KR102143785B1 - Heat melt type paint composition for a road marking with improved visibility in case of rain - Google Patents

Abstract

The present invention relates to a paint composition for thermally fusion-type road surface marking with improved visibility in rainy weather, and more particularly, by introducing a material of a specific component in the thermally fusion-type coating composition, lowering the surface energy of the coating film to improve water repellency and It relates to a paint composition for heat-sealing type road surface marking capable of exhibiting excellent visibility characteristics.

Description

Heat-sealing paint composition for road marking with improved visibility in rainy weather {HEAT MELT TYPE PAINT COMPOSITION FOR A ROAD MARKING WITH IMPROVED VISIBILITY IN CASE OF RAIN}

The present invention relates to a paint composition for thermally fusion-type road surface marking with improved visibility in rainy weather, and more particularly, by introducing a material of a specific component in the thermally fusion-type coating composition, lowering the surface energy of the coating film to improve water repellency and It relates to a paint composition for heat-sealing type road surface marking capable of exhibiting excellent visibility characteristics.

With the development of transportation means and the increase in the spread of automobiles, the need to transmit more information from the road surface to the driver has increased. In general, road lanes are used not only as indicator lines to guide the direction so that vehicles running on the road can safely move, but also destination information about speed limits and traveling directions are directly applied and displayed on the road surface. Marking paints have been developed and used in various types, and especially in special areas with dangers such as bus lanes, children's protection areas, road slip prevention, slopes or in front of schools, to increase driver visibility. The road surface is painted in various forms.

The paints used at this time can be largely classified into room temperature drying type road marking paints, water-soluble road marking paints, heating type road marking paints, and fusion type road marking paints, depending on the raw material components and construction method.

More specifically, 1 type is a room temperature drying type coating mainly composed of room temperature type paint coloring pigments, extender pigments and synthetic resin varnishes, and 2 types are water-soluble road sign paint coloring pigments, extender pigments and water-soluble resins. It is a water-soluble paint as the main raw material, and three types are paints used by heating colored pigments, extender pigments and synthetic resin varnishes as main ingredients, and four types are road coloring pigments for fusion-type road signs, extender pigments, and glass. It is a paint used by heating and melting beads, filling material, and synthetic resin as the main raw materials.

Generally, as a road surface paint for marking paints, it is largely divided into aqueous and oil-based, and water-based paints usually use acrylic emulsion resin as a binder. This is eco-friendly because the solvent is water, but the drying time is slow. The oil-based paint uses an acrylic resin containing an organic solvent as a binder.Since it contains an organic solvent, air pollution occurs when the solvent volatilizes during drying. There is a problem to let you.

The purpose of solving the above disadvantages is a fusion-type paint. The fusion-type road marking paint is manufactured in powder form by mixing a pigment, a filler, and glass beads in a thermoplastic resin, and is a lump of paint used by heat melting during construction. B It is a solvent-free lane marking material supplied in granular or powder form. If the composition in the form of powder is applied after melting by applying heat through a specific processing device, it has the advantage that the coating thickness is limited at the time of marking the road surface, and it is possible to pass immediately after cooling after construction. In addition, it has the advantage of being less limited in the thickness of the road marking line.

As the fusion-type road marking paint, a thermoplastic resin such as petroleum resin is currently used as a binder resin, and the petroleum resin cracks relatively easily as time passes, and the coating film formed on the road surface is easily damaged and at night or in rainy weather. In this case, visibility may be deteriorated, which may cause serious problems for driver safety.

As a prior art for the fusion-type paint, Korean Patent Application Publication No. 10-2018-0071606 (published on 28 June 2018) includes a hydrogenated petroleum resin and an ethylene vinyl acetate copolymer having a melting index in a certain range. A fusion-type paint composition for road signs is described, and as another conventional technique, Patent Publication No. 10-0832922 (announcement date: May 28, 2008) provides adhesion and elasticity to fusion-type paints used for road signs. It is described on a fusion-type paint composition prepared by adding a coarse aggregate and a large-diameter bead while preventing the precipitation of coarse aggregates and beads formed with large diameters with a reinforcing resin and a thixotropic agent that increase the coefficient of friction.

However, in spite of the prior art including the prior literature, the conventional heat-sealing type road surface coating improves adhesion and abrasion resistance between the binder and glass beads, which are properties necessary for long-term use, and at the same time, the fusion type paint As an additional requirement to be used as, it is urgent to develop a paint composition having excellent physical properties even in rain by increasing water repellency.

Unexamined Patent Publication No. 10-2018-0071606 (Publication date: 2018.06.28.) Registered Patent Publication No. 10-0832922 (Announcement date: 2008.05.28.)

The present invention was derived to solve the above problems, while satisfying the physical properties required to be used as a heat-sealing type coating, and having improved water repellency than conventional products, a fusion-type road surface coating coating having superior visibility in rainy weather. The composition is provided.

In addition, another object of the present invention is to provide a coating film for a road surface by applying the heat-sealed road surface coating composition to a road.

The present invention includes 10 to 30 wt% of a thermoplastic petroleum resin, and 2 to 15 wt% of a glycerol ester resin as a binder, and additionally 10 to 40 wt% of an inorganic filler, 15 to 40 wt% of aggregate, and 15 to 40 wt% of glass beads A fusion-type road surface marking coating composition comprising, wherein the glycerol ester resin is obtained by ester polymerization of glycerol and a silane compound containing at least two carboxyl groups at molecular ends. Provides.

As an example, the coating composition for road surface marking may additionally contain 0.01 to 10 parts by weight of at least one of a pigment, a wax, an antioxidant, a UV absorber, an anti-settling agent, and a plasticizer based on 100 parts by weight of the composition. .

As an embodiment, the silane compound containing at least two carboxyl groups at the molecular end used for polymerization of the glycerol ester resin is tris(2-carboxyethyl)silane, (2-carboxyethylsilyl)propanoic acid, It may be any one selected from 2-(10carboxyethylsilyl)propanoic acid, 3-[2-carboxyethyl(dimethyl)silyl]propanoic acid, or a mixture thereof.

As an embodiment, the glycerol ester resin may additionally contain 1 to 10 wt% of a silicone rubber-based elastomer, and in this case, the elastomer is a silicone rubber-based elastomer, polydimethylsiloxane, polydiphenyl It may be any one selected from siloxane, polymethylvinylsiloxane, polymethylphenylsiloxane, polytrimethylsiloxane, and polyhydroxysiloxane, or a mixture thereof.

As an embodiment, the content ratio of glycerol and the silane compound for polymerizing the glycerol ester resin is a molar ratio, and may range from 10:1 to 20:1.

As an embodiment, the content of the glycerol ester resin may be 15 wt% or more based on the sum of the petroleum resin and the glycerol ester resin as a binder, and preferably, the content of the glycerol ester resin is It may be 20 wt% or more.

As an example, the glass beads may have a particle size range of 300 um to 5000 um.

As an embodiment, the inorganic filler may be one or more selected from the group consisting of silica, talc, alumina, diatomaceous earth, magnesium oxide, magnesium carbonate, talc, calcium carbonate, kaolin, and mica.

In addition, the present invention provides a fusion-type road sign coating film obtained by heating and melting the fusion-type road sign coating composition and then applying it to a road.

The composition for a road surface according to the present invention can improve water repellency compared to a conventional road surface coating composition by lowering the surface energy of the coating film by polymerizing a silane compound containing a carboxyl group in a glycerol ester resin used as a binder with glycerol. , It can bring the effect of improving visibility by preventing water film phenomenon in rainy weather.

In addition, by adding a silicone rubber-based elastomer to the fusion-type road surface composition, it has an effect of improving water repellency and durability and chemical stability of the coating film.

1 is a diagram showing retroreflective performance as an evaluation of physical properties of a coating film using a composition for road marking obtained from Examples and Comparative Examples of the present invention.

Hereinafter, a preferred embodiment according to the present invention will be described in detail. However, the following examples are provided so that the present invention may be sufficiently understood by those of ordinary skill in the art, and may be modified in various other forms, and the scope of the present invention is limited to the examples described below. It is not.

The fusion-type road marking composition of the present invention includes a thermoplastic petroleum resin and a glycerol ester resin as a binder, and may additionally include an inorganic filler, an aggregate, and a glass bead.

More preferably, the fusion-type paint composition for road surface marking includes 10 to 30 wt% of a thermoplastic petroleum resin and 2 to 15 wt% of a glycerol ester resin as a binder, and additionally 10 to 40 wt% of an inorganic filler, and 15 to 40 of aggregate It may include wt% and 15 to 40 wt% of glass beads.

Here, the thermoplastic petroleum resin is the main raw material for forming the coating film of the paint composition, and serves to firmly attach various fillers used in the paint composition, and serves as a binder that imparts basic properties of all paints, and the paint composition The coating of the film itself becomes solid, improving durability, chemical resistance and flexibility.

In the present invention, the thermoplastic petroleum resin is a polymer produced by polymerizing monomers containing olefins or diolefins as an oil produced as a by-product of the petroleum refining process or petrochemical industry, and a thermoplastic synthetic resin is preferable, and is usually used as a paint composition for road surface marking. Ingredients used as can be used.

For example, aliphatic petroleum resins having 5 carbon atoms or aromatic petroleum resins having 9 carbon atoms, polyethylene, polypropylene, chromandene resin, terpene resin, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, and the like may be used.

In the present invention, the thermoplastic petroleum resin may be used in the range of 10 to 30 wt% based on the total content of the thermoplastic petroleum resin, glycerol ester resin, inorganic filler, aggregate, and glass beads. Here, when the content of the thermoplastic petroleum resin is less than 10 wt%, a stable coating film may not be formed, and problems such as adhesion, abrasion resistance, durability, workability, etc. may be deteriorated, and when it exceeds 30 wt%, The distribution of the glass beads in the coating film may be non-uniform, and the weight of inorganic fillers, glass beads, aggregates, etc. is relatively small, so there is a problem that the coloring rate, abrasion resistance, and retroreflectivity may decrease.

On the other hand, the glycerol ester resin according to the present invention can be obtained by ester polymerization of glycerol and a silane compound containing at least two carboxyl groups at the molecular end, which corresponds to the technical feature of the present invention.

Here, as the silane compound containing at least two or more carboxyl groups at the molecular terminal, a compound represented by the following formula (A) may be used.

[Formula A]

The linking groups L ₁ to L ₃ are each the same or different, and independently of each other, a single bond, or an alkylene group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, and 6 carbon atoms. It is selected from arylene groups of to 30;

Substituents R ₁ to R ₂ are each the same as or different from each other, and each independently selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carboxyl group Can be

That is, the silane compound represented by Formula A contains at least two carboxyl groups at both ends, and is a compound additionally containing carboxyl groups according to substituents R ₁ to R ₂ , and is polymerized when forming an ester bond with a polyol such as glycerol. A glycerol ester resin can be obtained by reaction.

As an exemplary method for producing the glycerol ester resin according to the present invention, a silane compound represented by Formula A and glycerol may be obtained by an esterification reaction according to Scheme B below.

[Scheme B]

Looking at this in more detail, the three hydroxy groups in the glycerol react with the two carboxyl groups of the formula A to lose up to three water molecules and condensate to cause an ester reaction.The resulting glycerol ester resin is the three hydroxyl groups of glycerol depending on the degree of polymerization. According to the number of carboxyl groups and the number of carboxyl groups contained in the formula (A), a polymer having a very complex structure is formed.

At this time, the glycerol ester resin obtained has an effect of lowering the surface energy of the coating film by including a silicone molecule together with a non-polar part in the polymer main chain, thereby improving hydrophobicity and water repellency according to a low surface tension.

Here, as a specific example of a silane compound containing at least two carboxyl groups at the molecular terminal, which is used for polymerization of the glycerol ester resin, these are tris(2-carboxyethyl)silane, (2-carboxyethylsilyl)propano It may be any one selected from ic acid, 2-(10 carboxyethylsilyl)propanoic acid, and 3-[2-carboxyethyl(dimethyl)silyl]propanoic acid, or a mixture thereof, but is not limited thereto.

The glycerol ester resin according to the present invention is used in combination with the thermoplastic petroleum resin as a binder, and in addition to the effect of improving the adhesion of the adherend, lowers the surface energy of the coating film to improve water repellency than the conventional paint composition for road surface. It is possible to prevent the water film phenomenon in rainy weather, thereby improving visibility.

The content of the glycerol ester resin of the present invention can be used in the range of 2 to 15 wt% based on the total content of the thermoplastic petroleum resin, glycerol ester resin, inorganic filler, aggregate, glad beads and color pigment, preferably It may have a range of 3 to 12 wt%, more preferably may have a range of 4 to 10 wt%.

Here, when the content of the glycerol ester resin is less than 2 wt%, the desired degree of abrasion resistance may not be improved or water repellency may not be sufficiently expected, and when it exceeds 15 wt%, it may be undesirable in terms of economy, In addition, it is preferable to use the above range because there is a disadvantage in that it does not exhibit physical properties as a paint for road surface marking.

In addition, in the present invention The coating composition for road surface marking may have a content of the glycerol ester resin of 15 wt% or more based on the sum of the petroleum resin and the glycerol ester resin as a binder, and preferably the glycerol ester resin of 20 wt% or more.

When the glycerol ester resin in the present invention has the above content range, when the coating composition for road marking is applied to the road surface after melting, the water repellency and abrasion resistance are better than that of the existing fusion coating film, thereby maintaining a long-term retroreflectivity. It can have an effect that can be.

In addition, the content ratio of glycerol and the silane compound for polymerizing the glycerol ester resin is a molar ratio, in the range of 10:1 to 20:1. In this case, if the content ratio is out of the above, any one of the two components becomes excessive, so that a composition having a desired physical property may not be obtained.

In addition, the degree of polymerization of the glycerol and silane compounds, which are monomers in the glycerol ester resin, may range from 2 to 20, respectively. That is, the content of each monomer in the glycero ester resin to be polymerized may have a range of 2 to 10, and preferably 2 to 5.

On the other hand, in the present invention, in order to improve water repellency and durability of the coating film, an additional silicone rubber-based elastomer may be added in an amount of 1 to 10 wt% based on the content of the total composition, preferably polydimethylsiloxane , Polydiphenylsiloxane, polymethylvinylsiloxane, polymethylphenylsiloxane, polytrimethylsiloxane, any one selected from polyhydroxysiloxane, or a mixture thereof may be used.

These silicone rubber-based elastomers have superior thermal and chemical stability compared to butadiene rubbers based on carbon-carbon double bonds, and are fused with ester resins due to the low surface energy of silicone rubber. It serves to increase the durability of the coating film and increase water repellency.

Here, if the content of the silicone rubber-based elastomer is less than 1 wt%, it may not have a significant effect on the additional reinforcement of the water repellency and durability according to the present invention, and if it exceeds 10 wt%, the economical efficiency may be lowered. There are disadvantages of lowering compatibility with resin and lowering adhesion.

On the other hand, the inorganic filler according to the present invention improves the mechanical properties of the coating film formed after it is applied to the road and cured to increase the durability of the coating film, thereby functioning to retain the road sign for a long time.

The inorganic filler may be at least one selected from the group consisting of silica, talc, alumina, diatomaceous earth, magnesium oxide, magnesium carbonate, talc, calcium carbonate, kaolin, and mica.

The content of the inorganic filler in the present invention is preferably in the range of 10 to 40 wt% based on the total content of the thermoplastic petroleum resin, glycerol ester resin, inorganic filler, aggregate, glass beads and color pigment. If the content of the inorganic filler is less than 10 wt%, the mechanical properties of the coating film are deteriorated, resulting in a problem of deteriorating durability, and if the content of the inorganic filler exceeds 40 wt%, the content of other essential components is reduced to inhibit the physical properties of the composition. There is a problem.

The road marking paint composition of the present invention may additionally include aggregates and glass beads in addition to the thermoplastic petroleum resin, glycerol ester resin, and inorganic filler.

The aggregate is generally made of silica-based dolomite or kaolin-based porcelain powder, and the physical properties required of the aggregate are physical strength with resin. The aggregate is present on the surface of the coating film to improve the sliding resistance and retroreflective function of the coated surface, and the important thing is strength and hardness, which should not be broken when the coating film is subjected to a vertical load, and the aggregate is hard to exhibit the anti-slip function. Should be maintained.

The aggregate is Based on the total content of thermoplastic petroleum resin, glycerol ester resin, inorganic filler, aggregate, and glass beads, a range of 15 to 40 wt% can be used, and if less than 15 wt%, slip resistance and retroreflective function may be deteriorated. In addition, when it exceeds 40 wt%, the mechanical properties of the road marking road may decrease or the viscosity of the mixture may increase, resulting in poor fluidity, which is not preferable.

In addition, the glass bead serves to prevent traffic accidents by easily identifying the coated surface by emitting light in a danger zone in which the driver needs to increase sliding resistance at night. That is, the use of glass beads in the lane coating is essential, and the use of glass beads increases the clarity and visibility of the lane through reflection of the refracted light, and the glass beads of the present invention have a particle size of 300 um to 5000 um. I can.

The content of the glass beads is preferably 15 to 40 wt% based on the total content of the thermoplastic petroleum resin, glycerol ester resin, inorganic filler, aggregate, and glass beads.

If the content of the glass beads is less than 15 wt%, there is a risk that the application section may not be properly identified at night due to the small amount of glass beads added.If the content of the glass beads exceeds 40 wt%, sedimentation occurs significantly during mixing. It is not preferable because uniform application becomes difficult.

The coating composition for road marking of the present invention may additionally contain at least one or more of a pigment, a wax, an antioxidant, a UV absorber, an anti-settling agent, and a plasticizer based on 100 parts by weight of the composition, and each component is 0.01 to It may have a range of 10 parts by weight.

The color pigment of the present invention is added to mark lanes on the road surface. The color required for road traffic can be selected and colored, and yellow, white or blue are generally used.

The content of the color pigment may be in the range of 0.01 to 10 parts by weight based on the total content of thermoplastic petroleum resin, glycerol ester resin, inorganic filler, aggregate, glass beads, and color pigment.

If the content of the pigment is less than 0.01 parts by weight, the coloring effect of the paint may be deteriorated, and if the content exceeds 10 parts by weight, cracking and crushing of the coating may occur, which is not preferable because it may decrease the durability of the paint.

The wax is added to improve flowability when mixing the coating composition for road marking and when working on the coated surface so that the components can be uniformly mixed.

The wax usable in the present invention is preferably used by selecting one or more of polyethylene wax and polypropylene wax.

The content of the wax is preferably 0.01 to 10 parts by weight based on 100 parts by weight described. When the content of the wax is less than 0.01 parts by weight, there is a concern that the components of the road marking composition may not be uniformly mixed, and when the content of the wax exceeds 10 parts by weight, components such as glass beads are added in an excessive amount. This is not preferable because there is a possibility that the particles may be separated or the performance of the slip resistance may be deteriorated after the application surface.

Antioxidants are used to prevent the coating film from being oxidized from ultraviolet rays, heat, and ozone since it receives intense sunlight after the lane paint is applied on asphalt or cement roads. The part with double bonds in the molecular structure is easily decomposed by the attack of oxygen, and if this is prevented, it can be sustained while maintaining its original properties for a long time. Antioxidants include primary antioxidants and secondary antioxidants.

Primary antioxidants are those that prevent oxygen from reacting with plastics to form peroxides. If hydrogen is given back to the polymer radicals, polymer peroxide radicals, and oxypolymer radicals created by oxygen, it returns to the original polymer and becomes a stable radical so that oxidation no longer occurs. As such antioxidants, substances having a large number of large carbon substituents around the hydroxyl groups of phenol as phenol derivatives are mainly used, because these substances easily transmit radicals and can exist as stable radicals.

Secondary antioxidants play a role in decomposing polymer radicals made like primary antioxidants and at the same time play a role in regenerating primary antioxidants. Substances containing sulfur are mainly used because this substance reacts with polymer radicals and converts itself into stable sulfur oxides, reducing primary antioxidants such as phenol derivatives.

The content of the antioxidant is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the substrate. When the content of the antioxidant is less than 0.01 parts by weight, it is not preferable because the antioxidant role is insufficient and the ability to maintain physical properties is deteriorated, and when the content of the antioxidant is 10 parts by weight or more, it is not preferable because the economy is poor.

As the antioxidant in the present invention, mainly hydroquinone, phenyl beta naphthylamine, dibutyl hydroxy toluene, butyl hydroxy anisole, and the like may be used.

The UV absorber prevents the polymer compound from being decomposed and denatured. In particular, ultraviolet rays, which are 290 to 400 nm of sunlight, have strong energy and act as a major cause of aging such as discoloration, surface cracking, mechanical and physical degradation of products. UV absorbers prevent the decomposition of plastic from ultraviolet rays by selectively absorbing ultraviolet rays from sunlight and converting them into thermal energy or by extinguishing free radicals generated by decomposition from ultraviolet rays.

The content of the UV absorber is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the substrate. When the UV absorber is less than 0.01 parts by weight, the role of absorbing ultraviolet rays is insufficient, resulting in aging of the resin properties, and when it exceeds 10 parts by weight, economical efficiency is lowered, which is not preferable.

Plasticizer is a material that imparts plasticity because petroleum resin used as a binder is very weak. It is a material that imparts plasticity. It is used to improve workability of construction. DOP, Soya oil, Alkyd resin, Process oil, etc. It can be used, and it is preferable to use a range of 0.01 to 10 parts by weight.

If the plasticizer is used in an amount of less than 0.01 parts by weight, the fluidity is lowered and the bonding strength with the composition may decrease, and if it exceeds 10 parts by weight, durability and abrasion resistance may be deteriorated or plasticizer migration occurs, resulting in surface stickiness. This can cause a problem to occur.

The anti-settling agent is a material that helps workability by giving thixotropy and prevents the precipitation of large grains such as coarse aggregates or large diameters. As the precipitation inhibitor, fumed silica, meerschaum, and amine compounds may be used, but preferably fumed Silica is used, and it is preferable to use a range of 0.01 to 10 parts by weight based on 100 parts by weight of the substrate.

If too little of the anti-settling agent is used, the effect is insignificant, and if it exceeds 10 parts by weight, the workability may deteriorate due to excessive viscosity increase and thixotropy.

In addition, the present invention provides a road sign coating film for a fusion-type road sign obtained by applying the above-described paint composition for road sign to a road.

Hereinafter, details of the process of the present invention will be described through Examples, Comparative Examples and Experimental Examples. This is a representative example related to the present invention, and it is to be understood that this alone cannot limit the scope of application of the present invention.

Preparation Example 1 (Production of glycerol ester resin)

As a silicone compound containing a carboxyl group in a 1L 4-neck flask, 0.105 mol of 3-[2-carboxyethyl(dimethyl)silyl]propanoic acid) and 1.5069 mol of Glycerol Glycerol at a concentration of 50 mol% and 0.05 mol% of zinc acetate as a catalyst Put in and slowly increase the temperature to 200 ℃ over 2 hours. At 140°C, which is the time when dehydration occurs, the heat stabilizer trimethyl phosphate is added. When the reactor temperature rises to 200°C, aging is performed for 2 hours and then the temperature is increased to 230°C under vacuum conditions. After that, let it react for an hour A polymer was obtained in a yield of 88%.

Example 1

For the preparation of a composition for use as a paint composition for road surface marking in the present invention, 18 wt% of a thermoplastic petroleum resin (Hi-Korez R-1100S, Kolon Industries) and 2 wt% of the glycerol ester resin obtained from the above Preparation Example, as an inorganic filler A road marking paint composition was prepared by mixing 20 wt% of calcium carbonate, 25 wt% of aggregate having a particle size of 0.1-2 mm, 30 wt% of glass beads having a particle size of 350 µm to 1500 µm, and 5 wt% of a color pigment.

Example 2

A coating composition for road marking was prepared under the same conditions as in Example 1, but the content of the thermoplastic petroleum resin was reduced to 16 wt% and the glycerol ester resin was increased to 4 wt% to prepare a road marking coating composition.

Example 3

A road marking composition was prepared under the same conditions as in Example 1, but the content of the thermoplastic petroleum resin was reduced to 14 wt% and the glycerol ester resin content was increased to 6 wt% to prepare a road marking coating composition.

Example 4

A coating composition for road marking was prepared under the same conditions as in Example 1, but the content of the thermoplastic petroleum resin was reduced to 12 wt% and the glycerol ester resin content was increased to 8 wt% to prepare a road marking coating composition.

Example 5

A coating composition for road marking was prepared under the same conditions as in Example 2, but the content of polydimethylsiloxane, a silicone rubber-based elastomer, was added to 1 wt%, and the petroleum resin content was reduced to 15 wt% to reduce the road marking coating composition. To manufacture.

Example 6

A coating composition for road marking was prepared under the same conditions as in Example 2, but the content of polydimethylsiloxane, which is a silicone rubber-based elastomer, was added 2 wt%, and the petroleum resin content was reduced to 14 wt%. To manufacture.

Example 7

A coating composition for road marking was prepared under the same conditions as in Example 2, but the content of polydimethylsiloxane, which is a silicone rubber-based elastomer, was added 3 wt%, and the petroleum resin content was reduced to 13 wt%. To manufacture.

Comparative Example 1

A road marking paint composition was prepared in the same manner as in Example 2, but instead of the glycerol ester resin according to the present invention, a modified glycerol ester resin (10-1563931 existing patent resin) used in the prior art was used in 4 w%.

The mixing ratio for preparing the coating composition for road marking prepared according to the Examples and Comparative Examples is shown in Table 1 below.

Component Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Petroleum resin 18 16 14 12 15 14 13 16 Glycerol ester 2 4 6 8 4 4 4 4 Elastomer 0 0 0 0 One 2 3 0 Inorganic filler
(Calcium carbonate) 20 20 20 20 20 20 20 20 aggregate 25 25 25 25 25 25 25 25 Glass bead 30 30 30 30 30 30 30 30 Color pigment 5 5 5 5 5 5 5 5

Evaluation example

Performance evaluation of the coating film formed from the composition for road marking obtained according to Examples 1 to 7 and Comparative Example 1 was performed, and the results are shown in Table 2 below.

For water repellency evaluation, refer to KS M 6080 5.2.16 for wet road surface evaluation conditions, and use a bucket of about 10 L capacity at a height of about 0.5 m from the road surface. Put in water) to make test conditions. Make sure the entire surface is wet evenly. Water repellency is measured 1 minute after pouring water.

The evaluation items were carried out as abrasion resistance, low-temperature impact resistance and surface energy evaluation tests.At this time, the abrasion resistance was evaluated for a result of 100 rotations (300mg or less) for abrasion resistance. 6080:2014”.

In addition, for the low-temperature impact test, specimens having a diameter of 5 cm and a height of 2.5 cm were prepared using the fusion-type paint composition of Examples or Comparative Examples according to the KS M 6080 standard. In addition, a steel ball having a height of 2 m was dropped on the specimen at low temperature, and the specimen was evaluated by observing whether there is crack or cracking.

In the low-temperature impact property evaluation, when 66.8 g of steel balls were dropped at 0°C and 6 or more of the 10 specimens were broken or there were no cracks, they were marked as Cl1 grade, and 10 samples by dropping 66.8 g of steel balls at -10°C If more than 6 of them are cracked or have no cracks, they were marked as Cl2 grade, and if more than 6 of the 10 specimens were broken or cracked by dropping 110g steel balls at -10℃, they were marked as Cl3 grade.

Evaluation item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Retroreflective performance
(Wet, 200,000 times) 78 107 112 145 113 121 130 75 Retroreflective performance
(In case of rain, 200,000 times) 53 68 87 94 76 81 93 44 Low temperature impact resistance CI3 CI3 CI3 CI3 CI3 CI3 CI3 CI3 Surface energy
(Water repellency evaluation) △ ○ ◎ ◎ ○ ○ ◎ X

(◎: excellent, ○: good, △: normal, X: poor)

Referring to the results of Table 2, looking at the abrasion resistance evaluations of Examples 1 to 7 and Comparative Example 1, as the content of the glycerol ester resin increases from the Examples according to the present invention, wetting by improving durability and water repellency of the coating film. It can be seen that the retroreflective performance in case of rain and the retroreflective performance in rainy weather are increased.

That is, in Comparative Example 1, when using a glycerol ester composition in the prior art that does not contain any glycerol ester resin according to the present invention, the retroreflective performance is the lowest, and the composition of Examples 2 to 4 according to the present invention In comparison, it can be seen that the retroreflectivity of the compositions of Examples 5 to 7 to which the silicone rubber-based elastomer is added exhibits much superior properties.

Therefore, the fusion-type paint composition for road surface marking according to the present invention has an advantage in that it has excellent water repellency compared to the paint composition according to the comparative example, and thus improves visibility in rainy weather, so that it can be used more effectively.

Claims (11)

10 to 30 wt% of a thermoplastic petroleum resin, and 2 to 15 wt% of a glycerol ester resin as a binder, and additionally 10 to 40 wt% of an inorganic filler, 15 to 40 wt% of aggregate, and 15 to 40 wt% of glass beads As a fusion-type road marking paint composition,
The glycerol ester resin is obtained by ester polymerization of glycerol and a silane compound containing at least two carboxyl groups at the molecular ends. The method of claim 1,
The coating composition for road surface marking further comprises 0.01 to 10 parts by weight of at least one of pigments, waxes, antioxidants, UV absorbers, precipitation inhibitors, and plasticizers based on 100 parts by weight of the composition. Paint composition for labeling. The method of claim 1,
The silane compound containing at least two carboxyl groups at the molecular end used for polymerization of the glycerol ester resin is tris(2-carboxyethyl)silane, (2-carboxyethylsilyl)propanoic acid, 2-(10carboxylate) Ethylsilyl)propanoic acid, 3-[2-carboxyethyl(dimethyl)silyl]propanoic acid, any one or a mixture thereof, characterized in that the fusion-type paint composition for road surface marking. The method of claim 1,
The glycerol ester resin additionally contains 1 to 10 wt% of a silicone rubber-based elastomer A coating composition for fusion-type road surface marking, characterized in that. The method of claim 4,
The elastomer is a silicone rubber-based elastomer, characterized in that any one selected from polydimethylsiloxane, polydiphenylsiloxane, polymethylvinylsiloxane, polymethylphenylsiloxane, polytrimethylsiloxane, and polyhydroxysiloxane, or a mixture thereof. A fusion-type paint composition for road surface marking. The method of claim 1,
The content ratio of glycerol and silane compound for polymerizing the glycerol ester resin is a molar ratio, in the range of 10:1 to 20:1 A paint composition for fusion-type road surface marking, characterized in that it is. The method of claim 1,
The coating composition for road surface marking is a fusion-type coating composition for road surface marking, characterized in that the content of the glycerol ester resin is 15 wt% or more based on the sum of the petroleum resin and the glycerol ester resin as a binder. The method of claim 7,
The coating composition for road surface marking is a fusion-type coating composition for road surface marking, characterized in that the content of the glycerol ester resin is 20 wt% or more based on the sum of the petroleum resin and the glycerol ester resin as a binder. The method of claim 1,
The glass bead is a fusion-type coating composition for road surface marking, characterized in that the particle size ranges from 300 um to 5000 um. The method of claim 1,
The inorganic filler is at least one selected from the group consisting of silica, talc, alumina, diatomaceous earth, magnesium oxide, magnesium carbonate, talc, calcium carbonate, kaolin, and mica. A fusion-type road sign coating film obtained by heating and melting the fusion-type road sign coating composition according to any one of claims 1 to 10 and then applying it to a road.

Images