JPS6337149B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composition for traffic paint, and more particularly, it relates to a composition for traffic paint, and more specifically, a composition prepared from a specific aliphatic unsaturated hydrocarbon-containing fraction and an internal olefin-containing fraction containing a specific aliphatic internal olefin as a main component. The present invention relates to a composition for traffic paint containing a modified hydrocarbon resin obtained by polymerizing and modifying a mixed distillate as a tackifying agent. Traditionally, in the field of traffic painting,
It is known that natural rosin resins such as rosin or modified products thereof, alkyd resins, xylylene resins, epoxy resins, etc. can be used as tackifiers. Among these tackifier resins, rosin-based resins such as maleated rosin are said to be the most superior, but these rosin-based resins rely on natural products for their raw materials, so they have become less popular in recent years. Unable to cope with significant demand growth. Hydrocarbon resins, which can be produced industrially at low cost and easily, are attracting attention as tackifiers that can replace conventional rosin-based resins, and many hydrocarbon resins have been proposed. In general, hydrocarbon resins include aromatic hydrocarbon resins produced from fractions containing aromatic unsaturated hydrocarbons, aliphatic hydrocarbon resins produced from fractions containing aliphatic hydrocarbons, and unsaturated There are aliphatic aromatic copolymerized hydrocarbon resins made by copolymerizing hydrocarbon-containing fractions, and each type is used for its appropriate purpose. Even when these hydrocarbon resins are used as tackifiers for hot-melt traffic paint compositions, they all have the following drawbacks. For example, when an aromatic hydrocarbon resin or a modified product thereof is used as a tackifying agent, the resin has a high softening point and a low melt viscosity, and also has excellent settling properties of the filler in the composition, resulting in the formation of a coating film. Although it has excellent stain resistance and compressive strength, it has the drawback of poor heat resistance stability of the composition and weather resistance of the coating film, and easy yellowing. On the other hand, when a conventional aliphatic hydrocarbon resin or its modified product is used as a tackifying agent, the composition has excellent heat resistance stability and the coating film has excellent weather resistance stability, and the color is excellent; however, the tackifying agent The disadvantages are that the melt viscosity of the resin is high, the filler sedimentation of the composition is large, and hair cracks are likely to occur in the coating film.
In addition, in conventional aliphatic hydrocarbon resins, if the melt viscosity of the resin is lowered, the softening point inevitably decreases, and as a result, the heat resistance, compressive strength, and stain resistance of the composition and coating film decrease. On the other hand, if an attempt is made to improve the performance of the composition or coating film, the melt viscosity of the resin increases. Therefore, recently, 1,3-pentadiene, isoprene, butadiene, 2-methyl-2-butene, diisobutylene, or two or more of these are used as aliphatic hydrocarbon resins with a high softening point and low melt viscosity. Aliphatic hydrocarbon resins obtained by polymerizing a mixture in the presence of a Friedel-Crafts type catalyst have also been proposed. However, this aliphatic hydrocarbon resin is produced by separating unsaturated components from aliphatic unsaturated hydrocarbon-containing fractions produced by thermal decomposition of petroleum by extraction, extractive distillation, distillation, or other methods. must be used as a raw material, the cost of the resulting resin naturally increases, and it is difficult to say that it is economically efficient. On the other hand, hydrocarbon resins have also been proposed that improve the respective disadvantages of the aliphatic hydrocarbon resins and aromatic hydrocarbon resins by using copolymerized hydrocarbon resins of aliphatic and aromatic types. ing. However, when a normal aliphatic unsaturated hydrocarbon-containing fraction and an aromatic unsaturated hydrocarbon-containing fraction are copolymerized, the hydrocarbon resin that can be used as a tackifying agent in a traffic paint composition is From the viewpoint of the softening point and melt viscosity of the resin, a combination of an aliphatic type and an aromatic type containing an aliphatic unsaturated hydrocarbon component as a main component and a small amount of an aromatic unsaturated hydrocarbon component is recommended. Limited to polymerized hydrocarbon resins or copolymerized hydrocarbon resins of aliphatic and aromatic types that contain an aromatic unsaturated hydrocarbon component as a main component and a small amount of aliphatic unsaturated hydrocarbon component. It is being However, with these aliphatic and aromatic copolymerized hydrocarbon resins, it is not possible to sufficiently improve the above-mentioned drawbacks of the aliphatic hydrocarbon resins or the aromatic hydrocarbon resins. Can not. The present inventors have improved the above-mentioned drawbacks of conventional hydrocarbon resins, have a high softening point and low melt viscosity, and have achieved caking of a composition for hot-melt traffic paint. As a result of studying hydrocarbon resins that can exhibit excellent performance in compositions and coatings when blended as agents, we found that aliphatic unsaturated hydrocarbon-containing fractions with specific compositions and aliphatic unsaturated hydrocarbon-containing fractions with specific compositions The above object is achieved by modifying the hydrocarbon resin obtained by polymerizing a mixed fraction consisting of an internal olefin-containing fraction containing internal olefin as a main component in the presence of a Friedel-Crafts catalyst. It was discovered that an aliphatic hydrocarbon resin can be obtained, and the present invention was achieved. The aliphatic hydrocarbon resin obtained by the present invention has good hue, heat resistance stability, and weather resistance stability, does not contain gel-like resin, has a high softening point, and has a low melt viscosity. This resin is used in hot-melt traffic paint compositions in modified states such as carboxylation modification, acid anhydride modification, and esterification modification. A traffic paint composition containing this modified aliphatic hydrocarbon resin as a tackifying agent has excellent filler settling properties, turning properties, and heat resistance stability, and the coating film obtained from the composition is It has excellent weather resistance, stain resistance and compressive strength, and is characterized by suppressing the occurrence of hair cracks. To summarize the present invention, the present invention provides (a) a boiling point of −10
It is a fraction in the range of 100°C to +100°C, and the 1,3-conjugated diene component in the total unsaturated components is 30 mol% or more, the terminal monoolefin component is 30 mol% or less, and the cyclopentadiene component is 5 mol. % or less, and (b) an aliphatic internal olefin component containing dihydrodicyclopentadiene in at least 80 mol % of the total unsaturated components. A fraction containing an aliphatic internal olefin in which the terminal monoolefin component is 15 mol % or less and the cyclopentadiene component is 5 mol % or less, and 1,3 mol % of the unsaturated components in the mixed fraction - Conjugated diene component is 10
The aliphatic internal olefin component containing at least dihydrodicyclopentadiene is in the range of 40 to 90 mol%, the terminal monoolefin component is in the range of 25 mol% or less, and the cyclopentadiene component is 5 mol%. % or less, this mixed fraction is polymerized in the presence of a Friedel-Crafts type catalyst, and then a modified hydrocarbon resin is blended as a tackifying agent. The gist is a composition for traffic paint. The polymerization raw materials used in the present invention are an aliphatic unsaturated hydrocarbon-containing fraction (a) with a specific composition and an internal olefin-containing fraction (b) whose main component is aliphatic internal olefin with a specific composition. It is a mixed fraction consisting of The aliphatic unsaturated hydrocarbon-containing fraction (a)
is a fraction with a boiling point in the range of -20 to +100℃, and the 1,3-conjugated diene component in the total unsaturated components is
In the range of 20 mol% or more, the terminal monoolefin component is
It is an aliphatic unsaturated hydrocarbon-containing fraction in which the cyclopentadiene component is in the range of 30 mol% or less and the cyclopentadiene component is in the range of 5 mol% or less. More preferably, the aliphatic unsaturated hydrocarbon-containing fraction (a) has a boiling point of -
It is a fraction in the range of 10 to +50℃, the 1,3-conjugated diene component in the total unsaturated components is in the range of 30 mol% or more, the terminal monoolefin component is in the range of 20 mol% or less, and the cyclopentadiene component is 3 It is a fraction containing aliphatic unsaturated hydrocarbons in the range of mol % or less. Specifically, the 1,3-conjugated diene component contained as a main component in the aliphatic unsaturated hydrocarbon-containing fraction includes 1,3-butadiene, 1,3-
Examples include pentadiene and isoprene. In addition to the 1,3-conjugated diene component, the unsaturated hydrocarbon components contained in the aliphatic unsaturated hydrocarbon-containing fraction include 2-butene,
Aliphatic internal olefins such as 2-methyl-2-butene, 2-pentene, and cyclopentene; terminal monoolefins such as 1-butene, isobutylene, 1-pentene, 2-methyl-1-butene, and 3-methyl-1-butyne; Olefin, cyclopentadiene and other olefins may be contained within the above range. Further, the aliphatic unsaturated hydrocarbon-containing fraction (a) may contain an aliphatic saturated hydrocarbon component within the boiling point range described above in addition to the unsaturated component. In this case, the content of all unsaturated components in the aliphatic unsaturated hydrocarbon-containing fraction is arbitrary, but is usually in the range of 30% by weight or more, preferably 40% by weight or more. Further, as the aliphatic unsaturated hydrocarbon-containing fraction, the 1,3-
A single conjugated diene component or a mixture of two or more types of conjugated dienes can be used, or a mixed component of the 1,3-conjugated diene and the unsaturated component can be used as long as the composition falls within the above-mentioned composition range. . The aliphatic unsaturated hydrocarbon-containing fraction (a) is an aliphatic unsaturated hydrocarbon-containing fraction, if the unsaturated fraction with the boiling point range produced by thermal decomposition of petroleum has the composition range described above. The fraction can be used as is. In addition, if this unsaturated hydrocarbon-containing fraction has a large composition of terminal monoolefin components or cyclopentadiene components, after heat soaking this unsaturated hydrocarbon-containing fraction by a known method,
The aliphatic unsaturated hydrocarbon-containing fraction can be obtained by collecting the fraction within the boiling point range. In addition, when the composition of the 1,3-conjugated diene component contained in this unsaturated hydrocarbon-containing fraction is small, the 1,3-conjugated diene component is added to this unsaturated hydrocarbon-containing fraction. The aliphatic unsaturated hydrocarbon-containing fraction may also be used. The aliphatic internal olefin-containing fraction (b) used in the present invention has a range in which the aliphatic internal olefin component containing at least dihydrodicyclopentadiene in the total unsaturated components is 80 mol% or more, It is an aliphatic internal olefin-containing fraction in which the terminal monoolefin component is in the range of 15 mol% or less and the cyclopentadiene component is in the range of 5 mol% or less, and more preferably at least in the total unsaturated components. Contains an aliphatic internal olefin in which the aliphatic internal olefin component containing dihydrodicyclopentadiene is 85 mol% or more, the terminal monoolefin component is 10 mol% or less, and the cyclopentadiene component is 3 mol% or less. It is a distillate. The aliphatic internal olefin contained in the aliphatic internal olefin-containing fraction includes linear aliphatic internal olefins and alicyclic internal olefins, and specifically includes dihydrodicyclopentadiene. Other examples include 2-butene, 2-methyl-2-butene, 2-pentene, and cyclopentene. In addition to the aliphatic internal olefin, the unsaturated components contained in the aliphatic internal olefin-containing fraction include:
Terminal monoolefins such as -butene, isobutylene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, cyclopentadiene and other olefins may be contained within the above range. Further, in addition to the aliphatic unsaturated hydrocarbon component, an aliphatic saturated hydrocarbon component may be contained. In that case, the content of all unsaturated components in the aliphatic internal olefin-containing fraction is arbitrary, but is usually in the range of 30% by weight or more, preferably 40% by weight or more. Specifically, the aliphatic internal olefin-containing fraction (b) is, for example, an aliphatic product produced by thermal decomposition of petroleum and having a boiling point usually in the range of -10 to +100°C, preferably 20 to 50°C. By contacting the unsaturated hydrocarbon-containing fraction and hydrogen in the presence of a hydrogenation catalyst, the diene component is partially hydrogenated to internal olefins, the terminal monoolefins are isomerized to internal olefins, and the aliphatic internal olefins are A containing fraction is obtained. Usual hydrogenation catalysts are used as hydrogenation catalysts, specifically palladium, rhodium, ruthenium, platinum, iridium,
Osmium, iron, cobalt, nickel, chromium,
Examples include metals such as molybdenum and tungsten, and catalysts in which these metals are supported on various carriers such as activated carbon, alumina, and silica.
In addition, in order to suppress further hydrogenation and disappearance of the isomerized internal olefin, it is also preferable to use a catalyst partially poisoned with a sulfur compound or the like as the metal catalyst. is generally reacted under pressure, usually 1 to 150 kg/
cm ² -G, preferably in the range of 5 to 50 Kg/cm ² -G. The temperature during the reaction is usually room temperature to 200℃,
Preferably it is in the range of 40 to 150°C. The composition of the fraction obtained by this partial hydroisomerization treatment usually satisfies the above composition range, and can be used as is as the aliphatic internal olefin-containing fraction. A mixed fraction consisting of the aliphatic unsaturated hydrocarbon-containing fraction (a) and the internal olefin-containing fraction (b) whose main component is the aliphatic internal olefin, which is the polymerization raw material used in the present invention. The composition is such that the 1,3-conjugated diene component is in the range of 10 to 60 mol%, the aliphatic internal olefin component is in the range of 40 to 90 mol%, and the terminal monoolefin component is in the range of 1 to 60 mol%. It is necessary that the cyclopentadiene component is in the range of 25 mol% and the cyclopentadiene component is in the range of 5 mol%, and more preferably the 1,3-conjugated diene component in the total unsaturated components therein is in the range of 15 to 50 mol%. , a mixed fraction in which the terminal monoolefin component is in the range of 20 mol% or less and the cyclopentadiene component is in the range of 3 mol% or less. Here, if the 1,3-conjugated diene component in the total unsaturated components in the mixed fraction becomes more than 60 mol% and the aliphatic olefin component becomes less than 10 mol%, the resulting hydrocarbon resin Regarding physical properties, the melt viscosity becomes significantly high, and gel-like substances are more likely to be produced as by-products. In addition, when the 1,3-conjugated diene component in the total unsaturated components is less than 20 mol% and the aliphatic internal olefin component is more than 80 mol%, the physical properties of the resulting hydrocarbon resin may be affected by increasing the softening point. be unable to do so. Furthermore, if the terminal monoolefin component in the total unsaturated components in the mixed fraction exceeds 10 mol %, the resulting hydrocarbon resin will have a low softening point. Furthermore, if the cyclopentadiene component in the total unsaturated components in the mixed fraction exceeds 5 mol %, the resulting hydrocarbon resin will produce more gel-like insoluble resin and will have a lower hue. In the present invention, the mixed fraction of polymerization raw materials is polymerized in the presence of a Friedel-Crafts type catalyst. Here, specific examples of Friedel-Crafts type catalysts include aluminum chloride, aluminum bromide, boron trifluoride, various complexes of boron trifluoride, tin chloride, tin bromide, antimony chloride, Examples include antimony bromide and titanium chloride. Among these Friedel-Crafts type catalysts, it is preferable to use aluminum chloride because it provides a hydrocarbon resin with a high yield, good hue, and high softening point. The proportion of the Friedel-Crafts type catalyst used is usually 0.1 to 10% of the total unsaturated components in the mixed fraction of the polymerization raw material.
mol %, preferably in the range of 0.5 to 2 mol %. In the present invention, the polymerization reaction of the polymerization raw material in the presence of a Friedel-Crafts type catalyst can be carried out in the absence of a solvent or in the presence of a solvent. Specifically, when carrying out in the presence of a solvent, the solvent used is:
Examples include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane, and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, cymene, and diisopropylbenzene. When a solvent is used, its proportion is usually in the range of 0.05 to 1, preferably 0.1 to 0.5 as a weight ratio to all unsaturated components in the mixed fraction. The polymerization reaction is usually carried out at a temperature ranging from -10 to +150°C, preferably from 10 to 120°C. The time required for the polymerization reaction varies depending on the catalyst used, reaction temperature and other conditions, but is usually in the range of 1 to 5 hours. A hydrocarbon resin is obtained by treating the reaction mixture after the completion of the polymerization reaction by conventional methods such as catalyst decomposition treatment, deashing treatment, and solvent distillation treatment, which is then subjected to carboxylation modification, acid anhydride modification, Alternatively, the desired hydrocarbon resin modified product can be obtained by performing modification such as esterification modification. Next, the present invention will be specifically explained using examples. The method for evaluating the physical properties and performance of hydrocarbon resins is shown below. [Method for evaluating resin physical properties] (1) Method for measuring softening point Softening point was measured by the method of JIS K-2531. (2) Melt viscosity measurement method: Use an EMILA rotational viscometer manufactured by EMILA (Denmark) at a temperature of 200℃ and a shear rate.
Measured at 344sec ^-1 . (3) Compatibility with other polymers Ethylene-vinyl acetate copolymer, natural rubber,
The compatibility of the styrene-isoprene-styrene block copolymer with modified rosin was measured by the following method, and the results were evaluated in the following three stages. 〇: Transparent, △: Translucent, ×: Opaque (i) Mitsui Polychemical Product Evaflex 410
(vinyl acetate content 19% by weight) or 210 (vinyl acetate content 19% by weight)
28% by weight) and hydrocarbon resin in equal amounts.
The mixture was mixed on a hot plate at 180°C and coated on a polyester film to a thickness of about 1 mm, and the transparency of the coating film was evaluated. (ii) Hydrocarbon resin in an amount equal to that of natural rubber was dissolved in a 10% solution of natural rubber in toluene, and this was applied onto a polyester film to a thickness of approximately 80 μm, and the transparency of the coating film was evaluated. . (iii) Compatibility with styrene-isoprene-styrene block copolymer (Ciel Chemical TR-1107) was measured in the same manner as in (ii). (iv) Modified rosin commercially available for traffic paint (maleated ester type; melting point 94°C, acid value 24, melt viscosity 150 cps)
and hydrocarbon resin were placed in equal amounts in test tubes, dissolved and mixed on a 180°C oil bath, and the mixture was cooled to room temperature, and its transparency was evaluated. (4) Heat resistance Put 25g of hydrocarbon resin in a test tube with an inner diameter of 15mm and a length of 180mm, heat it in an oil bath at 200℃ for 3 hours,
Hue was measured by the Gardner method. [Evaluation method for traffic paint] (1) Softening point: According to the method of JIS K-5665 (2) Melt viscosity: Using an Emirr type rotational viscometer, shear rate
Measured on a 200°C melt at 176/sec (3) Fluidity: Stir the 200°C melt and use a metal ladle (31 mm diameter,
Quickly scoop out a portion at a depth of 24 mm, pour it onto a smooth aluminum plate from a height of 30 mm, measure the long and short axes of the hardened disk on the plate, and take the average value. It was defined as fluidity. (4) Compressive strength: According to the method of JIS K-5665 (5) Filler settling property: Fill a 50ml beaker with the unmolten mixture,
After being left at 240° C. for 2 hours, it was cooled and cured, and the sedimentation rate of the filler on the vertical cut surface of the cured product was measured. (6) Paint film whiteness: A test piece was prepared according to the method described in JIS K-5665 5 to 6, and it was
The a and b values were each measured, and the whiteness (W%) was calculated from these values. W=100−[(100−L) ² +a ² +b ² ] ^1/2 (7) Post-accelerated whiteness: The test piece used for coating film whiteness measurement was accelerated for 100 hours using a Sunshine Weather-Ometer. After that, the whiteness was measured and defined as the whiteness after acceleration. Reference Example 1 6 A catalyst charging basket made of wire mesh is fixed in advance to the stirring blade of an autoclave (made of SUS304). Inside this basket is a palladium-based catalyst manufactured by Engelhunt Japan.
Add 284g of PGS-C. Next, 2100g of _C5 fraction obtained by thermal decomposition of naphtha is placed in an autoclave.
and 1.8 ml of ethyl mercaptan. Then add hydrogen from a hydrogen cylinder at a temperature of 90 to 100℃ and a pressure of 10℃.
The reaction was carried out at ~20 Kg/cm ² for about 9 hours. After cooling and depressurizing, the internal solution was taken out. This hydrogenation reaction solution is A
The compositions of the fractions and raw materials are shown in Table 1. Reference Example 2 A spent _C5 fraction (the remaining fraction after isobrene was extracted from the _C5 fraction) was treated under the same conditions as in Reference Example 1. This hydrogenation reaction solution was designated as fraction B, and its composition is shown in Table 2 along with the raw materials.

【table】

【table】

[Table] Polymerization example 1 1,3- with isoprene and pentane removed
The composition of the pentadiene fraction is shown in Table 3. This fraction is designated as C fraction. 108g of this C fraction (polymerization component
75 g) and 124 g of fraction A (polymerization component 75 g) prepared in Reference Example 1 were mixed in a pressure cylinder. Table 5 shows the composition of the mixed fraction. In advance, 2.0 g of anhydrous aluminum chloride pulverized product and 15 g of xylylene were suspended in a glass autoclave under a nitrogen atmosphere. From the pressure cylinder, set the reaction temperature to 60℃.
The mixed fraction was added dropwise over approximately 20 minutes while maintaining the temperature at °C. After polymerizing for 2 hours, the catalyst was decomposed with methanol, washed with water, and concentrated to obtain resin 71.
I got g. Softening point 94℃, melt viscosity 80cps, hue 6
It was hot. Polymerization Example 2 A fraction having a boiling point in the range of 20 to 50°C obtained by thermal decomposition of naphtha was heat soaked in an autoclave at 140°C for 3 hours, and the composition of the distillate obtained by distillation is shown in Table 4. This fraction is designated as the D fraction. 152g of this distillate (polymerization component 75g) and Reference Example 1
124 g of the product (75 g of polymerization component) were mixed in a pressure cylinder (the composition of the mixed fraction is shown in Table 5). 1. In a glass autoclave, 2.0 g of AlCl ₃ pulverized product is suspended in 15 g of hexane under a nitrogen atmosphere, and the mixed fraction is added dropwise from a pressure cylinder over about 15 minutes while maintaining the temperature at 60°C. 2
After reacting for a period of time, the catalyst was decomposed with methanol, and 68 g of resin was obtained by washing with water and concentrating as usual. softening point
The temperature was 94.5°C, the melt viscosity was 100 cps, and the hue was 6.

【table】

[Table] Polymerization example 3 1,3-butadiene manufactured by Tokyo Kasei Co., Ltd. (purity 99%)
above) 17g and 220g of A fraction prepared in Reference Example 1
(133 g of polymeric components) were mixed in a pressure cylinder. The composition of the mixed fraction is shown in Table 5. 1 in advance
Dilute 2.0 g of ethylaluminum dichloride with 30 g of hexane in a glass autoclave under a nitrogen atmosphere. The mixed fraction was added dropwise to the mixture from a pressure cylinder over approximately 20 minutes while maintaining the reaction temperature at 60°C. After polymerization for 2 hours, the catalyst was decomposed with methanol in a conventional manner, washed with water, and the polymerized oil was concentrated to obtain 56 g of resin. It had a softening point of 92.0°C, a melt viscosity of 120 cps, and a hue of 5. Polymerization Examples 4 to 6 Predetermined amounts of fractions shown in Table 5 were mixed in a pressure cylinder. In advance, 20 g of anhydrous aluminum chloride pulverized product was suspended in the specified amount of solvent shown in Table 6 in a nitrogen atmosphere in a glass autoclave, and the temperature was raised to 60°C.
The mixed distillate is dripped from the pressure cylinder over approximately 15 minutes while maintaining the temperature. After reacting for 2 hours, the catalyst was decomposed with methanol, washed with water, and concentrated to obtain a resin (the yield of each resin and the resin physical properties are shown in Table 6). Comparative Polymerization Examples 1 to 3 A predetermined amount of the fraction shown in Table 5 was taken into a pressure cylinder and mixed. Pre-autoclave 1 glass
2.0g of anhydrous aluminum chloride pulverized product under _N2 atmosphere
is suspended in a predetermined amount of solvent shown in Table 6, and while maintaining the temperature at 60°C, the mixed fraction is added dropwise from a pressure cylinder over approximately 15 minutes. After reacting for 2 hours, the catalyst was decomposed with methanol, washed with water, and concentrated to obtain a resin. Table 6 shows the yield and physical properties of each resin. Comparative Polymerization Example 4 Table ₅ shows the composition of the fraction with a boiling point of 25°C to 35°C obtained by distilling the remaining fraction (spent C ₅ fraction) after extracting isoprene from the C 5 fraction at normal pressure. . This fraction is designated as E fraction. This fraction was polymerized in the same manner as in Comparative Polymerization Example 1 to obtain the resins shown in Table 6.

【table】

【table】

[Table] Examples 1 to 6, Comparative Examples 1 to 2 0.5 parts of maleic anhydride was added to 100 parts each of the hydrocarbon resins obtained in Polymerization Examples 1 to 6 (polymerized, the same applies hereinafter), and the mixture was reacted at 200°C for 2 hours. A maleated hydrocarbon resin was obtained. For comparison, the hydrocarbon resins obtained in Comparative Polymerization Example 1 and Comparative Polymerization Example 4 were similarly reacted with maleic anhydride to obtain maleated hydrocarbon resins, which were designated as Comparative Examples 1 and 2. . Table 8 shows the resin properties.

[Table] [Evaluation results as a traffic paint] Evaluation examples 1 to 8 To 100 parts of the maleated hydrocarbon resin prepared in the above polymerization examples and comparative polymerization examples, 12 parts of a plasticizer (Tokushima Seisei Co., Ltd. Toxinol TS-100), 200 parts of coarse powdered calcium carbonate (Kansui Sand #30, manufactured by Nitto Konka), 200 parts of finely powdered calcium carbonate (Whiten H, manufactured by Shiraishi Calcium), 66 parts of titanium oxide (Tipeque A-220, manufactured by Ishihara Sangyo), and glass beads. Add 100 parts of (Toshiba Barodini GB-153T) and heat to 200℃.
Traffic paint was prepared by melt mixing on an oil bath. Its properties are shown in Table 9.

【table】

Claims (1)

[Scope of Claims] 1 (a) A fraction with a boiling point in the range of -20 to +100°C, a range in which the 1,3-conjugated diene component in the total unsaturated components is 20 mol% or more, and a terminal monoolefin component and (b) a fraction containing dihydrodicyclopentadiene in at least one of the total unsaturated components. An aliphatic internal olefin-containing fraction containing an aliphatic internal olefin component in a range of 80 mol% or more, a terminal monoolefin component in a range of 15 mol% or less, and a cyclopentadiene component in a range of 5 mol% or less,
The 1,3-conjugated diene component among the unsaturated components in the mixed fraction is in the range of 10 to 60 mol%, and the aliphatic internal olefin component containing at least dihydrodicyclopentadiene is in the range of 40 to 90 mol%. , terminal monoolefin component is 25 mol%
The following range and cyclopentadiene component is 5
The mixed fraction is polymerized in the presence of a Friedel-Crafts type catalyst, and then a modified hydrocarbon resin is blended as a tackifying agent. Composition for traffic paint. 2. Bringing the aliphatic internal olefin-containing fraction into contact with an aliphatic unsaturated hydrocarbon-containing fraction with a boiling point of -10 to +100°C produced by thermal decomposition of petroleum and hydrogen in the presence of a hydrogenation catalyst. The composition for traffic paint according to claim 1, which is a fraction obtained by.