JP2001329117A - Binder for color-paved road - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a binder for a color-paved road, improved in its weather resistance and thermal stability without collapsing its balance between practical physical properties such as a needle penetrating degree, softening point, toughness, tenacity, low temperature characteristics. SOLUTION: This binder for the color-paved road consists of 2-20 wt.% styrene-based thermoplastic elastomer containing a hydrogenated rubber component such as a SEBS, SEPS as a component (A), 25-80 wt.% hydrogenated stickiness-imparting resin such as a hydrogenated petroleum resin as a component (B) and 15-70 wt.% paraffin-based process oil as a (C) component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binder composition for a color pavement road, and more particularly, it is suitable for a color pavement such as a road, a sidewalk, a park and a plaza, and has good thermal stability and weather resistance in addition to good binder performance. The present invention relates to a binder composition for color paved roads having excellent properties.

[0002]

2. Description of the Related Art In general, a bus-only lane may be provided in order to facilitate the operation of a bus during a traffic jam. However, the display of characters alone does not readily reduce the intrusion of general vehicles. Therefore, a method of coloring the entire lane is often adopted. Also, sidewalks, bike paths, parks, plazas, and the like may be colored to enhance the appearance. The coloring is usually performed by using a binder to which a pigment is added.

Heretofore, as a binder for a color pavement road, a binder containing a thermoplastic resin, a tackifier and a mineral oil has been used. However, some of the ingredients are
Some of them had an unsaturated double bond, and were poor in thermal stability and durability. Specifically, it was clear immediately after the construction, but gradually changed to a dull color with the passage of time, and there was a drawback that the appearance was impaired. In addition, many binders for color paved roads are manufactured in a factory and then transported by heating lorry to a mixture plant, so during transportation,
There was also a drawback of coloring due to thermal degradation.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of the conventional binder for color paved roads, and does not break the balance of practical physical properties such as penetration, softening point, toughness, tenacity and low-temperature characteristics. Another object of the present invention is to provide a binder for a color paved road having improved weather resistance and thermal stability. By using such a binder for color paved roads, the aesthetic appearance of the road is maintained for a long time, so that the visual effect given to the driver can be maintained for a long time,
The period until rebuilding is extended, which is advantageous in terms of cost.

[0005]

Under such circumstances, the present inventors have been keen to develop a binder for color paved roads which is excellent in various practical physical properties and has improved weather resistance and thermal stability. Repeated research. As a result, they have found that a composition obtained by mixing a styrene-based thermoplastic elastomer in which a rubber component is hydrogenated, a hydrogenated tackifying resin, and a paraffin-based process oil in a fixed ratio has physical properties suitable for the purpose. . The present invention has been completed based on such findings.

That is, the present invention relates to (A) a styrene-based thermoplastic elastomer having a hydrogenated rubber component.
% By weight, (B) 25 to 80% by weight of a hydrogenated tackifying resin, and (C) 15 to 70% by weight of a paraffinic process oil.
And a binder composition for a color paved road comprising: Note that, in the present specification, the binder composition of the present invention is stipulated for color paved roads,
Here, the pavement road is a general term for not only ordinary roads but also general pavement surfaces such as sidewalks, bicycle-only roads, parks, and plazas.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the binder composition of the present invention contains the components (A), (B) and (C) as essential components. Here, as the styrene-based thermoplastic elastomer to which the rubber component (A) is hydrogenated, various types can be used. Specifically, a styrene-butadiene-styrene block copolymer (SBS A) a styrene-ethylene-butadiene-styrene rubber (SEBS) obtained by hydrogenating the rubber component of
Styrene-isoprene-styrene block copolymer (S
There is a styrene-ethylene-propylene-styrene rubber (SEPS) obtained by hydrogenating a rubber component of IS. The amount of the thermoplastic elastomer obtained by hydrogenating the rubber component in the binder composition is 2% of the total composition.
From 20% by weight, from the viewpoint of improving the balance of practical physical properties, 4 to 12% by weight is more preferable. If the amount of the thermoplastic elastomer in which the rubber component is hydrogenated is less than 2% by weight, the toughness, tenacity, softening point decreases,
In addition, there is a problem that the penetration is too high, and if it exceeds 20% by weight, disadvantages such as a decrease in penetration and an increase in melt viscosity occur.

[0008] The hydrogenated tackifying resin as the component (B) is a general term for hydrogenated petroleum resins and hydrogenated terpene resins. Here, the term “hydrogenated petroleum resin” refers to a mixture of hydrocarbons having various carbon-carbon unsaturated bonds and / or products produced by thermal decomposition of petroleum naphtha or the like obtained by cationic polymerization or radical polymerization (thermal polymerization). It is a compound obtained by further hydrogenating residual carbon-carbon unsaturated bonds of the obtained petroleum resin with a noble metal catalyst or the like. Here, the average molecular weight of the petroleum resin is about 200 to 2,000, and the softening point is about 40 to 180 ° C. Examples of such petroleum resins include aliphatic petroleum resins, dicyclopentadiene (DCPD) petroleum resins, aromatic petroleum resins, and copolymer petroleum resins.

The aliphatic petroleum resin, which is a kind of the petroleum resin, is obtained by cationic polymerization of a naphtha cracked oil with a fraction having a boiling point of about 20 to 80 ° C. (mainly a C5 fraction) using aluminum chloride or the like as a catalyst. It is presumed that the resin structurally includes a ring structure and a chain structure. Most of the polymerization components in the C5 fraction are composed of chain diolefins and chain monoolefins, so that it is relatively difficult to obtain a resin having a high softening point. In an aluminum halide catalyst or the like, the chain diolefin is
Although the softening point rises due to cyclization during polymerization, the cyclization reaction is partially hindered by the presence of the linear monoolefin. I have to make it big. Therefore, aliphatic petroleum resins generally have a large molecular weight and a wide distribution range.

Next, DCPD-based petroleum resin, which is a kind of petroleum resin, is obtained by adding cyclopentadiene (CPD) in a C5 cut.
And its dimer, dicyclopentadiene (DCP
D) is a resin obtained by concentrating and thermally polymerizing D), and structurally containing a ring structure in the main chain. Therefore, a resin having a relatively low molecular weight and a high softening point can be obtained.

An aromatic petroleum resin, which is a kind of petroleum resin, is obtained by cationically or thermally polymerizing an aromatic component mainly composed of a C9 fraction containing styrenes and indenes of a naphtha cracked oil. The aromatic component has an aromatic ring, and when these are polymerized, a resin having a ring structure in the side chain is generated. Therefore, compared to the aliphatic petroleum resin, the resin has a low molecular weight and a high softening point. Is obtained. However, the color tone of the resin itself is poor and the odor at the time of melting is strong. In order to improve this, there is also a pure monomer type resin having a small amount of other components such as styrenes such as α-methylstyrene and vinyltoluene and substituted styrenes.

Next, a copolymerized petroleum resin, which is a kind of petroleum resin, is a resin obtained by copolymerization of the above-mentioned aliphatic monomer, DCPD monomer, and aromatic monomer. A resin can be obtained.

On the other hand, the hydrogenated terpene resin is obtained by hydrogenating a terpene resin. Here, the terpene resin is a resin made from turpentine oil. Turpentine oil is mainly composed of α-pinene, and is also composed of cyclic terpenes such as β-pinene and dipentene. The terpene resin is a resin obtained by cationically polymerizing these cyclic terpenes using aluminum chloride or boron trifluoride as a catalyst.

In the binder composition of the present invention,
As described above, the hydrogenated tackifying resin used as the component (B) is a compound obtained by hydrogenating a residual carbon-carbon unsaturated bond of a petroleum resin or a terpene resin with a noble metal catalyst or the like. Hydrogenation may be performed by a conventional method. If hydrogenation is not performed, the bromine value is too high, and the physical properties, thermal stability, and weather resistance of the obtained binder are reduced, and the object of the present invention cannot be achieved. The hydrogenated tackifying resin preferred in the present invention is a hydrogenated product of any of DCPD petroleum resin, aromatic petroleum resin, copolymer petroleum resin, and terpene resin, and these may be used alone or in combination of two or more. Can be used.

In the present invention, as a more preferred component (B), for example, a bromine number obtained by hydrogenating a copolymer of cyclopentadiene and / or dicyclopentadiene and an aromatic-containing vinyl monomer is 10%.
(G / 100 g) or less. More specifically, the [cyclopentadiene and / or dicyclopentadiene and / or dicyclopentadiene and / or dicyclopentadiene] obtained by hydrogenating the [cyclopentadiene and / or dicyclopentadiene]-[styrene] copolymer has a bromine number of 10 (g / 100 g) or less. [Pentadiene]-[styrene] copolymer hydrogenated product.

In the present invention, among the hydrogenated products of these tackifying resins, the bromine value is 10 (g / 100 g).
Below, it is desirable to use the thing of 8 (g / 100g) or less. Here, the bromine number is 10 (g / 100
When a hydrogenated tackifying resin exceeding g) is used, mechanical properties, thermal stability, and weather resistance may be insufficient, and may not be practical. Usually, after polymerization of the tackifying resin,
By performing hydrogenation on carbon-carbon unsaturated bonds with hydrogen in the presence of a noble metal catalyst such as nickel or palladium, the content is reduced to 10 (g / 100 g) or less. In addition,
The bromine value may be measured according to JISK2605.

The amount of the hydrogenated tackifying resin (B) in the binder composition of the present invention is from 25 to 80% by weight of the whole composition, but from the viewpoint of improving the balance of practical physical properties. Is more preferably 50 to 65% by weight. If the amount of the hydrogenated tackifying resin is less than 25% by weight, there is a problem that the toughness and tenacity decrease and the penetration increases. If it exceeds 80% by weight, the toughness and tenacity decrease and the penetration decreases. The disadvantage of reduction occurs.

By the way, in the present invention, even if an unhydrogenated tackifying resin, a coumarone-based resin or a phenol-based resin is used instead of the component (B), the object of the present invention cannot be achieved.

The paraffin-based process oil used as the component (C) in the binder composition of the present invention is obtained, for example, by subjecting a heavy oil fraction obtained by distilling crude oil to atmospheric pressure, to distillation under reduced pressure, It is obtained by refining by quality, dewaxing and the like. The amount of the component (C) is 15 to 70% by weight of the whole composition.
However, from the viewpoint of improving the balance of practical physical properties,
More preferably, it is 25 to 55% by weight. If the amount of the paraffin-based process oil as the component (C) is less than 15% by weight, there is a problem that toughness, tenacity and penetration decrease, and the softening point and melt viscosity increase. , Toughness, tenacity and softening point are reduced, and penetration is increased.

The binder composition of the present invention comprises the above-mentioned components (A), (B) and (C) as essential components, but the production method thereof is not particularly limited. For example, a method of heat-melting stirring or kneading using a propeller type stirrer, a biaxial kneader, a kneader or the like can be used. The order of mixing the components is not particularly limited. In addition, the heating temperature is not particularly limited, but the heating can be usually performed at 150 ° C to 190 ° C.

The binder composition of the present invention contains the above-mentioned components (A), (B) and (C) as essential components. If desired, other components such as, for example, a component such as Antioxidants, waxes and the like can be appropriately compounded. Since the binder composition of the present invention is usually in a solid state at normal temperature, it can be pelletized by coating with a film such as polypropylene or polyethylene. When the binder composition of the present invention is hot-melt-blended with an aggregate and a pigment, a film of a packaging material such as polypropylene or polyethylene can be used as a part of the binder.

[0022]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 Hydrogenated styrene-based thermoplastic elastomer (SEBS)
(Asahi Kasei Kogyo Co., Ltd., trade name: Tuftec H1041
G) 5.0 parts by weight, hydrogenated petroleum resin (manufactured by Idemitsu Petrochemicals Co., Ltd., trade name: Iamarb P-125) 58.0 parts by weight and paraffin-based process oil I (manufactured by Idemitsu Kosan Co., Ltd., trade name) : PW-380) 37.1 parts by weight of 1
The mixture was heated, melted and mixed at 70 to 180 ° C. to prepare a binder. The performance of the obtained binder is shown in Table 1.

Example 2 In Example 1, the amount of the hydrogenated petroleum resin was 58.9.
A binder was produced in the same manner as in Example 1, except that the amount was 36.1 parts by weight and the amount of the paraffin-based process oil was 36.1 parts by weight. The performance of the obtained binder is shown in Table 1.

Example 3 In Example 1, the amount of the hydrogenated petroleum resin was changed to 64.6.
In terms of parts by weight, as a paraffinic process oil, a paraffinic process oil II having a lower viscosity than that of Example 1 (trade name: PW-90, manufactured by Idemitsu Kosan Co., Ltd.) 3
A binder was prepared in the same manner as in Example 1, except that 0.4 parts by weight was used. The performance of the obtained binder is shown in Table 1.

Comparative Example 1 10 parts by weight of a styrene-based thermoplastic elastomer (SBS), 35 parts by weight of a C5 petroleum resin and 55 parts by weight of an aroma-based process oil were heated and melt-mixed at 170 to 180 ° C.
A binder was prepared. The performance of the obtained binder is shown in Table 1.

COMPARATIVE EXAMPLE 2 170 parts by weight of 5 parts by weight of a styrene-based thermoplastic elastomer (SEBS) having a hydrogenated rubber component, 58 parts by weight of a hydrogenated petroleum resin, and 37 parts by weight of an aroma-based process oil were used.
The mixture was heated and mixed at 0 ° C. to prepare a binder. The performance of the obtained binder is shown in Table 1.

Comparative Example 3 5 parts by weight of a styrene-based thermoplastic elastomer (SEBS) having hydrogenated rubber components, 58 parts by weight of a C5-based petroleum resin, and 37 parts by weight of a paraffin-based process oil were added in an amount of 170 to 170 parts.
The mixture was heated and melted at 180 ° C. to prepare a binder. The performance of the obtained binder is shown in Table 1.

[0028]

[Table 1]

* 1: Penetration (1/10 mm) is based on JIS
It measured according to K2207. * 2: The formulation softening point was measured according to JIS K 2207. * 3: Melt viscosity is B according to JIS K6862.
It was measured using a mold viscometer. * 4: Toughness and tenacity were measured according to the Japan Road Association Pavement Test Method. * 5: The elongation at 7 ° C refers to the elongation at 7 ° C according to JIS K2.
207 was measured. The higher the elongation value, the better the low temperature properties. * 6: The heated hue was obtained by dissolving a binder heated in air at 180 ° C. for 24 hours in an equal weight of toluene and measuring the Gardner color of the sample according to ASTM D154. The smaller the value, the better the hue. * 7: Xenon weather resistance was measured by irradiating a xenon lamp for 1000 hours and 2000 hours (black panel temperature 60 ° C,
The binder after 60% humidity, no rainfall) was dissolved in an equal weight of toluene, and the hue of the sample was determined according to ASTM D154.
The Gardner color was measured according to. The smaller the value, the better the hue.

As shown in Table 1, in Examples 1 to 3, it was possible to obtain a binder for a color pavement road having a good balance of practical physical properties and little change in hue upon heating.

[0031]

EFFECT OF THE INVENTION The binder composition for color paved roads of the present invention has a good balance of practical physical properties such as penetration, softening point, toughness, tenacity, and low-temperature properties, as well as weather resistance and thermal stability. It has been improved, so if it is used as a binder for color paved roads, the aesthetics of the road will be maintained over a long period of time, so that the visual effect given to the driver can be maintained for a long time, and The period is extended and the cost is also advantageous. In addition, since the binder composition of the present invention is colorless and transparent, it is easy to be colored, and it is economically advantageous to use a small amount of pigment to be added as compared with a conventional binder.

Continued on the front page (72) Inventor Toshihiro Mine 1-1, Shingu-cho, Tokuyama-shi, Yamaguchi Prefecture (72) Inventor Matsunori 1-1, Shingu-cho, Tokuyama-shi, Yamaguchi F-term (reference) 4J002 AC082 AC112 AE053 BC052 BP012 CE001 GL00

Claims (3)

[Claims] (A) 2 to 20% by weight of a styrene-based thermoplastic elastomer having a hydrogenated rubber component, (B) 25 to 80% by weight of a hydrogenated tackifying resin, and (C) 15 to 70% of a paraffinic process oil. A binder composition for a color paved road, which comprises by weight. 2. The binder composition according to claim 1, wherein the hydrogenated tackifying resin (B) is a hydrogenated petroleum resin. 3. The binder composition according to claim 1, which is a solid at room temperature.