WO2008033059A2

WO2008033059A2 - Water-resistant luminescent pigment and luminescent printing ink based thereon

Info

Publication number: WO2008033059A2
Application number: PCT/RU2007/000489
Authority: WO
Inventors: Aleksandr Mikhailovich Andrievsky; Mikhail Konstantinovich Grachev
Original assignee: Andrievsky Aleksandr Mikhailov; Grachev Mikhail Konstantinovic
Priority date: 2006-09-15
Filing date: 2007-09-13
Publication date: 2008-03-20
Also published as: WO2008033059A3; RU2323955C1

Abstract

The invention relates to novel water-resistant luminescent pigments and to printing inks based thereon. The inventive water-resistant luminescent pigment is embodied in the form of an oxide matrix, which is based on aluminium oxide and at least on one type of oxide of elements selected from a Mg, Ca, Sr, Ba, Zn, Mn, Si, B, P and Ga group, is activated with at least one rare-earth element and which is treated with a mixture of salts selected from a Na3PO4, Na2HPO4, (NH4)2HPO4 and Ca3 (PO4)2 group with acids selected from a HCl, H2SO4 and HNO3 group with a pH equal to or less 4 at the end of treatment. Said oxide matrix can have the following formulas: MO-SiO2Al2O3:R, MAl2O4:R and MAlO4:R, wherein M is a metal selected from a Ca, Sr, Ba, Mg and Zn group and R is an element selected from a Dy, Nd, Eu, Tm, Tb, Y and Yb group. The inventive printing ink comprises novel water-resistant pigments and any known thickeners relating to said field.

Description

Waterproof luminescent pigment and luminescent printing ink based on it

The present invention relates to the field of luminescent pigments and inks for printing with their use.

In particular, the invention relates to the creation of water-resistant and weather-resistant luminescent pigments (phosphors) belonging to the class of aluminates that can be used for the manufacture of emergency and autonomous lighting systems, evacuation signs, workwear elements, road lighting, advertising, etc.

Currently, there is an increasing interest in the use of phosphors. They can be used in photoluminescent materials such as surface coatings, plastics, ceramic tiles, coatings for glass and enamel.

Phosphors are used in warning signs when designating safe passageways in rocks, metro stations, tunnels, public buildings, in fencing of dangerous places in ports, airports, and industrial territories.

There is an increasing need for protection against counterfeiting of banknotes, credit cards, passports and other documents and securities.

Phosphors are used in creating signs indicating the exit and other forms of marking in road signs, vests and jackets for workers.

For all these purposes, luminescent pigments are used, in particular the so-called “glow ip dark” pigments - glowing in the dark.

It is known that the market for signs visible in a fire, power outage, and evacuation, for example, in New York, doubles annually.

Due to the fact that both in our and foreign literature there is an inadequate use of terminology in relation to luminescent pigments, which makes it difficult to evaluate technical solutions, including those proposed for patenting, the following terminology is from the work:

“Chemistry and physics of special properties of pigments, dyes, printing inks, and coating inks) A.Nurhap Vesiduap [UPITER MIPERAL & CHEMISAL CORR, RAIPT SOUTIPG UPDATRU, 06/15/2003]

Luminescence: fluorescence and phosphorescence. Luminescent dye (pigment) - a substance that emits light (visible, UV or IR) with appropriate excitation, without heating.

Excitation is an active reason forcing a luminescent dye to emit light.

Fluorescence - the emission of light by a luminescent pigment in the presence of excitation (for example, fluorescence in daylight).

Phosphorescence is the emission of light by a luminescent pigment after excitation has ceased (for example, glow in the dark).

In fact, luminescent pigments glowing in the dark, in accordance with the above terminology, should more correctly be called phosphorescent pigments (phosphors). Both names are used in the literature. We used the term luminescent pigments in the description (as well as in the patent prototype).

There are many types of energy that certain luminescent pigments can absorb and convert to luminescence (radioactivity, X-ray radiation, cathode radiation, mechanical stress, electricity, UV, visible or IR radiation).

Inorganic luminescent pigments called phosphors differ from fluorescent pigments in that they are mostly colorless or pale pastel colored, but when excited by UV radiation, they begin to fluoresce quite brightly.

Classical inorganic fluorescent pigments were created on the basis of zinc sulfide and zinc sulfide - cadmium.

ZnS: Cu is the most widely used phosphor of this class. The material is relatively inexpensive and has moderate hydrolysis resistance at ordinary temperatures and in the absence of light.

However, this material has significant drawbacks and limitations. In particular, it has a low brightness of the initial afterglow and a short afterglow period.

In addition, its disadvantage is its low resistance to light and, in particular, to UV radiation, and therefore it is not suitable in cases requiring a long exposure outdoors. To improve the pigments, attempts have been made to introduce radioactive substances into their composition, but their use is extremely limited due to the harmful effects on the human body, since the radioactive effect cannot be neglected.

Therefore, pigments were developed that have a long glow period in the dark, based on metal oxides with the addition of rare earth elements.

The second generation of light-accumulating phosphors is based on the use of aluminates of the second main subgroup of the periodic system of elements (Ca, Sr, Ba) O: Al ₂ O ₃ .

There are a number of patents in which luminophores based on aluminates with various compositions and crystal-chemical structures are described.

RF patent Ns 2192444 proposes a phosphor based on calcium and strontium aluminates activated by manganese, europium, dysprosium and / or neodymium, as well as an additional activator Mg and Y of the general chemical formula:

Me _1-X-Y Mn _x Eu _y (Ali-q- _z YqLn _z ) ₂ O ₄ , where Ln is Nd and / or Dy

Me is a combination of Sr - Mg and Ca - Mg,

0.001 <x <0.002

0.01 <y <0.05

0.005 <z <0.05

0.005 <q <0.05 _s with the ratio y / (x + z) = l: 2 - 2: 1

RF patent Xa 2194736 describes an ultra-long afterglow photoluminophore containing alumina, silica, oxide of elements of the main subgroup of the second group of the Periodic system of elements and a rare earth element, while it additionally contains oxide of the fourth group element with a molecular ratio of MeO: Al ₂ θЗ: MeO ₂ : SiO ₂ = 3: 1: 2: 1.

The description of the patent states that the phosphor can be used, in particular, for special clothing, clothing for schoolchildren and divers.

In the patent of the Russian Federation Ns 2217467 a stable photoluminophore with a long afterglow of the general formula is described:

(SrO) _1-x-2y-z (EuO) _x (Ln ₂ Oz) _y (Me ₂ O) _z (Al2θz) _Iq (B ₂ Oz) _q where Ln is Dy or Nd Me - Na, K ₅ Li x = 0.005-0D y = 0.005-0, lz = 0.002-0, lq = 0.005-0, l

The description of the patent states that the new phosphor may find application, in particular, for special clothing, and that it has increased moisture resistance compared to known phosphors, largely due to the introduction of Na.

RF patent JNs 2236434 describes a photocumulative phosphor based on strontium-magnesium aluminate activated by at least europium (Eu), dysprosium (Dy), neodymium (Nd), with manganese oxide added to the cationic sublattice, and to the anionic sublattice - cerium oxide in the form of Ce ₂ O ₃ forming the general stoichiometric formula:

Mg _1-X-Y-Z Sr _x Eu _y ²⁺ Mnz ²⁺ (∑TR) _P Al _q O ₄ , where ∑TP = Dy, Nd, Ce, x = 0.80-0.96 y = 0.001- 0.03 z = 0.005-0.010 P = O ₅ 01-0.05 l, 99 <q <2.05 atomic fractions

The description indicates that the phosphor is weather and water resistant, and that various varnishes and polymer compositions are made from it for use in printing and silk-screen printing.

In US patent JN ° 5424006, in order to increase the afterglow duration, an aluminate phosphor is introduced in addition to the activator - europium, the second rare-earth element selected from the group: dysprosium, cerium, neodymium, erbium, lanthanum, praseodymium, samarium, gadolinium, holmium, thulium, itter, , lutetium, tin and bismuth.

The phosphor has the composition:

MAl ₂ O ₄ , where M is at least one metal selected from the group consisting of Ca, Sr, or Ba. The disadvantages of such phosphors are low resistance to the aquatic environment and to high ambient temperatures.

In addition, the technology for producing these phosphors requires very high temperatures during their synthesis, which increases the cost of the final product and reduces the reproducibility of their lighting characteristics.

A disadvantage of aluminate phosphors is their instability to moisture, which is noted both in the literature and in patent descriptions.

The analysis of patent descriptions allows us to distinguish two main directions in solving the problem of increasing the stability of phosphors to moisture.

The first is to change the composition and / or structure of the phosphor. For example, according to US patent N ° 5665793 elimination of hydrolytic instability contributes to the additional introduction of Al ₂ O ₃ . A change in the formula composition compared with US patent N ° 5424006 allowed to increase hydrolytic stability, but at the same time, light efficiency decreased.

In US patent Ni.6 and 7362, elements of the second (Zn, Mg) and third (B) groups are additionally introduced into the phosphor.

Compared with the previous one, the luminous efficiency increases, but the properties deteriorate upon contact with water.

In accordance with RF patent N ° 2217467, hydrolytic activity can be reduced by introducing monovalent alkali metal atoms into the lattice. It is assumed that the increase in hydrolytic stability occurs due to the filling of the voids of the crystal lattice, as well as due to a change in the type of crystal lattice. This approach is limited to a small class of structures and is not universal. In addition, the method requires the strict observance of technology.

Another proposed way to solve the instability to hydrolysis of certain phosphors is to use them in a composition that physically protects or encapsulates moisture-sensitive phosphor particles. Manufacturers of phosphors based on alkaline earth metal aluminates aluminates recommend protecting these materials from moisture by encapsulation or even with a transparent coating (for example, the manufacturer of luminescent pigments LumiNova - Nemoto & Co. Ltd., Japan, and their distributor - UMC, USA). US patent N ° 6005024 relates to non-aqueous epoxy systems containing phosphors. These systems are of limited use since their immediate use is required after mixing the two components, i.e. epoxy hardener and epoxy polymer.

US Pat. No. 6,359,048 describes a non-aqueous alkyd-based system containing a phosphor. This system has the disadvantage that it requires a base — an alkyd resin and a diluent that releases organic fumes that are flammable and usually have a strong odor. In addition, cleaning paint equipment also requires the use of a solvent with the same hazardous properties.

RF patent N ° 2236434 relates to a multistage process for producing a phosphor, which includes ultrasonic treatment of phosphor particles in water-silicone ash at 25 kHz at the last stage to cover them with a thin silicate film that protects the particles from water. The method includes the step of manually sorting the phosphor particles to remove non-luminous by-products and phosphors with different radiation wavelengths. The method is not practical for industrial use.

In a certain sense, this direction may include methods for producing modified water-resistant phosphors having films or membranes on the surface, presumably from insoluble salts formed by the reaction of oxides that make up phosphors with acid or acid-forming compounds.

Japanese patent N ° 2929162 proposes a method for improving the properties of a phosphor, which consists in the fact that on the surface of phosphors consisting of metal oxides (calcium, aluminum, strontium, barium, cerium) with the addition of activators from rare earth elements, a water-insoluble or water-insoluble film is obtained in water formed as a result of exposure to an aqueous medium of an acid or any compound having the properties of an acid to a metal oxide forming a phosphor.

The method consists in placing the phosphor in an aqueous solution that contains acid or at least one compound having an acidic effect. The processing of the phosphor can also be carried out by spraying on its surface an aqueous solution that contains acid or at least one compound having an acidic effect. The third embodiment of the method consists in the fact that the phosphor is placed in a gaseous medium containing in a high concentration water vapor of acid or water vapor of at least one compound having an acidic effect.

Japanese application N207292282A proposes a modified phosphor containing a metal oxide with the addition of a rare earth element treated with an acid, preferably a phosphoric or acid-forming substance.

The luminescent pigment is modified by immersion in a 0.5-4% acid solution for 10-60 minutes at 5O ⁰ C.

Regarding these solutions, US Pat. No. 6,264,855 describes that the phosphors obtained by the above methods lose their resistance to water when exposed to it for a long time at a temperature of 60 ° C, although their use does not cause particular problems at ordinary temperature. Thus, there is a need to solve the problem of water resistance in more severe temperature conditions.

Japanese application JVs 11140438 A describes a substance obtained by coating the surface of phosphor particles with organic derivatives of phosphoric acid, for example, an acidic ester of phosphoric acid or a chelating derivative of phosphoric acid.

Japanese application Ns 10273654 A proposes a waterproof fluorescent substance obtained by treating a phosphor (oxide of one or more metals from the group consisting of Ca, Sr and Ba, and aluminum oxide, as well as rare earth oxide, preferably lanthanide) with diammonium hydrogen phosphate or ammonium dihydrogen phosphate in aqueous solution subsequent heat treatment.

Japanese application N211140439A proposes a luminous fluorescent substance which, according to the inventors, has excellent resistance to light, weather and water for a long time. A fluorescent substance is a crystalline matrix of an alkaline earth metal aluminate doped with a rare earth element, coated on the surface with an insoluble salt of an alkaline earth metal (e.g., sulfate, carbonate, phosphate, oxalate or silicate).

The method of receipt is not specified.

The closest solution to the claimed technical solution is the product obtained by the method patented in US patent N ° 6264855. To increase the resistance to moisture at elevated temperatures, it is proposed to process the phosphor in two stages: in the first stage, with acid at pH no higher than 3, and in the second with alkali at pH 4-9.

According to the first claim of the patent in question, in the first stage, any acids or acid-forming compounds can be used, and in the second stage, any alkali or compounds forming them.

In the dependent claims, the acids are limited to a group: phosphoric acid, phosphorous acid, polyphosphoric acid, sodium dihydrogen phosphate, sulfuric acid.

Alkaline agents are limited to the group: hydroxides of sodium, potassium, calcium, strontium, lithium, trisodium phosphate, strontium oxide.

According to the claims, the above agents can be used separately and in combinations (combinations of alkalis and acids).

The description contains a long list of recommended acids, in which the following acids are available: nitric, boric, hydrochloric, carbonic, a number of organic acids.

As acid forming compounds, disodium phosphate, salts and anhydrides of the above acids are provided.

In the examples of US Pat. No. 6,264,855, only phosphoric acid is shown for acid treatment, trisodium phosphate and sodium hydroxide for alkaline treatment.

No experimental evidence of the use of any acid or any mixed agents is given in the patent specification.

At the same time, it is known from the prior art that when acting on phosphors that do not contain silicon, i.e. it is on those that are used in US Pat. No. 2,626,455, phosphoric or dilute hydrochloric acids, that they corrode (see US Pat. No. 5,961,884).

Our thorough experimental studies of the effects of various acids on luminescent pigments have shown that a number of acids recommended in US Pat. No. 6,264,855 do not protect against hydrolysis. Such acids include: H ₃ BO ₃ , HCl, HNO ₃ . Moreover, HCl and HNO ₃ , both diluted and concentrated, easily react with all of us used. luminescent pigments with the formation of the corresponding salts soluble in the reaction medium. So, if hydrochloric or nitric acid is added dropwise to an aqueous dispersion of a luminescent pigment, a reaction occurs with an increase in the temperature of the reaction medium. Moreover, a few minutes after adding each portion of the acid, the pH of the medium increases. This indicates that the acid is consumed by reacting with the phosphor. The reaction can be brought to the complete disappearance of the phosphor.

We found that a number of possible “acid-forming” compounds do not protect the phosphor from hydrolysis. These include: Na ₂ HPO ₄ , Na ₃ PO ₄ , (NH ₄ ) ₂ HPO ₄ . Those. treatment of the phosphor with aqueous solutions of these salts does not lead to the formation of waterproof phosphors.

The above data, which we have confirmed experimentally, indicate that the closest analogue (US patent Ns6264855) includes inoperable objects and does not disclose teachings on how a specialist, without resorting to creative research, can choose agents or their combinations for processing phosphor with obtaining the effect of resistance to the action of water, and even more so at high temperatures.

The objective of the present invention is to provide a waterproof luminescent pigment that retains its properties at high temperatures using available tools and simple techniques.

The problem is solved by creating a new luminescent pigment, which is an oxide matrix based on aluminum oxide and at least one of the oxides of elements selected from the group: Mg, Ca, Sr, Ba, Zn, Mn, Si, B, P, Ga, activated at least one rare earth element treated with a mixture of salts selected from the group: Na ₃ PO ₄ , Na ₂ HPO _4> (NH ₄ ) ₂ HPO _4> Ca ₃ (PO ₄ ) ₂ , with acids selected from the group: HCl, H ₂ SO ₄ , HNO ₃ .

Oxide matrices can be represented by the following structures:

- MO-SiO ₂ -Al ₂ O ^ R, where M is at least one metal selected from the group consisting of Ca, Sr, Ba, Mg, Zn; R is at least one element selected from the group consisting of Dy, Nd, Eu, Tm, Tb, Y ₅ Yb; - MA1 ₂ O ₄ : R where M is at least one metal selected from the group consisting of Ca, Sr, Mg, Ba ₅ and R is at least one element selected from the group Dy, Nd, Eu ₅ Tm, Tb , Y ₅ Yb;

- MAYU ₄ : R, where M is at least one metal selected from the group Sr, Ca ₅ Ba; R is at least one element selected from the group Dy ₅ Nd ₅ Eu ₅ Tm ₅ Tb, Y ₅ Yb.

The invention is not limited to these specific formulas and can be extended to any complex alumina-based oxides that are used as luminescent pigments.

Another object is printing ink based on a new luminescent pigment, for the preparation of which you can use components for thickening (binder, thickener, fixative, softener), offered by a wide range of companies for conventional pigment printing.

In the process of research, it was unexpectedly discovered that the task of obtaining a waterproof pigment can be solved by treating the luminescent pigment with a mixture of salts selected from the group: Na ₃ PO ₄ , Na ₂ HPO ₄ , (NIrLO ₂ HPO ₄ , Ca ₃ (PO ₄ ) ₂ , with acids selected from the group: HCl, H ₂ SO ₄ , HNO ₃ .

This decision is all the more unexpected because each agent individually, with the exception of H ₂ SO ₄ , does not protect the luminescent pigment from hydrolysis, despite recommendations not confirmed by experiment existing at a certain level.

Water-protected luminescent pigment is obtained in one stage, which greatly simplifies the process compared with the implementation of the protection proposed in US patent N ° 6264855.

The description examples show the results of the proposed solutions. These solutions make it possible to obtain luminescent pigments that are waterproof at high temperatures. It should be noted:

1. Each of the acids HCl or HNO ₃ interacts with luminescent pigments, destroying them. But mixed with H ₃ PO _{4 they} perform protective functions against hydrolysis of the luminescent pigment.

2. H ₃ PO ₄ and H ₂ SO ₄ - each of these acids individually in a certain concentration protects the luminescent pigment from hydrolysis. Their mixture in the same concentrations loses its protective function. 3. The processing of luminescent pigments in the conditions of the proposed solution does not reduce compared with the original lighting characteristics of the obtained waterproof luminescent pigments.

Giving water resistance to luminescent pigments is especially important because the instability of phosphors based on alkaline earth metal aluminates makes them difficult to use when water is part of the composition or when the final product is in contact with moisture.

Another objective of the present invention is to provide a printing ink based on waterproof luminescent pigment and thickeners.

For printing on fabrics or fabric products using pigments for textile printing. These pigments are produced as water-based dispersions. In dispersion, in addition to organic or inorganic pigments, dispersants and other surface-active substances (surfactants) are added, which provide the necessary complex of applied properties of pigment pastes. When using conventional luminescent pigments, for example, a yellow-green glow, it is impossible to prepare an outlet pigment form based on water, which is stable during storage for several hours. In an aqueous medium, a luminescent pigment is hydrolyzed and then coagulated. Overcoming this problem by encapsulating phosphors significantly increases the cost of production. On the other hand, any encapsulation of phosphors with the formation of surface polymer shells reduces their lighting characteristics.

We offer luminescent pigments can be used for the preparation of final pigment forms on a water basis, stable during long-term storage. On the other hand, they can be used for the preparation of printing inks based on conventional thickeners used in textile pigment printing. These printing inks can be used for printing both immediately after their preparation, and after 6-7 months. Their storage stability is determined by the water resistance of the inventive luminescent pigments. It should be noted their resistance to high temperatures in the aquatic environment. When luminescent pigments are heated in water at 90-95 ⁰ C for 6-8 hours or at 13O ⁰ C for 3 hours, they remain resistant to hydrolysis and retain luminescent properties. This property has great importance in printing processes both by screen printing (silk screen printing), and in production using flat and round patterns. The printing process involves stages of drying and fixing. At the drying stage, moisture evaporates from the printed fabric. The temperature reaches 90-95 ° C. During fixation, the temperature on the fabric is even higher (at the end of heating it can reach 60-165 °), and the residual moisture is removed at temperatures above 95 ° C. Protected by the described method, the luminescent pigment withstands such harsh processing without hydrolysis and preserving its lighting characteristics.

The proposed luminescent pigments are readily dispersible in aqueous media, even in the absence of a surfactant. This property is of great importance in the preparation of printed compositions for spray. When applying printing ink to the fabric using the spray method, the dispersion of the particles and their tendency to agglomerate are very important. If the particles agglomerate, clots form that clog the spray device, and patches of uneven suspension are formed on the tissue. In the case of using the proposed luminescent pigments, there are no such drawbacks, and there is no need to add special substances to increase the aggregative stability of the suspension.

As the initial luminescent pigments, luminescent pigments of a long afterglow (yellow-green) were used:

Table 1

Some chemical and physical properties of luminescent pigments

table 2

in accordance with the passport data of the manufacturer

General procedure for treating luminescent pigments with a mixture of salts selected from the group: Na ₃ PO ₄ , Na ₂ HPO ₄ , (NH ₄ ) IHPO ₄ , Ca ₃ (PO ₄ ) ₂ , with acids selected from the group: HCl, H ₂ SO ₄ , HNO ₃ .

Orthophosphoric acid salt and one of the acids selected from the group: HCl, HNO ₃ or H ₂ SO ₄ are added to the corresponding amount of water with stirring at room temperature. The mixture is stirred for 10 minutes. and a luminescent pigment is added in portions over 5 minutes to the resulting solution.

The mixture was stirred for 1 hour. The precipitate is filtered off, washed thoroughly first with ordinary, then with distilled water and dried to constant weight at 130-140 ° C.

When processing a luminescent pigment with a mixture of salts and acids, if necessary, the temperature of the reaction medium is increased by heating using an external heat source (water bath or electric heating). During the processing of the luminescent pigment, the pH of the aqueous suspension is measured.

For the treatment of luminescent pigments, acids are used: 35% HCl, 55% HNO _3, 96% H ₂ SO _4.

Water resistance test.

5 g of the luminescent pigment obtained as described in the examples, and 45 ml of water are placed in a 100 ml container and stirred at room temperature for 8 hours, controlling the pH of the suspension. The conclusion about water resistance is made on the basis of whether the pH of the test suspension becomes alkaline or not. Some processed luminescent pigments were tested in an aqueous medium at room temperature for several weeks.

The alkaline pH is explained by the fact that the alkaline earth metal oxide of the luminescent pigment reacts with water to form a water-soluble hydroxide. With prolonged contact with water, a luminescent pigment that is not resistant to hydrolysis, the concentration of hydroxides in water increases and they precipitate. This amorphous white precipitate can be decanted, separated from the heavier undecomposed phosphor. In parallel, crystallization occurs with the formation of light yellow compounds that do not have luminescent properties.

All luminescent pigments shown in Tables 1, 2, are not resistant to the action of water at room temperature (hydrolyzed). The luminescent pigment obtained as described in the examples, resistant to water at room temperature, is subjected to additional water resistance testing at 9O ⁰ C, and then at 130 ⁰ C. Testing is carried out on laboratory equipment of the drum type of the Swiss company "Mathis", intended for dyeing tissue samples. The device is equipped with 12 metal cups with screw caps. 45 ml of distilled water and 5 g of the tested luminescent pigment are placed in each 100 ml beaker. Cups are closed with lids and placed in special openings of the device. The temperature is adjusted to 9O ⁰ C and heated with stirring for 6 hours. Then cool, unscrew the lids and determine the pH of the solution. Water resistant luminescent pigments at 9O ⁰ C are subjected to additional heating at 130 ⁰ C for 3 hours according to a similar procedure. Then determine the pH.

EXAMPLES

Table 3 shows the luminescent pigments used in the description examples:

Table 3

EXAMPLE 1

16 g of water are placed in a glass cup equipped with a magnetic stirrer and 15.5 g of Na ₃ PO ₄ - 12H ₂ O are added with stirring, followed by 8.5 g of 35% HCl. To 40 g of the resulting solution, 10.0 g of a luminescent pigment was added portionwise over 5 minutes. As a result of spontaneous heating, the temperature of the reaction mixture increased to 28 ⁰ C. Stirred for 1 hour. At the end of the reaction the temperature of the phosphor suspension is 25-26 ⁰ C. The suspension is filtered off, the precipitate is washed with water and dried at 130-140 ° C. 9.82 g of a light yellow luminescent pigment are obtained.

After mixing water, salt and acid, the resulting solution had a pH of 5. At the end of the reaction, pH = 5, 5.

The resulting luminescent pigment is hydrolyzed in water at room temperature. When added to water, it begins to decompose immediately. the pH of the solution within 10-40 minutes reaches 10, and after 2 hours, pH = 1-12.

EXAMPLES 2-8

Examples 2-8 are summarized in Table 4. 10.0 g of a luminescent pigment is treated under the conditions of Example 1 40 g of a solution obtained by mixing a constant amount of Na ₃ PO ₄ - 12H ₂ O with various amounts of water and 35% hydrochloric acid. The pH of the reaction solution is controlled before and after pigment treatment. The resistance of the treated luminescent pigment to the action of water at room temperature is determined.

Table 4

The luminescent pigments treated under the conditions of Examples 3-7 are resistant to water at room temperature for 14 days, and are resistant to water at 9O ⁰ C and 130 ⁰ C. The yield of pigments dried to constant weight obtained in experiments 2–7 was 9.7–9.8 g.

EXAMPLE 9

To 40 g of a solution with pH = 1 obtained by mixing 15.5 g of H ₂ O, 15, 5 g of Na ₂ HPO ₄ - 12H ₂ O and 9, Or 35% HC1 add 10.0 g of a luminescent pigment. Processing and isolation of the product is carried out under the conditions of Example 1. At the end of mixing, the solution has a pH = 2. Obtain 9.83 g of a waterproof luminescent pigment.

EXAMPLE 10

To 40 g of a solution with pH = 1 obtained by mixing 25.3 g of H ₂ O, 6.2 g of (NH ₄ ) g of HPO ₄ and 8.5 g of 35% HC1, 10.0 g of a luminescent pigment was added. Processing and isolation of the product is carried out under the conditions of Example 1. At the end of mixing, the solution has a pH = 2. Obtain 9.72 g of a waterproof luminescent pigment.

EXAMPLE 11

To 40 g of a solution with pH = 1 obtained by mixing 20.8 g of H ₂ O, b, 3 g of Ca ₃ (PO ₄ ) 2 and 12.9 g of 35% HC1, 10.0 g of a luminescent pigment is added. Processing and isolation of the product is carried out under the conditions of Example 1. At the end of mixing, the reaction solution has a pH = 2. The precipitate is poorly filtered. 9.61 g of a waterproof luminescent pigment are obtained.

EXAMPLES 12-21

Under the conditions of Examples 2-11, the luminescent pigment SP-2 is treated. 9.0-9.3 g of waterproof luminescent pigments are obtained.

EXAMPLE 22

In the conditions of Example 4, the luminescent pigment Lumilux Greep SN-F2 is treated. 9.80 g of a waterproof luminescent pigment are obtained.

EXAMPLE 23

To 40 g of a 10% HCl solution, 10.0 g of the LumiNova G-300M luminescent pigment was added portionwise and stirred for one hour at 3 ^° C. The precipitate was filtered off, washed thoroughly with water and dried. Get l, 2 g of a phosphor unstable to water. The processed phosphor is easy hydrolyzed. When added to water, the solution immediately becomes alkaline.

EXAMPLE 24

To 40 g of a HNO ₃ solution, 10.0 g of the LumiNova G-ZOOM luminescent pigment is added portionwise. The mixture is stirred for 1 hour. The weight of the isolated product is 1.54 g. The product is easily hydrolyzed. When added to water, the solution immediately becomes alkaline.

EXAMPLE 25

The processing of the luminescent pigment is carried out under the conditions of Example 1, reducing the loading of the phosphor by 2 times (using 4Or solution and 5, Or phosphor). The output of the luminescent substance is 4.83 g. The product is easily hydrolyzed in water at room temperature.

EXAMPLE 26

To 35.5 g of H ₂ O, 4.7 g of 85% H ₃ PO ₄ , 10.0 g of luminescent pigment were added and stirred at 28-30 ° C for 1 hour. The product is isolated under the conditions of Example 1. Receive 9.82 g of a luminescent pigment resistant to water at room temperature. The initial solution has a pH = l, at the end of mixing pH = 3.

EXAMPLE 27

15.5 g of Na ₃ PO ₄ -12H ₂ O is dissolved at 50 ° C in 24 _{5 5} g of H ₂ O. The solution is cooled to 25 ° C, 10.0 g of luminescent pigment is added portionwise and stirred at 28-30 ^° C for 30 minutes. A suspension having a pH = 13-14 _{5 is} filtered off, washed 5 times with 30 ml of distilled water and dried. Get 8.94 g of a luminescent substance, easily hydrolyzed in water at room temperature.

EXAMPLE 28

To 40 g of an aqueous solution containing 9 g of Na ₂ HPO ₄ - 12H ₂ O, 10, Or of the luminescent pigment was added and stirred at 25 ° C for 30 minutes. The product is isolated in the same manner as in Example 27. 9.75 g of a luminescent substance is obtained, which reacts with water at room temperature to form an alkaline solution.

EXAMPLE 29 Luminescent pigment treatment is conducted under conditions of Example 28, except that instead of Na ₂ HPO ₄ taken 3,8g (NH ₄₎ ₂ HPO _4. 9.8 Ir of a luminescent substance is obtained, which, interacting with water at room temperature, forms a solution with an alkaline pH.

EXAMPLE 30

3.8 g of H ₃ BO _{3 was} dissolved at 50 ° C in 80 g of H ₂ O. To 40 g of a solution cooled to 3 ^{O 0} C, 2.0 g of luminescent pigment was added and stirred for 1 hour at this temperature. The solution at the beginning and end of mixing had a pH = 7. With the addition of a phosphor, a slight heating of the reaction mass was observed. The suspension is filtered off, washed with water and dried. Get l, 90 g of a luminescent substance, hydrolyzed in water at room temperature.

EXAMPLE 31

40 g of solution are prepared by mixing 15.5 g of Na ₃ PO ₄ -12H ₂ O, 10.5 g of H ₂ O and 14, Or 55% HNO ₃ . 10.0 g of a luminescent pigment is added to 40 g of the solution and stirred for 1 hour at 25 ° C. The initial solution has a pH = l. At the end of mixing, pH ^ 3. The suspension is filtered. The precipitate is washed with water and dried. 9.85 g of a light yellow luminescent pigment are obtained. The pigment is water resistant at room temperature, as well as at 90 ° C and 130 ° C.

EXAMPLE 32

To a 40 g solution of Na ₃ PO ₄ - 12H ₂ O in water, obtained under the conditions of Example 27, 10.0 g of a luminescent pigment was added with stirring, then over 10 minutes. 12.8 g of 35% HCl. The suspension is stirred at 28-3O ⁰ C for 1 hour. After adding the entire amount of HCl, the suspension has a pH = l, at the end of mixing pH-2. The suspension is filtered off, washed with water and dried. 9.25 g of a light yellow luminescent pigment are obtained. The pigment is water resistant at room temperature, as well as at 90 ° C and 130 ° C.

EXAMPLE 33

To 35.8 g of H ₂ O was added dropwise 4.2 g of 96% H ₂ SO ₄ . To the resulting aqueous solution of sulfuric acid cooled to room temperature, add 10.0 g of a luminescent pigment and raise the temperature to 40-45 ⁰ C. The suspension is stirred at this temperature for 1 hour. The initial solution has a pH = l. At the end of mixing, pH = 4. The precipitate is filtered off, washed with water and dried to constant weight. 9.54 g of a light yellow luminescent substance are obtained. The product is resistant to water at room temperature for 20-24 hours. Then the pH of the solution increases and after 30-35 hours the pH of the solution reaches 11-12.

EXAMPLE 34

In 40 g of the solution obtained by adding 15.5 g of Na ₃ PO ₄ -12 H ₂ O and 6.3 g of 96% H ₂ SO ₄ K 18.2 G H ₂ O Bring 10.0 G of luminescent pigment and mix at 28-30 ° C 1 hour. The initial solution has a pH = l. At the end of mixing, pH = 3. The suspension is filtered. The precipitate is washed with water and dried at 130-140 ° C to constant weight. Obtain 11.1 g of a waterproof luminescent pigment. The pH of the suspension of the pigment in water was controlled at room temperature; The pH of the solution was at 7 for 3 days. Upon further testing for water resistance under these conditions, the pH did not increase. The resulting luminescent pigment is waterproof at 9O ⁰ C and at 130 ° C.

EXAMPLE 35

Two solutions are mixed: 20 g obtained under the conditions of Example 26 with 20 g obtained under the conditions of Example 33. To 4Or of the total solution containing H ₃ PO ₄ and H ₂ SO ₄ , add 10.0 g of a luminescent pigment and mix at 28-30 ⁰ C 1 hour.

The product was isolated under the conditions of Example 1. 9.80 g of a luminescent product unstable to water at room temperature were obtained.

EXAMPLE 36

The experiment is carried out by analogy with Example 35, except that 5.0 g of luminescent pigment is used for processing. 4.85 g of a luminescent substance unstable to water at room temperature are obtained.

EXAMPLE 37

4.7 g of 85% H ₃ P0 ₄ and 2.0 g of 35% HC1 are added to 33.3 g of H ₂ O. To the resulting solution was added 10.0 g of a luminescent pigment. All other operations are carried out under the conditions of Example 1. Receive 9.8 Ir luminescent substance, resistant to water at room temperature.

EXAMPLE 38 In the conditions of Example 4 carry out ^• processing of 10.0 g of the luminescent pigment SP-4. 9.32 g of a waterproof luminescent pigment are obtained.

EXAMPLE 39

In the conditions of Example 5, 10.0 g of the luminescent pigment SP-6 are treated. 8.9 Ir of a waterproof luminescent pigment is obtained.

EXAMPLES 40-46

Under the conditions of Examples 4, 9, 10, 26, 31, 33, 34, the luminescent pigment LDP - 2M (10.0 g each) is processed. 9.1-9.3 g of water-resistant luminescent pigments are obtained at room temperature, as well as at 9O ⁰ C and 130 ° C.

EXAMPLES 47-49.

In the conditions of Examples 4, 31, 34, the luminescent pigment FB-530 D (10.0 g each) is processed. Get 9.2-9.4 g of waterproof luminescent pigments at room temperature, as well as at 9O ⁰ C and 130 ⁰ C.

EXAMPLE 50

Under the conditions of Example 33, 10.0 g of the Lumilux Greene SN-F2 luminescent pigment is treated. 9.42 g of a product resistant to water at room temperature for 16 hours are obtained. Then the pH of the solution increases and after 24-26 hours reaches pH = 12.

EXAMPLE 51

Under the conditions of Example 34, 10.0 l of SP-2 luminescent pigment is treated. Get 1 l, 0 g of a waterproof luminescent pigment at 9O ⁰ C and at 130 ⁰ C.

EXAMPLE 52

The treatment of the luminescent pigment Lumi No va G-300M is carried out as in Example 34, but instead of 15.5 g of Na ₃ PO ₄ • 12H ₂ O, 12.6 g of Ca ₃ (PO ₄ ) ₂ are taken, leaving the same amounts of 96% H ₂ SO ₄ and H ₂ O. The initial solution had pH = l, at the end of the reaction pH = 3. The resulting luminescent pigment is waterproof at 90 ⁰ C and at 130 ⁰ C.

EXAMPLE 53

The processing of the luminescent pigment Lumi Nova G-300M is carried out as in Example 31, only instead of 15.5 g of Na ₃ PO ₄ • 12H ₂ O take 12.6 g of Ca ₃ (PO ₄ ) ₂ , leaving the same amounts of H ₂ O and 55 % HNO ₃ . The initial solution had a pH = l, at the end of the reaction pH = 2. The obtained luminescent pigment is waterproof at 9O ⁰ C and at 13O ⁰ C.

EXAMPLE 54

The processing of the luminescent pigment Lumi No va G-300M is carried out as in Example 34, only instead of 15.5 g of Na ₃ PO ₄ • 12H ₂ O take 14.6 g of Na ₂ HPO ₄ • 12H ₂ O, leaving the same amount of 96% H ₂ SO ₄ and H ₂ O. The initial solution had pH = l, at the end of the reaction pH = 3. The resulting luminescent pigment is waterproof at 90 ⁰ C and at 13O ⁰ C.

EXAMPLE 55

The treatment of the luminescent pigment Lumi Nova G-300M is carried out as in Example 31, but instead of 15.5 g of Na ₃ PO ₄ • 12H ₂ O, 14) 6 g of Na ₂ HPO ₄ • 12H ₂ O are taken, leaving the same amounts of H ₂ O and 55% HNO ₃ . The initial solution had pH = l; at the end of the reaction, pH = 3. The resulting luminescent pigment is waterproof at 9O ⁰ C and at 130 ⁰ C.

EXAMPLE 56

The treatment is carried out as in Example 54, only instead of 14.6 g of Na ₂ HPO ₄ • 12H ₂ O take 5.38 g (NH ₄ ) ₂ HPO ₄ . The initial solution had pH = l; at the end of the reaction, pH = 3. The resulting luminescent pigment is waterproof at 90 ⁰ C and at 130 ⁰ C.

EXAMPLE 57

The treatment is carried out as in Example 55, only instead of 14.6 g of Na ₂ HPO ₄ • 12H ₂ O take 5.38 g (NH ₄ ) ₂ HPO ₄ . The initial solution had pH = l; at the end of the reaction, pH = 2. The resulting luminescent pigment is waterproof at 9O ⁰ C and at 130 ⁰ C.

For a more visual analysis of the experiment, examples 1-57 are summarized in the table:

Table 5

From the table it follows:

A) In examples 1-2, the treatment of the initial phosphor is carried out with the reagent included in the claims, however, at a pH at the end of the reaction more than 4 (5.5 and 4.5, respectively), the result is not achieved.

B) In examples 35 and 36, the reagent is H ₂ SO ₄ + H ₃ PO ₄ , which is not included in the scope of the claims and which demonstrates the fact that not all acids or mixtures thereof, presented in generic terms in the claims of analogues, including in the closest analogue, they provide a technical effect.

B) In Examples 23 and 24, hydrolysis-unstable products were obtained, i.e. technical effect is not achieved.

In Example 26, a product is obtained that is stable only at room temperature, i.e. the effect of resistance to hydrolysis at elevated temperature has not been achieved.

In Example 33, a product is obtained that is stable only at room temperature and only for a day, i.e. the effect of long-term resistance to hydrolysis at elevated temperature has not been achieved.

D) From the table it also follows that an essential feature of the proposed technical solution is the pH value, which should be no more than 4 at the end of the reaction.

Thus, in examples 3-11, 13-22, 26, 31, 32, 34, 37-49, 51-57, the preparation of hydrolysis resistant phosphors is described.

Inks

To prepare the printing ink, we used waterproof luminescent pigments, obtained as described in the examples, and components for the preparation of CIBA Specialty Chemicals thickeners: Binder - Alcoprint PB-HC Thickener - Alcoprint PT-XN Fixative - Alcoprint PFL Softener - Alcopint PLC

GENERAL METHODS

1. Preparation of a thickener for printing with a luminescent pigment. 200g of a binder is added to 370 ml of distilled water, the stirrer is turned on and with stirring for 10 minutes. add dropwise 10-20 g thickener to form a homogeneous mass, then add 10-3 Or softener, 10-3 Or fixative and mix for 10 minutes The viscosity of the resulting thickener is determined. Viscosity should be in the range from 60 to 80 dPas / Ses. Viscosity is controlled by adding a thickener or aqueous ammonia to the composition. Typically, the pH of the thickener is maintained at 9.

2. Preparation of luminescent ink for printing.

To 800-850 g of a thickener for printing with vigorous stirring, 150-200 g of fluorescent pigment powder is added in portions until a homogeneous mass of light yellow color is formed.

3. Preparation of a thickener for spray with a luminescent pigment.

To 750 ml of distilled water, a 20Or binder is added. Then, with stirring, dropwise over 10 minutes. add 10-13 g of thickener and mix for another 10 minutes. until a homogeneous mass is formed. Then, with stirring, add SOH of the emollient and South fixative. The viscosity of the thickener is determined. Viscosity should be 30-40 dPas / ses. To control the viscosity, either a thickener (for thickening) or a 20% aqueous NaCl solution (for dilution) is used. The consistency of the thickener should be such that it can be easily sprayed without clogging the nozzle of the spray device.

4. Preparation of luminescent paint for spray.

Spray paint is prepared similarly to preparing ink for printing using a spray thickener.

5.Printing screen printing manual.

For printing, templates with a mesh of N ° 34 (with a mesh size of 34 mesh) of Saati single-strand polyester were used.

A textile product (jeans, a T-shirt, a T-shirt, etc.) is placed on a printed table and pressed with a template.

Printing ink is evenly applied to the template (in the place where there is no picture). Then with a squeegee with a certain pressure along the template, printing ink is pressed in the place of the drawing. To ensure hiding power, it is necessary to make two to three passes with a squeegee. Then the template is lifted and the printed product is subjected to intermediate drying at a temperature of 100-110 ⁰ C for 20-30 seconds. Then the printed product is subjected to heat setting. The product is placed on the perforated tape of the dryer. When the tape moves, the product moves to heating zone, where the fixing process takes place. Fixation is carried out at a temperature on the surface of the fabric 158-160 ⁰ C for 80-90 seconds. Depending on the product and the area of the printed pattern, the fixing process is repeated 2-3 times. b. Application of luminescent paint on the product by spray method.

The product (e.g. jeans) is put on a mannequin. Prepare the compressor, connect all the components of the spray device (gun). Working pressure in the system "2 atm. Luminescent paint for spray is poured into a special container of the gun and regulate the air supply. Then the product is sprayed. At the end of the application of paint, the product is dried at room temperature, put on the mannequin again and re-applied the suspension of the thickener for the spray (without luminescent pigment). The product is removed from the mannequin and again dried at room temperature. Then it is subjected to a heat-setting process at 158-160 ⁰ C for 80-90 seconds. The process of heat setting is repeated 2-3 times.

The preparation of printing ink for printing or spraying on fabrics can be carried out without emitting a waterproof luminescent pigment after processing the original luminescent pigment in accordance with the proposed method. In fact, we are talking about the fact that it is not necessary to isolate the product in the form of a dry powder after processing, since the technology for the preparation of printing ink involves the addition of water to the thickener. So, after several decantations and rinses, the aqueous paste of the processed luminescent pigment can be used to prepare printing ink.

It should be noted that if decantation is not performed with the addition of new portions of water to remove reaction salts, a printing ink containing a luminescent pigment and thickening components begins to coagulate.

7. Preparation of printing ink without emitting luminescent pigment.

To a suspension of 15.5 g of Na ₃ PO ₄ - 12 H ₂ O in 13.9 g of H ₂ O is added dropwise with stirring. Yu. 35 g of HCl, stirred for 10 minutes, 10.0 g of luminescent pigment is added and stirred for 1 hour at 20 ° C. Before the introduction of the phosphor, the solution has a pH = 2, at the end of mixing pH = 4. A suspension of the luminescent pigment is settled for 3-5 minutes, the solution is drained, the precipitate is washed 3 times with 20 ml of H ₂ O, each time decanting the solution. After the last ^ ^

The washing solution has a pH = 7. After washing, decantation occurs practically without loss of product, since the latter has a high density. An aqueous paste of a luminescent pigment is obtained. 16, Or H ₂ O was added to the paste, then 8.0 g of Alcoprint PB-HC, 0.8 g of Alcoprint PT-XN, 0.8 g of Alcoprint PFL and 0.8 g of Alcoprint PSC were added successively with stirring. Stirred for 30 minutes. Get a printing ink in the form of a homogeneous mass of light yellow.

For the preparation of luminescent inks for printing and spray, you can use components for thickening (binder, thickener, fixative, softener), offered by a wide range of companies for ordinary pigment printing.

Claims

Claim

1. A waterproof luminescent pigment, which is an oxide matrix based on aluminum oxide and at least one of the oxides of elements selected from the group: Mg, Ca, Sr, Ba, Zn, Mn, Si, B, P, Ga, activated at least at least one rare earth element treated with a mixture of salts selected from the group: Na ₃ PO ₄ , Na ₂ HPO _4, (NH ₄ ) ₂ HPO ₄₎ Ca ₃ (PO ₄ ) ₂ , with acids selected from the group: HCl, H ₂ SO ₄ , HNO ₃ at a pH of not more than 4 at the end of processing.

2. The waterproof luminescent pigment according to claim 1, wherein the oxide matrix has the formula MO-SiO ₂ —Al ₂ O ₃ : R, where M is at least one metal selected from the group consisting of Ca, Sr, Ba, Mg Zn; R is at least one element selected from the group consisting of Dy, Nd, Eu, Tm, Tb, Y ₅ Yb.

3. The waterproof luminescent pigment according to claim 1, wherein the oxide matrix has the formula MA1 ₂ O ₄ : R where M is at least one metal selected from the group consisting of Ca, Sr, Mg, Ba, and R is at least one element selected from the group Dy ₃ Nd, Eu, Tm, Tb, Y ₅ Yb.

4. The waterproof luminescent pigment according to claim 1, wherein the oxide matrix has the formula MAYU ₄ : R, where M is at least one metal selected from the group Sr ₅ Ca, Ba; R is at least one element selected from the group Dy, Nd, Eu, Tm, Tb, Y, Yb.

5. Printing ink based on a thickener and a luminescent pigment, characterized in that the product according to claim 1 is used as a luminescent pigment.