CS250632B1 - Coating compositions for pavements' horizontal marking - Google Patents

Abstract

The solution is to improve properties coating films. This will be achieved a paint formulation consisting of chemically modified alkyd containing free hydroxyl groups, hydroxyl groups groups bonded with isocyanates and ester-bound hydroxyl groups, wherein of the total bound multivalent % of alcohols is 15 to 65 wt. acyclic alcohols having from 2 to 5 carbon atoms atoms and 2 to 4 hydroxyl groups and 35 to 85 wt. polymeric alcohols. Further, the compositions contain organic solvents from the group of aromatic hydrocarbons and acyclic and / or cyclic ketones with temperature boiling to 175 ° C, pigments, fillers of % of which at least 10 wt. form a filler fraction a particle size in the range of 0.1 to 0.5 mm and additives.

Description

The invention relates to road marking coatings prepared from chemically modified alkyd resin, aromatic and ketone solvents, pigments, inorganic and organic fillers, with a portion of fillers being specified by a certain particle size range and additives.

Coatings are used for horizontal marking of roads, which require a lot of often conflicting properties that are difficult to meet® The basic requirement for coatings for this application is very fast to extremely fast drying of extremely thick coatings, provided the good properties of the coatings are maintained This problem is very often solved by combining two or more binders, eg by combining alkyd resin with chlorinated rubbers. However, application of coating compositions based on binder combinations may cause film formation problems due to the limited miscibility of the binders, which occurs when the solvents evaporate during drying of the coating film. This deficiency can be overcome by appropriately selecting solvent mixtures and optimizing their proportions in the mixture.

The present invention removes this drawback by using a single binder for the formulation of a road marking coating, a chemically modified alkyd resin which can be dissolved and diluted with aromatic and ketone solvents, either alone or in their own.

250 632 mixtures in virtually any ratio, while evaporating from the paint film does not cause paint defects · Chemically modified alkyd resin has been specially developed to achieve extremely fast drying and is therefore very suitable for the preparation of paints for road marking · Paints are composed from 20 to 50 parts by weight of a chemically modified alkyde containing from 10 to 35% of hydroxyl groups of free, 6 to 11% of hydroxyl groups bound after reaction with isocyanates, in particular -NH-COO- and 50 to 85% of ester-linked hydroxyl groups, the total amount of polyhydric alcohols bound is 15 to 65 wt. acyclic alcohols having 2 to 6 carbon atoms and 2 to 4 hydroxyl groups and 35 to 85% 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 or methacrylic acid and acyclic monovalent alcohols having a carbon number of 1 to 4 0.02 to 0.30 moles of hydroxy esters derived from these acids and acyclic divalent alcohols having a carbon number of 2 to 4 and optionally up to 0.10 moles of acyclic unsaturated monocarboxylic acids having a carbon number of 13 to 22 and an iodine value of 120 to 200 g / 100 g, 20 to 50 parts by weight of organic solvents of the aromatic hydrocarbon group and of acyclic and / or cyclic ketones boiling up to 175 ° C, 10 to 45 parts by weight of titanium dioxide pigments, zinc white and lithopone, 15 to 40 parts by weight of fillers, in particular from the group comprising ground flake, and corundum, silica natural and ground sand, siliceous drift, barium sulphate, calcium carbonate natural ground and precipitated, mica, wolastonite, talc, porcelain flour, feldspar, powdered polyethylene, powdered polyvinyl chloride, of which at least 10% by weight 0.1 to 0.5 mm and up to 5 parts by weight of additives from the group of desiccant, anti-crusting agents

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In addition to the stated advantages, ie the use of a single binder, the proposed road marking coating has a number of other advantages. It has a low viscosity which, however, can be varied by utilizing the choice of aromatic and ketonic solvents, their amount and ratio. However, the viscosity can also be varied by the type and quantity of the components used, especially foams. Other rheological properties of the proposed coating compositions, such as thixotropy and flow limit, can also be favorably influenced by suitable filler selection. These properties need to be controlled not only with regard to the equipment used for spraying these coatings on the road, but also with regard to the properties of the applied film, especially the flow. By suitably utilizing the above-mentioned fillers, especially the inorganic and organic combinations, the flow can be favorably influenced, even with a coating of large wet film thicknesses (0.6 to 1 mm) as necessary to achieve a 0.15 to 0.30 mm dry coating on the road.

Another advantage of the chemically modified alkyd resin binder is that it dries in a combined manner, ie both physically and oxypolymerically. Such a method of drying allows very rapid, even extremely rapid drying of the paint in the first phase after application to the road, to the point where it is already possible to pass the paint film through the vehicles without breaking the paint. In the next stage, during the oxypolymerization process, an optimum cross-linking occurs, which prevents the aging of the coatings, respectively. its degradation and increases their resistance to weathering and thus extends their service life.

An important part of the proposed coating compositions are fillers which, besides a certain degree of hardness (6-8), also have a certain particle size range. The particle size is then selected according to the desired dry film thickness. For road marking coatings, the choice of filler with a certain range of particle size and hardness is of utmost importance. Such fillers and their amounts are directly related to the road friction coefficient. If the coefficient of friction of the paint is too low, it occurs when crossing the road

250 632 markings for deterioration of tire adhesion to coatings and thus for possible and unwanted slip or skidding. Thus, fillers are used alone or in mixtures with one another, for example, flake, corundum, natural and ground silica sand, silica drift, barium sulphate, calcium carbonate natural ground and precipitated, mica, wolastonite, talc, porcelain flour, feldspar, powder poles vinyl chloride and polyethylene.

Road marking coatings should have good visibility, therefore a white shade of these colors is required. The coating compositions of the present invention are very well pigraentable by all kinds of whites, especially titanium white, both anatase and rutile, but also lithium and especially zinc white. It is known that a number of synthetic resins, which are used as binders for paints, cannot be pigmented with zinc white, because during storage not only increase the viscosity of paints but also their thickening until they are no longer usable. The binder, which is a chemically modified alkyd, is completely compatible with zinc white and thus does not cause undesirable changes in the rheological properties of the coating compositions even during long-term storage. According to requirements it is possible to prepare paints of any shades by adding color shades incl. yellow shades, eg using chrome yellow.

The coating composition of the present invention dries very quickly without the use of a desiccant. Drying speeds up drying. The most important of the siccatives used are naphthenate and cobalt octoate, but other naphthenates and octoates may also be used, such as manganese, lead, calcium, zinc and the like.

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

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The invention is further illustrated by the following examples. In the examples the percentages given are the percentages hwttiesim '

Example 1%

Alkyd chemically modified A, 100% 17.5

Toluene 17.5

Acetone 16.8

Titanium, anatase white 20.5

Talc 11,5

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

Polyvinyl chloride powder 2.7

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

Methylethylketoxin 0.1

Example 2%

Alkyd chemically modified B, 100% 15.0

Toluene 15.0

Xylene 5.0

Acetone 10.3

Methylisobutylketone 5.0

Rutile titanium white 2.0

Anatase Titanium White 17.0

Micronized limestone 3,0

Talc 11.0

Silica drift 3.0

Fine quartz sand with a grain size of 0.1-0.5 mm 10.0 Fine quartz 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%

Alkyd chemically modified G, 100% 25.0

Toluene 17.0

Acetone 6.0

Methylcyclohexanone 3.0

Methylisobutylketone 5.0

Rutile titanium white 3.0

Zinc white 11.0

Litopon 2,0

Micronized limestone 5,0

Talc 6.4

Fine quartz sand with grain size 0,2 »0,4mm 15,0 Polyethylene powder 1,0

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

Methyl thylketoxin 0.1

Example 4%

Alkyd chemically modified A, 100% 15.0

Alkyd chemically modified C, 100% 5.0

Toluene 10,0

Acetone 15.0

Titanium, anatase white 10.0

Zink. white 6.5

Litopon 5,0

Micronized limestone 15.0

Silica drift 2.0

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

Polyvinyl chloride powder 1.0

Cobalt 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 the road marking coatings specified in the present invention and shown in Examples 1-4 are characterized by the composition contained in Table 1. Polymeric alcohols used to prepare these alkyds were prepared by radical copolymerization of a mixture of monomers containing The characterization of acyclic monocarboxylic acids and vegetable oils used in the preparation of chemically modified alkyd resins is reported in Table 3.

Tab. 1

Characteristics of alkyd resins used for preparation of coatings for horizontal marking of roads

Chemically modified alkyd resin ⁴ A (B) C Division of the original Free groups 31.2 10.2 35.0 hydroxyl groups reaction (% eq ·) with isocyanates 8.6 6.0 11.0 ester-linked 60.1 83.8 54.0 Investments in tied shares Acyclic Al- - of alcohols by type. plain with 2 to 6 (% by weight * of total * carbon atoms number of bound al- and 2 to 4 hydro- koholů) xyl groups 34.8 64.0 20.0 Polymer ζ _ς · ₉ alcohols 36.0 80.0 Composition of alkyds according to used LO, G, LO, P, KSO, default components TJáOP, EG, KB, KDRO, KDRO, BYE, P, P, BYE, PA II, TJáOP, PA I, TDI PA-III TDI IPDI

lab · 2

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Composition of polymeric alcohols prepared by free-radical polymerization of the following monomer mixtures (given in mol »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-hydroxyl thylacrylate - 0.020 - 2-hydroxyethyl methacrylate 0,028 411 - 2-hydroxypropyl acrylate · * - 0.23 dehydrated acid 0,086 0.003 . - castor oil

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

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The meaning of the abbreviations of the used components listed in Stroke® 1

and pull · 3: LO linseed oil KDRO dehydrated castor oil G glycerol TMOP trimethylolpropane P pentaerythritol EG ethylene glycol BYE phthalic anhydride THPA tetrahydrophthalic anhydride KB would be lina benzo ptBBK p-tert-butylbenzoic acid PA I to polymeric alcohol I to III III TDI 2,4 toluene diisocyanate IPDI isophorone diisocyanate

Some properties of paints, resp. The coatings of the invention are as follows:

discharge time, ČSN 67 3013 30 »» Drying time, dry film thickness 0.25 mm, CSN 67 3052 - st · 1 to 2 ' st · 2 to 1 < density 1200 color of dried paint (shade) White gloss of dry coat, ČSN 67 3063 s fc » coefficient of friction (pendulum RRL) 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,