RU2421499C1 - Luminescent composition and luminescent paint for marking roads (versions) - Google Patents

Abstract

FIELD: chemistry. ^ SUBSTANCE: disclosed is a luminescent composition for marking roads, which contains an aluminate type luminescent (phosphorescing) pigment and polymer binder selected from a group comprising: epoxy, urethane, acrylate, alkyd and composite polymer resins. The luminescent pigment is pre-treated in order to protect it from moisture using solutions of reagents selected from a group comprising mono-substituted phosphates, H2SO4, H3PO4, a mixture of tri- or disubstituted phosphates and at least one acid: HCl, H3SO4 or HNO3. Disclosed also is a luminescent paint for making roads, which contains an aluminate type luminescent (phosphorescing) pigment or a luminescent composition and a water or non-water based road paint or enamel. In another version, the luminescent paint is obtained by mixing a pigment which first protected from hydrolysis, polymer binder and a water or non-water based road paint or enamel: - luminescent pigment 2-60; polymer binder 4-20; road paint or enamel 94-20. ^ EFFECT: invention provides reliable protection of the pigment from hydrolysis, enables regulation of the amount of polymer binder which affects colour characteristics and technological aspects, as well as the size of particles of the luminescent pigment, which is important when mixing the pigment with components of compositions or paints. ^ 4 cl, 8 tbl, 58 ex

Description

FIELD OF TECHNOLOGY

The present invention relates to luminescent compositions and paints intended for marking coatings on objects such as roads, expressways, pedestrian crossings, runways of airfields, parking lots, direction indicators for traffic flows, traffic control devices, associated structures and objects.

Currently, many of these and other surfaces indoors and outdoors are marked by marking with paints or lamination.

Often such a marking, even when it contains reflective elements, ceases to be visible in low light or at night.

The visibility and durability of such markings can be significantly increased by coating with a product containing a luminescent pigment that provides highlighting without additional sources, so that the marking becomes visible in the dark.

This luminescence will also be useful for unmarked surfaces, helping people to better distinguish surfaces such as pedestrian walkways, the actual boundaries of structures and walls, curbs of expressways, etc.

In the literature and patent descriptions, there is often an incorrect use of terms such as luminescence, fluorescence and phosphorescence.

The effects of glow and light reflection are sometimes associated with these concepts. Inadequate use of terminology in relation to luminescent dyes and pigments leads to errors in attributing effects to various fields of technology. This makes it difficult to evaluate technical solutions, including those proposed for patenting. The following is the terminology associated with these concepts from the work: "Chemistry and physics with special properties of pigments, dyes, inks for printing and inks for coatings." A. Nurhan Becidyan [United Mineral & Chemical Corp., Paint Coating Industry, 06/15/2003].

Luminescence: fluorescence and phosphorescence.

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

Excitation: an active cause that causes a luminescent dye to emit light.

Fluorescence: light emission by a luminescent pigment in the presence of excitation (e.g. fluorescence in daylight).

Phosphorescence: light emission by a luminescent dye or pigment after the excitation has stopped (for example, glow in the dark).

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 infrared 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.

In fact, luminescent pigments glowing in the dark, in accordance with the above terminology, should more correctly be called phosphorescent pigments (phosphors). In the patent and technical literature, both names are used, which is reflected in this description.

Phosphorescence is similar to luminescence in that it is also associated with the absorption of radiation of a specific wavelength or a certain range of wavelengths and the release of photons with a different wavelength.

These phenomena differ in radiation time. The rule is this: if the radiation stops after removing the radiation source, this is fluorescence, but if the radiation continues (the so-called afterglow - “afterglow”), then this is called phosphorescence.

Thus, fluorescence and phosphorescence are special cases of the generalized concept of luminescence.

The authors use the term “luminescent pigment”, which is more general than the term “phosphorescent pigment”, indicating “phosphorescent” in parentheses to avoid misinterpretation, since both terms are used in patent descriptions and technical literature with respect to the same object. The validity of the chosen terminology can be confirmed by the fact that in the technical documentation phosphors are called luminescent pigments. It should be noted that the used retroreflective (retroreflective) effect is completely unrelated to the luminescence phenomenon. Retroreflective material interacts with light without causing the excitation of material molecules. Particles of such material in the form of balls or prisms perform only the function of light reflection due to the optical effect. In fact, a ray of light is reflected from a surface similar to a mirror. The material is characterized by optical characteristics, for example, a minimum coefficient of retroreflection at a certain angle of illumination. The retroreflective effect described above is realized only under artificial lighting (for example, when the headlights are in the dark).

In domestic practice, similar material is used for road marking (see, for example, “Methodological recommendations for applying road marking on cemented pavements of roads” No. ОС-1018-r dated November 19, 2003, order of the Ministry of Transport of the Russian Federation).

Currently, it is known to use fluorescent materials for marking coatings that emit light only when excited from a light source.

These materials can be selected to mark and underline marked surfaces in the daytime, such as step edges, wall corners, high-speed highway edges, walkways, direction indicators, road dividing strips, airfield runways, and building contours. The emission of light by these fluorescent materials, however, immediately ceases if the light source is removed.

Luminescent (phosphorescent) materials, on the contrary, when irradiated, continue to glow with soft, slowly fading radiation. This area is the real technical solution.

Phosphorescent materials can provide the required level of luminous flux for 10-12 hours after they have been activated by exposure to sunlight or artificial light (for example, the light of car headlights).

After an initial exposure from a light source, luminescence may be resumed by repeated exposure to natural or artificial light. Therefore, luminescent (phosphorescent) substances are introduced into the paints for road surfaces to mark the edges of the highway and the dividing strip to distinguish between the directions of traffic along the highway.

The most effective for this purpose are luminescent (phosphorescent) substances of the aluminate type. However, they have one common significant drawback - sensitivity to moisture. Under the influence of moisture during hydrolysis, the phosphor loses its light characteristics (luminescence).

BACKGROUND

The RF patents describe a number of paint compositions for road marking (see Table No. 1), none of which contain a luminescent pigment.

A number of US patents provide solutions to the problem of creating luminescent compositions for road surfaces with enhanced hydrolysis resistance.

In US Pat. US No. 5665793 proposed phosphorescent composition for coloring the highway, including:

- a luminescent substance representing a compound expressed by a matrix of MAl ₂ O ₄ , in which M is at least one metal selected from the group of calcium, strontium and barium, or expressed by a matrix of MAl ₂ O ₄ , in which M is a set of metals representing magnesium and at least one element, which is calcium, strontium and barium; and

- water-miscible resin.

The luminescent substance may contain, as an activator, europium and a coactivator, lanthanum, cerium, praseodymium, samarium, terbium, dysprosium, holmium.

As a water-miscible resin, a polyurethane resin is used, which, according to the authors, imparts moisture resistance to the luminescent substance.

The description contains the composition and method of its use.

Composition Composition:

- 5 parts of powdered LumiNova phosphorescent material;

- 7 parts water-based acrylic urethane and

- 88 parts of white water-based road paint.

The phosphorescent (luminescent) pigment and acrylic urethane are first separately mixed together at an ambient temperature of 73 ° ± 5 ° F, and then the resulting mixture is mixed with water-based highway paint.

The luminescent substance and the polyurethane resin can be added directly to the ink composition. In an advantageous embodiment of this invention, the pre-mixture is formed by mechanical mixing of small sequentially introduced amounts of a luminescent substance with a water-compatible or water-miscible resin, in which the luminescent substance is coated with a polyurethane resin. This mixture can be stored or can be immediately added to water-based paint by mechanical mixing.

Table number 1 RF patent number Film forming Filler Thickener Solvent Pigment 2.267.508 48-52% solution of a copolymer of styrene and butyl acrylate in toluene "Polyform-1" B " Fractional micromarble and aluminum proxy "Procal" Bentone SD-2 Organic Montmorillonite Derivative A mixture of toluene and ethyl acetate in a ratio of 2.4: 1 or a mixture of toluene and acetone in a ratio of 1: 1 Titanium dioxide 2.237.694 Latex butadiene styrene copolymer BS 65 18-22 Quartz crumb Dextrin and Hydol Water - 2.181.740 A copolymer of styrene, butyl acrylate, methyl methacrylate, methacrylic acid Aerosil, ground marble, quartz, talc, barite The solution of triethanolamine in ethanol Toluene, butanol Titanium dioxide 2.155.200 Butyl acrylate copolymer with methyl methacrylate and methacrylic acid Chalk, alumina, microcalcite, calcium thermosulfate, bleached microbarite, microtalc Polyvinyl chloride resin, chloroparaffin Acetone, butyl acetate, toluene Titanium dioxide 2.067.601 Styrene-butadiene thermoplastic elastomer, styrene-butadiene copolymer, Zinc oxide, chalk Petroleum resin Nefras, xylene, ethyl acetate - chlorosulfonated polyethylene 2.074.872 Polyester Resin (Phthalic Anhydride, Ethylene Glycol, Glycerin) Aerosil, quartz sand Transformer oil Titanium dioxide 2.089.584 Aromatic polyvinyl block copolymer Carbon resin 2.092.511 Dry-rolled paste based on colloxylin or a copolymer of butyl acrylate and acrylic acid Rosin glycerin ester Toluene Titanium dioxide 2.109.786 A copolymer of butyl acrylate, methacrylic acid and methacrylate. Amide Acrylic Resin Calcium Aerosil Dibutyl phthalate White spirit, xylene, acetone, butyl acetate Titanium dioxide 2.129.581 Styrene-butadiene copolymer latex Ceramic chips, expanded clay Hydrolyzed polyacrylonitrile, glue Application No.2000113750 / 04 A copolymer of styrene, butyl acrylate, methyl methacrylate and methacrylic acid Marble, Aerosil, Talc, Quartz The solution of triethanolamine in ethanol A mixture of toluene and butanol Titanium dioxide Application No. 97114960/04 Aqueous dispersion paint based on anion-stabilized emulsion polymer Glass beads, quartz sand Water

The road surface is pre-wiped clean and treated with compressed air to remove dirt and other debris in places where paint should be applied. The paint is dried dry until it sticks on contact. According to the authors, in water-based compositions obtained by mixing a water-compatible polyurethane resin with a water-sensitive luminescent substance, the luminescent substance is surprisingly protected from moisture in air and water. T.O. The luminescent substance is protected immediately after mixing with the polyurethane resin in the coloring composition.

In a later pat. US No. 6005024 proposed to use epoxy resins for coating a luminescent pigment.

In US Pat. US No. 6005024 claims a phosphorescence-luminescent epoxy coating for marking surfaces on the ground, structural surfaces and individual items, consisting of:

a) an almost colorless phosphorescent-luminescent material consisting of a compound expressed by the formula MAl ₂ O ₄ , where M is at least one element selected from the group consisting of calcium, strontium and barium, or, alternatively, expressed by the formula MAl ₂ O ₄ , where M is the set of metal elements, including magnesium and at least one element selected from the group comprising calcium, strontium and barium;

b) a two-component epoxy composition (consisting of resin and hardener), which after curing becomes completely transparent, resistant, durable, free of water and moisture resistant (insensitive to moisture). Moreover, this composition, when exposed to a light source, shows brightness properties higher than in the case of traditional sulfide-based phosphorescent materials, and the afterglow is about ten times higher than the afterglow time of traditional sulfide-based phosphorescent materials.

The composition contains europium as an activator.

The composition contains as an activator selected from the group comprising lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, manganese, tin and bismuth.

A method is also proposed for preparing (or “pre-mixing”) a phosphorescent-luminescent epoxy composition in which an increasing amount of a phosphorescent-luminescent substance is mixed with either a curing component or a resin component of a two-component epoxy resin before mixing and activating two epoxy components.

Thus, thorough coating, encapsulation and homogeneous distribution of phosphorescent-luminescent particles in the curing component or resin component of the two-component epoxy composition is ensured before mixing the two components.

In the description of US Pat. US No. 6005024 notes that the compositions disclosed by US patent No. 5665793 show a decrease in luminosity in the mixture due to the fact that the particles of the paint to some extent block the luminous component.

In addition, this composition contains a significantly larger number of mixed components than the composition based on epoxy resins.

In US Pat. US No. 5874491 according to the claims patented phosphorescent composition for roads, consisting of:

a) a luminescent substance, including a compound expressed by the formula MAl ₂ O ₄ , in which M is at least one metal selected from the group: calcium, strontium and barium, or alternatively the formula MAl ₂ O ₄ , in which M is a combination of metals representing magnesium and at least one element representing calcium, strontium and barium, and

b) epoxy resins with which the luminescent substance is mixed;

c) a dispersion of paint mixed with a) and b).

The luminescent substance may contain europium as an activator, and lanthanum, cerium, praseodymium, samarium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin and bismuth as a activator.

The composition may contain natural and synthetic abrasive materials.

In the description, when characterizing the essence of the invention, not only epoxy resins, but also polyurethanes are indicated as a component of the composition, while it is unproven that it is surprising that epoxy resin and polyurethane immediately protect the moisture-sensitive luminescent substance. When using epoxy resins, the hardener and resin components are mixed and then luminescent particles are introduced.

The composition can be applied directly to the surface or, if necessary, can be mixed with water-based paint.

As an example, a composition of the following composition is presented:

- 1 part - a powdery mixture of phosphorus (luminescent substance) and fluorescent substance (not characterized by chemical composition or formula);

- 6 parts - epoxy hardener;

- 13 parts - epoxy polymer.

The description of the patent does not contain any experimental data confirming the production of a moisture-resistant product and, in general, the ability to mix a moisture-sensitive product with a water-based system without destroying it. This is really not just surprising, but also contrary to reasonable ideas about the process, and therefore, of course, needs proof.

In US Pat. US No. 6359048 B1 describes an alkyd resin tinting luminescent paint containing an aluminate phosphor, white alcohol as a diluent and various modifying additives.

In the description of the patent it is noted that the paint is intended primarily for indoor use. At the same time, there is an indication that, with special brands of alkyd resins, compositions for more severe operating conditions can be obtained. The description of the patent emphasizes that aluminate phosphors have serious drawbacks - moisture sensitivity and difficulty of mixing due to their high density. In addition, it contains criticism of the technical solutions patented in the two previous patents.

For example, in relation to the paint described in US Pat. US No. 5874491, the following is indicated:

- the composition obtained by mixing the phosphor with a water-soluble polyurethane or epoxy resin, allows to obtain a fairly stable composition suitable for marking road surfaces;

- a mixture of a luminescent substance with a water-soluble polyurethane or epoxy resin agglomerates or encapsulates the pigment;

- they can be mixed with water-based paint to mark roads;

- unfortunately, these resins are expensive and unsuitable in cases where you need to get a natural looking, durable and economically painted surface;

- encapsulation of phosphorus leads to an increase in the actual particle size and makes it difficult to introduce significant amounts of phosphorus into the paint, reducing the amount that can glow, in addition to other features of this product, and makes it difficult to use.

In relation to US Pat. No. 6005024, the following is noted:

- tests have shown that the Luminova ™ pigment adds yellow color to any composition in which it is used in an amount of 5%;

- the two-stage nature of the epoxy system limits its use (i.e., it should be fully used immediately after mixing the two components);

- luminescent epoxy products have existed for many years, although for the most part they are used in the extrusion of plastics and packaging of products, initially luminous products were used for trinkets, toys, jewelry;

- experiments showed that the addition of a large amount of pigment masks the level of luminescence, since the added particles cover the luminescent particles;

- processing of the pigment is important, since it cannot be subjected to grinding;

- water should not act on it, otherwise it will lose its ability to glow;

- it cannot be exposed to heavy metals both in the system itself and in mixer devices.

US Patent Application No. 2004/0146349 A1 proposes a new photoluminescent material for marking, which is intended for marking lanes on roads, etc.

It has the necessary wear resistance and weather resistance, as well as high photoluminescence efficiency, can be used not only for white stripes, but also for stripes of any kind of color when suppressing green tones, and, in addition, can give properties that prevent slipping.

The marking material is mainly a material in which a resin-based paste containing transparent resin components and photoluminescent pigment components is applied to the road surface to form a photoluminescent layer.

Various types of transparent component are capable of forming a resin paste, provided that they are transparent and can subsequently be cured after being applied to the surface of the road.

They are permissible in the case when they are resistant as lanes on the road, etc., i.e. sufficient strength and resistance to weather, light and water.

Various types of components of the transparent layer may be presented, for example, based on methacrylic resin, unsaturated polyester resins, epoxy resin, silicone type resins, etc. resins.

The transparent resin component, the main component of the resin paste, provides adhesion of the luminescent layer when used for marking strips, etc. on the surface of roads and plays the role of a binder.

It is assumed that as the photoluminescent pigment introduced into the transparent component, not only known pigments are used, but also commercially available pigments and various other suitable pigments.

Examples of these pigments are products such as strontium aluminates and zinc sulfide products. Photoluminescent pigments with an average particle diameter of 10 μm or more are used. According to the present invention, an average diameter of from 20 μm to 2000 μm is preferred, and more preferably from 30 μm to 300 μm. Particles with a diameter of 100 μm or more may also be preferably used.

Previously, it was not easy to apply a photoluminescent pigment with particles of such a large diameter, since pigment particles with a large diameter are difficult to evenly distribute.

According to the invention, a photoluminescent pigment with a relatively large particle diameter, which was usually difficult to disperse uniformly, can be uniformly dispersed in the resin paste using a transparent resin component with a relatively high viscosity such as 1 Pa · s (20 ° C) or more.

To reduce glide on the photoluminescent layer, a transparent resin complex containing a photoluminescent pigment is mixed with the components of the resin paste, which is applied to the road surface and cured. The surface of the paste thus cured is then subjected to coarse polishing or water-jet treatment to remove part of the cured surface of the resin paste. Such coarsening treatment, in addition to the useful function of reducing slip, contributes to mechanical damage to part of the luminescent particles, due to which their photoluminescent properties are lost. On the other hand, increased moisture access to the surface luminescent pigment particles, contributing to hydrolysis.

An analysis of all previous decisions on the creation of phosphorescent (luminescent) compositions allows us to conclude that the proposed solutions were based on the choice of transparent resins capable of forming a film into which a luminescent pigment (phosphorus) is encapsulated. Such compositions are recommended for marking various surfaces. One of the main areas of use for US-protected phosphorescent compositions is highway marking.

Marking involves either applying the proposed compositions to ready-made markings made using conventional road paints of various colors, or introducing water-miscible or water-compatible phosphorescent compositions into ready-made aqueous highway paints for subsequent use in marking.

Before introducing a phosphor into the paint in the patent descriptions, it is recommended to pre-mix the initial fluorescent pigment with the resin or resin components, which, according to the authors of the patents, prevents the phosphor from reacting with the water contained in the paint by encapsulating the resin.

In the descriptions of these patents, it is stated that the water-resistant luminescent pigment in the selected resin or in the resin components becomes reliably protected from moisture.

Due to the formation of a transparent polymer film of any of the proposed phosphorescent compositions, the phosphor is protected from interaction with the external environment (moisture).

Transparent resins used in phosphorescent compositions capable of forming films are described in two types:

- a polymer resin forming a film on the surface to be marked after drying (solvent removal). For example, polyacrylurethane resin - US Pat. U.S. Pat. No. 5,665,793; US No. 5874491;

- a two-component composition forming a film as a result of "curing", "crosslinking" of the components. For example, a two-component epoxy composition consisting of resin and hardener, which forms a transparent film after curing, - US Pat. US No. 5874491, US Pat. US No. 6005024, alkyd resin followed by the addition of calcium and cobalt - US Pat. US No. 6359048 B1, methyl methacrylate resin, followed by the addition of a resin curing agent - US patent application No. 2004/0146349 A1.

In the described US patents, an epoxy resin luminescent composition is used for marking surfaces both individually and in admixture with road marking paints. Compositions based on other resins are recommended to be used in a mixture with water-based road marking paints. Thus, the two-component luminescent epoxy composition can also be considered as a luminescent marking varnish applied as a finishing layer to the finished road marking. A similar solution is offered by the German company Suedwest (www.suedwest.ru). For marking the carriageway of roads, parking lots, sidewalks, signs, etc. luminous (fluorescent) marking paints are applied first. Then on top, in order to avoid quick contamination, a transparent marking varnish on an acrylate base is applied as a final layer.

All known technical solutions are based on one principle - physical protection of aluminate luminescent pigment from hydrolysis, namely by encapsulating pigment particles with various types of polymer resins.

With such surface protection, there is always the possibility of disturbing the surface layer, especially in such harsh operating conditions as road surfaces. Even local access of moisture due to minor surface damage leads to the initiation of a hydrolysis reaction.

Thus, the protection of the luminescent pigment from hydrolysis by treatment with a polymer film does not provide sufficient reliability under conditions of real mechanical impact on the coating.

The creators of the solutions known from the prior art do not take into account three very important, according to the authors, circumstances:

- a high degree of probability of hydrolysis before encapsulation of the phosphor resin;

- incomplete protection against hydrolysis after encapsulation;

- the ability to access moisture and, therefore, the implementation of hydrolysis during the operation of the marking coating.

Regarding the latter circumstance, which is not discussed at all in the patents, it should be noted that after marking surfaces both indoors and outdoors, the phosphorescent films formed have natural defects: cracks, shells, etc.

On the other hand, a part of the luminescent pigment can act as its faces above the surface of the film. All this contributes to contact with environmental moisture.

The luminescent pigment begins to hydrolyze, reducing the total intensity of the luminescence of the film. The onset of hydrolysis in various places of the film provokes the formation of additional defects on the surface and inside, there is a change in its physical and mechanical properties.

The contact of the marking surfaces with the tires of cars or any other objects that contribute to the abrasion of the film leads to the destruction of the protective polymer shell of the phosphor, and its hydrolysis begins with the formation of non-luminous hydroxides.

With regard to the first two circumstances, it is necessary to point out two options for using patentable compositions based on luminescent pigments and polymer resins recommended in patents, namely:

- application of compositions (encapsulated luminescent pigments) directly on the finished markings made using conventional paints of various colors;

- preparation of paint based on encapsulated phosphor by mixing it with ready-made paints for water-based highways.

In both cases, water is present, and the approval of the authors of the patents on complete, reliable protection against hydrolysis of the initial phosphor appears to be unproven.

The experimental studies conducted by the authors showed that, regardless of the type of film-forming composition (polyurethane, epoxy, alkyd, acrylate, etc.), hydrolysis occurs with a visible decrease in the glow intensity when:

- the implementation of the encapsulation of a luminescent phosphor;

- mixing encapsulated luminescent pigment with water-based paints;

- mechanical damage to the encapsulated luminescent pigment and paint based on it.

Below are experimental confirmations of the above.

An experimental study of the progress of hydrolysis was carried out taking into account the possible stages of implementation and application of technical solutions, namely:

- preparation of compositions, paints and films;

- modeling of operating conditions for the impact of water on a marked surface.

Evidence of hydrolysis during encapsulation of a luminescent pigment

Lumi Nova® brand luminescent pigments (Lumi Nova G-300 M) were introduced into Huntsman's Araldite 2020 epoxy resin.

The resulting luminescent dispersion was mixed with water and a change in pH was observed. It was found that in an aqueous dispersion, the initial pH of 7 after 20 minutes increased to a pH of 8-9. An increase in the pH of the medium indicated the formation of phosphor hydroxides, i.e. about the progress of the hydrolysis reaction, and served as evidence that the epoxy resin does not protect the particles of the luminescent pigment.

After 30-40 minutes of stirring, a separation of the system was observed. Three phases formed in the tank: below, a luminescent pigment that continues to hydrolyze, above, a luminescent epoxy resin, and above, an aqueous solution of hydroxides. The high particle density of the luminescent pigment - 3.65 g / cm ³ explains its precipitation.

A similar situation developed when using other types of resin: polyurethane (Araldite 2026) and methacrylate (Araldite 2021). The results of these experiments were evidence of the occurrence of hydrolysis during the encapsulation of the luminescent pigment (when processing with polymer resins).

Evidence of hydrolysis under mechanical action on encapsulated luminescent pigment

A) Treatment of the luminescent pigment with film-forming compositions

It is shown that after mechanical grinding of the water-unstable luminescent pigment treated with a film-forming composition, the resulting powder becomes unstable to water, i.e., it is hydrolyzed.

The experiments were carried out using the luminescent pigment Lumi Nova G-300M and film-forming compositions based on:

- glue Araldite. Table 2 shows some characteristics of the adhesive and the ratio for mixing the resin and hardener;

- a special Degalan® LP 64/12 acrylate polymer, which is used as a 40% toluene solution;

- Diplex 070 thermoplastic acrylic polymer in toluene solution, which is used for road marking purposes (the coating based on this resin has a shiny surface, and on the basis of Degalan® LP 64/12 it is matte).

Table number 2 Araldite adhesive labeling Glue description The ratio of resin and hardener,% weight voluminous 2020 Transparent, epoxy, ideal for glass and ceramics 100: 30 100: 35 2026 Transparent, flexible polyurethane, for bonding plastics and glass 100: 100 100: 100 2021 Fast curing, multi-purpose, methacrylate 100: 90 100: 100

After processing the luminescent pigment with the specified film-forming and mechanical grinding of the obtained film, it was placed in water. In this case, the hydrolysis reaction immediately began.

This is confirmed by an increase in the pH of the aqueous solution as a result of the formation of hydroxides. After 30-40 minutes of water treatment, the filtered and dried luminescent powder of the ground film has a low residual luminous intensity

B) Treatment of a luminescent pigment with a curable epoxy composition in an aqueous medium

Lumi Nova G-300M luminescent pigment was added to the epoxy resin, a component of Araldite 2020 glue, and the mixture was mixed for 30 minutes. Then a hardener was added in proportion to the resin indicated in Table No. 2.

The suspension was mixed for 10 minutes, after which an equal volume of water was added. It was not possible to control the change in pH, since the hardener (mixture of amines) in the aqueous medium has a strongly alkaline reaction. After 30-40 minutes of stirring, curing of the epoxy resin was completed. Two phases formed: the polymerized luminescent composition in the form of a white solid lump and an aqueous suspension containing the remains of the cured phosphor resin. The suspension was filtered and the precipitate was washed several times with cold water. Then the precipitate was placed in cold water. After a few minutes, the pH of the medium began to increase, which indicated the occurrence of a hydrolysis reaction. After 4 hours, hydrolysis was almost complete with the formation of an additional amount of hydroxides in the form of white flakes.

The solid lump was thoroughly washed with cold water and dried. After light insolation, the lump intensely glowed in the dark with a yellow-green glow. The lump was broken into 6-8 large pieces. One of them was pulverized. Large pieces and powder were placed separately in two glasses of cold water. After a few minutes, the pH of the medium began to increase in each of them, indicating a hydrolysis reaction.

Thus, preliminary dispersion in both the epoxy resin and the epoxy resin + hardener system does not lead to subsequent protection against hydrolysis of the luminescent pigment particles.

Similar studies were conducted using other types of transparent resins: polyurethane (Araldite 2026) and methacrylate (Araldite 2021). Hardeners were added to the corresponding resins in the ratios shown in Table No. 2.

As a result, the course of the hydrolysis of the luminescent pigment at the control stages was established.

Evidence of hydrolysis in the manufacture and use of paints for marking road surfaces.

It should be noted that road paints for marking both on an aqueous and non-aqueous basis ultimately form a film on the marked surface. When a water-resistant luminescent pigment is introduced into a water-based paint, hydrolysis begins immediately after the phosphor is introduced into the paint, and the hydrolysis will continue until the pigment has completely decomposed. If, after introducing the pigment into the paint, it can be used for marking immediately, then encapsulation stops the hydrolysis, but during the operation of the marking in contact with water, the decomposition of the pigment will continue. The process of hydrolysis of the luminescent pigment in non-aqueous based paints should be considered only in the cured film formed after surface marking.

The following experiments to some extent model the behavior of water-resistant luminescent pigments in paints for road marking. These paints can be of two types - water-based and based on organic solvents. In both cases, they consist of five main components: film-forming, filler, thickener, solvent and pigment. For the formation of a luminescent (phosphorescent) film, the main component is film-forming.

For the study, paints that were widely used in Russia for road marking were selected: paint for road marking "Cork-S" - a suspension of pigments and fillers in a solution of domestic acrylic copolymers and special additives and waterproof paint road marking "Crossroads" - a suspension of pigments and fillers company “Omya” (Switzerland) in a solution of acrylic copolymers of the company “Forst” (Finland) and special additives.

Based on each of them, luminescent paints were obtained by introducing 20-30% (wt.) Of the luminescent pigment into the initial paints. After applying paints to the prepared surfaces and drying, the resulting films were ground into powder and placed in water. It was found that the hydrolysis reaction - the destruction of the phosphor.

The second series of experiments consisted of introducing a water-resistant luminescent pigment Lumi Nova G-300 M into the methacrylate resin of Araldite 2021 glue, adding a hardener and mixing it with the Crossroad paint.

After 25-30 minutes of stirring the suspension, a solid lump of luminescent polymer mass fell out. The lump was isolated, washed with water, crushed, crushed and placed in water. Almost immediately, the pH of the medium began to increase, which confirmed the progress of hydrolysis. Similar results were obtained using Cork-S paint.

Thus, it has been experimentally proved that all known technical solutions for creating compositions and paints for marking road surfaces containing luminescent (phosphorescent) pigments cannot provide reliable protection against water, i.e. hydrolysis.

All these technical solutions are based on the use of the encapsulation method, which, as was proved by the experiment, in any embodiment allows the possibility of hydrolysis at different stages of its implementation and application.

SUMMARY OF THE INVENTION

The present invention is the creation of luminescent compositions for marking road surfaces and other surfaces and luminescent paints based on these compositions, in which the luminescent (phosphorescent) pigment is reliably protected from hydrolysis in any operating conditions.

The problem is solved by the proposed technical solution, the essence of which is to create a luminescent (phosphorescent) composition containing a luminescent (phosphorescent) pigment, which is an oxide matrix based on aluminum oxide and oxides of at least one element selected from the group: Mg, Ca , Sr, Ba, Zn, Si, activated by at least one rare earth element, and a polymer binder selected from the group: epoxy, urethane, acrylate, alkyd and mixed polymer resins, which contains there is a luminescent (phosphorescent) pigment pretreated with aqueous solutions of reagents selected from the group: monosubstituted phosphates, H ₂ SO ₄ , H ₃ PO ₄ , mixtures of tri- or disubstituted phosphates with at least one of the acids: HCl, H ₂ SO ₄ or HNO ₃ , in the following ratio (weight) of components:

- pigment: 2-88 - binder: 12-98

The second object of the invention is a luminescent (phosphorescent) paint for road marking, containing: a luminescent (phosphorescent) pigment, which is an oxide matrix based on aluminum oxide and oxides of at least one element selected from the group: Mg, Ca, Sr, Ba, Zn, Si, activated with at least one rare earth element, pretreated with aqueous solutions of reactants selected from the group: monosubstituted phosphates, H ₂ SO _4, H ₃ PO ₄ mixture of tri- or disubstituted phosphates with at m D, one of the acids: HCl, H ₂ SO ₄ or HNO _3, and a road or enamel paint at the following ratio (by weight) of the components:

- pigment: 3-75 - paint: 25-97

Another embodiment of the invention is a luminescent (phosphorescent) paint for marking pavements containing the luminescent composition according to claim 1 and a road paint or enamel for marking, in the following ratio (weight) of components:

- luminescent composition: 8-52 - road paint or enamel: 48-92

or a luminescent pigment pretreated with aqueous solutions of reagents selected from the group: monosubstituted phosphates, H ₂ SO ₄ , H ₃ PO ₄ , mixtures of tri- or disubstituted phosphates with at least one of the acids: HCl, H ₂ SO ₄ or HNO ₃ , a polymer binder and road paint or enamel for marking, in the following ratio (weight) of components:

- luminescent pigment - 2-60 - polymer binder - 4-20 - road paint or enamel - 94-20

The proposed technical solutions differ from those known from the prior art in that they use luminescent (phosphorescent) pigments pretreated with aqueous solutions of reagents selected from the group: monosubstituted phosphates, H ₂ SO ₄ , H ₃ PO ₄ , mixtures of tri- or disubstituted phosphates with at least one of the acids: HCl, H ₂ SO ₄ or HNO ₃ .

It is known from the prior art that in order to impart resistance to hydrolysis, luminescent (phosphorescent) pigments are treated with aqueous solutions of reagents selected from the group: monosubstituted phosphates, H ₂ SO ₄ , H ₃ PO ₄ , mixtures of tri- or disubstituted phosphates with at least one of the acids: HCl, H ₂ SO ₄ or HNO ₃ . (RF patent No. 2323955, owned by the authors of the present invention).

However, neither the specified patent, nor any other source of information known from the prior art raised or solved the problem of the reliability of protection against hydrolysis of compositions for marking road surfaces containing luminescent (phosphorescent) pigments that are unstable to water (hydrolysis).

The authors of the present invention for the first time showed that in the specified field of technology there is a problem of reliability of protection against moisture even in the case of using encapsulated (protected) luminescent pigments due to the discovered circumstances:

- violation of the protective layer of the polymer film during mechanical damage, which are necessarily present during the operation of road surfaces;

- the occurrence of hydrolysis during the implementation of the encapsulation process, which is unprovenly denied by the authors of known technical solutions;

- the occurrence of hydrolysis in the manufacturing process of road paints on an aqueous and non-aqueous basis.

A new formulation of the problem, the existence of which is proved by the authors through an experiment, and its solution not described in the prior art, is a proof of the compliance of the proposed technical solution with the condition of an inventive step.

The proposed technical solution allows not only to provide reliable protection against hydrolysis, but also

- regulate the amount of polymer binder, which affects the light characteristics and technological aspects;

- adjust the particle size of the luminescent pigment, which is important when mixing it with the components of the compositions and paints.

The implementation of the invention

As the initial luminescent pigments to protect them from hydrolysis and subsequent use to create luminescent compositions and luminescent paints, the pigments shown in Table No. 3 were selected.

Table number 3 No. p / p Name of company and country of origin Name of luminescent pigment one Dalian Luminglight Science and Tehnology Co., Ltd - China SP-2, SP-4, PLO-8C, GPLOS-5-14, GPLOS-5-20, PLB-7C 2 Nemoto and Co., Ltd - Japan
Sample submitted by UM (United Mineral and Chemical Corp.) Lumi Nova G-300M 3 NPK Luminofor-Platan LLC - Russia LDP-2M, LDP-ZM four CJSC NPF Luminofor - Russia FV-530D 5 Nichia Corp. - Japan NP-2820

Table 4 presents some of their characteristics.

Table number 4 No. p / p Name of luminescent pigment Radiation wavelength Chemical composition one SP-2, SP-4, GPLOS-5-14, GPLOS-5-20, PLO-8C 520 MO · SiO ₂ · Al ₂ O ₃ : Eu
M - one or more elements selected from the group: Ca, Mg, Sr, Ba, Zn 2 LDP-2M 520 SrAl ₂ O ₄ : Eu, Dy 3 LDP-3M 490 four Lumi Nova G-300 M 520 SrAl ₂ O ₄ : Eu, Dy 5 NP-2820 490 Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy 6 PLB-7C 490 MO _x Al ₂ O _3y SiO ₂ : Eu
M - Ca, Mg, Sr, Ba, x = 1.2-2.0, y = 0.005-0.5 7 PLO-7C 520 MO _x Al ₂ O _3y SiO ₂ : Eu
M - Ca, Mg, Sr, Ba, x = 0.5-2.0, y = 0.05-0.5

Table 5 presents the conditions and results of the treatment of luminescent pigments to give them waterproof properties.

Table number 5 No. of examples Name of phosphors Reagents used for processing phosphors the pH of the solution when processing the phosphor Resistance to phosphor hydrolysis at the beginning of processing at the end of processing 1-1 SP-2 H ₃ PO ₄ , H ₂ O one 3 steady 2-1 LDP-2M H ₃ PO ₄ , H ₂ O one 3 - “- 3-1 FV-530D H ₃ PO ₄ , H ₂ O one 3 - “- 4-1 Lumi Nova G-300 M H ₃ PO ₄ , H ₂ O one 3 - “- 5-1 SP-2 H ₂ SO ₄ , H ₂ O one four - “- 6-1 LDP-2M H ₂ SO ₄ , H ₂ O one four - “- 7-1 SP-2 (NH ₄ ) H ₂ PO ₄ , H ₂ O 6 7 - “- 8-1 LDP-2M (NH ₄ ) H ₂ PO ₄ , H ₂ O 6 7 - “- 9-1 SP-2 NaH ₂ PO ₄ · 2H ₂ O, H ₂ O 6 7 - “- 10-1 SP-2 Na ₃ PO ₄ · 12H ₂ O, H ₂ O, HCl one 3 - “- 11-1 SP-4 Na ₃ PO ₄ · 12H ₂ O, H ₂ O, HCl one 3 - “- 12-1 LDP-2M Na ₃ PO ₄ · 12H ₂ O, H ₂ O, HCl one 3 - “- 13-1 FV-530D Na ₃ PO ₄ · 12H ₂ O, H ₂ O, HCl one 3 - “- 14-1 Lumi Nova G-300 M Na ₃ PO ₄ · 12H ₂ O, H ₂ O, HCl one 3 - “- 15-1 LDP-2M Na ₂ HPO ₄ · 12H ₂ O, H ₂ O, HCl one 3 - “- 16-1 LDP-2M (NH ₄ ) ₂ HPO ₄ , H ₂ O, HCl one 3 - “- 17-1 GPLOS-5-14 H ₃ PO ₄ , H ₂ O one 3 - “- 18-1 GPLOS-5-20 Na ₃ PO ₄ · 12H ₂ O, H ₂ O, HCl one 3 - “- 19-1 PLO-8C Na ₃ PO ₄ · 12H ₂ O, H ₂ O, HCl one 3 - “- 20-1 PLB-7C H ₃ PO ₄ , H ₂ O one 3 - “- 21-1 PLB-7C Na ₃ PO ₄ · 12H ₂ O, H ₂ O, HCl one 3 - “- 22-1 NP-2820 Na ₃ PO ₄ · 12H ₂ O, H ₂ O, HCl one 3 - “- 23-1 LDP-3M H ₃ PO ₄ , H ₂ O one 3 - “- 24-1 PLB-7C (NH ₄ ) H ₂ PO ₄ , H ₂ O 6 7 - “- 25-1 PLO-8C Na ₃ PO ₄ · 12H ₂ O, H ₂ O, HCl one 3 - “- 26-1 SP-2 Na ₃ PO ₄ · 12H ₂ O, H ₂ O, H ₂ SO ₄ one four - “- 27-1 SP-2 Na ₃ PO ₄ · 12H ₂ O, H ₂ O, HNO ₃ one 2 - “-

1. EXAMPLES OF PRODUCTION OF WATERPROOF LUMINESCENT PIGMENTS

General procedure for the processing of aluminate phosphors

In a 100 ml glass beaker equipped with a magnetic stirrer, an appropriate amount of aqueous solutions of phosphoric or sulfuric acid, monosubstituted phosphates or mixtures of salts of phosphoric acid with hydrochloric acid, sulfuric acid or nitric acid are placed and an aluminate phosphor is added over 10 minutes with stirring . The suspension is stirred for 2 hours, filtered, the precipitate is washed 5 times with 40 ml of distilled water and dried at 80 ° C to constant weight. When adding a phosphor to the solution, spontaneous heating of the reaction mass to 26-28 ° C can occur. During the processing of the phosphor, the pH of the aqueous suspension is determined at the beginning and end of the reaction. For the treatment of phosphors, acids are used: 85% H ₃ PO ₄ , 92% or 98% H ₂ SO ₄ , 35% HCl, 55% HNO ₃ ; monosubstituted phosphates: NaH ₂ PO ₄ · 2H ₂ O, (NH ₄ ) H ₂ PO ₄ ; phosphoric acid salts: Na ₃ PO ₄ · 12H ₂ O, Na ₂ HPO ₄ · 12H ₂ O, (NH ₄ ) ₂ HPO ₄ .

The processing temperature is not specifically limited to 28 ° C. It is possible to carry out processing at a higher temperature, up to the boiling point of the solution, however, this does not lead to an increase in the luminosity of the phosphor compared to the reaction without special heating.

The processing time is 10-120 minutes, preferably 120 minutes. The increase in processing time does not affect the luminosity of the phosphor.

Determination of resistance to hydrolysis of aluminate phosphors at room temperature

0.5 g of the phosphor processed as indicated in the Examples and 20 ml of distilled water are placed in a 50 ml glass cup equipped with a magnetic stirrer and stirred at room temperature for 6 hours, periodically determining the pH of the medium. The phosphor is considered resistant to hydrolysis if the pH of the medium does not exceed 7.

Table 5 shows the results of the processing of phosphors.

Example 1-1

35.3 g of H ₂ O, 4.7 g of 85% H ₃ PO ₄ are placed in a 100 ml glass glass equipped with a magnetic stirrer, and 10 g of phosphor SP-2 are added portionwise over 10 minutes. The suspension is stirred for 2 hours, filtered, the precipitate is washed 5 times with 40 ml of distilled water and dried at 80 ° C to constant weight. 9.64 g of a light yellow phosphor are obtained. After mixing water and acid, the solution had a pH of 1, at the end of the phosphor treatment pH 3.

Example 2-1

The processing is carried out under the conditions of Example 1-1, only as a phosphor use LDP-2M. 9.72 g of a light yellow phosphor are obtained.

Example 3-1

Processing is carried out under the conditions of Example 1-1, only as a phosphor use FV-530D. 9.57 g of a light yellow phosphor are obtained.

Example 4-1

The treatment is carried out under the conditions of Example 1-1, only Lumi Nova G-300 M is used as a phosphor. 9.83 g of a light yellow phosphor are obtained.

Example 5-1

39.4 g of H ₂ O, 0.6 g of 98% H ₃ SO ₄ are placed in a 100 ml glass beaker equipped with a magnetic stirrer and 10 g of phosphor SP-2 are added portionwise over 10 minutes. The suspension is stirred for 1 hour. The product is isolated as described in Example 1-1. 9.8 g of a light yellow phosphor are obtained. The initial solution had a pH of 1, at the end of the treatment a pH of 4.

Example 6-1

The phosphor LDP-2M is processed under the conditions of Example 5-1. 9.9 g of a light yellow phosphor are obtained. The initial solution had a pH of 1, at the end of the treatment a pH of 4.

Example 7-1

36.0 g of H ₂ O are poured into a 100 ml glass beaker equipped with a magnetic stirrer and 4.0 g of (NH ₄ ) H ₂ PO ₄ are added with stirring over 5 minutes. To the resulting solution, 10.0 g of phosphor SP-2 is added portionwise over 10 minutes with stirring. The suspension is stirred for 1 hour. The product is isolated as described in Example 1-1. 9.8 g of a light yellow phosphor are obtained. At the beginning of the treatment, the solution had a pH of 6, at the end of the treatment, a pH of 7.

Example 8-1

The phosphor LDP-2M is processed under the conditions of Example 7-1. 9.9 g of a light yellow phosphor are obtained. At the beginning of the treatment, the solution had a pH of 6, and at the end of the treatment, pH 7.

Example 9-1

10.0 g of phosphor SP-2 is treated with a solution prepared by dissolving 5.2 g of NaH ₂ PO ₄ · 2H ₂ O in 34.8 g of H ₂ O. Processing and isolation of the product is carried out under the conditions of Example 7-1. 9.9 g of a light yellow phosphor are obtained. At the beginning of the treatment, the solution had a pH of 6, at the end of the treatment, a pH of 7.

Example 10-1

To a suspension of 15.5 g of Na ₃ PO ₄ · 12H ₂ O in 11.7 g of H ₂ O, 12.8 g of 35% hydrochloric acid are added dropwise with stirring over 10 minutes. To the resulting homogeneous solution add 10.0 g of phosphor SP-2 and the processing and isolation of the product are carried out as described in Example 1-1. 9.5 g of a light yellow phosphor are obtained. After mixing the reagents, the solution had a pH of 1, at the end of the treatment a pH of 3.

Example 11-1

10.0 g of phosphor SP-4 is treated under the conditions as described in Example 10-1. 9.65 g of a light yellow phosphor are obtained. After mixing the reagents, the solution had a pH of 1, at the end of the treatment a pH of 3.

Example 12-1

10.0 g of the phosphor LDP-2M is processed under conditions as described in Example 10-1. 9.6 g of a light yellow phosphor are obtained. After mixing the reagents, the solution had a pH of 1, at the end of the treatment a pH of 3.

Example 13-1

10.0 g of the phosphor FV-530D is processed under conditions as described in Example 10-1. 9.4 g of a light yellow phosphor are obtained. After mixing the reagents, the solution had a pH of 1, at the end of the treatment a pH of 3.

Example 14-1

10.0 g of the phosphor Lumi Nova G-300 M is processed under conditions as described in Example 10-1. 9.8 g of a light yellow phosphor are obtained. At the beginning of the treatment, the solution had a pH of 1, at the end of a pH of 3.

Example 15-1

11.9 g of Na ₂ HPO ₄ · 12H ₂ O are mixed with 24.6 g of H ₂ O and 3.5 g of 35% hydrochloric acid, and 10.0 g of the LDP-2M phosphor are added to the resulting solution. Processing and isolation of the product is carried out under conditions as described in Example 10-1. 9.8 g of a light yellow phosphor are obtained. At the beginning of the treatment, the solution had a pH of 1, at the end of the treatment, a pH of 3.

Example 16-1

4.6 g of (NH ₄ ) ₂ HPO _{4 are} mixed with 28.2 g of H ₂ O and 7.2 g of 35% hydrochloric acid, and 10.0 g of the LDP-2M phosphor are added to the resulting solution. Processing and isolation of the product is carried out under conditions as described in Example 10-1. 9.9 g of a light yellow phosphor are obtained. At the beginning and at the end of the treatment, the solution had a pH of 1, at the end of the treatment a pH of 3.

Example 17-1

The processing is carried out in the conditions of Example 1-1, only as a phosphor use GPLOS-5-14. 9.83 g of a yellow-green phosphor are obtained.

Example 18-1

The processing is carried out in the conditions of Example 10-1, only as a phosphor use GPLOS-5-20. 9.56 g of a yellow-green phosphor are obtained.

Example 19-1

The processing is carried out under the conditions of Example 10-1, only as a phosphor use PLO-8C. 9.7 g of a light yellow phosphor are obtained.

Example 20-1

The processing is carried out under the conditions of Example 1-1, only as a phosphor use PLB-7C. 8.92 g of a light yellow phosphor are obtained.

Example 21-1

The processing is carried out under the conditions of Example 10-1, only as a phosphor use PLB-7C. 9.38 g of a light yellow phosphor are obtained.

Example 22-1

Processing is carried out under the conditions of Example 10-1, only NP-2820 is used as a phosphor. 9.86 g of a light yellow phosphor are obtained.

Example 23-1

Processing is carried out under the conditions of Example 1-1, only as a phosphor use LDP-3M. 9.47 g of a light yellow phosphor are obtained.

Example 24-1

The processing is carried out in the conditions of Example 7-1, only as a phosphor use PLB-7C. 9.52 g of a light yellow phosphor are obtained.

Example 25-1

The processing is carried out under the conditions of Example 10-1, only as a phosphor use PLO-7C. 9.8 g of a light yellow phosphor are obtained.

Example 26-1

To 40 g of a solution prepared by mixing 15.50 g of Na ₃ PO ₄ · 12H ₂ O, 17.99 g of H ₂ O and 6.51 g of 92.1% H ₂ SO ₄ , 10.0 g of phosphor are added in portions with stirring SP-2. Further processing and isolation of the product is carried out under the conditions of Example 1-1. 9.97 g of a light yellow phosphor are obtained.

Example 27-1

To 40 g of a solution prepared by mixing 15.50 g of Na ₃ PO ₄ · 12H ₂ O, 10.45 g of H ₂ O and 14.05 g of 55% HNO ₃ , 10.0 g of phosphor SP-2 are added portionwise with stirring. Processing and isolation of the product is carried out under the conditions of Example 1-1. 9.76 g of a light yellow phosphor are obtained.

2. EXAMPLES OF PRODUCING WATERPROOF LUMINESCENT COMPOSITIONS

Example 1-2

Used epoxy resin and hardener glue Araldite 2020. In a glass cup equipped with a magnetic stirrer, placed 100 g of epoxy resin and 30 g of fluorescent pigment Lumi Nova G-300M, processed in the conditions of Example 4-1. The mixture was stirred for 10 minutes, then 30 g of hardener was added. Stirring is continued for another 10 minutes. A liquid white luminescent composition with a yellowish tinge is obtained. After 10-15 minutes, the viscosity of the composition begins to increase. After 30-40 minutes, curing begins with the formation of a solid polymer mass of white with a yellowish tinge. Curing is completed after approximately 24 hours.

The liquid luminescent composition can be applied to any surface or placed in containers of any shape and made of any materials. After curing the luminescent composition, a polymer is obtained (in the form of a film or any given shape), which after illumination with any light source then glows in the dark with a yellow-green glow.

Part of the solid polymer mass is ground. 10 g of the obtained powder is placed in a glass equipped with a magnetic stirrer, 100 ml of water are added and stirred, controlling the pH of the medium, for 8 hours. At the beginning and at the end of the experiment, the pH of the medium did not change and was equal to 7. The pH control of the medium was continued. It was found that after 6 months the pH of the medium was equal to 7. The filtered powder after preliminary illumination intensely glowed in the dark.

The obtained waterproof luminescent composition is recommended for use as a signal material that glows in the dark.

Example 2-2

In the conditions of Example 1-2 receive a waterproof luminescent composition based on the luminescent pigment SP-2, processed in the conditions of Example 5-1. The luminescent material has a yellow-green glow.

Example 3-2

In the conditions of Example 1-2 process the luminescent pigment LDP-3M, processed in the conditions of Example 23-1. A water-resistant luminescent blue glow composition is obtained.

Example 4-2

Used polyurethane resin and hardener glue Araldite 2026. The resin (50 g), hardener (50 g) and luminescent pigment PLO-8C (20 g), processed in the conditions of Example 19-1, mixed and mixed in the conditions of Example 1-2. Get a waterproof luminescent composition of white color with a yellowish tint of yellow-green glow.

Example 5-2

In the conditions of Example 4-2 receive a waterproof polyurethane luminescent composition based on the luminescent pigment LDP-2M, processed in the conditions of Example 8-1. White fluorescent material with a yellowish tint of yellow-green glow.

Example 6-2

Used methacrylate resin and hardener glue Araldite 2021. The resin (50 g), hardener (45 g), luminescent pigment Lumi Nova G-300M (25 g), processed in the conditions of Example 14-1, mixed and mixed in the conditions of Example 1-2 . Get a waterproof luminescent composition of white color with a yellowish tint of yellow-green glow.

Example 7-2

20 g of a 40% toluene solution of Degalan® LP 64/12 acrylate polymer and 10 g of the Lumi Nova G-300M luminescent pigment treated under the conditions of Example 4-1 are thoroughly mixed and applied to a curbstone. After application, the coating (film) dries after 1 hour, finally after 24 hours. Part of the film is mechanically removed from the marked surface (the film glows intensely in the dark), crushed and suspended in water. Observe the change in pH. At the beginning of the water treatment and after a week, the aqueous suspension has a pH of 7.

Example 8-2

In the conditions of Example 7-2, a luminescent composition based on the Diplex 070 acrylate polymer is prepared. A waterproof luminescent film is obtained (after application to a horizontal surface).

Example 9-2

Use the composition (varnish + hardener) of the Polish company Ran Al®.

20 g of Akrylowy Lakier Eco acrylic varnish and 10 g of Utwardzacz hardener are thoroughly mixed with 20 g of SP-2 fluorescent pigment treated under the conditions of Example 5-1 for 1 hour. After application on any surface: markings on asphalt road, wooden, metal surface, the film hardens within 24 hours. Each of the films after mechanical grinding is not hydrolyzed.

Example 10-2

10 g of a 40% toluene solution of Degalan® LP 64/12 acrylate polymer and 20 g of the LDP-3M luminescent pigment treated under the conditions of Example 23-1 are thoroughly mixed and applied to a curbstone. After application, the coating (film) dries after 1 hour, finally after 24 hours. Get a waterproof luminescent film of blue glow.

Example 11-2

Under the conditions of Example 10-2, a luminescent composition was prepared using 30 g of the SP-2 luminescent pigment treated under the conditions of Example 5-1. Get a waterproof luminescent film of a yellow-green glow.

Example 12-2

The components of the luminescent composition are mixed under the conditions of Example 6-2 in amounts: resin - 53 g, hardener - 45 g, luminescent pigment - 2 g. The composition is applied to a curb stone. After drying, a luminescent film of a yellow-green glow is obtained.

3. EXAMPLES OF PRODUCTION OF WATERPROOF LUMINESCENT PAINTS

According to the proposed invention, luminescent road paints can be obtained by mixing a luminescent composition or directly a luminescent pigment pretreated with aqueous solutions of reagents selected from the group: monosubstituted phosphates, H ₂ SO ₄ , H ₃ PO ₄ , mixtures of tri- or disubstituted phosphates with at least , one of the acids: HCl, H ₂ SO ₄ or HNO ₃ , with road paint.

Luminescent waterproof pigment, glowing in the dark, can be introduced into any road marking paint, ready to use, both on an aqueous and non-aqueous basis. These paints have one common property - to form a film on the marked surface due to the presence of film-forming components in the composition.

As road paints, paints described in the patents of the Russian Federation (Table No. 1), or any paints that the domestic market offers and which are presented in Table No. 6, can be used.

Table number 6 No. p / p Paint brand, TU Working viscosity according to VZ-4, s Density g / cm ³ The content of non-volatiles,% Drying time, min Luminance factor,% Wear resistance (Soyuzdorniya technique),% one VMD, TU 2312.017-01393697-97 60-120 1.7 ± 0.05 80 ± 5 10-20 64 80-90 2 EP-5327, TU 3212-026-05015319-99 100-120 1,6 75 10-15 74 70-80 3 AK-505, TU 2313-010-49792662-99 80-100 1,6 78 15-17 71 80-90 four Acrylic paint for road marking, TU 2313-017-45822449-99 100-120 1.7 80 15-17 65 76 5 Dorstroyservis-2, TU 23131-003-04002214-98 60-80 1,6 79 15-20 60 73 6 AK-591, TU 6-27-18-302-2000 80-120 1.4 not less than 70 8-10 65 82 7 KO-525 road, TU 7.2312-002-1295793-98 45-120 1.4 66 7-10 71 70 8 AK-525 marking, TU 2312-011-42149549-02 80-200 1,57 70-80 5-7 69 92 9 Technocolor, TU 2316-020-07509505-2000 60-160 1,5 76 9-11 70 70-90 10 Spectrline, TU 2316-003-5988865-00 80-180 not less than 1,5 not less than 75 10-20 66 75-85 eleven Arctic, TU 2313-04100149274-2000 200-250 1.3 62.7 fifteen 67 62 12 DM-AK-521, TU 2316-001-02953342-2001 70-190 1.5 ± 0.1 70 eighteen 65 68 13 Highway, TU 2312-156-4695478-01 100-200 1.4 60-75 9 68 65 fourteen Road marking enamel D-1, TU 2332-027-05808020-01 40-120 1,56 not less than 70 8 70 63 fifteen Paint for road marking AK - "Kronos", TU 2313-039-20504464-2001 60-160 1.65 75 ± 2 4-6 68 75-85 16 Marking paint "Path", TU 2316-003-54503111-2001 60-160 1.68 75 ± 2 5 67 84-88 17 OD-AK-11, TU 2313-031-02424371-97 146 1.51 76.5 6 65 91 eighteen AK-511, TU 2316-156-05011907-98 100-160 1.48 not less than 70 13 67 90 19 AK-585, TU 2316-218-05011907-2002 not less than 40 1.47 not less than 70 four 65 90 twenty AC-5307, STP 6-3-121-2001 76 1.35 60.5 four 70 77 21 AK-539, TU 6-27-18-320-2001 20-60 (according to VZ-6) 1,52 not less than 70 10 78 76 22 Enamel EP-555 "Cotoline", TU-2312-231 -00204211 -2001 70-150 1.39 65-71 7 63 94 23 AK-522 "Basalt-2", TU 075-06-004-116-99 68 (according to VZ-6) 1,54 74.6 5 64 64 24 AK-517 (Stollreflex D-1163), TU RB 00204547.066-96 150 1,58 81.3 8 69 90 25 Road marking paint AK-501, AK-502, TU-2316-011-55856863-2002 not less than 40 1.45 65-75 12 72 70 26 Paint waterproof marking road AKRA-DOR, TU 2313-018-26294341-2002 40-120 not less than 1,5 not less than 70 6 67 81 27 AK-109 LOKO “SHTRIH”, TU 2312-021-48972729-2001 80-180 not less than 1,5 not less than 70 10 70 92 28 AK-508 Krasvol, TU 2316-008-57352960-02 60-160 not less than 1,5 not less than 70 twenty 75 83

As a rule, road paints are a complex system containing from 4 to 6 or more components, including pigment, filler, polymers, plasticizer, special additives, solvent, each of which plays an important role. However, the most important of them, determining the durability, is a polymer binder.

A common drawback of any phosphorescent paints is a decrease in the glow intensity due to the presence of pigment particles (titanium dioxide), fillers and other substances in the system that affect the spectral properties of the phosphor. Therefore, to eliminate this factor, you can use a two-stage surface marking.

In the examples used road paints:

- “Crossroads”, GOST R 51256-99, TU 2313-015-40165-03;

- “Highway”, TU 2312-156-4695478-01;

- Marking paint "Path", TU 2316-003-54503111-2001;

- Road marking enamel D-1, TU 2332-027-05808020-01;

- Enamel EP-555 “Cotoline”.

3.1. EXAMPLES OF PRODUCTION OF WATERPROOF LUMINESCENT PAINTS BASED ON LUMINESCENT COMPOSITIONS AND ROAD PAINTS OR ENAMELS

Example 1-3

To 50 g of Araldite 2020 epoxy resin add 15 g of the appropriate hardener (Table No. 1), 15 g of phosphor SP-2, processed in the conditions of Example 1-1, and mix for 5 minutes To the resulting suspension add 500 g of paint marking "Track". The mixture is stirred for 10 minutes and applied to any horizontal surface. After 8-10 hours, the hardened white fluorescent film is mechanically crushed, placed in water (1 g in 50 ml of water) and the pH is monitored. The initial pH of 7 did not change for one month, indicating the receipt of a waterproof luminescent film.

Example 2-3

The mixing of the components, film formation and control of the water resistance of the ground luminescent film was carried out under the conditions of Example 1-3, but the LDP-2M phosphor processed under the conditions of Example 2-1 was used as the luminescent pigment. Received waterproof luminescent paint.

Examples 3-3 ÷ 11-3

In the conditions of Example 1-3 were obtained waterproof luminescent paints using various waterproof luminescent pigments. Table 7 presents the results of the experiments.

Table number 7 No. of Examples Used waterproof luminescent pigments Resistance of luminescent paint to hydrolysis The original phosphor No. of Examples for the processing of phosphors 3-3 FV - 530D 3-1 Steady 4-3 Lumi Nova G-300M 4-1 - "- 5-3 SP-4 11-1 - "- 6-3 GPOLS - 5-4 17-1 - "- 7-3 GPOLS - 5-20 18-1 - "- 8-3 PLO-8C 19-1 - "- 9-3 PLB-7C 20-1 - "- 10-3 NP-2820 22-1 - "- 11-3 LDP-3M 23-1 - "-

Example 12-3

To 20 g of Araldite 2026 polyurethane resin add 20 g of the appropriate hardener (Table No. 1) and 20 g of phosphor LDP-3M, processed in the conditions of Example 23-1. The suspension is stirred for 10 minutes and 200 g of white paint is added for the Perekrestok road marking. The mixture is stirred for another 10 minutes and applied to the asphalt surface pre-marked with Crossroad paint. After drying and curing of the resulting luminescent film, it is subjected to control for hydrolysis in the conditions of Example 1-3. According to the results, it was concluded that the obtained luminescent paint is waterproof.

Example 13-3

To 50 g of Araldite 2021 methacrylate resin add 45 g of the appropriate hardener (Table No. 1), 50 g of the LDP-2M phosphor processed under the conditions of Example 12-1, and the mixture is stirred for 10 minutes. To the suspension add 400 g of road marking enamel D-1. Get a waterproof luminescent white paint. After application to a horizontal surface, the resulting luminescent film after light insolation intensely glows in the dark. Resistance to hydrolysis was checked as described in Example 1-3.

Example 14-3

In the conditions of Example 13-3, a waterproof luminescent paint is prepared using white road paint for marking the “Highway” roads as a paint. The ratio of the components:

- methacrylate resin Araldite 2021 - 38.5 g;

- hardener for resin - 11.5 g;

- phosphor - 30 g;

- paint for road marking - 920 g.

Example 15-3

In the conditions of Example 12-3, a waterproof luminescent paint is prepared using white enamel EP-555 “Cotoline” as a paint. The ratio of the components:

- Araldite 2026 polyurethane resin - 22 g;

- hardener for resin - 22 g;

- phosphor - 8 g;

- paint for road marking - 48 g.

3.2. EXAMPLES OF PRODUCING WATERPROOF LUMINESCENT PAINTS BASED ON COMPONENTS: LUMINESCENT PIGMENT, POLYMER BINDING, ROAD PAINT OR ENAMEL

Example 16-3

To 50 g of Araldite 2020 epoxy resin, 15 g of Lumi Nova-G 300M phosphor treated under the conditions of Example 4-1 are added and mixed for 10 minutes. To the resulting suspension add 500 g of white paint for road marking "Crossroads". The mixture is stirred for 10 minutes and 15 g of Araldite 2020 glue resin hardener is added. The mixture is stirred for 10 minutes. A white luminescent paint is obtained. The paint is applied to a horizontal surface and the resulting luminescent film is treated in the conditions of Example 1-3. Since the pH 7 of the aqueous suspension of the ground film does not change over time, it was concluded that the obtained luminescent paint is water resistant.

Table 8 presents examples of the production of luminescent paints for marking pavements using the mixing order of the components in the conditions of Example 16-3, varying the range of waterproof luminescent pigments, binders, travel paints or enamels. In Examples 17-3 ÷ 20-3, Perekrestok road paint was used; in Examples 21-3 ÷ 23-3, Magistral road paint was used; in Example 24-3, D-1 road marking enamel; in Example 25-3 - Enamel EP-555 “Cotoline”.

In each of the Examples, a waterproof luminescent paint was obtained.

3.3. EXAMPLES OF PRODUCTION OF WATERPROOF LUMINESCENT PAINTS BASED ON WATERPROOF LUMINESCENT PIGMENTS AND ROAD PAINTS OR ENAMELS

Example 26-3

To 97 g of paint for road marking "Magistral" add 3 g of phosphor LDP-2M, processed in the conditions of Example 12-1, and the mixture is stirred for 10 minutes. A waterproof luminescent paint for road marking is obtained.

Example 27-3

To 500 g of white paint for road marking "Dorozhka", TU 2316-003-54503111-2001, add 500 g of the phosphor used in Example 12-3, and mix for 30 minutes. A waterproof luminescent paint is obtained for marking roads and other vertical and horizontal surfaces.

Example 28-3

The components are mixed under the conditions of Example 26-3, using 25 g of road marking enamel D-1 and 75 g of luminescent pigment treated under the conditions of Example 10-1. A waterproof luminescent paint for road marking is obtained.

Table number 8 No. at
measures Used waterproof luminescent pigments The content of components in luminescent paint, g The original phosphor No. of Examples for the processing of phosphors Lumines
cent pigment Polymer binder Road paint or enamel Araldite 2020 Open-
child Araldite 2026 Open-
child Araldite 2021 Hardener 17-3 FV-530D 3-1 2 fourteen 7 - - - - 78 18-3 Lumi Nova G-300 M 4-1 thirty 6.5 3,5 - - - - 60 19-3 SP-4 11-1 60 5.5 2.5 - - - - 32 20-3 GPOLS - 5-4 17-1 10 - - 2 2 - - 86 21-3 GPOLS - 5-20 18-1 60 - - eleven 9 - - twenty 22-3 PLO-8C 19-1 2 - - 2.2 1.8 - - 94 23-3 PLB-7C 20-1 twenty - - - - 10 10 60 24-3 NP-2820 22-1 fifteen - - - - 8 7 70 25-3 LDP-3M 23-1 eighteen - - - - 7 7 68

Claims (4)

1. Luminescent composition for marking road surfaces, containing a luminescent (phosphorescent) pigment, which is an oxide matrix based on aluminum oxide and oxides of at least one element selected from the group: Mg, Ca, Sr, Ba, Zn, Si, activated by at least one rare earth element, and a polymer binder selected from the group: epoxy, urethane, acrylate, alkyd and mixed polymer resins, characterized in that the luminescent (phosphorescent) pigment is pretreated with water solutions of reagents selected from the group: monosubstituted phosphates, H ₂ SO ₄ , H ₃ PO ₄ , mixtures of tri- or disubstituted phosphates with at least one of the acids: HCl, H ₂ SO ₄ or HNO ₃ in the following ratio (weight ) components:
luminescent pigment 2-88 binder 12-98 2. Luminescent paint for marking road surfaces, containing road paint on an aqueous or non-aqueous basis or enamel and a luminescent (phosphorescent) pigment, which is an oxide matrix based on aluminum oxide and oxides of at least one element selected from the group: Mg, Ca, Sr, Ba, Zn, Si, activated by at least one rare earth element, characterized in that it contains a luminescent pigment pre-treated with aqueous solutions of reagents selected from the group: monosubstituted phosphates, H ₂ SO ₄ , H ₃ PO ₄ , a mixture of tri- or disubstituted phosphates with at least one of the acids: HCl, H ₂ SO ₄ or HNO ₃ , in the following ratio (weight) of the components:
luminescent pigment 3-75 paint (enamel) 25-97 3. Luminescent paint for marking road surfaces, containing the luminescent composition according to claim 1 and road paint on an aqueous or non-aqueous basis or enamel, in the following ratio of components:
luminescent composition 8-52 road paint or enamel 48-92 4. Luminescent paint for marking road surfaces, containing road paint on an aqueous or non-aqueous basis, a luminescent pigment, which is an oxide matrix based on aluminum oxide and oxides of at least one element selected from the group: Mg, Ca, Sr, Ba , Zn, Si, activated by at least one rare earth element, and a polymer binder selected from the group: epoxy, urethane, acrylate, alkyd and mixed polymer resins, characterized in that it contains a luminescent (phosphorescent) pygmy NT pretreated with aqueous solutions of reagents selected from the group: monosubstituted phosphates, H ₂ SO ₄ , H ₃ PO ₄ , mixtures of tri- or disubstituted phosphates with at least one of the acids: HCl, H ₃ SO ₄ or HNO ₃ in the following ratio of components:
luminescent pigment 2-60 polymer binder 4-20 road paint or enamel 20-94