Glass scales-based multilayer pigments
FIELD: pigment preparation.
SUBSTANCE: invention can be applied in production of multilayer pigments for laser marking of papers and plastics, said pigments being based on glass scales used in paints, lacquers, plastics, foil, ceramic materials, and cosmetic compositions. In these pigments, glass scales are coated with at least three alternate layers having high and low refraction index values. Pigments include at least one sequence of layers, which comprises: (A) coating with refraction index n≥1.8, (B) coating with refraction index n≤1.8, and (C) coating with refraction index n≥1.8. and, if necessary, (D) outer protective layer, provided that layer packet (A)+(B) can be present in standard layer-by layer assembly (A)+(B)+(C) up to four times.
EFFECT: intensified interferential color of multilayer pigments.
11 cl, 9 ex
The present invention relates to a multilayer pigments based on glass flakes, method of producing such pigments and their use in plastics, paints, coatings, coatings of the powder material, ink, inks, glasses, ceramic products, foil for agriculture, for the laser marking of paper and plastics and in cosmetic compositions.
Brilliant pigments or special effect pigments are used in numerous industries, especially in the sector of automotive finishes, decorative coatings, plastics, paints, inks and in cosmetic compositions.
Known multilayer interference pigments with alternating layers with high and low refractive index. They differ in the material of the carrier and the material of the individual layers, as well as the method of obtaining. Layers receive or deposition technology wet processing, or by vapor deposition or sputtering in a vacuum. The layers deposited on the carrier or the intermediate layer are optically active and contribute to the education of the interference colors.
Patent US 4434010 discloses multilayer interference pigment consisting of a Central layer of reflective metal, such as aluminum, and alternating layers of two transparent dielectric is historical materials with high and low refractive indices, respectively, such as, for example, titanium dioxide and silicon dioxide. This multilayer pigment preferably used for products that protect against counterfeiting, such as securities or banknotes.
JP H7-759 discloses multilayer interference pigment with a metallic sheen, for which the substrate is covered with alternating layers of titanium dioxide and silicon dioxide. The substrate includes flakes of aluminum, gold, or silver, or mica or glass, coated metals. However, the profound effect which is a characteristic and desirable for the interference pigments can not be obtained. This is due to the total reflection of light in the metal layer, which forms the basis. Therefore, the interference effect remains limited layers that are located above the metal layer. In addition, the lack of transparency of the substrate significantly limits the options for combinations with additional pigments in compositions that are associated with specific applications.
Patents US 3438796 and US 5135812 describe, for example, metal shiny pigments, which have a Central extremely opaque aluminum foil, coated on both sides with alternating dielectric films with a low refractive index, type of silicon dioxide or magnesium fluoride, and partly prose is acname metal films, type, for example, films of chromium or aluminum. Due process of obtaining the Central metal film these pigments cover only the upper and lower sides of the plates, while the side areas are broken face and lie towards the middle.
DE 4405494, DE 4437753, DE 19516181 and DE 19515988 reveal shiny pigments obtained by coating metal plates, especially aluminum flakes, metal oxide films with low refractive index, such as a layer of silicon dioxide, and selectivity absorbing metal oxide layers or metal layers with a high refractive index, using a chemical deposition from the vapor [gas] phase (CVD) or wet chemical methods.
Lustrous pigments based on metal substrates often have good properties, including good covering ability, but the result when applying, such as in paint, for example, is "hard" metallic luster, which is often undesirable.
Lustrous pigments based on transparent substrates having the form of plates that do not have this "hard" metallic luster, are the subject of WO 93/12182. Flakes of mica cover the metal oxide layer with a high refractive index, type TiO2and selectivity of the absorbent layer. Depending on the thickness of the layer is TiO 2when a direct angle, the pigments show a definite interference colors, which is becoming more and more weak, when the angle becomes more oblique, and which in the end turns to gray or black. The interference color is not changed, but a decrease in color saturation.
In JP 1992/93206 claimed lustrous pigments based on glass flakes or mica particles, which cover the reflective metal layer and alternating layers of SiO2and TiO2.
In EP 0753545 A2 disclosed lustrous pigments based on multiply coated, non-metallic, having the form of a plate substrates, which have a high refractive index and are at least partially transparent in relation to visible light area and have at least one layered structure including a colorless coating with a low refractive index and a reflective coating that selectively absorbs or selectivity.
The disadvantage of this invention is technically very complicated and expensive way to obtain, and often the difficulty of obtaining a pigment with the desired quality of the product.
Patent US 3331699 reveals that the glass flakes can be covered by a transparent layer of particles of metal oxide having a high refractive index such as titanium dioxide, in which the condition, that first glass flakes put nucleating agent which is insoluble in the acid solution, from which is applied a transparent layer of metaloxide. The patent does not mention that a smooth transparent film, particles, are required to obtain a quality of the interference pigments. The patent States that the nature of the glass is not critical, while the presence of the nucleating surface is critical. Further stated that there is only a small amount of compounds of metal oxides which are insoluble in the acid solution and capable of forming a nucleating surface on the glass flakes; tin oxide and fibrous form of the monohydrate boehmite alumina - only two such disclosed material. As shown in the following examples, the products obtained in accordance with this patent are not good enough quality.
Patent US 5436077 discloses a substrate of glass flakes, which has a metal covering layer, which formed a dense layer of protective coating of metal oxide, such as titanium dioxide. In this patent the nature of the glass no matter the metallic coating provides the desired appearance and the external coating of metal oxide is present to protect the metal is ical layer from the corrosive environments.
To get pearlescent pigments play an important role transparency and the thickness of the plate substrate. First EP 0289240 B1 discloses the production of extremely thin glass flakes at acceptable costs. According to the claimed method, the glass flakes can be made in any desired composition, for example, of pure SiO2and any thickness, specially designed for the envisaged use up to less than 1.0 μm.
The aim of the present invention is to overcome the deficiencies of the preceding prior art and provision of new multilayer pigments which have improved consumer properties.
Unexpectedly, was found interference pigment based on multiply coated glass flakes, including the specific location of the optically functional layers, through which were achieved specific optical effects.
Therefore, the invention provides interference pigments based on multiply coated glass flakes, which contain at least three alternating layers with high and low refractive index.
Preferably the layered structure is as follows:
(A) coating which has a refractive index of n>1,8,
(B) a coating which has a refractive index n≤1,8 and
(C) pokr is ment, which has a high refractive index of n > 1.8 and, if necessary,
(D) an external protective layer.
The invention also provides the pigments according to the invention for use in paints, varnishes, inks, plastics, agricultural foils, ceramic materials, glasses and cosmetic compositions, as well as for use in laser marking of papers and plastics.
Preferred glass flakes have a thickness of less than 1 μm, preferably <0.8 μm. Especially preferred are glass flakes with a thickness of <0.5 micron. Glass can be classified, for example, as glass A, glass, E glass, ECR glass. For the present invention, it is preferable quartz glass, but the glass is very expensive.
Suitable glass flakes, preferably obtained according to EP 0289240 B1, differ in that they contain an average particle size in the range of 5 to 1000 μm, preferably in the range from 5 to 150 μm. Preferred glass flakes have an average particle size of from 5 to 150 μm and a thickness of from 0.1 to 0.8 μm, preferably from 0.2 to 0.5 μm. The aspect ratio of the glass flakes is in the range from 10 to 300, preferably in the range from 50 to 200.
Glass flakes can be coated in the same manner as usual p is Genty luster of pearls. Coating of a metal oxide can be obtained by any known methods such as hydrolysis of a metal salt, by heating or in alkaline environments, guarding the hydrated metal oxide, followed by calcination. In General the procedure involves dispersing fine particles of glass flakes and combining the dispersion with a precursor that forms a film coating water metal oxide on the scales.
The thickness of the individual layers with high and low indices of refraction on the substrate basics is essential for the optical properties of the pigment. For pigment with intense interference colors thickness of the individual layers must be precisely adjusted relative to each other.
If n is the refractive index of the thin layer and d is its thickness, the interference color of this layer is determined by multiplying n·d (n·d = optical thickness). Colors derived from this film in the perpendicular angle of incidence of light in the reflected light, are the result of the amplification of light with a wavelength
and light attenuation with wavelength
where N is a positive integer.
The change in color that occurs with increasing film thickness, is a consequence of the intensification or weakened the I some wavelengths of light due to interference. If two or more layers in multilayer pigment have the same optical thickness, the color of the reflected light becomes more intense with increasing number of layers. In addition, it is possible by appropriate choice of layer thickness to achieve a particularly strong color change as a function of angle. There is an evident so-called color leap. The thickness of the individual layers, preferably of metal oxide layers, regardless of their refractive index depends on the application and is generally from 10 to 1000 nm, preferably from 15 to 800 nm and in particular from 20 to 600 nm.
Multilayer pigments according to the invention is preferably characterized by the presence of the coating (A) with a high refractive index in combination with a colorless coating (B) with lower refractive index and located after coating with high refractive index. The pigments may include two or more identical or different combinations of assemblies of layers, although preference is given to coating the substrate with only one layer-by-layer Assembly (A)+(B)+(C). To make the color of the races more intense pigment according to the invention may include up to 4 layer-by-layer assemblies, although the thickness of the combined layers on the substrate should not exceed 3 μm.
Glass particles can be covered with three and the large number of layers, preferably 3, 4, 5, 6 or 7 layers from the group consisting of metal oxides, suboxides metals, metal fluorides, halogenated metals, sulfides of metals, chalcogenides of metals, metal nitrides, oxynitrides metals, metal carbides, or mixtures thereof. Especially preferred are glass flakes coated with 3, 5 or 7 layers. Package layers (a) and (b) may be present in the standard layer-by-layer Assembly (A)+(B)+(C) up to four times.
Layer (A) with a high refractive index has a refractive index of n>1,8, preferably n≥2,1. Materials suitable as the material of the layer (A)are all materials known to the expert skilled in this art, which have a high refractive index, can take the form of a film and can be applied uniformly on the substrate particles. Particularly suitable materials are the oxides of metals, sulfides of metals or a mixture of metal oxides, such as TiO2, Fe2About3, TiFe2O5, Fe2O4, BiOCl, COO, Co3O4, Cr2O3, VO2V2About3, Sn(Sb)O2, ZrO2ZnO or SnO2, iron titanates, iron oxide hydrates, suboxide titanium (restored titanium particles having a degree of oxidation from <4 to 2), bismuth Vanadate, cobalt aluminate, and mixtures or mixed phases of the Pacific compounds with one another or with other metal oxides.
Metal sulfide coating is preferably selected from sulfides of tin, silver, lanthanum, rare earth metals, preferably cerium, chromium, molybdenum, tungsten, iron, cobalt and/or Nickel.
The thickness of the layer (a) is 10-550 nm, preferably 15-400 nm and in particular 20-350 nm.
Colorless materials with low refractive index, which are suitable for coating (B)are preferably metal oxides or the corresponding oxide hydrates type SiO2, MgF2, Al2About3, AlO(OH), IN2About3or a mixture of these metal oxides. The thickness of the layer (b) is 10-1000 nm, preferably 20-800 nm, and particularly 30-600 nm.
Materials particularly suitable for coating (S) with a high refractive index, are colorless or colored metal oxides, such as TiO2, Fe2About3, TiFe2O5, Fe3O4, BiOCl, COO, Co3O4, Cr2About3, VO2V2About3, Sn(Sb)O2, ZrO2, ZnO or SnO2, iron titanates, iron oxide hydrates, suboxide titanium, bismuth Vanadate, cobalt aluminate, and mixtures or mixed phases of these compounds with one another or with other metal oxides. Layers of TiO2additionally may contain an absorbent material, such as carbon, or the floor with him. Also particularly interesting is Vlada multilayer glass flakes, TiO2floor (S) which is partially restored and which, as well as unmodified TiO2contain the recovered titanium particles having a degree of oxidation from <4 to 2 (lower oxides such as Ti3About5, Ti2About3to TiO, oxynitride titanium and the titanium nitride). You can also use colourless, strongly refracting materials, for example metal oxides such as zirconium oxide, in particular titanium dioxide, painted selectively absorbing dyes by incorporating dyes into the metal oxide film by promazyvanija them selectively absorbing metal cations or by coating metal oxide film of a dye, such as, for example, Prussian blue or Carmine. The thickness of the layer (C) is 10-550 nm, preferably 15-400 nm and in particular 20-350 them.
In addition to the standard package of layers (A)+(B)+(C), in which a layer package (A)+(B) may contain up to four times in the pigment of the present invention, there are other preferred embodiments. For example, between the substrate (S) and layer (A)between the layer (a) and (B)between the layer (b) and (C) and/or between the layer (C) and top layer (D) pigment of the present invention may have additional absorbent or non-absorbent layer [(S1), (A1), (B1), (C1)]. The thickness of the intermediate layer is 1-50 nm, preferably 1-4 nm and, in particular, 1-30 nm. The pigments of the invention can contain many identical or different combinations (packet layer) (A)+(B).
Multi-layer glass flake with a coating obtained by this method are characterized in that at least three homogeneous layer cover homogeneous thin glass flakes.
Preferred target the pigments of the present invention are the following:
|glass flakes||+TiO2||+SiO2||+(Sn, Sb)O2|
|glass flakes||+(Sn, Sb)O2||+SiO2||+TiO2|
|glass flakes||+Fe2O3||+SiO2||+(Sn, Sb)O2|
|glass flakes||+TiO suboxide||+SiO2||+TiO2suboxide|
|glass flakes||+TiO2||+SiO2||+TiO2+SiO2+TiO2+ Prussian blue|
and if necessary the spine,
(D) an external protective layer.
Especially preferred embodiment is a coated glass flakes next layer-by-layer Assembly:
(S1) optional, SnO2
(A) TiO2or Fe2O3
(B1) optional, SnO2
(D) the final coating associated with the application.
The coating of the substrate layer (a) and (C) with a high refractive index, and optionally, colored or colorless coatings produce pigments whose color, gloss, hiding power and angular dependence of perceived colors may vary within wide limits.
The pigments of the present invention can easily be obtained through the formation of three or more interference layers with high and low refractive indices, a precisely defined thickness and a smooth surface on a thin glass flakes. In the case of layers with different metal oxides or mixtures of oxides of metals of the sequence of layers with a high refractive index multilayer set can be placed arbitrarily, because between them there is a layer with a low refractive index.
Metal oxide film is preferably applied wet-chemical method, it is possible to use methods wet chemical coatings are designed is for the production of pigments with a pearly luster; such methods are described, for example, in DE 1467468, DE 1959988, DE 2009566, DE 2214545, DE 2215191, DE 2244298, DE 2313331, DE 2522572, DE 3137808, DE 3137809, DE 3151343, DE 3151354, DE 3151355, DE 3211602, DE 3235017, DE 3842330 or other patent documents and other publications.
Layers of TiO2can be modified rutile or anatase. Preferred are TiO2(rutile) layers. Layers of titanium dioxide can also be recovered by known means, such as ammonia, hydrogen, steam, hydrocarbons, and mixtures thereof, or metal powders, as described in EP 0735114, DE 3433657, DE 4125134, EP 0332071, EP 0707050 or WO 93/19131. Mixed layers of iron oxide/titanium dioxide can be obtained as a sequential precipitation and coprecipitation of the individual metal oxides. In the case of wet coating, the substrate particles are suspended in water and add a hydrolyzable metal salt at a pH which is suitable for hydrolysis and are chosen so that the metal oxides or hydrates of metal oxides deposited directly on the plate without any options deposition on the sides. PH pH maintain a constant usually simultaneously measured by addition of a base and/or acid. Then the pigment is filtered off, washed and dried, and optionally calcined ability to regulate temperature annealing in relation to present specific coverage. Largely because the temperature of calcination is between 250 and 1000° With, preferably between 350 and 900°C. If necessary, the pigments can be calcined before their resuspending for applying the following layers by precipitation.
The coating process may also occur in the reactor with a fluidized bed of catalyst by gas-phase coating, in this case it is possible, for example, using appropriate methods proposed in EP 0045851 and EP 0106235 to obtain pigments with a pearly luster.
Used a metal oxide with a high refractive index is preferably titanium dioxide and/or iron oxide, and used a metal oxide of low refractive index is preferably silicon dioxide.
For applying layers of titanium dioxide are preferred to the method described in US 3553001.
An aqueous solution of titanium salt is added slowly to a suspension of the substrate to be coated is heated to approximately 50 to 100°and supported largely constant pH of about 0.5-5 by simultaneous addition of measured amounts of a base, for example aqueous ammonia or an aqueous solution of alkali metal hydroxide. Once achieved the desired thickness of the layer of sediment TiO2the addition of the titanium salt solution and the base ceased.
This technique, also called as the process Titus is Finance, is well-known due to the fact that it avoids excess of titanium salt. This is achieved by adding to the hydrolysis of only the number per unit time, which is necessary for uniform coating gidratirovannym TiO2and which can be obtained per unit of time available surface area of the particles that need to be covered. Thus, it can be minimized formation of hydrated particles of titanium dioxide, is not precipitated on the surface to be coated.
Application of a layer of silicon dioxide may be performed, for example, in the following way: a solution of silicate of potassium or sodium metered into a heated (50 to 100° (C) suspension of the substrate to be coated. maintain a constant pH at approximately 6-9 simultaneous addition of dilute inorganic acid, such as HCl, HNO3or H2SO4. Once achieved the desired thickness of the layer of SiO2the addition of a solution of silicate stop. Next, the suspension is stirred for approximately 0.5 hours
To enhance the light and weather stability, it is often desirable depending on the application area to expose the multilayer coated glass flakes of surface treatment. Useful surface treatment and additional processing can include, for example, with the person, described in DE-C 2215191, DE-A 3151354, DE-A 3235017 or DE-A 3334598, DE 4030727 A1, EP 0649886 A2, WO 97/29059, WO 99/57204, US 5759255. This surface treatment enhances the chemical resistance of the pigments and/or facilitates a processing of the pigment, especially its implementation in different environments for the application.
Multilayer pigments obtained in this way, result in significantly improved optical target pigments at a relatively low cost with
- excellent Shine
pure and saturated colors
an alternative high-performance properties of the optical filter
- very good transparency (important in mixed compositions)
and therefore suitable for almost all applications known in the field of pigments. At the same time, the size and shape of the particles can be freely adjusted to obtain optimal performance.
The latter aspect is very important, because for many applications it is absolutely necessary to adjust the shape of the particles. For cosmetic use, you must reduce the size and thickness to achieve a smooth and silky appearance. For automotive paints or printing inks, it is necessary to reduce the particle size of less than 40 microns or 20 microns in diameter. This of course means that the thickness is to ledout this trend, to maintain the aspect ratio required for attractive effects. Therefore, these examples are required thickness of the substrate <0.8 μm and <0.5 micron. Glass flakes made of the above-mentioned way, meet these necessary conditions. Furthermore, they show excellent flatness and smoothness (surface microstructure), which can be expressed by the relation BET (specific surface area) to WCA (water covering the surface), as described for aluminum pigments in patents US 4936913 and US 5127951. Values of approximately 3 indicate optimal suitability of the material. The high quality of these scales also explains the observed high transparency pigments, made in this way.
The preferred models for multilayer pigments of the present invention are:
>3 - <40 μm in diameter for applications for cars, or even more preferably 10-35 μm
>0,2 - <1 μm in average thickness, preferably 0.4 to 0.8 μm
>3 - <20 μm in diameter for applications for printing, preferably 5-20 microns
>0.2 to <0.5 micron average thickness.
Target the pigments of the present invention is mainly useful for many purposes, such as the coloration of plastics, glasses, ceramic products, agricultural foils, decorative cosmetic compositions is particularly coatings, especially automotive coatings, and inks, including printing inks. Can be used all conventional printing methods such as offset printing, gravure printing, bronzing, flexographic printing.
Target the pigments of the present invention also mainly useful for these assignments in a mixture with filling pigments or transparent covering white, colored and black organic and inorganic pigments, as well as with conventional transparent, colored and black glossy pigments based on mica coated with metal oxides, scales TiO2, scales SiO2or flakes Al2About3and coated or uncoated metal pigments, BiOCl pigments, iron oxides formed in the form of plates, or graphite flakes. The pigments of the invention can optionally be coated with organic or inorganic layers to get combined pigments.
Additionally, the mixture of the pigments of the invention can contain organic or inorganic pigments, thixotropic additives, wetting agents, dispersing agents, water, an organic solvent or mixture of solvents, etc.
The mixture of the pigments of the present invention is simple and easy to use. The mixture of the pigments can be introduced into the system by means of simple mixing. No n is needed in time-consuming grinding and dispersion of pigments.
Coated glass flakes of the present invention can be used for painting and/or coating materials, printing inks, plastics, agricultural films, pastes for the buttons to cover the seed, for colouring foods, coverage, drug, or cosmetic compositions. The concentration of pigments in the system in which they must be applied, is generally between 0.01 and 50 wt.%, preferably between 0.1 and 5 wt.%, on the basis of dry residue system. This concentration mainly depends on the specific application.
Plastic comprising the pigment mixture of the invention in amounts of from 0.1 to 50 wt.%, in particular from 0.5 to 7 wt.%, often distinguished by their brilliance.
Sector coverage, especially in the final finish of cars, the pigments according to the invention are used in quantities of from 0.5 to 10 wt.%.
When the pigmentation of binder systems components, for example for paints and printing inks for in-depth ornament, offset or screen printing, the pigment is introduced into the printing ink in quantities 2-50 wt.%, preferably 5-30 wt.% and in particular 8 to 15 wt.%.
The invention also provides compositions of pigments, including multi-layer coated glass flakes, optional target pigments, binder components and, if necessary, additives specified is oppozitsii, are mostly in the form of a solvent free, loose powder, not dust or granules. These granules contain up to 95 wt.% pigments of the present invention. The composition of the pigment, in which a multilayer coated glass flakes according to the invention glue binder component and water and/or organic solvent, with or without additives, and in which the paste is dried and lead to compact granular form, such as granules, beads, pellets, concentrates or pellets, is particularly suitable as a precursor for printing ink.
Therefore, the present invention also provides compositions containing pigments of this invention.
To further explain the invention, formulated below various examples, not limiting it. In them, as well as throughout the description and the claims, all parts and percentages are presented in wt., and all temperatures are given in degrees Celsius unless otherwise indicated.
100 g of glass flakes with a maximum diameter of 40 μm, and an average of 22 μm), and an average thickness of 0.5 μm (refractive index of 1.5) are suspended in 2 l of deionized water. Under vigorous stirring, the suspension is heated to 75°and begin With the floor, adding an aqueous solution of SnCl4that represents a 3% to icesto SnO 2in relation to glass scales for 0.5 hour. Once the pH reaches 2,0, simultaneously add 32% NaOH solution to maintain the pH at this level.
The suspension continue to mix for 15 minutes before adding the aqueous solution of TiCl4(400 g TiCl4/l H2O). By adding NaOH pH is maintained at the level of 2.0. The process continues until, until you reach the desired color. And the suspension continue to mix for an additional 15 minutes
Slowly adding NaOH, the pH was adjusted to 8.0. Then start to add 10%solution of sodium silicate (74 ml of sodium silicate solution with 8% Na 27% SiO2diluted with 170 ml of deionized water) at a rate of 1.35 ml/min. Quantity necessary to obtain a suitable thickness of the layer must be accurately calculated, because it is not optically visible during the coating process. After another stirring for 15 minutes the pH is reduced using 10% HCl to 2.0 and similar to the first perform the second floor TiO3until they reach the desired endpoint. The suspension continue to stir for a further one hour, then filtered off, washed of salts, dried, calcined at 800°With (within 30 minutes) and sifted.
The resulting pigment is applied to the surface to measure its color characteristics. He showed the t extremely brilliant pure color effect simultaneously with excellent transparency. Specifically, when the flat angle of the black background it is almost "disappears".
Example 2 (comparative example)
He was executed in a similar way as described in Example 1. But instead of the glass flakes used the mica of the same particle size distribution.
Deposited on the surface, the resulting pigment is a brilliant and intense color, but it does not show exceptional purity and, in particular, transparency at a flat angle, such as multilayer pigments based on glass flakes.
100 g of glass flakes with a maximum diameter of 40 microns (average 22 μm), and an average thickness of 0.8 μm (refractive index of 1.5) are suspended in 2 l of deionized water. The suspension is heated to 75°C, then diluted chloride-hydrogen acid pH adjusted to 1.8, first cover SnO2by adding a solution of SnCl4(from 2.2 g SnCl4and 7.5 ml of concentrated hydrochloric acid in 100 ml of deionized water) at a rate of 3.3 ml/min By addition of 32% sodium hydroxide solution maintain pH at a constant level.
Stirring is continued for 15 min and then carry out the coating of TiO2under the same conditions of pH/temperature, adding a solution of TiCl4(400 g TiCl4/l) at a rate of 1.5 ml/min and maintaining the pH at a constant level by using 32%Rast the ora of sodium hydroxide. Floor cease once reached the end point of the green of the second order, the stirring is continued for 15 minutes, diluted with sodium hydroxide solution the pH was adjusted to 8.0 (for about 15 minutes and then stirring is continued for another 10 minutes.
Perform coating of SiO2by adding a dilute solution of sodium silicate (of 7.3 g of sodium silicate solution with 8% Na 27% SiO2and 80 ml of deionized water) at a rate of 3 ml/min without compensation pH. Then stirring is continued for 15 minutes, the pH is again set at 1.8 using diluted hydrochloric acid (for about 10 minutes) and put the second layer of TiO2as described above, by adding a solution of TiCl4. Floor stop after reaching the end point of comparison, the green of the third order, the stirring is continued for 15 minutes and then the pigment is filtered off, washed, dried and calcined at 850°C for 30 minutes.
The resulting pigment has an intense green interference color.
The distribution of layers of TiO2is as follows:
1st layer: approximately 170 nm;
2nd layer: approximately 85 nm;
The entire layer: approximately 260 nm.
The thickness of the intermediate layer of SiO2approximately 5 nm.
100 g of the stack is constant scales with a maximum diameter of 40 microns (average 22 μm), and the average thickness of 0.5 μm (refractive index of 1.5) are suspended in 2 l of deionized water. The suspension is heated to 75°With diluted hydrochloric acid, the pH was adjusted to 1.8, first cover SnO2by adding a solution of SnCl4(from 2.2 g SnCl4and 7.5 ml of concentrated hydrochloric acid in 100 ml of deionized water) at a rate of 3.3 ml/min By addition of 32% sodium hydroxide solution the pH is maintained at a constant level.
Stirring is continued for 15 min, the pH was adjusted to 2.6 by using 32%sodium hydroxide solution, and put a layer of Al2About3/Fe2About3/TiO2by adding a solution of TiCl4/FeCl3/AlCl3(394 ml of 165 g of 30% solution of TiCl4, 274 g, 34% solution of FeCl3, 6.2 g of AlCl3× 6 H2Oh, and 63 ml of deionized water) at a rate of 1 ml/min
Stirring is continued for 15 min, the pH was adjusted to 7.5 using 32%sodium hydroxide solution with a speed of 1.3 ml/min, and then further continue to mix for 15 minutes Floor SiO2perform the addition of sodium silicate solution with 13.5% SiO2(out of 196 g of sodium silicate solution with 27% SiO2and 196 ml of deionized water) at a rate of 2 ml/min By the addition of 15%hydrochloric acid to maintain the pH at a constant level.
Stirring is continued for 30 min pH is adjusted to 1.8 by adding a solution of SnCl 4(from 3 g of SnCl410 ml of concentrated hydrochloric acid and 90 ml of deionized water) at a rate of 1 ml/min
Stirring is continued for 15 min, the pH is adjusted by 2.6 using 32%sodium hydroxide solution and put the second layer of TiO2/Fe2About3/Al2About3by adding a solution of TiCl4/FeCl3/AlCl3(394 ml of a composition similar to the first layer) at a rate of 1 ml/min. and Stirring is continued for an additional 15 minutes and then the pigment is filtered off, washed, dried and calcined at 850°C for 30 minutes
The resulting pigment shows a brilliant and intensely Golden interference color.
100 g of glass flakes with a maximum diameter of 40 microns (average 22 μm), and an average thickness of 0.5 μm (refractive index of 1.5) are suspended in 2 l of deionized water. The suspension is heated to 75°With diluted hydrochloric acid, the pH was adjusted to 1.8, first cover SnO2by adding a solution of SnCl4(from 2.2 g SnCl4and 7.5 ml of concentrated hydrochloric acid in 100 ml of deionized water) at a rate of 3.3 ml/min By addition of 32% sodium hydroxide solution the pH is maintained at a constant level.
Stirring is continued for 15 min and then carry out the coating of TiO2under the same conditions of pH/temperature is a, adding a solution of TiCl4(15 ml with 400 grams of TiCl4/l) at a rate of 1 ml/min and maintaining the pH at the same level using 32%sodium hydroxide solution.
Stirring is continued for 15 min, the pH was adjusted to 2.6 by using 32%sodium hydroxide solution and put a layer of Al2About3/Fe2About3/TiO2by adding a solution of TiCl4/FeCl3/AlCl3(376 ml of 157,5 g of 30% solution of TiCl4, 236 g of a 34% solution of FeCl3, 5.9 grams AlCl3× 6 H2About 60 ml of deionized water) at a rate of 1 ml/min
Stirring is continued for 15 min, the pH was adjusted to 7.5 using 32%sodium hydroxide solution with a speed of 1.3 ml/min and then further continue to mix for 15 minutes Floor SiO2perform the addition of sodium silicate solution with 13.5% SiO2(out of 196 g of sodium silicate solution with 27% SiO2and 196 ml of deionized water) at a rate of 2 ml/min By the addition of 15%hydrochloric acid the pH is maintained at a constant level.
Stirring is continued for 30 min, the pH is adjusted to 1.8 by adding a solution of SnCl4(from 3 g of SnCl410 ml of concentrated hydrochloric acid and 90 ml of deionized water) at a rate of 1 ml/min
Stirring is continued for 15 min and then carry out the coating with a second layer of TiO2under the same conditions of pH/temperature, adding R is the target TiCl 4(280 ml with 400 g of TlCl4/l) at a rate of 2 ml/min and maintaining the pH at the same level using 32%sodium hydroxide solution.
Stirring is continued for 15 min, the pH is adjusted by 2.6 using 32%sodium hydroxide solution and put the last layer of TiO2/Fe2About3/Al2About3by adding a solution of TiCl4/FeCl3/AlCl3(72 ml of a composition similar to the first layer) at a rate of 0.8 ml/min. and Stirring is continued for an additional 15 minutes, and then the pigment is filtered off, washed, dried and calcined at 850°C for 30 minutes
The resulting pigment shows even more brilliant and intense Golden interference color than the pigment according to example 4.
Examples of the application
Application Example 1: Base with glitter
|Filler W||Mica, CI 77891 (titanium Dioxide)||to 9.00% (1)|
|Microna®Matte Yellow||Mica, CI 77492 (iron Oxide)||4,00% (1)|
|Microna®Matte Red||CI 77491 (iron Oxides), Mica||0,40% (1)|
|Microna®Matte Black||CI 77499 (iron Oxides), Mica||0,30% (1)|
|Silica, CI 77891 (titanium Dioxide). Mica, tin Oxide||4,50% (1)|
|Ronasphere®||Silicon dioxide||to 5.00% (1)|
|Blanose 7 HF||The methylcellulose||0,20% (2)|
|Wigan||Aluminum silicate magnesium||1,00% (3)|
|Texapon To 1296||Sodium lauryl sulfate||0,60% (4)|
|Titriplex III||EDTA disodium||0,25% (1)|
|1,2-propandiol||Propylene glycol||10,90% (1)|
|Paraffin||Liquid paraffin (Mineral oil)||of 3.60% (1)|
|Crodamol SS||Citylove esters||2,60% (5)|
|Monomers 60-35||Hydrogenomonas glycerides of palmitic|
|Stearic acid||Stearic acid||1,50% (1)|
|Eusolex®6300||4-Methylbenzylidene camphor||1,30% (1)|
|RonaCare™ Tocopherylacetate||Tocopherylacetate||0,10% (1)|
|Magnesium stearate||Magnesium stearate||0,10% (1)|
|Odorant 200 529||Perfume||0,20% (6)|
|Axel 400||Phenoxyethanol, methyldibromo-glutaronitrile||0,20% (7)|
Heat all ingredients of Phase C to 75°with stirring to dissolve all components. Add separately blanose and wigum to the cold water Phase with vigorous shaking (Turrax). Heat to 75°and add remaining ingredients of Phase b and mix until homogeneous and uniform mixture. Add ingredients of Phase A. If 75°enter Phase With the Phase a/b and homogentisate for 2 minutes. Add Phase D at 40°C. Cool to room temperature under stirring and bring the pH to 6.0-6.5 (the example the citric acid solution).
(1) Merck KGaA/Rona®
(2) Aqualon GmbH
(4) Cognis GmbH
(5) Croda GmbH
(6) Fragrance Resources
(7) Schuike&Mayr GmbH
Application. Example 2: shower Gel
|The pigment according to Example 1||0,10% (1)|
|Central T||Xanthan gum (Xanthan Gum)||of 0.75% (2)|
|PLANTACARE 2000 UP||Decyl glucoside||20,00% (3)|
|Texapon ASV 50||Sodium Laureth sulfate||of 3.60% (3)|
|Sodium Laureth-8 sulfate,|
|Magnesium Laureth sulfate|
|Magnesium Laureth-8 sulfate,|
|Sodium IG sulfate, Magnesium IG sulfate|
|Bronidox L||Propylene glycol, 5-bromo-5-nitro-1,3-dioxane||0,20% (3)|
|Odorant Everest 79658 SB||Perfume||0,05% (4)|
|1% FD&C Blue No. 1 in the water||Water is, CI 42090 (FD&C Blue No. 1)||0,20% (5)|
|Citric acid monohydrate||Citric acid||0,15% (1)|
Dispersivity pigment in the water Phase A. Enter Central T with stirring and stir until complete dispersion. Add with stirring Phase and In Phase With successively to Phase a and stir slowly to obtain a homogeneous gel.
(1) Merck KGaA/Rona®
(3) Cognis GmbH
(4) Haarmann&Reimer GmbH
(5) BASF AG
Application Example 3: Ink for metallography
Ink for metallography, consisting of
|70 g||Binders on the basis of nitrocellulose from Gebruder Schmidt 95 MB 011 c dry matter content of 20%|
|15 g||Minatec®31 CM (conductive pigment from Merck KGaA, Darmstadt, Germany)|
|15 g||Coated glass flakes according to Example 1|
Application Example 4: the Product of plastic
1 kg of pellets of polyethylene (PE-HD) uniformly moisten in a mixing drum with 2 g of binder. Then add 10 g of coated glass flakes according to Example 4 and 2 g IRI the Dean LS 825 (conductive pigment from Merck KGaA, Darmstadt, Germany) with a particle size of <15 μm, and the components are stirred for 2 minutes.
These granules are processed under normal conditions in injection moulding parallel-planning machine with obtaining small multiple reticles from sizes 4×3×0,5 see These little animated masks are known for their brilliance and their ability to laser marking.
Application Example 5: Floor
|30 g||Coated glass flakes according to Example 5|
|10 g||Minatec®40 CM (conductive pigment from Merck KGaA, Darmstadt, Germany)|
|42 g||The binder of the paint system (AU-MF solids = 19%)|
|18 g||Solvent mixtures|
1. Multilayer pigments based on glass flakes, characterized in that the glass flakes coated with alternating layers with high and low refractive index and that the glass flakes coated with at least three layers, where the pigments include at least one sequence of layers, which contains
(A) coating which has a refractive index of n>1,8,
(B) a coating which has a refractive index n≤1,8 and
(C) coating that has p is the index of refraction n> 1.8 and, if necessary,
(D) an external protective layer
provided that the package of layers (A)+(b) may be present in the standard layer-by-layer Assembly (A)+(B)+(C) up to four times.
2. Multilayer pigments according to claim 1 or 2, characterized in that the glass flakes have a thickness of less than 1 μm
3. Multilayer pigments according to claim 1, characterized in that the layers consist of metal oxides, suboxides metals, metal fluorides, halogenated metals, chalcogenides of metals, sulfides of metals, metal nitrides, oxynitrides metals, metal carbides or mixtures thereof.
4. Multilayer pigments according to claim 1, characterized in that the layer with high refractive index consists of TiO2, Fe2O3, TiFe2O5, Fe3O4, BiOCl, Cr2O3, ZrO2, ZnO, SnO2, CoO, Co3O4, VO2V2O3, iron titanates, iron oxide hydrates, suboxides titanium, bismuth Vanadate, cobalt aluminate, sulfides of metals, metal halides, nitrides, oxynitrides metals, metal carbides or mixtures thereof.
5. Multilayer pigments according to claim 1, characterized in that the layer with a low refractive index consists of SiO2, Al2About3, AlO(OH), IN2About3, MgF2or mixtures thereof.
6. Multilayer pigments according to claim 1, characterized in that they have a trace of the expansion layer structure:
|glass flakes||+TiO2||+SiO2||+(Sn, Sb)O2|
|glass flakes||+(Sn, Sb)O2||+SiO2||+TiO2|
|glass flakes||+Fe2O3||+SiO2||+(Sn, Sb)O2|
|glass flakes||+TiO suboxide||+SiO2||+TiO2suboxide|
|glass flakes||+TiO2||+SiO2||+TiO2+SiO2+TiO2+ Prussian blue|
and, if necessary,
(D) an external protective layer.
7. Multilayer pigments according to claim 1, characterized in that the glass flakes coated with three layers.
8. A method of obtaining a multilayer pigment according to any one of claims 1 to 7, which comprises coating glass flakes by wet chemical coating or by chemical or physical vapor deposition and annealing covered Tiklanish scales.
9. The multilayer pigments according to any one of claims 1 to 7 in plastics, coatings, coatings of the powder material, paints, ink, inks, glasses, ceramic products, foil for agriculture, in cosmetic compositions, for laser marking of papers and plastics.
10. Compositions containing multilayer pigments according to any one of claims 1 to 7.
11. Pelteobagrus powders, pastes and granules containing multilayer pigments according to any one of claims 1 to 7.
FIELD: application of coat on surfaces of articles made from polymer scintillation materials.
SUBSTANCE: proposed method includes mechanical treatment of surface of article, degreasing of this surface, treatment of this surface and drying in air. Surface of article is subjected to treatment with mixture of solvent of aromatic and chlorinated hydrocarbon and precipitating agent of lower monatomic alcohol and aliphatic hydrocarbon at ratio of 1: (1-2.5) continued for 25-35 s, after which article is washed in precipitating agent for 60-120 s for effective light reflection and maximum light collection; as a result, light efficiency is increased by 1.1-1.2 times.
EFFECT: enhanced technology of method; reduction of time required for forming the coats.
1 tbl, 6 ex
FIELD: spatial material science and optical engineering.
SUBSTANCE: invention is designed for use in system of passive thermoregulation of spatial apparatuses for manufacturing cold-drying coatings of class "sun reflectors", which are applied onto outer surfaces of spatial apparatuses. Composition according to invention comprises: 9.49-9.54 wt parts amide-containing acrylic resin as binder; 52.36-52.49 wt parts monocrystalline superfine white-colored powder of zinc-gallium oxide with calculated formula ZnGaO1+n, wherein n=0.0064, and molecular mass 81.38; and 37.99038.15 wt parts solvent: xylene/butanol mixture at ratio 4:1; provided that binder-to-filler ratio is 1:5.5 and fraction of nonvolatile substances is 58.0% maximum.
EFFECT: preserved high optical characteristics of coating during prolonged operation of spatial apparatus.
3 cl, 1 dwg, 3 tbl
FIELD: chemical industry; printing industry; powder metallurgy industry; cosmetic industry; other industries; production and application of the highly anticorrosive metallic pigments.
SUBSTANCE: the invention is pertaining to production of the of the highly anticorrosive metallic pigments similar to laminas, which may be used in production of the printing ink, plastic materials, cosmetics, the powder coatings and in other branches of industry. The pigments have on their surfaces: the metallic substrates similar to the laminas and treated with the compounds of the phosphoric acid and-or the compounds of the boric acid; one or more layers of the coatings consisting of one or more hydrated oxides of the metals of one or more metals selected from the group, which includes silicon, aluminum, zirconium, titanium and tin. On the basis of the highly corrosive metallic pigments similar to laminas it is possible to produce the interferential colored pigments. The invention allows to increase the anticorrosive resistance of the metallic pigments at the expense of saving without the faults of the initial surface smoothness of the similar to the laminas metallic substrates, to increase the homogeneity and density of the layers of the hydrated oxides of the metals.
EFFECT: the invention ensures the increased anticorrosive resistance of the metallic pigments, saving the initial surface smoothness of the similar to the laminas metallic substrates, the increased homogeneity and density of the layers of the hydrated metals oxides.
40 cl, 9 ex, 4 tbl, 8 dwg
FIELD: paint and varnish materials.
SUBSTANCE: invention describes a composition used in decorative finishing and comprising the following components, wt.-%: 20% solution of polymethylmethacrylate in dichloroethane as a film-forming agent, 20.5-23.25; aromatic solvent, 70.5-74.5, and aluminum powder modified with an organic dye by grinding, 4.25-5.0, taken in the ratio = 1:(0.005-0.008). The proposed composition provides decorative effect of cover mimic to mother-of-pearl with good adhesion of the composition on plastics of different chemical nature. Invention can be used in coloring plastics with imitation of mother-of-pearl, in particular, for national consumption goods.
EFFECT: improved and valuable properties of composition.
2 tbl, 2 ex
FIELD: chemical industry; printing industry; other industries; methods of production of the composition of the paint including the optically changeable pigments.
SUBSTANCE: the invention may be used in production of the optically changeable pigments. The optically changeable pigment includes the stratified set composed of the different materials, in which, at least, one of the layers represents the reflecting layer and, at least, one of the other layers represents the dielectric layer. At least, one of the surfaces of the indicated layers is subjected to the chemical action. The indicated materials also include, at least, one of the layers, which represents the semitransparent metallic layer made out of chromium and also one or more metals and-or their inorganic compounds. At that the metal and-or its inorganic compound are subject to corrosion. The subjected to the chemical action surface of the reflecting and dielectric layer along the edge of the layering block of the edge structure of the pigment is coated with the passivating agent, which is selected from the group consisting of the organic esters and the fluorinated organic esters of the phosphoric acid, having the following structural formula: (Rf-CH2-CH2-O)xP(O)(OH)y, where Rf=F-(CF2-CF2)z, х=1 or 2, у=2 or 1, х+у=3, z=l-7. The composition of the printing paint includes the binding system, water and the optically changeable pigment. The invention allows to diminish oxidation of the metallic layers and dissolution of the dielectric layers of the optically changeable pigment and to use it in the compositions of the printing paint.
EFFECT: the invention allows to diminish oxidation of the metallic layers and dissolution of the dielectric layers of the optically changeable pigment and to use it in the compositions of the printing paint.
22 cl, 7 ex
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: 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: nonferrous metallurgy industry; aircraft industry; other industries; production of the heat-resistant alloys on the basis of the nickel.
SUBSTANCE: the invention is pertaining to the dispergated coloring agents intended for the ink-jet recording. The invention describes the dispergated coloring agent containing the coloring agent and the pseudo-finely-dispergated particles of the polarizable polymer having the dimension less, than the particles of the coloring agent. In the dispergated coloring agent the coloring agent itself and the particles of the polarizable polymer are attached to each other. At that the pseudo-finely-dispergated particles of the polarizable polymer contain the interpolymer consisting of the monomeric components containing, at least, one type of the hydrophobic monomer and, at least, one type of the hydrophilic monomer, where the hydrophobic monomer contains, at least, the monomer having the methyl group in α - position and the radically-polymerizable non-saturated double bond. The invention also describes the method of production of the indicated dispergated coloring agent and the water ink produced on its basis. The presented dispergated coloring agent has the high stability for a long time and practically in the absence of the surface-active substance or the dispergator. The ink produced on its basis has stability of blowout in the ink-jet printing method.
EFFECT: the invention ensures, that the ink produced on the basis of the presented dispergated coloring agent has the high stability of blowout in the ink-jet printing method.
20 cl, 14 dwg, 7 tbl, 15 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