 wt.%, from monomers, at least one hydrophobic not curable organic compound, a hydrophobic polymer of at least one olefin with 2 to 6 carbon atoms, with a molar mass Mwto 10000, siloxane with molar mass Mw up to 5000 and/or polystyrene with a molecular mass Mwto 10000.

Synthesis dispersed in water of the polymer particles is carried out according to the invention by polymerization in suspension. In contrast to the method known from the aforementioned European patent EP-B-0692517, in the method according to the invention, in addition to the monomers, of at least one fluorescent dye and surfactants, in addition there is a co-solvent with a very low solubility in water as a hydrophobic substance. The solubility of hydrophobic substances in water is, for example, less than 0.1 g/l, preferably less than 0.01 g/l (at 25°C and 1013 mbar). You can use all hydrophobic compounds that are usually used in mini-emulsion polymerization, cf. the international application WO-A-99/40123, page 7, line 27 to page 8, line 20. In contrast to the creation of a mini-emulsion according to the invention emulsification containing at least one fluorescent dye solution, at least from monomers and hydrophobic substances, not making such a large shearing force, so get the emulsion oil-in-water" with an average particle size of at least 1 μm. Thus, the average particle size of the emulsion oil-in-water" substantially exceeds the size of the particles, the usual mini-emulsions. From mulhorandi drops monomers occur dispersed particles of the polymer, which contain uniformly distributed fluorescent dye. This method can also be called polymerization mini suspension.

According to the invention obtain aqueous dispersions of polymers which contain at least one fluorescent dye has an average particle size in the range from 1 to 100 microns and are characterized by a narrow distribution of particle sizes than dispersions of polymers, which are produced, excluding hydrophobic compounds, cf. the European patent EP-B-0692517. In the method according to the invention produce less coagulate in comparison with the known method, and in addition, emulsion polymerization as an accompanying reaction is almost completely suppressed.

As the ethylene-unsaturated monomers can be used, for example,

(a) Hydrophobic monomers from the group of alkylation acrylic acid with 1-18 carbon atoms, alkylamino methacrylic acid with 1-18 carbon atoms, vinyl acetate, finalproject, vinylboronate, styrene, chloresterol and/or α-methylsterols,

(b) optionally, hydrophilic monomers from the group of ethylene-unsaturated carboxylic acid with 3-6 carbon atoms, vinylsulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, sulfopropyl, alphapapillomavirus, styrelseledamot acid, salts of these acids, and elytral, Methacrylonitrile, hydroxyalkylated with 1-8 carbon atoms of carboxylic acids with 1-6 carbon atoms, dialkylaminoalkyl with 1-3 carbon atoms in alkylamine and 2-4 carbon atoms in alkylacrylate, dialkylaminoalkyl with 1-3 carbon atoms in alkylamine and 2-4 carbon atoms in alkylmethacrylamide, acrylamide, methacrylamide, N-vinylformamide and/or N-vinyl pyrrolidone and

(C) optionally at least one monomer to effect cross-linking of at least two double bonds in the molecule.

In the polymerization in suspension, you can apply the monomers of group (a) alone, in mixtures with each other, and in combination with the monomers (b) and/or (C). Examples of monomers of group (a) are methyl acrylate, acrylate, isopropylate, n-propylacetate, n-butyl acrylate, isobutylamine, tert-butyl acrylate, sec-butyl acrylate, pentylaniline, n-hexylaniline, octylacrylate, 2-ethyl hexyl acrylate, dellaquila, dodecylamine, polymethylacrylate, stearylamine, methyl methacrylate, ethyl methacrylate, ISO-proletariat, n-propylbetaine, n-butylmethacrylate, isobutylacetate, second-butylmethacrylate, tert-butylmethacrylate, pendimethalin, n-hexyllithium, cyclohexylmethyl, gettimeformat, 2-ethylhexylacrylate, octylacrylate, decylmethacrylate, dodecylmercaptan, and polymethylmethacrylat art is helmetcrest, and vinyl acetate, finalproject, vinylboronate, styrene, chloresterol and/or α-methylsterol. Preferably used monomers of this group are methyl methacrylate and styrene.

The monomers of group (b), which, if necessary, apply for hydrophobic modification of polymers, chosen, for example, from the group comprising ethylene-unsaturated carboxylic acid with 3-6 carbon atoms, vinylsulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, sulfopropyl, alphapapillomavirus, styrelseledamot acid, salts of these acids, Acrylonitrile, Methacrylonitrile, hydroxyalkylated with 1-8 carbon atoms of carboxylic acids with 1-6 carbon atoms, dialkylaminoalkyl with 1-3 carbon atoms in alkylamine and 2-4 carbon atoms in alkylacrylate, dialkylaminoalkyl with 1-3 carbon atoms in alkylamine and 2-4 carbon atoms in alkylmethacrylamide, acrylamide, methacrylamide, N-vinylformamide and/or N-vinyl pyrrolidone.

Examples of the ethylene-unsaturated carboxylic acid is acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, taconova acid and feniluksousna acid. The ethylene-unsaturated carboxylic acid, and monomers containing sulfopropyl, can be used in the polymerization in the form of free acids, as well as in form, is completely or partially neutralized by bases, alkali metals, alkaline earth metals, ammonia or amines. Usually used sodium, potassium or ammonium salts of the acid monomers. Acidic monomers, however, it is also possible to neutralize such amines, such as butylamine, morpholine, ethanolamine, diethanolamine or triethanolamine and use in the polymerization in a fully or partially neutralized form. From hydroxyalkylated can be applied, in particular, 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate, hydroxypropanoyl, hydroxyethylacrylate and 2-hydroxypropylmethacrylate.

Examples of core monomers is dimethylaminoethylacrylate, dimethylaminoethylmethacrylate, dimethylaminopropanol, dimethylaminopropylamine, diethylaminoethylamine, diethylaminoethylmethacrylate, di-n-propylaminoethyl and di-n-propylaminosulfonyl. The basic monomers can be used in the polymerization in the form of a free base, salts with mineral acids, saturated carboxylic acids or sulfonic acids, such as para-toluensulfonate acid or benzosulfimide acid, and quaternionic form (for example, quaternidinum by methyl chloride, ethylchloride, n-propylchloride, dimethylsulfate, n-vexillaria, cyclohexylurea or benzylchloride).

The monomers of group (b) can be used in polymerization alone or in whom Oceania. Preferably used from this group of acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinylformamide and N-vinyl pyrrolidone.

As monomers (C) use monomers with the effect of cross-linkage, at least two double bonds in the molecule. Examples of such monomers are esters of polyatomic alcohols and the ethylene-unsaturated carboxylic acids as acrylic acid or methacrylic acid, such as etilenglikolevye, etilenglikolevykh, butanediamine, potentialtheorie, hexaniacinate, hexaniacinate, acrylates and methacrylates of polyalkylene glycols such as polyethylene glycols, polypropylenglycol or block copolymers of ethylene oxide and of propylene oxide with molecular weights, for example, from 100 to 5000, allylacetate, alismataceae, trimethylolpropane, trimethylolpropane, pentaerythrityl, pentaerythritoltetranitrate, pentaerythritoltetranitrate, pentaerythritoltetranitrate, divinylbenzene, diphenylacetone and methylenebisacrylamide. Preferable as the crosslinking agents used alismataceae, butanediol-1,4-diacrylate and trimethylolpropane.

The mixture of monomers used in the polymerization include, for example:

(a) from 60 to 100 wt.% at least one hydrophobic monomer,

(b) is t 0 to 30 wt.% at least one hydrophilic monomer and

(c) from 0 to 40 wt.% at least one monomer to effect cross-linking of at least two double bonds.

Preferably in the polymerization mixture of monomers, which contain

(a) from 60 to 99.9 wt.% at least one hydrophobic monomer,

(b) from 0 to 30 wt.% at least one hydrophilic monomer and

(c) from 0.1 to 25 wt.%, in particular from 5 to 15 wt.%, at least one monomer to effect cross-linking.

Fluorescent dyes are known to the specialist. They are described, for example, mentioned in the summary of the technical level of the international application WO-A-99/40123, starting on page 10, line 14, to page 25, line 25, and European patent EP-B-0692517, starting on page 3, line 7, to page 6, line 1. Appropriate fluorescent dyes include, for example, to classes coumarin, Pereladova, Terranova, kvaternionov, naphthalimide, cyanine, xanthene, oxazinone, anthracene, naftenovykh, antrahinonovye or casinovip dyes. It is preferable to use such fluorescent dyes, which have a higher solubility in the oil phase of the emulsion oil-in-water"than in the aqueous phase. For example, the solubility of the dyes in the oil phase should be at least about 0.001 wt.%, preferably at least 0.01 wt.%.

For the proizvodstva aqueous dispersions of fine particles of polymers, which contain a fluorescent dye and have an average size of at least 1 μm, it is possible to proceed, for example, so that first dissolving a fluorescent dye in a mixture consisting of at least one of usable monomers and at least one hydrophobic compound, and then emulsify the solution in the aqueous phase, containing at least one surface-active compound. Emulsification of the oil phase in the aqueous phase can, for example, performed using a rapid mixer or using devices that operate on the principle of "rotor-stator", such as Ultra-Turrax®. Get the emulsion oil-in-water" with an average size of oil droplets from at least 1 to 100 μm, preferably from 1.1 to 25 microns.

An important component of the aqueous dispersions of the polymers according to the invention, which contain at least a fluorescent dye, is a hydrophobic substance. Examples thereof is hydrophobic, is not subject to polymerization of organic compounds, hydrophobic polymers of at least one olefin with 2 to 6 carbon atoms and the molar mass Mwto 10000, siloxanes with molar mass Mwup to 5000 and/or polystyrenes with molecular mass Mwto 10000. Under hydrophobic, not subject to polymerization of organic compounds involve all connections, is the quiet characterized by, for example, the solubility in water of less than 0.01 g/l (at 25°C and 1013 mbar). Examples of such is an aliphatic or aromatic hydrocarbons having from 10 to 50 carbon atoms, preferably from 10 to 24 carbon atoms, alcohols having from 10 to 24 carbon atoms, tetraallylsilane, olive oil, performatively and/or di-n-butyl esters of dicarboxylic acids with 4 to 6 carbon atoms. Particularly preferably applied hydrophobic compounds from this group are hexadecan and liquid paraffins, such as technical or medical vaseline oil (white oil). This oil presents, for example, in the trade under the CAS number 8042-47-5. This refers to mineral oil as a complex combination of saturated hydrocarbons with the number of carbon atoms from 15 to 50. You can also apply a mixture of hydrophobic are not subject to polymerization of organic compounds, for example mixtures of hexadecane and white oil. It is used, like other hydrophobic compounds, for example, in amounts of from 0.5 to 50 wt.%, preferably in quantities of from 1 to 20 wt.%, from monomers.

In addition, as hydrophobic compounds can be used homopolymerization at least one olefin with 2 to 6 carbon atoms or copolymerizate of olefins with 2 to 6 carbon atoms, with a molar mass Mwup to 10 000, the polymers of this kind are for example:

wfrom 100 to 1000,

(ii) Copolymerizate from at least two monomers mentioned in (i), with an average molar mass Mwfrom 100 to 1000 and/or

(iii) polyisobutylene with an average molar mass Mw, component of at least 100.

Examples of the polymers of group (i) is a low molecular weight homopolymeric ethylene, propylene, butene-1, pentene-1 and hexene-1. They represent, for example, oligomers of ethylene, such as, in particular, polymers containing 8 or 12 carbon atoms per molecule, which, for example, represented in the trade by the company Shell under the trade name of Neodene® from the company BP as alpha-olefin, such as AO 2026, as well as from company Chevron Phillips Corporation. As the compound (i), in addition, you can use ceramicrete offered by the company Exxon-Mobil and distributed by the firm Oxeno Tetra-butene. Compounds (i) contain one double bond. Their average molar mass Mwis, for example, from 100 to 10000, preferably from 150 to 2000.

Examples of compounds (ii) is copolymerizate of ethylene and propylene, copolymerizate ethylene and butene-1, copolymerizate ethylene-butene-2, copolymerizate ethylene and hexene-1, copolymerizate propylene and butene-1 and copolymerizate propylene, butene-1 and butene-2, as well as other combinations. These copolymerizate which also contain one ethylene-unsaturated double bond. Their average molar mass Mware, for example, from the Mwfrom 100 to 10000, preferably from 150 to 2000.

As compounds of group (iii) can be used polyisobutylene. Their average molar mass Mwis, for example, at least 100, preferably at least 150. The average molar mass Mwthere are, for example, in the range from 200 to 10000. Typically, the average molar mass Mwproper polyisobutylene is at least 400 and preferably is in the range from 500 to 4000.

Proper polyisobutylene presents in trade. As examples, they can be called brand Glissopal® and Oppanol® production BASF, for example, the Glissopal® 550, Glissopal® 1000, Glissopal® 1300, Glissopal® 2300, Oppanol B10 and B12. Polyisobutylene receive, for example, by cationic polymerization of isobutene with catalysis by boron fluoride (BF3). These polyisobutylene are characterized by a high content of α-olefin groups, which is, for example, at least 80%, preferably at least 85%. They can also be synthesized via the so-called living polymerization with Lisovyi acids other than BF3for example, with AlY3, TiY4, SnY4and ZnY2moreover , in the above formulas Deputy Y represents fluorine, chlorine, bromine or iodine. It is preferable to use polyisobutylene with the content of α-olefin g is PP, constituting at least 80%. Further examples of compounds suitable for use as (iii)is offered by the company BP polyisobutylene under the trade name Indopol® designation L2-L-50, and from H-7 to H-18 000, molar mass which is in the range from 180 to 6000. These polyisobutylene also contain α-olefinic group, but only up to about 10%.

Depending on the method of polymerization rate polydispersity (PDI) of these polymers, i.e. the ratio of mass-average molecular weight to srednekamennogo is in the range of from 1.05 to 10, preferably in the range from 1.05 to 5, and in particular in the range from 1.05 to 2.0. How to determine polydispersity (PDI), as well as bulk and srednekamennogo molecular masses are described, for example, Analytiker-Taschenbuch, Band 4, Seiten 433-442, Berlin 1984.

Preferably applied hydrophobic compounds from these groups is, for example, (i) the tetramer-propene and butene tetramer, (ii) copolymerizate of ethylene and propylene, copolymerizate ethylene and butene-1, copolymerizate ethylene-butene-2, copolymerizate ethylene and hexene-1, copolymerizate propylene and butene-1 and copolymerizate propylene, butene-1 and butene-2 with a molar mass in each case from 150 to 2000 and/or (iii) polyisobutylene a molar mass ranging from 200 to 10000.

Other usable hydrophobic substance is silox the us with molar mass M wup to 5000 and/or polystyrenes with molecular mass Mwto 10000.

In order to stabilize the emulsion oil-in-water", is usually used at least one surface-active compound. Surface-active agent used, for example, in quantities of up to 15 wt.%, for example, from 0.05 to 15 wt.%, preferably from 0.05 to 5 wt.%, and in particular from 0.1 to 2 wt.%, in each case of the total variance.

It is present either in the aqueous phase in organic phase or in both phases. It is advisable to add it to the aqueous phase prior to emulsification. In principle, you can use all surface-active substances (surfactants). Surface-active products used preferably is anionic and/or nonionic surfactants and amphiphilic polymerizate with average molar masses Mw, for example, from 1000 to 100 000. Examples of appropriate surface-active agents is sodium lauryl sulfate, sodium dodecylsulfate, hexadecylsulfate sodium, dioctylsulfosuccinate sodium and/or addition products 15-50 mol of ethylene oxide and/or propylene oxide to 1 mol of the alcohol with 12-22 carbon atoms.

Additionally, the emulsion oil-in-water" can also be stabilized by amphiphilic polymers, which are used if necessary. If using amphiphilic polymers, their number is, for example, from 0.05 to 15 wt.%, preferably the t 0.5 to 5 wt.%, the number of monomers used in the polymerization. An example of amphiphilic polymers is copolymerizate that contain units

(i) a hydrophobic monoethylene-unsaturated monomers and

(ii) monoethylene-unsaturated carboxylic acids, monoethylene-unsaturated sulfonic acids, monoethylene-unsaturated phosphonic acids or their mixtures and/or basic monomers

Proper hydrophobic ethylene-unsaturated monomers

(i) is, for example, styrene, methylsterol, atillery, acrylnitrile, Methacrylonitrile, olefins with 2-18 carbon atoms, esters of monoethylene-unsaturated carboxylic acid having 3-5 carbon atoms and monatomic alcohols, fenilalkilamina, complex ventilatory or mixtures thereof. From this group of monomers are preferably used isobutene, Diisobutyl, styrene and esters of acrylic acid, as acrylate, isopropylate, n-butyl acrylate, and sec-butyl acrylate.

As hydrophilic monomers amphiphilic copolymerizate contain

(ii) preferably acrylic acid, methacrylic acid, maleic acid, maleic acid anhydride, taconova acid, vinylsulfonic acid, 2-acrylamidophenylboronic acid, acrylamidoethyl-3-sulfonic acid, 3-sulfopropyl, 3-alphapapillomavirus, styrelseledamot acid, vinylphosphonic acid or their mixtures and in the built-in polymer form. Acidic monomers may be present in the form of free acid or in partially or completely neutralized form.

Other usable hydrophilic monomers are the main monomers. They can be polimerizuet with hydrophobic monomers (i) alone or in mixture with the above-mentioned acidic monomers. In the case of mixtures of basic and acidic monomers occur amphoteric copolymerizate, which, depending on the molar ratio of built-acidic monomers and alkaline, you may incur a charge (to be presented in anionic or cationic form).

The basic monomers are, for example, dialkylaminoalkyl(meth)acrylates with 1 to 2 carbon atoms in alkylamine residues and 2-4 carbon atoms in the alkyl(meth)acrylic residues or chloride of diallyldimethylammonium. The basic monomers can be in the form of free bases, salts with organic or inorganic acids or to be quaternity alkylhalogenide. The formation of salts or quaternization, in which the main monomers become cations, can be fully or partially. Examples of such compounds are dimethylaminoethylmethacrylate, diethylaminoethylmethacrylate, dimethylaminoethylacrylate, diethylaminoethylamine, dimethylaminopropylamine, dimethylaminopropanol, diethylaminopropylamine, diethylaminopropyl is rilat and/or dimethylaminoethylacrylate, dimethylaminoethylmethacrylate, dimethylaminopropylamine, diethylaminopropylamine and/or chloride of diallyldimethylammonium.

As amphiphilic copolymerizate in the form of the free acid does not have sufficient solubility in water, they are used in the form of water-soluble salts, for example, use the corresponding salts of alkaline or alkaline earth metals and ammonium. These salts are synthesized, for example, partial or complete neutralization of the free acid groups of the amphiphilic copolymerization grounds; for neutralization is used, for example, caustic soda, caustic potash, magnesium oxide, ammonia or amines, as triethanolamine, ethanolamine, morpholine, triethylamine or butylamine. It is preferable to neutralize the acid groups of the amphiphilic copolymerization ammonia or caustic soda. The solubility of the basic monomers or copolymerization, having in its composition such monomers can, conversely, be improved by partial or complete neutralization of the mineral acid, such as hydrochloric or sulfuric acid, or addition of organic acids, such as acetic acid or para-toluensulfonate acid. The molar mass of the amphiphilic copolymerization is, for example, from 1000 to 100,000, and preferably is in the range from 1500 to 10000. Acid number of amphiphilic copolymerize the s form, for example, from 50 to 500, preferably from 150 to 350 mg KOH/g polymer.

Particularly preferred such amphiphilic copolymerizate, which contain

(i) from 95 to 45 wt.% isobutene, Diisobutylene, styrene or mixtures thereof and

(ii) from 5 to 55 wt.% acrylic acid, methacrylic acid, maleic acid, profirov maleic acid or mixtures thereof.

Particularly preferably used as stabilizers mini-emulsion copolymerizate, which include

(i) from 45 to 80 wt.% styrene,

(ii) from 55 to 20 wt.% acrylic acid and, if necessary

(iii) optionally other monomers.

If necessary, other monomers (iii) copolymerizate may contain monomers of profirov maleic acid. Such copolymerizate receive, for example, as follows: copolymerizate comprising as monomers styrene, Diisobutyl or isobutene or mixtures thereof, will copolymerized in anhydrous environment with the anhydride of maleic acid, and after polymerization, these copolymerizate subjected to reaction with alcohols, and mol anhydrous groups copolymerizate use from 5 to 50 mol.% monohydroxy alcohol. Appropriate alcohols, such as ethanol, n-propanol, isopropanol, n-butanol, Isobutanol and tert-butanol. You can, however, also to carry out the reaction of anhydrite groups of copolymerization with megaton the mi alcohols, for example, glycol or glycerol. However, the reaction is carried out only up until with anhydrite group does not react-only one Oh-group a polyhydric alcohol. If anhydrite group of copolymerization not react with alcohols, the ring is not reacted with alcohols anhydrite groups open water.

Other compounds that can be used as stabilizers of emulsions of oil-in-water"is, for example, available on the market normal polymerizate monoethylene-unsaturated acids, as well as grafted polymerizate N-vinylformamide on the polyalkylene glycols are described, for example, in international application WO-A-96/34903. Grafted vinylformamide unit can, if necessary, to hydrolyze, for example, up to 10%. It is advisable that the proportion of vaccinated vinylaromatic units ranged from 20 to 40 wt.% from polyalkyleneglycol. It is preferable to use polyethylene glycols with molar masses of from 2000 to 10000.

In addition, to stabilize emulsions oil-in-water" you can apply polyallylamine and zwitter-ion polyethylenimine. Such compounds are known, for example, from European patent EP-B-0112592. Get them, for example, first alkoxylate polyalkyleneglycol or polyethylenimine, for example, ethylene oxide, propylene oxide and/or butyleneglycol, then kV is temizuya products alkoxysilane, for example, bromide or dimethylsulfate, and then Solfatara quaternion alkoxysilane products chlorosulfonic acid or sulfur trioxide. Molar mass of zwitter-ion polyalkyleneglycol is, for example, from 1000 to 9000, preferably from 1500 to 7500. Zwitter-ion polyethylenimine preferably have molecular weights in the range from 1500 to 7500 daltons. Other above-mentioned stabilizers optionally used to stabilize emulsions in combination with surface-active agents. If used, they are used for example in amounts of from 0.05 to 15 wt.%, preferably from 0.5 to 5 wt.%, from monomers.

To obtain stable aqueous dispersions of polymers can, if necessary, to carry out the polymerization in the presence of protective colloids. As a rule, they average molar mass Mwexceed 500, preferably be more than 1000. Examples of protective colloids is polyvinyl alcohols, cellulose derivatives, such as carboxymethyl cellulose polyvinylpyrrolidone, polyethylene glycols, graft polymerizate vinyl acetate and/or miniproject on glycols, polyethylene glycols, end groups on one or both sides closed alkyl, carboxyl or amino groups, chlorides of polydiallyldimethyl and/or Polish the IDA, how, in particular, starch, derivatives of starch, and proteins. Such products are described, for example, in Römpp, Chemie Lexikon 9th. Edition, Band 5, Seite 3569 or in Houben-Weyl, Methods der organischen Chemie, 4. Edition, Band 14/2 Kapitel IV Umwandlung von Cellulose und von blitz chess E.Husemann und R.Werner, Seiten 862-915 and in Ullmanns Encyclopedia for Industrial Chemistry, 6. Edition, Band 28, Seiten 533 ff under "Polysaccharides".

You can use all kinds of starch, for example, as amylose and amylopectin, native starch, starches, past hydrophobic or hydrophilic modification, anionic starches, cation-modified starches, degraded starches, and degradation of starch can be, for example, by oxidative, thermally, hydrolytically or enzymatically and for the degradation can be both native and modified starch. Other usable protective colloids are water - soluble dextrins and types of starch cross-linking, swelling in water.

It is preferable to use as a protective colloid native water-soluble types of starch that can be converted to water-soluble form, for example, the modification of starch and anionic-modified starches, such as oxidized potato starch. Particularly preferred anionic-modified starch subjected to reduction in molecular weight. It is advisable about what contain the reduction of the molecular weight of the enzymatic method. The average molar mass of degraded starch Mwis, for example, from 500 to 100,000, preferably from 1,000 to 30,000. Degraded types of starch have, for example, the characteristic viscosity [η] of from 0.04 to 0.5 DL/g Such types of starch are described, for example, in European patents EP-B-0257412 and ER-IN-0276770. If polymerization is used protective colloids, the quantities used are, for example, from 0.5 to 50, in particular from 5 to 40 wt.%, most often from 10 to 30 wt.%, from the monomers used in the polymerization.

To modify the properties of polymers can, if necessary, to carry out the polymerization in the presence of at least one polymerization regulator. Examples of polymerization regulators are organic compounds containing sulfur in the bound state, as dodecylmercaptan, thiodiglycol, ethylthioethyl, di-n-butylsulfide, di-n-articulated, diphenylsulfide, diisopropanolamine, 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercaptopropyl-1,2-diol, 1,4-mercaptoethanol, thioglycolate acid, 3-mercaptopropionic acid, mercaptoethanol acid, acetic acid and thiourea, aldehydes, such as formaldehyde, acetaldehyde and propionic aldehyde, organic acid such as formic acid, formate or sodium formate ammonia, alcohols, particularly isopropanol, and with the unity of phosphorus, for example hypophosphite sodium. If polymerization is used, the regulator, used in every case the number is, for example, from 0.01 to 5, preferably from 0.1 to 1 wt.%, from the monomers used in the polymerization.

Polymerization of the emulsion oil-in-water" is a radical mechanism. Typically, the polymerization takes place in the presence of at least one radical polymerization initiator. As the polymerization initiator can be used all compounds able to start the polymerization. This is mainly peroxides, hydroperoxides, azo compounds and redox catalysts. Examples of initiators described in international application WO-A-99/40123, starting on page 32, line 45 to page 34, line 9. To start the polymerization by exposure to high-energy radiation, for example ultraviolet or actinic or radioactive radiation, and in this case, if necessary, operate in the presence of at least one sensitizer. It is preferable to apply such initiators that are soluble in the oil phase. Polymerization of the monomers in the mini-emulsion may also occur electrochemical means using microwave radiation and/or under the influence of ultrasound. The temperature of polymerization may be, for example, from 0 to 120 who With, moreover, at temperatures above 100°C is performed at high pressure in a pressure-sealed equipment. Usually the suspension polymerization emulsion oil-in-water" is carried out in the temperature range from 0 to 95°C.

The subject invention is also a method of making aqueous dispersions of polymers, which have a particle diameter of at least 1 μm and containing a fluorescent dye, by means of radical polymerization, suspension ethylene-unsaturated monomers in the emulsion oil-in-water", whose disperse phase comprises at least one fluorescent dye dissolved in at least one ethylene-unsaturated monomer, and is characterized by an average particle diameter of at least 1 μm, in the presence of at least one surface-active compound, wherein the polymerization is carried out in the presence of at least 0.5.%of the monomers, of at least one hydrophobic not curable organic compound, a hydrophobic polymer of at least one olefin with 2 to 6 carbon atoms, with a molar mass Mwto 10000, siloxane with molar mass Mwup to 5000 and/or polystyrene with a molecular mass Mwto 10000.

The suspension polymerization is carried out in the presence of, for example, from 0.5 to 50 wt.%, preferably in the presence of from 1 to 20 wt.%, from monomers, g is totalnogo not polymerized organic compounds, the hydrophobic polymer of at least one olefin with 2 to 6 carbon atoms, siloxane with molar mass Mwup to 5000 and/or polystyrene with a molecular mass Mwto 10000. It is preferable to carry out the suspension polymerization in the presence of from 0.5 to 50 wt.% hexadecane and/or white oil, particularly preferably in the presence of from 2 to 20 wt.% hexadecane and/or white oil.

The residual content of monomers in the dispersions according to the invention, manufactured in this way can be reduced by chemical deodorizing, as published, for example, ...Araújo, .Sayer, J.G.R.Poco, R.Giudici, Polymer Engineering and Science, 2002 (42), 1442-1468, or in European patent EP 1375530 B1.

The solids content in the aqueous dispersions is, for example, from 10 to 60 wt.%, preferably from 20 to 45 wt.%, and usually ranges from 30 to 45 wt.%.

Dispersed polymer particles contain a hydrophobic substance and at least one fluorescent dye. The average particle size is, for example, from 1 to 100 μm, preferably from 1.1 to 25 μm, and mainly from 1.1 to 4 μm, and they contain at least one fluorescent dye in an amount of from, for example, 0.001 to 10 wt.%, for the most part from 0.01 to 1.0 wt.%. The particle size of fine polymerizate represents a mass-average particle size, as can the of be determined by light scattering. This technique is known to the expert, for example, from .Wiese in D.Distler, Wässrige Polymerdispersionen, Wiley-VCH 1999, Kapitel 4,2 .1, S. 40ff and cited literature there, and .Auweter, D.Horn, J. Colloid Interf. Sci. 105 (1985) 399, D.Lilge, D.Horn, Colloid Polym. Sci. 269 (1991) 704 or .Wiese, D.Horn, J. Chem. Phys. 94 (1991) 6429.

Dispersed particles are characterized by a uniform (narrow) size distribution. Uniformity can be described, for example, using the so-called uniformelywhere dimean average diameter of size class i, Ximeasured by the share (contribution) of that class sizes in the distribution, d(ν,0.5) means averaged over the volume of the median, and the summation is carried out in each case for all classes of size i (Mastersizer Reference Manual, Malvern Instruments Ltd., Spring Lane South, Malvern, Worcs. WR14 1AT, UK). As thus defined, uniformely summarizes deviations from the average volume, the lower its value, the better the uniformity. Particles made according to the invention, when measuring the light scattering processing results of the mie theory are uniformally below 1.0.

Drying aqueous dispersions obtain polymer particles which have an average diameter of at least 1 μm and contain a fluorescent dye in powder form. Examples of the drying is spray drying and drying by freezing. Particles in the powders are usually gregate several individual particles. They can be, for example, dry or wet grinding. Aggregates of individual particles can be ground, for example, particles with an average size of from 1 to 100 μm. In the refining process, however, might be individual particles with an average diameter of 10 to 1000 nm, mostly from 200 to 1000 nm. These sizes in this case are in the range typical for polymer particles produced by the polymerization of mini-emulsions, for example, by the method known from the international application WO-A-99/40123.

In addition, the subject invention is the use of aqueous dispersions of polymers obtained by radical by radical suspension polymerization of the ethylene-unsaturated monomers in the emulsion oil-in-water", whose disperse phase comprises at least one fluorescent dye dissolved in at least one ethylene-unsaturated monomer, and is characterized by an average particle diameter of at least 10 nm, in the presence of at least one surface-active compound and at least 0.5 wt.%, from monomers, at least one hydrophobic not curable organic compound, a hydrophobic polymer of at least one olefin with 2 to 6 carbon atoms, with a molar mass Mwto 10000, siloxane with molar mass Mwup to 5000 and/or polystyrene with a molecular mass Mwto 1000, and the powder obtained from these dispersions of polymers in each case by means of drying, containing at least one fluorescent dye for labeling materials.

For marking materials preferably used obtained by suspension polymerization of aqueous dispersions of polymers containing at least one fluorescent dye and one hydrophobic substance, and is characterized by an average size of dispersed particles from 1 to 100 μm, in particular from 1.1 to 25 μm. You can, however, also use dispersion obtained by polymerization of the mini-emulsion according to the method known from the international application WO-A-99/40123, with an average particle diameter of less than 500 nm, and proper dispersion containing at least one fluorescent dye, and the dispersion of polymer particles which have an average diameter of from 500 to 1000 nm and contain at least one fluorescent dye. Such dispersions can be produced, for example, bringing the average size of the emulsified water droplets consisting of a solution of at least one hydrophobic ethylene-unsaturated monomer, at least one hydrophobic compound and at least one fluorescent dye, to a value in the range from 500 to 1000 nm, and polymerize on the radical mechanism thus obtained emulsion is oil-in-water in a known manner, according to the method of polymerization slurries.

Aqueous dispersions according to the invention and obtained by polymerization of mini-emulsions, aqueous dispersions of polymers, which in each case contain at least one fluorescent dye and one hydrophobic compound, and the polymer powders obtained from dispersions, for example by spray drying, using, for example, for marking textile materials, paper, paper products, paints, building materials, adhesives, fuels, synthetic films, clearmechanic masses for paper, tools, sizing for paper, liquid formulations for crop protection, pharmaceutical and cosmetic formulations, printing inks for printing packaging, paper and media. Of particular practical importance is the use of aqueous dispersions according to the invention and obtained by polymerization of mini-emulsions, aqueous dispersions of polymers, which in each case contain at least one fluorescent dye and one hydrophobic compound, and polymer powders produced from the dispersions, for example by spray drying, for marking packages of any kind. The use may be, for example, direct, by spraying a dispersion of polymers, or in conjunction with the printing ink. At the acouchi can represent for example, paper, cardboard, various plastic films, such as films of polyethylene, polypropylene, polyester or polyamide, or a combination of materials, such as, for example, a combination of paper and at least one synthetic film, a combination of metal foil and at least one synthetic film, such as blister films for packaging of tablets or composite materials from at least two different synthetic films. If necessary, synthetic (plastic) film can be coated dispersion such as variance polyvinylidenechloride, on one or both sides. In these composite materials, as already described above, either paper or paper material, or synthetic tape mark to be applied according to the invention dispersion or aqueous dispersion of polymers obtained by polymerization, mini-emulsion, which in each case contain at least one fluorescent dye and one hydrophobic substance, or obtained from these dispersions in each case, the polymer powders.

Aqueous dispersions that contain at least one fluorescent dye, preferably used for marking paper, paper products, paints, adhesives, clearmechanic masses of the paper, the medium is in sizing for paper and liquid formulations for plant protection. However, their type, for example, subject to the labeling substance in a quantity which is in most cases determined so that the marking on the material or within them was impossible or almost impossible to detect with the naked eye. Recognition marking is carried out, for example, by laser scanning microscopy using a fluorescent microscope or by using an. The content of solids in the aqueous dispersion is usually from 1 to 70 wt.%, preferably from 10 to 50 wt.%. These dispersions can be used for marking material directly or after dilution of the dispersion medium, preferably water.

Aqueous dispersions of polymers which contain at least one fluorescent dye, or derived from these powders are used for marking materials in at least such amounts that are reported (marked) materials can be determined by fluorescent dyes. For example, for marking paper, clearmechanic masses, sizing tools, adhesives, thinning agents for cement, primers in construction and varnishes used from 0.01 to 25 wt.%, preferably from 0.1 to 5 wt.%, at least one type of polymer dispersion particles, which contain at least one fluorescent dye. the example kleptomania mass marked according to the invention, applied to a raw paper with promanage unit number, for example, 11 g/m2and then dried coated paper.

This kleptomania weight of the paper include, in addition to dispersions of polymers containing at least one fluorescent dye, the usual sleeppromoting mass components, such as pigments, dispersants, thickeners and binders agents. Binding agents are usually emulsion polymerizate that at least 40 wt.%, preferably at least 60 wt.%, particularly preferably at least 80 wt.% consist of the so-called main monomers.

Preferred main monomers are alkyl(meth)acrylates with 1 to 10 carbon atoms and mixtures of the alkyl(meth)acrylates with vinylaromatic, in particular styrene (collectively also called polyacrylate binding agents) or hydrocarbons with 2 double bonds, in particular butadiene, or mixtures of such hydrocarbons with vinylaromatic, in particular styrene (collectively also called polybutadiene binding agents).

The mass ratio of butadiene and vinylaromatic (in particular styrene) in polybutadiene binding agents may be, for example, from 10:90 to 90:10, preferably from 20:80 to 80:20.

In addition to chapters who's the monomers, the polymer may contain other monomers, for example, the monomers of carboxylic acid, sulfonic acid or phosphonic acid group. A preferred group of carboxylic acids. Mention should be made of, for example, acrylic acid, methacrylic acid, taconova acid, maleic acid or fumaric acid and Aconitum acid. The content of the ethylene-unsaturated acids in the emulsion polymerizate in General is below 5 wt.%.

Other monomers include, for example, monomers containing hydroxyl groups, particularly hydroxyalkyl(meth)acrylates with 1 to 10 carbon atoms, or amides such as (meth)acrylamide.

Such binding agents are in retail, for example, under the trademarks Styronal® and Acronal® (both made by BASF).

According to the invention, these binding agents are first mixed with the aqueous dispersions according to the invention, containing at least one fluorescent dye. Thus obtained astringents are used then to produce sleeppromoting wt.

Thus, the object of the present invention are also astringents, including astringent agent and aqueous dispersions according to the invention, containing at least one fluorescent dye.

In addition, the subject of the present invention are kleptomania masses that contain such astringent agent.

POS is also marking the paper by to apply in the production of the means of sizing paper comprising at least one aqueous dispersion of a polymer containing at least one fluorescent dye. Proper mass size of the paper is, for example, aqueous dispersions of polymers, a water emulsion of alkylglycerol or anhydrides alkenylamine acid resin or glue. Surface size for paper can also include at least one aqueous dispersion of a polymer containing at least one fluorescent dye, and thus to bear labeling, and in addition, they can be used for marking of paper and paper products.

Thus, the object of the present invention is also a size for paper, comprising aqueous dispersions according to the invention, containing at least one fluorescent dye.

Of course, in order marking of paper and paper products, you can also directly apply containing at least one fluorescent dye aqueous dispersion of polymers, or obtained from the powder to the surface of paper or paper products such as cardboard. Drawing on aqueous dispersions of polymers containing at least one fluorescent dye, paper products can is on hold, for example, by means of gluing press or by using a spray device. Of equal way, it is possible to spray or printing necessary for marking the water dispersion of only part of paper products, to label the product only partially, for example, in the form of a barcode. This marking is of particular interest in relation to packaging materials. The polymer particles containing a fluorescent dye, can be localized, for example, by using confocal scanning laser microscopy, and uniquely identify marked on the materials using spectrofluorimetry.

For marking of fuels, particularly heating oil, aqueous dispersions of polymers containing at least one fluorescent dye, or derived from them by means of spray drying, the powder is used for example in amounts of from 0.00001 to 1 wt.%, preferably from 0.0001 to 0.1 wt.%, from the fuel, and the data for dispersion refers to solid substances contained in the dispersions. For marking liquid formulations for crop protection, pharmaceutical and cosmetic formulations polymer particle dispersions of polymers containing at least one fluorescent dye, or derived from them by means of spray drying powders are used, for example, in the amount of from 0.00001 to 1 wt.%, predpochtitelno from 0.0001 to 0.2 wt.%, for the most part from 0.0001 to 0.1 wt.%. Under liquid formulations for plant protection typically involves aqueous formulations, such as emulsions or dispersions, for example, pesticides, herbicides or fungicides.

Polymer particles containing at least one fluorescent dye, which according to the invention is used for marking materials, sotoscueva. In addition, they are resistant to migration, that is, do not fade.

Examples

Example 1

In a vessel with a capacity of 2 l, equipped with a stirrer (diameter 5 cm), put the following mixture:

450 gwater
250 gpolyvinyl alcohol (Mowiol®40/88 (10% in water)
52,5 mgNaNO2
30 gillimitability
270 gmethylmethacrylate
0.06 gfluorescent yellow dye -
yellow 083 (Lumogen®F)
15 ghexadecane

The mixture was dispersively at room temperature t is within 30 min at a rotation speed of 5000 rpm, and then moved to a 2-liter vessel with anchor stirrer. Added 1,575 g of tert-butylperbenzoate and within 1 hour, heated vessel to 60°C. Then the contents of the vessel for 2 hours and heated to 70°C and then for 30 min to 85°C and maintained at this temperature for 1 hour. Within 1 hour was added 7 g of a 10%aqueous solution of tert-butylhydroperoxide and a solution of 0.4 g of ascorbic acid in 20 g of water. The vessel is then cooled to room temperature.

Got a dispersion of cross-linked particles, stained with a fluorescent dye, with a volumetric average diameter of 2.0 μm and a narrow particle size distributions, with uniformally 0,5 determined using light scattering in the mie theory (Malvern Mastersizer), with respect to the particles came from a refractive index of 1.49 and the absorption coefficient of 0. The solids content was 30,85 wt.%.

Example 2

In a vessel with a capacity of 2 l, equipped with a stirrer (diameter 5 cm), put the following mixture:

441,45 gwater
45 gpolyvinyl alcohol (Mowiol®15/79 (10% in water)
180 gCulminal®MHPC 100 (5% in water)
methylhydroxypropyl is lulzy
52,5 mgNaNO2
30 gpotentialtarget
270 gthe methyl methacrylate
0.06 gfluorescent yellow dye -
Yellow 083 (Lumogen®F)
15 ghexadecane

Emulsification of the mixture and the polymerization of the monomers was performed as described in example 1. Got a dispersion of cross-linked particles, stained with a fluorescent dye, with a volumetric average diameter of 2.6 μm and a narrow particle size distributions, with uniformally of 0.5. The solids content of the dispersion was 29.6 wt.%.

Example 3

In a vessel with a capacity of 2 l, equipped with a stirrer (diameter 5 cm), put the following mixture:

15 g
450 gwater
250 gMowiol®40/88 (10% in water) partially
hydrolyzed polyvinyl alcohol
52,5 mgNaNO2
illimitability
285 gmethylmethacrylate
0.1 gyellow fluorescent dye (Lumogen®F Yellow 083)
0.1 gorange fluorescent dye (Lumogen® F Orange 240)
0.1 gred fluorescent dye (Lumogen®

F Red 300)

15 ghexadecane

Emulsification of the mixture and the polymerization of the monomers was performed as described in example 1. Got a dispersion of cross-linked particles, painted 3 fluorescent dyes, with an average diameter of 1.8 μm and a narrow particle size distributions, with uniformally of 0.4. The solids content of the dispersion accounted for 31.5 wt.%.

Example 4

In a vessel with a capacity of 2 l, equipped with a stirrer (diameter 5 cm), put the following mixture:

450 gwater
250 gpolyvinyl alcohol [Mowiol®40 / 88 (10% in water)]
52,5 mg NaNO2
30 gillimitability
270 gmethylmethacrylate
0.06 gyellow fluorescent dye (Lumogen®F Yellow 083)
0.3 gred fluorescent dye (Lumogen®F Red 300)
15 ghexadecane

Emulsification of the mixture and the polymerization of the monomers was performed as described in example 1. Got a dispersion of cross-linked particles, painted 2 fluorescent dyes, with an average diameter of 1.8 μm and a narrow particle size distributions, with uniformally of 0.5. The solids content of the dispersion was 31 wt.%.

Example 5

In a vessel with a capacity of 2 l, equipped with a stirrer (diameter 5 cm), put the following mixture:

450 gwater
250 gpolyvinyl alcohol [Mowiol®40/88 (10% in water)]
2.1 gNaNO2(2.5% in water)
30 gbulandi is diacrylate
270 gmethylmethacrylate
0.09 gred fluorescent dye (Lumogen®F Red 305)
15 ghexadecane

Emulsification of the mixture and the polymerization of the monomers was performed as described in example 1. Got a dispersion of cross-linked particles, stained with a fluorescent dye, with a mean diameter of 2.4 μm and uniformally of 0.5. It was found 10 g of coagulate. After physical deodorizing the solids content of the dispersion 33.4 wt.%.

Example 6

In a vessel with a capacity of 2 l, equipped with a stirrer (diameter 5 cm), put the following mixture:

0.06 g
450 gwater
250 gpolyvinyl alcohol [Mowiol®40/88 (10% in water)]
52,5 gNaNO2(2.5% in water)
30 gillimitability
270 gmethylmethacrylate
0.03 gyellow fluorescent dye (Lumogen® Yellow 083)
orange fluorescent dye (Lumogen®Orange 240)
0.09 gred fluorescent dye (Lumogen®F - Red)
15 ghexadecane

The mixture was dispersively at room temperature for 60 min at a speed of 6500 rpm, and then moved to a 2-liter vessel with anchor stirrer. Added 1,575 g of tert-butylperbenzoate and within 1 hour, heated vessel to 65°C. Then the contents of the vessel for 2 hours and heated to 70°C and then for 30 min to 85°C and maintained at this temperature for 1 hour. Within 1 hour was added 7 g of a 10%aqueous solution of tert-butylhydroperoxide and a solution of 0.4 g of ascorbic acid in 20 g of water. The vessel is then cooled to room temperature.

Got a dispersion of cross-linked particles, stained with a fluorescent dye, with a mean diameter of at 1.91 μm and uniformally of 0.5. The solids content of the dispersion was 31.7 wt.%.

Example 7

In a vessel with a capacity of 2 l, equipped with a stirrer (diameter 5 cm), put the following mixture:

502,7 gwater
30 gpolyvinyl JV the mouth [Mowiol ®15/79 (10% in water)]
120 gCulminal®MHPC 100 (5% in water) methylhydroxypropylcellulose
52,5 mgNaNO2
120 gpotentialtarget
150 gmethylmethacrylate
30 gmethacrylic acid
0.06 gyellow fluorescent dye (Lumogen®F Yellow 083)
0.015 ggidrokolonoterapiya
15 ghexadecane

Emulsification of the mixture and the polymerization of the monomers was performed as described in example 1. Got a dispersion of cross-linked particles, stained with a fluorescent dye, with a mean diameter of 4.9 μm. The solids content of the dispersion was 30.3 wt.%

Example 8

In a vessel with a capacity of 2 l, equipped with a stirrer (diameter 5 cm), put the following mixture:

450 gwater
250 gpolyvinyl alcohol [Mowiolthe 40/88 (10% in water)]
2.1 gNaNO2(2.5% in water)
30 gillimitability
240 gmethylmethacrylate
30 gn-butyl acrylate
0.09 gred fluorescent dye (Lumogen®F Red 305)
15 ghexadecane

Emulsification of the mixture and the polymerization of the monomers was performed as described in example 1. Got a dispersion of cross-linked particles, stained with a fluorescent dye, with an average diameter of 2.1 μm and uniformally of 0.4. It was found 6 g coagulate, the solids content of the dispersion was 29.9 wt.%.

Example 9

In a vessel with a capacity of 2 l, equipped with a stirrer (diameter 5 cm), put the following mixture:

370,1 gwater
of 208.3 gpolyvinyl alcohol [Mowiol® 40/88 (10% in water)]
1,75 gNaNO2(2.5% in water)
25 gBhutan is indiacanada
225 gmethylmethacrylate
0.75 gethylhexylacrylate
0.08 gred fluorescent dye (Lumogen®F Red 305)
12.5 ghexadecane

Emulsification of the mixture and the polymerization of the monomers was performed as described in example 1. Got a dispersion of cross-linked particles, stained with a fluorescent dye, with an average diameter of 1.6 μm and uniformally of 0.4, the solids content of the dispersion amounted to 28.3 wt.%.

Example 10

In a vessel with a capacity of 2 l, equipped with a stirrer (diameter 5 cm), put the following mixture:

450 gwater
250 gpolyvinyl alcohol [Mowiol®40/88 (10% in water)]
2.1 gNaNO2(2.5% in water)
1.35 gpotentialtarget
298,65 gmethylmethacrylate
0.09 gred fluorescent krassi is El (Lumogen ®F Red 305)
15 ghexadecane

Emulsification of the mixture and the polymerization of the monomers was performed as described in example 1. Got a dispersion of cross-linked particles, stained with a fluorescent dye, with an average diameter of 1.9 μm and uniformally of 0.5, the solids content of the dispersion was 31.4 wt.%.

Example 11

In a vessel with a capacity of 2 l, equipped with a stirrer (diameter 5 cm), put the following mixture:

450 gwater
250 gpolyvinyl alcohol [Mowiol®40/88 (10% in water)]
2.1 gNaNO2(2.5% in water)
300 gmethylmethacrylate
0.09 gred fluorescent dye (Lumogen®F Red 305)
15 ghexadecane

Emulsification of the mixture and the polymerization of the monomers was performed as described in example 1, and the total number tert-butylperbenzoate divided into three equal parts. The first part was added at 60°C, the second part is at 65°C, and the third at 70°C.

P is obtained a dispersion deprived of the cross-linkage of the particles, stained with a fluorescent dye, with an average diameter of 1.5 μm and uniformally of 0.4, the solids content of the dispersion was 31.3 wt.%.

Example 12

In a vessel with a capacity of 2 l, equipped with a stirrer (diameter 5 cm), put the following mixture:

450 gwater
250 gpolyvinyl alcohol [Mowiol®40/88 (10% in water)]
2.1 mgNaNO2
30 g1,4-potentialtarget
270 gmethylmethacrylate
0.09 gred fluorescent dye (Lumogen®F - red)
15 gwhite oil (CAS-Nr. 8042-47-5)

The mixture was dispersively at room temperature for 30 min with rotation speed of 5000 rpm, and then moved to a 2-liter vessel with anchor stirrer. Added 2.1 g of tert-butylperbenzoate and within 1 hour, heated vessel to 60°C. Then the contents of the vessel for 2 hours and heated to 70°C. and then for 30 min to 85°C and maintained at this temperature for 1 hour. Within 1 hour was added 7 g of 10%water is th solution of tert-butylhydroperoxide and a solution of 0.4 g of ascorbic acid in 20 g of water. The vessel is then cooled to room temperature.

Got a dispersion of cross-linked particles, stained with a fluorescent dye, with a volumetric average diameter of 1.2 μm and a wide distribution of particle sizes. The solids content was 27.6 wt.%.

Example 13

In a vessel with a capacity of 2 l, equipped with a stirrer (diameter 5 cm), put the following mixture:

450 gwater
250 gpolyvinyl alcohol [Mowiol®44/88 (10% in water)]
2.1 mgNaNO2
24 g1,4-potentialtarget
216 gmethylmethacrylate
0.09 gred fluorescent dye (Lumogen®F - Red)
60 ghexadecane

Emulsification of the mixture and the polymerization of the monomers was performed as described in example 12. There was obtained a dispersion of cross-linked particles, stained with a fluorescent dye, with a volumetric average diameter of 1.2 μm and a broad particle size distributions. The solids content of the composition is lo 29,0 wt.%.

Example 14

In a vessel with a capacity of 2 l, equipped with a stirrer (diameter 5 cm), put the following mixture:

450 gwater
250 gpolyvinyl alcohol [Mowiol®26/88 (10% in water)]
2.1 mgNaNO2
30 g1,4-potentialtarget
270 gmethylmethacrylate
0.09 gred fluorescent dye (Lumogen®F - Red)
15 ghexadecane

Emulsification of the mixture and the polymerization of the monomers was performed as described in example 12. There was obtained a dispersion of cross-linked particles, stained with a fluorescent dye, with a volumetric average diameter of 1.2 μm and a narrow particle size distributions. The solids content amounted to 29.0 wt.%.

Examples of the application

Creating colors for papers

In a vessel with a capacity of 1 l, equipped with a mixer, knead in the following table paint. The pH was about 9 and a viscosity brought to 1000 MPa*S.

Composition(1)(2)(3)(4)(5)(6)(7)
The pigment from caso3(Hydrocarb 90)100,070,070,070,070,070,070,0
Kaolin pigment (Amazon 88)97,030,030,030,030,030,030,0
A means of facilitating dispersed through of Polysalz S)45,30,300,300,300,300,300,30
NaOH25,00,050,050,050,050,050,05
Styrene-butadiene knit the second agent Styronal® D 808 49,710,010,010,010,010,010,0
Thickener (Sterocoll®)40,50,300,300,300,300,300,30
Marking variance 130,91,00,50,20,10,0100,200
Marking variance 232,51,00,50,20,10,0100,400
Marking variance 331,11,00,50,20,10,0100.800 to

Under normal industry the way records in the first data column marked(1), given the content of solids in the used components, and each of the 6 subsequent columns (2) to (7) contains the relative concentration for each sample application, calculated on the basis of 100 parts of pigment (in this case, Hydrocarb 90 + Amazon 88).

As marking dispersion 1 used a dispersion produced according to example 3.

Marking dispersion 2 was prepared similarly to dispersion according to example 3, but with the same total concentration of the dyes contained only red fluorescent dye (Lumogen®F Red 300).

Marking dispersion 3 was prepared in accordance with example 3, but with Lumogen dyes®F Red 300 and Lumogen®F Yellow 083 in equal shares. The dispersion consisted of two-colored particles.

Then the paint was applied to the raw paper produced by Scheufelen using a squeegee, having applied a weight of 15 g/m2. Then paper, colored thus dried properly dryer. To the naked eye marking paper with fluorescent particles markers cannot be found, and spectroscopic investigation using laser scanning microscopy allowed us to unambiguously identify all the types of particles used for labeling.

Marking means of sizing paper

Particle-markers, izgotovlenie according to the invention, used for additional processing of the surface of the paper. For this marking dispersions 1, 2 and 3 was mixed with Basoplast® 400DS, standard dispersion copolymers of acrylate, and then this mixture was mixed with an aqueous solution of starch (the ratio of synthetic product and starch - OK 1:100). The content of solids in the mixture ranged from 8%to 15%, in this form it using the squeegee inflicted on paper in the form of a film. The applied weight of the starch amounted to about 2 g/m2and polymer, respectively, 0.02 g/m2. Spectroscopic investigation using laser scanning microscopy allowed us to unambiguously identify all the types of particles used for labeling.

Marking coatings for films

With 1 kg of a 45%dispersion of acrylate Epotal®A 816 with gluing ability, mixed with 0.75 ml, 1.5 ml and 15 ml marking dispersion according to example 3 and manufactured similarly dispersions of single-color and two-color particles with the same total concentration of dye Lumogen® F Red 300 or Lumogen® F Red 300 and Lumogen® F Orange 240, respectively, and with the help of an air scraper caused this mixture on the film Warr (200 MB production ExxonMobil), which have previously been subjected to electrical treatment and provided with a layer of primer - polyurethane dispersions (Epotal® P 350). Spectroscopic investigation using the manhole is Noah scanning microscopy allowed us to unambiguously identify used particle-tokens.

1. Aqueous dispersion of the polymer marking material, which has a particle diameter of at least 1 μm and which contains a fluorescent dye, characterized in that it is derived by means of radical polymerization, suspension Ethylenediamine monomers in emulsion oil-in-water", the dispersed phase of which contains at least one fluorescent dye dissolved in at least one ethyleneamine monomer and has an average particle diameter of at least 1 μm, in the presence of at least one surface-active compound and at least 0.5 wt.%, based on the monomers, of at least one hydrophobic, depolymerizing organic compounds, hydrophobic polymer of at least one olefin with 2 to 6 carbon atoms, with a molar mass Mwto 10000, siloxane with molar mass Mwup to 5000 and/or polystyrene with a molecular mass Mwto 10000, and as the ethylene-unsaturated monomers using hydrophobic monomers from the group of alkylation of acrylic acid with 1 to 8 carbon atoms, alkylamino methacrylic acid with 1 to 8 carbon atoms, vinyl acetate, finalproject, vinylboronate, styrene, chloresterol and/or α-methylsterols, and as hydrophobic, depolymerizing organic compounds used al the factual or aromatic hydrocarbons, having 10 to 50 carbon atoms, alcohols having from 10 to 24 carbon atoms, tetraallylsilane, olive oil, performatively and/or di-n-butyl esters of dicarboxylic acids with 4 to 6 carbon atoms.

2. Aqueous dispersion according to claim 1, characterized in that as Ethylenediamine monomers optionally used
hydrophilic monomers from the group Ethylenediamine carboxylic acid with 3-6 carbon atoms, vinylsulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, sulfopropyl, alphapapillomavirus, styrelseledamot acid, salts of these acids, Acrylonitrile, Methacrylonitrile, complex hydroxyalkylated with 1-8 carbon atoms of carboxylic acids with 1-6 carbon atoms, dialkylaminoalkyl with 1-3 carbon atoms in alkylamine and 2-4 carbon atoms in alkylacrylate, dialkylaminoalkyl with 1-3 carbon atoms in alkylamine and 2-4 carbon atoms in alkylmethacrylamide, acrylamide, methacrylamide, N-vinylformamide and/or N-vinyl pyrrolidone and
optionally at least one crosslinking monomer with at least two double bonds in the molecule.

3. Aqueous dispersion according to claim 1 or 2, characterized in that the mixture of monomers used in the polymerization, contain
(a) from 60 to 100 wt.% at least one hydrophobic monomer,
(b) from 0 to 30 wt.% on m is Nisha least one hydrophilic monomer and
(c) from 0 to 40 wt.% at least one cross-linking monomer with at least two double bonds.

4. Aqueous dispersion according to claim 1 or 2, characterized in that the mixture of monomers used in the polymerization, contain
(a) from 60 to 99.9 wt.% at least one hydrophobic monomer,
(b) from 0 to 30 wt.% at least one hydrophilic monomer and
(c) from 0.1 to 25 wt.%, at least one cross-linking monomer with at least two double bonds.

5. Aqueous dispersion according to claim 1 or 2, characterized in that the hydrophobic polymers used homopolymerization at least one olefin with 2 to 6 carbon atoms or copolymerizate of olefins with 2 to 6 carbon atoms, with a molar mass Mwto 10000, siloxanes with molar mass Mwup to 5000 and/or polystyrenes with molecular mass Mwto 10000.

6. Aqueous dispersion according to claim 1 or 2, characterized in that as hydrophobic, depolymerizing organic compounds using hexadecane and/or white oil in an amount of from 0.5 to 50 wt.% based on the monomers.

7. Aqueous dispersion according to claim 1 or 2, characterized in that the dispersed polymer particles have an average size of from 1.1 to 25 μm and contain at least one fluorescent dye in an amount of from 0.001 to 10 wt.%.

8. A method of obtaining a water dispersion of the polymer, which has a medium is nd a particle diameter of at least 1 μm and which contains a fluorescent dye, by means of radical polymerization, suspension Ethylenediamine monomers in emulsion oil-in-water", the dispersed phase of which contains at least one fluorescent dye dissolved in at least one ethyleneamine monomer and has an average particle diameter of at least 1 μm in the presence of at least one surface-active compound, wherein the suspension polymerization is carried out in the presence of at least 0.5 wt.% in the calculation of the monomers of at least one hydrophobic depolymerizing organic compounds, hydrophobic polymer of at least one olefin with 2 to 6 carbon atoms, siloxane with molar mass Mwup to 5000 and/or polystyrene with a molecular mass Mwto 10000, and as Ethylenediamine monomers using hydrophobic monomers from the group of alkylation of acrylic acid with 1 to 8 carbon atoms, alkylamino methacrylic acid with 1 to 8 carbon atoms, vinyl acetate, finalproject, vinylboronate, styrene, chloresterol and/or α-methylsterols, and as hydrophobic, depolymerizing organic compounds using aliphatic or aromatic hydrocarbons having from 10 to 50 carbon atoms, alcohols having from 10 to 24 carbon atoms, tetraallylsilane, olive oil, performatively and/or di-n-BU is silt esters of dicarboxylic acids with 4 to 6 carbon atoms.

9. The method of claim 8, wherein the suspension polymerization is carried out in the presence of from 0.5 to 50 wt.%, based on the monomers, hydrophobic depolymerizing organic compounds, hydrophobic polymer of at least one olefin with 2 to 6 carbon atoms, siloxane with molar mass Mwup to 5000 and/or polystyrene with a molecular mass Mwto 10000.

10. The method according to one of p or 9, characterized in that the suspension polymerization is carried out in the presence of from 1 to 20 wt.% in the calculation of the hydrophobic monomers depolymerizing organic compounds, hydrophobic polymer of at least one olefin with 2 to 6 carbon atoms, siloxane with molar mass Mwup to 5000 and/or polystyrene with a molecular mass Mwto 10000.

11. The method according to one of p or 9, characterized in that the suspension polymerization is carried out in the presence of from 2 to 10 wt.% hexadecane and/or white oil.

12. Polymer particles having an average diameter of at least 1 μm and containing a fluorescent dye, characterized in that they are obtained by drying aqueous dispersions according to claims 1-7.

13. The use of aqueous dispersions of polymers obtained by radical polymerization, suspension Ethylenediamine monomers in emulsion oil-in-water", the dispersed phase of which contains at least one fluorescent dye, rest is provided in at least one ethyleneamine monomer, and has an average particle diameter of at least 1 μm, in the presence of at least one surface-active compound and at least 0.5 wt.% in the calculation of the monomers of at least one hydrophobic depolymerizing organic compounds, hydrophobic polymer of at least one olefin with 2 to 6 carbon atoms, with a molar mass Mwto 10000, siloxane with molar mass Mwup to 5000 and/or polystyrene with a molecular mass Mwto 10000 for marking materials, and as Ethylenediamine monomers using hydrophobic monomers from the group of alkylation of acrylic acid with 1 to 8 carbon atoms, alkylamino methacrylic acid with 1 to 8 carbon atoms, vinyl acetate, finalproject, vinylboronate, styrene, chloresterol and/or α-methylsterols, and as hydrophobic, depolymerizing organic compounds using aliphatic or aromatic hydrocarbons having from 10 to 50 carbon atoms, alcohols having from 10 to 24 carbon atoms, tetraallylsilane, olive oil, performatively and/or di-n-butyl esters of dicarboxylic acids with 4 to 6 atoms of carbon.

14. The application of the powder obtained from the aqueous dispersion of polymers according to claim 1 by drying and containing at least one fluorescent dye for labeling materials.

15. The application indicated in paragraph 13 of the tives such as those that obtained by the suspension polymerization of an aqueous dispersion of polymers containing at least one fluorescent dye and one hydrophobic substance, and with the average size of dispersed particles is from 1 μm to 100 μm, in particular from 1.1 to 25 μm, is used for the marking of materials.

16. Use item 13 or 14, characterized in that the quality of the materials labeled textile materials, paper, paper products, paints, building materials, adhesives, fuels, synthetic films, promusicae pulp for paper, tools sizing for paper, liquid compositions for plant protection, pharmaceutical and cosmetic compositions, printing inks for printing on packaging, paper and media.

17. The binder containing the binder and the water dispersion for marking materials according to one of claims 1 to 7.

18. Promotiona weight of the paper containing the binder by 17.

19. Means for sizing paper containing the aqueous dispersion according to one of claims 1 to 7.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: composition consists of 20-80 pts.wt bifunctional acrylic oligomer, (meth)acrylic groups in which are bound by a divalent organic group with an ester, carbonate or urethane group, 20-80 pts.wt acrylic monomer selected from a alkyl(meth)acrylates or oxyalkyl(meth)acrylates, where the alkyl is a lower alkyl; 5-25 pts.wt gold salt selected from a group of inorganic salts of gold which are soluble in said acrylic monomer; 0.1-3 pts.wt photoinitiator. Also disclosed is a spatial-mesh polymer material containing dissolved gold in zero valence. Under external thermal and/or photo action, said material, which is a colourless and transparent glass-like material with not less than 90% optical transmission in the visible region, is cable of generating a plasma resonance band in the visible region of the formed gold nanoparticles - gives a response point in the 500-640 nm range. the material is obtained through photo-exposure of the said gold-containing polymerisable acrylic composition.

EFFECT: material is a recoding medium for optical recording of information and is characterised by extremely high sensitivity.

7 cl, 6 dwg, 2 tbl, 28 ex

FIELD: chemistry.

SUBSTANCE: disclosed aqueous dispersion of copolymerisation products containing A) one or more hydroxy-functional copolymerisation products, obtained from the following (wt %): non-hydroxyl containing ester of (meth)acrylic acid and/or vinylaromatic compounds (53.5-87), hydroxy-functional ester of (meth)acrylic acid (2.5-45.9), ionic and/or potentially ionic monomers (0.6-19) capable of radical copolymerisation, as well as, if necessary, other monomers capable of radical copolymerisation which are different from compounds of components a)-c) (0-43.4) and B) at least one hydroxy-functional polycarbonate-polyol as a reactive diluent. Disclosed also is an aqueous coating agent which contains one or more of the disclosed aqueous dispersions of copolymerisation products and at least one cross-linking agent which interacts with hydroxyl groups.

EFFECT: disclosed aqueous dispersions have low solvent content and enable to obtain coatings with high level of resistance of lacquer films, with high scratch resistance and acid resistance.

5 cl, 1 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polymer composite materials, particularly a method of producing a nanocomposite based on a liquid crystal polymer and an inorganic semiconductor which can be widely used in laboratory experiments and in industry. The invention discloses a method of producing a nanocomposite which involves mechanical treatment of a solution of a liquid crystal polymer of the type poly-4-(n-acryloyloxyalkoxy)benzoic acid of formula: , where n=3-12, until interchain bonds of the polymer break.The solution is mixed with nanoparticles of the inorganic semiconductor coated with a low-molecular weight organic ligand which contains the same functional group as the polymer and is selected from a group of fatty acids. The obtained mixture is held, chemically bonded nanoparticles are formed and separated and the solvent is distilled off. The inorganic semiconductor used is cadmium selenide, cadmium sulphide or lead sulphide. The fatty acid used is oleic or palmic or linoleic acid.

EFFECT: disclosed method enables to obtain nanocomposites based on liquid crystal polymers which contain nanoparticles of inorganic semiconductors which are included in the volume of the composite in an ordered manner.

2 cl, 4 dwg, 3 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: declared invention concerns hydrogel compositions useful as a dressing material or protective agent, and for application of a wide range of active substances in relation to the skin and tissues of mucosas, such as mouth, including tooth bleaches. The faza-parted, film-forming composition containing an admixture is offered: (a) the first polymer bulking up in water, and the specified polymer is not dissolved in water at pH less than approximately 5.5, or water-soluble polymer; (b) an admixture of hydrophylic polymer and additional low-molecular polymer, capable to formation of hydrogen communications with hydrophylic polymer; (c) the second polymer bulking up in water, and the specified polymer we will not dissolve in water at all value pH; and (d) unessential active substance, in a dissolvent or in an admixture of dissolvents where the composition is exposed to separation of phases at hydration.

EFFECT: treatment of a disease state of various surfaces of a body (teeth, fingernails, skin, mucosas etc).

44 cl, 7 ex

FIELD: medicine.

SUBSTANCE: composition contains water-swelling, water-insoluble polymer, mixed hydrophilic polymer and complementary oligomer able to form hydrogen bond with hydrophilic polymer, and a bleaching agent, preferentially peroxide. The composition is applied a dental bleaching composition and applied on teeth to be bleached, and then removed as the required bleaching is reached. In best versions the composition is unstable and translucent. There are also methods of preparation and application of the compositions.

EFFECT: reduced dental sensitivity and damage or irritation of gums and oral mucous membranes, improved clinical effectiveness.

54 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: proposed method of producing a water and oil repellent agent involves emulsification of (a) 15-85 wt % perfluoroalkylethylacrylate, (b1) 5-65 wt % 2-ethylhexylmethacrylate and (b2) 1-40 wt % benzyl methacrylate in the presence of (c) a cation surface active substance of the polyethylene oxide adduct type, or neutralised organic acid compound of an amine, with polyethylene oxide chains, and (d) compounds based on polypropylene glycol, with molecular weight 300-3000, or hexylene glycol, with subsequent copolymerisation reaction in the presence of a polymerisation initiator, and mixing the obtained aqueous dispersion with (e) blocked isocyanate.

EFFECT: satisfactory water and oil repellent for synthetic and natural fibre.

5 cl, 22 ex, 5 tbl

FIELD: chemistry.

SUBSTANCE: invention refers to technology of hull-kernel particles which can be used to modify impact strength of poly(met)akrylate moulding compositions. According to method a) water and emulsifier b) are added with 25.0 to 45.0 mass fractions of the first composition containing A) alkylmetacrylate 50.0 to 99.9 mass fractions, B) alkylakrylate 0.0 to 40 mass fractions, C) cohesive monomers 0.1 to 10.0 mass fractions, and D) styrene monomers 0.0 to 8.0 mass fractions, and polymerised, c) added 35.0 to 55.0 mass fractions of the second composition containing E) (met)akrylates 80.0 to 100.0 mass fractions, F) cohesive monomers 0.05 to 10.0 mass fractions, and G) styrene monomers 0.0 to 20.0 mass fractions, and polymerised, d) added 10.0 to 30.0 mass fractions of the third composition containing H) alkylmetakrylates 50.0 to 100.0 mass fractions I) alkylakrylates 0.0 to 40.0 mass fractions and J) styrene monomers 0.0 to 10.0 mass fractions, and polymerised. Method is distinctive in that e) each polymerisation cycle is performed at temperature within 60 to 90°C and f) fractional content of all substances is selected so that total weight A) to J) per total weight of aqueous dispersion exceeds 50.0 mass %. Presented method is used to produce impact strength modifiers minimum content of which provides sufficient improvement of impact strength when tested on cut moulding composition samples, not degrading at the same time other important properties of moulding composition.

EFFECT: production of impact strength modifiers minimum content of which provides sufficient improvement of impact strength when tested on cut moulding composition samples, not degrading at the same time other important properties of moulding composition.

17 cl, 8 tbl

FIELD: heat-curable sealing compositions.

SUBSTANCE: composition is proposed, containing the following mass components: 100 (meth)acrylic monomer or its mixture with an allyic monomer, 0.5-2.5 initiator, 0.01-0.32 hydroquinone, 0.01-0.13 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, 0.004-0.05 disodium salt of ethylenediaminetetraacetic acid, 20-125 filler and 5-30 functional additives. The proposed composition has polymerising activity at 100-250°C for 3-8 minutes and breaking stress of 605-15.5 MPa. This adhesive strength is sufficient for withstanding steam pressure of up to 4 MPa. Use of the proposed composition allows for repairing steam pipes with constant supply of steam.

EFFECT: design of a heat-curable sealing composition for repairing steam pipes without interruption of steam supply.

1 cl, 1 tbl, 5 ex

FIELD: physics, photographic material.

SUBSTANCE: invention pertains to polymer cholesteric photoactive compounds, which can independently generate laser emission when irradiated with laser light. Such a compound can be used, for example, in photonics, optoelectronics and telecommunication systems. The cholesteric photoactive compound for generating laser emission consists of cholesteric liquid crystal, photoactive additive and laser dye. The liquid crystal used contains conjoint polymer n-(6-acrylyl oxycapril hydroxyphenyl)-n-methoxy benzoate with cholesterine-11-acrylyl undecanoate, containing molar quantities between 30% and 25% of the cholesterine-11-acrylyl undecanoate links. Photoactive additive used is 2.5-bis(4-methoxy cynnamoyl)-1.4;3.6-dianhydro-B-sorbitol, while the laser dye used is 4-(dicyano methylene)-2-methyl-6-(4-dimethyl amino styryl)-4H-pyran. The invention improves the temporal and thermal stability of the compound, and allows for its use at room temperatures and at lower temperatures as well. Sensitivity of the compound to external effects is also lowered.

EFFECT: increased thermal stability of photoactive compounds and lower sensitivity to external effects.

2 ex, 1 dwg

FIELD: rubber industry; production of the vulcanizable rubber mixture on the basis of the hydrogenated butadiene-nitrile caoutchouck.

SUBSTANCE: the invention is pertaining to production of the vulcanizable rubber mixture on the basis of the hydrogenated butadiene-nitrile caoutchouck used for manufacture of rubber-technical products efficient at the temperatures up to 150°С. The vulcanizable rubber mixture contains (in mass): the hydrogenated butadiene-nitrile caoutchouck - 70-95, the acrylate caoutchouck - 30-50, sulfur - 0.5-1.2, quaternary ammonium base - 2-6, sulfonamide Ц - 0.5-1.5, thiuram Д - 1-2, metallic stearate - 2-4, zinc oxide - 3-5, industrial carbon - 40-50, the stearic acid - 1-2, the antioxidant - 3.0-3.8. The technical result of the invention consists in reduction of the mixture viscosity, increase of the heat-resistance and the aggressive mediums-resistant properties with the simultaneous decrease of the residual compressive deformation.

EFFECT: the invention ensures the reduced mixture viscosity, the increased heat-resistant and the aggressive mediums-resistant properties at the simultaneously decreased of the residual compressive deformation.

3 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: peroxide-curable rubber compound contains a peroxide curing substance and a halobutyl ionomer with high content of multi-olefin. The halobutyl ionomer is obtained via polymerisation of a mixture of monomers containing 80-95 wt % isobutene monomer and 4-20 wt % isoprene monomer in the presence of AlCl3 and a source of protons and/or carbocationic compound or silyl cationic compound, capable of initiating polymerisation and 0.01-1.0 wt % multi-olefin cross-linking agent to obtain a butyl polymer with high content of multi-olefin, halogenation of the butyl polymer and reaction thereof with a phosphorus-based nucleophile.

EFFECT: invention enables to obtain a heat resistant peroxide-curable compound with a halobutyl ionomer with high content of multi-olefin and to obtain a moulded article from said compound without inorganic impurities.

13 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: peroxide-curable rubber compound contains a peroxide curing substance and a halobutyl ionomer with high content of multi-olefin. The halobutyl ionomer is obtained via polymerisation of a mixture of monomers containing 80-95 wt % isobutene monomer and 4-20 wt % isoprene monomer in the presence of AlCl3 and a source of protons and/or carbocationic compound or silyl cationic compound, capable of initiating polymerisation and 0.01-1.0 wt % multi-olefin cross-linking agent to obtain a butyl polymer with high content of multi-olefin, halogenation of the butyl polymer and reaction thereof with a phosphorus-based nucleophile.

EFFECT: invention enables to obtain a heat resistant peroxide-curable compound with a halobutyl ionomer with high content of multi-olefin and to obtain a moulded article from said compound without inorganic impurities.

13 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: peroxide-curable rubber compound contains a peroxide curing substance and a halobutyl ionomer with high content of multi-olefin. The halobutyl ionomer is obtained via polymerisation of a mixture of monomers containing 80-95 wt % isobutene monomer and 4-20 wt % isoprene monomer in the presence of AlCl3 and a source of protons and/or carbocationic compound or silyl cationic compound, capable of initiating polymerisation and 0.01-1.0 wt % multi-olefin cross-linking agent to obtain a butyl polymer with high content of multi-olefin, halogenation of the butyl polymer and reaction thereof with a phosphorus-based nucleophile.

EFFECT: invention enables to obtain a heat resistant peroxide-curable compound with a halobutyl ionomer with high content of multi-olefin and to obtain a moulded article from said compound without inorganic impurities.

13 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: composition consists of 1 part citrate ion source per 12.7-20 parts ammonium phosphate and 0.8-2.2 parts benzoate ion source. Alternatively, the composition consists of 1 part citric acid per 12.7-20 parts ammonium phosphate and 0.8-2 parts sodium benzoate.

EFFECT: composition can be granular or liquid with further addition of water and ingredients which are not harmful to humans and the environment.

17 cl

FIELD: chemistry.

SUBSTANCE: composition contains epoxy diane resin ED-20 75-85, mixture of triglycidyl esters of polyoxy-propylenetriol Laproxide-703 and Laproxide-301 in ratio 4:1 53-61, ethylene diaminomethyl phenol AF-2 35-40, polyhydrosiloxane liquid 136-41 18-20, catalyst K-1 type A 1.3-1.4, ethylsilicate-40 4.5-5.0, acetone 0.15-0.17.

EFFECT: composition has low water absorption, high radiation resistance and improved radio-technical properties after exposure to high moisture.

2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: composition contains epoxy diane resin ED-20 75-85, oligoester epoxy Laproxide-703 43.5-49.3, oligoester epoxy Laproxide-301 10.5-11.9, ethylene diaminomethyl phenol AF-2 30-34, low-molecular resin PO-300 30-34, polyhydrosiloxane liquid 136-41 18-20, catalyst K-1 type A 1.5-1.7, ethylsilicate-40 3.7-4.3, acetone 0.02-0.03.

EFFECT: composition has low water absorption, improved radio-technical properties after exposure to high moisture.

2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to use of terpolymers of propylene/butylene/ethylene with a nucleating agent to form sterilising films obtained via extrusion blowing. A film is obtained from a polymer composition containing (i) and (ii) 0.001-1.0 wt % of one or more phosphorus-containing and/or polymeric α-nucleating agents. The terpolymer of propylene, ethylene and butylene consists of 86.0-98.0 wt % propylene, 2.0-12.0 wt % butylene and 0.1 to less than 1.0 wt % ethylene. The obtained films have a) turbidity according to ASTM D 1003-92 for a 50 mcm film less than 8% before and after steam sterilisation at 121°C for 30 minutes and b) lustre at 20° according to DIN 67530 for a 50 mcm film of at least 55% before steam sterilisation at 121°C for 30 minutes and at least 60% after steam sterilisation at 121°C for 30 minutes. The films are sterilisable and have excellent optical and mechanical properties.

EFFECT: improved method of obtaining films.

16 cl, 4 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a rubber mixture based on oil-filled butadiene-α-methylstyrene rubber and can be used to make industrial rubber articles for different industries - oil refining, pipeline transport, railway transport, as well as household articles. The rubber mixture is prepared by mixing the following components in pts.wt: oil-filled butadiene-α-methylstyrene rubber - 100, sulphur - 2, dibenzthiazole disulphide -1.5, diphenylguanidine - 0.3, zinc oxide - 5, stearic acid - 2, technical carbon - 50 and 0.05-0.5 sodium alginate. Sodium alginate is pre-mixed with powdered ingredients in a powder mixer.

EFFECT: invention increases fatigue endurance of rubber during multiple stretching and reduces heat build-up at constant strain amplitude.

3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a rubber mixture based on oil-filled butadiene-α-methylstyrene rubber and can be used to make industrial rubber articles for different industries - oil refining, pipeline transport, railway transport, as well as household articles. The rubber mixture is prepared by mixing the following components in pts.wt: oil-filled butadiene-α-methylstyrene rubber - 100, sulphur - 2, dibenzthiazole disulphide -1.5, diphenylguanidine - 0.3, zinc oxide - 5, stearic acid - 2, technical carbon - 50 and 0.05-0.5 sodium alginate. Sodium alginate is pre-mixed with powdered ingredients in a powder mixer.

EFFECT: invention increases fatigue endurance of rubber during multiple stretching and reduces heat build-up at constant strain amplitude.

3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a rubber mixture based on oil-filled butadiene-α-methylstyrene rubber and can be used to make industrial rubber articles for different industries - oil refining, pipeline transport, railway transport, as well as household articles. The rubber mixture is prepared by mixing the following components in pts.wt: oil-filled butadiene-α-methylstyrene rubber - 100, sulphur - 2, dibenzthiazole disulphide -1.5, diphenylguanidine - 0.3, zinc oxide - 5, stearic acid - 2, technical carbon - 50 and 0.05-0.5 sodium alginate. Sodium alginate is pre-mixed with powdered ingredients in a powder mixer.

EFFECT: invention increases fatigue endurance of rubber during multiple stretching and reduces heat build-up at constant strain amplitude.

3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a moulding composition prepared from polyethylene with multimodal molecular weight distribution for making pipes, as well as a method of preparing said moulding composition via a multi-step sequence of reactions, comprising a sequence of polymerisation steps in the presence of a catalyst system, including a Ziegler catalyst and a cocatalyst. The composition contains 45-55 wt % ethylene homopolymer A with low molecular weight, 20-40 wt % high-molecular copolymer B consisting of ethylene and another olefin with 4-8 carbon atoms in amount of 1-8 wt % per weight of the high-molecular copolymer, and 15-30 wt % ethylene copolymer C with ultra-high molecular weight, containing 1-8 wt % of the weight of the ultra-high molecular weight copolymer C, ethylene and one or more olefins with 4-8 carbon atoms.

EFFECT: during storage, the composition has high processability as starting material for making pipes, has a good combination of properties, such as resistance to stress cracking caused by external conditions and mechanical strength, especially during a long period of time.

5 cl, 2 tbl, 2 ex

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