Thin aluminium body pigments, method of production thereof and application of these aluminium pigments

FIELD: chemistry.

SUBSTANCE: invention can be used in paint and varnish, cosmetic and other industries. Offered aluminium pigments are at least partially covered with greasing and having a) water spread coefficient within 40000 and 130000 cm2/g; b) average thickness h within less than 100 to 30 nm calculated from water spread coefficient and integral distribution h50 by data processing on thickness of scanning electron microscopy; c) relative width Δh of thickness distributions determined by data processing on thickness of scanning electron microscopy and calculated by corresponding relative frequencies integral curve by formula: 70% to 140%; d) form-factors d50/h more than 200; e) roughness degree calculated by specific surface area measured by BET method and spread coefficient according to the following formula: BET value/2 spread coefficient, from 0.30 to 0.9. Method of production of these pigments, as well as varnishes containing these pigments is offered.

EFFECT: production of very thin aluminium pigments without adhesive polymer film having excellent spreading capacity, high gloss value and improved metallic appearance, as well as reduced agglomeration tendency.

26 cl, 10 ex, 4 tbl, 5 dwg

 

The invention relates to aluminum pigments, which are at least partially coated with grease, as well as the way they are received. The invention relates also to the use of these aluminum pigments.

Aluminum pigments are eye-catching pigments and are distinguished by their unique metallic appearance and high hiding power (opacity). Because of the scaly structure of these eye-catching pigments, they are oriented in the environment of application parallel to the base (substrate) and by the combination of many separate mirrors are the metal effect. This metallic effect is particularly pronounced in the liquid paint coatings. In the case of full-color paint coating refers to the effect of brightness depending on the angle and/or angle of incidence, which is also called the "flop effect". On a good flop effect affect many properties of the pigments: for example, plays an important role in their orientation, their size and size distribution, texture of their surface (roughness) and texture edges.

The driving force for a plane-parallel orientation of the pigments, which are also called scales, is, along with the chemical incompatibility of aluminum pigments interphase with the binding system, especially the form factor of the pigments. Under form factor understand the attitude of rodallega size d to the thickness h of the pigments. The longitudinal size is determined using laser diffraction. In this case, as a rule, draw a value of d50the integral distribution curve.

Since the longitudinal size of the aluminum pigments strongly depends on the respective intended use, a higher form factor and, thus, the best possible orientation can be achieved due to the thickness of the pigments. Thin pigments focus better and have stronger flop effect.

Another important property metallicafan coatings (coating type "metallic") or printing inks is their lustre (gloss). Shine, except that it is physiologically and psychologically due to the amount may be, however, determined according to DIN 67530 "gloss" smooth surface on the testimony of the reflectometer. Measure the reflection at the angle of slip and assign it to the reference (usually black polished glass plate). According to this standard samples with strong luster (reading reflectometer >70) is measured at an angle of incidence or radiation in the 20°and a surface with an average degree of gloss at 60°. Condition good Shine metallicafan coatings is also the best possible plane-parallel orientation of the flake pigments in the environment of use.

The shiny aluminum the new pigments with the strong luster and flop effect is divided now into two classes: the first are the so-called pigments "silver dollar", which can be obtained from the wet milling of the aluminum powder and the other so-called "PVD pigments" ("physical vapor deposition" is condensation from the vapor phase). Pigments "silver dollar" is different in comparison with metal pigments obtained grinding grinding, relatively round shape and relatively smooth surface.

The obtained wet grinding of aluminium pigments with high reflectance and high hiding power are described, for example, in patent EP 0451785 B2. These pigments are characterized by the degree of coverage of the water surface (spreading coefficient) of 2.5-5.0 m2/g, degree of roughness of 2.0 or less and form factor d50/h 90 and more. From the examples of the patent EP 0451785 B2-known form factors with a maximum value of 140.

In the patent EP 0451785 B2 also indicates that the opacity of aluminum pigments depends not only on their longitudinal dimension, but also, in particular, from their thickness. The fine pigments have a higher opacity.

Aluminum pigments for paint cars usually have values of d50at the level of 15-20 microns. Obtained according to the basic principles of patent EP 0451785 B2 aluminum pigment with a degree of coating the surface of the water in 5.0 m2/g and form factor 90 would have the average thickness h at 80 nm and the value of d 507.2 μm. This pigment would be too small, for example, for paint cars.

Aluminum pigments with normal for this segment of the market values of d50at the level of 15-20 μm and form factor 90 would have the average thickness h in the range 167-222 nm.

In U.S. patent 4318747 disclosed thin aluminum pigments with an average size of less than 5 microns and with listwise character that have a spreading coefficient of at least 50000 cm2/g, and specific surface area measured by BET method, of 24 m2/g to 93 m2/year Based on these data, one can calculate that the degree of roughness is from 2.4 to 9.3.

A high degree of roughness of the surface of these pigments leads to strong scattering of the incident light and, consequently, to reduced brilliance compared to a smooth surface PVD pigment.

Also known from U.S. patent 4318747 aluminum pigments, as well as aluminum pigments known from the patent EP 0451785 B2, because of their small size are not suitable for use in paint and varnish coatings cars.

Pigments as described in U.S. patent 4318747 examples always grinded for a long period of time of grinding steel balls with a diameter of 5 mm, the Use of such balls is typical for processes of grinding.

In U.S. patent 3776473 described aluminum pigments are highly reflective and smooth surface and round shape. The pigments described in the embodiments in this patent, have a maximum degree of coverage of the surface of the water just 15600 cm2/year

In the case of PVD pigments receive ultra-thin (thickness of from 20 to 50 nm) of aluminum pigments. The distribution of the thickness of these pigments is extremely narrow. In this way the aluminum is applied by vapor deposition in high vacuum on the film substrate, provided with a removable film ("separating layer"). Under the removed film is meant, generally, a polymer. Then precipitated aluminum, as far as possible, separate the solvent from this film substrate, and the metal foil is crushed mechanically or by using ultrasound. Getting PVD pigments described, for example, in the work of J. Seubert and A. Fetz "PVD Aluminium Pigments: Superior Brillance for Coatings and Graphic Arts, Coatings Journal, Bd. 84, A6 225-264, July 2001, str-245.

These PVD pigments owing to its extreme subtlety have exceptional covering power. These thin pigments are so flexible that they really "fit" their base (clay sublayer). Therefore, for the manifestation of their optical capabilities they should be applied on a smooth base.

However, the disadvantage of these PV-pigments are extremely high production costs in their production process. In addition, the disadvantage is that the separation layer can hardly be completely removed from the pigment particles. However, this sticky polymer film may cause some disadvantages. So, in the case of printing ink may be incompatible with the solvent of printing ink. For example, polymer films, which are suitable for toluene, may be incompatible, in solvents such as alcohols or water. This is manifested in the formation of agglomerates, which completely negates the desired decorative effects.

Moreover, this adhesion of polymers can be especially negative when aluminum pigments after receiving supply of chemical protective shells, such as are described, for example, in document DE 19635085 to make them corrosion-resistant.

The same is true in the case of stabilization by using corrosion protection agents, such as described, for example, in document DE 10001437. In this case, remains stuck separation layer results in an uneven coating and prevent the application of the playback of the protective layer. In particular, the use of such coated substrates in water-based lacquers, in which non-stabilized aluminum pigments cause undesirable gas formation due to hydrogen evolution, one is the similar to the pre-coated substrates cannot be achieved in a reproducible manner.

The following aggravating disadvantage is that the PVD pigments have a very strong tendency to agglomeration. For this reason, PVD pigments are available only in very dilute dispersions with the content of the aluminum pigments usually at the level of 10 wt.%. And for greater ease of handling, it is desirable to have products with higher content of aluminum pigments.

The purpose of this invention is the creation of very thin aluminum pigments without sticking of the polymer film with excellent hiding power, strong luster and, compared with conventional aluminum pigments obtained by conventional wet milling, superior metal kind, the so-called "chrome effect".

The next task of the invention is the creation of very thin aluminum pigments with markedly reduced in comparison with the PVD pigments prone to agglomeration.

Next, you need to be able to get the kind of pigments by using method, which requires less cost in comparison with applied PDV-way receipt.

This problem is solved by creating aluminum pigments, which are at least partially coated with grease, and these aluminum pigments are:

a) spreading coefficient on the water between 40000 and 130,000 cm2/g;

b) calculated from the spreading coefficient is about water, and from the value of h50cumulative distribution by processing the data in thickness scanning electron microscopy, the average thickness h from less than 100 to 30 nm;

c) defined by processing the data on the thickness of the scanning electron microscopy relative width Δh distribution in thickness, which are estimated using the corresponding integral curve of the relative frequencies according to the formula:

,

from 70% to 140%;

d) form factor d50/h over 200;

(e) the degree of roughness, which is calculated from the measured by BET method specific surface area and spreading coefficient according to the following formula:

BET-value/2 × the spreading coefficient,

from 0.30 to 0.9.

Preferred embodiments of the aluminum particles according to the invention are given in the dependent claims.

Next, standing in the basis of the invention the task is solved by the method of obtaining aluminum pigments according to any one of items 1 to 15 of the claims, which includes the following stages:

a) grinding of aluminium particles using the grinding installation in the presence of a solvent, lubricants and grinding media, which are individually weighing from 2 to 13 mg, within a time period from 15 to 72 hours from receipt of aluminum is of igumenov.

Preferred embodiments of the this method are given in the dependent claims.

Next, the task is solved according to the invention through the use of items 23 or 24, as well as nail Polish, paragraph 25, and varnish water based on paragraph 26 of the claims.

The present invention relates to aluminum pigments, which are at least partially coated with grease, have a spreading coefficient on the water from 40000 to 130,000 cm2/g, calculated from the spreading coefficient for water, but also from the value of h50cumulative distribution by processing the data in thickness scanning electron microscopy, the average thickness h from less than 100 to 30 nm, defined according to the thickness of scanning electron microscopy relative width of the distribution in thickness, which are estimated using the corresponding integral curve of the relative frequencies according to the formula

,

from 70% to 140%, and the form factor d50/h over 200.

Preferred are aluminum pigments according to the invention with a spreading coefficient of water from 45,000 to 125,000 cm2/g and calculated from the spreading coefficient on the water, and by processing the data on the thickness of the scanning electron microscopy (value of h50cumulative distribution) environments is her thickness h from less than 89 to 32 nm. More preferred are aluminum pigments according to the invention with a spreading coefficient of water from 50000 to 120000 cm2/g, preferably from 50000 to 90000 cm2/g and an average thickness h, calculated from the spreading coefficient on the water, and by processing the data on the thickness of the scanning electron microscopy (value of h50cumulative distribution), from less than 80 to 33 nm, preferably from 80 to 44 nm.

Aluminum pigments according to the invention due to its small thickness have a very high opacity (hiding power).

Good orientation of the aluminum pigments prevents, in particular, poor placement of pigments in the environment of use. To achieve more uniform packing of pigments in the environment of application are preferred thin pigments with narrow distribution in thickness, and a low level of pigmentation.

In the case of conventional thick aluminum pigments and a wide distribution across the thickness easily get the heterogeneity in the placement of pigments. Thus, in particular, very thick pigments can serve as a "strip" (the spacer elements), which ultimately affects the orientation (Shine) and the opacity surrounding pigments.

Aluminum pigments according to the invention are unexpectedly is very thin and along with that have a narrow distribution in thickness. Aluminum pigments according to the invention unexpectedly similar in their optical properties on the PVD pigments, however, compared to the expensive PVD-method of obtaining are made significantly easier and have much better properties handling, for example, that allows the use of significantly higher concentrations of the drugs.

The exact average thickness of the metal flake pigments is very difficult to determine. DIN 55923 gives an instruction to measure the degree of surface water (flow) "limousine" pigments.

In this case, a specific sample of aluminum pigments in easily volatile organic solvent is applied on the surface of the water in the tub. In the form of "listusers" pigment aluminum pigment coated with, for example, stearic acid and is highly hydrophobic. The pigments spread on the water surface and form a silver metal film. By stirring with a glass rod, they are distributed to the uniform, "no clouds", the metal film. Then this film squeeze the two lines together, until it found the first fold. Then this film again open it, and so up until the crease disappears. Covered with metal foil square Oberau and, taking into account the amounts of pigments, indicate in the form of a CoE is ficient spreading in cm 2/g (or m2/g).

In this method, it is assumed that the metallic pigments, at least in the middle of the film, are one by one next to each other and, therefore, represent only a "monolayer" of pigment.

The average thickness h in nanometers (nm) of these pigments is calculated from the spreading coefficient according to the following formula:

where ρ is physical specific gravity adsorbed stearic acid pigments. Here substitute typically is approximately 2.5 g/cm3.

This standard stipulates the study only limousine pigments. Traditional nelimousine pigments can also be measured by this method, if they before spreading equipped with stearic acid.

On the basis of the spreading coefficient, we can only determine the average thickness h of the pigments, however, about the width of the distribution in thickness, this method does not allow to say anything.

The thickness of the pigments may also be calculated using a scanning electron microscope (SEM). When this measure is the number of particles, which is necessary in order to obtain a representative average. Usually measure about 100 particles. Using this method, unlike the method of spreading on the water, get well presents the e on the distribution of pigments in thickness.

As the average value of h50the integral distribution curve in thickness. Measure the width Δh distribution is determined by the following formula:

where the indices refer to the corresponding value of the cumulative distribution.

The pigments according to the invention have a relative width Δh distribution in thickness from 70 to 140%.

Preferably the pigments according to the invention have a relative width Δh distribution in thickness from 75 to 120%.

Under the form factor f is the ratio of the average value of the longitudinal size of the average thickness of the plates of aluminum pigment.

The longitudinal dimension d (dia) determined in experiments on the diffraction of laser beams on the basis of theory of Fraunhofer diffraction and/or Mi. The basis of data on diffraction is a model, which refers to the diameter of the equivalent sphere. Therefore, no absolute values are not, however, measured this way, the diameter has established itself as a reliable relative value when describing the dimensional characteristics of the metal flake pigments.

In this case, the dimensionless form factor f is defined as

The value of d50corresponds to 50% of the integral distribution curve, ismaren the th and assessed in the form of distribution of equivalent spheres by volume.

The next value for okharakterizovanie pigments is the dimensionless degree of roughness Under R. it is the ratio of specific surface area measured by BET method (DIN 66132), to the geometric surface area of the pigments. The latter can be calculated, neglecting the edges of pigments, as twice the spreading coefficient:

The degree of roughness should also be considered as a relative value, since both methods determine the surface area does not give accurate results. A perfectly smooth surface should theoretically have a degree of roughness that is equal to 1, but actually sometimes get a value less than 1.

Longitudinal size of the aluminum pigments according to the invention do not differ fundamentally from conventional, commercially available aluminum pigments that get wet grinding. In particular, the dimensions depend on the target application. The values of d50allocation length should preferably be more than 6 μm, more preferably in the range of 6 μm to 50 μm, preferably from 8 μm to 45 μm, more preferably from 12 μm to 40 μm, more preferably from 15 μm to 30 μm, most preferably from 20 μm to 25 μm.

The pigments according to the invention differ form f is a torus f more than 200. Preferably the pigments according to the invention have the form factor f over 220, more preferably more than 240, preferably more than 300. According to one preferred variant implementation, the aluminum pigments have a degree of roughness R of from 0.35 to 0.9, more preferably from 0.4 to 0.8.

These values show that we are talking about a very subtle pigments with relatively smooth surfaces.

Typical pigments according to the invention is, furthermore, a relatively low content of active aluminum.

This content can be determined using the fact that a certain amount of aluminum pigments completely dissolved in an alcohol solution and under conditions of a temperature volumetric register generated hydrogen. The content of aluminium in these pigments is from 85 to 93, preferably from 87 to 92%, based on total weight of aluminium pigments. This is comparable in the case of the aluminum pigments obtained wet grinding, with values ranging from 93 to 97% for conventional pigments.

The remaining part of the pigment may comprise aluminum oxide, as well as associated on the surface of the fatty acids. Due to the small thickness of the aluminum pigments according to the invention have a relatively high content of oxide. Also the content of fatty acids is relatively high is them. The latter can be roughly estimated from elemental analysis to content With. It in the pigments according to the invention of pre-washed with acetone or similar solvents and then dried aluminum powder is usually from 0.7 to 1.5 wt.%, preferably from 0.8 to 1.4 wt.%.

In the case of aluminum pigments according to the invention we are talking about a very subtle pigments with narrow distribution in thickness. Such pigments have a very high opacity. Aluminum pigments according to the invention preferably have a distribution in thickness with a value of d95less than 200 nm, preferably less than 150 nm. The narrow distribution of the thickness of a positive effect on good placement of pigments in the environment of use, such as lacquer or printing ink. With the pigments according to the invention can be obtained, for example, opaque paint with a very small thickness, for example with a layer thickness of less than 10 microns, with a very strong luster and a very good flop effect.

In particular, when applying coatings on cars there is a need for smaller layer thicknesses. Here the driving force is primarily a cost savings. To date, the thickness of the base layer of varnish is typical interval of about 15 μm. Now in the case of very curved molded parts, so is x as, for example, lever door handles are also commonly used layers of very small thickness. It would be desirable if it were possible to use layers with lower thickness down to less than 10 μm. Of course, the thickness of the layer should not be too low, because otherwise you will have problems with adhesion, coating and/or pigmentation.

The pigments according to the invention is extremely favourable suitable for use in coating the tools that should be applied with a layer of very small thickness.

Further detail will focus on the production method of aluminum pigments according to the invention. This method differs extremely gentle deformation of the grinding particles of aluminum. In particular, the method comprises the following steps:

Aluminum particles pulverized using a milling installation, preferably a ball mill, bead mill or attritor, in the presence of solvents and lubricants as an intensifier of milling and grinding media having an individual weight of from 2 to 13 mg, within a time period from about 15 to about 72 hours.

According to one preferred variant of the invention, the grinding media have an individual weight of from 5.0 to 12.0 mg as grinding media preferably used stereobase body, more preferably balls.

Aluminum pigments, obtained after milling aluminum particles, is separated from the grinding media, preferably the grinding balls. One further step of the method of the obtained aluminum pigment may be subjected to sorting (classification). Then aluminum pigments can be converted into a suitable form of the sentence. For example, sorted or unsorted aluminum pigments can be converted into powder form, preferably in a non-dusting powder form. But aluminum pigments can also be transferred via the seal into a paste, granules, pellets.

Under the granules in the spirit of the invention understand briquettes, tablets or "sausages".

Granulation may be carried out at the plate granulator in the usual way. Tableting can be conducted in a tablet-forming device. Sausages can be obtained by the method of extrusion of aluminum paste or powder, or by using the fact that the aluminum paste is extruded through the extruder, and the extruded filaments paste divide circulating blade device. The graining of aluminum pigments according to the invention can be carried out, for example, by spray granulation.

Aluminum pigments according to the invention can be made extremely beneficial in the form of granules or pellets with the high content of aluminum pigment, for example, from 98 wt.% up to 50 wt.%, preferably from 95 wt.% up to 70 wt.%. These drugs may very well be entered, for example, in paint systems or printing inks without causing undesirable agglomeration of the aluminum pigments.

The grinding can be carried out in a solvent at a mass ratio of solvent to the particles of aluminum from 2.8 to 10 mass ratio of grinding balls to the particles of aluminum 20-70 and lubricants as an intensifier of grinding.

An important parameter is the critical number of revolutions nCretethat indicates, when the balls are pressed by centrifugal force to the walls of the mill, and no longer will be virtually no grinding:

where D is the diameter of the drum, and g is the gravitational constant.

The rotation speed of the ball mill is preferably from 25% to 68%, more preferably from 50% to 62%, from the critical number of revolutions nCrete.

Low speed contribute to the slow deformation of aluminum particles. To cause slow deformation, in the method according to the invention preferably are also used for light grinding balls. Grinding balls with individual weighing more than 13 mg deform the aluminum particles too much, which leads to prezhdevremen the mu destruction. As particles of aluminum is preferably used aluminum powder.

The above conditions lead to very gentle grinding, in which the aluminium particles slowly shaped and destruction due to shock balls with high kinetic energy are prevented. Due to extremely gentle way of refining this type of grinding lasts relatively long. Refining is from 15 to 72 h, preferably from 16 to 50 hours Big time refining lead to a large number of collisions pigment-ball. Due to this pigment is formed very uniformly, resulting in a very smooth surface and narrow distribution in thickness.

Unlike conventional methods of grinding, in the method according to the invention the majority of the aluminium particles are not crushed or ground, but only gently deformed for a long period of time.

Under the milled raw material of aluminum preferably refers to aluminum powder. This aluminum powder preferably receive in the "atomizer" (the jets) by spraying molten aluminum. Can also be used a film of powder of aluminum foil, and waste foil. The powder may have a round or angular shaped particles. Aluminum particles in the form of needles in the method according to the invention as a source m of the material is not applied, because they cannot be ground to a thin eye-catching pigments. Preferably, the aluminum particles had a shape from circular to ellipsoidal.

Aluminum powder should preferably have an average diameter less than 100 microns, and preferably below 30 μm, more preferably below 20 μm, even more preferably below 10 μm. The purity of the applied aluminum is preferably from 99,0 to above 99.5 per cent.

As the lubricant can be applied to many compounds. Thus, the aluminum pigment may be at least partially covered with fatty acids. Here you can name used for a long time fatty acids with alkyl residues containing from 10 to 24 atoms C. Preferably, apply stearic acid, oleic acid or mixtures thereof. Thus stearic acid as a lubricant results in limousine pigments, and oleic acid, on the contrary, nelimousine pigments. Limousine pigments are distinguished by the fact that they float in the environment of use, such as lacquer or printing ink that is placed on the surface environment. Nelimousine pigments, on the contrary, are placed within the environment. To fatty acids can be optionally added, for example, long chain of amino compounds. Fatty acids may be of animal or RA the equipment origin. Also as a lubricant can be applied organic phosphonic acids and/or esters of phosphoric acids.

Grease should not be used in too small quantities, because otherwise, due to the strong deformation of aluminum particles is very large surface of the obtained aluminum plate pigments will be saturated with adsorbed lubricant insufficient. In this case, it may happen dense adhesion. Therefore, the typical number is from 1 to 20 wt.%, preferably from 2 to 15 wt.% lubricant based on the weight of the used aluminum.

The choice of the solvent itself is not critical. You can use the usual solvents such as white spirit, solvent-naphtha, etc. can also be used alcohols such as, for example, isopropanol, ethers, ketones, esters, etc.

Also as a solvent you can use water (at least in the predominant share). In this case, use of lubricants should, of course, to have a noticeable inhibiting corrosion of action. In this case, preferred are phosphonic acids and/or esters of phosphoric acid, which may also be ethoxylated side chains. In this case, when the grinding is also preferably the addition of corrosion inhibitors.

The preferred way used sarichioi preferably an individual weighing from 2 to 13 mg More preferably, the preferred way used balls had individual weight of from 5.0 to 12.0 mg are Preferred balls with smooth surfaces, if possible, round shape and uniform in size. Material beads can be a steel, glass or ceramics, such as, for example, zirconium oxide or corundum.

Temperature during the milling process are in the range from 10°C to 70°C. are Preferred temperature in the range from 25°C to 45°C.

Thanks to the method according to the invention, the aluminum pigments according to the invention proved to be very beneficial not contain sticky polymer films. Therefore, the aluminum pigments according to the invention does not have the disadvantage of aluminum pigments obtained PVD method, which is the presence of sticky residue separation layers. Furthermore, the method of obtaining them cheaper than expensive PVD-methods of obtaining. The separation of the aluminum pigments obtained from the grinding media, preferably the grinding balls can be carried out in the usual way by sifting.

After separation of the grinding balls aluminum pigments are preferably subjected to sorting by size. This sorting should be done gently so as not to destroy the thin aluminum pigments. Under this the m can be implied for example, wet sieving, decanting or separation by sedimentation. Wet sieving is usually will be disqualified large fraction. The other methods can be separated, in particular, and the fine fraction. Finally, the suspension is separated from the excess solvent (for example, using a filter press).

At the last stage of processing in a desirable form of the sentence. It may include the addition of a solvent to obtain a paste or drying to obtain powder.

The dried powder can be processed in a suitable homogenizer in non-dusting metal powder by adding a very small amount of solvent (<10%). Also the filter cake can be dried, and then the other solvent again to be translated into a paste (wetting).

Finally, the pigments according to the invention can be recovered by transferring the sediment on the filter by means of a suitable dispersion of a suitable resin pellets, granules or tablets. These forms of proposals have the advantage that they do not produce dust, easily dosed and are easily dispersible.

Because of the very high specific surface area of aluminum pigments according to the invention, for example, granulation aluminum pigments according to the invention should be applied on the relatively large number of dispersing resin.

Preferably used 2-50 wt.%, more preferably from 5 to 30 wt.% resin in the total formulation of granules.

For granulation can be used a large number of dispersing resins. Examples are resins of both synthetic and natural origin. They include, for example, alkyd resins, carboxymethyl resin and resin karboksimetilcelljulozy, cellulose acetate, acetotrophic cellulose (CAP) and acetylbutyrate cellulose (CAB), coumarone-indene resins, epoxy esters, epoxy-melanin and epoxy-phenolic condensates, ethyl and methyl cellulose, hydroxyethyl cellulose, hypromellose, ketones and maleic acid resin, melamine resin, nitrocellulose resin, phenolic and modified phenolic resins, polyacrylamide, polycarbonate, polyamide, complex polyester resin, a simple polyester resin, polyurethane and polyvinylene resin.

Among these resins, mention should be made, in particular, acrylate copolymers and resins of acrylic esters, resins, polyacrylonitrile and Acrylonitrile copolymers, copolymers of butadiene and vinylidenechloride, butadiene-styrene copolymers, methacrylate and methyl methacrylate copolymers, and polybutene, polyisobutylene, polyvinyl acetate resin, resin polyvinyl is on alcohol, polyvinyl chloride resin, resin, polyvinyl ether, polyvinylpyrrolidone and polystyrene. Other copolymers include resins of copolymers of styrene with maleic acid anhydride, styrene with shellac, vinyl chloride with vinyl acetate, vinyl chloride with vinyl ester and vinyl chloride with vinylidenechloride.

It also covers the resin of natural origin, such as gum Arabic, gutta-percha, casein and gelatin.

Are preferred aldehyde resin, such as a series of Laboral production BASF AG, Ludwigshafen, Germany. In addition, as a binder materials applicable waxes. Here, as examples, should be called natural waxes, such as beeswax, candelilla, Carnauba, montany waxes and paraffin waxes. Also discusses synthetic waxes, such as, for example, polyethylene waxes.

Unexpectedly it was found that the tendency to agglomeration of the aluminum pigments according to the invention is much smaller than the PVD pigments.

It was hypothesized that this effect, in addition to the thickness of the pigments, is also connected with the distribution of the thickness and degree of roughness of the aluminum pigments according to the invention. If the width of the distribution of thickness in the range from 70% to 140% strong decline in the propensity to agglomerate. In addition, aluminum is the pigments according to the invention because of the way their receipt have some degree of roughness or waviness, preventing plane-parallel laying, i.e. agglomeration of aluminum pigments on each other, suddenly do not result in a significant negative impact on the optical properties of aluminum pigments according to the invention, both the reflectivity and Shine.

Unlike PVD pigments, stacked on top of each aluminum pigments according to the invention due to their roughness or waviness have only point contact surfaces with each other. Therefore, in contrast to PVD pigments formation of short-range attractive forces, such as forces van der Waals forces or hydrogen bridges, will be minimal, and therefore the agglomerating or aggregation difficult.

In yet another embodiment of the invention, the aluminum pigments according to the invention optionally coated or lined pestiviruses layer of inhibitor and/or pestiviruses corrosion-protective layer. Such coatings allows, first, to reliably apply the pigments according to the invention in water-based lacquers and/or in outdoor applications.

The mechanism of action of passivating layers is difficult. In the case of inhibitors is based mainly on steric effects. Therefore, most of the inhibitors has also orienting effect in the sense of "limousine" and "nelito is present", that is pop or not pop-up in the environment.

Inhibitors are added, inter alia, in low concentrations, in the order of magnitude of 0.5 wt.% up to 15 wt.% by weight applied aluminum pigment.

For inhibition are particularly suitable:

organic modified phosphonic acids of General formula R-P(O)(OR1)(OR2), where R = alkyl, aryl, alkylaryl, arylalkyl and simple alkilany ether, in particular ethoxylated alkilany ether, a R1, R2=H, CnH2n+1with n=1-6, and the alkyl may be branched or unbranched. R1may be equal to or different from R2;

organic modified phosphoric acid and their esters of the General formula R-O-P(OR1)(OR2) with R = alkyl, aryl, alkylaryl, arylalkyl and simple alkilany ether, in particular ethoxylated alkilany ether, and R1, R2=H, CnH2n+1with n=1-6, and the alkyl may be branched or unbranched.

Can be used pure phosphonic acids or their esters or phosphoric acid or their esters, or their arbitrary mixture.

In the case of grinding of aluminum particles predominantly in an aqueous solvent such inhibitors are used as intensifiers grinding in order to prevent dangerous from the point of view of safety education is the development of hydrogen in the refining process.

Next, a passive layer of inhibitor may consist of or contain inhibiting corrosion of organic functionalityand silanes, aliphatic or cyclic amines, aliphatic or aromatic nitro compounds, oxygen-, sulfur - and/or nitrogen-containing heterocycles, such as, for example, derivatives of thiourea, sulfur and/or nitrogen-containing compounds of higher ketones, aldehydes and alcohols (fatty alcohols), thiols, β-etherketone, β-diketones or their mixtures. However, the passivating layer of the inhibitor may consist also of the above substances. Preferred are organic phosphonic acids and/or esters of phosphoric acid or mixtures thereof.

Passivation using corrosion-protective barriers with chemical and physical protective action can be implemented in a variety of ways.

Pestiviruses corrosion protective layers, which provide the aluminum pigments are particularly good protection against corrosion, contain or consist of silicon oxide, chromium oxide, which is preferably applied by way of chrome, zirconium oxide, aluminum oxide, polymerized synthetic resins, oxides of vanadium, oxides and/or peroxides molybdenum, phosphates, phosphites or borates or mixtures thereof.

Preferred are layers of silicon oxide and chromium oxide (Kramerov the tion). Layers of SiO2preferably get method the Sol-gel in organic solvents with a thickness of 20-150 nm. Passivating corrosion-protective layer most preferably contains silicon dioxide, and the surface of the silicon dioxide is preferably coated with silanes.

Preferably, the aluminum pigments oxidized wet-chemical methods of water and have a painted look.

Aluminum pigments according to the invention find application in coatings, varnishes, printing inks, powder paint coatings, plastics, protective printing, ceramics and cosmetic preparations (compositions). Preferably, the aluminum pigments according to the invention is used in the formulations of nail Polish. The nail Polish according to the invention has excellent metal.

Passivated additional coated aluminum pigments according to the invention is preferably used in water-based lacquers and exterior applications. The water-based lacquer according to the invention contains, in addition to such passivated aluminum pigments according to the invention, compatible with normal water binder, such as polyesters, polyacrylates, polymethacrylates and/or polyurethanes, etc.

The following examples explain the invention without limiting it.

Examples and according to the finding from 1 to 3:

Example 1:

In bowl eraser (length 32 cm, width 19 cm) add 3.1 kg of glass beads (diameter 2 mm), 310 g of white spirit, 93 g of aluminum powder (average diameter of <8 μm) and 9.3 g of oleic acid. Then grind for 20 h at 57 rpm Product is separated from the grinding balls by washing with white spirit and then sieved wet sieving through a sieve with cells of 25 μm. Small fraction using the suction filter is essentially free from white spirit and then in a laboratory mixer through a white spirit turn into a paste (the proportion of the solid phase about 70%).

Example 2:

Grinding is the same as in example 1, but with the powder of average diameter of <6 μm and the length of the grinding 23 PM

Example 3:

In bowl eraser (length 32 cm, width 19 cm) enter 5,0 kg of steel balls (diameter 1.1 mm, weight 5,5 mg), 160 g of white spirit, 150 g of aluminum powder (average diameter of <8 μm) and 6 g of oleic acid. Then grind for 16 h at 60 rpm, the Product is separated from the grinding balls by washing with a sufficient number of white spirit and then sieved wet sieving through a sieve with cells of 25 μm. Fine fraction by filtration through a suction filter essentially free from white spirit and then in a laboratory mixer with white spirit turn into a paste (the proportion of the solid phase about 70%).

EUR. example 4: Metalure L 55300 (company Eckart).

EUR. example 5: MN 8801 (firm Asahi).

EUR. example 6: MN 9901 (firm Asahi).

EUR. example 7: VP 53534 (company Eckart), pigment "silver dollar".

EUR. example 8: FUR 2192 (company Eckart), pigment "silver dollar".

The samples of the examples according to the invention and the comparative examples was characterized by the spreading coefficient and calculated her average thickness.

The determination of the spreading coefficient was performed following the standard DIN 55923. In addition to this standard, which applies only to listwise pigments, nelimousine pigments before spreading translated in limousine by the following processing: were given 200 mg of aluminum pigments in paste form or precipitate on the filter was dispersible in a solution of 3.15 g of stearic acid and 63 ml of white spirit and 12 min was treated in an ultrasonic bath. Then the dispersion was pumped at a glassy Frit, 3 times was additionally washed with acetone, was pumped dry and dried in a vacuum desiccator. Then in the normal case, approximately 4 mg of aluminum powder, lubricated with stearic acid, a glass rod was turned into a paste in a watch glass with a few drops of n-butanol, and then all the paste was introduced into the tank for spreading.

However, in the case of very thin aluminum pigments according to the invention when receiving clicks scow found one feature. Here the values of the spreading coefficient were so high that the metal film was too large for the water bath, the relevant DIN 55923. Metal mirror metal is properly installed size could be obtained only at portions of the sample in 1 mg. However, in this case, the measured values becomes clear dispersion (>10%), which is due to occur the error weighting.

Alternatively, these samples with lubricated with stearic acid aluminum powder was obtained a dispersion in n-butanol. The concentration was calculated so that 1 ml of this dispersion contained approximately 1 mg of pigment. For sampling with vigorous stirring (to reduce sedimentation of the pigment particles) were collected approximately 1 ml of the dispersion using a pipette with the scale and the dispersion was carefully placed in the bath for spreading. Relative dispersion is the spreading coefficient was way less than 10%.

The samples of examples 1-3 according to the invention and the comparative examples for a more detailed definition of the thickness of the particles was characterized using field-emission scanning electron microscope. For studies using SEM samples were prepared as follows:

a) Aluminum pigments according to the invention and conventional pigments, the floor is obtained by a wet grinding

Aluminum pigments according to the invention or a conventional aluminum pigments obtained by conventional wet milling, which was in the form of a paste or sludge on the filter, first washed with acetone, and then dried.

Resin, conventional electron microscopy, for example, TEMPFIX (Gerhard Neubauer Chemikalien, D-48031 münster, Germany), was applied on a plate for samples on the hot plate was heated to softening. Then the plate samples were removed from the tiles, and aluminum powder sprinkled on the softened resin. Resin when cooled again becomes solid, and poured aluminum pigments can, as a result of mutual influence of adhesion and gravity, to be received standing almost upright and motionless on the plate for samples. Therefore, to measure pigments electron microscope better side. When measuring the thickness is estimated azimuthal angle α pigment to the plane normal to the surface, and it assesses the thickness according to the formula:

heff=hu/cosα.

From the values of heffon the basis of relative frequency (frequency) of occurrence is set to the integral distribution curve. Calculated at least about 100 particles.

b) PVD pigments

Suspension PVD pigments several times washed with a large excess of acetone to essentially to release her from ostad is in the separation layer. Then PVD pigments were dispersible in acetone, and one drop of the dispersion was placed in the glass of the microscope. After volatilization of the solvent, the glass broke. Individual fragments can be introduced in the electron microscope, standing upright. When the sharp edges of the fault could be measured a sufficient number of PVD pigments. Here due to the narrow distribution in thickness to achieve convincing results quite about 50 particles.

Cumulative distribution for the thickness of the different samples according to the invention and comparative samples presented on figa and 1b. The curves on fig.1b represent an increased plot curves with figa. The number of measured particles is from 50 (PVD pigments) to 192 (conventional pigments). Statistical analysis showed that the integral distribution curve for pigments according to the invention and conventional pigments, obtained by wet milling, was essentially constant, ranging from 75 to 100 particles.

The results are summarized in table 1.

Usually it turns out good according to a certain method of spreading coefficient average thickness hspreadingand the median (middle value) of h50the integral distribution curve in thickness. See also surface area according to BET, the values of d50for size distribution and rasschitannaya degree of roughness R and form factor f pigment. To calculate this value was used, as usual, the spreading coefficient or calculated according to him, the average thickness.

The longitudinal size d was determined using a laser granulometer (Cilas 1064, the company Cilas, France), as a measure of the average longitudinal dimension, as usual, the selected value of d50cumulative distribution in microns.

For a comparative assessment of the pigments according to the invention with conventional pigments, the pigment in several concentrations in traditional nitrocellulose lacquer (Erco-Bronzemischlack 2615e sold by the company Rohm und Haas, Germany, Werk Strullendorf, Reinhard-Reichnow-Str. 4, D-96129 Strullendorf) was applied using a layer with a doctor blade on a black and white contrast paper (depth squeegee 36 μm) and dried for 24 h at room temperature.

Table 1
Physical characterization
SampleCilas: d50[µm]The spreading coefficient [cm2/g]The average thickness hspreading[nm]Statistics REMBET [m2/g]The content of the active AlThe degree of roughness (flow)Form factor (flow)
h50 [nm](h90-h10)/h50
Example 11950100807884%6,692,2%0,69238
Example 21984600476097%7,6for 91.1%0,45402
Example 322529007679104%7,292, 8%0,68291
EUR. example 412,5--4941%---255
EUR. example 51730000133163180%---128
EUR. example 62224800161259221%---137
EUR. example 7of 17.531700126148210%4,596,2%0,71139
EUR. example 820700193--5,694,8%1,3572
Example 1: the example according to the invention
Example 2: the example according to the invention
Example 3: the example according to the invention
EUR. example 4: Metalure L55350 (Eckart) PVD pigment
EUR. example 5: MN 8801 (Asahi)
EUR. example 6: MN 9901 (Asahi)
EUR. example 7: VP 53534 (Eckart), pigment silver dollar
EUR. example 8: FUR 2192 (company Eckart), pigment silver dollar

These coatings are characterized, first, optically, by measuring brightness, respectively, at 20° and 60° according to DIN 67530 (unit: micro-TRI-gloss from Byk-Gardner, D-82538 Geretsried, Germany). Calibration performed by the calibration in the dark and with black mirror plate with indications 92 for 20° and 95 to 60°. Secondly, it was held colorimetric determination of the brightness values L* at constant irradiation angle 45° at different angles (with respect to the angle of glide) (unit: Multiflash M 45, the firm Optronics).

From the brightness values at 15°, 45° and 110° according to the formula, isnac is correctly given by DuPont, can be defined indicator flop effect, i.e. the flop index (Flopindex), which for traditional metallicafan coatings conveys the change in brightness depending on the angle (A.B.J. Rodriguez, JOCCA, (1992(4)) str-153):

To assess opacity coating was used, the ratio of the brightness L* viewing angle 110° on the black to the white base. This ratio was >and 0.98, so that the coating is characterized as opaque. Measurement at such a flat angle of observation is especially sensitive, as in case of insufficient coating of the base will be metrologically evaluated almost "between" oriented predominantly parallel-plate metallic pigments. The agreement with the visual impression of the observer is very good. However, in the literature it is usual to estimate the difference of brightness in the diffuse measurement (for example, in EP 0451785), which, however, leads to a noticeably lesser sensitivity and, in addition, is not consistent with the visual impression.

Hiding power of coatings depends critically on the concentration of aluminum pigments. As a measure of this concentration was calculated surface concentration of aluminum pigments WithAlin mg/cm2. This value is calculated from the thickness of the wet lacquer, which is given by the squeegee, follow the her the formula:

where:

mAl: hitch aluminum pigments;

mNassiack,Al: suspension liquid lacquer and aluminium pigments, including solvent aluminum pigment paste (typically 10.0 g);

ρNassiack;Al: density of liquid varnish, mixed with aluminum pigment;

RH: the height of the squeegee in microns.

The figure 2 shows the optical criterion opacity depending on the estimated surface concentration of the aluminum pigment for the selected examples.

From figure 2 it is clear that aluminum pigments according to the invention have significantly higher hiding power compared to conventional aluminum pigments. From these data by interpolation was determined that the surface concentration at which the ratio of L*110°black/L*110°whitewas 0,98.

Examples according to the invention 1 to 3 find exceptional covering power when the surface concentration of less than 0.15 mg/cm2. The best hiding power have only PVD pigments obtained by expensive PVD method (comparative example 4).

Figure 3 shows the measured gloss coatings in geometry with the angle of incidence/reflection 60° and 20° depending on the surface concentration of aluminum is of egment. The gloss decreases with increasing surface concentration is almost linear. This is due to the increasing deterioration of the orientation of metallic pigments with increasing level of pigmentation. The deterioration of orientation is called all large irregularities in the placement of pigments to each other within the layer of varnish. This effect is especially pronounced because the floor because of the small solids in the varnish (the fraction of solids of about 6%) has a high ratio of Al/binder.

Thus, from figure 3 it is seen that except for PVD pigment Metalure®(EUR. example 4), aluminum pigments according to the invention (examples 1 to 3) at all surface concentrations are significantly better gloss than conventional aluminum pigments (EUR. examples 7 and 8).

Figure 4 shows the values of the flop-index according DuPonfc depending on the surface concentration of the aluminum pigment. At a high level of pigmentation is the flop index of the pigments according to the invention and conventional pigments comparable. However, below about 0.15 mg/cm2when the covering power of traditional pigments already very bad, noticeable difference. Aluminum pigments according to the invention, due to their much greater hiding power, can particularly preferably be used at low levels of pigmentation, PR is the traditional pigments are not opaque. Thus, a coating with very high luster, good flop effect and strong metallic appearance, that is, with very good effect chrome".

Figure 5 as a standard colorimetric values for the brightness values L* 15° depending on the surface concentration of the aluminum pigment. First, at a high level of pigmentation, these values for traditional pigments above, however with greater reduction in coverage, they are significantly lower.

However, this result of chromaticity characteristics contrary to the visual impression: the observer assigns coating with pigments according to the invention significantly higher brightness than all traditional pigments.

Presumably, this discrepancy can be explained as follows:

The pigments according to the invention due to their small thickness of the demonstrate, like PVD pigments, exceptionally good orientation and, thus, a very strong specular reflection, i.e. high gloss, so that even when the angle of observation 15° close to the corner of the slip, the proportion of scattered light is already small. Therefore, when the colorimetric estimation of the brightness seems to be smaller. However, this is contrary to the visual impression of the coverage of traditional pigments (EUR. examples 7 and 8) show, on the contrary, significantly more white, more milk is Aty" light. On the contrary, the pigments according to the invention look like and PVD pigments (EUR. example 4), significantly more metallic in nature. Accordingly, and flop-effect pigments according to the invention it is necessary to put much higher than it seems from the value of the flop-index defined according to DuPont. This also corresponds to the visual impression from the cover.

Such misrepresentation colorimetric data could possibly lie in the basis of claim as described in the document EP 0451785 connection between the loss of brightness with increasing values of the spreading coefficient on the water and, thus, with increasing opacity. In figure 1 of this patent, the maximum brightness L is attributed to the spreading coefficient 3.2 m2/g and indicates a marked decline, in particular, when the spreading coefficient is above 5 m2/, But the brightness did not apply to corner measurement, but rather was measured in the scattering. It was overlooked that thin pigments due to their higher specular reflection of the incident light must inevitably have a less significant share of diffuse scattered light.

Table 2 shows some of the 2 critical surface coating concentration, and interpolated colorimetric data for this concentration.

Table 2
Optical data by coating the surface concentration of Al-pigment WithAl,98%
SampleCoating the surface concentration of Al-pigment CAl,98%[mg/cm2]Gloss 20° CAl,98%Gloss 60° CAl,98%Flop index on DuPont CAl,98%L*15°CAl,98%The overall visual impression
Example 1 according to the invention0,1344912425,8137very metal, "chrome effect"
Example 2 according to the inventionapproximately 0,125212324,2136very metal, "chrome effect"
Example 3 according to the inventionis 0.1355913726,4134very metal, "chrome effect"
EUR. example 70,29368728,2153metal
EUR. example 80,27257227,1 150metal, relative to the "white"
EUR. example 4approximately 0.057914425,4134very metal, "chrome effect"

Stronger luster pigments according to the invention was observed when applying liquid varnish. Table 3 presents colorimetric data when the liquid coating to selected examples. Always pigments obtained in example 1 according to the invention, have more lustre than traditional pigments obtained traditional wet grinding. However, the Shine is not as strong as the PVD pigments (see EUR. example 4).

Applying in table 3 were made by spraying on the coating, i.e. coating pigmentation was determined by a series of concentrations. The relevant used levels of pigmentation (based on the formulation of the lacquer) and the measured thickness of the layers in the coating. The thickness of the layer was measured by the instrument Qua Nix 1500 (firm Lau GmbH, D-58675 Hemer, Germany). There was also a noticeable higher opacity and the associated lower the thickness of the pigments according to the invention compared with conventional pigments. But here PVD pigment had the best hiding power and a more pronounced metallic properties.

Table 3
The application of liquid paint, clear varnish with different layer thickness and pigmentation by a sputtering method on the surface. Paint system: Lacquer with chrome effect 2K with a low solids content ("Metalure" Brochure, the company Eckart).
SampleGlitterFlop index on DuPontThe level of pigmentation (per song)The thickness of the layer
60°20°
Example 1 according to the invention842924,01,8%4-6 microns
Metalure L 55700 (EUR. example 4)1285724,61,5%2-3 microns
VP 53534 (EUR. example 7)74,42524,54%6-8 microns

Examples of the passivation of aluminum pigments according to the invention is:

Example 9: (aluminum coated with SiO2)

with 55.1 g of paste with aluminum pigments of example 1 (corresponding to 38.5 g of Al) was dispersible in 375 ml of isopropanol and brought up to the boiling point. Added 13,35 g of tetraethoxysilane. Then for 3 h to this was added a solution of 5.4 g of 25%NH3

Example 10: (chromed aluminum)

18 g of a solution of chromic acid was obtained by using the fact that 4.5 g CrO3was dissolved in 13.5 g of water (softened).

In a 1-liter reactor was heated to 220 g of water (softened) up to 90°C. With vigorous stirring (mixer: Stollenscheibe) was added first 21 g butylglycol, and then 125 g described in example 1, an aluminum pigment paste in white-spirit with a solids content of 70%. After a few minutes, was added a solution of chromic acid at the reaction temperature of 80°C. the Mixture was left to react for another 50 min under vigorous stirring. Then left to cool for 30 min, and the reaction mixture decantation several times in a beaker with 250 ml of a 5%solution of VE-N2About/butylglycol up until no longer has any yellow staining of distilled solution. Then the product was filtered on a suction filter and washed with plenty of water (about 3 liters).

Test gas:

8.6 g Al paste was introduced in 315 g of a colourless compound of the water-based lacquer (ZW42-1100, BASF, würzburg, Germany) and using diethanolamine brought the pH to 8.2. 300 g et the th varnish was poured into Gazpromavia flask, which was closed with double meter gas bubbles. The amount of gas can be determined through the displaced amount of water in the lower chamber of the meter of gas bubbles. Gazpromavia flask thermostatically in a water bath at 40°and the test conducted within 30 days. The test was considered passed if after 7 days stood out not more than 4, and 30 days - not more than 20 ml of hydrogen.

Table 4
The results of the test gas for coating thin aluminum pigments
SampleThe gas in 7 daysThe evolution of gas after 30 days
Example 92 ml8 ml
Example 101 ml5 ml
EUR. example 11 (uncoated pigment of example 1)<3 hours !!-

From table 4 it follows that the aluminum pigments according to the invention can be perfectly stable against corrosion.

The method according to the invention allows to obtain aluminum pigments that their physical properties are very close to the PVD pigments, however, can be obtained much more simple way. Unlike traditional the aluminum pigments, aluminum pigments according to the invention show, especially in relation to the opacity and gloss, improved properties. Finally, the aluminum pigments according to the invention does not have a negative tendency to agglomeration, as the PVD pigments. Therefore, the aluminum pigments according to the invention can be added to the drugs, such as coating systems, printing inks or cosmetics, in much higher concentrations. This greatly facilitates handling.

Thus, the aluminum pigments according to the invention combine the favorable properties of conventional aluminum pigments, particularly simple manufacture and convenience in use, and properties of PVD pigments, in particular, high opacity, high gloss and strong metallic appearance.

1. Aluminum pigments, which are at least partially coated with a lubricant, characterized in that they have:

a) spreading coefficient on the water between 40000 and 130,000 cm2/g;

b) calculated from the spreading coefficient for water, but also from the value of h50cumulative distribution by processing the data in thickness scanning electron microscopy, the average thickness h from less than 100 to 30 nm;

c) defined by processing the data on the thickness of the scanning electron micro is a copy of the relative width Δ h distribution in thickness, which are estimated using the corresponding integral curve of the relative frequencies according to the formula

from 70 to 140%;

d) form factor d50/h over 200;

e) the degree of roughness, which is calculated from the measured by BET method specific surface area and spreading coefficient according to the following formula:

BET-value/2 × the spreading coefficient,

from 0.30 to 0.9.

2. Aluminum pigments according to claim 1, characterized in that they have a certain way of processing data in thickness scanning electron microscopy relative width Δh distribution in thickness, which are estimated using the corresponding integral curve of the relative frequencies according to the formula

from 75 to 120%.

3. Aluminum pigments according to claim 1 or 2, characterized in that they have a form factor d50/h more than 220.

4. Aluminum pigments according to claim 1, characterized in that they have a degree of roughness, which is calculated from the measured by BET method specific surface area and spreading coefficient according to the following formula: BET-value/2 × the spreading coefficient, from 0.35 to 0.9.

5. Aluminum pigments according to claim 1, characterized in that as the grease they less is th least partially coated with fatty acids.

6. Aluminum pigments according to claim 1, characterized in that the lubricant they are at least partially coated with stearic acid.

7. Aluminum pigments according to claim 1, characterized in that the lubricant they are at least partially coated with oleic acid.

8. Aluminum pigments according to claim 1, characterized in that the lubricant they are at least partially covered with a mixture of stearic acid and oleic acid.

9. Aluminum pigments according to claim 1, characterized in that the lubricant they are at least partially covered phosphonic acids, esters of phosphoric acid or their mixture.

10. Aluminum pigments according to claim 1, characterized in that they are covered pestiviruses layer of inhibitor or pestiviruses corrosion-protective layer.

11. Aluminum pigments of claim 10, wherein the passivating layer of the inhibitor contains inhibiting corrosion of organic phosphonic acids and/or esters of phosphoric acids, organic functionalityand silanes, aliphatic or cyclic amines, aliphatic or aromatic nitro compounds, oxygen-, sulfur - and/or nitrogen-containing heterocycles, sulfur and/or nitrogen-containing compounds of higher ketones, aldehydes and alcohols, thiols, β-etherketone, β-diketones or their mixtures.

12. Aluminum pigments of claim 10, wherein the passivating corrosion-protective layer contains silicon oxide, zirconium oxide, aluminum oxide, chromium oxide, polymerized synthetic resin, the oxides of vanadium, oxides and/or peroxides, molybdenum, phosphates, phosphites, borates or mixtures thereof.

13. Aluminum pigments of claim 10, wherein the passivating corrosion-protective layer contains silicon dioxide, and the surface of the silicon dioxide is preferably coated with silanes.

14. Aluminum pigments according to claim 1, characterized in that they are oxidized wet-chemical methods of water and have a painted look.

15. Aluminum pigments according to claim 1, characterized in that they are available in powder form, preferably non-dusting powder, or in aggregated form, preferably in the form of pastes, granulates or pellets.

16. The way to obtain an aluminum pigment according to any one of claims 1 to 15, which includes the grinding of aluminium particles using the grinding installation in the presence of a solvent, lubricants and grinding media during the period of time from 15 to 72 h with obtaining aluminium pigments, while the balls are individually weighing from 2 to 13 mg, the mass ratio of solvent to aluminum particles ranges from 2.8 to 10, the mass ratio of grinding media to the aluminum particles is from 20 to 70, and aluminum particles have an average diameter less than 20 microns.

17. The method according to item 16, characterized in that the grinding is eaten have an individual weight of from 5.0 to 12 mg.

18. The method according to item 16 or 17, characterized in that after the grinding of aluminium pigments are sorted by size.

19. The method according to item 16, characterized in that obtained after grinding or subsequent sorting aluminum pigments is transferred in compacted form, preferably into a paste, granules or pellets.

20. The method according to item 16, characterized in that obtained after grinding or subsequent sorting aluminum pigments transferred to aluminum powder, preferably non-dusting aluminum powder.

21. The method according to item 16, characterized in that the solvent used is an organic solvent, preferably white spirit, solvent-naphtha, isopropanol, alcohols, ketones or mixtures thereof.

22. The method according to item 16, characterized in that the solvent used water, as well as lubricants and organic phosphonic acids and/or their esters and/or phosphoric acid, and/or their esters.

23. The use of aluminum pigments according to any one of claims 1 to 15 in coatings, varnishes, printing inks, powder paint coatings, plastics, protective printing, ceramics and cosmetic preparations, preferably in the nail Polish.

24. The use of coated aluminum pigments according to any one of p-12 in water-based lacquers and coating means for external use.

25. Nail Polish, trichosis fact, it contains aluminum pigments according to any one of claims 1 to 15.

26. The water-based lacquer, characterized in that it contains aluminum pigments according to any one of PP-14.



 

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2 tbl

FIELD: chemistry.

SUBSTANCE: new cyclic carboxylic acid is obtained in reaction which includes performing connection [J] of, at least one terpen-based diene connection (conjugate diene connection), chosen from group consisting of alloocymen, ocymen, mircen, α-terpinen and α-phellandren, and [K], at least one unsaturated carboxylic acid, chosen from α,β-unsaturated carboxylic acids and monoethers of α, β-unsaturated dicarboxylic acids. Connecting agent (A) for antifouling paint is also revealed. It containes one or more substances chosen from new cyclic carboxylic acid, derivative from cyclic carboxylic acid (excluding metal salt), metal salts of cyclic carboxylic acid and metal salts of the derivative of cyclic carboxylic acid, as well as composition of antifouling paint, which contains connecting agent (A) and copolymer (B) for antifouling paint of self-cleaning type, which is a polymerising copolymer based on basic metal salt of unsaturated carboxylic acid or polymerising unsaturated copolymer based on silyl ether of unsaturated carboxylic acid. From composition of antifouling paint covering film can be formed, which has only slight influence on environment, it is evenly subjected to erosion with definite rate, is able to retain excellent properties against fouling for a long period of time and can be applied to the surfaces of ships and other objects, which are used in marine territories with high risk of fouling.

EFFECT: obtaining film of antifouling paint, which has only slight influence on environment, is evenly subjected to erosion with definite rate, is able to retain excellent properties against fouling for a long period of time.

26 cl, 12 dwg, 4 tbl

FIELD: chemistry.

SUBSTANCE: invention pertains to compositions based on soluble fluoropolymers, meant for protecting metallic surfaces from action of water and aggressive media. The compositions can be used in the chemical industry and other industries when making equipment. Description is given of the anticorrosive composition is given. It consists of a soluble copolymer of tetrafluoroethylene with vinylidene fluoride, organic solvents - acetone, ethylacetate, cyclohexanone and amyl acetate, low molecular epoxide diane resin of the "ЭД-8" or "ЭД-10" type, amine hardening agent product of condensation of formaldehyde and phenol with ethylenediamine of the "АФ-2" type, diluting agent - ethyl cellosolve and an extra filler - graphite or molybdenum sulphide with proposed ratios of the components. Description of the method of coating metals is also given, in which the above mentioned composition is deposited on a non-greasy surface. The first and subsequent layers are dried under the same conditions at temperature of 15-25°C for a period of 20-30 minutes, and final coating is done at 120-200°C for 4-6 hours.

EFFECT: protection of metal surfaces from water and aggressive media.

3 cl, 5 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention pertains to production of coating materials, in particular to finishing materials, used for external and internal finishing of buildings and other structures, and more specifically relates to materials for coating concrete surfaces. Description is given of the latex priming composition, which contains a latex film-forming agent in form of a 50% syrup of acrylic dispersion DL-430 or Acronal-290 based on a copolymer of methylacrylate, butylacrylate, acrylamide, styrene and ethylbenzene in quantity of 5-50 mass %, plasticiser - dibutylphtalate or dioctylphtalate in quantity of 0.2-3.0 mass %, surface active substances based on polyoxyethylene esters of alkylphenols in quantity of 0.2-1.0 mass %, kaolin 20-30 mass %, fine-dispersed chalk 20-30 mass %, thickener 0.4-6.0 mass %, carbon black 0.2-1.0 mass % and water. The composition contains an extra technical target additive, chosen from a group containing a coalescent additive, anti-foaming agent, antiseptic additive, alkali, antifreeze or their mixture.

EFFECT: obtaining latex priming with short drying time, low water absorption and vapour permeability, high freezing and heat resistance.

2 cl, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to production of coating materials, in particular to finishing materials, used for external and internal finishing of buildings and other structures, and more specifically relates to materials for coating concrete surfaces. Description is given of the latex priming composition, which contains a latex film-forming agent in form of a 50% syrup of acrylic dispersion DL-430 or Acronal-290 based on a copolymer of methylacrylate, butylacrylate, acrylamide, styrene and ethylbenzene in quantity of 5-50 mass %, plasticiser - dibutylphtalate or dioctylphtalate in quantity of 0.2-3.0 mass %, surface active substances based on polyoxyethylene esters of alkylphenols in quantity of 0.2-1.0 mass %, kaolin 20-30 mass %, fine-dispersed chalk 20-30 mass %, thickener 0.4-6.0 mass %, carbon black 0.2-1.0 mass % and water. The composition contains an extra technical target additive, chosen from a group containing a coalescent additive, anti-foaming agent, antiseptic additive, alkali, antifreeze or their mixture.

EFFECT: obtaining latex priming with short drying time, low water absorption and vapour permeability, high freezing and heat resistance.

2 cl, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to the method of obtaining low-dimensional filling materials, which can be used in engineering materials for making composite materials with given functional characteristics. The method involves grinding the raw materials of the layer mineral and thermal treatment of the ground up dispersed particles. Thermal treatment is done by putting the dispersed particles into a non-oxidising thermal gas stream with density of 3·106-8·107 W/m2 for a period of 10-4-10-3 s. The above mentioned stream, containing dispersed particles, is applied to a substrate in form of a steel sheet, heated to 20-100°C. The obtained particles are collected and cooled down to 100-120°C.

EFFECT: invention allows obtaining a filling material with size of not more than 10 nm, with low energy consumption, and is effective when making polymer nano-composites.

3 tbl

FIELD: industrial inorganic synthesis.

SUBSTANCE: method of preparing high-quality titanium nanoxide with particle size 10 to 100 nm comprises generation of gas plasma, introducing gas plasma flow, oxygen, and titanium tetrachloride vapors, oxidation of titanium tetrachloride with oxygen in synthesis zone to form titanium dioxide and chlorine, and quenching synthesis products in supersonic nozzle by way of transforming subsonic synthesis products flow escaping synthesis zone into supersonic flow, which is then expanded and cold quenching gas is injected thereto. Prior to enter synthesis zone, titanium tetrachloride is mixed with oxygen at molar ratio between 0.05 and 0.25, respectively. Cold quenching gas is injected when supersonic flow is expanded inside expanding portion of supersonic nozzle having opening angle 10-15°.

EFFECT: improved quality of titanium nanoxide.

1 dwg, 2 tbl

FIELD: methods and plants for increase of volume density of aerated powders.

SUBSTANCE: proposed method of compacting the powder containing oxide or phosphate of metal consists in placing the powder in container and increasing the pressure in its area above atmospheric pressure sufficient for compacting the powder before diffusion of considerable part of gas into powder. Powder containing oxide or phosphate of metal is placed in container and its volume density is increased. Then, concentrated suspension of pigment which is titanium dioxide is prepared. Specification gives description of plant proposed for increase of volume density of powder containing oxide or phosphate of metal and plant for increase of volume density of aerated loose pigment which is just titanium dioxide.

EFFECT: increased volume density of aerated powder; improved consistency; facilitated dispersion in latex paints.

22 cl, 6 dwg, 3 tbl, 8 ex

FIELD: varnish-and-paint industry.

SUBSTANCE: process of producing titanium dioxide pigment according to chloride technology comprises oxidation of titanium tetrachloride with oxygen or oxygen-containing gas in plasmachemical reactor followed by cooling of reaction products in tempering chamber and subsequent multistep fine grinding of intermediate product, titanium dioxide, by way of affection with supersonic gas flow at 100-500°C and ratio of gas mass intake to titanium dioxide mass intake = 0.2. In the first step of titanium dioxide fine grinding, treatment of titanium dioxide is performed with a dry gas supplemented by vapor of organic or organosilicon modifier having in its molecule at least one of the following functional groups: -OH, -NH2, NH, SH at mass intake of modifier representing 0.1-2.0% of the mass intake of titanium dioxide.

EFFECT: improved quality of titanium dioxide pigment and simplified process of production thereof.

1 dwg, 1 tbl

FIELD: production of composite materials on base of polymer material at preset functional characteristics.

SUBSTANCE: proposed method includes subjecting the ground fractions of natural laminar minerals to thermal shock continued for 1.0-30 min at temperature gradient no less than 800-1000°C. Proposed method includes mechanical grinding, separation and heat treatment by introducing the weighed portion into working space of heating appliance for realization of thermal shock. To increase gradient of thermal shock, ground semi-finished product is additionally subjected to treatment at temperatures of (-)60-(-)195°C. To enhance efficiency of grinding, semi-finished product is heated to 100-300°C before low-temperature treatment and cycle "heating-cooling-heat treatment by thermal shock" is repeated at least twice. Proposed method makes it possible to obtain dispersed powders at size no more than 10 nm.

EFFECT: reduced power requirements; enhanced efficiency of nano-composites.

4 cl, 3 tbl, 5 ex

The invention relates to the processing of inorganic fibrous materials in order to enhance their pigmenting and filling properties, and more precisely relates to a white pigment and method of its production

The invention relates to the field of physical chemistry, specifically to a method for producing a hydrophobic particulate materials, and can be applied in the chemical and oil and gas industries

The invention relates to the field of powder metallurgy, namely, to obtain white radiation resistant reflective coatings, in particular the production of a pigment based on zirconium dioxide, used as one of the components used for thermal control coatings spacecraft

The invention relates to elements of the pigment with the changing optical characteristics, which form a color shift between two distinct colors, to methods of manufacture of such elements of the pigment compositions of the coatings with variable optical properties, which contain such elements pigment and method of making labels containing such elements pigment in accordance with the independent claims
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