KR102465239B1 - Hot-melt type paint composition for road marking with excellent wear resistance and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a coating composition for fusion-type road markings which contains a thermoplastic petroleum resin, an ester resin, ultra-high molecular weight polyethylene particles and surface-modified cordierite, and specifically, provides a coating composition, which is excellent in abrasion resistance, water resistance, impact resistance and durability and has excellent adhesion to asphalt and concrete road surfaces.

Description

A fusion-type paint composition for road marking with excellent abrasion resistance and a manufacturing method thereof {Hot-melt type paint composition for road marking with excellent wear resistance and manufacturing method thereof}

The present invention relates to a coating composition for a fusion-bonded road surface excellent in abrasion resistance and a method for manufacturing the same.

Paints for road markings are paints used to draw traffic signs, and are divided into two-component paints, fusion paints, heating paints or water-soluble paints.

These paints for road markings are installed on the road surface such as concrete or asphalt, and they must be fast-setting to minimize the safety of the constructor and traffic restrictions of vehicles and pedestrians during construction. As the adhesiveness to the road surface, adhesion to glass beads, and abrasion resistance must be excellent, research on paints for road markings to satisfy these needs is continuing.

On the other hand, as a similar prior literature thereto, Republic of Korea Patent Publication No. 10-1563931 is presented.

Republic of Korea Patent Publication No. 10-1563931 (2015.10.22)

An object of the present invention is to provide a coating composition for a fusion-type road sign excellent in abrasion resistance, water resistance, impact resistance and durability as well as excellent adhesion to asphalt and concrete road surfaces.

Another object of the present invention is to provide a method for manufacturing the fusion-type coating composition for a road surface sign and a method for forming a coating film for a road surface using the same.

However, the above purpose is illustrative, and the technical spirit of the present invention is not limited thereto.

One aspect of the present invention for achieving the above object relates to a coating composition for a fusion-type road sign excellent in abrasion resistance, comprising a thermoplastic petroleum resin, an ester resin, ultra-high molecular weight polyethylene particles and a surface-modified cordierite.

In one aspect, the weight average molecular weight of the ultra-high molecular weight polyethylene particles may be 1,000,000 to 10,000,000 g / mol.

In one aspect, the ultra-high molecular weight polyethylene particles may have a particle diameter of 50 to 300 μm.

In one aspect, the surface-modified cordierite may be surface-modified with a silane-based compound, wherein the silane-based compound may be a silane-based compound containing an alkyl group having 3 to 20 carbon atoms.

In one aspect, the coating composition for a fusion-type road sign may further include a cellulosic compound.

In addition, another aspect of the present invention is a method for producing a coating composition for a fusion-type road sign excellent in abrasion resistance, comprising the step of blending a thermoplastic petroleum resin, an ester resin, ultra-high molecular weight polyethylene particles, and a surface-modified cordierite. it's about

In addition, another aspect of the present invention is a) melting a coating composition for a fusion-type road marking comprising a thermoplastic petroleum resin, an ester resin, ultra-high molecular weight polyethylene particles, and a surface-modified cordierite and coating it on the surface of the floor. step; and b) curing.

The coating composition for fusion-type road marking according to the present invention can provide excellent abrasion resistance, water resistance and impact resistance by including ultra-high molecular weight polyethylene particles with a very large molecular weight, and has excellent compatibility with a resin binder compared to inorganic particles, resulting in improved durability It has the advantage of being able to provide

In addition, by including the surface-modified cordierite, it is possible to effectively prevent cracks in the road surface coating film due to seasonal temperature changes.

Hereinafter, the coating composition for a fusion-bonded road surface excellent in abrasion resistance according to the present invention and a method for manufacturing the same will be described in detail. The drawings introduced below are provided as examples so that the spirit of the present invention can be sufficiently conveyed to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, if there is no other definition in the technical terms and scientific terms used, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may be unnecessarily obscure will be omitted.

One aspect of the present invention relates to a coating composition for a fusion-bonded road surface excellent in abrasion resistance, comprising a thermoplastic petroleum resin, an ester resin, ultra-high molecular weight polyethylene particles, and a surface-modified cordierite.

As such, the coating composition for a fusion-bonded road surface according to the present invention can provide excellent abrasion resistance, water resistance and impact resistance by including ultra-high molecular weight polyethylene particles having a very large molecular weight, and has excellent compatibility with a resin binder compared to inorganic particles. It has the advantage of being able to provide improved durability.

In addition, by including the surface-modified cordierite, it is possible to effectively prevent cracks in the road surface coating film due to seasonal temperature changes.

Hereinafter, the coating composition for a fusion-bonded road surface according to an embodiment of the present invention will be described in more detail.

First, in one embodiment of the present invention, the thermoplastic petroleum resin may be used to firmly fix glass beads and pigments as an oil generated as a by-product of petroleum refining or petrochemical industry. The thermoplastic petroleum resin may be used without particular limitation as long as it is commonly used in the art. For example, a thermoplastic synthetic resin prepared by polymerizing monomers containing olefin or diolefin is preferable. As a more specific example, aliphatic or C6-C20 aromatic petroleum resins having 2 to 10 carbon atoms, polyethylene, polypropylene, chromane indene resin, terpene resin, ethylene-ethyl acrylate copolymer, and ethylene-vinyl acetate copolymer It may be any one or two or more selected from the group consisting of coalescing.

In an example of the present invention, the ester resin is added to prevent cracks from occurring in the road surface coating film, and as long as it is commonly used in the art, it can be used without particular limitation, and specifically, for example, hydrogen It may be any one or two or more selected from the group consisting of an added hydrocarbon rosin ester resin, an acrylic rosin ester resin, a disproportionated rosin ester resin, a dibasic acid-modified rosin ester resin, a polymerized rosin ester resin, and a phenol-modified rosin ester resin.

The ester resin may be added in an amount of 10 to 50 parts by weight based on 100 parts by weight of the thermoplastic petroleum resin, and more preferably 20 to 40 parts by weight. In this range, it is possible to secure excellent adhesion and crack prevention effect.

In an example of the present invention, the ultra-high molecular weight polyethylene particles are polyethylene having a very large molecular weight, as the name suggests, and have very high strength but a small coefficient of friction, which can greatly improve the abrasion resistance of the coating film, and also impact resistance, chemical resistance and It has the advantage of excellent thermal stability. Preferably, the weight average molecular weight of the surface-modified ultra-high molecular weight polyethylene particles may be 1,000,000 to 10,000,000 g/mol, more preferably 2,000,000 to 9,000,000 g/mol, even more preferably 3,000,000 to 7,000,000 g/mol have. In this range, the surface-modified ultra-high molecular weight polyethylene particles have the best abrasion resistance and impact resistance, so that the road marking can be maintained for a long time even after the fusion-type road marking paint composition is applied to the road surface.

The particle diameter of the ultra-high molecular weight polyethylene particles may be 50 to 300 μm, more preferably 100 to 200 μm. In such a range, it can provide excellent wear resistance and impact resistance, and it can be uniformly mixed with a thermoplastic petroleum resin and an ester resin, so that it can have excellent adhesion to the road surface after construction.

The ultra-high molecular weight polyethylene particles may be added in an amount of 30 to 150 parts by weight based on 100 parts by weight of the thermoplastic petroleum resin, more preferably 50 to 120 parts by weight, and even more preferably 80 to 100 parts by weight. In this range, excellent abrasion resistance and durability can be secured.

In one embodiment of the present invention, the surface-modified cordierite is added to more effectively prevent cracks from occurring in the road surface coating film, and the cordierite has a coefficient of thermal expansion of 1.59 × 10 ^-6 /°C. It is very low and has high thermal shock resistance, so it has the advantage of effectively preventing cracks in the road surface coating film due to seasonal temperature changes.

Preferably, the surface-modified cordierite may be surface-modified with a silane-based compound. More specifically, the silane-based compound may be a silane-based compound containing an alkyl group having 3 to 20 carbon atoms, and more preferably, modifying the surface of cordierite with a silane-based compound containing an alkyl group having 6 to 12 carbon atoms. It is good because it can be more uniformly mixed with thermoplastic petroleum resin and ester resin. As a more specific example, the silane-based compound is hexyl trimethoxysilane, hexyl triethoxysilane, octyl trimethoxysilane, octyl triethoxysilane, dodecyl trimethoxysilane and dodecyl triethoxysilane. It may be any one or two or more selected from the group consisting of.

The surface-modified cordierite may be added in an amount of 3 to 100 parts by weight based on 100 parts by weight of the thermoplastic petroleum resin, more preferably 15 to 60 parts by weight, and even more preferably 20 to 40 parts by weight. In such a range, the crack prevention effect and adhesion of the road marking coating film may be excellent.

On the other hand, the coating composition for a fusion-bonded road surface according to an embodiment of the present invention may further include a cellulosic compound. As such, it is possible to more easily control the viscosity of the paint by further including a cellulosic compound, and it is possible to provide excellent retroreflectivity by effectively preventing sedimentation of glass beads, etc. after construction, as well as to more effectively reduce the occurrence of cracks after the formation of the coating film. It has the advantage of being able to improve durability by preventing it.

It is preferable to use any one or two or more selected from the group consisting of methyl cellulose, ethyl cellulose, and ethyl methyl cellulose as the cellulose-based compound. In addition, the weight average molecular weight of the cellulosic compound may be 100,000 to 500,000 g/mol, more preferably 200,000 to 400,000 g/mol. By satisfying this, the anti-settling effect of the glass bead and the anti-cracking effect after the formation of the coating film are excellent.

The cellulosic compound may be added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the thermoplastic petroleum resin, preferably 1 to 8 parts by weight, even more preferably 3 to 6 parts by weight. In this range, the viscosity control and anti-settling effect are excellent. On the other hand, when the cellulose-based compound is added in an amount of less than 0.1 parts by weight, the anti-settling effect and the cracking prevention effect may be insignificant, and when it is added in more than 10 parts by weight, the viscosity may be excessively high and workability may be deteriorated.

Furthermore, the coating composition for fusion-type road marking according to an embodiment of the present invention may further include a component added to the conventional coating for fusion-type road marking, that is, four types of paint for road marking, specifically, for example, coloring It may further include a pigment and an extender pigment.

In one embodiment of the present invention, the coloring pigment is added to realize the color of the paint and to impart coloring and hiding power, and as long as it is commonly used in the art, it can be used without particular limitation, and it can be used for the purpose of a road sign. You can adjust the color differently depending on your needs. As a specific example, the colored pigment may be any one or two or more selected from the group consisting of titanium dioxide, red iron oxide, yellow iron oxide, purple iron oxide, black iron oxide, chromium oxide (Cr ₂ O ₃ ), carbon black and whiskers, and the like. , but is not limited thereto.

The coloring pigment may be added in an amount of 30 to 100 parts by weight, more preferably 50 to 80 parts by weight, based on 100 parts by weight of the thermoplastic petroleum resin. In such a range, the effect of imparting coloring and hiding power is excellent. On the other hand, when the amount of the coloring pigment is added in less than 30 parts by weight, the coloring and hiding power may decrease, and when it is added in more than 100 parts by weight, the adhesion of the paint composition may decrease, and the viscosity may increase and workability may be deteriorated.

In one embodiment of the present invention, the extender pigment is for controlling the fluidity, viscosity, etc. of the paint composition for road marking, and for controlling the hardness and abrasion resistance of the coating film after fusion construction, especially if it is commonly used in the art. It can be used without limitation. Specifically, for example, it may be any one or two or more selected from the group consisting of calcium carbonate, talc, silica sand, mica and kaolin, but is not limited thereto.

The extender pigment may be added in an amount of 50 to 500 parts by weight, more preferably 100 to 300 parts by weight, based on 100 parts by weight of the thermoplastic petroleum resin. On the other hand, when the extender pigment is added in less than 50 parts by weight, high fluidity and low viscosity, paintability may be reduced, and when the extender is added in more than 500 parts by weight, the storage stability and adhesion of the paint composition may be reduced , the viscosity may increase and workability may decrease.

In addition to this, any one or two or more additives selected from the group consisting of a quick-drying agent, an antifoaming agent, a surfactant, a plasticizer, an antifreeze agent, a wax and a dispersant, etc. It can be adjusted to, specifically, for example, may be added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the thermoplastic petroleum resin, but is not necessarily limited thereto.

In addition, another aspect of the present invention is a method for producing a coating composition for a fusion-type road sign excellent in abrasion resistance, comprising the step of blending a thermoplastic petroleum resin, an ester resin, ultra-high molecular weight polyethylene particles, and a surface-modified cordierite. In this regard, the constituent components and content of the fusion-bonded road surface coating composition are the same as described above, and thus redundant descriptions are omitted, and the compounding may be performed according to a method commonly used in the art.

In addition, another aspect of the present invention is a) melting a coating composition for a fusion-type road marking comprising a thermoplastic petroleum resin, an ester resin, ultra-high molecular weight polyethylene particles, and a surface-modified cordierite and coating it on the surface of the floor. step; and b) curing. Again, since the components and contents of the coating composition for fusion-type road marking are the same as those described above, redundant descriptions are omitted, and painting and curing may be performed according to methods commonly used in the art.

Hereinafter, the coating composition for a fusion-bonded road surface excellent in abrasion resistance according to the present invention and a method for manufacturing the same according to the present invention will be described in more detail through Examples. However, the following examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention. In addition, the unit of additives not specifically described in the specification may be weight %.

[Production Example 1]

10 parts by weight of n-octyl trimethoxysilane and 50 parts by weight of cordierite were added to 100 parts by weight of ethanol, stirred for 24 hours, filtered and dried to prepare a surface-modified cordierite.

[Example 1]

Based on 100 parts by weight of thermoplastic petroleum resin (weight average molecular weight: 2,750 g/mol, softening point: 100°C, specific gravity: 0.99), hydrogenated hydrocarbon rosin ester resin (softening point: 84°C, melt viscosity at 140°C: 340 cP, density : 1.06 kg/DM ³ ) 30 parts by weight, ultra-high molecular weight polyethylene particles (UHMWPE) 30 parts by weight and surface-modified cordierite (m-CDR) prepared in Preparation Example 1 30 parts by weight, ethyl cellulose (EC, Mw 300,000) g/mol) 5 parts by weight, 65 parts by weight of a coloring pigment (TiO ₂ ), 200 parts by weight of an extender pigment (CaCO ₃ ), and 160 parts by weight of glass beads to prepare a coating composition.

[Examples 2 to 6]

All processes were carried out in the same manner as in Example 1 except that the content of ultra-high molecular weight polyethylene particles was differently adjusted.

[Examples 7 to 10]

All procedures were carried out in the same manner as in Example 1 except that ultra-high molecular weight polyethylene particles having different weight average molecular weights were used.

[Examples 11 to 14]

All processes were performed in the same manner as in Example 1, except that the content of the surface-modified cordierite was differently adjusted.

[Comparative Example 1]

All procedures were carried out in the same manner as in Example 3 except that ultra-high molecular weight polyethylene particles were not added.

[Comparative Example 2]

All processes were performed in the same manner as in Example 3 except that the surface-modified cordierite was not added.

[Comparative Example 3]

All processes were carried out in the same manner as in Example 3 except that ethyl cellulose was not added.

parts by weight petroleum resin Rosin Ester UHMWPE m-CDR EC Mw (×10 ⁴ g/mol) parts by weight Example 1 100 30 550 30 30 5 Example 2 100 30 550 50 30 5 Example 3 100 30 550 80 30 5 Example 4 100 30 550 100 30 5 Example 5 100 30 550 120 30 5 Example 6 100 30 550 150 30 5 Example 7 100 30 50 80 30 5 Example 8 100 30 100 80 30 5 Example 9 100 30 250 80 30 5 Example 10 100 30 700 80 30 5 Example 11 100 30 550 80 3 5 Example 12 100 30 550 80 15 5 Example 13 100 30 550 80 60 5 Example 14 100 30 550 80 100 5 Comparative Example 1 100 30 - - 30 5 Comparative Example 2 100 30 550 80 - 5 Comparative Example 3 100 30 550 80 30 -

[Characteristic evaluation]

According to the standards of the Korean Industrial Standard KS M 6080 (road marking road) type 4 fusion plastic paint, the paint compositions prepared according to Examples 1 to 14 and Comparative Examples 1 to 3 were applied to the surface to be coated with a hot-dip coating film. formed. As an evaluation of wheel load abrasion resistance, the retroreflectivity of the dry road surface according to the traffic volume from 200,000 to 2 million times was evaluated according to KS M 6080:2014, and the results are shown in Table 2 below. In Table 2 below, ΔR is the difference between the initial retroreflectance and the retroreflectance at 2 million traffic volumes.

Retroreflectivity, mcd/(㎡·lx) Early 200,000 times 500,000 times 1 million times 2 million times Example 1 461 441 422 405 359 Example 2 457 439 421 413 371 Example 3 471 460 449 443 417 Example 4 465 453 447 442 421 Example 5 457 445 438 431 380 Example 6 468 455 442 436 376 Example 7 456 423 382 349 235 Example 8 469 448 429 403 362 Example 9 459 445 431 425 391 Example 10 463 455 447 443 423 Example 11 460 432 415 409 361 Example 12 468 457 444 439 394 Example 13 468 458 448 442 419 Example 14 472 460 442 435 386 Comparative Example 1 454 420 376 335 221 Comparative Example 2 464 433 409 389 329 Comparative Example 3 452 429 411 396 337

Referring to Tables 1 and 2, in the case of the coating compositions of Examples 1 to 6 in which ultra-high molecular weight polyethylene particles having a weight average molecular weight of 5 million g/mol are added, the ultra-high molecular weight is 80 to 100 parts by weight relative to 100 parts by weight of the petroleum resin. When polyethylene particles were added, the abrasion resistance was the best. When the amount added was smaller than this, the effect of improving the abrasion resistance was smaller than in Example 3, and when the amount was added in excess, the adhesive force was slightly lowered, and as the traffic volume increased, the retroreflectivity was further decreased. On the other hand, in the case of the paint composition without the addition of ultra-high molecular weight polyethylene particles, the abrasion resistance was greatly reduced, and it was confirmed that the retroreflectivity according to the traffic volume was gradually decreased.

In addition, in the case of Examples 3 and 7 to 10, in which the molecular weight of the ultra-high molecular weight polyethylene particles were different, the wear resistance improvement effect was exhibited only when the weight average molecular weight was 1 million or more, preferably 2.5 million or more, particularly preferably 5 million or more. In particular, it showed excellent wear resistance.

In addition, when the surface-modified cordierite was added in an amount of 15 to 60 parts by weight relative to 100 parts by weight of the petroleum resin, the crack prevention effect was the best, and the retroreflectivity was excellent as the traffic volume increased.

On the other hand, in the case of Comparative Example 2 to which the surface-modified cordierite was not added and Comparative Example 3 to which ethyl cellulose was not added, the anti-cracking effect or the anti-settling effect was inferior, and the initial retroreflectivity was low compared to the Example, and the traffic volume increased. It was confirmed that the retroreflection also gradually decreased significantly.

Although the present invention has been described through specific matters and limited examples as described above, these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the present invention pertains to Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims described below, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (8)

A composition comprising a thermoplastic petroleum resin, an ester resin, a cellulose compound, ultra-high molecular weight polyethylene particles, and surface-modified cordierite,
The ultra high molecular weight polyethylene particles are added in an amount of 50 to 120 parts by weight based on 100 parts by weight of the thermoplastic petroleum resin, and the weight average molecular weight of the ultra high molecular weight polyethylene particles is 1,000,000 to 10,000,000 g/mol,
The surface-modified cordierite is added in an amount of 15 to 60 parts by weight based on 100 parts by weight of the thermoplastic petroleum resin, and the surface-modified coating composition for a fusion-type road sign with excellent abrasion resistance is a silane-based compound.
delete The method of claim 1,
The particle diameter of the ultra-high molecular weight polyethylene particles is 50 to 300 ㎛, a coating composition for a fusion-type road sign excellent in abrasion resistance.
delete The method of claim 1,
The silane-based compound is a silane-based compound containing an alkyl group having 3 to 20 carbon atoms, and has excellent abrasion resistance.
delete Including; mixing a thermoplastic petroleum resin, an ester resin, a cellulose-based compound, ultra-high molecular weight polyethylene particles, and surface-modified cordierite;
The ultra high molecular weight polyethylene particles are added in an amount of 50 to 120 parts by weight based on 100 parts by weight of the thermoplastic petroleum resin, and the weight average molecular weight of the ultra high molecular weight polyethylene particles is 1,000,000 to 10,000,000 g/mol,
The surface-modified cordierite is added in an amount of 15 to 60 parts by weight based on 100 parts by weight of the thermoplastic petroleum resin, and is surface-modified with a silane-based compound.
a) Melting a coating composition for a fusion-type road marking comprising a thermoplastic petroleum resin, an ester resin, a cellulose compound, ultra-high molecular weight polyethylene particles, and surface-modified cordierite and coating the coating on the surface of the floor; and
b) curing;
The ultra high molecular weight polyethylene particles are added in an amount of 50 to 120 parts by weight based on 100 parts by weight of the thermoplastic petroleum resin, and the weight average molecular weight of the ultra high molecular weight polyethylene particles is 1,000,000 to 10,000,000 g/mol,
The surface-modified cordierite is added in an amount of 15 to 60 parts by weight based on 100 parts by weight of the thermoplastic petroleum resin, and is surface-modified with a silane-based compound.