Luminescent composition and luminescent paint for marking roads (versions)
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
The technical FIELD
The present invention relates to fluorescent compositions and paints intended for marking pavements such as roads, highways, pedestrian crossings, runway airfields, Parking lots, signs of transport flows, devices for traffic control, appropriate structures and objects.
Currently, many of these and other surfaces inside and outside indicate by marking with paint or laminating.
Often such a label, even when it contains reflective elements, is no longer visible in low light or at night.
The visibility and durability of these markings can be greatly increased by coating product containing fluorescent pigment, which provides highlighting without additional sources, so that the marking is visible in the dark.
This luminescence is also useful for surfaces unmarked, helping people to see better in the dark surfaces such as pedestrian walkways, the actual boundaries of structures and walls, curb highways, etc.
In the literature and patent descriptions often is the incorrect use of terms such as Liu who inessence, fluorescence and phosphorescence.
With these concepts is sometimes associated effects glow and reflect. The inappropriate use of terminology in relation to fluorescent dyes and pigments leads to errors when assigning effects to various fields of technology. It is difficult to assess technical solutions, including those proposed for patenting. Below is the terminology associated with these concepts from the work: "Chemistry and physics with special properties of pigments, dyes, printing inks and paints for coatings". A.Nurhan Becidyan [United Mineral &Chemical Corp., Paint Coating Industry, 15.06.2003].
Luminescence: fluorescence and phosphorescence.
Fluorescent dye or pigment: a substance that emits light (visible, UV and IR) with appropriate excitation, not hot.
Excitement: the valid reason that causes the fluorescent dye to emit light.
Fluorescence: the emission of fluorescent light by the pigment in the presence of excitation (e.g., fluorescence in daylight).
Phosphorescence: the light emitted by the luminescent dye or pigment, after the excitation has stopped (for example, glow in the dark).
There are many types of energy that certain fluorescent pigments can absorb and turn into luminescence (radioactiv the guard x-rays, cathode rays, mechanical impact, electricity, UV, visible, or infrared radiation).
Inorganic fluorescent pigments, called phosphors differ from fluorescent fluorescent pigments the fact that most of them are colorless or colored in pale pastel colors, but when excited by UV-irradiation begin to fluoresce quite brightly.
In fact, fluorescent pigments, glow in the dark, according to the more correct terminology would be called fluorescence pigments (phosphors). In the patent and technical literature uses both names, as reflected in this description.
Phosphorescence is similar to the luminescence in the fact that it is also related to the absorption of radiation of a specific wavelength or a specific wavelength range and release photons of a different wavelength.
The difference between these phenomena on the time of radiation. The rule is: if the radiation is stopped after removal of the source of radiation is fluorescence, if the radiation continues (the so-called afterglow - afterglow"), it is called phosphorescence.
Thus, fluorescence and phosphorescence are special cases of the generalized notion of luminescence.
The authors use the term "fluorescent pigmentation treatment is NT", which is more General than the term "fluorescence pigment", indicating in brackets "fluorescence" to exclude incorrect interpretation, as in patent descriptions and technical literature are used both terms in relation to one and the same object. The validity of the chosen terminology can be confirmed by the fact that in the technical documentation of the phosphors is called fluorescent pigments. It should be noted that is not connected with the phenomenon of luminescence is used reflective (reflective) effect. Retroreflective material interacts with light, without causing excitation of the molecules of the material. Particles of such material in the form of balls or wedges only the function of reflecting by means of an optical effect. In fact, the beam of light is reflected from the surface, similar to a mirror. The material is characterized by the optical characteristics, such as the minimum ratio svetovozvrascheniya at a certain angle. The effect of svetovozvrascheniya described above, is realized only in artificial light (for example, when the light of car headlights in the dark).
In domestic practice, such material is used for road markings (see, for example, "guidelines for road marking on cemented coverage auto is rich road" №OS-1018-R dated November 19, 2003, the Ministry of transport of the RF).
Currently known application of fluorescent materials for marking coatings that emit light only when the excitation from the light source.
These materials can be selected for in the day time to celebrate and highlight the marked surface such as the edge of the stairs, corners of walls, the edges of highways, passages, direction signs, road dividing strip, runway airfield, the contours of the buildings. The light emission of these fluorescent materials, however, immediately terminated if the removed light source.
Luminescent (phosphorescent) materials, on the contrary, being irradiated continue to glow with a soft, slowly fading light. This field is present technical solution.
Fluorescence materials can provide the required level of luminous flux within 10-12 hours after they have been activated by exposure to solar or artificial light (e.g. light car headlight).
After the initial exposure from the light source, the luminescence can be renewed by repeated exposure to natural or artificial light. Therefore, in paints for pavement enter luminescence (fluorescence) substances for marcinowice line and the dividing line to distinguish between directions of traffic on the highway.
The most effective for this purpose are luminescence (fluorescence) substances aluminate type. However, they have one common significant drawback is the sensitivity to the action of moisture. Under the influence of moisture by the hydrolysis of the phosphor loses its lighting characteristics (luminescently).
The LEVEL of TECHNOLOGY
In the patents described a number of compositions of paints for road marking (see table 1), none of which contains a fluorescent pigment.
In a number of U.S. patents suggests solutions to the problem of creating fluorescent compositions for road surfaces with high resistance to hydrolysis.
In Pat. U.S. No. 5665793 proposed fluorescence composition for the painting of the highway, including:
- fluorescent substance, representing a compound expressed by the matrix MAl2O4in which M is at least one metal selected from the group calcium, strontium and barium, or expressed by the matrix MAl2O4in which M is a set of metals that represents magnesium and at least one element represents calcium, strontium and barium; and
- vadomarius resin.
The luminescent substance may contain as activator is europium and coactivator lanthanum, cerium, praseodymium, samarium, terbium, dysprosium, holmium.
As sadomasy is audace resin used polyurethane resin, which, according to the authors, gives moisture resistance luminescent substance.
In the description of the composition and the manner of its application.
- 5 parts powdered LumiNova phosphorescent material;
7 parts of acrylic urethane water based and
- 88 parts white road paint is water-based.
Fluorescence (fluorescent) pigment and acrylic urethane first separately mixed together at ambient temperature 73°±5° F, and then the obtained mixture is mixed with road paint is water-based.
Fluorescent substance and a polyurethane resin can be added directly to the ink composition. In an advantageous execution of the invention the pre-mixture is formed by mechanical mixing gradually introduce small amounts of fluorescent substances with videofestival or vodosmeshivayuschego resin, which is coated fluorescent substance polyurethane resin. This mixture can be stored or can be immediately added to the water-based paint with mechanical mixing.
|Table No. 1|
|No. of patent of the Russian Federation||Film-forming||N is politely||Thickener||Solvent||Pigment|
|2.267.508||48-52% solution of a copolymer of styrene and butyl acrylate in toluene "polyform-1 "In"||Mikromramor fractionated and oxyhydroxide aluminum "ProCal"||Organic derivative of montmorillonite "Benton SD-2"||A mixture of toluene and ethyl acetate in the ratio of 2.4:1, or a mixture of toluene and acetone in the ratio 1:1||Titanium dioxide|
|2.237.694||Latex is the best choice copolymer BS 65 18-22||Quartz crushed||Dextrin and Gidal||Water||-|
|2.181.740||Copolymer of styrene, butyl acrylate, methyl methacrylate, methacrylic acid||Aerosil, ground marble, quartz, talc, barite||A solution of triethanolamine in ethanol||Toluene, butanol||Titanium dioxide|
|2.155.200||Copolymer of butyl acrylate with methyl methacrylate is m and methacrylic acid||Chalk, alumina, microsilica, termosolar calcium, mikrobasic bleached, micro-talc||The polyvinylchloride resin, chloroparaffin||Acetone, butyl acetate, toluene||Titanium dioxide|
|2.067.601||The best choice of thermoplastic elastomer, the best choice copolymer,||Zinc oxide, chalk||The petroleum resin||Nefras, xylene, ethyl acetate||-|
|2.074.872||Polyester resin (phthalic anhydride, ethylene glycol, glycerol)||Aerosil, silica sand||Transformer oil||Titanium dioxide|
|2.089.584||The block copolymer is a polyvinyl aromatic||Carbon resin|
|2.092.511||Shuvalovka pasta-based collocalia or a copolymer of butyl acrylate and acrylic acid||Glycerol ester of rosin||Toluene||Titanium dioxide|
|2.109.786||Copolymer of butyl acrylate, methacrylic acid and methacrylate. Resin acrylic amylostereum||Calcium, Aerosil||Dibutyl||Weidert, xylene, acetone, butyl acetate||Titanium dioxide|
|2.129.581||Latex is the best choice copolymer||Ceramic chips clay||Hydrolyzed polyacrylonitrile, mezdrovyj glue|
|Application No. 2000113750/04||Copolymer of styrene, butyl acrylate, methyl methacrylate and methacrylic acid||Marble, Aerosil, talc, quartz||A solution of triethanolamine in ethanol||A mixture of toluene and butanol||Titanium dioxide|
|Application No. 97114960/04||Water dispersion paint based on anion-stabilized emulsion polymer||Glass beads, quartz sand||Water|
The road surface pre wiped clean and is treated with compressed air to remove dirt and other residues in the places where there should be applied the paint. The paint dried with a dry cloth until then, until it sticks on contact. According to the authors of the compositions are water-based, obtained by blending videofestival polyurethane resin with water-sensitive fluorescent substance, wonderfully luminescent substance is protected from the action of moisture, air and water. Thus, the fluorescent substance is protected immediately after mixing with polyurethane resin in the ink composition.
In a later U.S. Pat. U.S. No. 6005024 proposed to cover the fluorescent pigment to use epoxy resin.
In Pat. U.S. No. 6005024 claimed fosforescente-luminescent epoxy coating for marking surfaces on earth, surfaces, structures and individual items, consisting of:
a) almost colorless fosforescente-luminescent material is, consisting of compounds expressed by the formula MAl2O4where M is at least one element is a metal selected from the group comprising calcium, strontium and barium, or, alternatively, expressed by the formula MAl2O4where M is the set of elements-metals, including magnesium and at least one element selected from the group comprising calcium, strontium and barium;
b) two-component epoxiconazole (consisting of resin and hardener), which after curing becomes completely transparent, stable, durable, does not contain water and moisture resistant (insensitive to moisture). Moreover, this composition being exposed from the light source, shows the properties of brightness higher than in the case of traditional fluorescence-based materials sulphides, and time of the afterglow above about ten times than the time of persistence of traditional fluorescence-based materials sulphides.
The composition contains as europium 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 of preparing (or "pre-mixing") fosforescente-luminescent epoxiconazole, predatora growing number fosforescente-fluorescent substance is mixed with either curing component, or with a resin component of a two component apoximately before mixing and activation of two apoxyomenos.
This ensures a thorough coating, encapsulating and homogeneous distribution fosforescente-fluorescent particles in the curing component or Smolyan component of two-component epoxiconazole before mixing the two components.
In the description of U.S. Pat. U.S. No. 6005024 it is noted that the compositions disclosed by U.S. patent No. 5665793, shows a decrease in the luminescence in the mixture due to the fact that the paint particles to some extent blocking the light-emitting component.
In addition, this composition contains a significantly larger number of mixed components than composition based on epoxy resins.
In Pat. U.S. No. 5874491 according to the formula of the invention being patented fluorescence composition for roads, consisting of:
a) a fluorescent substance, including the compound expressed by the formula MAl2O4in which M is at least one metal selected from the group of calcium, strontium and barium, or an alternative formula MAl2O4in which M is a set of metals that represents magnesium and at least one element represents calcium, strontium and barium, and
b) apoximately, which mixed fluorescent substance;
C) paint dispersions, see what shanna with a) and b).
The luminescent substance may contain as europium activator, and as coactivator - lanthanum, cerium, praseodymium, samarium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin and bismuth.
The composition may contain natural and synthetic abrasives.
In the description when the description of the invention as a component of the composition is not only apoximately, and polyurethanes, with unsubstantiated claims that amazing Apeksimova and polyurethane immediately protect sensitive to the action of moisture fluorescent substance. When applying apoximately hardener and resin components are mixed and then injected fluorescent particles.
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:
1 part powdered mixture of phosphor (fluorescent substance and the fluorescent substance (not characterized by chemical composition or formula);
- 6 pieces - epoxytetradecane;
13 parts of the epoxy.
In the description of the patent does not contain any experimental data, confirming receipt resistant to moisture the product and in General the ability in order to suscestvitel mixture of moisture-sensitive product works with water-based without its destruction. It really is not just amazing, but contrary to reasonable expectations about the process, and therefore, undoubtedly, requires evidence.
In Pat. U.S. No. 6359048 B1 described tinted fluorescent paint based on alkyd resin containing aluminate phosphor, white alcohol as a diluent and various modifying additives.
In the description of the patent it is noted that the paint is designed primarily for use indoors. At the same time, there is an indication that when special marks of alkyd resins can be obtained by composition to more severe operating conditions. In the description of the patent emphasizes that the aluminate phosphors have serious drawbacks - sensitivity to moisture and the difficulty of mixing due to their high density. In addition, it contains a criticism of technical solutions, patented in two prior patents.
For example, the color is described in U.S. Pat. U.S. No. 5874491, as follows:
the composition obtained by mixing the phosphor with a water-soluble polyurethane or apoximately, you can be reasonably stable composition suitable for marking road surfaces;
a mixture of fluorescent substances with water-soluble polyurethane or apoximately aluminium or encapsulates the pigment;
- they can in order to mesyatsa with water-based paint for road marking;
unfortunately, these resins are expensive and unsuitable in cases when you need to get natural-looking, durable and economical painted surface;
- encapsulation of phosphorus leads to an increase in the actual size of the particles and hinders the introduction of significant quantities of phosphorus in the paint, reducing the amount that can glow, in addition to the other features of this product and makes it difficult to use.
In relation to U.S. Pat No. 6005024 States the following:
the tests showed that the pigment Luminova TM adds yellow staining in any composition in which it is used in an amount of 5%;
- the two-phase process of epoxysilane limits its application (i.e. it should be used immediately after mixing the two components);
- luminescent epoxypropoxy existed for many years, although for the most part they are used in the extrusion of plastics and packaging products, original luminous products used for knick-knacks, toys, decorations;
experiments showed that the addition of a large amount of pigment masks the level of luminescence, as the added particles close a fluorescent particle;
an important pigment treatment, because it cannot be subjected to grinding;
he should not act water, otherwise it will lose SPO is functioning to glow;
- it should not be exposed to heavy metals in the system, and apparatus-mixers.
In the patent application U.S. No. 2004/0146349 A1 proposes a new photoluminescent material for marking, which is used for marking lines on the roads, etc.
He has the necessary durability and weather resistance, and high efficiency photoluminescence can be applied not only to the white stripes, but the stripes of any color during the suppression of the green tones, and, in addition, can give properties that prevent slipping.
The marking material is, basically, a material in which the paste-based resin containing a transparent resin components and components photoluminescent pigment, is applied to the road surface with the formation of the photoluminescent layer.
Allow various types of transparent component capable of forming a resin paste, provided that they are transparent and can be solidified after application to the surface of the road.
They are valid in the case when resistant as bands on the road, etc., i.e. sufficient strength and resistance to weather, light and water.
Can be represented by various types of components transparent layer, for example, based on the methacrylic resin, nenas the seal polyester resins, amaximal, resins, silicone type, and other resins.
Transparent resin component, the main component of the resin paste, provides adhesion of fluorescent layer when applying for marking strips, etc. on the surface of roads and plays the role of the binder.
It is assumed that as the photoluminescent pigment is introduced into the transparent component, are used not only known pigments, but also commercially available pigments and various other suitable pigments.
Examples of these pigments may be products of the type strontium aluminates and sincalide products. Apply photoluminescent pigments with an average particle diameter of 10 μm or more. According to the present invention, the preferred average diameter of from 20 μm to 2000 μm, and more preferred from 30 µm to 300 µm. Can also preferably be applied to particles with a diameter of 100 μm or more.
Previously it was not easy to apply photoluminescent pigment particles of such large diameter, since the pigment particles with a large diameter, it is difficult to evenly distribute.
According to the invention photoluminescent pigment with a relatively large particle diameter, which is usually difficult was uniformly dispersing, can evenly dispergirujutsja in the resin paste with the use of a transparent resin component such from siteline high viscosity, as 1 PA·s (20°C) or more.
To reduce sliding on the photoluminescent layer, a transparent resin complex containing photoluminescent pigment, mixed with the components of the resin paste, which is applied to the road surface and hardens. Then the surface utverzhdenii thus the paste is subjected to rough polishing or water-jet treatment to remove part utverzhdenii surface of the resin paste. Such coarsening processing in addition to useful functions - reduce slip, contributes to the mechanical damage of the fluorescent particles, which lost their photoluminescent properties. On the other hand, increases the access of moisture to the surface fluorescent pigment particles, facilitating the hydrolysis.
Analysis of all previous decisions on the creation of fluorescence (fluorescent) compositions allows us to conclude that the proposed solution was based on the choice of transparent resin that can form a film in which the encapsulated fluorescent pigment (phosphorus). Such compositions are recommended for marking various surfaces. One of the main areas of use are protected by U.S. patents fluorescence songs - marking of roads.
Marking involves either the application of the proposed compositions of the finished p is smedi, made using conventional highway inks of different colors, or the introduction vodosmeshivayuschego or Volosovsky fluorescence compositions in finished water highway paint for later use in the markup.
Before the introduction of the phosphor in the paint in the descriptions to patents, it is recommended to mix the original fluorescent pigment with a resin or resin components, which according to the authors of the patent prevents reaction of the phosphor with water contained in the paint, due to the encapsulating resin.
In the descriptions to these patents argues that vodonepronicaemyj fluorescent pigment in the selected resin or components of the resin becomes protected from moisture.
Due to the formation of the transparent polymer film of any of the proposed fluorescence compositions is to protect the phosphor from the interaction with the external environment (moisture).
The transparent resin used in fluorescence compositions, capable of forming a film described two types:
polymer resin forming the film are marked on the surface after drying (solvent removal). For example, polyacrylonitrile resin - Pat. U.S. No. 5665793, Pat. U.S. No. 5874491;
- two-component composition, forming a film in the "curing", "matching" components. E.g. the measures two-component epoxiconazole, consisting of resin and hardener, after forming the cured transparent film, " U.S. Pat. U.S. No. 5874491, Pat. U.S. No. 6005024, alkyd resin, followed by addition of calcium and cobalt - Pat. U.S. No. 6359048 B1, methyl methacrylate resin, followed by addition of curing agent resin - patent application U.S. No. 2004/0146349 A1.
In the above U.S. patents fluorescent composition based on epoxy resin used for marking surfaces, both individually and in a mixture of paints for road marking. Compositions on the basis of other resins is recommended to use a mixture of paints for road marking water-based. Thus, two fluorescent epoxy composition can be considered as fluorescent marking varnish applied as a final layer on the finished road markings. A similar solution offers a German firm Suedwest (www.suedwest.ru). For marking carriageway roads, Parking lots, sidewalks, signs, etc. initially applied luminescent (fluorescent marking paint. Then on the top, avoid rapid contamination, is applied as a final layer of clear marking lacquer on acrylic basis.
All known technical solutions are based on the same principle - physical protection aluminate luminescente the pigment from hydrolysis, namely, by encapsulating the particles of pigment polymer resins of various types.
When such a surface protection there is always the possibility of a violation of the surface layer, especially in such tough conditions, as the road surface. Even local access of moisture due to minor damage to the surface leads to the initiation of the hydrolysis reaction.
Thus, protection of the fluorescent pigment from the hydrolysis treatment of the polymer film does not provide sufficient reliability in terms of a real mechanical impact on the surface.
The creators are known from the prior art solutions do not take into account three very important, according to the authors, the circumstances:
- high degree of likelihood of the hydrolysis before encapsulating the phosphor resin;
incomplete protection against hydrolysis after encapsulation;
- the access of moisture and, therefore, implementation of hydrolysis during operation of the marking surface.
Concerning the latter, which is not discussed in the patent, it should be noted that after marking surfaces both indoors and outside, resulting fluorescence films have natural defects: cracks, shells and other
On the other hand, part of the fluorescent pigment may high is in their campaigns their faces above the surface of the film. All this contributes to contact with moisture environment.
Fluorescent pigment begins to either hydrolyzed, reducing the total intensity of the film. The beginning of hydrolysis at various places in the film provokes the formation of additional defects on the surface and inside, there is a change in its physical-mechanical properties.
Contact marking surfaces with tires of cars or any other subjects that promote abrasion of the film, leads to the destruction of the protective polymer shell phosphor, and begins its hydrolysis with the formation of non-luminous hydroxides.
As regards the first two circumstances, you must specify two featured in the patents use case patentable compositions on the basis of fluorescent pigments and polymer resins, namely:
- the application of the compositions (encapsulated fluorescent pigments) directly on the finished layout made using conventional inks of different colors;
- preparation based on the encapsulated phosphor ink by mixing it with ready-made paints for roads, water-based.
In both cases water is present, and the approval of the authors of the patents on complete, reliable protection from hydrolysis of the original phosphor appears to be unsubstantiated.
Made the authors of the experimental study showed that regardless of the type of film-forming composition (polyurethane, epoxy, alkyd, acrylate, and others) hydrolysis occurs with a visible decrease in the intensity of fluorescence at:
- the implementation of the encapsulation of luminescent phosphor;
- mixing the encapsulated fluorescent pigment with water-based paints;
- mechanical damage encapsulated fluorescent pigment and dye based.
Below is the experimental confirmation of the above.
Experimental study of the flow of hydrolysis was carried out taking into account the possible stages of implementation and application of technical solutions, namely:
- preparation of the compositions, paints and films;
- simulation of operating conditions effect of water on the labeled surface.
Evidence of course of hydrolysis when encapsulating fluorescent pigment
Fluorescent pigments brand Lumi Nova® (Lumi Nova G-300 M) were introduced in the epoxy resin Araldite 2020 company "Huntsman".
The obtained fluorescent dispersion was mixed with water and observed the change in pH of the medium. It is established that a water dispersion of initial pH 7 after 20 minutes, increased to pH 8-9. The increase in pH of the medium testified to the formation of hydroxides of the phosphor, i.e. the reaction of hydrolysis, and served as the proof is by construction to epoxy resin does not protect the particles of the fluorescent pigment.
After 30-40 min of mixing was observed stratification system. In the vessel formed of three phases: at the bottom of fluorescent pigment, continuing to either hydrolyzed above - luminescent epoxy resin, and an upper aqueous solution of hydroxides. The high density of particles of the fluorescent pigment of 3.65 g/cm3explains the precipitation.
A similar situation when using other types of resin: polyurethane (Araldite 2026) and methacrylate (Araldite 2021). The results of these experiments was proof of course of hydrolysis when performing encapsulation of fluorescent pigment (when processing polymer resins).
Proof of the occurrence of hydrolysis of manual pressure on the encapsulated fluorescent pigment
A) Processing a fluorescent pigment film-forming compositions
It is shown that after the mechanical grinding of the processed film-forming composition vodopostachal fluorescent pigment obtained powder becomes unstable to the action of water, i.e undergoes hydrolysis.
The experiments were carried out using fluorescent pigment Lumi Nova G-300M and film-forming compositions based on:
glue Araldite. Table 2 shows some of the diversified characteristics of the adhesive and the ratio for mixing the resin and hardener;
- special acrylate polymer innovations for this® LP 64/12, which is used in the form of a 40% toluene solution;
- thermoplastic acrylic polymer Diplex 070 in solution of toluene, which is used for traffic purposes (based coating this resin has a shiny surface, but on the basis of innovations for this® LP 64/12 - opaque).
|Table No. 2|
|Marking glue Araldite||Description glue||The ratio of resin and hardener %|
|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 fluorescent pigment mentioned film-forming the mi and mechanical grinding of the obtained film was placed in the water. This immediately started hydrolysis reaction.
This is confirmed by the increase in the pH of the aqueous solution due to the formation of hydroxides. After 30-40 min of processing water, filtered and dried fluorescent powder of the crushed film has a low residual intensity of illumination
B) Processing the fluorescent pigment curable epoxiconazole in the aquatic environment
In the epoxy resin component of the adhesive Araldite 2020, was added fluorescent pigment Lumi Nova G-300 M, and the mixture is stirred 30 minutes and Then was added to the hardener in ratio to the resin specified in Table No. 2.
The suspension was mixed for 10 minutes, after which was added an equal volume of water. To control the pH change was not possible, because the curing agent (a mixture of amines in aqueous medium has a strongly alkaline reaction. After 30-40 min of mixing, the curing of epoxy resin was completed. Formed two phases: sopolimerizatsiya luminescent composition in the form of a solid lump of white and water suspension containing residues utverzhdenii resin phosphor. The suspension was filtered and the precipitate washed several times with cold water. Then the precipitate was placed in cold water. After a few minutes began to increase the pH of the medium, indicating that the reaction of hydrolysis is. After 4 hours the hydrolysis practically ended with the formation of additional amounts of the hydroxides in the form of white flakes.
Hard lump thoroughly washed with cold water and dried. After the insolation light lump intense glow yellow-green glow. The lump was divided into 6-8 large pieces. One of them was crushed to powder. Large pieces and powder were placed separately in two cups of cold water. After a few minutes, each of them began to increase the pH of the medium, indicating that the reaction of hydrolysis.
Thus, the preliminary dispersion in the epoxy resin and the epoxy system resin + hardener does not lead to further protection from hydrolysis of the fluorescent particles of pigment.
Similar studies have been conducted using other types of transparent resin: polyurethane (Araldite 2026) and methacrylate (Araldite 2021). Hardeners were added to the respective resins in the ratios shown in Table 2.
In the result, it was found the reaction of hydrolysis of fluorescent pigment on the stages of the control.
Evidence of course of hydrolysis in the manufacture and application of paints for marking road surfaces.
It should be noted that traffic paint for marking as water, t is K and non-aqueous-based form at the end are marked on the surface of the film. With the introduction of the water-based paint vodopostachal fluorescent pigment hydrolysis begins immediately after the introduction of the phosphor in the paint, and hydrolysis will continue up until the pigment is not completely degraded. If after the introduction of pigment into the paint to use for markup immediately, the encapsulating suspends hydrolysis, but in the process of operation of the marking in contact with water, the decomposition of the pigment continues. The hydrolysis of fluorescent pigment in paints on a nonaqueous basis should only be considered in utverzhdenii the film formed after marking the surface.
The following experiments are to some extent simulate the behavior vodonepronicaemyj fluorescent pigments in paints for road marking. These paints can be of two types - water-based and organic-based solvents. And in that and in other case they consist of five main components: film-forming, filler, thickener, solvent and pigment. For the formation of luminescence (fluorescence) of the film the main component is film-forming.
Were chosen for the study paints, widely used in Russia for road marking paint road marking "cork" is a suspension of pigments and fillers in a solution of acrylic copolymer domestic the CSOs production and special additives and waterproof paint road marking "Crossroads" - the suspension of pigments and fillers firm Omya (Switzerland) in a solution of acrylic copolymer firm "Forst" (Finland) and special additives.
On the basis of each of them were obtained fluorescent dye is injected into the original paint 20-30% (wt.) fluorescent pigment. After applying the paint to the prepared surface and drying the formed films were crushed into powder and placed in water. It was determined the course of the reaction of hydrolysis - the destruction of the phosphor.
The second series of experiments was that in methacrylate resin glue Araldite 2021 introduced vodonepronicaemyj fluorescent pigment Lumi Nova G-300 M, was added to the hardener and mixed with paint "Crossroads".
After 25-30 minutes of stirring the suspension fell hard lump fluorescent polymer mass. The lump was isolated, washed with water, broke, to grind and put in the water. Almost immediately began to increase the pH of the medium, which confirmed the course of hydrolysis. Similar results were obtained when using paint "cork."
Thus experimentally proved that all known technical solutions for creating compositions and paints for road marking coatings containing luminescence (fluorescence) pigments, can't protect them from the action of water, i.e. hydrolysis.
All of decree the major technical solutions based on the application of the method of encapsulating, which, as has been proved by experiment in any versions allow the possibility of occurrence of hydrolysis at different stages of its implementation and application.
The present invention is the creation of fluorescent compositions for marking road surfaces and other surfaces and fluorescent paints on the basis of these compositions, in which the luminescence (fluorescence) the pigment is protected from hydrolysis in all operating conditions.
The problem is solved by the proposed technical solution, the essence of which is to create luminescence (fluorescence) of the composition containing the luminescence (fluorescence) of the pigment, represents an oxide matrix based on aluminum oxide and oxides of at least one element selected from the group of Mg, Ca, Sr, Ba, Zn, Si, activated at least one rare earth element, and a polymer binder selected from the group: epoxy, urethane, acrylate, alkyd and mixed polymer resin that contains a fluorescent (fluorescence) pigment, pre-treated with aqueous solutions of reagents selected from the group monosubstituted phosphate, H2SO4H3PO4, a mixture of three - or disubstituted phosphate with at least one of the sour is: HCl, H2SO4or HNO3, in the following ratio (weight) of the components:
The second object of the invention is the luminescence (fluorescence) paint for marking road surfaces, comprising: luminescence (fluorescence) of the pigment, represents an oxide matrix based on aluminum oxide and oxides of at least one element selected from the group of Mg, Ca, Sr, Ba, Zn, Si, activated at least one rare earth element, pre-treated with aqueous solutions of the reagents selected from the group monosubstituted phosphate, H2SO4H3PO4, a mixture of three - or disubstituted phosphate with at least one of the acids: HCl, H2SO4or HNO3and road paint or enamel in the following ratio (weight) of the components:
Another variant of the invention is the luminescence (fluorescence) paint for road marking coatings containing lumines entou composition according to claim 1 and road paint or enamel for markup in the following ratio (weight) of the components:
|- luminescent composition:||8-52|
|road paint or enamel:||48-92|
or luminescent pigment, pre-treated with aqueous solutions of the reagents selected from the group monosubstituted phosphate, H2SO4H3PO4, a mixture of three - or disubstituted phosphate with at least one of the acids: HCl, H2SO4or HNO3, polymer binder and road paint or enamel for marking, in the following ratio (weight) of the components:
|- fluorescent pigment||- 2-60|
|polymer binder||- 4 - 20|
|road paint or enamel||- 94-20|
Proposed technical solutions differ from those known from the prior art in that it uses fluorescent (fluorescence) pigments, pre-treated with aqueous solutions of the reagents selected from the group monosubstituted phosphate, H2SO4H3PO4, a mixture of three - or disubstituted who phosphate, at least one of the acids: HCl, H2SO4or HNO3.
In the prior art it is known that in order to give stability to hydrolysis luminescence (fluorescence) pigments treated with aqueous solutions of the reagents selected from the group monosubstituted phosphate, H2SO4H3PO4, a mixture of three - or disubstituted phosphate with at least one of the acids: HCl, H2SO4or HNO3. (Patent RF №2323955 belonging to the authors of the present invention).
However, in the mentioned patent, nor in any other known from the prior art the source of information was not raised and not resolved the problem of reliability of protection from hydrolysis compositions for marking road surfaces containing luminescence (fluorescence) pigments, resistant to the action of water (hydrolysis).
The authors of the present invention first shown that, in the field of technology arises the problem of reliability of protection from the action of moisture, even in the case of application of encapsulated (protected) fluorescent pigments in force discovered circumstances:
violation of a protective layer of polymer film in case of mechanical damages, which are always present in the operation of road surface;
flow of hydrolysis during the process of encapsulation, which is the homeless persons is notable denied by authors known technical solutions;
flow of hydrolysis in the process of manufacture of road paints in aqueous and non-aqueous basis.
A new formulation of the problem, the existence of which is proved by the authors in an experiment, and is not described in the prior art it solution are proof of compliance with the proposed technical solutions to the condition of inventive step.
The proposed solution allows not only to provide reliable protection against hydrolysis, but
- to adjust the amount of polymeric binder, which affects light characteristics and technological aspects;
- to adjust the particle size of the fluorescent pigment, which is important when carrying out mixing it with the components of the compositions and colors.
The implementation of the invention
As a source of fluorescent pigments to protect them from hydrolysis and subsequent use for creating luminescent compositions and fluorescent dyes were selected pigments are presented in Table No. 3.
|Table No. 3|
|№ p/p||Company name and country of origin||The name of the fluorescent pigment|
|1||Dalian uminglight Science and Tehnology Co., Ltd - China||SP-2, SP-4, PLO-8C, GPLOS-5-14, GPLOS-5-20, PLB-7C|
|2||Nemoto & Co., Ltd - Japan|
The sample presents American company UM (United Mineral and Chemical Corp.)
|Lumi Nova G-300M|
|3||LLC "NPK "Phosphor - plane" - Russia||LDP-2M, LDP-SM|
|4||ZAO "NPF "Phosphor" Russia||PV-D|
|5||Nichia Corp. - Japan||NP-2820|
In Table No. 4 presents some of their characteristics.
|Table No. 4|
|№ p/p||The name of the fluorescent pigment||The wavelength||The chemical composition|
|1||SP-2, SP-4, GPLOS-5-14, GPLOS-5-20, PLO-8C||520||MO·SiO2·Al2O3:The Eu|
M is one or more elements selected from the group of CA, Mg, Sr, Ba, Zn
|2||LDP-2M||520SrAl2O4: Eu, Dy|
|4||Lumi Nova G-300 M||520||SrAl2O4: Eu, Dy|
|5||NP-2820||490||Sr4Al14O25: Eu, Dy|
|6||PLB-7C||490||MOxAl2About3USiO2: The Eu|
M - CA, Mg, Sr, Ba, x=1,2-2,0, y=0,005-0,5
|7||PLO-7C||520||MOxAl2About3USiO2: The Eu|
M - Ca, Mg, Sr, Ba, x=0.5 to 2.0, y=0,05-0,5
Table 5 presents the conditions and results of treatments of fluorescent pigments to make them waterproof properties.
|Table No. 5|
|no examples||Name phosphors||The reagents used for processing of phosphors||the pH of the solution during the processing of a phosphor||The stability of the phosphor to hydrolysis|
|at the beginning of the treatment||at the end of the treatment|
|4-1||Lumi Nova G-300 M||H3PO4N2About||1||3||-“-|
|10-1||SP-2||Na3PO4·12H2O, H2O, HCl||1||3||-“-|
|11-1||SP-4||Na3PO4·12H2O, H2O, HCl||1||3||-“-|
|12-1||LDP-2M||Na3PO4·12H2O, H2O, HCl||1||3||-“-|
|13-1||PV-D||Na3PO4·12H2O, H2O, HCl||1||3||-“-|
|14-1||Lumi Nova G-300 M||Na3PO4·12H2O, H2O, HCl||1||3||-“-|
|15-1||LDP-2M||Na2HPO4·12H2O, H2O, HCl||1||3||-“-|
|18-1||GPLOS-5-20||Na3PO4·12H2O, H2O, HCl||1||3||-“-|
|19-1||PLO-8C||Na3PO4·12H2O, H2O, HCl||1||3||-“-|
|21-1||PLB-7C||Na3PO4·12H2O, H2O, HCl||1||3||-“-|
|22-1||NP-2820||Na3PO4·12H2O, H2O, HCl||1||3||-“-|
|25-1||PLO-8C||Na3PO4·12H2O, H2O, HCl||1||3||-“-|
|26-1||SP-2||Na3PO4·12H2O, H2O, H2SO4||1||4||-“-|
|27-1||SP-2||Na3PO4·12H2O, H2O, HNO3||1||2||-“-|
1. EXAMPLES of RECEIVING water RESISTANT LUMINESCENT PIGMENTS
A General method of processing aluminate phosphors
In a glass beaker of 100 ml, equipped with a magnetic stirrer, place the appropriate amount of aqueous solutions of phosphoric or sulfuric acids, monosubstituted phosphate or mixtures of salts of orthophosphoric acid with hydrochloric acid, sulfuric acid or nitric acid under stirring at room temperature for 10 minutes add the aluminate phosphor. The suspension is stirred for 2 hours, filtered, the precipitate washed 5 times with 40 ml of distilled water and dried at 80°LMS constant weight. When adding a phosphor to the solution may occur spontaneous heating of the reaction mass up to 26-28°C. In the process of the phosphor determines the pH of the aqueous suspension at the beginning and at the end of the reaction. For processing of phosphors used acid: 85% H3PO4, 92% or 98% H2SO4, 35% HCl, 55% HNO3; monosubstituted phosphate: NaH2PO4·2H2O, (NH4)H2PO4; salt of phosphoric acid: Na3PO4·12H2O, Na2HPO4·12H2O, (NH4)2HPO4.
Temperature treatment is not specifically limited to 28°C. it is Possible to carry out the processing at higher temperatures up to the boiling point of the solution, but it does not increase the intensity of luminescence of the phosphor compared to the test without special heating.
The processing time for 10-120 minutes, preferably 120 minutes Increase the processing time does not influence the intensity of luminescence of the phosphor.
Determination of the resistance to hydrolysis of the aluminate phosphors at room temperature
0.5 g of the phosphor material is processed as described in Examples, and 20 ml of distilled water placed in a glass Cup with a capacity of 50 ml, equipped with a magnetic stirrer, and stirred at room temperature for 6 hours, periodically determining the pH of the medium. Luminiaries resistant to hydrolysis, if the pH of the medium does not exceed 7.
Table 5 shows the results of processing of phosphors.
In a glass Cup with a volume of 100 ml, equipped with a magnetic stirrer, is placed 35,3 g H2O, 4.7 grams of 85% H3PO4and under stirring for 10 minutes add portions of 10 g of the phosphor SP-2. The suspension is stirred for 2 hours, filtered, the precipitate washed 5 times with 40 ml of distilled water and dried at 80°C to constant weight. Get for 9.64 g of the phosphor light yellow color. After mixing water and acid solution had a pH of 1 at the end of the processing of the phosphor pH 3.
Treatment is carried out under the conditions of Example 1-1, only as a phosphor used LDP-2M. Get 9,72 g phosphor light yellow color.
Treatment is carried out under the conditions of Example 1-1, only as a phosphor used PV-D. Get to 9.57 g of the phosphor light yellow color.
Treatment is carried out under the conditions of Example 1-1, only as a phosphor used Lumi Nova G-300m Receive 9,83 g phosphor light yellow color.
To a glass beaker, volume 100 ml, equipped with a magnetic stirrer, is placed 39,4 g H2Oh, 0.6 g of 98% H3SO4and under stirring for 10 minutes add portions of 10 g of the phosphor SP-2. The suspension is stirred 1 h the Product emit, as described in the Example is 1-1. Gain of 9.8 g of the phosphor light yellow color. The original solution had a pH of 1 at the end of the processing pH 4.
Spend processing phosphor LDP-2M in the conditions of Example 5-1. Get to 9.9 g of the phosphor light yellow color. The original solution had a pH of 1 at the end of the processing pH 4.
In a glass beaker of 100 ml, equipped with a magnetic stirrer, pour in 36,0 g H2Oh and add under stirring 4.0 g (NH4)H2PO4within 5 minutes To the resulting solution was added with stirring in portions during 10 minutes, 10.0 g of phosphor SP-2. The suspension is stirred 1 h the Product emit as described in Example 1-1. Gain of 9.8 g of the phosphor light yellow color. At the beginning of the processing solution had a pH of 6, at the end of the processing pH 7.
Spend processing phosphor LDP-2M in the conditions of Example 7-1. Get to 9.9 g of the phosphor light yellow color. At the beginning of the processing solution had a pH of 6, at the end of the processing pH 7.
10.0 g of the phosphor SP-2 is treated with a solution prepared by dissolving 5.2 g NaH2PO4·2H2O of 34.8 g H2O. the Processing and secretion of the product is carried out in the conditions of Example 7-1. Get to 9.9 g of the phosphor light yellow color. At the beginning of the processing solution had a pH of 6, at the end of the processing pH 7.
To a suspension of 15.5 g of Na3PO4·N2About 11.7 g H2O when paramashiva the AI is added dropwise 12.8 g of 35% hydrochloric acid for 10 minutes To the resulting homogeneous solution was added 10.0 g of phosphor SP-2 and the processing and selection of the product were carried out as described in Example 1-1. Obtain 9.5 g of the phosphor light yellow color. After mixing of the reagent solution had a pH of 1 at the end of the processing pH 3.
10.0 g of the phosphor SP-4 is treated under conditions as described in Example 10-1. Get 9,65 g phosphor light yellow color. After mixing of the reagent solution had a pH of 1 at the end of the processing pH 3.
10.0 g of the phosphor LDP-2M treated under the conditions as described in Example 10-1. Obtain 9.6 g of phosphor light yellow color. After mixing of the reagent solution had a pH of 1 at the end of the processing pH 3.
10.0 g of the phosphor PV-D treated under the conditions as described in Example 10-1. Obtain 9.4 g of phosphor light yellow color. After mixing of the reagent solution had a pH of 1 at the end of the processing pH 3.
10.0 g of the phosphor Lumi Nova G-300 M is treated under conditions as described in Example 10-1. Gain of 9.8 g of the phosphor light yellow color. At the beginning of the processing solution had a pH of 1, at the end of pH 3.
Mix 11.9 g Na2HPO4·12H2O C to 24.6 g H2O and 3.5 g of 35% hydrochloric acid and the resulting solution was added 10.0 g of phosphor LDP-2M. Processing and secretion of the product is carried out in conditions as described in Example 10-1. Get 9,8 g lumino the ora light yellow color. At the beginning of the processing solution had a pH of 1 at the end of the processing pH 3.
Mix of 4.6 g (NH4)2HPO4from 28.2 g H2O and 7.2 g of 35% hydrochloric acid and the resulting solution was added 10.0 g of phosphor LDP-2M. Processing and secretion of the product is carried out in conditions as described in Example 10-1. Get to 9.9 g of the phosphor light yellow color. At the beginning and at the end of the processing solution had a pH of 1 at the end of the processing pH 3.
Treatment is carried out under the conditions of Example 1-1, only as a phosphor used GPLOS-5-14. Get 9,83 g phosphor, a yellow-green color.
Treatment is carried out under the conditions of Example 10-1, only as a phosphor used GPLOS-5-20. Get of 9.56 g of the phosphor, a yellow-green color.
Treatment is carried out under the conditions of Example 10-1, only as a phosphor used PLO-8C. Obtain 9.7 g of phosphor light yellow color.
Treatment is carried out under the conditions of Example 1-1, only as a phosphor used PLB-7C. Get of 8.92 g of the phosphor light yellow color.
Treatment is carried out under the conditions of Example 10-1, only as a phosphor used PLB-7C. Get 9,38 g phosphor light yellow color.
Treatment is carried out under the conditions of Example 10-1, only as a phosphor used NP-2820. On ucaut 9,86 g phosphor light yellow color.
Treatment is carried out under the conditions of Example 1-1, only as a phosphor used LDP-3M. Get for 9.47 g of the phosphor light yellow color.
Treatment is carried out under the conditions of Example 7-1, only as a phosphor used PLB-7C. Get 9,52 g phosphor light yellow color.
Treatment is carried out under the conditions of Example 10-1, only as a phosphor used PLO-7C. Gain of 9.8 g of the phosphor light yellow color.
To 40 g of the solution prepared by mixing 15,50 g Na3PO4·N2Oh, 17,99 g H2O and 6,51 g of 92.1% H2SO4add portions with stirring, 10.0 g of phosphor SP-2. Further processing and secretion of the product is carried out in the conditions of Example 1-1. Get becomes 9.97 g of the phosphor light yellow color.
To 40 g of the solution prepared by mixing 15,50 g Na3PO4·12H2O, 10,45 g H2O and 14,05 g 55% HNO3add portions with stirring, 10.0 g of phosphor SP-2. Processing and secretion of the product is carried out in the conditions of Example 1-1. Get 9,76 g phosphor light yellow color.
2. EXAMPLES of RECEIVING water RESISTANT LUMINESCENT COMPOSITIONS
Used epoxy resin and hardener glue Araldite 2020. In a glass Cup, equipped with a magnetic stirrer, was placed 100 g of epoxy resin I g fluorescent pigment Lumi Nova G-300M, processed under the conditions of Example 4-1. The mixture is stirred for 10 minutes, then add 30 g of hardener. Stirring is continued for another 10 minutes to Receive the liquid fluorescent composition of white color with a yellowish tinge. After 10-15 minutes starts to increase viscosity of the composition. After 30-40 min begins solidification with the formation of a solid polymer mass of white color with a yellowish tinge. The curing is completed in approximately 24 hours.
Liquid fluorescent composition can be applied to any surface or placed in containers of any shape and made of any materials. After curing luminescent compositions have the polymer (in the form of a film or any specified form), who, after lighting all lights then glow in the dark yellow-green glow.
Part of the solid polymer mass is crushed. 10 g of the obtained powder is placed in a glass, equipped with a magnetic stirrer, add 100 ml of water and stirred while controlling the pH of the medium within 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. Control the pH 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 the preliminary lighting intensively shining in the darkness.
The obtained water resistant luminescent composition is recommended for use as base the capacity of the material, glowing in the darkness.
In the conditions of Example 1-2 receive water resistant luminescent composition based fluorescent pigment SP-2, treated under the conditions of Example 5-1. The luminescent material has a yellow-green glow.
In the conditions of Example 1-2 is treated with a fluorescent pigment LDP-3M-treated under the conditions of Example 23-1. Get water resistant luminescent composition blue glow.
Used polyurethane resin and hardener glue Araldite 2026. The resin (50 g), curing agent (50 g) and fluorescent pigment PLO-8C (20 g), treated under the conditions of Example 19-1, mixed and stirred under the conditions of Example 1-2. Get water resistant luminescent composition of white color with a yellowish shade of yellow-green glow.
In the conditions of Example 4-2 receive water resistant polyurethane luminescent composition based fluorescent pigment LDP-2M-treated under the conditions of Example 8-1. The luminous material in white color with a yellowish shade of yellow-green glow.
Used methacrylate resin and hardener glue Araldite 2021. The resin (50 g), compound (45 g), fluorescent pigment Lumi Nova G-300M (25 g), treated under the conditions of Example 14-1, mixed and stirred under the conditions of Example 1-2. Get water resistant luminescent compositions is the Oia white color with a yellowish shade of yellow-green glow.
20 g of 40% toluene solution of acrylic polymer innovations for this® LP 64/12 and 10 g of fluorescent pigment Lumi Nova G-300M, treated under the conditions of Example 4-1, mix thoroughly and put on the curb. After application, the coating (film) dries in 1 hour, finally after 24 hours. Part of the film is mechanically removed from the marked surface (film intensively glows in the dark), crushed and suspended in water. Observe the change in pH. At the beginning of the treatment water, and a week later the aqueous suspension has a pH of 7.
In the conditions of Example 7-2 preparing a luminescent composition based on acrylate polymer Diplex 070. Get water resistant luminescent film (after application on a horizontal surface).
Use composition (varnish + hardener) Polish firm Ran Al®.
20 g of acrylic lacquer Akrylowy Lakier Eco and 10 g of hardener Utwardzacz thoroughly mixed with 20 g of fluorescent pigment SP-2, treated under the conditions of Example 5-1, within 1 h After application on any surface: the markings on the asphalt road, wooden, metal surface, the film hardens within 24 hours. Each of the films after mechanical grinding is not hydrolyzed.
10 g of 40% toluene solution of acrylic polymer innovations for this® LP 64/12 and 20 g of fluorescent pigment LDP-M, processed under the conditions of Example 23-1, mix thoroughly and put on the curb. After application, the coating (film) dries in 1 hour, finally after 24 hours. Get water resistant luminescent film blue glow.
In the conditions of Example 10-2 preparing a luminescent composition using 30 g of fluorescent pigment SP-2, treated under the conditions of Example 5-1. Get water resistant luminescent film yellow-green glow.
Mix the components of the luminescent composition in the conditions of Example 6-2 in quantities: resin - 53 g hardener 45 g, fluorescent pigment - 2, the Composition is applied on the curb. After drying receive fluorescent film yellow-green glow.
3. EXAMPLES of RECEIVING water RESISTANT LUMINESCENT PAINTS
According to the proposed invention luminescent road paint can be obtained by mixing the fluorescent composition directly or fluorescent pigment, pre-treated with aqueous solutions of the reagents selected from the group monosubstituted phosphate, H2SO4H3PO4, a mixture of three - or disubstituted phosphate with at least one of the acids: HCl, H2SO4or HNO3road paint.
Fluorescent waterproof pigment, luminous in fact the OTE, you can enter any paints for road marking, ready to use, water and non-aqueous basis. These paints have one common feature is to form a film on the surface are marked due to the presence in the composition of film-forming components.
As road paint can be used paints that are described in the patents of the Russian Federation (table 1), or any paint that serves the domestic market and are presented in Table No. 6.
|Table No. 6|
|№ p/p||Brand of paint, THE||The working viscosity according to the OT-4||Density g/cm3||The content of non-volatiles, %||The drying time, min||Reflectance, %||Abrasion resistance (method Soundarya), %|
|1||AMD, THE 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, THE 2313-010-49792662-99||80-100||1,6||78||15-17||71||80-90|
|4||Acrylic paint for road marking, THE 2313-017-45822449-99||100-120||1,7||80||15-17||65||76|
|5||"Dorstroiservis-2", THE 23131-003-04002214-98||60-80||1,6||79||15-20||60||73|
|6||AK-591, THE 6-27-18-302-2000||80-120||1,4||at least 70||8-10||65||82|
|7||TO-525 road, THE 7.2312-002-129579-98||45-120||1,4||66||7-10||71||70|
|8||AK-525 marking, THE 2312-011-42149549-02||80-200||of 1.57||70-80||5-7||69||92|
|9||Technocolor, THE 2316-020-07509505-2000||60-160||1,5||76||9-11||70||70-90|
|10||Spectrin, THE 2316-003-5988865-00||80-180||at least 1.5||at least 75||10-20||66||75-85|
|11||The Arctic, THE 2313-04100149274-2000||200-250||1,3||62,7||15||67||62|
|12||DM AK-521, TO-001-02953342-2001||70-190||1,5±0,1||70||18||65||68|
|13||Highway, THE 2312-156-4695478-01||100-200||1,4||60-75||9||68||65|
|14||Road marking enamel D-1, TU 2332-027-05808020-01||40-120||1,56||at least 70||8||70||63|
|15||Paint for road marking AK - "Kronos", THE 2313-039-20504464-2001||60-160||1,65||75±2||4-6||68||75-85|
|16||Paint marking "Track", THE 2316-003-54503111-2001||60-160||1.68||75±2||5||67||84-88|
|18||AK-511, THE 2316-156-05011907-98||100-160||1,48||at least 70||13||67||90|
|19||AK-585, THE 2316-218-05011907-2002||at least 40||1,47||at least 70||4||65||90|
|20||AC-5307, STF 6-3-121-2001||76||1,35||of 60.5||4||70||77|
|21||AK-539, THE 6-27-18-320-2001||20-60 (OT-6)||1,52||at least 70||10||78||76|
|22||Enamel EP-555 "Katalin", TU-2312-231 -00204211 -2001||70-150||1,39||65-71||7||63||94|
|23||AK-522 "Basalt-2", THE 075-06-004-116-99||68 (OT-6)||1,54||74,6||5||64||64|
|24||AK-517 (Stylepix D-1163), TU RB 00204547.066-96||150||1,58||81,3||8||69||90|
|25||Paint for road marking AK-501, AK-502, TU-2316-011-55856863-2002||at least 40||1,45||65-75||12||72||70|
|26||The waterproof paint road marking ACRE-DOR, THE 2313-018-26294341-2002||40-120||at least 1.5||at least 70||6||67||81|
|27||AK-109 Loco "BAR", THE 2312-021-48972729-2001||80-180||at least 1.5||at least 70||10||70||92|
|28||AK-508 "Cresol", THE 2316-008-57352960-02||60-160||at least 1.5||at least 70||20||75||83|
Typically, road paints represent a complex system containing from 4 to 6 or more components, including a pigment, a filler, a polymer, a plasticizer, additives, solvent, each of which plays its own important role. However, the most important of them, determining the durability of a polymeric binder.
The General lack of any fluorescence dyes is the reduction of light intensity due to the presence of the particles of the pigment (titanium dioxide), fillers and other substances that affect the spectral properties of the phosphor. Therefore, to eliminate this factor, you can use the two-stage labeling surfaces.
In CA the arts used road paint:
"Crossroads", GOST R 51256-99, THE 2313-015-40165-03;
- "The highway", THE 2312-156-4695478-01;
- Paint marking "Track", THE 2316-003-54503111-2001;
Road marking enamel D-1, TU 2332-027-05808020-01;
Enamel EP-555 "Catalin".
3.1. EXAMPLES of RECEIVING water RESISTANT LUMINESCENT PAINTS BASED LUMINESCENT COMPOSITIONS AND ROAD PAINTS OR ENAMELS
To 50 g of epoxy resin Araldite 2020 add 15 g of the corresponding hardener (table 1), 15 g of the phosphor SP-2, treated under the conditions of Example 1-1, and stirred for 5 minutes To the resulting suspension is added 500 g of paint marking "Track". The mixture is stirred for 10 min and applied on any horizontal surface. After 8-10 hours solidified fluorescent film white mechanically chopped, placed in water (1 g in 50 ml water) and pH control. The initial pH of 7 is not changed within one month, indicating that the receiving water resistant luminescent film.
The components are mixed, film formation and control of water-stability of crushed fluorescent film was carried out under the conditions of Example 1-3, but as a fluorescent pigment used phosphor LDP-2M-treated under the conditions of Example 2-1. The obtained water-resistant fluorescent paint.
In the conditions of Example 1-3 were obtained water-resistant luminescen the nye paints using various waterproof fluorescent pigments. In Table 7 presents the results of the experiments.
|Table No. 7|
|No examples||Used waterproof fluorescent pigments||The stability of the luminescent paint to hydrolysis|
|The original phosphor||No examples of processing of phosphors|
|3-3||PV - D||3-1||Stable|
|4-3||Lumi Nova G-300M||4-1||-"-|
|6-3||GPOLS - 5-4||17-1||-"-|
|7-3||GPOLS - 5-20||18-1||-"-|
To 20 g of polyurethane resin Araldite 2026 added 20 g of the corresponding hardener (table 1) and 20 g of phosphor LDP-3M-treated under the conditions of Example 23-1. The suspension is stirred 10 min and add 200 g of white paint for road marking "Crossroads". The mixture is stirred for another 10 min and applied on the pre-marked paint "Crossroads" asphalt surface. After drying and curing the formed fluorescent film, it is subjected to control by hydrolysis under the conditions of Example 1-3. According to the results it was concluded that the obtained luminescent paint is water-resistant.
To 50 g of methacrylate resin Araldite 2021 add 45 g of the corresponding hardener (table 1), 50 g of the phosphor LDP-2M-treated under the conditions of Example 12-1, and the mixture is stirred for 10 minutes To a suspension add 400 g road marking enamel D-1. Get water resistant luminescent white paint. After application on a horizontal surface formed fluorescent film after INSOL is the light intensively glows in the dark. Hydrolytic stability was tested as described in Example 1-3.
In the conditions of Example 13-3 prepare water resistant luminescent paint, using as the dye a white traffic paint for road marking "Magistral". The ratio of the components:
- methacrylate resin Araldite 2021 - 38,5 g;
- hardener for resin - 11.5g;
- phosphor - 30 g;
- paint for road marking - 920,
In the conditions of Example 12-3 prepare water resistant luminescent paint using paint white enamel EP-555 "Catalin". The ratio of the components:
- polyurethane resin Araldite 2026 - 22 g;
- hardener for resin - 22 g;
- phosphor - 8 g;
- paint for road marking - 48,
3.2. EXAMPLES of RECEIVING water RESISTANT LUMINESCENT PAINTS BASED COMPONENTS: a FLUORESCENT PIGMENT, a POLYMERIC BINDER, ROAD PAINT OR ENAMEL
To 50 g of epoxy resin Araldite 2020 add 15 g of phosphor Lumi Nova-G 300M treated in the conditions of Example 4-1, and stirred for 10 minutes the resulting suspension is added 500 g of white paint for road marking "Crossroads". The mixture is stirred for 10 min and add 15 g of hardener to resin glue Araldite 2020. The mixture is stirred for 10 minutes Receive fluorescent white paint. The paint is applied on a horizontal surface and the resulting fluorescent film education is anywayt in the conditions of Example 1-3. Because pH 7 aqueous slurry of the crushed film does not change in time, it was concluded that the obtained luminescent paint is water-resistant.
In Table 8 presents examples of making luminescent paints for road marking coatings, using the order of mixing the components under the conditions of Example 16-3, varying assortment of waterproof fluorescent pigments, binders, road paints or enamels. In the Examples 17-3÷20-3 used road paint "the Crossroads", in the Examples 21-3÷23-3 road paint "Highway", in Example 24-3 Road marking enamel D-1 in Example 25-3 - Enamel EP-555 "Catalin".
In each of the Examples was obtained waterproof fluorescent paint.
3.3. EXAMPLES of RECEIVING water RESISTANT LUMINESCENT PAINTS BASED ON water-RESISTANT FLUORESCENT PIGMENTS AND ROAD PAINTS OR ENAMELS
To 97 g of paint for road marking "Highway" add 3 g of the phosphor LDP-2M-treated under the conditions of Example 12-1, and the mixture is stirred for 10 minutes. Get water resistant luminescent paint for road markings.
To 500 g of white paint for road marking "Track", THE 2316-003-54503111-2001, add 500 g of the phosphor used in Example 12-3, and stirred for 30 minutes Get water resistant luminescent paint for road marking and other Vertica is lnyh and horizontal surfaces.
The mixture of components is carried out in the conditions of Example 26-3 using 25 g road marking enamel D-1 and 75 g of fluorescent pigment, treated under the conditions of Example 10-1. Get water resistant luminescent paint for road markings.
|Table No. 8|
|Used waterproof fluorescent pigments||The content of components in fluorescent paint, g|
|The original phosphor||No examples of processing of phosphors||Lumines-|
|Polymer binder||Road paint or enamel|
|Araldite 2021||The hardener|
|18-3||Lumi Nova G-300 M||4-1||30||6,5||3,5||-||-||-||-||60|
|20-3||GPOLS - 5-4||17-1||10||-||-||2||2||-||-||86|
|21-3||GPOLS - 5-20||18-1||60||-||-||11||9||-||-||20|
1. Fluorescent composition for marking road surfaces containing luminescence (fluorescence) of the pigment, represents an oxide matrix based on aluminum oxide and oxides of at least one element selected from the group of Mg, CA, Sr, Ba, Zn, Si, activated at least one rare earth element, and a polymer binder selected from the group: epoxy, urethane, acrylate, alkyd and mixed polymer resin, characterized in that the luminescence (fluorescence) pigment pre-treated with aqueous solutions of the reagents selected from the group monosubstituted phosphate, H2SO4H3PO4, a mixture of three - or disubstituted phosphate with at least one of the acids: HCl, H2SO4or HNO3in the following ratio (weight) of the components:
2. Fluorescent paint for road marking coatings containing road paint on aqueous or non-aqueous based or enamel and luminescence (fluorescence) of the pigment, represents an oxide matrix on the basis of the aluminum oxide and oxides,
at least one element selected from the group of Mg, CA, Sr, Ba, Zn, Si, activated at least one rare earth element, characterized in that it contains a fluorescent pigment, pre-treated with aqueous solutions of the reagents selected from the group monosubstituted phosphate, H2SO4H3PO4, a mixture of three - or disubstituted phosphate with at least one of the acids: HCl, H2SO4or HNO3, in the following ratio (weight) of the components:
3. Fluorescent paint for road marking coatings containing luminescent composition according to claim 1 and road paint on aqueous or non-aqueous based or enamel, in the following ratio of components:
|road paint or enamel||48-92|
4. Fluorescent paint for road marking coatings containing road paint on aqueous or non-aqueous-based, fluorescent pigment, represents oxen the th matrix based on aluminum oxide and oxides,
at least one element selected from the group of Mg, Ca, Sr, Ba, Zn, Si, activated at least one rare earth element, and a polymer binder selected from the group: epoxy, urethane, acrylate, alkyd and mixed polymer resin, characterized in that it contains luminescence (fluorescence) pigment, pre-treated with aqueous solutions of the reagents selected from the group monosubstituted phosphate, H2SO4H3PO4, a mixture of three - or disubstituted phosphate with at least one of the acids: HCl, H3SO4or HNO3in the following ratio of components:
|road paint or enamel||20-94|
SUBSTANCE: road marking paint contains an acrylic film-forming agent - copolymer of methylmethacrylate and butylmethacrylate - DIANAL BR-116 resin, calcite filler - finely ground white marble Omicarb and micronised calcite filler MK, barite filler - fractionated microbarite Mibari, plasticiser - chloroparaffin KP-470, organic solvent - toluene and ethylacetate, pigment - titanium dioxide, thickener - organic derivative of montmorillonite Bentone SD-2, dispersing agent - mixture of natural phospholipids Soya lecithin, anti-sedimentation agent - 20% solution of emulsion polyethylene resin in xylene M-P-A 2000X, with components in a defined ratio. Chrome yellow and/or technical carbon can also be contained as pigment.
EFFECT: maintaining high level of the rest the of factors.
3 cl, 2 tbl, 11 ex
SUBSTANCE: pedestrian crossing consists of traffic lights for motor transport and pedestrians mounted on posts on the road shoulders, zebra crossing made in form of longitudinal white stripes painted on the road surface, two white transverse stripes on each side of the road in front of the zebra lines indicating lines where motor transport should stop before the crossing. On the road surface and on the same level as the surface, there are metal boxes in which lights are mounted and armoured glass in reflectors with a corrugated inner surface to ensure bright illumination in all directions. The boxes also contain a wire for heating the glass controlled by a device with a light-emitting diode, placed inside the reflector of each light, a system for removing condensate from the lights and boxes in the ground. The box with green lights is placed between white stripes of the zebra crossing and has two modes of illumination - constant during green pedestrian crossing and red transport traffic lights and blinking when simultaneously showing red pedestrian and amber transport traffic lights. The box with red lights is placed on the white transverse lines where motor transport stops before crossing and illuminate a uniform red light during green pedestrian, red transport and when simultaneously showing red pedestrian and amber transport traffic lights, thus preventing movement and enabling the pedestrian to finish crossing.
EFFECT: invention increases safety on the roads.
SUBSTANCE: compound for road marking comprises main resins - n-butylacrylate and methyl methacrylate and hardener. Additionally it contains reactive resin on the basis of acrylic resins, hardener and accelerant of hardening reaction, containing the following components: 2-ethyl hexyacrylate, N,N-dihydroxyethyl-r-toluidine, N,N-dimethyl-r-toluidine, 2 (2-hydroxy-3,5-ditret-butylphenyl) benzotriazol, heavy hydrosulfonated oil, at the same time ratio of main resins and reactive resin is in the range from 1:3 to 3:1.
EFFECT: expansion of possibility to use compound in climatic conditions with low temperatures, which increases efficiency of marking operation with preservation of high speed of hardening.
SUBSTANCE: road marking paint contains an acrylic filming agent, inorganic filler, a plasticiser, a mixed organic solvent, a pigment - titanium dioxide, a thickener based on organobentonite and a dispersing agent based on lecithin. The inorganic filler used is acid plagioclase in form of particle with size ranging from 12 to 60 mcm with sodium content ranging from 10.50 to 10.60 wt % in terms of Na2O. The paint additionally contains microtalc.
EFFECT: increased resistance of the road mark to prolonged effect of water, salt and alkali.
2 tbl, 3 ex
SUBSTANCE: thermoplastic for marking automobile roads and aerodromes contains polyester resin with melting point of 70-85°C and acid number 35-40 mg KOH/g, obtained based on phthalic anhydride and glycerin in amount of 20-30 wt %, rutile titanium dioxide in amount of 3-10 wt %, white quartz sand 21-37 wt %, glass microspheres in amount of 4-24 wt %, Laprol 3003 - polyether with molecular weight of 3000 based on propylene and ethylene oxides in amount of 1-10 wt % and 10-30 wt % crushed marble.
EFFECT: thermoplastic is characterised by high wear resistance, does not cause skidding, dries fast when deposited on the road surface, has good adhesion to the road surface and can be used in different climatic regions under the temperature of -40°C - +40°C.
2 tbl, 3 ex
SUBSTANCE: composition, apart from film-forming substance - hydrocarbon aliphatic resin, pigment, mineral fillers, glass balls and waxes additionally contains block-copolymers of styrene with unlimited aliphatic hydrocarbons, copolymers of ethylene and vinyl acetate, in combination with plasticisers, esters of aromatic and aliphatic acids and mineral oils. In composition hydrocarbon aliphatic resin may be partially or completely replaced for pentaerythritol or glycerin esters of white resin without damage to quality.
EFFECT: combination of components in certain ratio makes it possible to increase elasticity of roadbed compositions and as a result, its wear resistance and functional durability.
1 cl, 1 tbl, 1 ex
SUBSTANCE: composition of spray-plastic contains the following components as film-forming substance - aliphatic hydrocarbon resins or their mixtures with glycerin or pentaerythritol ester of white resin in combination with block-copolymer on the basis of styrene and isoprene. Plasticiser used is represented by esters of aromatic acids or paraffin mineral oils.
EFFECT: increased elasticity and wear resistance of spray-plastic.
1 cl, 1 tbl, 1 ex
SUBSTANCE: invention relates to paint and varnish industry, in particular to production of paints for carriageway of automobile roads and aerodromes with asphalt, concrete or asphalt-concrete covering. Roadway marking paint contains copolymer of methyl methacrylate and H-butylmethacrylate - resin "Degalan LP 64/12" as acryl film-forming agent, contains as calcite filler finely-crashed white marble Omicarb and micronised kalidit filler MK and additionally contains fractioned microbarite Mirabi, plasticiser- clorparaffin "ХП"-470, organic solvent - toluol and ethyl acetate, pigment - titanium dioxide, thickener - organic derivative of montmorillonite Bentone SD-2, dispersant - mixture of natural phospholipids Soya lecithin, anti-sedimentation preparation - 20% solution of organic compound in xylol "М-П-А-2000Х" with claimed component ratio.
EFFECT: obtaining paint for roadway marking with white colour brightness coefficient 80-85% preserving values of other characteristics at the same level.
2 tbl, 11 ex
FIELD: polymer materials and road marking.
SUBSTANCE: invention relates to compositions of thermoplastic mastic designed for marking bituminous concrete pavements. Thermoplastic mastic comprises film-forming butyl methacrylate/methacrylic acid/styrene terpolymer having acid number 6.0-9.0 mg KOH/g, softening temperature 90-112°C, and relative viscosity of 2% solution in butyl acetate 1.4-1.8; titanium dioxide; mineral fillers: mixture of quartz sand with fractioned micro-marble; lighting additives: mixture of glass microbeads with organic optical bleacher; plasticizer: mixture of dibutyl o-phthalate with colophony pentaerythritol ether having acid number not higher than 12.0 mg KOH/g and softening temperature not below 90°C; all taken in specified proportions.
EFFECT: reduced dirt retention level of highway strips.
FIELD: pant and varnish industry.
SUBSTANCE: invention relates to producing dyes for public automobile roads and airdromes with asphalt, concrete or asphalt concrete coating. Proposed road marking dye involves the following components: 65% solution of thermoplastic acrylic resin in toluene or ethyl acetate - "Khromakril TP-130" as an acrylic film-forming agent, 22-28 mas. p. p.; fractionated micromarble as a filling agent, 36-43 mas. p. p., and aluminum oxyhydroxide - "Prokal", 10-14 mas. p. p.; chloroparaffin KHP-470 as a plasticizer, 1-3 mas. p. p.; dye comprises mixture of toluene and ethyl acetate in the ratio = 2.4:1, or mixture of toluene and acetone in the ratio = 1:1 as an organic solvent, 7-16 mas. p. p.; 7-13 mas. p. p. of titanium dioxide and it comprises additionally a thickening agent - organic derivative of montmorillonite - "Bentone SD-2", 0.2-0.8 mas. p.; mixture of natural phospholipids - "Soya letsitin Nalec 10-F" as a disperser, 0.2-0.5 mas. p.; anti-sedimentation agent - 20% solution of organic compound in xylene - "M-P-A 2000X", 0.1-0.3 mas. p. Dye can comprise additionally a modifying additive - 45-60% solution of linear thermoplastic polyurethane based on polytetramethylene glycol and toluylenediisocyanate in butyl acetate - "Plastur", up to 5 mas. p. p. Proposed road marking dye possesses impact film strength 100 cm, film hardness by pendulum device of type M-3 0.75-0.80 conditional units, and whiteness value is 92-94%.
EFFECT: improved and valuable properties of dye.
2 cl, 2 tbl
SUBSTANCE: polymer luminescent composition for obtaining white light excited by a blue light-emitting diode contains the following components, pts. wt: transparent polymer 100; photoluminescent phosphor based on garnet Y3Al5O12:Ce or Gd3Al5O12:Ce, or based on a mixture of said compounds 1.5-5.0; polyethylene wax in form of powder with particle size of 18-30 mcm 0.1-0.7; stabiliser 0.2-1.0. The transparent polymer used can be polycarbonate, polystyrene or a copolymer of styrene with acrylonitrile and butadiene. The stabiliser can be a compound from a group of sterically hindered phosphites.
EFFECT: Invention enables to obtain a protective lighting composition which provides low colour temperature, improved colour coordinates.
5 cl, 1 dwg, 2 tbl
FIELD: physics, optics.
SUBSTANCE: invention relates to photoluminophors designed for converting emission of blue light-emitting diodes to the yellow-red region of the spectrum in order to obtain resultant white light, particularly to a cerium doped luminophor based on yttrium aluminium garnet used in two-component light-emitting diode light sources. The invention describes a luminophor for light sources which contain aluminium, yttrium, cerium, lutetium and oxygen in the following ratio: (Y1-xCex)3Al5O12 and 5-60 wt % over 100% (Lu1-yCey)2O3, where x=0.005-0.1; y=0.01-0.1. The invention provides a fine-grained luminophor with luminescent emission band maximum at λ≈590 nm, while lowering temperature and duration of synthesis.
EFFECT: use of such a luminophor in a two-component light source with a blue light-emitting diode enables to obtain resultant "warm" white light with high colour rendering index, increases uniformity of light scattering and reduces energy consumption during synthesis.
1 cl, 1 dwg, 6 ex
FIELD: fire safety.
SUBSTANCE: luminescent composition for hidden marking, exposed when radiated with visible, infrared or ultraviolet radiation, contains binary mix, which includes luminophore with long afterglow on the basis of strontium aluminate, which is activated with europium, dysprosium and yttrium - LDP-1-3M, and photoluminophore with yellow, blue, red or white glow colour. Luminophores are taken with the mass ratio of 70:30. For even glow field, size of luminophore particles is selected in the range of 1-25 mcm, and flow glow of "Star sky" type - in the range of 20-180 mcm. Fire-prevention fireproofing composition includes fire-prevention composition and luminescent additive - specified binary mix. Method for marking of fire-prevention compositions consists in preparation of specified binary mixture, its introduction in amount of 0.01-35 wt parts per 100 wt parts of polymer binder. Produced marking is applied manually, by explication and printing methods in the form of information or graphic symbols, signs, text.
EFFECT: afterglow brightness and duration increase, as well as fire resistance, temperature range of afterglow expands, as a result, fast and reliable detection of fire-prevention composition is provided, as well as visualisation of extinguishing site.
3 cl, 4 tbl
SUBSTANCE: invention can be used for making dyes, plastics, resins, glass and ceramic objects, cements, adhesives, fibres, yarn. Aluminate luminophores, which are a matrix based on aluminium oxide and oxides of at least one element chosen from: Mg, Ca, Sr, Ba, Zn, Si, activated by at least one rare-earth element, are treated with aqueous solutions of monosubstituted phosphates at pH 6 at the beginning and pH above 7 at the end of treatment or solutions of agents chosen from: H2SO4, H3PO4, monosubstituted phosphates, mixture of tri- or disubstituted phosphates with at least one acid from: HCl, H2SO4 or HNO3 at pH 1 at the beginning and pH not above 4 a the end of treatment. The oxide matrix can have formula: MO-SiO2-Al2O3: R, MAl2O4:R, -MAlO4:R, Sr4Al14O25: R, where M - is a metal, chosen from: Ca, Mg, Sr, Ba, Zn; R - at least one rare-earth metal, chosen from a group consisting of Dy, Nd, Eu, Tm, Tb, Y,Yb.
EFFECT: invention increases luminous intensity of aluminate luminophores without reducing hydrolytic stability.
5 cl, 3 tbl, 27 ex
SUBSTANCE: water-resistant fluorescent pigment is an oxide matrix based on aluminium oxide and, at least, one of the following elements: Mg, Са, Sr, Ва, Zn, Mn, Si, В, Р, Ga, activated with, at least, single rare earth element, treated with a mixture of salts from the following group: Na3PO4, Na2HPO4, (NH4)2HPO4, Ca3(PO4)2, with acids from the following group: HCl, H2SO4, HNO3, pH not exceeding 4 at the end of treatment. Oxide matrix may be of formula MO-SiO2Al2O3:R, where М stands for, at least, a single metal from the following group: Ca, Sr, Ba, Mg, Zn; R stands for, at least, a single element from the following group: Dy, Nd, Eu, Tm, Tb, Y, Yb; MAl2O4:R, where М stands for, at least, a single metal from the following: Ca, Sr, Mg, Ba, while R stands for, at least, a single element from the following: Dy, Nd, Eu, Tm, Tb, Y, Yb; MAlO4:R, where М stands for, at least, a single metal from the following: Sr, Ca, Ba; R stands for, at least, a single element from the following group: Dy, Nd, Eu, Tm, Tb, Y, Yb. Ink contains the said fluorescent pigment and thickening agent.
EFFECT: water-resistant at room or elevated temperature, fluorescent properties being retained.
5 cl, 5 tbl, 57 ex
FIELD: polymer materials.
SUBSTANCE: polymeric layer is made in the form of polydimethylsiloxane or polycarbonate-based film uniformly filled with luminophor mixture in amount 10 to 80%, which mixture contains ZnS·Co·Ni and/or ZnS·CsS·Cu·Co Ni and CeAl2O4·Eu·Dy. Weight ratio of zinc sulfide to aluminate luminophor ranges from 1:99 to 10:90. Molecular weights of polydimethylsiloxane and polycarbonate are more than 30000 and 30000-35000, respectively. Luminophor particle size is 10 to 60 mcm. Thickness of polymer film is ranges from 90 to 2000 mcm. In case of polycarbonate polymeric film, informational graphic symbols, marks, and text are applied onto surface of the film by offset print technique and, in case of polydimethylsiloxane film, by explication technique. Polymeric layer may be supported by light-reflecting carrier whose thickness id comparable with that of luminophor grains. Initial brightness and accumulated light are in excess as compared to prior art analogues.
EFFECT: increased strength, elasticity, resistance to mechanical and environmental effects, reduced cost, and prolonged after-excitation emission.
6 cl, 3 tbl
SUBSTANCE: disclosed is a colourless phosphorescing luminophor, which is a coordination compound of terbium (III) with [2-(aminocarbonyl)phenoxy]acetic acid (HL2) and having formula Tb(L2)3, and specifically: , having high quantum efficiency of luminescence, considerable luminescence intensity and fluorescence maxima at 20500, 18300, 17000, 16000 cm-1.
EFFECT: possibility of use in protecting bond payer and documents from forgery, and as radiating substances in electroluminescent devices.
1 dwg, 1 ex