JP2007106792A - Melting type road surface-displaying material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a melting type road surface-displaying material being a material for forming a road surface-displaying line having projections on the surface, suppressing occurrence of crack and excellent in deformation resistance even under high temperature. <P>SOLUTION: The melting type load surface-displaying material is used for formation of a load surface-displaying coated film having projections on the surface and contains a thermoplastic resin having 80-150°C softening point, a rubber elastic resin and filler. In the displaying material, the content of the thermoplastic resin is 8.0-25.0 mass% and the content of the rubber elastic resin is 1.0-10.0 mass% and the rubber elastic resin comprises an ethylene-ethylacrylate copolymer resin and an olefin-based thermoplastic elastomer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a melt-type road marking material suitable for forming a road marking coating film having protrusions on an asphalt pavement surface, a concrete pavement surface, or the like.

Conventional melt-type road marking materials used for forming road marking lines having protrusions, for example, materials used for guidance for visually impaired persons and high-intensity road markings, are thermoplastic resins having a softening point of 80 to 110 ° C. (petroleum Resin, rosin, terpene resin, etc.), fillers and glass beads as the main components, but the formed coating film generates cold cracks in winter and aging cracks in the winter, and the road surface temperature in summer is 60 ° C. When the temperature is too high, the material softens, and the vehicle or the like travels to dent the coating film, resulting in a problem that the guidance effect due to visibility and shape recognition is reduced (see, for example, Patent Document 1). ).
JP-A-9-003840

  The present invention provides a molten road marking material that suppresses the occurrence of cracks and is excellent in deformation resistance even at high temperatures.

That is, the present invention relates to the following melt-type road marking material.
(1) A melt-type road marking material used for forming road marking lines having protrusions on the surface, which includes a thermoplastic resin having a softening point of 80 to 150 ° C., a rubber elastic resin, and a filler. The content is 8.0 to 25.0 mass%, the content of the rubber elastic resin is 1.0 to 10.0 mass%, and the rubber elastic resin is an ethylene ethyl acrylate copolymer resin and an olefin-based thermoplastic elastomer. A melt-type road marking material characterized by comprising:

  (2) The melt type road marking material according to (1), wherein the rubber elastic resin has a softening point of 40 to 150 ° C.

  (3) Ethylene ethyl acrylate copolymer resin has an ethyl acrylate content of 20 to 40% by mass, a melt index of 200 to 1,200 g / 10 min, an olefin thermoplastic elastomer is a propylene ethylene copolymer elastomer, and is softened The melt road marking material according to (1) or (2), wherein the point is 120 to 150 ° C. and the melt viscosity at 200 ° C. is 1,500 to 9,000 mPa · s.

(4) The melt type road marking material according to any one of (1) to (3), wherein the content of the filler in the melt type road marking material is 35 to 75% by mass.
(5) The melt type road marking material according to any one of (1) to (4), further containing 10 to 30% by mass of a reflective material.
(6) The melt type road marking material according to any one of (1) to (5), further containing 0.5 to 3.0% by mass of a plasticizer.

  It is confirmed that the melt-type road marking material of the present invention is superior in crack resistance and dent resistance at the initial stage and over time (not deformed even in summer and midsummer, maintaining shape) compared to conventional materials. did it.

  Examples of the thermoplastic resin used in the present invention include petroleum resin, maleated rosin, maleated rosin ester, hydrogenated rosin, hydrogenated petroleum resin, terpene resin, polypropylene resin, polyethylene resin and the like, and the softening point is 80. The thing of the range of -150 degreeC is used. If the softening point of the thermoplastic resin is less than 80 ° C., the effect of improving the dent resistance tends to be reduced, and if it exceeds 150 ° C., the viscosity tends to increase when the melt type road marking material is used as a paint. Also, the flexibility tends to decrease.

  As the thermoplastic resin, it is particularly preferable to use a petroleum resin (unmodified aliphatic petroleum resin, acid-modified aliphatic petroleum resin) and a terpene phenol resin obtained by copolymerizing a terpene resin with a phenol resin. As a result, the deformation resistance is greatly improved. In addition to petroleum resin and terpene phenol resin, other thermoplastic resins may be used in combination. The softening point of the petroleum resin is preferably from 80 to 100 ° C, particularly preferably from 85 to 95 ° C. If the softening point of the petroleum resin is less than 80 ° C., the effect of improving the dent resistance tends to be reduced, and if it exceeds 100 ° C., the viscosity tends to increase when the melt-type road marking material is used as a paint, Moreover, there exists a tendency for flexibility to fall. The softening point of the terpene phenol resin is preferably 125 to 150 ° C, particularly preferably 145 to 150 ° C. If the softening point of the terpene phenol resin is less than 125 ° C, the effect of improving the dent resistance tends to be reduced, and if it exceeds 150 ° C, the viscosity tends to increase when the molten road marking material is used as a paint. Also, the flexibility tends to decrease.

  The total amount of the thermoplastic resin in the melt-type road marking material according to the present invention is 8.0 to 25.0% by mass, preferably 9.0 to 20.0% by mass, and more preferably 10.0 to 15%. 0.0% by mass. If the blending amount of the thermoplastic resin is less than 8.0% by mass, the paint tends to thicken when the melt-type road marking material is used as a paint, and crack resistance and dent resistance tend to decrease. If it exceeds 25.0% by mass, crack resistance and dent resistance are lowered, and further, blocking of the kneaded material tends to occur.

  When the petroleum resin and the terpene phenol resin are used in combination, the blending amount of the petroleum resin in the melt-type road marking material of the present invention is preferably 7.9 to 24.9% by mass, more preferably 8 to 20% by mass, 0.1-5.0 mass% is preferable and, as for the compounding quantity of resin, 0.5-3.0 mass% is more preferable. When the blending amount of the terpene phenol resin is small, the improvement in deformation resistance may be small, and when the blending amount is large, the tendency to increase the viscosity of the marking material and the flexibility may be observed.

  As a rubber elastic resin which is a material used for improving crack resistance, one having a softening point of 40 to 150 ° C is preferable, and one having a softening point of 80 to 140 ° C is more preferable. If the softening point is too low, it may dip into the coating film in the summer and block the kneaded material. If the softening point is too high, the marking material may increase in viscosity, decrease in solubility, and decrease in crack resistance. .

  The rubber elastic resin used in the present invention includes (A) ethylene ethyl acrylate copolymer resin and (B) olefin-based thermoplastic elastomer (for example, ethylene / butylene copolymer elastomer, ethylene / propylene copolymer elastomer, propylene / ethylene copolymer). Olefin-based copolymer elastomers such as elastomers, olefin-based thermoplastic elastomers using polypropylene, polyethylene for the hard segment, and ethylene, propylene, and diene copolymers for the soft segment are included as essential components. In addition to this essential component, ethylene vinyl acetate copolymer resin, low-density polyethylene, etc. may be used as required, and thermoplastic synthetic rubbers other than olefinic thermoplastic elastomers, such as styrene thermoplastic elastomers, urethanes Thermoplastic elastomers, polyester thermoplastic elastomers, PVC thermoplastic elastomers, polybutadiene thermoplastic elastomers, polyamide thermoplastic elastomers, polyester thermoplastic elastomers composed of aromatic polyester and amorphous polyether or aliphatic polyester, etc. May also be used as needed.

  (A) ethylene ethyl acrylate copolymer resin and thermoplastic synthetic rubber (B) olefin thermoplastic elastomer (especially olefin copolymer elastomers such as propylene / ethylene copolymer elastomer and ethylene / propylene copolymer elastomer) Then, the improvement of crack resistance is remarkably preferable. The mass ratio of (A) / (B) is preferably 1/4 to 3/2, and particularly preferably 2/5 to 3/5. When the mass ratio of (A) / (B) is less than 1/4, the crack resistance tends to decrease, and even if it exceeds 3/2, the crack resistance tends to decrease. The ethylene ethyl acrylate copolymer resin preferably has an ethyl acrylate content of 20 to 40% by mass, and more preferably 25 to 35% by mass. If this content is less than 20% by mass, the compatibility with the thermoplastic resin will be poor, and the viscosity of the marking material will tend to increase and the solubility will decrease. If it exceeds 40% by mass, it will be applied in summer. There is a tendency that the film is dented and the kneaded material is blocked. The melt index of the ethylene ethyl acrylate copolymer resin is preferably 200 to 1,200 g / 10 minutes, and more preferably 250 to 1,000 g / 10 minutes. If the melt index of the ethylene ethyl acrylate copolymer resin is less than 200 g / 10 min, the marking material tends to increase in viscosity and decrease in solubility. If it exceeds 1,200 g / 10 min, the compressive strength of the marking material There is a tendency that the dent resistance over time decreases. The olefinic thermoplastic elastomer preferably has a softening point of 120 to 150 ° C, more preferably 128 to 138 ° C, and a melt viscosity at 200 ° C of 1,500 to 9,000 mPa · s. Preferably, it is 2,400 to 9,000 mPa · s, more preferably 3,000 to 9,000 mPa · s, and particularly preferably 3,500 to 8,500 mPa · s. If the softening point of the olefinic thermoplastic elastomer is less than 120 ° C, the effect of improving crack resistance tends to be small, and if it exceeds 150 ° C, the effect of improving crack resistance tends to be small. Further, if the melt viscosity of the olefinic thermoplastic elastomer is less than 1,500 mPa · s, the compression strength of the marking material tends to be lowered, and the dent resistance over time tends to decrease. There is a tendency for the marking material to increase in viscosity and decrease in solubility.

  In this specification, the softening point is a value measured according to JIS K2207, the melt index is measured according to JIS K6924-2, and the melt viscosity is a value measured according to JIS K2207.

  The compounding amount of the rubber elastic resin is preferably 1.0 to 10.0% by mass, particularly preferably 2.0 to 6.0% by mass, in the melt-type road marking material according to the present invention. If the amount of the rubber elastic resin is too small, the effect of improving the crack resistance is small, and if it is too large, dents are likely to occur in summer with a decrease in the deformation resistance of the material.

  In addition to the above resins, the melt-type road marking material of the present invention contains a filler as an essential component, and further contains a reflector, a plasticizer, a color pigment, other additives, etc. as necessary. Also good.

  As the filler, conventionally used ones such as calcium carbonate fine powder, cold water stone, and talc can be used. The blending amount is preferably 35 to 75% by mass, and more preferably 40 to 65% by mass in the melt-type non-slip labeling material according to the present invention. If the amount of the filler is too small, the wear resistance tends to be lowered, and if the amount of the filler is too large, the workability during construction tends to be lowered.

  As the reflective material, for example, conventionally used materials such as glass beads and glass powder can be used. The glass beads preferably have a refractive index of 1.5 to 2.5 and a particle size of 0.1 to 3.0 mm. If the refractive index is less than 1.5, the visibility tends to be insufficient, and if it exceeds 2.5, the light tends to be refracted too much to be retroreflected, resulting in poor visibility. . When the particle size exceeds 3.0 mm, the glass beads are likely to be detached from the paint, which tends to reduce visibility. 10-30 mass% is preferable in the melt type road marking material which becomes this invention, and the compounding quantity of a reflecting material has more preferable 15-25 mass%. If the amount of the reflecting material is too small, the visibility at night (rainy weather) is likely to be lowered when used for high-luminance marking, and if it is too much, the workability at the time of construction is likely to be lowered.

  Examples of the plasticizer include vegetable oil, vegetable oil-modified alkyd resin, mineral oil, and liquid synthetic rubber. The blending amount is preferably 0.5 to 3.0% by mass, and more preferably 0.7 to 2.0% by mass in the melt-type road marking material according to the present invention. If there is too much plasticizer, it may dent into the coating film in summer and block the kneaded material. When there are few plasticizers, the flexibility and workability at low temperatures tend to be reduced.

  There are no particular restrictions on the color pigment, but there are many uses that call attention to pedestrians and drivers, so there are mainly yellowish and heat-resistant yellow lead, organic yellow pigments and the like. In addition, red type includes bengara (iron oxide). The blending amount of the color pigment is preferably 1.5 to 6.0% by mass, more preferably 2.0 to 5.0% by mass in the melt-type road marking material according to the present invention. When the addition amount is small, the fading resistance due to ultraviolet rays tends to decrease, and when the addition amount is large, the fading resistance is good, but the workability and flexibility tend to decrease.

  In addition, additives such as an antisettling agent, an ultraviolet absorber, and a viscosity reducing agent may be added as necessary. In the present invention, the amount of each component described above is adjusted so that the total amount becomes 100% by mass.

  The marking method using the melt-type road marking material of the present invention includes, for example, a ground treatment (primer coating) on the road surface, and then the above components are melted at 180 to 210 ° C. with a melting pot, and a convex rib molding dedicated construction machine, etc. It is possible to carry out by performing construction on a road surface that has been ground-treated using a construction machine, and forming a road marking coating film having protrusions on the surface.

  The protrusions are preferably on a base marking line having a constant thickness, and the shape and size thereof are not particularly limited, and examples thereof include dot-like protrusions, linear protrusions, parallel array protrusions, and half dome-shaped protrusions. Usually, for example, linear protrusions in which convex ribs 2 (linear protrusions having a trapezoidal cross section) integrated with the base marking line 1 are preferable as shown in FIGS. 1 and 2. 1 is a perspective view of such a road marking line, and FIG. 2 is a cross-sectional view taken along line AA of FIG. The height of the protrusion from the base marking line surface is preferably 0.5 to 7.0 mm, and more preferably 3.0 to 6.0 mm. 10-150 mm is preferable and, as for the width | variety or diameter of a processus | protrusion bottom part, 10-50 mm is more preferable. In the case of linear protrusions, the length (construction direction) is not limited, but is preferably 30 to 300 mm, and the interval is preferably 10 to 100 mm. The width of the marking line is not limited, but is generally about 100 to 450 mm.

  In the present invention, a melt type road marking material in which an ethylene ethyl acrylate copolymer resin and an olefinic thermoplastic elastomer are used in combination with a thermoplastic resin having a softening point of 80 to 150 ° C. has a crack resistance and a dent resistance over time. Improvement effect is obtained.

EXAMPLES Next, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.
Tables 1-1 and 2-1 show the compositions of the melt-type road marking materials prepared in Examples and Comparative Examples, and Tables 1-2 and 2-2 show the test results of these melt-type road marking materials. The amount of each component described in Table 1-1 and Table 2-1 is shown in parts by mass. Table 3 shows the criteria for each test.

Examples 1-8 and Comparative Examples 1-7
The components described in Table 1-1 and Table 2-1 were mixed with a mixer and then packed in a polyethylene bag to obtain a melt-type road marking material. Next, after being put into an in-vehicle kneader and heated and melted, a visually impaired person guiding line as shown in FIGS. 1 and 2 with a melting temperature of 180 to 210 ° C., a marking line width of 30 cm, and a length of 13 m using a special construction machine. The markings were applied to public road surfaces (asphalt pavement surface and concrete road surface) according to JIS T 9251, and the crack resistance and dent resistance of the coating film after 3 months were visually evaluated.
In addition, initial test results (15 ° C. crack resistance test, deformation resistance test) were also evaluated.

Evaluation methods for initial tests (15 ° C crack resistance test, deformation resistance test), crack resistance, and dent resistance are as follows.
15 ° C. crack resistance test: An indicator material melted at 200 ° C. was applied to a 100 × 300 × 1.5 mm aluminum plate to a width of 60 mm and a thickness of 5 mm to obtain a test plate. One end of the test plate was fixed at a measurement temperature of 15 ° C., bent around a 6 mm mandrel, and the coating was cracked. The amount of displacement at the bent end is shown.

Deformation resistance test: A sample of 20 mm × 20 mm × 20 mm was loaded with a weight of 2 kg, and the deformation resistance was tested at 80 ° C. for 60 minutes. (The larger the value, the better the deformation resistance)
Deformation resistance (%) = [height of sample after test (mm) / 20 (mm)] × 100

The physical properties of each component in Table 1-1 and Table 2-1 are shown below.
Acid-modified aliphatic petroleum resin (Marcaretz R-100GS)
Softening point: 96 ° C
Unmodified aliphatic petroleum resin (R-100)
Softening point: 96 ° C
Terpene phenol resin (YS Polystar S145)
Softening point: 145 ° C
Ethylene ethyl acrylate copolymer resin (NUC6070)
Ethyl acrylate content: 30% by mass
Softening point: 96 ° C
Melt index: 250 g / 10 min olefin copolymer elastomer (RT2330A, propylene / ethylene copolymer elastomer)
Softening point: 141 ° C
Melt viscosity at 200 ° C .: 2,500 mPa · s
Ethylene vinyl acetate copolymer resin (Ultrasen 720)
Melt index: 150 g / 10 min Softening point: 92 ° C.
Melt viscosity at 200 ° C .: 350 mPa · s
Reflective material (GB-153, glass beads)
Refractive index: 1.52
Particle size: 0.106-0.85mm

Criteria for crack resistance and dent resistance after construction

  The melt-type road marking material of the present invention (Examples 1 to 8) was excellent in crack resistance and dent resistance, and an improvement effect was obtained even over time. Those not using the thermoplastic resin and rubber elastic resin, which are essential components of the melt-type road marking material of the present invention (Comparative Example 1), the thermoplastic resin (Comparative Examples 2 and 3) in mass% outside the scope of the present invention, or It is not preferable that rubber elastic resin is used in combination (Comparative Examples 4 and 5) because of poor crack resistance and dent resistance. In Comparative Examples 6 and 7, a rubber elastic resin is used alone, and crack resistance and dent resistance are remarkably inferior.

It is a perspective view of an example of a road marking line formed using the fusion type road marking material of the present invention. It is AA sectional drawing of FIG.

Explanation of symbols

1 Base marking line 2 Convex rib

Claims (6)

  A melt-type road marking material used for forming a road marking coating film having protrusions on the surface, containing a thermoplastic resin having a softening point of 80 to 150 ° C., a rubber elastic resin and a filler, and a thermoplastic resin content Is 8.0 to 25.0 mass%, the content of the rubber elastic resin is 1.0 to 10.0 mass%, and the rubber elastic resin contains an ethylene ethyl acrylate copolymer resin and an olefin-based thermoplastic elastomer. A melt-type road marking material characterized by:   The melt type road marking material according to claim 1, wherein the rubber elastic resin has a softening point of 40 to 150 ° C.   The ethylene ethyl acrylate copolymer resin has an ethyl acrylate content of 20 to 40% by mass, a melt index of 200 to 1,200 g / 10 min, the olefinic thermoplastic elastomer is a propylene ethylene copolymer elastomer, and has a softening point of 120. The melt-type road marking material according to claim 1 or 2, wherein the melt viscosity at -150 ° C and 200 ° C is 1,500-9,000 mPa · s.   The melt type road marking material according to any one of claims 1 to 3, wherein the content of the filler in the molten type road marking material is 35 to 75 mass%.   Furthermore, the fusion type road marking material in any one of Claims 1-4 containing 10-30 mass% of reflective materials.   Furthermore, the melt type road marking material in any one of Claims 1-5 containing 0.5-3.0 mass% of plasticizers.

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