Titanium dioxide based pigment (versions), method for production thereof, methods of making decorative paper and coating materials, decorative paper, decorative coating material and liminate

FIELD: chemistry.

SUBSTANCE: titanium dioxide based pigment contains titanium dioxide particles in rutile form, having a coating. The coating contains aluminium phosphate, aluminium oxide, titanium oxide and silicon oxide. The particles are characterised by specific surface area, calculated according to a Brunauer-Emmet-Teller (BET) equation, of at least 15 m2/g. To obtain coated pigments, an aqueous suspension of uncoated titanium dioxide particles is prepared first, followed by addition of aluminium-containing and phosphorus-containing components. Further, while maintaining pH 4-9, an alkaline silicon-containing component and at least one pH regulating component, one of which is an acidic titanium-containing component, are then added. The formed suspension is then filtered, washed and dried and the precipitate is ground to obtain coated particles.

EFFECT: invention increases opacity of decorative paper.

22 cl, 5 ex, 1 tbl

 

The technical field to which the invention relates.

The invention relates to a pigment based on titanium dioxide with high opacity, as well as to the method of its production and application in the production of decorative paper or decorative foil.

The level of technology

Decorative paper or decorative foil are the main 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 stove. 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 others the x naprotechnology (opacity), lightfastness (resistance to darkening), color stability, moisture resistance, and ability to the application and printing properties.

The validity of the new method of producing 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 (cellulose, pigment, auxiliary and additional substances, water) between favorable for receiving paper and is determined by this parameter, as the retention of pigment. Under the retention 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 in a mixture of cellulose/fiber.

It is known that one of potamosiren improved opacity is a special modification of the surface of particles of a pigment based on titanium dioxide.

In EP 0713904 B1 described surface treatment, in which the first layer of oxyphosphate aluminum is etched in an acidic environment at pH 4 to 6, and the second layer of aluminum oxide is precipitated at pH 3 to 10, preferably at pH of about 7. Improvement in retention is achieved by a third layer of magnesium oxide so that the resulting pigment is characterized by the following one behind the other layers of oxyphosphate aluminum, aluminum oxide and magnesium oxide.

In the application DE 10236366 A1 describes a method of modifying the surface of a pigment based on titanium dioxide, which initially allowed to precipitate phosphorus, titanium and aluminium-containing components, and then when the pH from 8 to 10 precipitated magnesium-containing component. These pigments show improved light-fastness and high opacity.

In the application DE 10332650 A1 describes a method of modifying the surface of a pigment based on titanium dioxide, in which the aluminum and phosphorus components contribute in a certain number of modifications to the suspension of TiO2when the pH is at least 10, and then produce precipitation at pH less than 9. This method improves retention at the same opacity.

In U.S. patent No. 6200375 described pigment based on titanium dioxide, which is resistant to weathering, for exterior coatings, and surface particles include successive layers: the Hydra is xed zirconium, the titanium hydroxide, phosphate or oxide of silicon and oxyhydrate aluminum.

Disclosure of inventions

The objective of the present invention to provide decorative paper, which in comparison with existing analogues will have increased opacity. The invention also consists in the improvement and development of the method of obtaining dioxide-titanium pigments, which would provide a high opacity.

The task can be solved through the application dioxide-titanium pigment, the particles of which have a modified surface. Modifying the coating contains aluminum phosphate, aluminum oxide, titanium oxide and silicon oxide, the specific surface of which is calculated by the equation of brunauer-Emmett-teller (BET), is at least 15 m2/year

In a preferred embodiment, the modifying coating pigment contains 1,09,0 wt.% aluminum, in terms of aluminum oxide (Al2O3), 1,05.0 wt.% phosphorus, in terms of P2O5, 0,15.0 wt.% silicon oxide (SiO2) and 0.16.0 wt.% titanium oxide (TiO2).

A further challenge lies in the implementation of the method of obtaining dioxide-titanium pigment and includes the following stages:

a) receiving water suspension is not covered with a film of particles of titanium dioxide,

b) adding aluminum is the third - and phosphorus-containing components,

C) adding an alkaline silicon and at least one pH-regulating component, and as a pH-regulating component use acidic reaction of such component, and the pH of the suspension regulate in the range from 4 to 9.

In one embodiment, the present invention relates to a decorative paper containing particles dioxide-titanium pigment with modifying coating.

In yet another embodiment, the present invention provides for the use of dioxide of titanium pigment with modifying coating in the manufacture of decorative paper.

Further variants of the invention described below.

The implementation of the invention

Hereinafter, the term "oxide" is implied oxide containing water, that is, respectively, - hydrate. All subsequent data on pH, temperature, concentration in mass % volume % cover all values that lie in the area of the respective accuracies of the measurements.

The designation of "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.

According to the invention as titanium-dioxide pigment, prepact the tion of such mineral as rutile (TiO2). Its peculiarity is that the surface of its particles have a layer of aluminum - phosphorus - and silicon-containing compounds.

Speaking of silicon-containing compounds, referring to silicon oxide and/or, optionally, silicon titanate.

The combination of silicon and titanium components on stage) process leads to deposition in a friable form that results in high specific surface according to BET of at least 15 m2/g, preferably from 20 to 60, in particular from 20 to 35 and excellent opacity. Acidic titanium containing component in this case contributes to the process.

According to the invented method on the surface of particles of titanium dioxide precipitated layer of aluminum-, phosphorus - and silicon-containing compounds, hereinafter regarded simplistically as a mixed layer. First add the aluminum and phosphorus components in the suspension of TiO2and pH can be acidic and alkaline.

Then add alkaline silica-containing component and an acidic reaction titanium containing component and the selected at least one pH-regulating component in any order or all together to the slurry so that the pH was in the range of 4 to 9, and so fell mixing layer on the surface of the particles.

Method of surface modification according to the invention envisage the included water, preferably wet grinding TiO2(stage a)).

Wet grinding is carried out at the necessity of using a dispersant.

When wet grinding is not surface modification.

Under TiO2mean particles of titanium dioxide, that is, the particles of the basic substance (TiO2)obtained sulphate (SP) or chloride (CP) method.

Base material (TiO2) chloride (CP) method is usually stabilized by the addition of aluminum in the amount of 0.33 wt.% in terms of Al2O3and 215% excess oxygen in the oxidation of titanium tetrachloride to titanium dioxide. In sulfate (SP) method, the stabilization is carried out by adding certain impurities, such as, for example, Al, Sb, Nb or Zn.

Preferably use rutile, especially obtained in the chloride method.

The process of surface modification is conducted preferably at temperatures below 80C. the most preferred temperature range 5565C. the Suspension at the stage a) can have both alkaline and acidic.

At the stage b) add the aluminum and phosphorus components.

Suitable aluminium-containing component for surface modification according to the invention is acidic or alkaline water-soluble salt, such as sodium aluminate, aluminum sulfate, aluminum nitrate, chlorine is d aluminium acetate of aluminum, etc. should Not assume that this list is limited listed representatives. Aluminium-containing component should be added in quantities of 19 wt.%, more preferably 1,54,5 wt.% in terms of Al2O3regarding the number of TiO2. Suitable phosphorus-containing components are inorganic compounds such as ammonium phosphate, polyphosphates, phosphoric acid, etc. should Not assume that this list is limited listed representatives. Particularly suitable is dvuhkamernyi sodium phosphate or phosphoric acid. The amount of added phosphorus-containing component (in terms of P2O5regarding the number of TiO2) is 15 wt.%, more preferably 1,54 wt.%.

At the stage b) add alkaline silica-containing component and an acidic titanium containing component and the at least one component that regulates the pH so that the pH was 49, predominantly 46, particularly preferably about 5. Under alkaline silica-containing component understand silicates of sodium and potassium. Adds 0.15 wt.%, preferably 13 wt.% SiO2regarding the number of TiO2.

Under acidic titanium-containing component understand oxychloride titanium or oxysulfate titanium. Adds 0,16 wt.% in terms of n is TiO 2regarding the number of uncovered TiO2. Component regulating the pH value, can be acid or alkali. The acid can be used, for example, sulfuric acid, hydrochloric and phosphoric acid or other suitable acid. Alternatively, the acid may be used the corresponding acid salt such as aluminum sulfate.

One should not assume that this list is limited listed representatives. As the alkali, preferably using sodium hydroxide. Apply salt having an alkaline reaction. Suitable connections, regulating pH.

Turned out to be favorable, at the next stage (d) mixed layer is applied a film of aluminum oxide, so that the pH value was maintained in the field 49 one of the following ways:

- parallel addition of alkaline and acidic aluminium-containing component (for example, sodium aluminate and aluminum sulfate);

- parallel addition of aluminium-containing alkaline component such as sodium aluminate and acid, for example sulphuric acid or hydrochloric acid;

- parallel addition of acidic aluminium-containing component, such as, for example, aluminum sulfate with alkali, such as NaOH.

The components can be added so that p is derivate constant pH in the range 49. Or components may be added in combination to the pH value was changed in the field 49. This method is known in the art. For the regulation of pH suitable alkali or acid (e.g., NaOH and H2SO4), or alkaline or acid solutions of salts (for example sodium aluminate and aluminum sulfate). It should be emphasized that the pH is in the implementation stage) constant support. If necessary, apply the final stage d) regulating the pH in the range 6+7 alkalis or acids (for example, NaOH or H2SO4) or alkaline or acidic solutions of salts, such as sodium aluminate and aluminum sulfate.

The amount of aluminium-containing component used in the stages C), d) and e) in terms of Al2O3must be taken into account already at the stage b).

Total aluminium-containing components in terms of Al2O3preferably should be 19 wt.%, even more preferably 2 to 8 wt.%, and particularly preferably 3% to about 6.5 wt.% by weight not covered with particles of TiO2.

You should also consider used in stage b) the amount of the phosphorus-containing component, in terms of P2O5accordingly, in the stages C) and d).

Total phosphorus-containing component, in terms of P2O5preferably should be 15 wt.%, even more preferred the equipment 1,54 wt.% by weight not covered with particles of TiO 2.

The peculiarity of the process, as claimed in the invention consists in the fact that they did not use significant amounts of Zr and CE-containing components. As a rule, there is no need to expose the surface of the pigment of the final heat treatment at a temperature of >200C.

The peculiarity of the process, as claimed in the invention is that the use of alkaline suspension of TiO2. To do this on stage a) first, using a suitable alkaline component, such as NaOH, set the pH value of at least 10.

This procedure (alkalizing) is carried out at the wet grinding, the best option is to grind. At the stage b) to a suspension sequentially add the aluminum and phosphorus components, in each case in the form of aqueous solutions.

When adding components, the pH of the suspension support is not lower than 10, preferably not lower than 10.5, particularly preferably 11.

As alkaline aluminium-containing component particularly suitable is sodium aluminate. Mean acidic aluminium-containing reagent, such as aluminum sulfate, together with which type suitable alkaline component, such as NaOH is required to neutralize the acidic effect and to maintain a pH of not lower than 10. Suitable alkaline compounds that support pH not lower than 10, and necessary to the number of well-known specialists.

In the case of phosphorus-containing component, adding which leads to a decrease of pH below 10, was also required to neutralize the acidic effect of adding an alkaline component, such as NaOH. Specialists are well known suitable alkaline compounds and their necessary quantity to maintain a pH of not lower than 10. The aluminum and phosphorus components can be added to the suspension in any order, simultaneously or sequentially.

At the stage b) type alkaline silica-containing component and an acidic titanium-containing component and, optionally, a component for regulating the pH, so to bring it up to 49.

The addition of silicon-containing and acidic titanium containing components, as well as other regulating pH of the components may be carried out sequentially or simultaneously, or in several stages in any order.

As the silicon-containing component is preferably used silicates of sodium or potassium.

As the titanium containing component preferably use oxalicacid titanium.

As an additional acid component preferably using hydrochloric acid.

In an alternative embodiment of the method according to the invention modify the surface in an acidic environment. At stage b) is dobavlaut such aluminum and phosphorus components, thereafter the pH of the suspension was less than 4.

The specialist may choose to lower the pH or by using a suitable acid already at the stage a), or by using an appropriate combination of components, adding acid only when necessary - so that the pH does not exceed 4. Examples of suitable combinations are: phosphoric acid, and sodium aluminate or centripetal Na2HPO4and aluminum sulfate.

Components can be supplied in suspension in any order, or simultaneously. At the stage b) type alkaline silica-containing component, preferably sodium silicate or potassium, and then the acidic titanium containing component, preferably oxalicacid titanium.

If necessary, add the regulating pH of the component to bring the pH to 49.

Add components to stage C) can be carried out sequentially or simultaneously, as well as in several stages in any order.

Depending on the amount, method and sequence added component on the stage) the pH of the suspension may briefly increase to 9 and above.

Subjected to surface modification of pigment TiO2allocate the known methods of filtration of the suspension, and the obtained residue on the filter is washed to remove soluble salts. In washed on the filtered pasta before, during or at the end of drying, you can add a little 0,051,0 wt.% (in terms of NO3) nitrosoureas compounds for improving the light fastness of the pigment in the laminate. As nitrosoureas compounds are suitable, for example, KNO3, NaNO3AI(NO3)3. In the final grinding, for example, in a ball mill for pigment may be added organic compound from a number of substances commonly used in obtaining pigment TiO2and well known in the art, such as a polyalcohol (trimethylolpropane).

Alternative, instead of adding nitrosoureas compounds prior to or during drying can add these compounds during grinding.

The pigment obtained by this method is characterized by increased opacity relative to the reference sample and is perfect for making decorative paper.

Another distinctive feature of the claimed invention of the pigment is titanium dioxide that when a certain quantity of precipitated TiO2or SiO2at the stage b) or Al2O3in stage d) can be achieved isoelectric point (IEP).

Isoelectric point is the pH of the aqueous suspension of the pigment in which the surface charge of the pigment particles is approximately equal to zero.

Thus, it is possible to displace the surface charge of the particles is of egment, claimed in the invention, both positive and negative, depending on the needs of the method of producing paper. Method of surface modification of pigment particles according to the invention is usually carried out as a periodic process.

It is also possible to make a modification in a continuous mode using suitable mixing devices known in the art. This should be guaranteed the necessary mixing.

Examples

The following are examples of implementation, leading to a better understanding of the present invention.

Example 1

In the crushed state of the sand suspension of TiO2-rutile, chloride obtained by the method with the concentration of TiO2350 g/l at 60was added NaOH to pH=10. With stirring, was added sodium aluminate, up to 3.5 wt.% (in terms of Al2O3). Was stirred for 10 minutes Under stirring was added 2.4 wt.% (in terms of P205) solution dinitrigenoxide. Was stirred for another 10 minutes At the next stage, to the suspension was added oxalicacid titanium (respectively 3.0 wt.% in terms of TiO2) and sodium silicate, 2.4 wt.% (in terms of SiO2). Watched raising the pH to 5. While SiO2added in two stages - 1.2 wt.% SiO2and the first portion of dobavlyala at pH of 10.5, and the second at pH=7 with doba the population of oxalicacid titanium. Was stirred 10 min and was added sodium aluminate 1.9 wt.% (in terms of Al2O3), were simultaneously added a solution of HCl, - maintaining the pH between 5. The suspension was stirred 30 min, then was added alkaline sodium aluminate solution, maintaining the pH between about 5.8 to. The suspension was filtered and washed to remove soluble salts. The washed and filtered paste was dried in a stacked dryer and crushed in a ball mill.

Specific surface area of the obtained pigment on BET - 32 m2/g, isoelectric point at pH=5,2.

In the manufacture of paper electrokinetic potential of finely dispersed suspension was maintained in the range from +16 mV to -12 mV by the addition of water repellent products.

Example 2

In the crushed state of the sand suspension of TiO2-rutile, chloride obtained by the method with the concentration of TiO2350 g/l, was added at 60 NaOH to pH 10. With stirring, was added sodium aluminate, in the amount of 3.5 wt.% (in terms of Al2O3). Was stirred 10 min and was added to 2.4 wt.% (in terms of P2O5) intrigejosa in the form of a solution. Was stirred for another 10 minutes At the next stage, to the suspension was added oxalicacid titanium (respectively 2.8 wt.% in terms of TiO2), the pH of the solution was 5. Then were added to 1.2 wt.% (in terms of n the SiO 2) of sodium silicate. Was stirred for 10 minutes and brought the pH to 5 with hydrochloric acid. Then added sodium aluminate 1.9 wt.% (in terms of Al2O3)while maintaining a pH=5 by addition of HCl solution. The suspension was stirred 30 min, then was added alkaline sodium aluminate solution to approximately pH to 5.8. The suspension was filtered, washed to remove soluble salts. The washed and filtered paste was dried in a stacked dryer and crushed in a ball mill.

Specific surface area of the obtained pigment on BET - 26 m2/g, isoelectric point at pH of 6.0. In the manufacture of paper Zeta-potential of finely dispersed suspension supported range from +18 to -14 mV mV by adding (if necessary) water repellent products.

Example 3

Analogously to example 2, except that sodium silicate (respectively 2.4 wt.% in terms of SiO2) was added to the suspension before adding oxalicacid titanium (respectively 3.0 wt.% TiO2). Specific surface area of the obtained pigment on BET - 30 m2/g, isoelectric point at pH=5,9. In the manufacture of paper Zeta-potential of finely dispersed suspension was maintained in the range of +12 mV to -16 mV by adding (if necessary) water repellent products.

Example 4

Analogously to example 3, except that FR is used to 1.2 wt.% SiO 2and 2.9 wt.% TiO2.

Specific surface area of the obtained pigment on BET - 27 m2/g, isoelectric point at pH of 6.2.

Example 5

Analogously to example 3, except that he used to 0.6 wt.% Si02and 2.9 wt.% TiO2.

Specific surface area of the obtained pigment on BET - 26 m2/g, isoelectric point at pH of 6.4. In the manufacture of paper Zeta-potential of finely dispersed suspension was maintained in the range of +12 mV to -16 mV by adding (if necessary) water repellent products.

Comparative example 1

In the crushed state of the sand suspension of TiO2-rutile, chloride obtained by the method with the concentration of TiO2350 g/l at 60, was added NaOH to pH=10. With stirring was added a solution of sodium aluminate to 2.0 wt.% (in terms of Al2O3). Was stirred 10 min and was added to 2.4 wt.% (in terms of P2O5) intrigejosa in the form of a solution. Was stirred for another 10 minutes At the next stage, to the suspension was added aluminum sulfate (respectively, 2.6 wt.% in terms of Al2O3), the pH value when=5. Then simultaneously added to the solution of aluminum sulfate and sodium aluminate, and the concentration of aluminum (in terms of Al2O3) 0.8 wt.% and pH=5. An acidic suspension was stirred 30 min, then was added to the alkaline solution of aluminate NAT the Oia to a pH of approximately 5.8.

The suspension was filtered and washed to remove soluble salts. The washed and filtered paste was dried in a stacked dryer and crushed. Specific surface area of the obtained pigment on BET - 12 m2/g, isoelectric point at pH of 6.0. In the manufacture of paper Zeta-potential of finely dispersed suspension was maintained in the range from +16 mV by adding (if necessary) water repellent products. The negative Zeta-potential leads to insufficient water resistance of paper.

Comparative example 2

In the crushed state of the sand suspension of TiO2-rutile, chloride obtained by the method with the concentration of TiO2350 g/l at 60, was added NaOH to pH=10. With stirring, to the suspension was added to 2.0 wt.% (in terms of Al2O3), the sodium aluminate solution. Was stirred 10 min and was added to 2.4 wt.% (in terms of P2O5) intrigejosa in the form of a solution. Was stirred for another 10 minutes To the suspension was added 1% SiO2in the form of sodium silicate. At the next stage, to the suspension was added a solution of aluminum sulfate (2.7 wt.% in terms of Al2O3) to pH=5. Then simultaneously added a solution of aluminum sulfate and sodium aluminate, and the concentration of aluminum (in terms of Al2O3) to 0.8 wt.% and pH=5.

An acidic suspension was stirred 30 min, after which we use and alkaline sodium aluminate solution to a pH of approximately 5.8.

The suspension was filtered and washed to remove soluble salts. The washed and filtered paste was dried in a stacked dryer and grinded in a ball mill. Specific surface area of the obtained pigment on BET - 12 m2/year

Test methods

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. This produced sheets of decorative paper with a density of sheet 80 g/m2and ash content of 30 g/m2.

Sheets of decorative paper produced in two different ways.

According to the so-called "one-step method for the manufacture of sheets at the same time was dispersible in water analyzed pigment, cellulose and standard water repellent agent. Then spent the formation of the sheet. Such technique known in the art. Was added so many hydrophobic means that the Zeta-potential of finely dispersed suspension, measured at the device Mutek COMMANDER-06, was in the range of from +10 mV to +20 mV.

According to the so-called "separate ways" in the beginning was crushed pulp and pre-selected quantity of water repellent products. Analyzed pigment was added and dispersively only after some time delay. Then spent four is the key sheet. This technique is also known in the art.

The required number of water repellent products expected for a special experience, based on the value of the Zeta potential of the dispersed suspension. For this purpose in the water grinds the specified number of cellulose and titanium-dioxide pigment. After this was added so many hydrophobic means that the Zeta-potential of finely dispersed suspension was in the range of -10 mV to -20 mV. The amount of used water repellent products suitable for both methods and typically ranged from 1 to 4% water repellent products (active substance) in terms of cellulose (kiln dried). Then the sheet was determined by the content of titanium dioxide (ash) and the ability of a pigment to resist.

a) Ash content

To determine the content of titanium dioxide, of a hinge made of paper turned to ash in a device for determining the ash content of paper with rapid heating up to 900C. Knowing the loss of mass was determined by mass fraction of TiO2(ash) wt.%. To calculate the ash content was used in the following formula:

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

b) Optical properties

The optical properties of the pigment was determined on the example of the laminate. This decorative paper impregnated modified melaminovoi resin and received the laminate is pressed.

Resin-impregnated sheet is fully immersed in a solution of melamine resin, and then stretched between two reklame (to ensure the application of resin) and immediately after this was allowed to dry at 130C in a chamber dryer air circulation. The resin was applied in a quantity of 120140% of the weight of the original sheet. The sheet contained traces of moisture, about 6 wt.%. Multi-layer laminate was obtained by gluing together impregnated with phenol-formaldehyde resin sheets and white/black sheets of substrate.

The test pigment was evaluated on the example of 11-ply laminate: decorative paper, white/black background, sheet, sheet, sheet, white background, sheet, sheet, sheet, white/black background, decorative paper. Package extruded on the press Wickert Laminat-Presse Tour 2742 at a temperature of 140C and a pressure of 900 N/cm2when the time pressing of 300 seconds.

Measuring optical properties of a laminate produced using 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.

Matte is the amount of transparency or translucency of the paper. As values for the opacity of the following: CIELAB L*black; reflective sposobnostey, measured for black paper backing; opacity L [%]=(Yblack/Ywhite)100, which was determined from the value Y of decorative paper, measured for black paper backing (Yblack), and the value Y measured for a white paper substrate (Ywhite).

c) Specific surface area calculated by BET equation

The BET surface measured on the device Tristar 3000 der Fa. Micromeritics based on statistical volumetric principle.

d) Isoelectric point

The measuring method is based on the determination of the electrophoretic mobility of the pigment particles in the electrolyte solution when applying the electric field.

Analyzed pigment was dispersible in 0.01 M aqueous solution of KCL. Then determined the nature of changes in Zeta-potential of the sample depending on the pH of the instrument Zetasizer 3000 HSA der Fa. Malvern.

Isoelectric point characterizes the pH at which the Zeta-potential vanishes.

The results of the study

Table
PigmentBETopacity (+)
[m2/g]L*black L [%]L*blackL [%]
Example 13290,791,990,892,2
Example 22690,491,590,892,3
Example 33090,5to 91.690,892,2
Example comparison 11290,291,0----
Example of comparison 21290,391,0NiNi
(+) Zeta-potential tonkodispersnoe suspension is positive
(-) Zeta-potential of finely dispersed suspension is negative
--not achieved sufficient water resistance of paper
Ni is not measured

Samples of the pigments obtained in this invention in examples 1, 2 and 3, demonstrate superior opacity and a large amount of surface on BET, relative to the pigment of comparison, the receipt of which is described in the examples for comparison 1 and 2.

The pigments obtained in examples 1, 2, or 3, 4, 5, furthermore, demonstrate that the increase in the content of SiO2in the surface coating of the pigment particles shifts the isoelectric point in the direction of decreasing pH.

In contrast to the pigment obtained in comparative example 1, the pigments obtained according to the method of the present invention with the addition of a certain quantity of water repellent products you can get both positive and negative Zeta-potential.

1. The pigment based on titanium dioxide, containing particles of titanium dioxide in the rutile containing coating, wherein the coating includes aluminum phosphate, aluminum oxide, titanium oxide and silicon oxide, and particles are characterized by specific surface area, calculated according to the equation of brunauer-Emmett-teller (BET), a component of at least 15 m2/year

2. The pigment according to claim 1, characterized in that the aluminium content in the coating is 1,09,0 wt.%, in terms of aluminum oxide (Al2O3).

3. The pigment according to claim 1, the best of the decomposing those the phosphorus content in the coating is 1.05.0 wt.%, in terms of P2O5.

4. The pigment according to claim 1, characterized in that the coating includes 0,15.0 wt.% silicon oxide (SiO2).

5. The pigment according to claim 1, characterized in that the coating includes 0,16.0 wt.% titanium oxide (TiO2).

6. The pigment according to claim 1, characterized in that it is characterized by specific surface area, calculated according to the BET equation, representing 2060 m2/year

7. A method of obtaining a coated pigment according to claim 1, wherein the first receive aqueous suspension of uncoated particles of titanium dioxide, then add the aluminium-containing and phosphorus-containing components, and then while maintaining the pH from 4 to 9 add alkaline silica-containing component and at least one component, regulating pH, as one of them use acidic titanium containing component, with formation of a suspension of coated particles of titanium dioxide, then filter the resulting suspension with the formation of sludge covered with particles of titanium dioxide, and then washed, dried and pulverized precipitate to obtain coated particles.

8. The method according to claim 7, characterized in that upon receipt of a suspension of uncoated particles of titanium dioxide and adding aluminium-containing and phosphorus-containing components maintain a pH of at least 10.

9. The method according to claim 7, different is the present, that it additionally includes applying a layer of aluminum oxide while maintaining the pH from 4 to 9 by adding an alkaline aluminium-containing component and an acidic aluminium-containing component or alkaline aluminium-containing component and acid.

10. The method according to claim 9, characterized in that it further includes bringing the pH to about 67 alkali or acid, or alkaline or acidic salt solution.

11. The method according to claim 10, characterized in that it aluminium-containing component is added to the content of 1,09,0 wt.%, in terms of aluminum oxide (Al2O3).

12. The method according to claim 10, characterized in that it phosphorus-containing component is added to the contents of 1.05.0 wt.%, in terms of P2O5.

13. The method according to claim 7, characterized in that it silicon-containing component is added to a content of 0.1 to 5.0 wt.%, in terms of silicon oxide (SiO2).

14. The method according to claim 7, characterized in that it titanium containing component is added to a content of 0.16.0 wt.%, in terms of titanium oxide (TiO2).

15. The method according to claim 7, characterized in that it further includes processing the pigment nitrate content of 0.05 to 1.0 wt.%, in terms of NO3.

16. The method according to claim 7, characterized in that the pigment is additionally milled with the addition of organic compounds.

17. egment on the basis of titanium dioxide, characterized in that it is obtained by the method according to claim 7.

18. The use of a pigment based on titanium dioxide according to any one of claims 1 or 17 as a tool in the manufacture of decorative paper.

19. Decorative paper, characterized in that it includes a pigment according to any one of claims 1 or 17.

20. Use decorative paper containing a pigment based on titanium dioxide according to any one of claims 1 or 17, as a tool in the manufacture of coating materials.

21. Decorative coating material, characterized in that it contains the decorative paper according to claim 19.

22. Laminate, characterized in that it contains the decorative paper according to claim 19.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention can be used in production of tissue paper. Surface-treated natural calcium carbonate is used as filler in tissue paper products, where said calcium carbonate is a product of reaction of natural calcium carbonate with an acid and carbon dioxide. The carbon dioxide is formed in situ by treatment with the acid and/or is fed from an external source. The surface-treated natural calcium carbonate is obtained as an aqueous suspension having pH higher than 6.0, measured at 20C.

EFFECT: invention improves softness of tissue paper products such as facial tissue, toilet paper, ornamental paper, towels, napkins or tissue paper cloths.

47 cl, 1 dwg, 5 tbl, 3 ex

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

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/d70100, 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.

SUBSTANCE: invention can be used in chemical industry. The method of producing jointly ground calcium carbonate material, which contains ground calcium carbonate (GCC) material and precipitated calcium carbonate (PCC) 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 at step (b); d) optional drying of the jointly ground calcium carbonate material obtained at step (b) or (c). The fraction of particles of the obtained material with size smaller than 1 mcm is greater than 80%, preferably greater than 85%, more preferably greater than 90% and even more preferably greater than 95%. BET specific surface area is less than 25 m2/g.

EFFECT: invention enables to increase lustre of enamel paper.

44 cl, 2 tbl, 5 ex

FIELD: chemistry.

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

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

17 cl, 22 ex

FIELD: printing industry.

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 70C 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.

22 cl, 5 dwg, 17 tbl, 9 ex

FIELD: printing industry.

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 70C 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 without using an agent that promotes dispersion or with application of a cationic disperser under quite moderate or mild conditions, which do not cause considerable damage of aggregates/agglomerates, until concentration from 15 to 50% is achieved, preferably in the range from 20 to 30%, most preferably - from 23 to 26 wt % of hard substances.

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: textiles, paper.

SUBSTANCE: method includes the sequential addition of flocculating agents of high and low molecular weight to aqueous dispersion of the filler particles followed by grinding of the resulting flakes of the filler to the desired particle size to obtain flakes of the filler resistant to grinding with a specific and controlled particle distribution.

EFFECT: improvement of quality of printed products, cost reduction for raw materials and energy.

14 cl, 10 ex, 7 tbl, 1 dwg

FIELD: textiles, paper.

SUBSTANCE: composition comprises: a) a filler, b) a cationic inorganic compound - polyaluminumchloride, c) a cationic organic compound, and d) anionic polysaccharide. The filler is present in an amount of at least about 1% by weight, based on the total weight of the composition. Anionic polysaccharide is present in an amount from about 1 to about 100 kg/ton based on the weight of the filler. The composition is substantially free of fibers. Filler composition of the version contains the components a), b), c) and d), as defined above. The only difference is that the component c) is a cationic polyamine condensation polymer, and the component d) has a degree of substitution of stoichiometrically excess anionic groups of up to about 0.65. At that each of b) and c) components present in an amount from about 0 to about 30 kg/ton based on the weight of the filler. At that the composition comprises at least one of b) and c) components. Methods of obtaining compositions of filler comprise mixing a), b), c) and d), as defined above. The invention also relates to a filler composition, which is obtained by this method, an application of the filler composition as an additive to an aqueous suspension of cellulose in the production process of paper and to manufacturing paper comprising adding a filler composition to an aqueous suspension of cellulose. The invention also relates to a paper obtained with this method, and paper comprising the filler composition.

EFFECT: improvement of composition.

35 cl, 1 dwg

FIELD: textiles, paper.

SUBSTANCE: invention relates to the production of hydrophilic fibrous composite materials for medical purposes, having bactericidal, hemostatic and anesthetic effect. Biologically active fiber sheeting is made in the form of fibrous base that contains cellulose, viscose fiber and a binder; the base is coated with a material containing additives in the immobilised form. The material has a weight of 75-90 g/m2, the weight of the coating is 35-50% relative to the weight of the fibrous weight. As a binder in the base a polyamine-poliamidepichlorohydrin resin is used. The coating is made on the basis of a cationic polysaccharide of natural origin. At that the additive is a blood-coagulation factor IV, antifibrinolytics, anesthetic, antimicrobial and plastifying agents.

EFFECT: reduction of quantity of fibrous materials in manufacture of the basics, and also it has new favourable features, namely, antimicrobial, hemostatic and analgesic effects.

3 cl, 1 tbl, 3 ex

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

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 50C. 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 40-98C. 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: chemistry.

SUBSTANCE: invention can be used in production of tissue paper. Surface-treated natural calcium carbonate is used as filler in tissue paper products, where said calcium carbonate is a product of reaction of natural calcium carbonate with an acid and carbon dioxide. The carbon dioxide is formed in situ by treatment with the acid and/or is fed from an external source. The surface-treated natural calcium carbonate is obtained as an aqueous suspension having pH higher than 6.0, measured at 20C.

EFFECT: invention improves softness of tissue paper products such as facial tissue, toilet paper, ornamental paper, towels, napkins or tissue paper cloths.

47 cl, 1 dwg, 5 tbl, 3 ex

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