RU2378308C1 - Thermoplastic for marking automobile roads and aerodromes - Google Patents

Abstract

FIELD: chemistry.

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

Description

The invention relates to thermoplastic materials that can be used for marking a roadbed with an asphalt concrete coating.

Horizontal marking of the roadway is one of the most important technical means of organizing traffic, ensuring its safety. The main reasons for the destruction of the markings are the harsh weather conditions in Russia, the use of aggressive anti-icing agents, the effects of fuels and lubricants, the poor condition of the roadway, and also a fairly frequent violation of the technology for making marking materials. It is believed that the service life of road marking paints does not exceed one year, and thermoplastics does not exceed two years. The advantage of thermoplastic materials over paints is that the thickness of the applied layer can be increased to 1.5-4 cm, which allows to extend the life of the road marking.

Currently, there is a problem of increasing the life of thermoplastic marking materials.

Known thermoplastic materials for marking the roadbed with an asphalt concrete coating, the compositions of which include various types of synthetic binders that determine the main technical parameters of the material, as well as fillers, pigments and other target additives.

Thus, in Australian patent AI-B-33-909 / 33, MKI ⁵ C09D 001/08, 005/10, 007/12, С04В 024/126, polyacrylates and copolymers of acrylates with styrene were used as modifiers.

The compositions of the marking thermoplastics based on petroleum resins are described in patent No. 1324553 (England), No. 420135 (Austria), and in patent No. 4713404 (USA) a composition based on epoxy resin is claimed. The most widespread for regions with severe climatic conditions are marking materials based on polyester resins - hot-applied thermoplastics (Platonov A.P. Polymeric materials in road and airfield construction. - L .: Avtodor, - 1994. - 137 p .; Synthetic materials, used in the construction and repair of roads. - Review, inform. - M .: NIITEHIM, 1994. - Issue 2-31 p.).

In the patents of the Russian Federation 2074872 (MKI ⁶ C09D 167/02), Russian Federation 2074921 (MKI ⁶ C09D 167/02, E01F 9/04), Russian Federation 2167901 (MKI ⁶ C09D 167/02, E01F 9/04) and Russian Federation 2216564 (MKI ⁶ C09D 167/02, E01F 9/04) proposed compositions of thermoplastic marking materials for horizontal marking of roads based on polyester resins modified with low molecular weight esters, glycols, waste thermoplastic polyurethane, various types of waxes. The disadvantages of the known inventions include the abundance of components, which, however, does not lead to the improvement of such important marking properties as water absorption and adhesion to asphalt concrete.

Closest to the proposed material is a thermoplastic composition for marking a roadbed on the basis of a solid polyester resin, containing a polyester resin with 40% terephthalic acid, including a plasticizer - a polyester based on aliphatic dibasic acids and glycols, a pigment, a filler, an anti-sedimentation additive and lighting additives (patent RF 2216564, MKI ⁶ C09D 167/02, E01F 9/04). The known composition of a thermoplastic material (prototype) solves the problem of improving the operational properties of a road-marking coating, however, its resistance to pollution and water absorption is not high enough, and such properties as hardness, wear rate and gloss are not given in the description of the known material.

The objective of the proposed technical solution is to improve the operational characteristics of a thermoplastic as a road marking material, namely: increasing its hardness, resistance to the destructive effect of anti-icing agents, reducing the intensity of marking wear and water absorption, as well as reducing the dependence of coating quality on temperature difference and increasing the gloss of the coating.

The task is achieved in that the thermoplastic for marking roads and airfields, including a polyester resin with a softening temperature of 70-85 ° C and an acid number of 35-40 mg KOH / g, obtained on the basis of phthalic anhydride and glycerol, rutile titanium dioxide, quartz sand white and glass beads, according to the invention, additionally contains Laprol 3003 - a polyester with a molecular weight of 3000 based on ethylene and propylene oxides and marble chips in the following ratio, wt.%:

Polyester resin 20-30 Laprol 3003 1-10 Rutile titanium dioxide 3-10 Marble chips 10-30 Sand quartz white 21-37 Glass beads 4-24

The inventive composition of thermoplastic material provides a marking that is clearly visible to drivers both in the daytime and in the dark in any weather, is characterized by low wear rate, does not cause the wheels of cars to slip, dries quickly when applied to the road surface, has good adhesion to it and can operate in various climatic zones of Russia in the temperature range from -40 ° C to + 40 ° C. The high wear resistance of the thermoplastic ensures its long service life - from 3 to 4 years on roads with heavy traffic. The inventive thermoplastic makes it possible to significantly reduce the cost of restoring marking lines, to increase the productivity of road repair services. Clear and vivid markings reduce traffic accidents.

The proposed thermoplastic consists of a binder: polyester resin and Laprol 3003, pigment: rutile titanium dioxide and fillers: marble chips, white quartz sand, glass beads. It has been found that the introduction of a polyester based on ethylene and propylene oxides - Laprol 3003, which is a modifier of polyester resin, exhibits surface-active properties, increases hardness and reduces water absorption of the composition allows to improve the properties of the thermoplastic. Laprol 3003 does not freeze at a temperature of -20 ° C and does not mix with water, so seasonal temperature changes do not have a destructive effect on the marking. The introduction of Laprol 3003 in the composition below 1 wt.% Does not reduce the water absorption and fluidity of the material, and above 10 wt.% It is impractical due to the limited combination with a polyester resin. The use of a Laprol thermoplastic with a lower molecular weight leads to an increase in the water absorption of the composition. The use of a Laprol thermoplastic with a higher molecular weight increases the viscosity of the composition, which impairs its spreadability and thereby complicates the application of the composition to asphalt concrete. A decrease in the amount of polyester resin in the composition below 20 wt.% Leads to a decrease in the strength properties of the thermoplastic, and an increase in its amount above 30 wt.% Is unprofitable from an economic point of view, since it does not lead to a further increase in strength properties. Rutile titanium dioxide gives the composition a white color and ensures its visibility, a decrease in its concentration below 3 wt.% In the composition of the thermoplastic reduces the whiteness of the composition, and an increase of more than 10 wt.% Is economically disadvantageous. Glass beads give the marking thermoplastic reflective properties, ensuring traffic safety at night and in adverse weather conditions (rain, fog, etc.) and this determines the choice of the quantitative range of beads in the composition of the thermoplastic. A decrease in their concentration below 4 wt.% Does not provide the reflective properties of the thermoplastic, and an increase in the number of beads above 24 wt.% Adversely affects its technological properties, for example, reduces fluidity and also unreasonably increases the cost of the thermoplastic. The introduction of marble chips provides an additional reflective effect of the marking of roads and airfields and reduces the slip of the wheels of vehicles, and also positively affects the strength properties of the markings (hardness, wear, etc.). A decrease in the content of marble chips in the composition below 10 wt.% Leads to a decrease in the strength properties of the thermoplastic, and an increase in excess of 30 wt.% Is economically unjustified. White quartz sand, as a filler, provides the technological, operational and economic properties of the thermoplastic. The introduction of it in an amount of less than 21 wt.%, Increases the cost of the composition as a whole, and an increase of more than 37 wt.% Reduces the operational properties of the marking (reduces adhesion to asphalt concrete, increases water absorption).

In the study of the prior art, it was not revealed that the claimed thermoplastic compositions for marking roads and airfields, which would be characterized by an identical set of features with the same technical result as obtained in the proposed technical solution, which allows us to conclude that it meets the criteria of "novelty" and "inventive step". The inventive thermoplastic marking material can be obtained using known materials and technical means, which indicates its compliance with the criterion of "industrial applicability".

The manufacturing process of thermoplastics for marking roads and airfields consists of two stages:

1) preparation of raw materials, which includes drying of rutile titanium dioxide and fillers (white quartz sand, marble chips, glass beads) at a temperature of 100 ° C and heating the polyester resin to 160-180 ° C;

2) the manufacture of thermoplastic material.

For the manufacture of thermoplastic material using a polyester resin based on glycerol and phthalic anhydride brand PF-R1 TU2226-002-53938077-2001, which is a transparent solid mass, almost colorless. The required amount of polyester based on ethylene and propylene oxides-Laprol 3003 (TU2226-022-10488057-95), having a molecular weight of 3000 and functionality 3, which is a mobile transparent liquid that does not freeze at -20 ° C, is introduced into the polyester resin.

Mixing of all components can be carried out directly in a marking machine, or in reactors equipped with an anchor mixer, or in horizontal type mixers equipped with paddle mixers. The quality of the thermoplastic material is affected by the loading order of the components.

Example 1. To prepare 100 kg of thermoplastic, first mix 20 kg (20 wt.%) Of polyester resin with 1 kg (1 wt.%) Of Laprol 3003 and 10 kg (10 wt.%) Of rutile titanium dioxide at 160 ° C. The resulting composition acquires good surface-active and wetting properties. Next, the temperature of the reaction mixture is raised to 170 ° C and fillers are sequentially introduced: marble chips - 10 kg (10 wt.%), White quartz sand - 35 kg (35 wt.%) And glass beads - 24 kg (24 wt.%) .

Analogously to example 1, the compositions were prepared according to examples 2 and 3 (table 1).

The finished thermoplastic material, which is an organomineral composition, can be crushed, for example, in a ball mill, to a powder with a particle size of 0.5 to 1 cm, packaged in plastic bags and delivered to the consumer in this form. Its properties were determined by known methods (Kryzhanovsky V.K., Burlov V.V. Applied Physics of Polymers. - SPb .: Publishing House of SPbGTI (TU), 2001. - 99 p. And 116 p.). Water absorption was determined in accordance with GOST R 4650, and Brinell hardness in accordance with GOST R 4570. To determine the wear rate, samples were made in the form of a circle with a diameter of 10 mm and a height of 5 mm in accordance with the procedure (Laboratory workshop on rubber technology. Basic properties of rubbers and methods their definitions / N.D. Zakharova, N.V. Belozerov, V. Chernykh et al. - L .: Chemistry, 1976.- 82 p.). The tests were carried out on a MI-2 machine, a steel surface was used as the abrasive material, the pressing force was 30 N, and the sliding velocity was 0.27 m / s.

The flow rate of the melt and the gloss of the coating were determined by the methods (Karyakina M.I. Laboratory workshop on technical analysis and control of the production of paints and coatings. - M .: Chemistry, 1989. - p. 74 and p. 138).

The properties of the thermoplastic material are presented in table 2.

As can be seen from table 2, the claimed composition of the thermoplastic improves the operational characteristics of the road marking material: increase its hardness, resistance to the destructive effect of anti-icing compositions, reduce the abrasion of the marking and water absorption, and also reduce the dependence of the quality of the coating on the temperature difference, and thereby increase the resource the work of thermoplastic marking material up to 3-4 years.

Table 1
The composition of the thermoplastic for marking roads and airfields. Components Prototype, parts by weight The inventive, wt.% one 2 3 Polyester resin based on glycerol and phthalic anhydride PF-R1 TU 2226-002-53 93 8077-2001 - twenty 23 thirty Polyester resin with 40% phthalic acid 22.0 - - Ethylene and Propylene Oxide Polyester - Laprol 3003 one 2 10 Adipic Acid Ethylene Glycol Polyester 3.0 - - - Kaolinite 5,0 - - - Titanium dioxide (rutile) 4.0 10 3 5 Glass beads 30,0 24 twenty four Quartz sand white GOST 22551 36.0 35 37 21 Marble chips - 10 fifteen thirty Montan wax (parts by weight per 100 parts by weight of the above composition) 1,5 - - -

table 2
Thermoplastic properties for marking roads and airfields Prototype The claimed one 2 3 The flow rate of the melt, g / s 5,0 6.5 5.5 5,0 Softening point, ° С 85 85 85 85 Adhesion to asphalt concrete, MPa 0.85 1,6 1.8 2.0 Gloss,% - twenty twenty twenty Water absorption,% 0.08 0.02 0.02 0.02 The degree of contamination of the material,% 9 7 6 5 Wear rate, g / m - 2.6 · 10 ^-4 2.7 · 10 ^-4 2.8 · 10 ^-4 Brinell hardness, MPa - 28 31 thirty

Claims (1)

Thermoplastic for marking roads and airfields, including a polyester resin with a softening temperature of 70-85 ° C and an acid number of 35-40 mg KOH / g, obtained on the basis of phthalic anhydride and glycerol, rutile titanium dioxide, white quartz sand and glass beads, characterized the fact that it additionally contains Laprol 3003 - a polyester with a molecular weight of 3000 based on ethylene and propylene oxides and marble chips in the following ratio of components, wt.%:
Polyester resin 20-30 Laprol 3003 1-10 Rutile titanium dioxide 3-10 Marble chips 10-30 Sand quartz white 21-37 Glass beads 4-24