Composites of inorganic and/or organic microparticles and nanoparticles of calcium carbonate

FIELD: chemistry.

SUBSTANCE: invention can be used in producing pigments and/or filler materials for paper, paint and plastic. The composite contains particles of an inorganic and/or organic pigment and/or filler having equivalent diameter of 0.2-100 mcm, coated at least partially with a composition containing calcium carbonate particles having equivalent diameter less than 200 nm, and binder based on copolymers containing monomers in form of one or more dicarboxylic acids and one or more monomers from a group comprising diamines, triamines, dialkanolamines or trialkanolamines. Particles of the inorganic pigment and/or filler are selected from talc, mica or mixtures thereof. Particles of the organic pigment and/or filler are selected from polyethylene, polypropylene, polyethylene terephthalate or polystyrene. To obtain the composite, particles of the pigment and/or filler are mixed with a calcium carbonate composition, mainly in form of an aqueous suspension, and binder is added and the mixture is homogenised. In another version, the binder can be added to particles of the pigment and/or filler or to the calcium carbonate composition. Calcium carbonate is ground using ball mills, jet mills, burr mills or combination thereof cyclones and sieves.

EFFECT: obtained composites have high opacity, whiteness and lustre, high capacity for printing and resistance to segregation.

57 cl, 11 dwg, 4 ex

 

The present invention relates to composites containing inorganic and/or organic pigments and/or fillers in the form of microparticles, the surface of which is at least partially coated with a binder melkoizmelchennye particles of calcium carbonate nanometer size, to a method for producing such composites, their aqueous suspensions and their use in paper production or in the field of production of paints and plastics, as well as to the application of the proposed binder for the coating of microparticles nanoparticles of calcium carbonate.

The pigments and/or fillers based on particles of calcium carbonate nanometric size (the so-called nanoparticles) are known and used in various fields, including the manufacture of paper, paints and plastics.

Also known and are used similarly, organic and/or inorganic pigments and/or fillers micron size (the so-called microparticles, such as hollow spheres or particles based on polystyrene, and particles of pigments and/or fillers on the basis of inorganic minerals, such as talc or mica.

A mixture of nanoparticles and microparticles of different chemical composition are used because of their characteristics, allowing to give the desired properties to the final product, such as paper. Mixtures of such substances are used in manufacturing the paper as pigments or fillers, especially when finishing a paper, for example, for coating, improving such quality paper, as the opacity, whiteness and gloss or suitability for printing. It is known that such microparticles and nanoparticles successfully combine the ability to hold in the manufacture of paper and "covering power" when finishing a paper, for example in the coating. Specialists in this field it is clear that covering capacity determines the ability of the coating to remain on the paper surface or partially or completely penetrate into the paper, and the ability of the binder and/or pigment or a separate part of the pigment to separate and to penetrate through the surface of the paper. This problem is known to experts in this field, especially when the coating of the adsorbent caused by dyes with low solids content.

When using mixtures of such microparticles and nanoparticles for these purposes, there is often undesirable separation of the components, the so-called segregation associated with uneven distribution of coating thickness under the surface of the paper, under a layer of pre-coating or on the surface of the paper, which can lead, for example, to uneven printing on paper. The term "segregation" refers to the process of separation of the various elements in the observed field with a tendency to simply antinomy distribution of the elements according to their special properties.

Segregation of mixtures of pigments and/or fillers leads to different volumes of pores in the coating, for example, when finishing a paper by coating, as individual nanoparticles are separated from the microparticles and therefore can either fill the pores of the paper and/or coatings, or "float", i.e. to gather, for example, on the outer surface of the coating, which is important, in particular, when the next printing surface must absorb a certain amount of liquid type water, oil and/or organic solvents from the ink.

At the present state of Affairs there are many such compounds, their production and use.

The widely used technique of obtaining such mixtures of pigments or fillers are described, for example, in patents DE 3312778 A1 and DE 4312463 C1, and consists in mixing or joint grinding of mineral filler type of natural calcium carbonate and mineral filler type talc.

However, in the production of paper or coating such mixtures usually are segregated, because communication between the components of the mixture are often not able to withstand such conditions. It is known that in the manufacture of the coating are observed shear rate of more than 106with-1on the doctor knife at 1500 m/min

So I developed additional methods of obtaining such composites by Popper is knogo stitching particles of pigment and/or filler with the formation of multiple internal cavities, which were to improve the physical properties and particularly the optical properties of pigments and/or fillers.

In WO 92/08755 describes a method for chemically aggregated porous composites pigments, which are prepared aqueous suspension of mineral particles, such as particles of calcium carbonate, and the suspension type polymer or copolymer containing carboxyl groups, to initiate the formation of flakes. Calcium ions are added to a suspension in excess in order to cause precipitation of the calcium salt of the polymer flakes of the mineral and thus to obtain aggregates of mineral particles associated calcium salt having a structure of porous flakes. Excess calcium ions enter into the reaction with carbon dioxide and precipitated as calcium carbonate polymer is a salt of calcium. However, since calcium ions added in the form of alkaline chemical compounds, such as calcium hydroxide, they form an intermediate alkali compounds, which can have a negative impact, for example, when using some of dispersants. In addition, further precipitation of calcium carbonate alter the original structure of the nanoparticles/microparticles and inevitably leads to the introduction of another pigment, in particular precipitated calcium carbonate formed during neutralization. Globewide the s units can create problems in the use of paper, because they cause diffuse scattering of light on the surface, resulting in a loss of gloss paper. In addition, the initial pore volume in the composite is changed, first, the result of falling flakes and, secondly, due to the deposition of the formed calcium carbonate.

In U.S. patent 5449402 described functionally modified pigment particles obtained by mixing precipitated flake pigments of the type of calcium carbonate and regulator with opposite charge compared to the charge flaky pigment. Preferably, flaky pigment represented an aqueous suspension of sediment particles on the filter. Preferred regulators include not soluble in water or dispersed latex binder, soluble in water or in alkaline environments, organic and/or inorganic polymer binder and organic particles that do not form films that are electrostatically associated with the pigment particles when mixed with them.

In U.S. patent 5454864, 5344487 and EP 0573150 also described the composite pigments obtained due to electrostatic attraction between the particles of the carrier and the coating particles. However, in some cases, the use of such composites can create problems due to the interaction with other charged components.

Another way to enhance the whiteness according to WO 97/32934 side is raised in the application of the pigment particles of the coating of the particles of another pigment, such as finely ground particles of precipitated calcium carbonate in the form of agglomerates, but without a binder, which can cause the above problems, such as the falling flakes. The stability of such composites is based mainly on van der Waals forces of attraction that are implemented only in very specific conditions. For example, to get the best possible Zeta-potential, which varies for each combination of substances, it is necessary to maintain a specific pH value. As soon as conditions deviate from optimal, begin to dominate the forces of repulsion and segregation of components.

WO 99/52984 relates to composites of isostructural or co-adsorbed fillers comprising at least two different types of mineral or organic fillers or pigments, such as calcium carbonate, talc or polystyrene, and their application. Different types of pigments or fillers are hydrophilic and/or organohalide area that allows you to associate them with specific binder.

Binders which for the manifestation of coherence function must have an affinity for hydrophilic components, as well as to organophilized components, which are selected from specific polymers and/or copolymers. Particle diameter of the pigments and/or fillers plays no role, as in the given examples are not exactly specify any diameter and/or the diameters of the particles are at best less than 1 μm. Thus, the advantages of fillers or pigments and, therefore, associated problems in the case of segregation are not discussed here.

In the application WO 03/078734 described composition for surface treatment, in particular, for coating paper, containing the fraction of the nanoparticles, for example, precipitated calcium carbonate, and the fraction of the medium constituting the plate-like pigment particles, including the pigment particles of talc or plastic, and at least one binder. However, the nanoparticles do not cover media. When the desired location of the lamellar particles on the paper surface pores are closed and the nanoparticles may not be further penetrate deep into. Described as lamellar particles migrate to the surface of the paper as a result of segregation and thus close the pores between the fibers and prevent the penetration of nanoparticles through the surface. Thus, the goal is the desired segregation of nanoparticles and microparticles. Microparticles are separated from the nanoparticles and are located under the floor, while the nanoparticles are at the top of the coating. During drying of the coating on the paper binder, preferably a polymeric latex binder, causes the formation of links between individual particles and the two fractions of particles above the floor and below it. In this place time and take the and the desired segregation.

The application of the U.S. 2005/0287313 relates to fusible print media on the substrate and the layer on the substrate, devouring the paint. Layer, an absorbent ink, contains many hollow spheres, for example, from polystyrene, which have the same diameter of 0.3-10 μm. This layer also includes a binder, such as polyvinyl alcohol or polyvinylpyrrolidone, etc. to bind hollow spheres with each other. Hollow spheres can also partially replace the microporous and/or mesoporous inorganic particles such as calcium carbonate or talc, and polymer particles that are hollow and can have a diameter of 0.2-5 microns.

Thus, the application of the U.S. 2005/0287313 described mixture simultaneously present microparticles, which are held together by fixing in a binder that is selected in accordance with the requirements of the method of melting. This type of etching bath, which consists of some cationic polymers and copolymers containing amino groups, are used for better chemical interaction between the printed ink and absorbing the paint layer. No matter how related different components in the layer. The problem of segregation is not considered.

Application WO 2006/016036 relates inter alia to a method for grinding of minerals in water in the presence of the binder and to the resulting suspension, and their use in compositions for n is carrying. In the description and in the claims referred to a large number of materials, such as talc, which can be split up in the presence of a binder. However, the examples are given only calcium carbonate. None of the examples are not described grinding, for example, two chemically different substances in the presence of a binder. In addition, no mention of the fact that with this method of grinding the formed nanoparticles or nano-microcomposite. A binder is not used to obtain a composite material, and as a means to achieve finer grind, but the average diameter of particles in suspensions of pigment can be up to 30 μm. With the shredding of used binder based on styrene-acrylate or styrene-butadiene copolymers, i.e. binders which are well known to the specialists in this field and are used in coatings for paper or as a binder in the wall paints. Thus, the method described in WO 2006/016036, necessarily involves the step of grinding, in which micro-size particles are formed of particles, and it is not described binder to obtain a composite material, practically resistant to segregation.

Thus, the aim of the present invention is to provide a composite pigment and/or filler, as well as their aqueous suspensions with very good optical properties, including opacity, white is the first and the gloss or the ability to print, and at the same time resistant or substantially resistant to segregation in the treatment conditions to which they are exposed.

However, this task does not apply to thermal paper, receipt and processing as it relates to the application of composites of organic particles and inorganic nanoparticles in the production and finishing of paper.

Another objective of the present invention is to provide a method of producing such composites, the use of these composites in paper production and finishing, for example, in the coating, if it contains composites of organic particles and inorganic nanoparticles, and the use of composites in the manufacture of paints or plastics, sealants, and the use of some binder for the coating of pigment microparticles and/or filler nanoparticles of calcium carbonate.

The purpose of the invention is achieved by a composite material containing a binder and particles of inorganic and/or organic pigment and/or filler, which at least partially covered with composition of calcium carbonate.

A binder consisting of a copolymer comprising as monomers one or more dicarboxylic acids and one or more monomers from the group of diamines, triamines, dialkanolamines or trialkanolamines.

The proposed junction has acce is a good binder properties in combination with the compositions of microparticles and nanoparticles of calcium carbonate. A large part of the composition of the nanoparticles of calcium carbonate is strongly associated with the surface of the microparticles, which creates an open structure when using the composite and allows among other things to reduce the packing density and/or increase the pore volume.

According to this invention is equivalent spherical particle diameter of the pigment and/or filler is generally in the micrometer range, while the equivalent spherical particle diameter of the calcium carbonate is mainly in the nanometer range.

In the scope of the present invention nanoscale particle is defined as a particle with an equivalent spherical diameter of less than or equal to 200 nm.

Micro-size particles particle defined in this invention as a particle with an equivalent spherical diameter greater than 0.2 microns to micrometer intervals of approximately 0.3-100 μm, in particular about 1-25 microns.

The so-called equivalent spherical diameter is a measure of the size of particles of irregular shape. It is calculated from the comparison of the properties of particles of irregular shape with the properties of particles of regular shape. Depending on the properties selected for comparison, receive different equivalente diameters. In this case, the equivalent diameter considered in connection with the sedimentation properties of the investigated particles.

Sedimentation and equivalent is entry particle diameter, as well as their distribution is determined in this invention by the method of sedimentation, i.e. sedimentation analysis in the field of gravity, with the help of the device Sedigraph 5100 from the company Micromieritics, USA. Professionals in this field are known, and this method and this apparatus, which is commonly used to determine the degree of grinding of fillers and pigments. The measurements were carried out in an aqueous solution of 0.1 wt.% Na4P2O7. Samples were dispersively using high-speed stirrers and ultrasound.

In a preferred aspect of the pigment microparticles and/or filler are inorganic particles such as particles of talc, mica, or mixtures thereof. In this invention, the calcium carbonate is not suitable as microparticles. Suitable pellets talc produces, for example, MONDO Minerals. You can also use mica from Aspanger Bergbau mid Mineralwerke GmbH, Austria.

Preferably, the pigment particles and/or filler had an almost spherical structure, in particular in the form of hollow spheres and hollow hemispheres, or plates, and under the "hemispherical" structure understand any structure derived from a hollow sphere, whose surface is not closed. It was shown that plates and hollow hemispherical micropigment and/or microsatellites especially preferred, because of their shape they are highly opaque ways is steadily increasing. Under lamellar particles here understand particles in which the ratio of length and width and/or height >1.

Preferably, the microparticles of inorganic pigments and/or fillers had a lamellar form.

However, the proposed particles of pigment and/or filler may also be organic, for example, based on polyethylene, polypropylene, polyethylene terephthalate, polystyrene, or mixtures thereof.

Organic pigments and/or fillers that can be used in the present invention include, for example, products of Rohm & Haas under the trademark Ropaque, for example, Ropaque HP-1055 or Ropaque AF-1353. The advantage of organic particles in the composite due to, among other things, the fact that they have different physical properties such as density, conductivity and color of organic substances, in comparison with inorganic substances.

In a preferred embodiment, particles of organic pigment and/or filler are almost spherical in shape, preferably the shape of hollow spheres or hollow hemispheres. Hollow spherical particles may also contain a liquid such as water which can be removed from hollow spheres at any other stages of physical processing, such as drying, during and/or after use in the present invention. The advantage of hollow spheres among other things is reduced portion is Naya density compared to populated areas. Therefore, any of them made object such as paper or plastic, it will be easier that can be an advantage, for example, during transportation. In the case of closed hollow spheres or open hemispheres there is an increased scattering, which leads among other things to increased opacity. In addition, the closed hollow sphere, for example, filled with air, are thermoisolation. This may be seen as an advantage when used in compositions for dyeing the walls inside and outside the premises and in coatings for buildings.

In a preferred embodiment, the equivalent particle diameter of the pigment and/or filler is practically in the range of from 0.2 to about 100 microns, for example, from about 0.3 to about 100 microns, preferably in the range of about 0.3 to 75 μm, more preferably in the range of about 0.3-50 μm, even more preferably in the range of about 0.3 to 25 μm, most preferably in the range of about 0.3 to 15 μm, in particular in the range of about 0.3 to 12 μm.

Preferably, the equivalent particle diameter of the organic pigment and/or filler was in the range of from 0.2 to 25 μm, more preferably in the range of about 0.3-10 μm, for example, in the range of about 0.5 to 1.5 μm, about 0.25-1.5 μm, or about 0.7-1.1 μm, in particular approximately 0.9-1.0 μm.

In the present invention special is on the preferred particles of the organic pigment and/or filler, based on polystyrene, for example, in the form of hollow spheres made of polystyrene with an equivalent spherical diameter of about 0.3 to 2 μm, preferably about 0.7-1.5 μm, particularly preferably about 0.9-1.1 μm, for example, about 1 μm or 0.25-1.5 mm.

Preferred particles of inorganic pigment and/or filler, based on talc, in which approximately 95-98 wt.%, for example, 96 wt.%, the talc particles have an equivalent spherical diameter <10 μm, about 79-82 wt.%, for example, 80 wt.%, have an equivalent spherical diameter <5 μm and approximately 43-46 wt.%, for example, 45 wt.%, have an equivalent spherical diameter less than 2 microns.

Nanoparticles of calcium carbonate used in coatings, can be a synthetic precipitated calcium carbonate (PCC), which can have, for example, the structure of Wouter, calcite or aragonite.

Particularly preferable to use nanoparticles crushed natural calcium carbonate (ground calcium carbonate, GCC), for example, in the form of marble, limestone and/or chalk containing at least 95 wt.%, preferably more than 98 wt.% of calcium carbonate. Known pigments and/or fillers with a large nanometer fraction produces, for example, OMYA.

In a special embodiment, about 90-100%, preferably 92-99%, more preferably 94-98%, particularly preferably 96-98%, for example, 97±0.5% cha is TIC calcium carbonate, that is reflected in the number N of particles of calcium carbonate, have an equivalent spherical diameter of less than 200 nm, preferably less than 150 nm and even more preferably less than 100 nm. Preferably, the diameter was in the range of 20-200 nm, 50-180 nm or 70-150 nm.

The distribution of particle size was determined by the sedimentation method as described above, with the use of the device Sedigraph 5100 from Micromeritics, USA and has been printed in a total curve on the graph X-Y, where the X-axis of the specified diameter of the particles in the form of equivalent spherical diameter, and the Y-axis denotes the content of the corresponding particles in mass percent (see, for example, P.Belger, Schweizerische Vereinigung der Lack - und Farben-Chemiker, XVII FATIPEC Congress, Lugano, September 23-28, 1984).

Percentage N% nanoparticles from all of the particles was calculated from the measurement results by the following method.

Values taken from the curve on the Sedigraph instrument. The difference between 0 and 0.2 μm gives a value of 0.1 μm (100 nm), the difference between 0.2 and 0.4 μm gives a value of 0.3 μm (300 nm), etc. the Sum of differences normalized to 100 mg, and from this calculated amount in each interval. The calculation was carried out assuming that the particles have a spherical shape with a diameter d, the average interval of the difference. It is used to calculate the particle volume V

V=0.5236d3

and then the mass of a particle W (by dividing by the specific gravity; for CaCO3it does correspond 2.7 g/cm 3)

W=V/2.7

From the mass of the particle, we can calculate the number of particles of mass of the corresponding faction and then be used to calculate the allocation percentages as N%.

If the calcium carbonate is not enough crushed to the required or desired particle size, it is possible to grind one or more stages of wet or dry grinding, preferably in several stages of grinding, for example, two dry and/or wet stages, preferably with the participation of water to achieve the equivalent spherical diameter.

The grinding of calcium carbonate can be performed in any known equipment for grinding, known to specialists in this field. For dry grinding is especially suitable traditional ball mill; jet or Burr mill is suitable for wet grinding and also very suitable combinations of such mills or a combination of one or more mills cyclones and screens. Wet grinding is especially suitable traditional stone mills of the company's products Dynomill.

When dry grinding as Kobasa environment used preferably balls and preferably of iron and/or porcelain small balls with a diameter of 0.5-10 cm, particularly preferred steel cylinders with a diameter of 2.5 see

For wet crushing suppose the equipment grinding balls made of zirconium silicate, zirconium dioxide and/or baddeleyite with a diameter of 0.2-5 mm, preferably 0.2-2 mm, but also from 0.5 to 5 mm, for example, 0.5-2 mm. you Can also use silica sand equivalent spherical particle diameter of 0.1-2 mm

However, nano-sized particles of calcium carbonate, it is preferable to get wet grinding and/or to bring to the desired equivalent diameter, in particular in the case of natural calcium carbonate.

The stage of dry or wet grinding can be performed sequentially one after the other, but preferably the last stage was wet grinding.

Izmelchenny natural calcium carbonate can be atomized and/or crumble, for example, in the form of an aqueous suspension in the presence of one or more grinding tools and/or dispersant, preferably with a solids content of more than 10 wt.%, for example, 15-30 wt.%, preferably more than 30 wt.%, more preferably more than 50 wt.%, for example, if the solids content of 65-68 wt.%, particularly preferably more than 70 wt.%, for example, if the solids content of 72-80 wt.%.

In the absence of grinding tools and/or dispersants calcium carbonate preferably atomized and/or crumble when the solids content of 30 wt.%, for example, 15-30 wt.%. When the solids content of more than 30 wt.% better dispersing and/or the fragmentation in the presence of grinding tools and/or dispersants.

At concentrations less than or equal to 30 wt.% you can also wet crushing even in the absence of chemical additives. Products such as suspension of calcium carbonate with a low solids content of less than or equal to, for example, 60 wt.%, it is preferable to concentrate the mechanical ways, such as by pressing on the filter and/or centrifugation and/or thermally and with the use of one or more of dispersants. Especially preferably the combining stages mechanical and thermal concentration. Preferably, the final concentration of solids after stages of concentration was more than 60 wt.%, particularly preferably elm), 65-78 wt.%, for example, 72±2 wt.%.

For example, as grinding tools and/or dispersants you can use anionic grinding tool and/or dispersant, preferably selected from the group consisting of homopolymers and copolymers on the basis of salts of polycarboxylic acids, for example acrylic acid, methacrylic acid, maleic acid, fumaric acid or basis of itaconic acid, acrylamide or mixtures thereof. Particularly preferred homopolymers or copolymers of acrylic acid, such as products of BASF, Ludwigshafen, Allied Colloids, Great Britain or SEATECH, France. Preferably, the molecular weight Mw such products nahodilas is in the interval 200-15000 g/mol; especially preferred Mw, equal 3000-7000 g/mol. However, it is also preferred Mw of such products, equal 2000-150000 g/mol, and particularly preferred magnitude Mw 15000-50000 g/mol, for example, 35000-45000 g/mol. The molecular weight of the grinding means and/or dispersants chosen so that they act as an integral part of, and not binding. The polymers and/or copolymers can be neutralized by using single-shot and/or multiply charged cations, or they may contain free acid groups. Suitable singly charged cations include, for example, the cations of sodium, lithium, potassium and/or ammonium. Suitable multicharged cations include, for example, divalent cations such as the cations of calcium, magnesium, strontium, or trivalent cations, for example, aluminum. Particularly preferred cations are sodium and magnesium. It is preferable to use a grinding tool and/or dispersant type of polyphosphates sodium or sodium citrate alone or in combination with each other.

For dry grinding is especially suitable grinding means and/or dispersant that can be selected from the group consisting of glycols, polyglycols such as polyethylene glycols, ethylene oxide-propylene oxide-ethyleneoxide block copolymers or alkanolamines, such as triethanolamine and triisopropanolamine or mixtures thereof.

Dispersancy and/or m the covering means can be used in an amount of about 0.01-5 wt.% calculated on the total dry weight of the composite, for example, when dry grinding in an amount of about 0.01-0.5 wt.%, preferably 0.1-0.3 wt.%. Particularly preferable to use them in the amount of 0.2-1 mg/m2the surface of the nanoparticles, for example, in amounts of 0.3-0.7 mg/m2the surface of the nanoparticles.

When wet grinding is preferable that dispersant and/or grinding tool is present in an amount of about 0.05-2.0 wt.%, preferably in a quantity of 0.3-1.5 wt.%, for example, 1 wt.%, but also in the amount of about 0.85-0.95 wt.%.

The grinding tool and/or dispersancy contribute to the grinding of particles of calcium carbonate to nanometer size by reducing the viscosity and increasing the mobility and the free length of the grinded particles and the grinding of small balls. This is especially important for the subsequent formation of the composite.

Preferably, the viscosity of the suspension at a wet grinding was less than 2500 MPa·s, more preferably less than 1500 MPa·s, in particular less than 1000 MPa·s or even better less than 500 MPa·s and especially preferably in the range of 50-500 MPa·s, for example, 50-250 MPa·s; the viscosity is determined on the traditional Brookfield viscometer, for example, EV-2t+ rotating disk 3 and a rotation speed of 100 rpm

During the grinding and/or dispersion can also be applied to other monomer or polymer is haunted additives in addition to the grinding means and/or dispersants, for example copolymers of ethylene with acrylic acid (EAA) or their salts individually or in combination. Preferably, the ratio of the monomers acrylic acid and ethylene in the copolymer was 1:4 to 1:50, particularly preferably from 1:4 to 1:10 and especially 1:5. Preferred EAA and/or their salts are such that after neutralization have a melt viscosity 3000-25000 MPa·s, 15000-100000 MPa·s and 50000-400000 MPa·s at 200, 170 and 140°C respectively, preferably 3000-7000 MPa·s, 15000-20000 MPa·s and 50000-100000 MPa·s at 200, 170 and 140°C, respectively, and, in particular, have a melt viscosity 15000-25000 MPa·s, 50000-100000 MPa·s and some 300,000-400,000 MPa·s at 200, 170 and 140°C respectively.

Especially preferred all EAA copolymers with melt viscosity 24300 MPa·s at 200°C, 88300 MPa·s at 170°C and 367000 MPa·s at 140°C.

Quite suitable and affordable EAA copolymers preferably contain 20 mol.% acrylic acid is produced, for example, by BASF, Germany, and Dow, USA.

The use of EAA copolymers or their salts leads to partial or complete waterproofing pores of the substrate, for example, coated paper, and/or pores of the composite, so that the wetting water to open pores of the paper and/or coating and/or a composite material can be reduced, to regulate and/or to inhibit.

When using salts EAA their partially or completely neutralized, for example, with amines, preference is sustained fashion selected from the group includes 2-amino-2-methyl-1-propanol, 3-amino-1-propanol, 2-[bis(2-hydroxyethyl)amino]ethanol, and/or ions of alkali metals such as potassium ions, lithium and/or sodium, or a mixture thereof, preferably sodium. For example, neutralizing at least 70 mol.% or at least 95 mol. % carboxylate groups.

EAA and their salts can be used in amounts of 0.01-10 wt.% calculated on the total dry weight of the composite, preferably 0.01-5 wt.%, more preferably 0.05-5 wt.%, 0.1-2 wt.%, for example, in the amount of 1.0 wt.%.

Preferably, the proposed composite contains 5 to 95 wt.%, more preferably 20-80 wt.% and even more preferably 25-75 wt.% particles of pigment and/or filler, calculated on the total weight of the dry composite. Preferably, the proposed composite contained 95-5 wt.%, preferably 80-20 wt.%, more preferably 75-25 wt.% particles of calcium carbonate in the calculation on the total weight of the dry composite.

It is preferable to use particles of pigment and/or filler and nanoparticles of calcium carbonate in a ratio of from 1:20 to 20:1, especially in a ratio of from 1:4 to 4:1, more preferably in a ratio of from 1:3 to 3:1 or from 1:2 to 2:1, but also in the ratio of 1:1 based on dry weight. Most preferably, the mass ratio of the particles of inorganic and/or organic pigment and/or filler with one the hand and nanoparticles of calcium carbonate on the other was 3:1 or 1:3.

Binder in the proposed composite consists of a copolymer comprising as monomers one or more dicarboxylic acids and one or more monomers from the group of diamines, triamines, dialkanolamines or trialkanolamines.

This facilitates the adhesion of the nanoparticles on the surface of the microparticles.

As monomers - dicarboxylic acid, it is preferable to use saturated or unsaturated, branched or unbranched dicarboxylic acid C2-C10preferably dicarboxylic acids (C3-C9, dicarboxylic acid C4-C8, dicarboxylic acid C5-C7especially adipic acid.

As the second monomer in the binder polymer is particularly suitable diamines and triamine straight or branched chain, substituted and unsubstituted, especially N-(2-amino-ethyl)-1,2-amandemen. Preferred dialkanolamine and trialkanolamines include, for example, diethanolamine, N-alkyldiethanolamine, such as N-methyl - and N-ethyldiethanolamine, and triethanolamine.

For control and regulation of the molecular weight, i.e. chain length, during the polycondensation, you can use one or more monohydroxy amines, such as monoalkanolamines. It is preferable to use monoethanolamine.

In a preferred aspect in the scope of the present invention in the quality of the ve binder used is a copolymer, cross-linked with epichlorohydrin.

In a particularly preferred embodiment of the present invention in use as a binder a copolymer of adipic acid with N-(2-amino-ethyl)-1,2-ethanediamine and epichlorohydrin.

A binder may also contain other substances for copolymerization or other traditional means of additives, such as isocyanates.

Binder is best to take in an amount of about 0.1-10 wt.%, preferably about 0.3-5 wt.%, especially preferably about 0.5-3 wt.% calculated on the total weight of the dry composite.

Another aspect of the present invention is a production method of the proposed composite, which is injected and mixed pigment microparticles and/or filler microparticles, the composition of the nanoparticles of calcium carbonate and a binder. A binder is added to the pigment particles and/or filler or to the composition of calcium carbonate, and the resulting mixture is combined with the corresponding second component and homogenized.

In an alternative aspect of the pigment particles and/or filler is first mixed with composition of calcium carbonate and the reaction mixture is combined with a binder and homogenized.

However, it is possible to first prepare an aqueous solution or a slurry of binder and then add the first pigment microparticles and/or fill the appropriate fields and then a composition of nanoparticles of calcium carbonate or first add a composition of nanoparticles of calcium carbonate and then the pigment microparticles and/or filler and then homogenize.

In General, as particles of pigment and/or filler, and composition of nanoparticles of calcium carbonate can be used either dry or in aqueous suspension. However, if the pigment microparticles and/or filler, and composition of nanoparticles of calcium carbonate used dry, it is first necessary to take a sufficient amount of water to obtain a water suspension.

The composition of the nanoparticles of calcium carbonate is usually used in the form of an aqueous suspension, while the pigment microparticles and/or filler can be used in solid form or in aqueous suspension. Microparticles of inorganic pigment and/or filler, it is often preferable to use, in solid form, and microparticles of an organic pigment and/or filler often in the form of an aqueous suspension.

Used here, the term "solid" is not necessarily to be understood as "dry". The term "solid" should be used only to describe the consistency of the substance, which may contain significant amounts of moisture. For example, a mixture of 80 wt.% particulate inorganic pigment and/or filler and 20 wt.% water may nevertheless have firm texture.

Binder preferably take the form of an aqueous suspension, particularly preferably in the form of a solution.

To achieve the best dispersion in each suspension or mixture EXT is to provide one or more of dispersants, for example, in the form of powder or aqueous solution. Dispersancy you can add, for example, after the introduction of the binder in the resulting reaction mixture, or before adding the binder to the pigment particles and/or filler or before adding the composition of calcium carbonate to the component to which you then add binding or with which it is mixed.

Best dispersant include, for example, salts of polyacrylic acid, such as sodium salt, sodium polyphosphate or copolymers of polyacrolein/acrylate.

However, you can also add cationic and/or amphoteric polymer dispersant, such as polydiallyldimethyl chloride (PolyDADMAC) or copolymers of acrylic acid with a cationic monomer or a mixture of such dispersants. Such products are described, for example, in the patent DE 4018162 and issued by the company Stockhausen GmbH, Krefeld, for example, under the trademark Prastol.

These dispersant can be added to the binder in the amount of 0.01-1 wt.% calculated on the total weight of the dry composite, preferably in quantities of 0.1-0.5 wt.%, for example, 0.25 wt.%. They promote adsorption of the binder.

Mixing and homogenization of the suspension of pigment particles and/or filler and/or composition of calcium carbonate, including adding and mixing a binder, can be done with the help of a mixer type Pendraulik, for example, a toothed disk with a diameter of 3. see, preferably at room temperature.

You can also mix and homogenize the suspension using Limehouse mixer, especially when you first join the pigment particles and/or filler with a binder. Semenovii mixers operate on the principle of mechanically generated fluidized bed. Semenovii the blades mix the components of the mixture by rotating close to the inner wall of the horizontal cylindrical drum and move the components of the mixture layer of products in open space for mixing. Created mechanically fluidized bed provides intensive mixing of even large quantities of components in a very short time. For dispersion of dry pieces of used crushers and/or sprays. The equipment produced by the company Gebruder Lodige Maschinenbau GmbH, Paderborn, Germany. If the suspension compositions of calcium carbonate is not added before the pigment particles and/or filler already processed binder, this Association can be accomplished, for example, by using a tubular mixer, for example, pumping the slurry centrifugal pump through the tubular mixer and continuously feeding the slurry of the pretreated particles of pigment and/or filler in a tubular mixer through the receiving tube. Such tubular mixers produces, for example, Ystral Gmbh Ballrechen-Dottingen, Germany.

The mixing is carried out at room temperature, about 20-25°C. the Heated during cooking, for example, due to friction in the process of dispersion, does not require the adoption of special measures. For example, typically, the temperature at this time may be 20-90°C, preferably 20-70°C.

You can also use a combination of different mixers.

The composites obtained by the proposed method, it is possible to dry up and get them in solid form, but you can also process them in the form of the newly formed aqueous slurry of the dried composite, so that not only offer composite, but its suspension in water are the subject of this invention.

The water content in the suspension of the composite obtained by the proposed method, it is possible to reduce, for example, thermally or, for example, spray drying or microwave drying or drying in an oven or mechanically, for example by filtering, so that the result is a composite in the form of dry or wet solids, such as sludge on the filter. To obtain the dry composite it is dried, for example, in a drying Cabinet at 105°C to constant weight.

Additional aspects of the present invention include the possibility of using a composite material in hard, wet or dry state or in aqueous suspension.

Thus, one of the main aims is the first application of the composite or its suspension is its use as a filler or pigment, for example, in paper and/or pigment for coatings, but not in the production or processing of thermal paper, if the composite contains organic microparticles.

The composite can be used as a filler or pigment in the manufacture of paper or paper finishing, for example, for deposition of the coating on the paper, but not thermal paper, if the composite contains organic microparticles.

In the manufacture of paper composite is preferably used in amounts of 0.5-50 wt.%, preferably 1-30 wt.% calculated on the total weight of the paper. In paper finishing, for example the coating, the preferred amount of the proposed composite amount of 0.5 to 100 g/m2preferably 2-50 g/m2especially preferably 5 to 25 g/m2on one side of the paper.

The composite can also be used in multilayer coatings, for example, for applying a preliminary coating and/or intermediate coatings and/or surface coatings and/or single coverage. If the composite is preliminary and/or intermediate coating, you can apply another coating using traditional pigments, which are known to experts in this field. The composite can be used for coating one or both sides of the paper, and in this case, one or more coatings on one or both sides will contain the comp the zit.

Paper that is coated on one or both sides, or not covered, you can calendering or not calendering.

By targeted selection of the composite on its composition and particle size pore volume of paper and/or coatings can also be varied by coating of the particles of the composite or without it; for example, the pore volume can be increased or adjusted, and in this case, the application of the proposed composites, if they contain organic microparticles, does not apply to the area thermobag, receipt or processing.

The proposed composite can also be used with other conventional pigments and/or fillers, when this application does not apply thermal paper, receipt or processing, due to the fact that the composite contains organic microparticles.

Thus, an object of the present invention also includes fillers or pigments containing the proposed composite or suspension.

Another aspect of the present invention includes the use in paints or plastics, for example, to increase the opacity of paint or plastics. In particular, the composites containing hollow spherical organic particles may also enhance the insulation effect.

Similarly, the proposed composites because of their structure can also be used to reduce the brilliance of the Term "gloss" refers to surface gloss paper under a very small angle; often this is very annoying sight of the observer. To reduce the Shine you want a very wide scattering, which is achieved using the proposed composites.

The proposed composites can also be used in sealants, for example, as thickeners or reagents that regulate the viscosity.

Due to the lamellar structure of inorganic micropigments and microcapillaries, such as talc and/or mica, and the surface properties of calcium carbonate proposed composite allows to use, for example, plate-like calcium carbonate".

Due to the fact that organic micropigment and/or fillers have a structure of hollow spheres such as hollow small polystyrene beads, as well as the characteristics of the surface properties of calcium carbonate proposed composite also allows the use of "light calcium carbonate, for example, in plastics and paints that can be applied, for example, in aviation technology.

Another aspect of the present invention relates to the application of the proposed composite or suspension to filter or as a filter layer or such a layer of natural and/or synthetic media or in it, such as fibers of cotton, cellulose and polyamide. Due to the porous structure and low segregation composite is at the same time optimizes the transfer of fluids and good retention of suspended particles.

Thus, the present invention also relates to the filter containing the proposed composite or suspension.

Another aspect of the present invention relates to dye to cover, including the proposed composite, but it cannot be used to obtain and furnish the paper, if the composite contains organic microparticles.

This dye to cover contains solids in the amount of 25-75 wt.%, more preferably 30-60 wt.% particularly preferably 30-40 wt.%. The number of composite dye to cover in the calculation of the total mass of solids can be 3-97 wt.%, preferably 10-90 wt.%. Particularly preferably 85±10 wt.%.

Due to the extremely high binding properties of the binding offer in the proposed composites and especially a surprisingly high binding nanoparticles of calcium carbonate with the surface of the microparticles another aspect of the present invention includes the use of a copolymer comprising as monomers one or more dicarboxylic acids and one or more monomers from the group of diamines, triamines, dialkanolamines or trialkanolamines, for at least partial coating of the pigment particles and/or filler composite containing such nanoparticles of calcium carbonate, as described above. The person who but preferably used as a binder of a copolymer of adipic acid with N-(2-amino-ethyl)-1,2-atendimento and epichlorohydrin.

The following figures and examples and experiments serve to illustrate the present invention and in no way shall it limit.

Description of figures

The following figures are scanning electron micrograph (SEM) of various mixtures used in this area, and the proposed composites. Mixtures and composites offer brought to a concentration of 20 wt.% in water using a rotary suction dispersant. A few drops of the resulting suspension (approximately 100 mg) was diluted with 250 ml of distilled water and was filtered through a membrane filter with pores of 0.2 μm. On the thus obtained preparations of membrane filter napisali gold and withdrew scanning micrographs at different degrees of magnification.

The figure 1 shows a scanning micrograph of a mixture of nanoparticles of calcium carbonate and organic particles without a binder.

The figure 2 shows a scanning micrograph of another drug mixture of nanoparticles of calcium carbonate and organic particles without a binder.

The figure 3 shows a scanning micrograph of a preparation of a mixture of nanoparticles of calcium carbonate and inorganic particles without a binder.

The figure 4 shows a scanning micrograph of a preparation of a mixture of nanoparticles of calcium carbonate and inorganic mi is Rochester without binder.

Figure 5 shows a scanning micrograph of the preparation of the proposed composite of organic microparticles, nanoparticles of calcium carbonate and a binder.

The figure 6 shows a scanning micrograph of another drug of the proposed composite of organic microparticles, nanoparticles of calcium carbonate and a binder.

Figure 7 shows a scanning micrograph of another drug of the proposed composite of organic microparticles, nanoparticles of calcium carbonate and a binder.

The figure 8 shows a scanning micrograph of another drug of the proposed composite of inorganic microparticles, nanoparticles of calcium carbonate and a binder.

Figure 9 shows a scanning micrograph of another drug of the proposed composite of inorganic microparticles, nanoparticles of calcium carbonate and a binder.

The figure 10 shows a scanning micrograph of another drug of the proposed composite of inorganic microparticles, nanoparticles of calcium carbonate and a binder.

The figure 11 shows a scanning micrograph of another drug of the proposed composite of organic microparticles, nanoparticles of calcium carbonate and a binder.

EXAMPLES

Receipt and description of the nanoparticles, which can be used according to the present invention

the who describes the obtaining compositions of the nanoparticles of calcium carbonate, suitable for the proposed composites.

The composition of the nanoparticles of calcium carbonate 1 received continuous grinding particles of marble from Norway, pre-shredded in a traditional ball mill dry method to the equivalent spherical diameter of 45 μm by wet grinding in a vertical 160 l ball mill in two passes using as a dispersant/shredder 0.85 wt.% polyacrylate sodium/magnesium with Mw of about 6000 g/mol based on the total weight of the dry composite, with a solids content of 72 wt.%, and received the following size distribution:

Diameter (nm)The number (N) of particles in N%Wt.%
<20097.423.6
200-4002.022.4
400-6000.418.7
600-8000.114
800-1000<0.19.1

The viscosity Brookfield suspension obtained after wet grinding amounted to 285 MPa·S.

Used grinding balls made of zirconium silicate and baddeleyite had a size of 0.5-2 mm.

The composition of the nanoparticles of calcium carbonate 2 received continuous grinding particles of marble from Norway, pre-shredded in a traditional ball mill dry method to obtain equivalent spherical diameter of 45 μm by wet grinding in a vertical 160 l ball mill in two passes, using as a dispersant/shredder 0.85 wt.% polyacrylate sodium/magnesium with Mw of about 6000 g/mol based on the total weight of the dry composite and 1 wt.% sodium salt of a copolymer of polyethylene and poly (acrylic acid) (Primacor I 5880, DOW, neutralized at 95°C the equivalent amount of NaOH in the calculation of the number of carboxyl groups) calculated on the total weight of the dry composite material with a solids content of 72 wt.% and received the following size distribution:

Diameter (nm)The number (N) of particles in N%Wt.%
<20096.526.1
200-4002.720
400-600 0.517.8
600-8000.113.3
800-1000<0.18.9

The viscosity Brookfield the resulting suspension was 450 MPa·S.

Used grinding balls made of zirconium silicate and baddeleyite had a size of 0.5-2 mm.

The composition of the nanoparticles of calcium carbonate 3 received continuous grinding particles of marble from Norway with an equivalent spherical diameter of 45 μm by wet grinding in a vertical 1500 l ball mill in two passes, using as a dispersant/shredder 0.95 wt.% polyacrylate sodium/magnesium with Mw of about 6000 g/mol based on the total weight of the dry composite material with a solids content of 75 wt.%, and received the following size distribution:

Diameter (nm)The number (N) of particles in N%Wt.%
<20097.434.3
200-4002.019.2
400-6000.4 17.9
600-8000.111.7
800-1000<0.16.5

The viscosity Brookfield the resulting suspension was 285 MPa·S.

Used grinding balls made of zirconium silicate and baddeleyite had a size of 0.5-2 mm.

The composition of the nanoparticles of calcium carbonate 4 received continuously from limestone in the South of France, Provence, with equivalent spherical particle diameter of 45 μm by wet grinding in a horizontal mill with stirring (Dynomill, the volume of 1.4 l), using as a dispersant/shredder 0.45 wt.% polyacrylate sodium/magnesium with Mw of about 6000 g/mol based on the total weight of the dry limestone with a solids content of 65 wt.%, and received the following size distribution:

Diameter (nm)The number (N) of particles in N%Wt.%
<20097.417.4
200-4002.210.5
400-6000.510.
600-8000.29.4
800-10000.18.5

The viscosity Brookfield the resulting suspension was 285 MPa·S.

Used grinding balls made of zirconium silicate and baddeleyite had a size of 0.5-2 mm.

Then the suspension was treated with a spray dryer (dryer from NIRO) at the initial temperature of 105°C. the water Content after drying was <0.3 wt.%.

Description of microparticles that can be used according to the invention

Organic microparticles 1: suspension Ropaque® HP-1055 (Rohm & Haas):

Particle size: a relatively homogeneous 1.0 μm.

The particle size determined by scanning electron microscopy.

The solids content of 27 wt.% (determined at 120°C for 2 hours in a drying Cabinet).

Organic microparticles 2: dispersion in polyethylene

Particle size: about 0.25-1.5 mm.

The particle size determined visually by scanning electron microscopy.

The solids content of: 25.1 wt.% (determined at 120°C for 2 hours in a drying Cabinet).

Neorganicheskie microparticles 1: suspension Finntalc 10 (MONDO Minerals, Finland):

<10 microns
Particle size: 95 wt.%
80 wt.%<5 µm
45 wt.%<2 μm

The particle size determined by the method of sedimentation on the device Sedigraph 5100, Micromeritics, USA.

The solids content of: 61.5 wt.% (determined at 120°C for 2 hours in a drying Cabinet).

Inorganic microparticles 2: powder Finntalc P 05, MONDO Minerals, Finland

Particle size: 96 wt.%<10 microns
79 wt.%<5 µm
43 wt.%<2 μm

The particle size determined by the method of sedimentation on the device Sedigraph 5100, Micromeritics, USA.

Moisture content: <0.5 wt.% water (determined at 120°C. for 2 hours in a drying Cabinet).

Description binders which can be used according to this invention

Binder 1

15±0.5 wt.% an aqueous solution of a copolymer of adipic acid with N-(2-amino-ethyl)-1,2-atendimento and epichlorohydrin with the following characteristics:

the total chlorine content: about 1.5 wt.%;

- the content of organic chlorine: <0.5 wt.%;

- mw>1000 g/mol;

the viscosity of the aqueous solution on Brookfield: 80 MPa·s ± 30 MPa·s (Brookfield, type EV-2H+, rotating disk type 3 100 the b/min);

- pH 3.0.

Such products can be obtained by two-stage synthesis, known to experts in the field of organic synthesis. You can, for example, to obtain an intermediate product consisting of the reaction product of Diethylenetriamine, monoethanolamine and adipic acid in distilled water. In the second reaction the obtained intermediate compound is introduced into the reaction with epichlorohydrin in the presence of sulfuric acid and potassium sorbate as a catalyst for the formation of the final product, diluted with water to a solids content of 12-20 wt.% and set to pH 3 with sulfuric acid. Such copolymers sold by the company Lanxess, Germany, and the company the Magician, Italy, for example, under the trademark Nadavin, for example Nadavin DHN (15%).

Binder 2

60±0.5 wt.% active aqueous solution of a copolymer of adipic acid with N-(2-amino-ethyl)-1,2-atendimento and epichlorohydrin with the following characteristics:

the viscosity Brookfield 60 wt.% active aqueous solution: 1300 MPa·s ± 100 MPa·s (Brookfield, type EV-2H+, rotating disk type 3, 100 rpm);

- acid value: 12 mg KOH/g solids;

- color number on Gardner; 4;

- pH 8.9.

Such products can be obtained with the one-stage synthesis, which is known to experts in the field of organic synthesis.

In this invention the reaction is injected 300.0 g diethanolamine, 18.7 g of monoethanolamine and 446.9 g adipin the howling acid in 439.4 g of distilled water. Monoethanolamine added slowly in portions to diethanolamine. At this time, the temperature of the support at the level of 110-120°C. after the exothermic reaction the reaction mixture is slowly heated to 160-170°With respect to temperature the water vapour maximum 103°C. At this temperature the mixture is maintained until an acid number of about 20 mg KOH/g Then it is cooled to 130°C. and carefully in small portions add distilled water to achieve a solids content of 60 wt.%.

EXAMPLES

Example 1

Comparative experiment 1: a mixture of organic particles 1 and the composition of the nanoparticles of calcium carbonate 3

473.3 g of the composition of the nanoparticles of calcium carbonate 3 was mixed with 438.2 g suspension of organic microparticles 1 in the dispersant with a Pendraulik toothed disc with a diameter of 3.5 cm and a speed of mixing 7500 rpm when the initial temperature of 22°C during 15 min under stirring. The final temperature after mixing was 45°C.

The resulting mixture had the following characteristics:

the viscosity Brookfield defined in 5 min/60 min/120 min: 77/79/81 MPa·s;

- pH 8.23;

the solids content of: 52.22 wt.%.

The figure 1 clearly shows that nanoparticles of calcium carbonate is separated from the organic microparticles. Scanning electron micrograph visible is only a small part of the 75 wt.% the carbon nanoparticles is and calcium.

To illustrate the tendency to segregation test was performed on filtering through preparation of 200 ml of suspension with 0.5 wt.% solids from a mixture of nanoparticles/microparticles and filtering the suspension through a membrane filter with a pore diameter of 0.2 μm (pressure: about 25 mbar, the water-jet pump; room temperature). Measured time filtering 200 ml In the presence of the segregation of nanoparticles of calcium carbonate to first pass through the pores, but after some time on the membrane filter, a secondary precipitate and block the pores.

Time filter: >24 h After 10 h remains filtered 90 ml of suspension.

Time filtering clearly indicates the segregation of nanoparticles and microparticles.

Comparative experiment 2: a mixture of organic microparticles 2 and composition of nanoparticles of calcium carbonate 3

900 g of a composition of nanoparticles of calcium carbonate 3 calculated on dry substance was mixed with 100 g of the dry substance of the suspension of the organic microparticles 2 disperser with a Pendraulik toothed disc with a diameter of 3.5 cm and a speed of mixing 7500 rpm when the initial temperature of 22°C during 15 min under stirring. The final temperature after mixing was 40°C.

The resulting mixture contained 62.5 wt.% solid substances.

Figure 2 clearly shows that nanoparticles of calcium carbonate CTD is Lena from organic microparticles. Scanning electron micrograph visible is only a small part of 90 wt.% nanoparticles of calcium carbonate.

Comparative experiment 3: a mixture of inorganic microparticles 2 together and crushed calcium carbonate

Mixture

- 47.0 wt.% Norwegian marble, crushed dry method in traditional ball mill to an average spherical particle diameter of 45 μm,

- 23.3 wt.% microparticles 2,

- 28.9 wt.% water,

- 0.4 wt.% solution of sodium polyacrylate as the grinding means,

- 0.4 wt.% the solution is neutralized with potassium copolymer (acrylic acid/butyl acrylate) as dispersant to grind to reach the next distribution of wet grinding in a horizontal ball mill with stirring from the company Dynomill holding 2 l:

- particle size: 99 wt.%<10 microns
76 wt.%<2 μm
51 wt.%<1 μm
12 wt.%<0.2 mm

The particle size determined by the method of sedimentation on the device Sedigraph 5100, Micromeritics, USA,

the viscosity Brookfield defined in 5 min/60 min/120 min: 182/194/210 MPa·s

- pH 9.4

- the obsession solids: 69.8 wt.%.

Figure 3 clearly shows that nanoparticles of calcium carbonate is separated from the inorganic microparticles.

To illustrate the tendency to segregation test was performed on filtering through preparation of 200 ml of suspension with 0.5 wt.% solids from together the crushed mixture and filtering the suspension through a membrane filter with a pore diameter of 0.2 μm (pressure: about 25 mbar, the water-jet pump; room temperature). Measured time filtering 200 ml In the presence of the segregation of nanoparticles of calcium carbonate to first pass through the pores, but after some time on the membrane filter, a secondary precipitate and block the pores.

Time filter: >24 h After 12 h remains filtered 50 ml suspension.

Time filtering indicates segregation of nanoparticles and microparticles.

Comparative experiment 4: a mixture of inorganic particles and compositions of nanoparticles of calcium carbonate 1

753.4 g of the composition of the nanoparticles of calcium carbonate 1 was mixed with 882.0 g of a suspension of inorganic particles 1 in the dispersant with a Pendraulik toothed disc with a diameter of 3.5 cm and a speed of mixing 7500 rpm when the initial temperature of 22°C during 15 min under stirring. The final temperature after mixing was 48°C.

The resulting mixture had the following characteristics:

the viscosity Brookfiel the remote control, defined in 5 min/60 min/120 min: 142/138/138 MPa·s;

- pH 8.28;

the solids content of: 66.5 wt.%.

Figure 4 clearly shows that the nanoparticles of calcium carbonate is separated from the inorganic microparticles. Scanning electron micrograph visible is only a small part of the 50 wt.% nanoparticles of calcium carbonate.

To illustrate the tendency to segregation test was performed on filtering through preparation of 200 ml of suspension with 0.5 wt.% solids from a mixture of nanoparticles/microparticles and filtering the suspension through a membrane filter with a pore diameter of 0.2 μm (pressure: about 25 mbar, the water-jet pump; room temperature). Measured time filtering 200 ml In the presence of the segregation of nanoparticles of calcium carbonate to first pass through the pores, but after some time on the membrane filter, a secondary precipitate and block the pores.

Time filter: >24 h After 10 h remains to be filtered, an additional 70 ml of suspension.

Time filtering indicates segregation of nanoparticles and microparticles.

Offer examples

Example 2. Composites of organic microparticles, the composition of the nanoparticles of calcium carbonate and a binder 1

Experiment 5. A composite of 25 wt.% organic microparticles and 75 wt.% the composition of the nanoparticles of calcium carbonate 3

2100 g of the composition of the nanoparticles of calcium carbonate 3 a is placed into the disperser Pendraulik and added to the composition 1944.4 g suspension of organic microparticles 1 for 2 minutes The solid content was diluted with water to a concentration of 50 wt.%; to the mixture was added 272.7 g of the binder in the aqueous solution with a solids content of 15.4 wt.% for another 2 min and diluted with water to a solids content of 35 wt.%. The resulting reaction mixture was dispersively for 15 min; after half time the dispersion was set to pH 9 using 10 wt.% NaOH and then was dispersively using 0.525 wt.% in the calculation of the total solids content of 42 wt.% active aqueous solution of sodium salt of polyacrylic acid (Mw: approximately 4000 g/mol; pH 8.5). Dispersant was equipped with a Pendraulik toothed disc with a diameter of 3.5 cm and a speed of 7500 rpm Initial temperature was equal to 21°C and the final temperature after 15 minutes the dispersion was 38°C. the suspension Obtained composite had the following characteristics:

the viscosity Brookfield defined in 5 min/60 min/120 min: 610/580/583 MPa·s;

- pH 9.04;

the solids content of: 35.1 wt.%.

From figure 5 it is clear that nanoparticles of calcium carbonate are not separated from the organic particles are on the surface of the organic microparticles. It is easy to see that the volume of pores in example 2, experiment 5 is significantly greater than in example 1, experiment 1.

To illustrate the tendency to segregation test was performed on the filtering by p the production of 200 ml suspension with 0.5 wt.% solids from a mixture of nanoparticles/microparticles and filtering the suspension through a membrane filter with a pore diameter of 0.2 μm (pressure: about 25 mbar, the water-jet pump; room temperature). Measured time filtering 200 ml If segregation occurs first nanoparticles of calcium carbonate pass through the pores, but after some time on the membrane filter, a secondary precipitate and block the pores.

Time filter: 1.5 hours

Time filtering clearly shows that the segregation of nanoparticles and microparticles decreased markedly. The secondary layer of sediment on the filter, which could block pores, practically not formed on the membrane filter. The filtering process was very short due to the open structure of the composite in comparison with experiment 1, the example 1.

Experiment 6: a composite of 50 wt.% organic microparticles 1 and 50 wt.% the composition of the nanoparticles of calcium carbonate 3

1457 g of the composition of the nanoparticles of calcium carbonate 3 was placed in a disperser Pendraulik and added to the composition 4047 g suspension of organic microparticles 1. The solid content was diluted with water to a concentration of 40 wt.%. To this mixture was added 283.8 g binder 1 in the form of an aqueous solution with a solids content of 15.4 wt.% and diluted with water to a solids content of 30 wt.%. The reaction mixture was stirred for 15 min, and initially set to pH 9 using 10 wt.% NaOH and dispersible mixture with 0.3 wt.% in the calculation of the total solids content of 42 wt.% act the main aqueous solution of sodium salt of polyacrylic acid (Mw: approximately 4000 g/mol; pH 8.5). Disperser equipped with a Pendraulik toothed disc with a diameter of 3.5 see working speed of mixing was 7500 Rev/min Initial temperature was equal to 21°C. Within 15 minutes of mixing, the temperature rose to a final temperature of 42°C.

The suspension obtained composite had the following characteristics:

the viscosity Brookfield defined in 5 min/60 min/120 min: 459/574/616 MPa·s;

- pH 9.03;

the solids content of: 28.9 wt.%.

Figure 6 clearly shows that nanoparticles of calcium carbonate is not separated from the organic particles are on the surface of the organic microparticles. It is easy to see that the volume of pores in example 2, experiment 6 was significantly increased in comparison with example 1, experiment 1.

Experiment 7: a composite of 9 wt.% organic microparticles 1 and 91 wt.% the composition of the nanoparticles of calcium carbonate 4

a) stage 1: obtain an intermediate composition of nanoparticles of calcium carbonate 4 and binder 1

2500 g of the composition of the nanoparticles of calcium carbonate 4 was placed in a 1 l semenovii a mixer, a Lodige, Germany, and added 324.7 g of an aqueous solution of the binder 1 for 10 min with stirring and then homogenized for 10 minutes

After adding the binder 1, the solids content of the intermediate amounted to 90.2 wt.% the mixture had the consistency of a solid powder.

b) tadia 2: obtaining a composite material of the intermediate and organic microparticles 1

111 g of a suspension of microparticles 1 was placed in a disperser Pendraulik and added 332.6 g of the intermediate from step a) and diluted with water to a concentration of 46 wt.% and then components of the prepared composite.

The suspension obtained composite had the following characteristics:

the viscosity Brookfield 2 hours after cooking 795 MPa·s;

- pH 7.6;

the solids content of: 46.7 wt.%.

Scanning electron micrograph of the proposed composite there is a good coating of microparticles with nanoparticles of calcium carbonate compared with the mixture.

Experiment 8: a composite of 10 wt.% organic microparticles 2 and 90 wt.% the composition of the nanoparticles of calcium carbonate 3

1800 g calculated on the dry matter of the composition of the nanoparticles of calcium carbonate 3 was placed in a disperser Pendraulik and mixed with 200 g of a suspension of organic microparticles 2 calculated on the dry portion within 2 minutes of Solid content was diluted with water to a concentration of 50 wt.%. To the mixture was added binder 1 in the form of an aqueous solution with a solids content of 15.4 wt.% for a further 2 minutes until a concentration of 5 wt.% based on the solid content of nanoparticles and microparticles and diluted with water to a solids content of 40 wt.%. The resulting reaction mixture was dispersively for 15 min; after half time the dispersion was set to pH 9 with what omashu 10 wt.% NaOH and the mixture was dispersively using 1 wt.% in the calculation of the total solids content of 40 wt.% active aqueous solution of sodium salt of polyacrylic acid (Mw: approximately 4000 g/mol; pH 8.5). Disperser equipped with a Pendraulik toothed disc with a diameter of 3.5 cm, and the working speed of mixing was 7500 Rev/min Initial temperature was 23°C and the final temperature after 15 minutes the dispersion was 42°C.

pH 9.0.

The solids content of: 40.9 wt.%.

Figure 7 clearly shows that nanoparticles of calcium carbonate is not separated from the organic particles are on the surface of the organic microparticles.

Example 3. Composites of inorganic microparticles, the composition of the nanoparticles of calcium carbonate and a binder 1

Experiment 9: composite of 50 wt.% inorganic microparticles 2 and 50 wt.% the composition of the nanoparticles of calcium carbonate 1

a) stage 1: preparation of intermediate of microparticles 2 and binder 1

400 kg of inorganic microparticles 2 was placed in semenovii mixer FKM 2000 D, Lodige, Germany and added 53.3 kg of an aqueous solution of the binder 1 for 10 min with stirring and then homogenized for 10 minutes After addition of the binder 1, the solids content of the intermediate amounted to 88 wt.% the mixture had the consistency of a solid powder.

b) stage 2: preparation of a composite of intermediate and composition of nanoparticles of calcium carbonate

522.6 kg of a composition of nanoparticles of calcium carbonate 1 and 388 kg of water were mixed in a container with a capacity of 2 m3to containing the Oia solids in suspension 41.63 wt.%. Then added 8.9 kg 42 wt.% active aqueous solution of sodium salt of polyacrylic acid (Mw: approximately 4000 g/mol, pH 8.5) and 3 kg of 10 wt.% NaOH. The suspension is pumped by the centrifugal pump through the tubular mixer, a tubular mixer was added continuously 427.5 kg of the intermediate from step 1 with a solids content of 88 wt.% through the receiving tube for 2 min and intermediate brought into contact with the suspension. The resulting suspension was stirred for another 8 minutes

Then the material was sifted directly into the container through a sieve with apertures 104 microns.

The suspension obtained had the following characteristics

after 5 days after preparation:

the viscosity Brookfield defined in 5 min/60

min/120 min: 76/75/77 MPa·s;

pH 8.65;

the solids content of: 58.6 wt.%.

Figure 8 clearly shows that nanoparticles of calcium carbonate is not separated from the inorganic particles are on the surface of the inorganic microparticles. It is easy to see that the volume of pores in example 3, experiment 9 significantly increased in comparison with example 1, experiment 4.

To illustrate the tendency to segregation test was performed on filtering through preparation of 200 ml of suspension with 0.5 wt.% solids from a mixture of nanoparticles/microparticles and filtering the suspension through a membrane filter with a pore diameter of 0.2 μm (pressure: about 25 mbar, water is truly pump; room temperature). Measured time filtering 200 ml If segregation occurs first nanoparticles of calcium carbonate pass through the pores, but after some time on the membrane filter, a secondary precipitate and block the pores.

Time filter: 6.0 hours

Time filtering clearly shows that the segregation of nanoparticles and microparticles decreased markedly. The secondary layer of sediment on the filter, which could block pores, practically not formed on the membrane filter. The filtering process was very short due to the open structure of the composite compared with experiment 4, example 1.

Experiment 10. A composite of 50 wt.% inorganic microparticles 2 and 50 wt.% the composition of the nanoparticles of calcium 2

a) stage 1: preparation of intermediate of microparticles 2 and binder 1

400 kg of inorganic microparticles 2 was placed in semenovii mixer FKM 2000 D, Lodige, Germany and added 53.3 kg of an aqueous solution of the binder 1 for 10 min with stirring and then homogenized for 10 minutes After addition of the binder 1, the solids content of the intermediate amounted to 88 wt.%.

b) stage 2: preparation of a composite of intermediate and composition of nanoparticles of calcium carbonate 2

518.3 kg of a composition of nanoparticles of calcium carbonate 2 and 348 kg of water were mixed in a container with a capacity of 2 m3. Stampabile 3.6 kg 42 wt.% active aqueous solution of sodium salt of polyacrylic acid (Mw: approximately 4000 g/mol, pH 8.5) and 1.35 kg of 10 wt.% NaOH with stirring. The suspension is pumped by the centrifugal pump through the tubular mixer, a tubular mixer was introduced continuously 424 kg of the intermediate from step 1 with a solids content of 88 wt.% through the receiving tube and stirred.

Then the material was sifted directly into the container through a sieve with apertures 104 microns.

the suspension obtained had the following characteristics

after 5 days after preparation:

the viscosity Brookfield defined in 5 min/60 min/120 min: 422/405/409 MPa·s;

pH 8.3;

the solids content of: at 58.35 wt.%.

Figure 9 clearly shows that nanoparticles of calcium carbonate is not separated from the inorganic particles are on the surface of the inorganic microparticles. It is easy to see that the volume of pores in example 3, experiment 10 significantly increased in comparison with example 1, experiment 4.

To illustrate the tendency to segregation test was performed on filtering through preparation of 200 ml of suspension with 0.5 wt.% solids from a mixture of nanoparticles/microparticles and filtering the suspension through a membrane filter with a pore diameter of 0.2 μm (pressure: about 25 mbar, the water-jet pump; room temperature). Measured time filtering 200 ml If segregation occurs first nanoparticles of calcium carbonate pass through the pores, but after some time on ebrandon the filter, a secondary precipitate and block the pores.

Time filter: 2.5 hours

Time filtering clearly shows that the segregation of nanoparticles and microparticles decreased markedly. The secondary layer of sediment on the filter, which could block pores, practically not formed on the membrane filter. The filtering process was very short due to the open structure of the composite compared with experiment 4, example 1.

Experiment 11: a composite of 25 wt.% inorganic microcosmic and 75 wt.% the composition of the nanoparticles of calcium carbonate 2:

a) stage 1: preparation of intermediate of microparticles 2 and binder 1

400 kg of inorganic microparticles 2 was placed in semenovii mixer FKM 2000 D, Lodige, Germany and added 53.3 kg of an aqueous solution of the binder 1 for 10 min with stirring and then homogenized for 10 minutes After addition of the binder 1, the solids content of the intermediate amounted to 88 wt.%.

In semenovii Lodige mixer was placed first 77.5 kg of the composition of the nanoparticles composite 2 and mixed with 17.5 kg of water. Then added 180 g of a 42 wt.% an aqueous solution of sodium salt of polyacrylic acid (Mw: approximately 4000 g/mol, pH 8.5) and after a short homogenization for 2 min was added 21.1 kg of the intermediate from step 1 with a solids content of 88 wt.% and thoroughly mixed for 30 min using two Semenovich mixer FKM 130 D as d is genetator and mixer.

Then the material was sifted directly into the container through a sieve with apertures 104 microns.

The suspension obtained composite had the following characteristics

after 5 days after preparation:

the viscosity Brookfield: 108/109/112 MPa·s;

pH 8.86;

the solids content of: 64.76 wt.%.

Figure 10 clearly shows that nanoparticles of calcium carbonate is not separated from the inorganic particles are on the surface of the inorganic microparticles. It is easy to see that the volume of pores in example 3, experiment 11 significantly increased in comparison with example 1, experiment 4.

This experiment shows that even when using other equipment that differs from previously described, and another time adding pigments and/or fibers and a binder still have a good linking inorganic particles with nanoparticles of calcium carbonate.

Example 4: polymers from organic microparticles, the composition of the nanoparticles of calcium carbonate 3 and binder 2

Experiment 12: the composite of 25 wt.% organic microparticles 1 and 75 wt.% the composition of the nanoparticles of calcium carbonate 3 and binder 2

654.2 g organic microparticles 1 was placed in a disperser Pendraulik added 17.6 g of 20 wt.% the PolyDADMAC solution was stirred 5 min and then added 23.5 g of the binder 2, was stirred 5 min and then added to 700 g of the composition of nanocast the calcium carbonate 3 and diluted with distilled water to a concentration of about 30 wt.%. The resulting reaction mixture was stirred for 15 minutes, checking pH 9 using 10 wt.% NaOH and dispersively the mixture using 16.8 g 42 wt.% active aqueous solution of sodium salt of polyacrylic acid (Mw: approximately 4000 g/mol; pH 8.5). Disperser equipped with a Pendraulik toothed disc with a diameter of 3.5 see the stirring Speed was 7500 Rev/min Initial temperature was 23°C. After a 15-minute dispersion temperature of the suspension was increased to a final temperature of 44°C.

The suspension obtained composite had the following characteristics:

the viscosity Brookfield defined in 5 min/60 min/120 min: 317/338/358 MPa·s;

- pH 9.26;

- solid content: 32.0 wt.%.

From figure 11 it is clear that nanoparticles of calcium carbonate is not separated from the organic particles are on the surface of the organic microparticles. It is easy to see that the volume of pores in example 4, experiment 12 is significantly increased in comparison with example 1, experiment 1.

To illustrate the tendency to segregation test was performed on filtering through preparation of 200 ml of suspension with 0.5 wt.% solids from a mixture of nanoparticles/microparticles and filtering the suspension through a membrane filter with a pore diameter of 0.2 μm (pressure: about 25 mbar, the water-jet pump; room temperature). Measured time filtering 200 ml If segregation has months is about, first, the nanoparticles of calcium carbonate pass through the pores, but after some time on the membrane filter, a secondary precipitate and block the pores.

Time filtering: 13 minutes

Exceptionally short time filtering clearly shows that the segregation of nanoparticles and microparticles decreased. The secondary layer of sediment on the filter, which could block pores, practically not formed on the membrane filter. The filtering process was very short due to the open structure of the composite in comparison with experiment 1 of example 1.

Experiment on erosion and drying the ink on the coated paper

a) the Test dilution on uncalendered paper

Put paint was prepared from the proposed composite of experiment 11 and a mixture of modern technology, as described in experiment 1, and had the following composition:

A) to get the paint mixed with 350 g of dry composite of experiment 11 and 35 g of dry styrene-acrylate latex (Acronal S 360 D; BASF) and stirred 5 min at a speed of 200 rpm using a disk with a diameter of 5 cm;

B) to get the paint mixed with 500 g of dry composite of experiment 1 and 50 g of dry styrene-acrylate latex (Acronal S 360 D; BASF) and stirred 5 min at a speed of 2000 rpm using a disk with a diameter of 5 cm

15 g of anhydrous inflicted on paper for ofsatellite type Magnostar, Sappi, a density of 58 g/m2. The coating was applied using a desktop machine company Ericksen with a doctor blade, model 624. Depending on the size of the doctor knife stabbed different amounts of suspension. Then set the speed to 5, the doctor blade is positioned on top of the coated paper. In order to keep the blade from rotating, it is necessary to keep the left hand, without exerting pressure on the coated paper.

To ensure a density of 15 g/m2when applying the mixture from experiment 1 were used doctor blade No. 2, and to obtain a density of 22 g/m2the doctor blade No. 3. The doctor blade No. 3 was also used for composite from experiment 11 to obtain the density of the coating 15 g/m2.

After drying with hot air at a temperature of about 105°C for 15 min on the paper was printed using an inkjet printer HP DeskJet 6540 print cartridge HP Tri-Colour and HP 344 Black 339.

The speed of paint drying was monitored with the help of the device FOGRA when the pressing force of 30 N. The device FOGRA finger wipe tester production Forschungsgesellschaft Druck, Munich is designed to determine the degree of consolidation of the ink. With this tester was determined by the dilution of the painted layer on standard paper Magnostar coated. It served as a model for the erosion of the paint, wiping a hand or finger.

On the strip of coated paper printed on standard instructions the AI. Then the printed surface was tested on the device FOGRA when the pressing force of 30 N at 360°.

Analyzed visually. It was required to obtain a uniform coating without distorting colors.

The results:

Experiment 11 (offer)Experiment 1 (modern art)
Time after printing15 g/m215 g/m222 g/m2
1 minweak blurblurblur
3 minno erosionblurblur
5 minno erosionblurblur
10 minno erosionblurblur
16 hthere is otmyvanija blurblur

The results clearly indicate the improvement achieved by the present invention. In a comparative experiment of modern technology even increase the amount deposited mass has not led to an increase in the speed of drying.

b) Test with printing on calendered paper

The paper sample area of 5×10 cm with a coating applied as described in (a), Kalandarishvili and published as indicated above.

The calendering conditions:

laboratory calender Dixon model 8000;

the temperature of the roll: 90°C;

pressure calendering: 40 bar 4 push (4 passes).

Result

In the test print in this case, special attention was paid to the clash of black paint on the substrate, on which was already yellow print. Analyzed visually in 1 hour without any additional extension.

Experiment 11 (offer)Experiment 1 (mo. the prior art)
15 g/m222 g/m2
No visible crowdingStrong surging
No visible erosion of letters and numbers A sudden blur of letters and numbers, not sharply

This result clearly shows advances in the printing quality thanks to the present invention without external influence on calendered paper.

1. The composite for the manufacture of paper, paints and plastics containing particles of inorganic and/or organic pigment and/or filler particles, equivalent spherical diameter from about 0.2 to about 100 microns, coated at least partially with a composition containing particles of calcium carbonate equivalent spherical diameter less than 200 nm, and a binder which is a copolymer comprising as monomers one or more dicarboxylic acids and one or more monomers from the group of diamines, triamines, dialkanolamines or trialkanolamines.

2. The composite according to claim 1, characterized in that the pigment particles and/or filler are inorganic particles, preferably selected from the group consisting of talc, mica, or mixtures thereof.

3. The composite according to claim 1, characterized in that the pigment particles and/or filler are organic particles, preferably selected from the group consisting of particles of pigment and/or filler, based on polyethylene, polypropylene, polyethylene terephthalate or polystyrene.

4. The composite according to claim 1, characterized who eat that the pigment particles and/or filler are almost spherical structure, preferably the structure of the hollow spheres or hollow hemispheres, or lamellar structure.

5. The composite according to claim 1, characterized in that the equivalent spherical particle diameter of the pigment and/or filler is in the range from more than about 0.3 and up to about 100 microns, preferably in the range of about 0.3 to 75 μm, more preferably in the range of about 0.3 to 50 μm.

6. The composite according to claim 5, characterized in that the equivalent spherical particle diameter of the organic pigment and/or filler is in the range from more than about 0.2 to 25 μm, preferably about 0.3 to 10 μm, more preferably in the range of approximately 0.5 to 1.5 μm and most preferably in the range of about 0.9 to 1 μm.

7. The composite according to claim 3, characterized in that the pigment particles and/or filler particles are based on polystyrene, preferably in the form of hollow spheres of polystyrene with an equivalent spherical diameter of about 0.3 to 2 μm, preferably about 0.7 to 1.5 μm, particularly preferably about 0.9 to 1.1 μm, in particular 1 μm.

8. The composite according to claim 5, characterized in that the pigment particles and/or filler particles are talc, and about 95-98 wt.%, for example, 96 wt.%, the talc particles have an equivalent spherical diameter less than 10 microns, about 9-82 wt.%, for example, 80 wt.%, have an equivalent spherical diameter less than 5 microns and approximately 43-46 wt.%, example 45 wt.%, have an equivalent spherical diameter less than 2 microns.

9. The composite according to claim 1, characterized in that the calcium carbonate is chosen from the group consisting of synthetic precipitated calcium carbonate, preferably with a crystal structure Wouter, calcite or aragonite or crushed natural calcium carbonate, preferably marble, limestone or chalk.

10. The composite according to claim 1, characterized in that about 90-100%, preferably 92-99%, more preferably 94-98%, particularly preferably 96-98%, for example (97±0,5)%, particles of calcium carbonate in the calculation of the number N of particles of calcium carbonate have an equivalent spherical diameter of less than 200 nm, for example in the range of 20-200 nm or 50-180 nm, preferably less than 150 nm, for example in the range of 70-150 nm, more preferably less than 100 nm.

11. The composite according to claim 1, characterized in that it contains 5 to 95 wt.%, preferably 20-80 wt.%, more preferably 25-75 wt.% particles of pigment and/or filler, calculated on the total weight of the dry composite.

12. The composite according to claim 1, characterized in that it contains 95-5 wt.%, preferably 80-20 wt.%, more preferably 75-25 wt.% particles of calcium carbonate in the calculation on the total weight of the dry composite.

13. The composite according to claim 1, characterized in that the cha is based pigment and/or filler and calcium carbonate are present in a ratio of preferably from 1:20 to 20:1, especially in a ratio of from 1:4 to 4:1, more preferably in a ratio of from 1:3 to 3:1 or from 1:2 to 2:1, especially in the ratio of 1:1, 1:3 or 3:1 based on dry weight.

14. The composite according to claim 1, wherein as monomers of the binder - dicarboxylic acid - use saturated or unsaturated, branched or unbranched dicarboxylic acid With2-C10preferably dicarboxylic acids With3-C9, dicarboxylic acid C4-C8, dicarboxylic acid C5-C7especially adipic acid.

15. The composite according to claim 1, characterized in that as djaminovich, triaminic, dialkanolamines or trialkanolamines monomers of the binder used diamines and triamine and diethanolamine and triethanolamines with linear and branched chain, substituted and unsubstituted, especially N-(2-amino-ethyl)-1,2-amandemen, diethanolamine, N-alkyldiethanolamine, such as N-methyl - and N-ethyldiethanolamine, and triethanolamine.

16. The composite according to claim 1, characterized in that the copolymer used as a binder, cross crosslinked with epichlorohydrin.

17. The composite according to claim 1, characterized in that the binder is a copolymer of adipic acid with N-(2-amino-ethyl)-1,2-ethanediamine and epichlorohydrin.

18. The composite according to claim 1, characterized in that it contains about 0.1-10 wt.%, preferably about 0,-5 wt.%, especially preferably about 0.5-3 wt.% binder calculated on the total dry weight of the composite.

19. A method of producing a composite according to any one of claims 1 to 18, comprising the stage of:
a) obtaining a pigment and/or filler;
b) a composition of calcium carbonate;
c) obtaining a binder;
d) mixing particles of a pigment and/or filler and the composition of calcium carbonate in a) and b),
moreover, the particles of pigment and/or filler in a) or to the composition of the calcium carbonate b) add binding and the resulting reaction mixture is homogenized.

20. A method of producing a composite according to any one of claims 1 to 18, comprising the stage of:
a) obtaining a pigment and/or filler;
b) obtaining particles of the composition of calcium carbonate;
c) obtaining a binder;
d) mixing particles of a pigment and/or filler and the composition of calcium carbonate in a) and b),
moreover, the binder added to the mixture of pigment particles and/or filler in a) and the composition of the calcium carbonate b) after stage (d) and the resulting reaction mixture is homogenized.

21. The method according to any of PP or 20, characterized in that the composition of the nanoparticles of calcium carbonate is a water suspension.

22. The method according to any of PP or 20, characterized in that the pigment particles and/or filler particles are used in solid form or in aqueous suspension.

23. The method according to any of the C p or 20, characterized in that the particles of inorganic pigment and/or filler used in solid form.

24. The method according to any of PP or 20, characterized in that the particles of the organic pigment and/or filler used in the form of an aqueous suspension.

25. A method of producing a composite according to any one of p or 20, characterized in that the binder is used in the form of an aqueous suspension or solution.

26. The method according to any of PP or 20, characterized in that after adding a binder to the obtained reaction mixture add one or more dispersants.

27. The method according to any of PP or 20, characterized in that add one or more dispersants before add a binder to the pigment particles and/or filler in a) or to the composition of the calcium carbonate b).

28. The method according to any of PP or 27, characterized in that dispersant selected from the group consisting of salts of phosphoric acid such as sodium salt; polyacrolein/acrylate copolymers; polymer cationic and/or amphoteric of dispersants, such as polydiallyldimethyl chloride, or copolymers of acrylic acid and cationic monomers or mixtures of such dispersants.

29. The method according to any of PP or 27, characterized in that dispersant added in an amount of 0.01-1 wt.% calculated on the total weight of the dry composite, predpochtitel is but in an amount of 0.1-0.5 wt.%, for example, a 0.25 wt.%.

30. The method according to any of PP and 20, characterized in that the water content of the resulting suspension of the composite lower.

31. The method according to any of PP or 20, characterized in that the calcium carbonate is ground to a size equivalent spherical diameter at one or more stages of dry or wet grinding, preferably two dry and/or wet, preferably water stages of grinding.

32. The method according to p, characterized in that grinding used ball mills, jet mills, Burr mills, or combinations of such mills or a combination of one or more of these mills cyclones and screens.

33. The method according to p, characterized in that the dry grinding is carried out in a ball mill, preferably with steel and/or porcelain balls with a diameter of 0.5-10 cm, particularly preferably a steel cylinder with a diameter of 2.5 cm, and wet grinding is carried out in Burr mill, preferably with crushing balls of zirconium silicate, zirconium dioxide and/or baddeleyite with a diameter of 0.2-5 mm, preferably 0.2 to 2 mm, or 0.5-5 mm, for example 0.5 to 2 mm.

34. The method according to p, characterized in that the natural ground calcium carbonate is dispersed and/or ground in the form of an aqueous suspension containing solid calcium carbonate is more than 10 wt.%, example : the 15-30 wt.%, for example, more than 30 wt.%, more preferably more than 50 wt.%, for example, the solids content of 65-68 wt.%, particularly preferably more than 70 wt.%, for example, the solids content of 72-80 wt.%.

35. The method according to clause 34, wherein the suspension of calcium carbonate with a solids content of less than 60 wt.%, for example less than 30 wt.%, mechanical focus, for example, pressing on the filter and/or centrifugation and/or thermally, in particular, by combining the stages of the mechanical and thermal concentration, preferably dispersed in the presence of one or more of dispersants, to a final concentration of, preferably higher than 60 wt.%, solids, particularly preferably elm), 65-78 wt.%, for example (72±2) wt.%.

36. The method according to any of PP-35, characterized in that the crushed natural calcium carbonate is dispersed and/or ground in the presence of one or more means of grinding and/or dispersants, especially when it is an aqueous suspension with a solids content of more than 60 wt.%.

37. The method according to p, characterized in that the means of grinding and/or dispersancy are anionic means of grinding and/or desperatly, preferably selected from the group comprising homopolymers or copolymers based on salts of polycarbone what's acids, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, basis of itaconic acid or mixtures thereof; sodium polyphosphates, sodium citrate or mixtures thereof.

38. The method according to clause 37, wherein the homopolymers or copolymers of salts of polycarboxylic acids partially or completely neutralized with sodium ions, lithium, potassium, ammonium, calcium, magnesium, strontium and/or aluminum or mixtures thereof, preferably sodium ions, and magnesium.

39. The method according to any of PP or 38, characterized in that dispersancy and/or shredders used for wet grinding in an amount of about 0.05 to 2 wt.%, preferably in the amount of 0.3-1.5 wt.%, for example, 1 wt.%, especially in the amount of approximately 0,85-0,95 wt.%.

40. The method according to p, characterized in that the viscosity of the suspension of calcium carbonate in the wet grinding is less than 2500 MPa·s, preferably less than 1500 MPa·s, more preferably less than 1000 MPa·s, especially less than 500 MPa·s, for example in the range of 50-250 MPa·S.

41. The method according to p, characterized in that the shredders and/or dispersancy, especially for dry grinding, selected from the group consisting of glycols, polyglycols such as polyethylene glycols, ethylene oxide-propylene oxide-ethyleneoxide block copolymers or alkanolamines, such as triethanolamine, triisopropanolamine or mixtures thereof.

42. The method according to p, from which causesa fact, what shredders and/or dispersant for dry grinding is used in an amount of about 0.01 to 5 wt.% calculated on the total weight of the dry composite, preferably in an amount of about 0.01 to 0.5 wt.%, in particular 0.1 to 0.3 wt.%.

43. Composite on p, characterized in that dispersancy and/or shredders for dry grinding is present in amount of 0.2-1 mg/m2the surface of the nanoparticles, preferably in the amount of 0.3-0.7 mg/m2the surface of the nanoparticles.

44. The method according to p, characterized in that the shredders and/or dispersancy during grinding and/or dispersion combined with the copolymers of ethylene and acrylic acid (EAA) or their salts.

45. The method according to item 44, wherein the salt EAA partially or completely neutralized amines, preferably selected from the group comprising 2-amino-2-methyl-1-propanol, 3-amino-1-propanol, 2-[bis(2-hydroxyethyl)amino]ethanol, and/or ions of alkali metals such as potassium, lithium and/or sodium, or a mixture thereof, preferably sodium.

46. The composite according to any one of paragraphs 44 or 45, characterized in that the EAA and their salts are used in an amount of 0.01-10 wt.% calculated on the total dry weight of the composite, in particular in an amount of 0.01-5 wt.%, preferably in an amount of 0.1-2 wt.%, for example in the amount of 1.0 wt.%.

47. Suspension in water, used as a filler or pigment, different is connected with the fact, that contains the composite according to any one of claims 1 to 18.

48. The use of the composite according to any one of claims 1 to 18 or suspension p in paints, plastics or sealants.

49. The use of the composite according to any one of claims 1 to 18 or suspension p in filters in the form of a layer of natural and/or synthetic media, such as cotton, cellulose or polyamide fibers.

50. The filter tool containing composite according to any one of claims 1 to 18 or suspension by p.

51. The filler-containing composite according to any one of claims 1 to 18 or suspension by p.

52. The pigment-containing composite according to any one of claims 1 to 18 or suspension by p.

53. The paint containing the composite material according to any one of claims 1 to 18 or suspension by p.

54. The paint in item 53, characterized in that it contains solids in the amount of 25-75 wt.%, more preferably 30-60 wt.%, particularly preferably 30-40 wt.%.

55. Paint on any of PP or 54, characterized in that the quantity of the composite based on the total solid content in the paint is 3-97 wt.%, preferably 10-90 wt.%, particularly preferably (85±10) wt.%.

56. The use of a copolymer comprising as monomers one or more dicarboxylic acids and one or more monomers from the group of diamines, triamines, dialkanolamines or trialkanolamines, for at least partial coating of inorganic particles and/or organizes the first pigment and/or filler with a spherical equivalent diameter in the micrometer range composition, containing particles of calcium carbonate with an equivalent spherical diameter in the nanometer range.

57. Use p, characterized in that the copolymer contains as a monomer adipic acid, N-(2-amino-ethyl)-1,2-amandemen and epichlorohydrin.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: paint with thermo-, fire-protective properties contains (wt %): binder based on acrylic (co)polymers and/or silicone resins and organosoluble polyurethanes - (20-40), filler in form of a mineral component - (10-30), antipyrene additive - (10-20), modifying additive in form of ceramic and/or glass microspheres with diameter of 20-150 mcm -(10-30) and an organic solvent - the rest. The paint composition additionally contains bentonite powder, intercalated with cobalt Co2+ ions and/or cerium Ce3+ ions in amount of 3-7 wt %.

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FIELD: coating production.

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EFFECT: mar-proof, anticorrosion, easily cleared, fingermark-free, antireflective, non-weep, scale-protective, diffuse-barrier, radiation-protective, or as self-cleaning, antibacterial, antimicrobic, tribological or hydrophobic coating.

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FIELD: chemistry.

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FIELD: chemistry.

SUBSTANCE: invention relates to compositions for protective coating for window glass. The invention discloses a composition which contains a) one or more film-forming resins which contain acrylic and/or methacrylic functional fragments; b) one or more reactive diluents which contain an acrylate functional group; c) one or more compounds which promote adhesion of the composition to glass, which contain a product of a Michael reaction, having four or more siloxane groups, at least one acrylate group and a tertiary amine group; d) one or more filler substances, capable of endowing compositions with wear-resistance in solidified state; and e) one or more compounds which can react with a film-forming resin, which contain at least one acid fragment.

EFFECT: composition ensures high adhesion of the coating to adhesive substances on a structure in the absence of an undercoat.

16 cl, 5 dwg, 28 tbl, 38 ex

FIELD: chemistry.

SUBSTANCE: disclosed is an actinic radiation hardened coating material which essentially or completely does not contain organic solvents and contains: (A) two compounds of formula I, in which X is an aromatic residue with 6-14 carbon atoms, a heterocyclic aromatic residue with 5-20 ring atoms or an alkyl residue with 6-30 carbon atoms, Y is a trivalent aliphatic residue, Z is a binding functional group and Gr is an organic residue with at least one actinic radiation activated group, where of the two compounds (A), one has one aromatic or heterocyclic aromatic residue X (= A1 compound) and one has an alkyl residue X (=A2 compound); X - O - Y{-OH) - Z - Gr (I), (B) oligourethanes or polyurethanes and/or oligoesters and polyesters with two or three actinic radiation activated groups; (C) at least one component selected from a group consisting of colour and/or decorative effect endowing pigments; (D) wax; (E) amorphous silicon dioxide and (F) is a polysiloxane additive with an actinic radiation activated group. The invention also discloses a method of producing said coating material and use thereof to obtain coil coatings.

EFFECT: invention discloses coating material which is highly reactive, has high pigment content but is stable during storage, can be easily and quickly applied and solidifies at low temperatures without evaporation of volatile organic compounds, the method of producing the disclosed coating material is simple and easily producible.

25 cl, 16 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chlorionated thermoplastic materials with mineral filler, having compatibility between said filler and chlorinated thermoplastic resin. The mineral filler compatibility agent in form of calcium when producing chlorinated thermoplastic material contains a comb-shaped polymer which contains at least one polyalkylene oxide group which is grafted onto at least one ethylenically unsaturated anionic monomer. The comb-shaped polymer contains at least one anionic monomer with ethylenic unsaturation and a monocarboxyl or phosphoric group or mixtures thereof, at least one non-ionic monomer containing at least one monomer of formula (I): , where m and p denote the number of alkylene oxide groups, which is less than or equal to 150, n denotes the number of ethylene oxide groups, which is less than or equal to 150, q denotes a whole number equal to or less than 1, where 5≤(m+n+p)q≤150, R1 denotes hydrogen or a methyl or ethyl radical, R2 denotes hydrogen or a methyl or ethyl radical, R denotes a radical which contains an unsaturated polymerisable group, preferably associated with a group of vinyl compounds, or a group of acrylic, methacrylic, maleic esters, or a group of allyl or vinyl ethers, which are substituted or unsubstituted, R' denotes hydrogen or a hydrocarbon radical with 1-40 carbon atoms or a ionic or ionisable group, such as carboxyl, and preferably denotes a hydrocarbon radical with 1-12 carbon atoms. The invention also relates to chlorinated thermoplastic materials containing at least one chlorinated thermoplastic resin, calcium carbonate and at least one compatibility agent.

EFFECT: high impact strength.

22 cl, 4 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to production of powder, use thereof in aqueous suspensions, in waste treatment, as a chemical additive or as a soil conditioner. The invention includes a method of producing powder based on a metal hydroxide and a metal oxide which is self-dispersed in water. Metal oxide powder is treated partially with a polymer in the form of an aqueous emulsion and/or solution, so that the dry weight content of metal hydroxide in said powder is lower than 99% of the total weight thereof. Said polymer is a water-soluble homopolymer or copolymer containing at least one vinyl monomer. In a particular version, the polymer is a water-soluble copolymer containing a vinyl monomer and a non-ionic monomer, and the metal is calcium and/or magnesium.

EFFECT: invention improves dispersibility of metal hydroxides in water.

22 cl, 2 dwg, 7 tbl

FIELD: chemistry.

SUBSTANCE: method of producing titanium dioxide involves reaction of tetrabutoxytitanium with a surfactant and a precipitating component - ethyl alcohol. The surfactant used is polyoxyethylated (7) hydrogenated castor oil or polyoxyethylated (10) isooctylphenol. First, tetrabutoxytitanium and the surfactant are mixed, after which ethyl alcohol with 4 vol. % water is added, followed by stirring, holding and gelation. Calcination is then carried out while gradually heating to 300°C and holding for 50 hours.

EFFECT: invention enables to obtain titanium dioxide with average particle size of 0,071-0,091 mcm with glase properties which provide lustre.

1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: method of producing granular modified soot involves mixing, while heating, powder thereof with a water-soluble modifying agent - polyether with molecular weight between 290 and 3000 with hydroxyl number between 50 and 800 mg KOH/g in amount of 1.0-5.0% of the weight of the soot, granulation of the mixture followed by drying the wet granules at 285-320°C for a period of time which is 5-30% longer than needed to achieve moisture content of 0.5%. The obtained granular soot contains 2-8% volatile substances, where the content of oxygen in the volatile substances is not less than 71%, and content of oxygen in quinine and phenol groups is not less than 74%.

EFFECT: polymer compositions based on said soot have high resistance to UV radiation, which allows their use in making articles in contact with drinking water and food products.

6 cl, 6 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: particulate material contains a particulate substrate having size of 0.1-3 mm and a dispersion which covers at least 50% of the surface of the particulate substrate. At the time of application onto the particulate substrate, the dispersion contains a thermoplastic olefin polymer, a dispersion medium and a stabilising compound. The dispersion medium is selected from a group comprising organic solvent, water and combinations thereof. Particulate materials meant for applying coating in form of a polymer cladding, may include mineral granular materials and sand.

EFFECT: polymer coated particulate materials obtained using the invention provide lasting wear resistance due to low surface roughness, and may be useful as filler for other fields of using artificial grass, such as golf courses and landscaping, and in insulating layers for damping vibrations and noise.

23 cl

FIELD: chemistry.

SUBSTANCE: invention relates to grain materials with multilayer polymer coating and a method of producing said material. The method involves mixing a first thermoplastic polymer with a grainy substrate to form a mixture at temperature higher than the melting point of the first thermoplastic polymer, cooling the mixture to temperature lower than the melting point of the first thermoplastic polymer and merging the cooled mixture with a second thermoplastic polymer, where the melting point of the second thermoplastic polymer is lower than the temperature of the cooled mixture. Further, the merged mixture is cooled to temperature lower than the melting point of the second polymer. Use of polymers with low melting point in the grain material can successfully lower requirements for heating and cooling, thus reducing power consumption of the process, leading to shorter duration of the cycle. The obtained grain material is used as filler for artificial coatings.

EFFECT: grainy filler has uniform and homogeneous coating, which makes the surface of the filler soft, thereby giving excellent wear resistance, good aesthetic and tactual properties, and ensures safety for the player.

45 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention can be used in chemical industry, automobile and other industries. The modified sheet filler contains at least one sheet filler and at least one modifying agent which contains at least one polymer chain E containing a carbon chain with length from C40 to C500 and a group suspended from the polymer chain E, in which values of each of R, R1 and R2 can be identical or different and independently selected from a hydrogen atom, alkyl, alkenes and aryls with C1 to C26, substituted alkyl, alkens and aryls with C1 to C26, aliphatic alcohols and ethers with C1 to C26, carboxylic acids, nitriles, oxyethylated amines, acrylates and esters with C1 to C26, and X denotes a counter-ion such as Br- Cl- and PF6-. Proposed is a method of preparing such a sheet filler, a nanocomposite containing a modified sheet layer, a method of preparing such a nanocomposite and an article containing the said nanocomposite.

EFFECT: invention improves barrier properties of a diaphragm, membrane, inner lining of tyres, chambers and other similar articles.

13 cl, 6 dwg, 4 tbl, 13 ex

Paper filler // 2345189

FIELD: textile, paper.

SUBSTANCE: filler is designed for paper making and can be used in pulp-and-paper industry. Filler contains calcium salt and cellulose derivative with lattice ionic fractional substitutionality up to approximately 0.65, where filler is essentially free from either cellulose fibre or fibrils or lignocellulose. Filler contains calcium salt and cellulose derivative with lattice ionic fractional substitutionality up to approximately 0.65, where cellulose derivative can contain cationic groups. Besides the invention refers to production process of filler involving mixing the agent substance containing calcium salt and cellulose derivative with lattice ionic fractional substitutionality up to approximately 0.65, essentially without cellulose fibre or fibrils or lignocellulose. Other production process of filler consists in mixing the agent substance containing calcium salt and cellulose derivative with lattice ionic fractional substitutionality up to approximately 0.65, where cellulose derivative contains cationic groups. The invention refers to method for making paper including preparation of aqueous suspension containing cellulose fibre, suspension addition with filler containing calcium salt and cellulose derivative with lattice ionic fractional substitutionality up to approximately 0.65, where filler is essentially free from either cellulose fibre or fibrils or lignocellulose; dehydration of suspension thus making web or paper sheet. The invention also refers to method for making paper including preparation of aqueous suspension containing cellulose fibre; suspension addition with filler containing calcium salt and cellulose derivative with lattice ionic fractional substitutionality up to approximately 0.65, where cellulose derivative contains cationic groups; dehydration of suspension thus making web or paper sheet.

EFFECT: higher sizing efficiency with good drainage, retention and serviceability of papermaking machine.

24 cl, 3 tbl, 4 ex

FIELD: textiles; paper.

SUBSTANCE: method relates to obtaining white pigment for making paper and cardboard and is designed for use in paper and cardboard production. The method involves reaction of the suspension calcium hydroxide with a solution of aluminium sulphate in the presence of a modifying agent. The modifying agent used is a salt of carboxymethylcellulose in quantity of 1.0-2.0 mass of white pigment. The modifying agent is put into the dispersion of calcium hydroxide before its reaction with aluminium sulphate solution.

EFFECT: lower viscosity of the pigment dispersion and improved flow characteristics.

FIELD: polymer materials.

SUBSTANCE: invention provides powdered composite extender for elastomer materials intended for manufacturing articles operated under dry friction or increased wear conditions and applied in engine, compressor, and pump manufacture industries as well as in other industry fields. Extender particles contain at least one metal oxide nucleus and polymeric shell of thermoplastic having modulus of elasticity between 1.5 and 5.0 GPa, volume percentage of nuclei in extender particle ranging from 1 to 10%. Method of preparing composite powder extender consists in that metal oxide particles are activated in mechanochemical activator at mechanical energy supply intensity 1 to 5 kW/kg and dose from 30 to 1000 kJ/kg in medium selected from air, nitrogen, argon, and vacuum between 1 and 10-2 atm to obtain particles with average size no higher than 15 μm, after which shell polymer is added to mechanochemical activator and metal oxide particles are modified with intensity of mechanical energy supply from 1 to 5 kW/kg and dose from 30 to 100 kJ in above indicated medium.

EFFECT: reduced coefficient of friction and lowered summary rate of wear of friction couple under hydroabrasive wear conditions.

4 cl, 2 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: suspension containing calcium carbonate is obtained by adding one or more zirconium compounds and possibly one or more other additives which do not contain phosphate, acting as a dispersant and/or an additive which assists in grinding. Calcium carbonate in dry form and/or in form of an aqueous dispersion or filtered residue is added an aqueous suspension and/or aqueous emulsion and/or aqueous solution containing one or more zirconium compounds. The zirconium compounds used is ammonium zirconium carbonate or calcium zirconium carbonate or mixture thereof.

EFFECT: invention enables to avoid the use of phosphate dispersants when preparing stable aqueous suspensions of calcium carbonate and increases content of solid substance in the suspension.

17 cl, 22 ex

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