CS250632B1 - Paints for road marking - Google Patents

Abstract

The purpose of the solution is to improve the properties of paint films. This is achieved by a suitable formulation of a paint composition consisting of a chemically modified alkyd containing free hydroxyl groups, hydroxyl groups bound after reaction with isocyanates and hydroxyl groups bound by esters, whereby of the total amount of bound polyhydric alcohols, 15 to 65 wt. % are acyclic alcohols with 2 to 5 carbon atoms and 2 to 4 hydroxyl groups and 35 to 85 wt. % are polymeric alcohols. Furthermore, the compositions contain organic solvents from the group of aromatic hydrocarbons and acyclic and/or cyclic ketones with a boiling point of up to 175 °C, pigments, fillers of which at least 10 wt. % are fillers with a particle size in the range of 0.1 to 0.5 mm and additives.

Description

The invention relates to road marking paints prepared from chemically modified alkyd resin, aromatic and ketone solvents, pigments, inorganic and organic fillers, where the fillers are specified by a certain range of particle sizes and additives.

For horizontal road marking, paint compositions are used, which require a number of often contradictory properties that are difficult to meet. The basic requirement for paints for this use is very fast to extremely fast drying of exceptionally thick paint films, while maintaining good properties of the created paints, such as a smooth surface without cracks and surface defects, etc. This problem is very often solved by combining two or more binders, e.g. by combining alkyd resin with chlorinated rubbers. However, when applying paints based on combinations of binders, difficulties may arise in film formation, caused by limited miscibility of the binders, manifested by evaporation of solvents during drying of the paint film. This deficiency can be countered by appropriate selection of solvent mixtures and optimization of their representation in the mixture.

The present invention eliminates the aforementioned deficiency by using a single binder for the formulation of a coating for horizontal road markings, namely a chemically modified alkyd resin, which can be dissolved and diluted with aromatic and ketone solvents either alone or in their mixtures.

250 632 mixtures in practically any ratio, while their evaporation from the paint film does not cause paint defects. The chemically modified alkyd resin was specially developed with the aim of achieving extremely fast drying and is therefore very suitable for the preparation of road marking paints. The paints are composed of 20 to 50 parts by weight of chemically modified alkyd containing 10 to 35% free hydroxyl groups, 6 to 11% hydroxyl groups bound after reaction with isocyanates, mainly by the -NH-COO- bond, and 50 to 85% ester-bound hydroxyl groups, with 15 to 65% of the total amount of bound polyhydric alcohols. acyclic alcohols with 2 to 6 carbon atoms and 2 to 4 hydroxyl groups and 35 to 85% by weight of polymeric alcohols, prepared by radical copolymerization of 1 mole of styrene with 0.35 to 1.70 moles of esters derived from acrylic or methacrylic acid and acyclic monohydric alcohols with 1 to 4 carbon atoms, 0.02 to 0.30 moles of hydroxyesters derived from these acids and acyclic dihydric alcohols with 2 to 4 carbon atoms and optionally up to 0.10 moles of acyclic unsaturated monocarboxylic acids with 13 to 22 carbon atoms and an iodine number of 120 to 200 gJg/100 g, 20 to 50 parts by weight of organic solvents from the group of aromatic hydrocarbons and acyclic and/or cyclic ketones with a boiling point of up to 175 °C, 10 to 45 parts by weight of pigments from the group of titanium whites, zinc whites and lithopone, 15 to 40 parts by weight of fillers, in particular from the group including ground slate and corundum, natural and ground silica sand, silica fume, barium sulfate, natural ground and precipitated calcium carbonate, mica, wollastonite, talc, porcelain flour, feldspar, powdered polyethylene, powdered polyvinyl chloride, of which at least 10% by weight is the proportion of fillers with a particle size in the range of 0.1 to 0.5 mm and up to 5 parts by weight of additives from the group of drying agents, flow agents, anti-caking agents

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The proposed road marking paint has, in addition to the above-mentioned advantages, i.e. the use of a single binder, a number of other advantages. It has a low viscosity, which can, however, be changed by using the choice of aromatic and ketone solvents, their quantity and ratio. However, the viscosity can also be changed by the type and quantity of components used, especially pniv. By appropriately choosing fillers, other rheological properties of the proposed paints can also be favorably influenced, such as thixotropy and flow limit. These properties must be regulated not only with regard to the equipment used for spraying these paints on roads, but also with regard to the properties of the applied film, especially the spillage. By appropriately using the proposed fillers, especially the combination of inorganic and organic ones, the spillage can be favorably influenced, even in the case of a coating with large wet film thicknesses (0.6 to 1 mm) as is necessary to achieve 0.15 to 0.30 mm of dry coating on the road.

Another advantage of the coating based on chemically modified alkyd resin is that it dries in a combined way, i.e. both physically and by oxypolymerization. This method of drying allows for very fast, even extremely fast drying of the coating in the first phase after application to the road, to a state where the coating film can be driven over by vehicles without the coating being damaged. In the next phase, during the oxypolymerization process, optimal crosslinking occurs, which prevents the aging of the coatings, or rather its degradation, and increases their resistance to weathering, thereby extending their service life.

An important part of the proposed coatings are fillers, which, in addition to a certain degree of hardness (6 to 8), also have a certain range of particle sizes. The particle size is then selected according to the required thickness of the dry coating film. For road marking coatings, the selection of a filler with a certain range of particle sizes and hardness is of particular importance. Such fillers and their quantity are directly related to the coefficient of friction of the road. If the coefficient of friction of the coating is too low, the vehicle will skid when crossing the road.

250 632 markings to worsen the adhesion of tires to coatings and thus to possible and undesirable slipping or skidding. Therefore, fillers are used either separately or in mixtures, e.g. shale, corundum, natural and ground silica sand, silica fume, barium sulfate, natural ground and precipitated calcium carbonate, mica, wollastonite, talc, porcelain flour, feldspar, powdered polyvinyl chloride and polyethylene.

Road marking paints should be characterized by good visibility, therefore a white shade of these colors is required. The paints that are the subject of this invention are very well pigmented with all types of whites, especially titanium white, both anatase and rutile, but also lithopone and especially zinc white. It is known that a number of synthetic resins that are used as binders for paints cannot be pigmented with zinc white, because during storage not only the viscosity of the paints increases, but also their thickening to the point where they are no longer usable. The binder, which is a chemically modified alkyd, is completely compatible with zinc white and thus there are no undesirable changes in the rheological properties of the paints even during long-term storage. According to requirements, it is possible to prepare paints of any shades by adding color shades, including yellow shades, e.g. using chrome yellow.

The coating material according to this invention dries very quickly even without the use of a siccative. Drying is further accelerated by siccative. The most important siccatives used are naphthenate and cobalt octoate, but other naphthenates and octoates can be used, e.g. manganese, lead, calcium, zinc, etc.

The road marking coatings according to this invention are produced by conventional coating production technologies, i.e. by dissolving, mixing, homogenizing, dispersing, while it is economically significant that the dispersion can be carried out only for a minimally short period of time, or it is possible to exclude dispersion from the production process with reliable homogenization.

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The invention is further illustrated by examples. The percentages given in the examples are percentages of hwttiesim'

Example 1%

Chemically modified alkyd A, 100% 17.5

Toluene 17.5

Acetone 16.8

Titanium, anatase white 20.5

Talc 11.5

Fine silica sand with a grain size of 0.2-0.4 mm 13.0

Powdered polyvinyl chloride 2.7

Cobalt naphthenate (xylene solution with 1% Co 0.4 as metal)

Methylethylketoxin 0.1

Example 2%

Chemically modified alkyd B, 100% 15.0

Toluene 15.0

Xylene 5.0

Acetone 10.3

Methyl isobutyl ketone 5.0

Titanium white rutile 2.0

Titanium white anatase 17.0

Micro-ground limestone 3.0

Talc 11.0

Silica drift 3.0

Fine silica sand with a grain size of 0.1-0.5 mm 10.0 Fine silica sand with a grain size of 0.2-0.4 mm 3.0

Lead octoate (xylene solution with 2% Pb 0.6 as metal)

Butylaldoxin

0.1

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Example 3%

Chemically modified alkyd G, 100% 25.0

Toluene 17.0

Acetone 6.0

Methylcyclohexanone 3.0

Methyl isobutyl ketone 5.0

Titanium white rutile 3.0

Zinc white 11.0

Lithopone 2.0

Micro-ground limestone 5.0

Talc 6.4

Fine silica sand with a grain size of 0.2 » 0.4mm 15.0 Powdered polyethylene 1.0

Cobalt(II) octoate (xylene solution with 1% Co 0.5 as metal)

Methyl ethyl ketoxine 0.1

Example 4%

Chemically modified alkyd A, 100% 15.0

Chemically modified alkyd C, 100% 5.0

Toluene 10.0

Acetone 15.0

Titanium, anatase white 10.0

Zinc white 6.5

Lithopone 5.0

Micro-ground limestone 15.0

Silica drift 2.0

Fine quartz sand with a grain size of 0.1 « 0.5 mm 15.0

Powdered polyvinyl chloride 1.0

Cobalt(II) octoate (xylene, solution with 1% Co 0.4 as metal)

Butylaldoxin

0.1

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The chemically modified alkyd resins used for the preparation of road marking paints specified in the subject of the invention and given in Examples 1 to 4 are characterized by the composition contained in Table 1. The polymer alcohols used for the preparation of these alkyds were prepared by radical copolymerization of a mixture of monomers with the composition given in Table 2. The characterization of the acyclic monocarboxylic acids and vegetable oils used in the preparation of the chemically modified alkyd resins is recorded in Table 3.

Table 1

Characteristics of alkyd resins used for the preparation of road marking paints

Chemically modified alkyd resin ⁴ A B C The division of the original Free groups 31.2 10.2 35.0 hydroxyl groups bound by reaction (% eq) with isocyanates 8.6 6.0 11.0 ester bound 60.1 83.8 54.0 Shares of tied Acyclic alcohols - alcohols by type. bare with 2 to 6 (% mass* of total*) carbon atoms many bound al- and 2 to 4 hydro- alcohol) xyl» groups 34.8 64.0 20.0 Polymeric ζ· _{ς 9} alcohols 36.0 80.0 Composition of alkyds according to LO, G, used LO, P, KSO, output components TJAP, EG, KB, KDR, KDRO, PA, M, P, PA, PA II, TJAP, PA I, TDI PA-III TDI IPDI

lab· 2

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Composition of polymer alcohols prepared by radical polymerization of the following monomer mixtures (given in molar ratios)

Polymer alcohol (PA) X II III Monomers : styrene 1 1 1 ethyl acrylate - 1.06 butyl acrylate - 0.036 0 A2 methyl methacrylate 1.04 0.38 0.36 2-hydroxyethyl acrylate - 0.020 - 2-hydroxyethyl methacrylate 0.028 411 - 2-hydroxypropyl acrylate ·* - 0.23 dehydrated acid 0.086 0.003 . - castor oil

Tab. 3 Iodine value of the used vegetable oil and the corresponding acyclic monocarboxylic acids Component _Iodine number gI ₂ »100 g”^ LO 172.9 KSO 124.7 . KDRO 127.5

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Meaning of abbreviations of components used in tah® 1

and in turn 3: LO linseed oil KDRO acid of dehydrated castor oil G glycerol TMOP trimethylolpropane P pentaerythritol EG ethylene glycol PA phthalic anhydride THPA tetrahydrophthalic anhydride KB by lina benzoova ptBBK p-tertbutylbenzoic acid PA I to polymer alcohol I to III III TDI 2,4 toluene diisocyanate IPDI isophorone diisocyanate

Some properties of the coatings or paints that are the subject of the invention are as follows:

discharge time, ČSN 67 3013 30 »» drying time, -dry coating thickness 0.25 mm, ČSN 67 3052 - st· 1 within 2' st· 2 to 1< specific gravity 1200 color of the dried paint (hue) white gloss of dried paint, ČSN 67 3063 with fc» · coefficient of friction (RRL pendulum) min·

Claims (1)

Coatings for the horizontal marking of pavements based on synthetic resins, organic solvents, pigments, fillers and optionally additives, characterized in that they consist of 20 to 50 wt. parts of chemically modified alkyd containing 10 to 35% hydroxyl groups of free, 6 to 11% hydroxyl groups bound after reaction with isocyanates, in particular -NH-COO- and 50 to 85% ester-linked hydroxyl groups, of which the total amount of polyhydric alcohols bound is 15 to 65% by weight of acyclic alcohols having 2 to 6 carbon atoms and 2 to 4 hydroxyl groups and 35 to 85 parts by weight of polymeric alcohols prepared by the free-radical copolymerization of 1 mole of styrene with 0.35 to 1.70 mole of esters derived from acrylic acid or methacrylic and acyclic monohydric alcohols having a carbon number of 1 to 4, 0.02 to 0.30 moles of hydroxy esters derived therefrom and acyclic divalent alcohols having a carbon number of 2 to 4 and optionally up to 0.10 moles of acyclic unsaturated monocarboxylic acids the number of carbon atoms from 13 to 22 and an iodine value of 120 to 200 GJ _2/1 00 g, 20 to 50 wt. parts of organic solvents from the group of aromatic hydrocarbons and acyclic and / or cyclic ketones having a boiling point of up to 175 ° C, 10 to 45 wt. % by weight of pigments from the group of titanium white, zinc white and lithopone; filler parts, in particular from the group comprising ground flake, corundum, natural and ground silica, silica fume, barium sulphate, natural calcium ground and precipitated calcium, mica, wolastonite, talc, porcelain flour, feldspar, powdered polyvinyl chloride, powdered polyethylene, at least 10 wt. parts comprise a proportion of fillers having a particle size in the range of 0.1 to 0.5 mm and up to 5 wt. parts of additives from the group of desiccants, leveling agents and anti-crusting agents * Printed by Moravian Printing Works,