Titanium dioxide based pigment, methods of producing titanium dioxide based pigment and pigment obtained using one of said methods, decorative paper, method of making decorative paper, method of making decorative coating materials and decorative coating materials

FIELD: chemistry.

SUBSTANCE: titanium dioxide based pigment, containing titanium dioxide particles, has a coating layer containing aluminium phosphate and aluminium oxide, and said layer additionally contains hollow particles. To obtain said pigment, aqueous suspension of titanium dioxide is prepared first, and aluminium- and phosphorus-containing components are then added, after which hollow particles are added and pH of the suspension is brought to 4-9. Also, aqueous suspension of titanium dioxide can be obtained at pH not lower than 10, and aluminium- and phosphorus-containing components can then be added while maintaining pH of at least 10, after which hollow particles are added. Further, pH of the suspension is brought to 4-9 and an aluminium oxide coating is then applied at pH from 4 to 9.

EFFECT: invention increases opaqueness and retention of pigment when making decorative paper.

22 cl, 1 dwg, 1 tbl, 1 ex

 

The technical field to which the invention relates.

The invention relates to a pigment based on titanium dioxide with good opacity and the method of its production and use in the manufacture of decorative paper and decorative foil.

The level of technology

Decorative paper or decorative foil are an essential part of a decorative thermosetting coating materials, which are used mainly for finishing furniture surfaces, laminate flooring and interior finishes. Laminate called layered, pressed from several materials products, such as laminated multi-layer impregnated paper, or paper and hard fiber, or wood particle Board. Thanks to the application of synthetic resins is achieved extremely high temperature resistance, resistance to scratches, shock, exposure to chemical substances.

The application of the decorative paper (all of the following must also be attributed to the decorative foil) provides the ability to get decorated surfaces, with decorative paper serves not only as a coating, for example, unattractive, chipboards, but also as a carrier for synthetic resins.

To the requirements of decorative paper include, among other repros agnosti (opacity), lightfastness (resistance to darkening), color stability, moisture resistance, and ability to the application and printing properties.

The validity of the new method of obtaining decorative paper is determined primarily by the degree of opacity of the pigment in the paper. To achieve the required opacity decorative paper fundamentally suitable basis is pigment based on titanium dioxide. In paper production, as a rule, mix the pigment based on titanium dioxide or suspension containing a pigment based on titanium dioxide, with a suspension of cellulose. In addition to the input materials of pigment and cellulose, as a rule, require the addition of auxiliary substances, for example substances which impart moisture resistance, in some cases it is necessary to introduce other additional substances as fillers. The interaction of the individual components (such as pulp, pigment, auxiliary and additional substances, water) between favorable for receiving paper and is determined by this parameter, as the retention of pigment. Under the fixation understand the ability of all inorganic compounds in the paper be maintained in a homogeneous state when it is received. An important role is played by the surface charge of the pigment relative to the cellulose fiber.

It is known that one of the ways to achieve improved opacity is a special modification of the surface of particles of titanium-dioxide pigment.

In U.S. patent No. 5942281 and US 5665466 describes a method of modifying the surface of the pigment particles. According to this method, the first stage particle is covered with oxyphosphate of aluminum at a pH value of from 4 to 6. Then, at the next stage, the particle of the pigment is precipitated by a second layer consisting of aluminum oxide at pH from 3 to 10, preferably at pH of about 7. Improving the value of uderzhivaemoi is achieved by applying a third layer consisting of magnesium oxide. Thus, a characteristic feature of the obtained pigment is that its particles contain three covering layers, one after the other: oxyphosphate aluminum, aluminum oxide and magnesium oxide.

In U.S. patent No. 6962622 describes pigment based on titanium dioxide in the mixture. It consists of a pigment with high resistance to darkening (pigment a-type) and pigment modified with a surface coating that has a high content of silicon oxide and aluminum oxide (pigment b-type).

In U.S. patent No. 6143064 describes the deposition of calcium carbonate on the pigment particles, and the particles of calcium carbonate have a size of from 30 to 100 nm. Paper, manufactured using titanium dioxide coated with a layer of calcium carbonate, has a high degree of opacity. Particles of calcium carbonate and thereby provide a gap between the particles pigman is a, which leads to improved distribution of the particles of the pigment in the paper. The minimum distance between the pigment particles should correspond to the size of the pigment particles. In U.S. patent No. 5886069 and 5650002 describes pigment containing TiO2the particles of which have a continuous inorganic coating, and the coating of individual inorganic particles with a diameter of 5-100 nm. The particles can have any shape, coated, nanesennymi in any sequence. The pigment produced by mixing a colloidal suspension of individual particles with a suspension of TiO2.

In the application U.S. No. 2003/0024437 A1 describes a pigment in the form of a mixture of particles of different pigments on the surface of which is in situ precipitated spherical particles of calcium carbonate, silicon oxide, aluminum oxide, zirconium dioxide and titanium oxide.

Disclosure of inventions

The objective of the present invention to provide an alternative titanium-dioxide pigments with good opacity and fixation for creating decorative paper. Another object of the invention consists in the expansion and development of methods for such titanium-dioxide pigments.

The solution of the first problem is that the titanium-dioxideis pigment contains particles of titanium dioxide on the surface of which is a layer comprising aluminum phosphate, aluminum oxide and hollow particles.

[Daln] ISEE solution of the problem consists in a method of producing titanium-dioxide pigment with modified surface, in accordance with the following stages:

a) obtaining a water suspension still uncoated particles of titanium dioxide;

b) adding the aluminum and phosphorus components;

C) adding hollow particles;

g) bringing the pH of the suspension to 4÷9.

Further variants of the invention are described below.

Brief description of drawings

Figure 1 shows a photograph of the pigment particles based on titanium dioxide, having a layer comprising aluminum phosphate, aluminum oxide and hollow particles.

The implementation of the invention

Hereinafter, the term "oxide" is implied oxide containing water, i.e., respectively, hydrate. All subsequent data on pH, temperature, concentration in mass % volume % cover all values that lie in the area of the respective precisions of measurements known in the art. Specifying a "significant amount" or "significant part" in the framework of this patent means the minimum quantity of the component, above which is within the measurement accuracy there is a change in the properties of the mixture.

A distinctive feature of the pigment obtained according to the present invention is the use of hollow particles. Under the hollow particles are hollow understand different body shape: beads and other particles. Hollow particles used according to the invention, n is the final stage of processing. Hollow particles are precipitated on the surface of the pigment particles, and serve as a kind of intermediate layers between the pigment particles. Hollow particles can be made from organic substances and inorganic substances. Their average diameter is 5÷1000 nm. Hollow particles are characterized by the fact that have inclusions of air, and these inclusions appear in this case only after drying. Organic hollow particles, typically used as a filler in paints. Hollow particles are layers between the pigment particles. It should be emphasized that the hollow particles contain inclusions of air. The specific refractive index between the pigment and air increases the opacity (see "improving the quality of the polymer RopaqueTMOpaque to improve varnishes and paints", journal Phanomen Farbe 2/98, 1/99). To obtain hollow organic particles are guided by the publication of "Hollow latex particles: synthesis and applications" (McDonald et al., Advances in Colloid and Interface Science, 2002, 99:181-213). Obtaining hollow inorganic particles described in "Nanoengineering of Inorganic and Hybrid Hollow Spheres by Colloidal Templating" (Caruso et al., Science, 1998, 282:1111). In international publication WO 02/074431 A1 disclosed a method of obtaining a hollow inorganic particles and their application in catalysis and in fiber optics.

According to the method proposed in this invention, on the surface of the particles of TiO2beset with the Oh, containing compounds of aluminum and phosphorus in the mixture with hollow particles and aluminum oxide. The composition of this mixture depends on the loaded amount of the aluminum and phosphorus components. In the future, this layer simplistically considered as hollow particles oxyphosphate aluminum. Subsequent processing based on the present invention, based on water, preferably wet grinding suspensions of TiO2(stage a). The wet grinding is carried out in this case in the presence of dispersing the funds.

Under the titanium dioxide TiO2it should be understood uncoated particles of TiO2i.e. mean base material TiO2received or sulphate (SP), or chloride (CP) method. This is a basic substance, usually stable. In CP-way stabilization adds aluminium-containing component in an amount of from 0.3 to 3 wt.% in terms of Al2O3and oxidizes the titanium tetrachloride to titanium dioxide excess oxygen (2÷15%) in the gas phase. In SP-stabilization process is performed by adding a small amount of Al, Sb, Nb or Zn. Upon receipt of the particles of TiO2preferably use the chloride process.

The process is carried out at a temperature below 80°C, preferably at 55÷65°C. the Suspension at the stage a) can have both alkaline and acidic reaction with preferably pH >9 or <4. At the stage b) is dobavlaut aluminum and phosphorus components.

Suitable aluminium-containing component, for a method of surface modification proposed in the present invention are the corresponding water-soluble alkaline or acidic salts, such as sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum acetate, etc. should Not assume that the list is limited to the listed substances. Aluminium-containing component should be added in quantities of from 1.0 to 5.0 wt.%, preferably from 1.5 to 4.5 wt.% and particularly preferably 2.0 wt.% in terms of Al2O3(relative to TiO2-particles).

Suitable phosphorus-containing components are inorganic compounds such as phosphates of alkali metals, ammonium phosphate, polyphosphates, phosphoric acid, etc. should Not assume that the list is limited to the listed substances. The most appropriate is odinokiy sodium phosphate (Na2HPO4or phosphoric acid. Phosphorus-containing component is added in a concentration of from 1.0 to 5.0 wt.%, preferably from 1.5 to 4.0 wt.%, particularly preferably from 2.0 to 3.0 wt.% in terms of R2O5(relative to the particles of TiO2). The aluminum and phosphorus components can be added to the suspension in any order, simultaneously or in turn. At the next stage, the added organic or inorganic hollow particles with an average diameter of from 5 to 1000 nm, preferably from 400 to 600 nm.

As the organic hollow particles is suitable, for example, the product RopaqueTMfrom Rohm & Haas. Under the product RopaqueTMit should be understood hollow particles of styrene-acrylic copolymer in the form of spheres. Also suitable hollow spheres made of latex or other polymer. One should not assume that the list is limited to the listed substances. Fit basically any hollow organic particles having the desired diameter in the range from 5 to 1000 nm and which is stable at the respective pH values. As the inorganic hollow particles being treated hollow glass particles and ceramic hollow beads, and hollow balls of TiO2. Has a value and that any type of hollow inorganic particles are applicable according to the present invention if they have the required average diameter of from 5 to 1000 nm, because they are stable when used values of pH. On the basis of predetermined factors, such as technological properties, price, etc., professionals can find suitable hollow particles. Hollow particles are added in an amount of from 1 to 15 wt.% relative to the weight of uncoated particles of TiO2. At a later stage g) the pH of the suspension was adjusted to 4 to 9 by adding a component that regulates pH. Used component regulating the pH may be acidic is whether alkaline. As acids can be used, for example, sulfuric, hydrochloric, phosphoric, or any other suitable acid. Alternatively, instead of the acids to apply the corresponding salts with acidic reaction, such as aluminum sulfate. You can also use acid solutions of salts of metals: cerium, titanium, zirconium, so that happened a joint deposition of a layer of Ti, Ce, Zr connections, hollow balls and oxyphosphate aluminum on the surface of the pigment particles. As the alkali, it is preferable to use sodium hydroxide. Also suitable salt with an alkaline reaction. Specialist known suitable connections, regulating pH. One should not assume that in the above examples, lists all possible substances.

Turned out to be beneficial at a later stage (e) a layer of hollow beads and oxyphosphate aluminum to put a layer of aluminum oxide; this can be done in several ways. First, by parallel addition of alkaline and acidic aluminium-containing component (for example, sodium aluminate and aluminum sulfate). Secondly, by adding alkaline aluminium-containing component, such as sodium aluminate and acid, such as sulfuric or hydrochloric. In-teteh by adding acidic aluminium-containing component, such as, for example, of aluminum sulfate with alkali, such as NaOH. When atongo all three cases, the pH is maintained within the range of 4 to 9. In addition, components can be added in two ways: 1) so that the pH value remains constant in the range from 4 to 9, or 2) the components are added so that the pH during the addition was varied in the range from 4 to 9. Experts know the relevant procedure. For adjusting the pH are suitable, in particular, alkali and acid (for example, NaOH and H2SO4or salt solutions with alkaline or acidic properties (for example, sodium aluminate and aluminum sulfate). As it turns out, is particularly favorable treatment at pH installed in stage d).

Optionally, in stage e) regulate pH in the range from 5 to 8, for example, with alkali (NaOH etc) or acid (H2SO4, HCl and so on). In addition, at this stage to adjust the pH of suitable aqueous solutions of salts with acidic or alkaline properties, for example a solution of sodium aluminate or aluminum sulfate.

The amount of aluminium-containing compounds introduced in stages d), d) and e), count on Al2O3and take into account already at the stage b). Total aluminium-containing component, calculated on Al2O3introduced into the suspension at stages b) to (e) relative to the weight of uncoated particles of TiO2must be from 1.0 to 9.0 wt.%, preferably from 3.5 to 7.5 mA is from.% and particularly preferably 5.5 wt.%. Also the amount of phosphorus-containing component is introduced in stages d) and e), recalculate the P2O5and take into account at the stage b). Total phosphorus-containing component in terms of P2O5introduced into the suspension at stages b) to e)should be from 1.0 to 5.0 wt.%, relative to the weight of uncoated particles of TiO2, more preferably from 1.5 to 3.5 wt.% and particularly preferably from 2.0 to 3.0 wt.%.

Also in suspension together with the aluminum and phosphorus components can be added some metal salts, for example, cerium, titanium, zirconium, zinc, and silicon compounds, which are then precipitated together with a layer of hollow beads and oxyphosphate aluminum in the form of phosphates or oxides.

Further, it is possible to cause the pigment particles to the following inorganic layer. This can be done as before stage d)and after study d), well-known technology (for example, you can put a layer of zinc, titanium and silicon-containing compounds).

According to the invention, in the proposed method, it is preferable to use an alkaline suspension of TiO2. To do this on stage a) in suspension in lead suitable alkaline component, such as NaOH, in order to establish a pH of at least 10. It is desirable, if damp grinding, which is the best way is omogenisatio.

At the stage b) in suspensio sequentially add the aluminum and phosphorus components in the form of aqueous solutions. When adding components, it is preferable to maintain the pH of the suspension at least 10, preferably 10.5 and particularly preferably 11.

As alkaline aluminium-containing component is particularly suitable sodium aluminate. When added acid components, such as, for example, aluminum sulfate, pH decreases below 10; to eliminate this effect, add a connection with the alkaline properties, for example sodium hydroxide. Specialists known suitable compounds with alkaline properties, and the required amount to maintain ulicina pH of at least 10.

In the case of adding a phosphorus-containing components also may decrease the pH below 10, in order for this effect to resolve, add compounds with alkaline properties, for example sodium hydroxide. Specialists known suitable compounds with alkaline properties, and the required amount to maintain the pH below 10.

The aluminum and phosphorus components can be added to the suspension in any sequence. At a later stage) add organic or inorganic hollow particles with an average diameter of from 5 to 1000 nm, preferably from 400 to 600 nm, and the pH suspe the Ziya should not fall below 10, preferably not lower than 10.5, particularly preferably not lower than 11.

At the next stage g) add a component that regulates the pH so that the pH was in the range of from 4 to 9.

According to an alternative method of the present invention, the surface modification of pigment can be performed at acidic pH values.

According to this method, at the stage b) add the aluminum and phosphorus components, so that the pH value of the suspension was less than 4. The specialist may choose to acidify the suspension at the stage a), using a suitable acid, or at the stage b), using a combination of aluminum and phosphorus components; in any case, the pH value must be less than 4. Examples of suitable combinations of aluminum and phosphorus components can be any of the following combinations: phosphoric acid and sodium aluminate or gentrigication and aluminum sulfate. Components can be introduced into the suspension in any order.

At the stage b) apply only hollow particles are stable at acidic pH.

At stage g) again add the component regulating the pH, so as to maintain a pH from 4 to 9.

Surface-modified Tio2the pigment is recovered from the suspension by known laboratory techniques; after filtering, produce washing of the crude pigment removal in rastvorimykh salts. To improve the light fastness of the pigments in the laminate to sizepolicy on the filter paste pigment type inorganic nitrates, for example, KPO3The NN3, Al(NO3)3in the amount of from 0.05 to 0.5 wt.% in terms of NO3after which produce drying. When the final grinding, for example, using a ball mill, a pigment may be added organic compound from a number of substances commonly used in obtaining pigment TiO2and which are well known in the art as, for example, a polyalcohol (trimethylolpropane). An alternative to adding nitrosoureas compounds before or during the drying process may be adding these compounds during grinding.

The pigment obtained by this method shows a high opacity relative to the reference sample and is best suited for the manufacture of decorative paper. Decorative paper can be used for the manufacture of decorative surface materials.

The modification of the surface of the pigment particles, as claimed in this invention, usually as a periodic process. It is also possible to carry out the modification process continuously, and with the help of suitable mixing devices known in the art. This mixing device is guaranteed to make neo the required mixing.

Examples of carrying out the invention

Below are examples of the invention, contributing to a better understanding.

Example (according to the invention)

In the crushed state of the sand suspension of TiO2-rutile, chloride obtained by the method, with a concentration of TiO2350 g/l at 60°C add NaOH to pH=10. With stirring, was added sodium aluminate, in the amount of 2.0 wt.% in terms of Al2O3. After 15 min stirring was added intrigejosa in the form of a solution of 2.4 wt.%, in terms of R2O5. Was kept under stirring for another 15 minutes At the next stage, the suspension is added a 30%emulsion Ropque Ultra (polymeric hollow beads from the company Rohm & Haas), so that the active component in the form of a styrene-acrylic copolymer on dioxide titanium amounted to 2 wt.%. After this was stirred another 15 minutes At the next stage, the suspension is added a solution of aluminum sulfate, so that the amount of aluminum in terms of Al2O3amounted to 2.6%, while the pH value becomes approximately equal to 5. Then to the resulting suspension type aluminium-containing components in the amount of 0.7 wt.% in terms of Al2O3; to do this, carry out the simultaneous addition of solutions of sodium aluminate and aluminum sulfate, so that the pH=5.

After 30 min displaced the air traffic management pH of the suspension was adjusted to approximately 5.8 by the addition of alkaline sodium aluminate solution. Then filtered and washed solid residue on the filter to remove water-soluble salts. To sizepolicy on the filter paste pigment type NaNO30.25 wt.% in terms of NO3, then dried and crushed dry pigment in a ball mill.

Studies using transmission electron microscope showed that the surface of the pigment particles are hollow microspheres.

Comparative experiment

In the crushed state of the sand suspension of TiO2-rutile, chloride obtained by the method, with a concentration of TiO2350 g/l at 60°C add NaOH to pH=10. With stirring, add the sodium aluminate to the content of 2.0 wt.% in terms of Al2O3. Stirred for 15 min and add intrigejosa in the form of a solution of 2.4 wt.%, in terms of R2O5. Stirred for further 15 minutes At the next stage, the suspension is added a solution of aluminum sulfate, to the aluminum content in terms of Al2O32.6 wt.%, when the pH value becomes approximately equal to 5. Then to the resulting suspension type aluminium-containing components in the amount of 0.8 wt.% in terms of Al2O3; this simultaneously add solutions of sodium aluminate and aluminum sulfate, so that the pH=5.

Stirred for 30 min, then the pH of the suspension was adjusted to approximately 5.8 d is the addition of alkaline sodium aluminate solution. Then filtered and washed solid residue on the filter to remove water-soluble salts. To sizepolicy on the filter paste pigment type NaNO30.25 wt.% in terms of NO3, then dried and crushed dry pigment in a ball mill.

Test method.

To assess the optical properties of the decorative paper and the quality of the pigment based on titanium dioxide should compare the ash content of samples of decorative paper. For this purpose produced sheets of decorative paper with a density of sheet 80 g/m2and ash content of 30 g/m2. Procedure and used auxiliary materials known in the art.

The content of titanium dioxide (ash) in sheets of paper, as well as the fixation of pigment is determined by the following methods.

a) Ash content

To determine the content of titanium dioxide in the produced paper we take up a certain sample analyzed paper and turn it into ashes with the help of the device to determine the ash content of paper with rapid heating up to 900°C. By the mass loss of determine the mass percent of TiO2(ash) wt%. To calculate the ash content use the following formula:

Ash [g/m2]=(ash [wt.%-%]* weight, referred to the unit area [g/m2])/100 [%]

b) Fixation

Under the fixation understand the ability of all reorganizes is their substances to remain on the sheet of paper on the grid paper machine. The so-called one-pass fixation which is defined here, is characterized by part (percentage) of inorganic substances held in a single loading paper machine. Percentage of ash relative to the weight of the used pigment in the total solid phase of the suspension is characterized fixation:

C) Optical properties

Optical properties of pigments determine the laminate.

This decorative paper impregnorium, using a modified melamine glue is pressed into the laminate. Covered with resin sheets fully immersing in melamine glue, then twice put through squeegee to ensure the application specific layer resin and, immediately thereafter, placed for pre-drying chamber in the dryer with circulating air at 130°C. a layer of resin is from 120 to 140% of the mass of leaves. The sheets had a residual moisture content of about 6 wt.%. The dried compacted sheets are pressed together with a paper base impregnated with phenolic resin, and with a white or black paper backing. For assessment of the test pigment made of 11-ply laminate: decorative paper, a white-black base paper base paper base paper base, white background, paper base paper base paper base, white-black base, decorative paper. Preparation of the laminate was pressed at the press Wickert Laminat-Presse Tour 2742 at a temperature of 140°C and a pressure of 900 N/cm2when the time pressing of 300 seconds.

The optical properties of the laminate was measured by a standard spectrophotometer.

To assess the optical properties of the laminates were determined color components of the decorative paper (CIELAB L*, -a*, -b*) according to DIN 6174 using an ELREPHO®3000 colorimeter, white and black substrate.

Opacity is a measure of the transparency or translucency of the paper. As values for the opacity of the following: CIELAB L*blackreflecting the ability of the laminate measured for the black backing paper, the opacity value L[%]=(Yblack/Ywhite)×100, is determined from the value of Y decorative paper, measured for black paper backing (Yblack), and the value Y measured for a white paper substrate (Ywhite).

Results

Table 1 shows test results of laminate. These results were obtained for pigment prepared according to the method of the present invention (example) and according to the method described in comparative experiment. The pigment obtained according to the method proposed in this invention shows improved performance on neprorachnost is relatively pigment, obtained in the comparative experiment.

Table 1
PigmentOpacityFixation
L*blackL[%][%]
Example90,3to 91.169
Example (comparative)90,190,771

1. The pigment based on titanium dioxide, containing particles of titanium dioxide having a coating layer comprising a phosphate of aluminum and aluminum oxide, wherein the layer further includes a hollow particle.

2. The pigment according to claim 1, characterized in that the hollow particles are characterized by a mean diameter of from 5 to 1000 nm.

3. The pigment according to claim 1, characterized in that the layer comprises aluminium-containing component at a content in terms of aluminum oxide (Al2About3), wt.%: 1,0÷9,0.

4. The pigment according to claim 1, characterized in that the layer includes phosphorus-containing component at a content in terms of P2O 5, wt.%: 1,0÷5,0.

5. A method of producing a pigment based on titanium dioxide, the particles of which are coated with a layer, wherein the first receive aqueous suspension of a source of titanium dioxide, then add the aluminium-containing and phosphorus-containing components, after which add hollow particles and, finally, bring the pH of the suspension to 4÷9.

6. The method according to claim 5, characterized in that when receiving a water suspension of a source of titanium dioxide and adding aluminium-containing and phosphorus-containing components maintain a pH of at least 10.

7. The method according to claim 5, wherein adding aluminium-containing and phosphorus-containing components maintain the pH of the suspension is less than 4.

8. The method according to claim 5, characterized in that it uses hollow particles characterized by an average diameter of from 5 to 1000 nm.

9. The method according to claim 5, characterized in that it further includes applying a layer of aluminum oxide at pH from 4 to 9.

10. The method according to claim 5, wherein the aluminium-containing components add to the content in terms of aluminum oxide (Al2About3), wt.%: 1,0-9,0.

11. The method according to claim 5, characterized in that the phosphorus-containing components add to the content in terms of P2O5, wt.%: 1,0÷5,0.

12. How to claim 5, characterized in that simultaneously with the addition of a suspension of aluminum is ImageReady and phosphate components in it additionally add salt solutions, such as salts of CE, Ti, Si, Zr or Zn.

13. The method according to claim 9, characterized in that it further includes bringing the pH of the suspension to 5÷8.

14. The method according to claim 5, characterized in that it at bringing the pH to 4÷9 use acidic solutions of metal salts such as salts of CE, Ti or Zr.

15. The method according to claim 5, characterized in that it further includes processing the pigment particle nitrate to nitrate content in the finished pigment from 0.05 to 0.5 wt.%.

16. The method according to claim 5, characterized in that it further includes grinding of the pigment particles by adding organic substances.

17. A method of producing a pigment based on titanium dioxide, the particles of which are coated with a layer, wherein the first receive aqueous suspension of a source of titanium dioxide at a pH of at least 10, then add the aluminium-containing and phosphorus-containing components while maintaining a pH of at least 10, then add components containing hollow particles, and then bring the pH of the suspension to 4÷9 and, finally, at pH from 4 to 9 put the aluminum oxide coating.

18. The pigment based on titanium dioxide, characterized in that it is obtained by the method according to claim 5.

19. The use of a pigment based on titanium dioxide according to any one of claims 1 or 18 as a tool in the manufacture of decorative paper.

20. Decorative paper, featuring the jaś fact, it includes a pigment based on titanium dioxide according to claim 1 or 18.

21. Use decorative paper comprising a pigment based on titanium dioxide according to claim 1 or 18, as a tool in the manufacture of decorative surface materials.

22. Decorative coating materials, characterized in that they contain decorative paper according to claim 20.



 

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FIELD: chemistry.

SUBSTANCE: invention can be used in chemical industry. The method of producing jointly ground calcium carbonate material, which contains ground calcium carbonate (GCC) and precipitated calcium carbonate (PCC) with coefficient of curvature at least equal to approximately 30, preferably at least approximately 40 and even more preferably at least approximately 45, comprises the following steps: a) obtaining at least one calcium carbonate material, optionally, in form of an aqueous suspension; b) combined grinding of GCC and PCC, optionally, with at least another mineral material which is selected from talc, clay, Al2O3, TiO2 or mixtures thereof; c) optional sieving and/or concentration of the jointly ground calcium carbonate obtained after step (b); d) optional drying of the jointly ground calcium carbonate material obtained after step (b) or (c). The coefficient of curvature is defined as d30/d70×100, where d30 and d70 denote equivalent spherical diameters, relative which 30 wt % and 70 wt % particles have a smaller size.

EFFECT: invention enables to improve optical properties of enamel paper and exclude the PCC deagglomeration step.

40 cl, 2 tbl, 4 ex

FIELD: chemistry.

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

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SUBSTANCE: to produce a precipitated calcium carbonate, a suspension of calcium hydroxide is made by mixing of quicklime with water in a reactor with a mixer or in a tank, then the produced suspension is filtered via a 100-mcm filter. The filtered suspension is sent into a reactor of stainless steel equipped with a mixer. Temperature from 10 to 70°C is set, afterwards the suspension is sent into a reactor or a tank for carbonisation, where a carbon-containing gas is bubbled through the suspension. The suspension is drained from the tank, when electric conductivity achieves the minimum level, and pH falls below 8. Coarse particles are removed at a 45-mcm filter. At the same time the carbonisation stage is carried out at speed of carbonising gas flow of below 30 litres per minute under normal conditions per kg of calcium hydroxide in process of deposition. Concentration of precipitated calcium carbonate is increased using a cationic, anionic or combined disperser under quite moderate or mild conditions, which do not cause considerable damage of aggregates/agglomerates, until concentration from 25 to 60% is achieved, preferably in the range from 35 to 50%, most preferably - from 39 to 40 wt % of hard substances.

EFFECT: invention makes it possible to produce porous stable agglomerates of precipitated calcium carbonate with size of 1-5 mcm.

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EFFECT: invention makes it possible to produce porous stable agglomerates of precipitated calcium carbonate.

22 cl, 5 dwg, 9 tbl, 12 ex

FIELD: textile fabrics, paper.

SUBSTANCE: method is related to production of coated paper or cardboard. Method includes application of pigment composition as coating on at least one side of paper or cardboard web. Specified pigment composition is water dispersion, which includes optionally aggregated colloidal particles of silicon dioxide or aluminium silicate as pigment particles, which are prepared from alkali metal silicate by ion exchange or pH reduction and having surface area of approximately from 30 m2/g to approximately 450 m2/g. Coating contains also at least one cationic component selected from group that consists of water-soluble aluminium salts and cationic polymers with molecular weight from approximately 2,000 to approximately 1,000,000 and charge density from approximately 0.2 mEq/g to approximately 12 mEq/g, in which at least approximately 0.4 g of pigment particles from pigment composition is applied on m2 of coated side of paper or cardboard web. Invention is also related to paper or cardboard produced by this method. It is also related to composition of above mentioned pigment in the form of water dispersion, which includes less than approximately 3 wt % of organic binders and to method of above mentioned pigment composition production, in which mixing is done to produce water dispersion in order to avoid gel formation and deposition.

EFFECT: improvement of printing and strength properties of coating, and also lower scuffing of paper.

26 cl, 5 tbl, 4 ex

FIELD: textiles; paper.

SUBSTANCE: composition is designed for refining fibrous material, can be used in the production of enamelled cardboard and paper and relates to the cellulose-paper industry. The composition contains a modified pigment and a water soluble binding substance. The pigment is calcium sulfoaluminate, modified starch or polyvinyl alcohol with mass ratio content of 0.5-1.5. The water soluble binding substance is starch.

EFFECT: resistance to fluffing and whiteness of the coating with considerable lowering of consumption of the binding substance when making the composition.

1 tbl

FIELD: textiles, paper.

SUBSTANCE: solution is meant for rifining of fibrous material. It pertains to the field of paper manufacturing and cardboard during manufacturing of chalk-overlay types of cardboard and paper. The solution consists of water soluble binder. A mixture of calcium salfoaluminate and kaolin, modified starch or polyvinyl spirit is used as the pigment. The technical result is high stability to picking, whiteness, colour perception and smoothness. The solution enhances adhesion of the coating to the base (cardboard or paper), which makes it possible to use the refined coating as a sub-layer when dual or tri-coating cardboard or paper, with obtaining products with a given range of characteristics.

EFFECT: obtaining of a solution for refining material for production of paper and cardboard during production of chalk-overlay types of cardboard and paper.

1 tbl, 1 exr

FIELD: light industry; composition of decorative coats for wallpaper; manufacture of pearly ink for intaglio printing on wallpaper.

SUBSTANCE: composition of proposed printing ink for wallpaper contains 16-16.5 mass-% of pearly pigment; 12-12.5 mass-% of ethyl alcohol; 46-46.4 mass-% of binder - acrylic latex of butyl acrylate copolymer (19-21%) and methacrylic acid (10-12%) and water; copolymer acrylic latex is produced by method of radiation emulsion polymerization of butyl acrylate, vinyl acetate and methacrylic acid under action of ionizing radiation at dose rate of 0.05-0.1 g/s to absorbed doses of 1.5-2 kgr.

EFFECT: avoidance of lamination of ink; easily washable ink; enhanced heat resistance of ink.

1 tbl, 2 ex

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: chemistry.

SUBSTANCE: method of obtaining at least one inorganic substance and/or at least one pigment containing natural and/or precipitated calcium carbonate, preferably natural, simultaneously partially organophilic and partially hydrophilic, comprises the following steps: a) obtaining at least one inorganic substance and/or at least one pigment containing natural and/or precipitated calcium carbonate, preferably natural, in dry form or in form of aqueous dispersion and/or suspension, b) if needed, dry grinding and/or grinding in aqueous medium of the inorganic substance and/or pigment obtained at step a), c) treating the inorganic substance and/or pigment obtained at step a) and/or step b), d) if needed, drying the inorganic substance and/or pigment obtained at step a) and/or b) and/or c). Step c) corresponds to a step for mixing in aqueous medium and/or grinding in aqueous medium and/or concentration in aqueous medium of the inorganic substance and/or pigment obtained at step a) and/or step b) in the presence of at least one ethylene acrylic acid salt. A dispersant and/or grinding agent is added before and/or during the treatment step c).

EFFECT: invention enables to increase content of dry substance in calcium carbonate suspensions while maintaining satisfactory viscosity without formation of agglomerates.

67 cl, 1 tbl, 1 ex

FIELD: textile, paper.

SUBSTANCE: method includes moistening pulp lap with water solution of sodium salt of carboxymethylcellulose (NaCMC), included into composition of the paste made of a filler (chalk), mixed with a solution of NaCMC at the filler ratio of NaCMC equal to 100:(1-2). Production of moisture-saturated air suspension of fibres with filler from it. Forming a fibrous later on a shaping mesh. Moistening of a fibrous layer between two clothes, pressing and drying of a paper leaf. The filler is added as a paste, which contains 30% of dry substance. Moistening of a fibrous layer prior to pressing is carried out with a starch solution with concentration of 0.7-1.3%.

EFFECT: increased retention of filler in paper at simultaneous increase of paper strength index.

3 cl, 1 tbl, 4 ex

FIELD: textile, paper.

SUBSTANCE: method of filler treatment includes formation of a mixture of an aqueous suspension of filler and aqueous anion latex. The latter is a dispersion of acrylic polymer with vitrification temperature (T v) from - 3 to 50°C. This mix is mixed with water at the temperature that is higher than T v of latex, at the same time the specified water has temperature of 40-98°C. The specified suspension of the filler comprises a solid disperse filler selected from the group containing kaolin clay, ground calcium carbonate, deposited calcium carbonate, deposited calcium sulfate, talc and mix of two or more of them. The specified acrylic polymer is selected from the group containing copolymers n-butylacrylate-acrylonitrile-sterol and copolymers n-butylacrylate-sterol. The aqueous composition of the filler contains the solid dispersed filler specified above with solid particles of anion latex polymer specified above and adsorbed on them, in aqueous carrier. The treated filler contains the solid dispersed filler specified above with solid particles of anion latex polymer specified above and adsorbed on them. The pulp charge contains pulp fibres and the solid dispersed filler specified above with solid particles of anion latex polymer specified above and adsorbed on it, in aqueous carrier. Method to make paper from the above specified pulp charge containing pulp fibres. The paper product made of pulp fibres and solid disperse filler, where the specified filler has solid particles of anion latex polymer specified above absorbed on it, with size of solid polymer particles of 30-200 nm and in amount of 1-100 kg of latex per 1 t of filler relative to dry mass of solid substances of latex and filler, and the specified filler has average size of particles of 0.1-30 mcm.

EFFECT: improved retention of the filler, continuous execution of the filler treatment method to improve fixation of anion latex on the filler for a short period of time due to irreversible fixation of anion latexes on particles of the filler and time stability of aggregated filler suspension, latex-treated deposited calcium carbonate is more acid-resistant, and when used to make paper from wood mass under neutral conditions less acid is required to control pH.

21 cl, 14 dwg, 8 ex

FIELD: textile, paper.

SUBSTANCE: method includes dissolution of cellulose and its grinding down to specified extent of grinding. Preparation of the first dispersion with application of return water, containing fibres of microcrystal cellulose, produced by its grinding in mixture with titanium dioxide and calcium hydroxide in specified amount. The second dispersion is prepared from cellulose fibres with application of return water. Then the first suspension is mixed with the second, and produced mixture is treated with carbon dioxide. In case of this treatment calcium hydroxide under action of carbon dioxide results in production of chemically deposited chalk and production of paper mass at specified ratio of components. Grinding of microcrystalline cellulose in mixture with titanium dioxide and calcium hydroxide is carried out in vibration mill with provision of impact and wear effect at mixture.

EFFECT: increased extent of fillers retention in paper, improvement of its printing properties, provision of possibility to vary bulk and porosity of paper, provision of possibility to use fully closed cycle of return water.

1 tbl, 8 ex

FIELD: medicine.

SUBSTANCE: described is material for application in wound care. Material is made in form of fibrous base with applied on it functional coating, which contains polyvinyl alcohol with degree of water absorption up to 2100%, carnon-modified aluminium oxide with specific surface area up to 300cm2/g, as well as sodium-carboxymethylcellulose as binding agent. From the side of coating material is provided with atraumatic material which ensures non-adherence of material to wound.

EFFECT: improvement of therapeutic and preventive care.

2 cl, 1 tbl

Paper filler // 2345189

FIELD: textile, paper.

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

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

24 cl, 3 tbl, 4 ex

FIELD: textiles; paper.

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

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

FIELD: papermaking industry.

SUBSTANCE: paper is produced from matrix obtained from composition containing pulp fibers, filler particles and retention system for said filler based on composition comprising complex of granules of ionic non-destructed swelled starch and ionic latex in aqueous carrier. Said composition contains from 60% to 95% by weight of said granules and form 40% to 5% by weight of latex of total 100 wt% on the basis of total content of solid substances of granules and latex. Granules are latex particles carriers in said complex. Processing of carrier involves producing composition of swelled starch-latex prepared in the presence of combined-action admixture or in the absence thereof, and adding said composition to filler suspension for producing of paper having improved retention of filler and allows paper to be produced, which contains filler wherein filler admixture produces minimal negative effect upon strength characteristics. Starch-latex composition may be used with compositions free of wood or with wood-containing compositions. Processed filler is readily retained in paper web in the process of paper making, improves dehydration and creates well-formed sheets. Sheets manufactured with the use of processed filler have higher adhesion strength and tensile strength as compared to sheets containing filler processed with the use of only swelled starch or only latex.

EFFECT: improved quality of paper produced with the use of starch-latex composition.

41 cl, 4 dwg, 4 tbl, 4 ex

FIELD: pulp and paper industry; methods of production of the pigment for manufacture of the cardboard and paper.

SUBSTANCE: the invention is pertaining to the method of production of the pigment for manufacture of the cardboard and paper and may be used in pulp and paper industry at production of the filled paper, the coated paper and the cardboard. Calcium carbonate is treated with aluminum sulfate in the aqueous medium. The treatment is conducted at aluminum sulfate consumption of 25-105 % to the mass of absolutely dry calcium carbonate at the temperature of 80-85°С during 90-180 minutes with production of the suspension containing 25-35 % dry substances in it. The suspension may be additionally dried and to produce the powder. The technical result of the invention is improvement of the pigment quality and expansion of the field of its application.

EFFECT: the invention ensures improvement of the pigment quality and expansion of the field of its application.

2 cl, 2 tbl

FIELD: pulp and paper industry; methods of production of the pigment for manufacture of the cardboard and paper.

SUBSTANCE: the invention is pertaining to the method of production of the pigment for manufacture of the cardboard and paper and may be used in pulp and paper industry at production of the filled paper, the coated paper and the cardboard. Calcium carbonate is treated with aluminum sulfate in the aqueous medium. The treatment is conducted at aluminum sulfate consumption of 25-105 % to the mass of absolutely dry calcium carbonate at the temperature of 80-85°С during 90-180 minutes with production of the suspension containing 25-35 % dry substances in it. At that they use the aqueous medium containing the binding chosen from the group, which includes starch and polyvinyl alcohol in the amount of 0.5-3.0 mass % from the mass of the absolutely dry pigment, and-or the water soluble colorant in the amount of 0.1-0.5 mass % from the mass of the absolutely dry pigment. The suspension is additionally dried and grinded. The technical result of the invention is the improved quality of the pigment as well as expansion of its field of application.

EFFECT: the invention ensures the improved quality of the pigment as well as expansion of its field of application.

2 tbl

FIELD: chemistry.

SUBSTANCE: invention can be used in chemical industry. The method of producing jointly ground calcium carbonate material, which contains ground calcium carbonate (GCC) and precipitated calcium carbonate (PCC) with coefficient of curvature at least equal to approximately 30, preferably at least approximately 40 and even more preferably at least approximately 45, comprises the following steps: a) obtaining at least one calcium carbonate material, optionally, in form of an aqueous suspension; b) combined grinding of GCC and PCC, optionally, with at least another mineral material which is selected from talc, clay, Al2O3, TiO2 or mixtures thereof; c) optional sieving and/or concentration of the jointly ground calcium carbonate obtained after step (b); d) optional drying of the jointly ground calcium carbonate material obtained after step (b) or (c). The coefficient of curvature is defined as d30/d70×100, where d30 and d70 denote equivalent spherical diameters, relative which 30 wt % and 70 wt % particles have a smaller size.

EFFECT: invention enables to improve optical properties of enamel paper and exclude the PCC deagglomeration step.

40 cl, 2 tbl, 4 ex

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