JPH11172193A - Thermal fusion type material for marking road surface-dividing line - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermal fusion type material used for marking road surface-dividing lines, containing a petroleum-based hydrocarbon resin binder, and exhibiting a low melt viscosity and good flowability at relative low temperature. SOLUTION: This thermal fusion type material for marking road surface- dividing line uses a non-modified or acid-modified petroleum resin as a binder. Therein, the non-modified or acid-modified petroleum resin comprises a hydrocarbon resin having a softening point of 60-130 deg.C and obtained by cationically copolymerizing a monoolefin with a 4-5C linear conjugated diene in the presence of an acidic metal halide catalyst in a polymerization solvent comprising a cycloolefin alone or a hydrocarbon mixture solvent containing the cycloolefin in an amount of >=5 wt.%, or the hydrocarbon resin into which carboxyl groups or acid an hydride groups have been introduced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat sealing type road marking line marking material containing a specific hydrocarbon resin as a binder. The heat fusion type road marking line marking material of the present invention has low melt viscosity and improved fluidity.

[0002]

2. Description of the Related Art Conventionally, thermoplastic resins and pigments are essential components used for marking road division lines such as pedestrian crossings, center lines, outer lines, and the like. A heat-sealing type material containing an antioxidant, an aggregate, glass beads and the like is used. As the thermoplastic resin component of such a heat fusion type material, a resin obtained by modifying a petroleum hydrocarbon resin with an unsaturated carboxylic acid or an anhydride thereof (for example, JP-B-50-39451, JP-B-57-28429). No., JP-A-62-212473
No. Gazette) has been awarded.

However, when applying the heat-sealing type marking line marking material to the road surface, the melt viscosity is set to be as short as possible in order to shorten the heating and melting time of the material as much as possible and to avoid thermal deterioration of the heated and melted material. Low, good flowability,
Materials that can be applied at relatively low temperatures are desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat seal type marking line marking material having a low melt viscosity and exhibiting good fluidity at a relatively low temperature.

The present inventors have proposed a petroleum hydrocarbon resin, particularly a hydrocarbon resin produced by cationically polymerizing a conjugated diene having 4 to 5 carbon atoms and a monoolefin using an acidic metal halide catalyst, or an acid thereof. As a result of repeated examination of the properties of the modified product as a binder, when cationic polymerization of a conjugated diene and a monoolefin is carried out using an aluminum chloride catalyst, a cycloolefin or cycloolefin is contained as a polymerization solvent in an amount of 5% by weight or more. By using a hydrocarbon mixed solvent, they have found that a hydrocarbon resin obtained as a result of polymerization and an acid-modified product thereof become a binder having more excellent properties, and based on this finding, have completed the present invention. Was.

[0006]

Thus, according to the present invention, there is provided a heat sealing type road marking line marking material comprising a petroleum resin as a binder, wherein the petroleum resin is composed of a monoolefin and a carbon It is obtained by cationically polymerizing a chain conjugated diene of Formulas 4 to 5 with a cycloolefin or a hydrocarbon mixed solvent containing 5% by weight or more of a cycloolefin as a polymerization solvent in the presence of an acidic metal halide catalyst. A heat fusion type road marking line marking material characterized by being a hydrocarbon resin having a softening point of 60 to 130 ° C.

Further, according to the present invention, there is provided a heat sealing type road marking line marking material comprising an acid-modified petroleum resin as a binder, wherein the acid-modified petroleum resin is a monoolefin and a C4 Softening obtained by cationically polymerizing a chain conjugated diene of 1 to 5 with a cycloolefin or a hydrocarbon mixed solvent containing 5% by weight or more of cycloolefin as a polymerization solvent in the presence of an acidic metal halide catalyst. A heat fusion type road marking line marking material is provided which is obtained by introducing a carboxyl group or an acid anhydride group into a hydrocarbon resin having a temperature of 60 to 130 ° C.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The heat-sealing type road marking line marking material of the present invention comprises a monoolefin and a chain conjugated diene having 4 to 5 carbon atoms in the presence of an acidic metal halide catalyst as a polymerization solvent. Cycloolefin or cycloolefin 5
A hydrocarbon resin having a softening point of 60 to 130 ° C., obtained by cationic polymerization using a hydrocarbon mixed solvent containing at least% by weight, or a resin obtained by introducing a carboxyl group or an acid anhydride group into the hydrocarbon resin It was blended as an agent.

Hydrocarbon Resin Binder In the present invention, the hydrocarbon resin used as a binder is prepared by using a cycloolefin alone or a mixed solvent of hydrocarbons containing at least 5% by weight of cycloolefin as an acidic halogenated solvent. A hydrocarbon resin having a softening point of 60 to 130 ° C. obtained by cationically polymerizing a monoolefin and a conjugated diene having 4 to 5 carbon atoms in the presence of a metal fluoride catalyst.

The polymerization solvent used in the production of the hydrocarbon resin is a cycloolefin alone, or a mixed solvent of a cycloolefin and another hydrocarbon. Specific examples of the cycloolefin include cyclohexene, methylcyclohexene, cyclopentene, methylcyclopentene and the like, and among them, cyclohexene and cyclopentene are preferable.

Specific examples of the hydrocarbon mixed with the cycloolefin include pentane, hexane, heptane,
Examples thereof include aliphatic hydrocarbons such as cyclopentane, cyclohexane, isopentane, and methylpentane; and aromatic hydrocarbons such as benzene, toluene, and xylene. In the present invention, any of them can be used. However, in consideration of the problem of environmental pollution, it is preferable to avoid aromatic hydrocarbons and use aliphatic hydrocarbons. Even when an aromatic hydrocarbon is not used as a solvent, generation of a large amount of gel can be avoided and a hydrocarbon resin having an excellent hue can be obtained.

The mixing ratio of cycloolefin to other hydrocarbons in the mixed solvent must be such that the cycloolefin content is at least 5% by weight. If the cycloolefin content is less than 5% by weight, the gel suppressing effect and the hue improving effect will be insufficient. Good results are also obtained when only cycloolefin is used as the polymerization solvent. The amount of the solvent to be used is usually 20 to 1,000 parts by weight, preferably 50 to 50 parts by weight, per 100 parts by weight of the monomer containing the monoolefin and the chain conjugated diene having 4 to 5 carbon atoms except for the cycloolefin.
５００500 parts by weight.

The monomer composition to be subjected to polymerization for the production of the hydrocarbon resin is a mixture of a monoolefin and a chain conjugated diene having 4 to 5 carbon atoms. Preferred specific examples of the chain conjugated diene having 4 to 5 carbon atoms include 1,3-pentadiene, isoprene, and 1,3-butadiene.
Specific examples of the monoolefin include chain monoolefins such as butenes, pentenes, methylbutenes, methylpentenes, and diisobutylene; aromatic monoolefins such as styrene and methylstyrene; and cyclopentene, methylcyclopentene, and cyclohexene. And cyclic monoolefins such as methylcyclohexene.

The ratio of the monoolefin except the cycloolefin to the chain conjugated diene having 4 to 5 carbon atoms is usually 94%.
/ 6 to 15/85 (weight ratio). A typical monomer mixture containing a monoolefin and a conjugated diene having 4 to 5 carbon atoms in this ratio is generally obtained as a naphtha cracking fraction at -20 to + 60 ° C or, if desired, various olefins can be added to this fraction. It is obtained by combining the unsaturated hydrocarbon fractions. Such commercially available monomer mixtures usually contain significant amounts of saturated hydrocarbons, such as butanes, pentanes, cyclopentane, etc.
The presence of these components does not interfere with the purpose of the present invention. Further, as long as the effects of the present invention are not substantially impaired, cyclopentadiene, a dimer thereof, a co-dimer of cyclopentadiene and a chain conjugated diene, and the like may be contained. It is preferable that a pentadiene-based monomer or the like is not substantially contained in the monomer mixture because it reduces the hue of the hydrocarbon resin.

The acidic metal halide catalyst used in the present invention is a Friedel-Crafts type catalyst, which is in a gaseous or solid state at room temperature. A typical example is a metal fluoride such as aluminum, boron or iron. Chloride, bromide and iodide, among which aluminum halides such as aluminum chloride and aluminum bromide are preferred. Aluminum halide is usually 5-
It is used as particles of 200 mesh size, but is not particularly limited. The amount of the catalyst used is usually based on the weight of the monomer.
0.1 to 10% by weight.

It is preferred that the acidic metal halide polymerization catalyst is brought into contact with a monocyclic monoolefin before polymerization. By the contact treatment with the monocyclic monoolefin, the effect of the present invention of preventing the formation of a gel and obtaining a resin having an excellent hue can be further enhanced. As the monocyclic monoolefin to be brought into contact with the acidic metal halide catalyst, a cyclic monoolefin having 5 to 6 carbon atoms is preferable, and specific examples thereof include cyclopentene, methylcyclopentene and cyclohexene, and among them, cyclopentene and cyclohexene are preferred. preferable. The amount of the monocyclic monoolefin contacted with the acidic metal halide catalyst is preferably at least 5 times (weight ratio) the amount of the catalyst.

The polymerization operation can be carried out by a known method,
An ordinary method of adding a solvent and a catalyst to a reactor in advance and adding a polymerization monomer may be used. The mixed solvent may be prepared in a predetermined ratio in advance into the reactor, or may be prepared by mixing both in the reactor. The polymerization temperature is usually
The temperature ranges from 20 ° C to + 100 ° C, preferably from 0 to + 80 ° C. The obtained polymer is treated by a conventional method and dried.

The hydrocarbon resin thus obtained is ASTM
JI having a Gardner chromaticity of 6 or less as measured by D-1544-63T, a number average molecular weight of 500 to 3,000, and 60 to 130C, preferably 70 to 120C.
It has a softening point specified in SK-2531 and is soluble in aliphatic and aromatic hydrocarbons such as pentane, hexane, benzene, toluene, xylene, chloroform, carbon tetrachloride or halogenated hydrocarbon solvents. And a resinous polymer having a low melt viscosity.

The petroleum-based hydrocarbon resin produced as described above can be used as it is for preparing a heat-sealing type road marking material, but in order to further improve the fluidity, an unsaturated carboxylic acid or It is preferable to introduce a carboxyl group or an acid anhydride group by treating with an unsaturated dicarboxylic acid anhydride. Specific examples of the unsaturated carboxylic acid used to introduce the carboxyl group include ethylenically unsaturated carboxylic acids having 8 or less carbon atoms such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid. And a Diels-Alder adduct of a conjugated diene such as 3,6-endomethylene-1,2,3,6-tetrahydrophthalic acid with an α, β-unsaturated dicarboxylic acid having 8 or less carbon atoms. Specific examples of the unsaturated dicarboxylic anhydride used for introducing the acid anhydride group include α, β-unsaturated dicarboxylic acids having 8 or less carbon atoms such as maleic anhydride, itaconic anhydride, citraconic anhydride, and itaconic anhydride. Diels-Alder addition of anhydrides and conjugated dienes such as 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride to α, β-unsaturated dicarboxylic anhydrides having 8 or less carbon atoms Things. From the viewpoints of easiness of reaction, economy and the like, α, β-unsaturated aliphatic dicarboxylic anhydride having 8 or less carbon atoms is preferable, and maleic anhydride is most preferable. These acid modifiers can be used alone or in combination of two or more.

The reaction between the petroleum resin and the unsaturated carboxylic acid or acid anhydride is usually carried out at a temperature of 50 to 300 ° C. for 5 minutes to 20 minutes.
Done for hours. If necessary, a diluent, an anti-gelling agent, a reaction accelerator and the like may be present. The amount of the unsaturated carboxylic acid or the acid anhydride used as the acid modifier in this reaction is generally 0.01 to 50 parts by weight based on 100 parts by weight of the hydrocarbon resin in consideration of the color of the obtained resin. .

The acid-modified petroleum hydrocarbon resin obtained by adding an unsaturated carboxylic acid or an anhydride thereof can be further modified if necessary. Specific examples of denaturing agents and denaturing reaction formats used for such denaturation include monohydric alcohols such as methanol, ethanol, propanol, butanol and allyl alcohol and polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol and glycerin. Esterification; Amidation with amines such as methylamine, ethylamine, diethylamine, triethylamine, ethanolamine, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine or ammonia; alkali metals such as sodium, potassium, calcium, magnesium or alkaline earth Salt formation by a class of metals.

Heat fusion type road marking line marking material The heat fusion type road marking line marking material is obtained by adding the above-mentioned unmodified or acid-modified hydrocarbon resin to a pigment which is an essential component and a plasticizer or glass beads as an optional component. Is prepared by blending

The pigment is appropriately selected from white pigments, coloring pigments and extender pigments used for ordinary road marking lines, such as calcium carbonate, zinc oxide, titanium oxide and silica sand. The amount of the pigment is usually 50 to 800 parts by weight per 100 parts by weight of the petroleum hydrocarbon resin. Further, an appropriate amount of glass beads can be blended to improve the reflectivity of the lane marking.

Further, a plasticizer can be added to the heat-sealing type road marking line marking material of the present invention. Specific examples of the plasticizer include natural oils such as linseed oil, cottonseed oil, soybean oil, and castor oil; ester synthetic oils such as phthalic acid ester and adipic acid ester; and polymer oils such as polybutene oil, polybutadiene oil, and polypentadiene oil. Liquid resins such as liquid hydrocarbon resins, liquid terpene resins, and liquid rosins; mineral oils such as naphthene-based process oils, aromatic process oils, and paraffin-based process oils; and alkyd resins and xylene resins. In consideration of the viscosity and fluidity of the road marking line marking material, the amount of
It is selected from the range of 3 to 30 parts by weight per 00 parts by weight.

The preparation of the road marking line marking material and the application to the road surface can be performed in the same manner as the conventional road marking line marking material containing a petroleum resin binder.

[0026]

EXAMPLES Hereinafter, the traffic paint composition of the present invention will be specifically described with reference to examples. In Examples and Comparative Examples, all parts and percentages are by weight.
In the Examples and Comparative Examples, the properties of the traffic paint composition were evaluated by the following methods.

(1) Fluidity An inner diameter of 30 mm and a depth of 50 having a hole of 8 mm in the bottom.
using a jig called a Ford cup with a handle for holding by hand in a stainless steel container of 150 mm.
Fill formulation adjusted to ° C. into Ford cup until full. From when I lifted the Ford Cup,
The fluidity was evaluated by measuring the time (unit: seconds) required to see the hole at the bottom of the Ford cup from above.

(2) Melt Viscosity The blend was heated and melted at about 200 ° C. for 30 minutes to form a uniform mixture. The melt viscosity (unit: cps) was measured at two points.

(3) Aggregate sedimentation The mixture heated and mixed at 200 ° C. is placed in a 100 cc glass beaker and placed in an oven adjusted to 150 ° C.
After standing for a while, cool and cut the solidified composition in the vertical direction, measure the thickness of the upper layer that does not contain aggregates such as glass beads, coarse calcium carbonate, etc. The settling property of the aggregate was evaluated by indicating the percentage.

(4) Compression strength Using a Tensilon compression strength meter (Instron type), a compression test is performed under the conditions of a compression speed of 30 mm / min and a temperature of 20 ° C. to obtain a compression strength unit (unit: kgf / cm ² ). evaluated. (5) Yellowness The yellowness was measured according to the method defined in JIS K-5665.

Polymerization Example 1 In an autoclave made of SUS, 1.0 part of aluminum chloride was added.
And 30.5 parts of cyclopentene and cyclopentane 5
6.7 parts were mixed and the whole amount of the mixed solvent was added, and the mixture was stirred to maintain the temperature of the system at 60 ° C. for 10 minutes. Next, 112.8 parts of a monomer mixture having the following composition (the total amount of 1,3-pentadiene, cyclopentene and diisobutylene was 100 parts) was gradually added to the above solution continuously over 60 minutes.

Monomer mixture 1,3-pentadiene 49.7 parts by weight 44.1% Cyclopentene 15.3 parts by weight 13.6% Diisobutylene 35.0 parts by weight 31.0% C _4-6 unsaturated hydrocarbon 3.9 parts by weight 3.5% C _4-6 saturated hydrocarbon 8.9 parts by weight 7.9%

Since the temperature of the system rises due to the heat generated by the reaction, the heating temperature was adjusted to maintain the internal temperature at 70 ° C. After completion of the addition, the polymerization system was maintained at 70 ° C. and stirred for further 10 minutes, and then an equal volume mixture of methanol and 28% aqueous ammonia was added to decompose aluminum chloride. The catalyst particles deactivated by the decomposition were removed by filtration, the filtrate was transferred to a glass flask, and heated while blowing in nitrogen to distill off unreacted hydrocarbons, and then heated to 240 ° C. . Next, saturated steam was blown into the system to remove the liquid polymer generated by the polymerization reaction, and after confirming that almost no oil layer was present in the distillate, the blowing of steam was stopped to stop the molten residue. Was taken out and cooled to room temperature to obtain a yellow resinous substance (hydrocarbon resin A).

With respect to the obtained hydrocarbon resin A, the resin yield (1,3- in the cycloolefin and monomer mixture)
Yield based on the total weight of pentadiene, cyclopentene, styrene and diisobutylene), softening point (JIS K-
2531), weight-average molecular weight and number-average molecular weight (both average molecular weights are measured by gel permeation chromatography,
(Converted to standard polystyrene), and Gardner chromaticity (measured by ASTM D-1544-63T and expressed as a measured value for a solution obtained by dissolving a hydrocarbon resin in an equal amount of toluene). Table 1 shows the results.

Polymerization Examples 2 and 3 (Preparation of Hydrocarbon Resins B and C) The same operations as in Polymerization Example 1 were carried out except that the solvents and monomer mixtures shown in Table 1 were used. C was obtained.

Comparative Polymerization Example 1-3 (Hydrocarbon resins D, E,
Preparation of F) The same operation as in Polymerization Example 1 was carried out using benzene as a solvent and the monomer mixture shown in Table 1 to obtain a hydrocarbon resin D,
E and F were obtained.

[0037]

[Table 1]

In Table 1, the resins obtained in Polymerization Examples 1 and 2 and the resins obtained in Comparative Polymerization Examples 1 and 2 are resins having substantially the same softening point. However, the resins obtained in Polymerization Examples 1 and 2 using a hydrocarbon mixed solvent containing a monocyclic monoolefin have a smaller weight average molecular weight than the resins of Comparative Polymerization Examples 1 and 2 using a benzene solvent. It is clear that it is. Similar results were obtained when styrene was copolymerized (Comparison between Polymerization Example 3 and Comparative Polymerization Example 3 in Table 1).

Modified Example 1-3, Comparative Modified Example 1-3 (Acid Modification of Hydrocarbon Resin) To 100 parts of the hydrocarbon resin obtained in Polymerization Example 1-3, 0.4 part of maleic anhydride was added. The reaction was carried out at a temperature of 1 ° C. for 1 hour to obtain maleated hydrocarbon resins G, H and I. For comparison, maleic anhydride was also reacted with the hydrocarbon resin obtained in Comparative Polymerization Example 1-3 to prepare maleated hydrocarbon resins J, K, and L. -3
And Table 2 shows the properties of each resin.

[0040]

[Table 2]

Example 1-3, Comparative Example 1-3 (Preparation and Evaluation of Heat-Sealable Marking Line Marking Material) Modified Example 1-3 and Comparative Modified Example 1-3 for comparison. Using a maleated hydrocarbon resin and a plasticizer and a pigment in accordance with the following formulation,
The mixture was heated and melted for 0 minutes to obtain a uniform heat-fusible lane marking composition. The composition prepared in this manner is subjected to JIS K-
Tests were conducted by various physical property test methods such as the method specified in 5665, and the performance was evaluated. Table 3 shows the results.

Blending composition Modified hydrocarbon resin 12 parts Heavy calcium carbonate 26 parts Granulated calcium carbonate 40 parts Titanium dioxide 5 parts Glass beads 15 parts Plasticizer (equivalent mixture of soybean oil and soybean oil-modified alkyd) 2 parts

[0043]

[Table 3]

Example 4 and Comparative Example 4 (Preparation and Evaluation of Material for Marking Heat-Sealable Section Line) Using Polymerized Example 1 and the unmodified hydrocarbon resin obtained in Comparative Polymerized Example 1 for comparison. It was blended with a plasticizer, a pigment and the like according to the blending recipe shown below, and was heated and melted at about 200 ° C. for 30 minutes to obtain a uniform blend. The composition thus prepared was tested by the physical property test method described above, and its performance was evaluated. Table 4 shows the results.

Blending composition Modified hydrocarbon resin 16 parts Heavy calcium carbonate 24 parts Coarse calcium carbonate 38 parts Titanium dioxide 5 parts Glass beads 15 parts Plasticizer (equivalent mixture of soybean oil and soybean oil-modified alkyd) 2 parts

[0046]

[Table 4]

[0047]

As compared with the conventional heat-sealing type road marking line marking material containing a petroleum-based hydrocarbon resin binder, the heat-sealing method containing a specific petroleum-based hydrocarbon resin binder of the present invention is used. The mold road marking material has a low melt viscosity and exhibits good fluidity at relatively low temperatures. Therefore, the heat-fusible road marking line marking material of the present invention has good workability and the resin material is less thermally degraded.

(Preferred Embodiment of the Invention) The heat-sealing road marking line material of the present invention, that is, a heat-fusing road marking line obtained by blending an unmodified or acid-modified petroleum resin as a binder. Material, wherein the unmodified or acid-modified petroleum resin is prepared by converting a monoolefin and a chain conjugated diene having 4 to 5 carbon atoms in the presence of an acidic metal halide catalyst.
Softening point 60 to 13 obtained by cationic polymerization using a cycloolefin alone or a hydrocarbon mixed solvent containing 5% by weight or more of cycloolefin as a polymerization solvent.
A preferred embodiment of a heat-fusible road marking line marking material characterized by being a hydrocarbon resin at 0 ° C., or a material obtained by introducing a carboxyl group or an acid anhydride group into the hydrocarbon resin, is summarized below. It is as follows.

1. The cycloolefin is cyclohexene or cyclopentene. 2. The hydrocarbon mixed with the cycloolefin is an aliphatic hydrocarbon. 3. The chain conjugated diene having 4 to 5 carbon atoms is at least one selected from 1,3-pentadiene, isoprene and butadiene. 4. The monoolefin to be copolymerized with the chain conjugated diene having 4 to 5 carbon atoms is at least one selected from monoolefinically unsaturated hydrocarbons having 4 to 10 carbon atoms.

5. Monoolefin to be copolymerized with a chain conjugated diene having 4 to 5 carbon atoms is selected from butenes, pentenes, methylbutenes, methylpentenes, diisobutylene, cyclopentene, cyclohexene, methylcyclopentenes, styrene and methylstyrenes At least one kind. 6. The ratio between the monoolefin and the conjugated diene having 4 to 5 carbon atoms is 94/6 to 15/85 (weight ratio). 7. The acidic metal halide catalyst is an aluminum, boron or iron fluoride, chloride, bromide or iodide, more preferably an aluminum halide.

8. Prior to polymerization, the acidic metal halide catalyst is contacted with a monocyclic monoolefin at least 5 times (by weight) the catalyst. 9. In the above item 8, the monocyclic monoolefin contacted with the acidic metal halide catalyst is a cyclic monoolefin having 5 to 6 carbon atoms, more preferably cyclopentene or cyclohexene. 10. The softening point of the hydrocarbon resin produced by polymerization is 70
~ 120 ° C.

11. A binder, a hydrocarbon resin produced by polymerization, a Diels-Alder adduct of an ethylenically unsaturated carboxylic acid having 8 or less carbon atoms, a conjugated diene and an α, β-unsaturated dicarboxylic acid having 8 or less carbon atoms, Acid modification selected from α, β-unsaturated dicarboxylic anhydride having 8 or less carbon atoms and Diels-Alder adduct of conjugated diene and α, β-unsaturated dicarboxylic anhydride having 8 or less carbon atoms A carboxyl group or an acid anhydride group is introduced by treating with at least one agent. 12. The heat sealable road marking line marking material contains 50 to 800 parts by weight of a pigment selected from a white pigment, a colored pigment and an extender pigment per 100 parts by weight of the petroleum hydrocarbon resin. 13. The heat sealable road marking line marking material contains 3 to 30 parts by weight of a plasticizer per 100 parts by weight of petroleum hydrocarbon resin.

Claims (2)

[Claims] 1. A heat sealing type road marking line marking material comprising a petroleum resin as a binder, wherein the petroleum resin is
Monoolefin and a chain conjugated diene having 4 to 5 carbon atoms are cationically polymerized in the presence of an acidic metal halide catalyst using a cycloolefin or a hydrocarbon mixed solvent containing 5% by weight or more of a cycloolefin as a polymerization solvent. A heat fusion type road marking line marking material, which is a hydrocarbon resin having a softening point of 60 to 130 ° C. obtained as described above. 2. A heat sealing type road marking line marking material comprising an acid-modified petroleum resin as a binder, wherein the acid-modified petroleum resin is a monoolefin and a chain having 4 to 5 carbon atoms. Softening point 60-130 ° C obtained by cationic polymerization of conjugated diene with cycloolefin or a hydrocarbon mixed solvent containing 5% by weight or more of cycloolefin as a polymerization solvent in the presence of an acidic metal halide catalyst. A heat fusion type road marking line marking material, characterized in that a carboxyl group or an acid anhydride group is introduced into the above hydrocarbon resin.