KR102132329B1 - Hot melt plastic paint for road marking and manufacturing method thereof - Google Patents

Abstract

Fusion-type plastic paint for road surface marking according to the present invention includes an aliphatic petroleum resin, an aromatic petroleum resin, an amorphous polyolefin, amide wax, a heat-shielding pigment surface-modified with a first aromatic surface modifier, and nanosilica surface-modified with a second aromatic surface modifier, and thus has an advantage of having excellent binding capacity and durability.

Description

Hot melt plastic paint for road marking and manufacturing method thereof

The present invention relates to a fusing type plastic road surface coating material that exhibits heat shielding performance and has high surface hardness and excellent durability.

A road sign displayed on a road or road surface is used for guiding lanes, directions, or displaying various information on roads to ensure smooth communication between vehicles and pedestrians and for safe passage. In order to improve the visibility of the driver, such road markings are generally mixed with paint to form a road marking, or it is common to apply on a road marking on paints for road markings. Most of the particles use glass beads.

Such paints require fast construction, and since vehicles, etc., pass through and are placed in a strong friction environment, they are required to have excellent durability and wear resistance. Furthermore, it is possible to prevent the problem of reduced visibility even when used for a long period of time with excellent binding force with the above-mentioned glass beads.

However, most of the known road surface coating materials have low durability and abrasion resistance, and there is a problem in requiring frequent construction and repair due to detachment of glass beads.

Republic of Korea Registered Patent Publication No. 10-1255239

An object of the present invention is to provide a fusion-type plastic road surface coating material capable of manufacturing a road surface material having excellent adhesion strength and abrasion resistance.

Another object of the present invention is to provide a fusion-type plastic road surface coating material having excellent binding force with glass beads.

Another object of the present invention is to provide a coating material for a fusion-type plastic road surface having excellent durability as a heat shielding performance.

The fusion-type plastic road surface coating according to the present invention is an aliphatic petroleum resin, an aromatic petroleum resin, an amorphous polyolefin, an amide wax, a heat-resistant pigment surface-modified with a first aromatic surface modifier and a nano-modified surface with a second aromatic surface modifier Silica.

The first aromatic surface modifier or the second aromatic surface modifier in the fusion-type plastic road surface coating material according to an embodiment of the present invention may be characterized in that it comprises a benzene group or a styrene group at the terminal.

The first aromatic surface modifier or the second aromatic surface modifier in the fusion-type plastic road surface coating material according to an embodiment of the present invention may be characterized in that the molecular weight is 50 to 500.

The first aromatic surface modifier or the second aromatic surface modifier in the fusion-type plastic road surface coating material according to an embodiment of the present invention is 3-(n-styrylmethyl-2-aminoethylamino)-propyltrimethoxysilane And styryl ethyl trimethoxysilane.

In the coating for fusing plastic road surface according to an embodiment of the present invention, the amorphous polyolefin may have a melt index of 400 to 1000 g/10min.

In the paint for fusing plastic road surface according to an embodiment of the present invention, the aliphatic hydrocarbon resin may have a softening point of 94 to 105°C, and a weight average molecular weight of 1600 to 2300.

In the coating for fusing plastic road surface according to an embodiment of the present invention, the nano-silica has an average particle diameter of 5 to 60 nm, and a specific surface area may be 60 to 250 m 2 /g.

In the fusion-type plastic road surface coating material according to an embodiment of the present invention, the fusion-type plastic road surface coating material is 5 to 30 parts by weight of aromatic petroleum resin and 5 to 20 parts by weight of amorphous polyolefin compared to 100 parts by weight of aliphatic petroleum resin. , 1 to 10 parts by weight of amide wax, 1 to 10 parts by weight of the heat-resistant pigment surface-modified with the first aromatic surface modifier, and 0.1 to 1 part by weight of nano-silica with the second aromatic surface modifier.

The fusion-type plastic road surface coating according to the present invention is an aliphatic petroleum resin, an aromatic petroleum resin, an amorphous polyolefin, an amide wax, a heat-resistant pigment surface-modified with a first aromatic surface modifier and a nano-modified surface with a second aromatic surface modifier Including silica, there is an advantage that it is possible to manufacture a road surface cover having excellent heat-insulating performance, excellent binding strength with a road surface and binding strength with a glass bead, and excellent durability and abrasion resistance.

Advantages and features of the embodiments of the present invention, and methods for achieving them will be made clear by referring to embodiments described below in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, and only these embodiments allow the disclosure of the present invention to be complete, and common knowledge in the art to which the present invention pertains. It is provided to fully inform the person having the scope of the invention, and the present invention is only defined by the scope of the claims. The same reference numerals refer to the same components throughout the specification.

In describing embodiments of the present invention, when it is determined that a detailed description of known functions or configurations may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. In addition, terms to be described later are terms defined in consideration of functions in an embodiment of the present invention, which may vary according to a user's or operator's intention or practice. Therefore, the definition should be made based on the contents throughout this specification.

The paint for fusing plastic road surface according to the present invention includes an aromatic petroleum resin, an amorphous polyolefin, a heat-resistant pigment surface-modified with a first aromatic surface modifier, and nanosilica surface-modified with a second aromatic surface modifier. The paint for fusing plastic road surface according to the present invention comprises an aromatic hydrocarbon resin, an amorphous polyolefin, an amide wax, a heat-modifying pigment surface-modified with a first aromatic surface modifier, and nano silica surface-modified with a second aromatic surface modifier, It has the advantage of being excellent in adhesion strength and abrasion resistance while being heat-resistant.

Specifically, the aliphatic petroleum resin may be a C5 petroleum resin, more specifically, a softening point of 94 to 105 °C, and a molecular weight of 1600 to 2300. By satisfying such a range, it is possible to exhibit excellent compatibility with other compositions of the coating material for the road surface cover while smoothly performing the welding construction of the coating material for the fusion type road surface sign. In addition, the road surface cover made of a fusion-type plastic road surface coating has the advantage of having excellent weather resistance.

The aromatic petroleum resin may be a C9-based or DCPD-based petroleum resin, more specifically, a softening point of 90 to 100°C, and an average molecular weight of 800 to 1500 may be used. When the softening point is low, there is a problem in that the abrasion resistance of the manufactured road surface cover is significantly lowered, and when the softening point is high, there may be a problem that welding construction is not smooth.

The paint for fusing plastic road surface according to an embodiment of the present invention may include 5 to 30 parts by weight, preferably 10 to 25 parts by weight of an aromatic petroleum resin, compared to 100 parts by weight of the aliphatic petroleum resin. When a small amount of the aromatic petroleum resin is included, a problem that compatibility with other compositions is lowered may occur, and when a large amount of the aromatic petroleum resin is included, weathering resistance may decrease.

The paint for fusing plastic road surface according to the present invention includes a heat-resistant pigment surface-modified with a first aromatic surface modifier and nanosilica surface-modified with a second aromatic surface modifier. The first aromatic surface modifier and the second aromatic surface modifier may use the same or different surface modifiers, but the present invention is not limited thereto, and is hereinafter described as “aromatic surface modifier” for convenience of explanation. do.

The heat shielding pigment and nanosilica according to the present invention are each characterized by being surface-modified with an aromatic surface modifier. The surface modification significantly improves the dispersibility of the heat-insulating pigment and nano-silica, and according to the excellent dispersibility, even when a small amount of the heat-insulating pigment and nano-silica are added, there is an advantage that can exhibit excellent effects.

In the coating for fusing plastic road surface according to an embodiment of the present invention, the nano-silica can improve the binding force between the road surface and the glass bead while improving durability and wear resistance. The nano-silica has an average particle diameter of 5 to 60 nm, a specific surface area may be 60 to 250 m 2 /g, and when the average particle diameter of the nano-silica is too small, the particles are intended to improve the intended durability and wear resistance by fine particles. There is a difficult problem, and when the average particle size of the nano-silica is large and the specific surface area is small, the effect of adding the nano-silica is lowered.

The fusion-type plastic road surface coating according to the present invention includes a heat shielding pigment, and by including such a heat shielding agent, suppresses excessive temperature rise due to direct sunlight exposure, thereby preventing durability from being deteriorated due to continuous heating. In this case, the heat-insulating pigment can be used without limitation in the case of metal oxide particles having heat-insulating properties. As a specific and non-limiting example, the heat-insulating pigment is titanium dioxide, iron oxide, chromium oxide, tin oxide, zinc oxide, zirconium oxide, oxidation It may include one or more selected from cerium and antimony oxide, but the present invention is not limited thereto.

Each of these heat shielding pigments and nanosilica is characterized by being surface-modified with an aromatic surface modifier, and as described above, it is possible to achieve an improvement in dispersibility with the surface modification.

Specifically, in the fusion-type plastic road surface coating material according to an embodiment of the present invention, the aromatic surface modifier may be characterized in that it comprises a benzene group or a styrene group at the terminal, and by including such a benzene group or a styrene group, petroleum It has the advantage of ensuring high compatibility with resins.

Furthermore, the aromatic surface modifier may have a molecular weight of 50 to 500 g/mol. At this time, when the molecular weight of the surface modifier is too large, there is a problem that it is difficult to sufficiently exhibit the surface modification effect due to the excessively large molecular weight.

More preferably, the aromatic surface modifier may be at least one selected from 3-(n-styrylmethyl-2-aminoethylamino)-propyltrimethoxysilane and styrylethyltrimethoxysilane. By using it, there is an advantage of improving the dispersibility of the nano-silica and heat-shielding pigment, and at the same time, improving the binding force with the glass beads.

The paint for fusing plastic road surface according to an embodiment of the present invention comprises 1 to 10 parts by weight, preferably 1.5 to 5 parts by weight of the first aromatic surface modifier, compared to 100 parts by weight of the aliphatic petroleum resin. It can contain. When a small amount of heat-insulating pigment is included, it is difficult to exhibit heat-insulating performance, and when a large amount of heat-insulating pigment is included, the color of the entire road surface may be affected, and durability is also deteriorated.

The fusion-type plastic road surface coating material according to an embodiment of the present invention is 0.1 to 1 part by weight, preferably 0.2 to 0.8 part by weight of the second aromatic surface modifier, compared to 100 parts by weight of the aliphatic petroleum resin. Includes. When a small amount of nano-silica is included, it is difficult to improve durability and abrasion resistance by adding nano-silica, and when a large amount of nano-silica is included, a problem in that overall physical properties may be deteriorated by aggregation despite surface modification.

The paint for fusing plastic road surface according to the present invention includes an amorphous polyolefin. Including an amorphous polyolefin, it has the advantage of securing fluidity during construction and preventing cracks on the road surface.

Specifically, in the fusion-type plastic road surface coating material according to an embodiment of the present invention, the amorphous polyolefin has a crystallinity of 10% or less, preferably 5% or less. In addition, the amorphous polyolefin may have a melt index of 400 to 1000 g/10min, preferably 500 to 950 g/10min. When the melt index is too low, it is difficult to secure hardness, and when the melt index is high, there is a problem in that construction by thermal fusion is difficult.

The paint for fusing plastic road surface according to an embodiment of the present invention may include 5 to 20 parts by weight of amorphous polyolefin compared to 100 parts by weight of the aliphatic petroleum resin. When a small amount of the amorphous polyolefin is included, it is difficult to secure a crack prevention performance, and when a large amount of the amorphous polyolefin is included, a surface hardness decrease may occur.

The fusion-type plastic road surface coating according to the present invention includes an amide wax, and by using the amide wax, binding power to an asphalt concrete or concrete substrate can be improved.

If the amide wax is a product used for heat-sealable plastic, it can be used without limitation, and the present invention is not limited thereto, and preferably, Ethylene-Bis-Stearamide wax can be used. When using the amide wax, it is easy to construct the road surface marker, and has an advantage of improving compatibility with other compositions.

The fusion-type plastic road surface coating material according to an embodiment of the present invention may include 1 to 10 parts by weight of amide wax compared to 100 parts by weight of the aliphatic petroleum resin, and when a small amount of amide wax is included, the amide wax is added. It is difficult to exhibit the effect of improving the binding power, and when a large amount of amide wax is included, a problem that some compatibility decreases may occur.

The paint for fusing plastic road surface according to an embodiment of the present invention may further include a filler. The road surface cover manufactured by including such a filler may have a thickness and hardness of a certain level or higher. At this time, the filler may be used without limitation when it is usually used for a road surface coating material, and the present invention is not limited thereto. As a specific and non-limiting example, the filler may be one or more selected from calcium carbonate, silica, talc and clay, but the present invention is not limited thereto.

The paint for fusing plastic road surface according to an embodiment of the present invention may include 50 to 90 parts by weight of a filler compared to 100 parts by weight of an aliphatic petroleum resin, and it is difficult to achieve a hardness improvement effect when a small amount of a filler is included, When a large amount of filler is included, there is a problem in that adhesion to the substrate is low and cracks are easily generated.

The paint for fusing plastic road surface according to an embodiment of the present invention may further include other additives such as a pigment, a dispersant, an antifoaming agent, an ultraviolet stabilizer, and a heat stabilizer, but the present invention is not limited thereto.

Specifically, the pigment may be titanium dioxide or a diarylide-based organic pigment, but the present invention is not limited thereto. The pigment may be included in an amount of 10 to 35 parts by weight compared to 100 parts by weight of the aliphatic petroleum resin, but the present invention is not limited thereto.

In addition, the ultraviolet stabilizer may use one or more selected from benzophenone-based or benzotriazole-based, and may be included in an amount of 0.5 to 5 parts by weight compared to 100 parts by weight of the aliphatic petroleum resin, but the present invention is not limited thereto.

The paint for fusing plastic road surface according to an embodiment of the present invention may further include glass beads. By using these glass beads, it is possible to secure retroreflectivity and significantly improve the visibility of a vehicle driver. These glass beads can be used either alone or in combination with ordinary glass beads or rainy glass beads, but the present invention is not limited thereto. Further, such a glass bead may be one that satisfies the standard of KS L 2521, which is a glass grain standard for road signs, but the present invention is not limited thereto.

The paint for fusing plastic road surface according to an embodiment of the present invention may include 20 to 40 parts by weight of glass beads compared to 100 parts by weight of the aliphatic petroleum resin, but the present invention is not limited thereto.

The present invention also provides a method for manufacturing a fusion-type plastic road surface coating, and the method for manufacturing a fusion-type plastic road surface coating according to the present invention is to prepare a surface-modified heat-resistant pigment by modifying the heat-resistant pigment with a first aromatic surface modifier. First step;

A second step of modifying the nano silica with a second aromatic surface modifier to prepare the surface-modified nano silica; And

And a third step of mixing and heating the surface-modified heat shielding pigment, surface-modified nanosilica, aromatic hydrocarbon resin, and ethylene vinyl acetate resin.

The fusion-type plastic road surface coating material manufactured through these steps has excellent bonding strength with base materials such as asphalt, and has the advantage of minimizing damage to the road surface due to high temperature by having heat shielding performance.

Hereinafter, the present invention will be specifically described by examples and comparative examples. The examples below are only to aid the understanding of the present invention, and the scope of the present invention is not limited by the examples below.

[Production Example 1]

1. Preparation of surface-modified heat-resistant pigment

500 ml of a mixed solvent was prepared by mixing 460 ml of acetone and 40 ml of ethanol. 15 g of titanium dioxide heat-resistant pigment (TITANIX JR-1000) was mixed in the prepared mixed solvent and stirred for 1 hour, followed by 3-(n-styrylmethyl-2-aminoethylamino)-propyltrimethoxysilane 2 g was added, and a surface modification reaction was performed for 3 hours, and the solid phase was separated and dried to prepare a surface-modified heat-resistant pigment.

2. Preparation of surface-modified nano silica

3-(n-styrylmethyl-2-aminoethylamino)-propyltrime after adding 3 g of nano-silica particles having a specific surface area of about 200 m 2 /g to 500 ml of ethanol and satisfying a specific surface area of about 200 m 2 /g. Surface modification was performed for 3 hours by adding 1 g of oxysilane, and the solid phase was first separated through centrifugation, and then dried to prepare surface-modified nanosilica.

3. Production of fusion-type plastic road sign paint

100 g of an aliphatic petroleum resin having a softening point of about 98°C and a molecular weight of 1600 to 2300 (hereinafter referred to as AHR), a C9 aromatic petroleum resin having a softening point of about 93°C and having a molecular weight of 800 to 1500 (hereinafter referred to as CHR). 100 g, 2.5 g of heat-resistant pigment surface-modified with a first aromatic surface modifier, 0.5 g of nano-silica surface-modified with a second aromatic surface modifier, amorphous polyolefin having a melt index of about 800 g/10 min (hereinafter referred to as APO, AFFINITY GA 1900) 12 g, amide wax, 5 g of Ethylene-Bis-Stearamide wax (hereinafter referred to as WAX), 65 g of calcium carbonate filler with an average particle size of 30 μm, 25 g of titanium dioxide pigment and 30 g of glass beads, mixed and 180° C. The furnace was heated and stirred to prepare a coating material for fusion-type plastic road markings.

[Production Examples 2 to 12]

Prepared in the same manner as in Preparation Example 1, the composition shown in Table 1 was mixed to prepare a fusion-type plastic road surface coating material.

The unit indicated in Table 1 is g, and for the sake of convenience, the addition amount of the pigment and glass beads was omitted, but the addition amount is the same as in Production Example 1.

In the case of Production Example 10, a heat shielding pigment having the same composition as Production Example 1 but not undergoing surface modification was added immediately, and Production Example 11 also immediately added nanosilica having the same composition as Production Example 1 but not undergoing surface modification.

Manufacturing example AHR CHR Heat shielding pigment Nano silica APO WAX Filler Remark One 100 15 2.5 0.5 12 5 65 2 100 18 3.0 0.75 14 5.5 60 3 115 - 2.5 0.5 12 5 65 4 110 4.5 2.5 0.5 12 5 65 5 80 35 2.5 0.5 12 5 65 6 100 15 2.5 1.5 12 5 65 7 100 15 2.5 0.5 3.5 5 65 8 100 15 2.5 0.5 22 5 65 9 100 15 2.5 0.5 12 0.5 65 10 100 15 2.5 0.5 12 12 65 11 100 15 2.5 0.5 12 5 65 No heat-resistant pigment surface modification 12 100 15 2.5 0.5 12 5 65 No nano-silica surface modification

Preparation of samples

Each of the fusion-type plastic road surface coating materials of each manufacturing example was applied to the asphalt substrate to a thickness of 5 mm, and heat fusion was performed with a heat fusion device at about 170°C.

Check adhesion strength, abrasion resistance, and glass bead adhesion

The adhesion strength was measured by the KS F 2561 test method and the abrasion resistance by the KS F 2429 test method.

Heat insulation performance check

Inside the styrofoam box, test pieces of each manufacturing example were installed on the floor, and after installing a 100 W incandescent lamp at a height of 30 cm from the test piece, the light was turned on for 30 minutes and the styrofoam box was sealed. After 30 minutes, the temperature of the surface of the test piece was measured, and the result was shown in Table 2 as to how much the temperature was increased compared to the temperature before the measurement.

Manufacturing example Bond strength (N/mm ² ) Wear resistance (mg/mm ² ) Temperature difference (℃) One 2.0 0.18 16.7 2 1.9 0.17 16.8 3 1.3 0.26 17.9 4 1.5 0.21 17.2 5 1.6 0.41 18.5 6 1.7 0.16 17.5 7 1.7 0.34 17.0 8 1.1 0.22 17.1 9 1.2 0.20 16.9 10 1.7 0.39 17.2 11 1.4 0.35 19.2 12 1.1 0.42 17.1

Referring to Table 2, it includes an aliphatic petroleum resin, an aromatic petroleum resin, amorphous polyolefin, amide wax, a heat-resistant pigment surface-modified with a first aromatic surface modifier, and nanosilica surface-modified with a second aromatic surface modifier, and aliphatic. 5 to 30 parts by weight of aromatic petroleum resin, 5 to 20 parts by weight of amorphous polyolefin, 1 to 10 parts by weight of amide wax, 1 to 10 parts by weight of heat-resistant pigment surface-modified with a first aromatic surface modifier, It can be seen that Preparation Examples 1 and 2, which contain 0.1 to 1 part by weight of nanosilica surface-modified with a second aromatic surface modifier, have excellent adhesion strength and abrasion resistance, mechanical strength, and excellent temperature suppression by suppressing temperature rise as much as possible.

Particularly, in the case of adding heat shielding pigments or nanosilica without surface modification in Preparation Examples 11 and 12, it can be seen that their dispersibility is lowered and agglomeration occurs, so that the overall mechanical strength is lowered. In particular, the surface modification of heat shielding pigments is not performed. If not, it can be seen that the heat dissipation performance is also lowered by inhibiting the even dispersion of the heat insulating pigment.

Claims (8)

A fusion-type plastic road surface coating material comprising an aliphatic petroleum resin, an aromatic petroleum resin, an amorphous polyolefin, an amide wax, a heat-resistant pigment surface-modified with a first aromatic surface modifier, and nanosilica surface-modified with a second aromatic surface modifier. According to claim 1,
The first aromatic surface modifier or the second aromatic surface modifier has a benzene group or a styrene group at the end, a fusion-type plastic road surface coating material. According to claim 2,
The first aromatic surface modifier or the second aromatic surface modifier has a molecular weight of 50 to 500, a fusion-type plastic road surface coating material. According to claim 2,
The first aromatic surface modifier or the second aromatic surface modifier is at least one fused plastic selected from 3-(n-styrylmethyl-2-aminoethylamino)-propyltrimethoxysilane and styrylethyltrimethoxysilane. Paint for road signs. According to claim 1,
The amorphous polyolefin has a melt index of 400 to 1000 g/10min. According to claim 1,
The aliphatic petroleum resin has a softening point of 94 to 105°C, and a weight average molecular weight of 1600 to 2300. According to claim 1,
The nano-silica has a mean particle diameter of 5 to 60 nm, and a specific surface area of 60 to 250 m2/g, a fusion-type plastic road surface coating material. According to claim 1,
The fusion-type plastic road surface coating material is an aliphatic petroleum resin compared to 100 parts by weight of an aromatic petroleum resin 5 to 30 parts by weight, 5 to 20 parts by weight of amorphous polyolefin, 1 to 10 parts by weight of amide wax, the surface of the first aromatic surface modifier 1-10 parts by weight of a modified heat shield pigment, a fusion-type plastic road surface coating material comprising 0.1 to 1 part by weight of nanosilica surface-modified with a second aromatic surface modifier.