Asphalt composition and asphalt mixture

Abstract

An asphalt composition is provided comprising: a petroleum resin (A); and pure asphalt, wherein the petroleum resin (A) is a petroleum resin obtained by copolymerization of: a monomer containing at least one type of cyclic olefin with an ethylene unsaturated group selected from a C5 fraction, a C8 fraction, and a C9 fraction of cracked naphtha, and a cyclopentadiene-based compound; and a silane, and wherein the petroleum resin (A) satisfies the following conditions (a1) and (a2): (a1) the petroleum resin (A) contains 0.1 wt% or more and 10 wt% or less silicon element, expressed in silicon atoms; and (a2) the petroleum resin (A) has a weight mean molecular weight (Mw) of 500 or more and 3,000 or less.

Description

Technical field

[0001] The present invention relates to an asphalt composition and an asphalt mixture, as well as a petroleum resin and a hydrogenated petroleum resin for use in the asphalt composition and the asphalt mixture. background

[0002] In recent years, asphalt delamination has been identified as a major factor in the damage of asphalt pavements. This phenomenon occurs when the asphalt covering the aggregate surface detaches due to the penetration of water such as rainwater or groundwater between the asphalt and the aggregate. When this delamination occurs, the bond between the aggregates is weakened, potentially leading to damage such as cracks or potholes. Therefore, research and development of asphalt compounds capable of suppressing delamination has been pursued.

[0003] For example, PTL 1 discloses a process for producing a modified hydrogenated petroleum resin, wherein the process comprises reacting a hydrogenated petroleum resin and a compound having a carbon-carbon double bond and an alkoxysilyl group in the presence of a compound generating a radical, and also discloses an asphalt composition comprising a modified hydrogenated petroleum resin and pure asphalt, wherein the content of pure asphalt is 70.00 wt% to 99.99 wt%. Citation list for patent literature

[0004] PTL 1: WO 2021 / 161672 A1 Technical problem

[0005] In PTL 1, an investigation was carried out to obtain an asphalt composition that can suppress asphalt delamination, however, there is still potential for improvement in terms of improving the water resistance of an asphalt mixture.

[0006] In view of the foregoing, it is an object of the present invention to provide an asphalt composition that can suppress asphalt flaking and improve the water resistance of an asphalt mixture. Solution to the problem

[0007] The inventors of the present invention have determined that the above-mentioned problem can be achieved by an asphalt composition comprising: a petroleum resin (A) containing a specific amount of silicon element, having a specific weight-average molecular weight, and possessing a specific structure; and pure asphalt. That is to say, the present invention comprises the following: <1> until <8> . <1> Asphalt composition, comprehensive: a petroleum resin (A); and pure asphalt, wherein the petroleum resin (A) is a petroleum resin obtained by copolymerization of: a monomer containing at least one type of cyclic olefin with an ethylene unsaturated group selected from a C5 fraction, a C8 fraction and a C9 fraction of cracked naphtha, and a cyclopentadiene-based compound; and a silane, and wherein the petroleum resin (A) satisfies the following conditions (a1) and (a2): (a1) the petroleum resin (A) contains 0.1 wt% or more and 10 wt% or less silicon element, expressed in silicon atoms; and (a2) the petroleum resin (A) has a weight-average molecular weight (Mw) of 500 or more and 3,000 or less. <2> The asphalt composition according to the above-mentioned point <1> where the petroleum resin (A) satisfies the following condition (a3): (a3) the petroleum resin (A) has a softening point of 70 °C to 150 °C. <3> The asphalt composition according to the above-mentioned point <1> or <2> , wherein the silane has a structure that is represented by the following formula (1): Formula (1): CH2=CR-(COO) x (C n H 2n ) y SiR'3 where in formula (1) R represents a hydrogen atom or a methyl group, “x” and “y” represent 0 or 1 respectively, provided that if “x” represents 1, “y” represents 1, “n” represents an integer from 1 to 12, and R’s each independently represent an alkoxy group with 1 to 12 carbon atoms, an aryloxy group, an aralkyloxy group, an aliphatic acyloxy group with 1 to 12 carbon atoms, an amino or substituted amino group, or a lower alkyl group with 1 to 6 carbon atoms, provided that two or fewer of the three R’ groups are each an alkyl group. <4> The asphalt composition according to one of the above points <1> until <3> , wherein the silane is at least one type selected from vinyltrimethoxysilane, vinyltriethoxysilane and 3-(trimethoxysilyl)propyl methacrylate. <5> The asphalt composition according to one of the above points <1> until <4> , wherein the monomer contains dicyclopentadiene. <6> The asphalt composition according to one of the above points <1> until <5> , wherein the petroleum resin (A) is a hydrogenated product. <7> The asphalt composition according to one of the above points <1> until <6> , wherein the content of petroleum resin (A) in the asphalt composition is 0.1 wt% or more and 5 wt% or less. <8> An asphalt mixture, including: the asphalt composition according to one of the points mentioned above <1> until <7> ; and Aggregate, where the content of the asphalt composition is 1% by mass to 20% by mass.

[0008] Furthermore, the inventors of the present invention have determined that the aforementioned objective can be achieved by a petroleum resin (B) containing a specific amount of silicon element, having a specific weight-average molecular weight, and possessing a specific structure. That is to say, the present invention comprises the following points: <9> until <17> .

[0009] <9> A petroleum resin (B) obtained by copolymerization of: a monomer containing at least one type of cyclic olefin with an ethylene-unsaturated group selected from a C5 fraction, a C8 fraction and a C9 fraction of cracked naphtha, and a cyclopentadiene-based compound; and a silane wherein the petroleum resin (B) satisfies the following conditions (b1) and (b2): (b1) the petroleum resin (B) contains 0.1 wt% or more and 10 wt% or less silicon element, expressed in silicon atoms; and (b2) the petroleum resin (B) has a weight-average molecular weight (Mw) of 500 or more and 3,000 or less.

[0010] <10> The petroleum resin (B) according to the above point <9> , wherein the petroleum resin (B) satisfies the following condition (b3): (b3) the petroleum resin (B) has a softening point of 70 °C to 150 °C.

[0011] <11> The petroleum resin (B) according to the above point <9> or <10> , wherein the silane has a structure that is represented by the following formula (1): CH2=CR-(COO)x (C n H 2n )ySiR'3 Formula (1): where in formula (1) R represents a hydrogen atom or a methyl group, “x” and “y” represent 0 or 1 respectively, provided that if “x” represents 1, “y” represents 1, “n” represents an integer from 1 to 12, and R’s each independently represent an alkoxy group with 1 to 12 carbon atoms, an aryloxy group, an aralkyloxy group, an aliphatic acyloxy group with 1 to 12 carbon atoms, an amino or substituted amino group, or a lower alkyl group with 1 to 6 carbon atoms, provided that two or fewer of the three R’ groups are each an alkyl group.

[0012] <12> The petroleum resin (B) according to one of the points mentioned above <9> until <11> , wherein the silane is at least one type selected from vinyltrimethoxysilane, vinyltriethoxysilane and 3-(trimethoxysilyl)propyl methacrylate.

[0013] <13> The petroleum resin (B) according to one of the points mentioned above <9> until <12> , wherein the monomer contains dicyclopentadiene.

[0014] <14> The petroleum resin (B) according to one of the points mentioned above <9> until <13> , wherein the petroleum resin (B) is a hydrogenated product.

[0015] <15> Asphalt composition, comprehensive: the petroleum resin (B) according to one of the points mentioned above <9> until <14> ; and pure asphalt.

[0016] <16> The asphalt composition according to the above-mentioned point <15> , wherein the content of petroleum resin (B) in the asphalt composition is 0.1 wt% or more and 5 wt% or less.

[0017] <17> An asphalt mixture, including: the asphalt composition from the point mentioned above <15> or <16> ; and aggregate, where the content of the asphalt composition is 1% by mass to 20% by mass.

[0018] Furthermore, the inventors of the present invention have determined that the aforementioned objective can be achieved by a hydrogenated petroleum resin (C) containing a specific amount of silicon element, having a specific weight-average molecular weight, and possessing a specific structure. That is to say, the present invention comprises the following points: <18> until <25> .

[0019] <18> A hydrogenated petroleum resin (C) obtained by copolymerization of: a monomer containing at least one type of cyclic olefin with an ethylene-unsaturated group selected from a C5 fraction, a C8 fraction and a C9 fraction of cracked naphtha, and a cyclopentadiene-based compound; and a silane wherein the hydrogenated petroleum resin (C) satisfies the following conditions (c1) and (c2): (c1) the hydrogenated petroleum resin (C) contains 0.1 wt% or more and 10 wt% or less silicon element, expressed in silicon atoms; and (c2) the hydrogenated petroleum resin (C) has a weight-average molecular weight (Mw) of 500 or more and 3,000 or less.

[0020] <19> The hydrogenated petroleum resin (C) according to the above point <18> , wherein the hydrogenated petroleum resin (C) satisfies the following condition (c3): (c3) The hydrogenated petroleum resin (C) has a softening point of 70 °C to 150 °C.

[0021] <20> The hydrogenated petroleum resin (C) according to the above point <18> or <19> , wherein the silane has a structure that is represented by the following formula (1): Formula (1): CH2=CR-(COO) x (C n H 2n ) y SiR'3 where in formula (1) represents a pure hydrogen atom or a methyl group, “x” and “y” each represent 0 or 1, provided that if “x” represents 1, “y” represents 1, “n” represents an integer from 1 to 12, and R’s each independently represent an alkoxy group with 1 to 12 carbon atoms, an aryloxy group, an aralkyloxy group, an aliphatic acyloxy group with 1 to 12 carbon atoms, an amino or substituted amino group, or a lower alkyl group with 1 to 6 carbon atoms, provided that two or fewer of the three R’ groups are each an alkyl group.

[0022] <21> The hydrogenated petroleum resin (C) according to one of the above points <18> until <20> , wherein the silane is at least one type selected from vinyltrimethoxysilane, vinyltriethoxysilane and 3-(trimethoxysilyl)propyl methacrylate.

[0023] <22> The hydrogenated petroleum resin (C) according to one of the above points <18> until <21> , wherein the monomer contains dicyclopentadiene.

[0024] <23> Asphalt composition, comprehensive: the hydrogenated petroleum resin (C) according to one of the above points <18> until <22> ; and pure asphalt.

[0025] <24> The asphalt composition according to the above-mentioned point <23> , wherein the content of hydrogenated petroleum resin (C) in the asphalt composition is 0.1 wt% or more and 5 wt% or less.

[0026] <25> An asphalt mixture, including: the asphalt composition from the point mentioned above <23> or <24> ; and aggregate, where the content of the asphalt composition is 1% by mass to 20% by mass. Advantageous effects of the invention

[0027] According to the present invention, an asphalt composition can be provided which can suppress the peeling of asphalt and improve the water resistance of an asphalt mixture. Description of embodiments

[0028] The present invention is described in detail below. However, the scope of the present invention is not limited to the embodiments described below. <begriffsbestimmungen>

[0029] In the present invention, the expression “from X to Y” (where X and Y each represent any number) includes the meanings “preferably more than X” and “preferably less than Y” as well as the meaning “X or more and Y or less”, unless otherwise specified. [First invention: Asphalt composition]

[0030] An asphalt composition according to a first invention is described below.

[0031] The asphalt composition includes a petroleum resin (A) and pure asphalt.

[0032] The petroleum resin (A) is a petroleum resin obtained by copolymerization of: a monomer containing at least one type of cyclic olefin with an ethylene unsaturated group selected from a C5 fraction, a C8 fraction and a C9 fraction of cracked naphtha, and cyclopentadiene; and a silane.

[0033] The petroleum resin (A) meets the following conditions (a1) and (a2): (a1) the petroleum resin (A) contains 0.1 wt% or more and 10 wt% or less silicon element, expressed in silicon atoms; and (a2) the petroleum resin (A) has a weight-average molecular weight (Mw) of 500 or more and 3,000 or less.

[0034] The above-mentioned physical properties of the petroleum resin (A) can be appropriately adjusted by selecting a monomer starting material, a polymerization solvent and a catalyst, their amounts used, a polymerization temperature, a reaction pressure and other polymerization conditions.

[0035] According to the first invention, the following effect is achieved. An asphalt composition can be provided that suppresses asphalt delamination and improves the water resistance of an asphalt mixture. The reason for this effect is not entirely clear, but is suspected to be as follows.

[0036] An asphalt road is formed by the bonding of aggregates to each other through adhesion between the aggregates and the asphalt. These aggregates are substances that possess a hydroxyl group on their surface and have high polarity, which means their affinity for water is greater than their affinity for asphalt. Consequently, the presence of water inhibits the adhesion between the aggregates and the asphalt, and asphalt detachment can occur. Furthermore, the asphalt road can be damaged by the stress of cars, trucks, and similar vehicles.

[0037] According to the first invention, the affinity between the aggregate and the asphalt is improved by a reaction between a hydroxyl group on the surface of the aggregate and a silane-containing group of the petroleum resin (A) in the asphalt composition. Thus, it is assumed that the detachment of the asphalt is suppressed, even in the presence of water, and therefore the adhesion between the aggregate and the asphalt is improved.

[0038] The mechanism mentioned above relating to the effect of the present invention is a conjecture, and the mechanism is not limited to it. <Petroleumharz (A)>

[0039] The petroleum resin (A) meets the following conditions (a1) and (a2): (a1) The petroleum resin (A) contains 0.1 wt% or more and 10 wt% or less silicon element, expressed in silicon atoms; and (a2) the petroleum resin (A) has a weight-average molecular weight (Mw) of 500 or more and 3,000 or less.

[0040] The petroleum resin (A) contains 0.1 wt% or more and 10 wt% or less, preferably 0.3 wt% or more, more preferably 0.4 wt% or more, more preferably 0.5 wt% or more, more preferably 1.0 wt% or more, more preferably 1.5 wt% or more, more preferably 2.0 wt% or more, more preferably 2.5 wt% or more, more preferably more than 2.9 wt%, more preferably 3.0 wt% or more, and preferably 8 wt% or less, more preferably 6 wt% or less, and more preferably 5 wt% or less, of silicon element, expressed in silicon atoms. The silicon element is preferably derived from an organic silane structure.

[0041] If the concentration of silicon element in the petroleum resin (A) is below the above-mentioned ranges (less than 0.3 wt%), it may be difficult to suppress the detachment of the asphalt from the aggregate.

[0042] If the concentration of silicon element in the petroleum resin (A) exceeds the above-mentioned ranges (more than 10 wt%), molecules of the petroleum resin (A) can cross-link, thereby reducing the solubility of the petroleum resin (A) in the asphalt. Therefore, the expected performance may not be achieved.

[0043] The concentration of silicon element can be measured by ICP emission spectroscopy and specifically determined by a method described in the examples.

[0044] The petroleum resin (A) has a weight-average molecular weight (Mw) of 500 or more and 3,000 or less, preferably 700 or more, more preferably 1,000 or more, more preferably 1,200 or more, more preferably 1,300 or more and preferably 3,000 or less, more preferably 2,800 or less, more preferably 2,500 or less, more preferably 2,000 or less, more preferably 1,500 or less.

[0045] If the weight mean molecular weight (Mw) of the petroleum resin (A) is below the above-mentioned ranges (less than 500), the asphalt composition may have insufficient hardness and become brittle at normal temperature, thereby reducing the strength and thus potentially affecting the durability of an asphalt road.

[0046] However, if the weight-mean molecular weight (Mw) of the petroleum resin (A) exceeds the aforementioned ranges (above 3,000), its viscosity may be increased when mixed with asphalt at high temperatures, which can impair its miscibility with the asphalt. Consequently, sufficient water resistance may not be achieved.

[0047] Furthermore, the petroleum resin (A) has a molecular weight distribution (Mw / Mn) of preferably 5.0 or less, more preferably 4.0 or less, more preferably 3.5 or less, more preferably 3.0 or less, more preferably 2.5 or less, with the aim of improving the adhesion properties between the aggregate and the asphalt.

[0048] The weight-mean molecular weight (Mw) and the number-mean molecular weight (Mn) are each molecular weights expressed in terms of polystyrene. These molecular weights can each be measured by gel permeation chromatography (GPC) and specifically determined using a method described in the examples.

[0049] The petroleum resin (A) preferably meets the following condition (a3): (a3) The petroleum resin (A) has a softening point of 70 °C to 150 °C.

[0050] The petroleum resin (A) has a softening point of preferably 70 °C to 150 °C, more preferably 80 °C to 140 °C, more preferably 90 °C to 140 °C, and more preferably 95 °C to 135 °C, with the aim of improving the adhesion properties between the aggregate and the asphalt.

[0051] The softening point can be measured according to JIS K 6863:1994.

[0052] The petroleum resin (A) preferably meets the following condition (a4): (a4) The petroleum resin (A) has a bromine number of 0.5 g / 100 g to 30 g / 100 g.

[0053] The petroleum resin (A) has a bromine number of preferably 0.5 g / 100 g to 30 g / 100 g, more preferably 1.0 g / 100 g to 25 g / 100 g, more preferably 2.0 g / 100 g to 20 g / 100 g, more preferably 3.0 g / 100 g to 18 g / 100 g, more preferably 3.0 g / 100 g to 15 g / 100 g, from the point of view of improving the adhesion properties between the aggregate and the asphalt.

[0054] The bromine number can be measured according to JIS K 2605:1996.

[0055] The petroleum resin (A) contains a repeating unit derived from a monomer and a repeating unit derived from a silane, and is preferably obtained by copolymerization of a monomer and a silane. (monomer)

[0056] The monomer for the formation of the petroleum resin (A) contains at least one type of cyclic olefin with an ethylene-unsaturated group selected from a C5 fraction, a C8 fraction and a C9 fraction of cracked naphtha, and a cyclopentadiene-based compound, preferably containing a cyclopentadiene-based compound and more preferably containing dicyclopentadiene.

[0057] Furthermore, a cyclopentadiene-based compound is preferably used as the first raw material component and a vinylaromatic compound as the second raw material component as monomers, wherein the first raw material component can be used alone without using the second raw material component.

[0058] Examples of cyclopentadiene-based compounds include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, and their dimers and codimers. Among these, dicyclopentadiene is the preferred cyclopentadiene-based compound.

[0059] Examples of vinylaromatic compounds include styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, vinylxylene, indene, methylindene, and ethylindene. Among these, styrene is the preferred vinylaromatic compound.

[0060] The mixing ratio between the cyclopentadiene-based compound and the vinylaromatic compound is not particularly restricted, and the ratio “cyclopentadiene-based compound : vinylaromatic compound” is preferably 80:20 to 20:80, more preferably 75:25 to 25:75, based on the mass ratio. (Silane)

[0061] The silane for the formation of the petroleum resin (A) is not particularly restricted, but preferably has a structure that is represented by the following formula (1): Formula (1): CH2=CR-(COO) x (C n H 2n ) y SiR'3 where In formula (1), R represents a hydrogen atom or a methyl group, “x” and “y” each represent 0 or 1, provided that if “x” represents 1, “y” represents 1, “n” represents an integer from 1 to 12, preferably from 1 to 4, and each of the R’s independently represents an alkoxy group with 1 to 12 carbon atoms (e.g., a methoxy, ethoxy, or butoxy group), an aryloxy group (e.g., a phenoxy group), an aralkyloxy group (e.g., a benzyloxy group), an aliphatic acyloxy group with 1 to 12 carbon atoms (e.g., a formyloxy, acetyloxy, or propaneoxy group), an amino or substituted amino group (an alkylamino or arylamino group), or a lower alkyl group with 1 to 6 carbon atoms, provided that two or fewer of the three R' groups are each an alkyl group.

[0062] In formula (1) R preferably represents a hydrogen atom, from the point of view of improving the adhesion properties between the asphalt composition and the aggregate, “x” and / or “y” preferably represent 0, and “x” and “y” each more preferably represent 0.

[0063] Furthermore, in formula (1) R's preferably represent an alkoxy group with 1 to 12 carbon atoms (e.g. a methoxy, ethoxy or butoxy group), more preferably an alkoxy group with 1 to 5 carbon atoms, and even more preferably an alkoxy group with 1 to 3 carbon atoms, with the viewpoint of improving the adhesion properties between the asphalt composition and the aggregate.

[0064] The silane is preferably at least one type selected from vinyltrimethoxysilane, vinyltriethoxysilane and 3-(trimethoxysilyl)propyl methacrylate, with the viewpoint of improving the adhesion properties between the asphalt composition and the aggregate.

[0065] The petroleum resin (A) is preferably a hydrogenated product obtained by hydrogenation (addition of hydrogen) to improve the adhesion properties between the asphalt composition and the aggregate. The hydrogenated product of the petroleum resin (A) can be a partially hydrogenated product, in which the petroleum resin (A) is partially hydrogenated, or a fully hydrogenated product, in which the petroleum resin (A) is completely hydrogenated.

[0066] The petroleum resin (A) can have a form of copolymer as described above, and the difference in structure compared to the resin of PTL 1, which can have a form of a modified product, is described as follows.

[0067] In the modified product, a radical attacks the petroleum resin, and a silane is added to a decomposed unit, resulting in a low molecular weight modified unit and the addition of silicon to a low molecular weight side. Meanwhile, in the copolymer, the monomers each exhibit essentially the same copolymerizability, so silicon is added uniformly.

[0068] This means that silicon is introduced uniformly into the copolymer, so that even with an increase in the silicon content, no areas of localized silicon concentration are created. This allows a high silicon content to be achieved without gelation. In the modified product, however, silicon is introduced unevenly, resulting in a molecule with areas of high silicon concentration (localized silicon concentrations). This reduces the proportion of silicon that effectively reacts with a hydroxyl group on the surface of the aggregate and increases the likelihood of molecules lacking silicon. Consequently, the improvement in water resistance is less pronounced.

[0069] Accordingly, a greater improvement in water resistance can be expected when the petroleum resin (A) is used for an asphalt mixture, from the point of view that a higher Si content can be achieved through the form of the copolymer than through the form of the modified product. <Verfahren zur Herstellung von Petroleumharz (A)>

[0070] The process for producing the petroleum resin (A) is not particularly restricted, and, for example, the petroleum resin (A) is preferably formed as follows: the above-mentioned monomer, the above-mentioned silane and a solvent for polymerization are placed in a polymerization reaction vessel; and the above-mentioned monomer and the above-mentioned silane are subjected to a copolymerization reaction under predetermined conditions.

[0071] The amount of silane used is preferably 0.1 to 80 mass parts, more preferably 0.5 to 50 mass parts, more preferably 1 to 30 mass parts, and more preferably 5 to 28 mass parts, based on 100 mass parts of the monomer.

[0072] Typical examples of solvents for polymerization are aromatic solvents, naphthene-based solvents, and aliphatic hydrocarbon solvents. Specific examples of suitable solvents for polymerization include toluene, xylene, cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane.

[0073] The amount of solvent used for the polymerization is preferably 10 to 300 mass parts, more preferably 20 to 200 mass parts, most preferably 30 to 100 mass parts, based on 100 mass parts of the monomer.

[0074] The predetermined conditions in the copolymerization reaction are not particularly restricted, and a reaction temperature is preferably between 150 °C and 350 °C, more preferably between 200 °C and 350 °C, most preferably between 230 °C and 300 °C; a reaction pressure is preferably between 0 MPaG and 5 MPaG, more preferably between 0 MPaG and 3 MPaG, more preferably between 0.1 MPaG and 2 MPaG; and the reaction time is preferably between 1 hour and 10 hours, more preferably between 1 hour and 8 hours, more preferably between 1 hour and 5 hours. "G" in "MPaG" refers to a pressure gauge pressure.

[0075] Furthermore, a process for producing the petroleum resin (A) as a hydrogenated product is not particularly restricted, and for example, the hydrogenated product of the petroleum resin (A) is preferably formed as follows: in a hydrogenation reaction vessel, the petroleum resin (A) is dissolved in a hydrogenation solvent; and hydrogen is added under predetermined conditions in the presence of a hydrogenation reaction catalyst in an amount required to carry out a hydrogenation reaction.

[0076] Examples of hydrogenation solvents include cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, and tetrahydrofuran.

[0077] The amount of hydrogenation solvent used is preferably 30 to 300 mass parts, more preferably 50 to 250 mass parts, and even more preferably 70 to 150 mass parts, based on 100 mass parts of the petroleum resin (A).

[0078] Furthermore, an example of a catalyst for the hydrogenation reaction is a catalyst containing at least one metal component selected from nickel, palladium, cobalt, platinum, and rhodium.

[0079] The predetermined conditions in the hydrogenation reaction are not particularly restricted, and a reaction temperature is preferably in the range of 100 °C to 300 °C, more preferably in the range of 150 °C to 280 °C, and even more preferably in the range of 180 °C to 250 °C; the supply pressure of hydrogen is preferably in the range of 0.5 MPaG to 10 MPaG, preferably between 1 MPaG and 8 MPaG, and even more preferably between 2 MPaG and 7 MPaG; and the reaction time is preferably between 1 hour and 20 hours, preferably between 2 hours and 15 hours, and even more preferably between 3 hours and 10 hours.

[0080] The petroleum resin (A) may be in the form of a copolymer as described above, and the difference in its manufacturing process compared to the resin of PTL 1, which may be in the form of a modified product, is described below.

[0081] Unlike the modified product, the copolymer does not require a step in which a petroleum resin is first produced and then modified with a silane, thus simplifying the manufacturing process. Consequently, an economic advantage can also be expected. <Reiner Asphalt>

[0082] The asphalt composition includes petroleum resin (A) and pure asphalt.

[0083] Pure asphalt is used as asphalt base oil.

[0084] The asphalt specified in Table 3 of JIS K 2207 or a mixture thereof can be used as pure asphalt.

[0085] The penetration level of the pure asphalt is preferably 30 to 100, more preferably 40 to 90 and most preferably 50 to 80.

[0086] The degree of penetration can be measured according to section 6.3 “Test procedure for the degree of penetration” of JIS K 2207. <asphaltzusammensetzung>

[0087] The asphalt composition includes petroleum resin (A) and pure asphalt.

[0088] The petroleum resin (A) content in the asphalt composition is preferably 0.1 wt% or more and 5 wt% or less, preferably 0.1 wt% or more and 3 wt% or less, more preferably 0.15 wt% or more and 3 wt% or less, more preferably 0.3 wt% or more and 3 wt% or less, with the viewpoint of improving the adhesion properties between the asphalt composition and the aggregate.

[0089] The content of pure asphalt in the asphalt composition is preferably 70.00 wt% to 99.99 wt%, more preferably 90 wt% to 99.90 wt%, and even more preferably 93 wt% to 99.90 wt%, with the aim of improving the adhesion properties between the asphalt composition and the aggregate.

[0090] In addition to the petroleum resin (A) and the pure asphalt, the asphalt composition may contain various additives to an extent that does not impair the effect of the present invention. Examples of additives include antioxidants, adhesion promoters, emulsifiers, chemical modifiers, fibers, pigments, rubber-based additives, tackifiers, and regeneration additives.

[0091] If an additive is used, its content in the asphalt composition is preferably 20% by mass or less, more preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 3% by mass or less. <Verfahren zur Herstellung einer Asphaltzusammensetzung>

[0092] The method for producing the asphalt composition is not particularly restricted, and, for example, the asphalt composition is preferably produced as follows: The petroleum resin (A) is pulverized to a predetermined diameter or less; the pulverized petroleum resin (A) and the pure asphalt are then placed in a stainless steel container in a predetermined ratio; and heating, stirring, and mixing are carried out under predetermined conditions.

[0093] The stirring and mixing time can be reduced by pulverizing the petroleum resin (A) to a diameter of preferably 10 mm or less, more preferably 7 mm or less, or more preferably 5 mm or less, before stirring and mixing the petroleum resin (A) and the pure asphalt.

[0094] The predetermined conditions for stirring and mixing are not particularly restricted, and the heating condition is preferably 80 °C to 100 °C, more preferably 100 °C to 150 °C, the stirring condition is preferably 500 rpm to 8,000 rpm, more preferably between 700 rpm and 7,000 rpm, more preferably between 1,000 rpm and 5,000 rpm, and the stirring and mixing time is preferably between 3 minutes and 60 minutes, more preferably between 5 minutes and 45 minutes, more preferably between 10 minutes and 30 minutes. <asphaltmischung>

[0095] An asphalt mixture according to one aspect of the first invention comprises the asphalt composition of the first invention and aggregate. The content of the asphalt composition is preferably 0.1 wt% to 30 wt%, more preferably 1 wt% to 20 wt%, more preferably 1 wt% to 15 wt%, more preferably 1 wt% to 10 wt%, and more preferably 2 wt% to 7 wt%.

[0096] Regarding the asphalt mixture, an asphalt mixture with a desired property can be obtained by adding aggregate with a predetermined particle diameter to the asphalt composition and mixing the materials at a predetermined rotational speed. The temperature at the time of mixing the asphalt composition and the aggregate is preferably about 150 °C to about 200 °C. [Second invention: Petroleum resin (B)]

[0097] A petroleum resin (B) according to a second invention is described below.

[0098] The petroleum resin (B) is obtained by copolymerization of: a monomer comprising at least one type of cyclic olefin with an ethylene-unsaturated group selected from a C5 fraction, a C8 fraction and a C9 fraction of cracked naphtha, and dicyclopentadiene; and a silane.

[0099] The petroleum resin (B) meets the following conditions (b1) and (b2): (b1) the petroleum resin (B) contains 0.1 wt% or more and 10 wt% or less silicon element, expressed in silicon atoms; and (b2) the petroleum resin (B) has a weight-average molecular weight (Mw) of 500 or more and 3,000 or less.

[0100] The above-mentioned physical properties of the petroleum resin (B) can be appropriately adjusted by selecting a raw material monomer, a polymerization solvent and a catalyst, their quantities used, a polymerization temperature, a reaction pressure and other polymerization conditions.

[0101] According to the second invention, the following effect is achieved. A petroleum resin (B) can be provided which, when added to asphalt, can improve the water resistance of the asphalt mixture (mixture of asphalt and aggregate) in order to extend the service life of an asphalt road. The reason for this effect is not entirely clear, but is suspected to be as follows.

[0102] Typically, on asphalt roads, when moisture is present at an interface between the aggregate and the asphalt, the affinity between the hydroxyl group on the surface of the aggregate and the moisture is greater than the affinity between the surface of the aggregate and the asphalt. Consequently, the asphalt detaches from the surface of the aggregate, and the load from a motor vehicle or similar vehicle leads to damage to the asphalt road. However, when the asphalt is mixed with petroleum resin (B), the aggregate and the petroleum resin (B) chemically bond through the reaction between the hydroxyl group on the surface of the aggregate and a silane-containing group in the petroleum resin (B), thereby improving the affinity between the aggregate and the asphalt and enhancing the adhesion between the aggregate and the asphalt.At this point, the aggregate and the petroleum resin (B) are chemically bonded together, even when moisture is present near the surface of the aggregate, so the asphalt does not detach. Accordingly, it is assumed that the water resistance of the asphalt road is improved, and thus its durability is enhanced, as the adhesion between the aggregate and the asphalt is maintained.

[0103] The above-mentioned mechanism regarding the effect of the present invention is a conjecture and the mechanism is not limited to it.

[0104] The petroleum resin (B) contains 0.1 wt% or more and 10 wt% or less, preferably 0.3 wt% or more, more preferably 0.4 wt% or more, more preferably 0.5 wt% or more, and preferably less than 3.1 wt%, more preferably less than 1.7 wt%, more preferably 1.0 wt% or less, of silicon element, expressed in silicon atoms. The silicon element is preferably derived from an organic silane structure.

[0105] If the concentration of silicon element in the petroleum resin (B) is below the above-mentioned ranges (less than 0.1 wt%), the petroleum resin (B) hardly reacts with the surface of the aggregate, which may result in insufficient water resistance of the asphalt mixture.

[0106] However, if the concentration of silicon element in the petroleum resin (B) exceeds the aforementioned ranges (more than 10 wt%), the molecules of the petroleum resin (B) react with each other, thereby increasing their molecular weight. This reduces the miscibility with the asphalt, so the water resistance of the asphalt mixture cannot be improved.

[0107] The concentration of silicon element can be measured by ICP emission spectroscopy and specifically determined by a method described in the examples.

[0108] If the petroleum resin (B) is used as an asphalt compound and the concentration of silicon element in the petroleum resin (B) is, for example, more than 1.0 wt%, molecules of the petroleum resin (B) can cross-link under certain conditions, such as exposure to high temperatures in the presence of water or in the presence of an acid or an alkali. As a result, the improving effect on water resistance may be reduced.

[0109] The petroleum resin (B) has a weight-average molecular weight (Mw) of 500 or more and 3,000 or less, preferably 700 or more, more preferably 1,000 or more, more preferably 1,200 or more, more preferably 1,500 or more and preferably 3,000 or less, more preferably 2,800 or less, more preferably 2,500 or less.

[0110] If the weight-average molecular weight (Mw) of the petroleum resin (B) is below the above-mentioned ranges (less than 500), the asphalt composition may have insufficient hardness or become brittle at normal temperature, thereby reducing the strength and thus potentially affecting the durability of an asphalt road.

[0111] However, if the weight-mean molecular weight (Mw) of the petroleum resin (B) exceeds the aforementioned ranges (above 3,000), the viscosity may be increased when mixed with asphalt at high temperatures, which can impair miscibility with the asphalt. Consequently, sufficient water resistance may not be achieved.

[0112] Furthermore, the petroleum resin (B) has a molecular weight distribution (Mw / Mn) of preferably 5.0 or less, more preferably 4.0 or less, and more preferably 3.0 or less, with the aim of improving the adhesion properties between the aggregate and the asphalt.

[0113] The weight-mean molecular weight (Mw) and the number-mean molecular weight (Mn) are each molecular weights expressed in terms of polystyrene. These molecular weights can each be measured by gel permeation chromatography (GPC) and specifically determined using a method described in the examples.

[0114] The petroleum resin (B) preferably meets the following condition (b3): ​​(b3) The petroleum resin (B) has a softening point of 70 °C to 150 °C.

[0115] The petroleum resin (B) has a softening point of preferably 70 °C to 150 °C, more preferably 80 °C to 140 °C, most preferably 90 °C to 140 °C, from the point of view of improving the adhesion properties between the aggregate and the asphalt.

[0116] The softening point can be measured according to JIS K 6863:1994.

[0117] The petroleum resin (B) preferably meets the following condition (b4): (b4) The petroleum resin (B) has a bromine number of 0.5 g / 100 g to 30 g / 100 g.

[0118] The petroleum resin (B) has a bromine number of preferably 0.5 g / 100 g to 30 g / 100 g, more preferably 1.0 g / 100 g to 25 g / 100 g, most preferably 2.0 g / 100 g to 20 g / 100 g, from the point of view of improving the adhesion properties between the aggregate and the asphalt.

[0119] The bromine number can be measured according to JIS K 2605:1996.

[0120] The petroleum resin (B) contains a repeating unit derived from a monomer and a repeating unit derived from a silane, and is preferably obtained by copolymerization of a monomer and a silane. (monomer)

[0121] The monomer for the formation of the petroleum resin (B) contains at least one type of cyclic olefin with an ethylene-unsaturated group selected from a C5 fraction, a C8 fraction and a C9 fraction of cracked naphtha, and a cyclopentadiene-based compound, preferably containing a cyclopentadiene-based compound and more preferably containing dicyclopentadiene.

[0122] Furthermore, a cyclopentadiene-based compound is preferably used as the first raw material component and a vinylaromatic compound as the second raw material component as monomers, wherein the first raw material component can be used alone without using the second raw material component.

[0123] Examples of cyclopentadiene-based compounds include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, and their dimers and codimers. Among these, dicyclopentadiene is the preferred cyclopentadiene-based compound.

[0124] Examples of vinylaromatic compounds include styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, vinylxylene, indene, methylindene, and ethylindene. Among these, styrene is the most commonly used vinylaromatic compound.

[0125] The mixing ratio between the cyclopentadiene-based compound and the vinylaromatic compound is not particularly restricted, and the ratio “cyclopentadiene-based compound : vinylaromatic compound” is preferably 80:20 to 20:80, more preferably 75:25 to 25:75, based on the mass ratio. (Silane)

[0126] The silane for the formation of the petroleum resin (B) is not particularly restricted and preferably has a structure that is represented by the following formula (1): CH2=CR-(COO) x (C n H 2n ) y SiR'3 Formula (1): where In formula (1), R represents a hydrogen atom or a methyl group, “x” and “y” represent 0 or 1 respectively, with the proviso that, where “x” represents 1, “y” represents 1, “n” represents an integer from 1 to 12, preferably from 1 to 4, and R’s each independently represent an alkoxy group with 1 to 12 carbon atoms (e.g., a methoxy, ethoxy, or butoxy group), an aryloxy group (e.g., a phenoxy group), an aralkyloxy group (e.g., a benzyloxy group), an aliphatic acyloxy group with 1 to 12 carbon atoms (e.g., a formyloxy, acetyloxy, or propaneoxy group), an amino or substituted amino group (an alkylamino or arylamino group), or a lower alkyl group with 1 to 6 carbon atoms, with the proviso that two or fewer of the three R' groups are each an alkyl group.

[0127] In formula (1) R preferably represents a hydrogen atom, from the point of view of improving the adhesion properties between the asphalt composition and the aggregate, “x” and / or “y” preferably represent 0, and “x” and “y” each more preferably represent 0.

[0128] Furthermore, in formula (1) R's preferably comprise an alkoxy group with 1 to 12 carbon atoms (e.g. a methoxy, ethoxy or butoxy group), more preferably an alkoxy group with 1 to 5 carbon atoms, and even more preferably an alkoxy group with 1 to 3 carbon atoms, with the viewpoint of improving the adhesion properties between the asphalt composition and the aggregate.

[0129] The silane is preferably at least one type selected from vinyltrimethoxysilane, vinyltriethoxysilane and 3-(trimethoxysilyl)propyl methacrylate, with the viewpoint of improving the adhesion properties between the asphalt composition and the aggregate.

[0130] The petroleum resin (B) is preferably a hydrogenated product obtained by hydrogenation (addition of hydrogen) to improve the adhesion properties between the asphalt composition and the aggregate. The hydrogenated petroleum resin (B) product can be a partially hydrogenated type, in which the petroleum resin (B) is partially hydrogenated, or a fully hydrogenated type, in which the petroleum resin (B) is completely hydrogenated.

[0131] The petroleum resin (B) can be in the form of a copolymer as described above, and the difference in its structure compared to the resin of PTL 1, which can be in the form of a modified product, is described as follows.

[0132] In the modified product, a radical attacks the petroleum resin, and a silane is added to a decomposed unit, resulting in a modified unit with a low molecular weight and the addition of silicon to a low molecular weight side. In the copolymer, however, the monomers each exhibit essentially the same copolymerizability, so silicon is added uniformly.

[0133] This means that silicon is introduced uniformly into the copolymer, so that even with an increase in the silicon content, no areas of localized silicon concentration are created. This allows a high silicon content to be achieved without gelation. In the modified product, however, silicon is introduced unevenly, resulting in a molecule with areas of high silicon concentration (localized silicon concentrations). This reduces the proportion of silicon that effectively reacts with a hydroxyl group on the surface of the aggregate and increases the likelihood of molecules without silicon being present. Consequently, the improvement in water resistance is less pronounced.

[0134] Accordingly, a greater improvement in water resistance can be expected when the petroleum resin (B) is used for an asphalt mixture, from the point of view that a higher Si content can be achieved through the form of the copolymer than through the form of the modified product. <Verfahren zur Herstellung von Petroleumharz (B)> ;

[0135] The process for producing the petroleum resin (B) is not particularly restricted, and, for example, the petroleum resin (B) is preferably formed as follows: the above-mentioned monomer, the above-mentioned silane and a solvent for polymerization are placed in a polymerization reaction vessel; and the above-mentioned monomer and the above-mentioned silane are subjected to a copolymerization reaction under predetermined conditions.

[0136] The amount of silane used is preferably 0.1 to 80 mass parts, more preferably 0.5 to 50 mass parts, and even more preferably 1 to 30 mass parts, based on 100 mass parts of the monomer.

[0137] Typical examples of solvents for polymerization include aromatic solvents, naphthene-based solvents, and aliphatic hydrocarbon solvents. Specific examples of suitable solvents for polymerization are toluene, xylene, cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane.

[0138] The amount of solvent used for the polymerization is preferably 10 to 300 mass parts, more preferably 20 to 200 mass parts, and even more preferably 30 to 100 mass parts, based on 100 mass parts of the monomer.

[0139] The predetermined conditions in the copolymerization reaction are not particularly restricted, and a reaction temperature is preferably between 150 °C and 350 °C, more preferably between 200 °C and 350 °C, most preferably between 230 °C and 300 °C; a reaction pressure is preferably between 0 MPaG and 5 MPaG, more preferably between 0 MPaG and 3 MPaG, more preferably between 0.1 MPaG and 2 MPaG; and the reaction time is preferably between 1 hour and 10 hours, more preferably between 1 hour and 8 hours, more preferably between 1 hour and 5 hours. "G" in "MPaG" refers to a pressure gauge pressure.

[0140] Furthermore, a process for producing the petroleum resin (B) as a hydrogenated product is not particularly restricted, and, for example, the hydrogenated product of the petroleum resin (B) is preferably formed as follows: In a hydrogenation reaction vessel, the petroleum resin (B) is dissolved in a hydrogenation solvent; and hydrogen is added under predetermined conditions in the presence of a hydrogenation reaction catalyst in an amount required to carry out a hydrogenation reaction.

[0141] Examples of hydrogenation solvents include cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, and tetrahydrofuran.

[0142] The amount of hydrogenation solvent used is preferably 30 to 300 mass parts, more preferably 50 to 250 mass parts, and even more preferably 70 to 150 mass parts, based on 100 mass parts of the petroleum resin (B).

[0143] Furthermore, an example of a catalyst for the hydrogenation reaction is a catalyst containing at least one metal component selected from nickel, palladium, cobalt, platinum, and rhodium.

[0144] The predetermined conditions in the hydrogenation reaction are not particularly restricted, and a reaction temperature is preferably between 100 °C and 300 °C, more preferably between 150 °C and 280 °C, and even more preferably between 180 °C and 250 °C; the supply pressure of hydrogen is preferably between 0.5 MPaG and 10 MPaG, more preferably 1 MPaG to 8 MPaG, and even more preferably 2 MPaG to 7 MPaG; and a reaction time is preferably between 1 hour and 20 hours, more preferably 2 hours and 15 hours, and even more preferably 3 hours and 10 hours.

[0145] The petroleum resin (B) may be in the form of a copolymer as described above, and the difference in its manufacturing process compared to the resin of PTL 1, which may be in the form of a modified product, is described below.

[0146] Unlike the modified product, the copolymer does not require a step in which a petroleum resin is first produced and then modified with a silane, thus simplifying the manufacturing process. Consequently, an economic advantage can also be expected. <Reiner Asphalt>

[0147] The petroleum resin (B) can be used by incorporating it into the asphalt composition.

[0148] If the asphalt composition contains petroleum resin (B) and pure asphalt, the pure asphalt is used as the asphalt base oil.

[0149] The asphalt specified in Table 3 of JIS K 2207 or a mixture thereof can be used as pure asphalt.

[0150] The penetration level of the pure asphalt is preferably between 30 and 100, more preferably between 40 and 90, and most preferably between 50 and 80.

[0151] The degree of penetration can be measured according to section 6.3 “Test procedure for the degree of penetration” of JIS K 2207. <asphaltzusammensetzung>

[0152] If the asphalt composition contains the petroleum resin (B) and the pure asphalt, the content of the petroleum resin (B) in the asphalt composition is preferably 0.1 wt% or more and 5 wt% or less, preferably 0.1 wt% or more and 3 wt% or less, more preferably 0.15 wt% or more and 3 wt% or less, more preferably 0.3 wt% or more and 3 wt% or less, from the point of view of improving the adhesion properties between the asphalt composition and the aggregate.

[0153] The content of pure asphalt in the asphalt composition is preferably 70.00 wt% to 99.99 wt%, more preferably 90 wt% to 99.90 wt%, and even more preferably 93 wt% to 99.90 wt%, with the aim of improving the adhesion properties between the asphalt composition and the aggregate.

[0154] In addition to the petroleum resin (B) and the pure asphalt, the asphalt composition may contain various additives to an extent that does not impair the effect of the present invention. Examples of additives include antioxidants, adhesion promoters, emulsifiers, chemical modifiers, fibers, pigments, rubber-based additives, tackifiers, and regeneration additives.

[0155] If an additive is used, its content in the asphalt composition is preferably 20% by mass or less, more preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 3% by mass or less. <Verfahren zur Herstellung einer Asphaltzusammensetzung>

[0156] The method for producing the asphalt composition is not particularly restricted, and, for example, the asphalt composition is preferably produced as follows: The petroleum resin (B) is pulverized to a predetermined diameter or less; the pulverized petroleum resin (B) and the pure asphalt are then placed in a stainless steel container in a predetermined ratio; and heating, stirring, and mixing are carried out under predetermined conditions.

[0157] The stirring and mixing time can be reduced by pulverizing the petroleum resin (B) to a diameter of preferably 10 mm or less, more preferably 7 mm or less, or more preferably 5 mm or less, before stirring and mixing the petroleum resin (B) and the pure asphalt.

[0158] The predetermined conditions for stirring and mixing are not particularly restricted, and the heating condition is preferably 80 °C or more, more preferably 100 °C or more, more preferably 150 °C or more, the stirring condition is preferably 500 rpm to 8000 rpm, more preferably 700 rpm to 7000 rpm, more preferably 1000 rpm to 5000 rpm, and the stirring and mixing time is preferably 3 minutes to 60 minutes, more preferably 5 minutes to 45 minutes, more preferably 10 minutes to 30 minutes. <asphaltmischung>

[0159] An asphalt mixture according to one aspect of the second invention comprises the asphalt composition containing the petroleum resin (B) of the second invention and aggregate. The content of the asphalt composition is preferably 0.1 wt% to 30 wt%, more preferably 1 wt% to 20 wt%, more preferably 1 wt% to 15 wt%, more preferably 1 wt% to 10 wt%, and more preferably 2 wt% to 7 wt%.

[0160] Regarding the asphalt mixture, an asphalt mixture with a desired property is obtained by adding aggregate with a predetermined particle diameter to the asphalt composition and mixing the materials at a predetermined rotational speed. The temperature at the time of mixing the asphalt composition and the aggregate is preferably about 150 °C to about 200 °C. [Third invention: Hydrogenated petroleum resin (C)]

[0161] In the following, a hydrogenated petroleum resin (C) according to a third invention is described.

[0162] The hydrogenated petroleum resin (C) is obtained by copolymerization of: a monomer comprising at least one type of cyclic olefin with an ethylene unsaturated group selected from a C5 fraction, a C8 fraction and a C9 fraction of cracked naphtha, and a cyclopentadiene-based compound; and a silane.

[0163] The hydrogenated petroleum resin (C) meets the following conditions (c1) and (c2): (c1) The hydrogenated petroleum resin (C) contains 0.1 wt% or more and 10 wt% or less silicon element, expressed in silicon atoms; and (c2) the hydrogenated petroleum resin (C) has a weight mean molecular weight (Mw) of 500 or more and 3,000 or less.

[0164] The above-mentioned physical properties of the hydrogenated petroleum resin (C) can be appropriately adapted by selecting a monomer starting material, a polymerization solvent, a catalyst, their amounts of use, a polymerization temperature, a reaction pressure, and other polymerization conditions.

[0165] According to the third invention, the following effect is achieved. A petroleum resin (C) can be provided which, when added to asphalt, can improve the water resistance of the asphalt mixture (mixture of asphalt and aggregate) in order to extend the service life of an asphalt road. The reason for this effect is not entirely clear, but is suspected to be as follows.

[0166] Typically, on asphalt roads, when moisture is present at an interface between the aggregate and the asphalt, the affinity between the hydroxyl group on the aggregate surface and the moisture is greater than the affinity between the aggregate surface and the asphalt. Consequently, the asphalt detaches from the aggregate surface, and the impact of a vehicle or similar vehicle damages the asphalt road. However, when hydrogenated petroleum resin (C) is added to the asphalt, the aggregate and the hydrogenated petroleum resin (C) chemically bond through the reaction between the hydroxyl group on the aggregate surface and a silane-containing group in the hydrogenated petroleum resin (C), thereby improving the affinity between the aggregate and the asphalt and enhancing the adhesion between the aggregate and the asphalt.At this point, the aggregate and the hydrogenated petroleum resin (C) are chemically bonded together, even when moisture is present near the surface of the aggregate, preventing the asphalt from detaching. Accordingly, it is assumed that the water resistance of the asphalt road is improved, thus enhancing its durability, as the adhesion between the aggregate and the asphalt is maintained.

[0167] The above-mentioned mechanism regarding the effect of the present invention is a conjecture and the mechanism is not limited to it.

[0168] The hydrogenated petroleum resin (C) contains 0.1 wt% or more and 10 wt% or less, preferably 0.3 wt% or more, preferably 0.4 wt% or more, more preferably 0.5 wt% or more, and more preferably 3.1 wt% or less, more preferably 1.7 wt% or less, and more preferably 1.0 wt% or less, of silicon element, expressed in silicon atoms. The silicon element is preferably derived from an organic silane structure.

[0169] If the concentration of silicon element in the hydrogenated petroleum resin (C) is below the above-mentioned ranges (less than 0.1 wt%), the hydrogenated petroleum resin (C) hardly reacts with the surface of the aggregate, which may result in insufficient water resistance of the asphalt mixture.

[0170] However, if the concentration of silicon element in the hydrogenated petroleum resin (C) exceeds the aforementioned ranges (more than 10 wt%), the molecules of the hydrogenated petroleum resin (C) react with each other, thereby increasing their molecular weight. This reduces the miscibility with the asphalt, so the water resistance of the asphalt mixture cannot be improved.

[0171] The concentration of silicon element can be measured by ICP emission spectroscopy and specifically determined by a method described in the examples.

[0172] When hydrogenated petroleum resin (C) is used as an asphalt compound and the concentration of silicon element in the hydrogenated petroleum resin (C) is, for example, more than 1.0 wt%, molecules of the hydrogenated petroleum resin (C) can cross-link under conditions such as exposure to high temperatures in the presence of water or in the presence of an acid or an alkali. As a result, the improving effect on water resistance can be reduced.

[0173] The hydrogenated petroleum resin (C) has a weight-average molecular weight (Mw) of 500 or more and 3,000 or less, preferably 700 or more, preferably 1,000 or more, more preferably 1,200 or more, more preferably 1,500 or more and more preferably 3,000 or less, more preferably 2,800 or less, more preferably 2,500 or less.

[0174] If the weight-average molecular weight (Mw) of the hydrogenated petroleum resin (C) is outside the above-mentioned ranges (less than 500), the asphalt composition may have insufficient hardness or become brittle at normal temperature, thereby reducing the strength and thus impairing the durability of an asphalt road.

[0175] However, if the weight-mean molecular weight (Mw) of the hydrogenated petroleum resin (C) exceeds the aforementioned ranges (above 3,000), its viscosity may be increased at high temperature when mixed with asphalt, and its miscibility with the asphalt may be impaired. Consequently, sufficient water resistance may not be achieved.

[0176] Furthermore, the hydrogenated petroleum resin (C) has a molecular weight distribution (Mw / Mn) of preferably 5.0 or less, more preferably 4.0 or less, and more preferably 3.0 or less, with the aim of improving the adhesion properties between the aggregate and the asphalt.

[0177] The weight-mean molecular weight (Mw) and the number-mean molecular weight (Mn) are each molecular weights expressed in terms of polystyrene. These molecular weights can each be measured by gel permeation chromatography (GPC) and specifically determined using a method described in the examples.

[0178] The hydrogenated petroleum resin (C) preferably meets the following condition (c3): (c3) The hydrogenated petroleum resin (C) has a softening point of 70 °C to 150 °C.

[0179] The hydrogenated petroleum resin (C) has a softening point of preferably 70 °C to 150 °C, more preferably 80 °C to 140 °C, most preferably 90 °C to 140 °C, from the point of view of improving the adhesion properties between the aggregate and the asphalt.

[0180] The softening point can be measured according to JIS K 6863:1994.

[0181] The hydrogenated petroleum resin (C) preferably meets the following condition (c4): (c4) The hydrogenated petroleum resin (C) has a bromine number of 0.5 g / 100 g to 30 g / 100 g.

[0182] The hydrogenated petroleum resin (C) has a bromine number of preferably 0.5 g / 100 g to 30 g / 100 g, preferably 1.0 g / 100 g to 25 g / 100 g, more preferably 2.0 g / 100 g to 20 g / 100 g, from the point of view of improving the adhesion properties between the aggregate and the asphalt.

[0183] The bromine number can be measured according to JIS K 2605:1996.

[0184] The hydrogenated petroleum resin (C) contains a repeating unit derived from a monomer and a repeating unit derived from a silane, and is preferably obtained by copolymerization of a monomer and a silane. (monomer)

[0185] The monomer for the formation of the hydrogenated petroleum resin (C) contains at least one type of cyclic olefin with an ethylene-unsaturated group selected from a C5 fraction, a C8 fraction and a C9 fraction of cracked naphtha, and a cyclopentadiene-based compound, preferably containing a cyclopentadiene-based compound and more preferably containing dicyclopentadiene.

[0186] Furthermore, a cyclopentadiene-based compound is preferably used as the first raw material and a vinylaromatic compound as the second raw material as monomers, and the first raw material can be used alone without using the second raw material.

[0187] Examples of cyclopentadiene-based compounds include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, and their dimers and codimers. Among these, dicyclopentadiene is the preferred cyclopentadiene-based compound.

[0188] Examples of vinylaromatic compounds include styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, vinylxylene, indene, methylindene, and ethylindene. Among these, styrene is the most commonly used vinylaromatic compound.

[0189] The mixing ratio between the cyclopentadiene-based compound and the vinylaromatic compound is not particularly restricted, and the ratio “cyclopentadiene-based compound : vinylaromatic compound” is preferably 80:20 to 20:80, more preferably 75:25 to 25:75, based on the mass ratio. (Silane)

[0190] The silane for the formation of the hydrogenated petroleum resin (C) is not particularly restricted and preferably has a structure that is represented by the following formula (1): CH2=CR-(COO) x (CnH 2n ) y SiR'3 Formula (1): where In formula (1), R represents a hydrogen atom or a methyl group, “x” and “y” represent 0 or 1 respectively, provided that where “x” represents 1, “y” represents 1, “n” represents an integer from 1 to 12, preferably from 1 to 4, and R’s each independently represent an alkoxy group with 1 to 12 carbon atoms (e.g., a methoxy, ethoxy, or butoxy group), an aryloxy group (e.g., a phenoxy group), an aralkyloxy group (e.g., a benzyloxy group), an aliphatic acyloxy group with 1 to 12 carbon atoms (e.g., a formyloxy, acetyloxy, or propaneoxy group), an amino or substituted amino group (an alkylamino or arylamino group), or a lower alkyl group with 1 to 6 carbon atoms, provided that two or fewer of the three R' groups are each an alkyl group.

[0191] In formula (1) R preferably represents a hydrogen atom from the point of view of improving the adhesion properties between the asphalt composition and the aggregate, “x” and / or “y” preferably represent 0, “x” and “y” each more preferably represent 0.

[0192] Furthermore, in formula (1) R's preferably comprise an alkoxy group with 1 to 12 carbon atoms (e.g. a methoxy, ethoxy or butoxy group), more preferably an alkoxy group with 1 to 5 carbon atoms, and even more preferably an alkoxy group with 1 to 3 carbon atoms, with the viewpoint of improving the adhesion properties between the asphalt composition and the aggregate.

[0193] The silane is preferably at least one type selected from vinyltrimethoxysilane, vinyltriethoxysilane and 3-(trimethoxysilyl)propyl methacrylate, with the viewpoint of improving the adhesion properties between the asphalt composition and the aggregate.

[0194] The hydrogenated petroleum resin (C) can take the form of a copolymer as described above, and the difference in its structure compared to the resin of PTL 1, which can take the form of a modified product, is described below.

[0195] In the modified product, a radical attacks the hydrogenated petroleum resin, and a silane is added to a decomposed unit, resulting in a low molecular weight modified unit and the addition of silicon to a low molecular weight side. In the copolymer, however, the monomers each exhibit essentially the same copolymerizability, so silicon is added uniformly.

[0196] This means that silicon is introduced uniformly into the copolymer, so that even with an increase in the silicon content, no areas of localized silicon concentration are created. This allows a high silicon content to be achieved without gelation. In the modified product, however, silicon is introduced unevenly, resulting in a portion of a molecule with a high silicon concentration (creating a site of localized silicon concentration). This reduces the proportion of silicon that effectively reacts with a hydroxyl group on the surface of the aggregate and increases the likelihood of molecules lacking silicon. Consequently, the improvement in water resistance is less pronounced.

[0197] Accordingly, a greater improvement in water resistance can be expected when the hydrogenated petroleum resin (C) is used for an asphalt mixture, from the point of view that a higher Si content can be achieved through the form of the copolymer than through the form of the modified product. <Verfahren zur Herstellung von Petroleumharz zur Bildung von hydriertem Petroleumharz (C)>

[0198] A process for producing a petroleum resin to form the hydrogenated petroleum resin (C) is not particularly restricted, and, for example, the petroleum resin is preferably produced as follows: the above-mentioned monomer, the above-mentioned silane and a solvent for polymerization are placed in a polymerization reaction vessel; and the above-mentioned monomer and the above-mentioned silane are subjected to a copolymerization reaction under predetermined conditions.

[0199] The amount of silane used is preferably 0.1 to 80 mass parts, more preferably 0.5 to 50 mass parts, and even more preferably 1 to 30 mass parts, based on 100 mass parts of the monomer.

[0200] Typical examples of solvents for polymerization include aromatic solvents, naphthene-based solvents, and aliphatic hydrocarbon solvents. Specific examples of suitable solvents for polymerization are toluene, xylene, cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane.

[0201] The amount of solvent used for the polymerization is preferably 10 to 300 mass parts, more preferably 20 to 200 mass parts, most preferably 30 to 100 mass parts, based on 100 mass parts of the monomer.

[0202] The predetermined conditions in the copolymerization reaction are not particularly restricted, and a reaction temperature is preferably between 150 °C and 350 °C, more preferably between 200 °C and 350 °C, and even more preferably between 230 °C and 300 °C; a reaction pressure is preferably between 0 MPaG and 5 MPaG, more preferably between 0 MPaG and 3 MPaG, and even more preferably between 0.1 MPaG and 2 MPaG; and the reaction time is preferably between 1 hour and 10 hours, more preferably between 1 hour and 8 hours, and even more preferably between 1 hour and 5 hours. "G" in "MPaG" refers to a pressure gauge pressure.

[0203] Furthermore, a process for producing the hydrogenated petroleum resin (C) by hydrogenating the petroleum resin is not particularly restricted, and, for example, the hydrogenated petroleum resin (C) is preferably formed as follows: In a hydrogenation reaction vessel, the above-mentioned petroleum resin is dissolved in a hydrogenation solvent; and hydrogen is added under predetermined conditions in the presence of a hydrogenation reaction catalyst in an amount required to carry out a hydrogenation reaction.

[0204] Examples of hydrogenation solvents include cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, and tetrahydrofuran.

[0205] The amount of hydrogenation solvent used is preferably 30 to 300 mass parts, more preferably 50 to 250 mass parts, and even more preferably 70 to 150 mass parts, based on 100 mass parts of the petroleum resin.

[0206] An example of a catalyst for the hydrogenation reaction is a catalyst containing at least one metal component selected from nickel, palladium, cobalt, platinum, and rhodium.

[0207] The predetermined conditions in the hydrogenation reaction are not particularly restricted, and a reaction temperature is preferably between 100 °C and 300 °C, more preferably between 150 °C and 280 °C, and even more preferably between 180 °C and 250 °C; the supply pressure of hydrogen is preferably between 0.5 MPaG and 10 MPaG, more preferably 1 MPaG to 8 MPaG, and more preferably 2 MPaG to 7 MPaG; and the reaction time is preferably 1 hour to 20 hours, more preferably 2 hours to 15 hours, and more preferably 3 hours to 10 hours.

[0208] The hydrogenated petroleum resin (C) can take the form of a copolymer as described above, and the difference in its manufacturing process compared to the resin of PTL 1, which can take the form of a modified product, is described below.

[0209] Unlike the modified product, the copolymer does not require a step in which a petroleum resin is first produced and then modified with a silane, thus simplifying the manufacturing process. Consequently, an economic advantage can also be expected. <Reiner Asphalt>

[0210] The hydrogenated petroleum resin (C) can be used by incorporating it into the asphalt composition.

[0211] If the asphalt composition contains the hydrogenated petroleum resin (C) and the pure asphalt, the pure asphalt is used as the asphalt base oil.

[0212] Asphalt as pure asphalt can be asphalt according to Table 3 of JIS K 2207 or a mixture thereof.

[0213] The penetration level of the pure asphalt is preferably between 30 and 100, more preferably between 40 and 90, and most preferably between 50 and 80.

[0214] The degree of penetration can be measured according to section 6.3 “Test procedure for the degree of penetration” of the standard JIS K 2207. <asphaltzusammensetzung>

[0215] If the asphalt composition contains the hydrogenated petroleum resin (C) and the pure asphalt, the content of the hydrogenated petroleum resin (C) in the asphalt composition is preferably 0.1 wt% or more and 5 wt% or less, preferably 0.1 wt% or more and 3 wt% or less, more preferably 0.15 wt% or more and 3 wt% or less, more preferably 0.3 wt% or more and 3 wt% or less, from the point of view of improving the adhesion properties between the asphalt composition and the aggregate.

[0216] The content of pure asphalt in the asphalt composition is preferably 70.00 wt% to 99.99 wt%, more preferably 90 wt% to 99.90 wt%, and even more preferably 93 wt% to 99.90 wt%, with the aim of improving the adhesion properties between the asphalt composition and the aggregate.

[0217] In addition to the hydrogenated petroleum resin (C) and the pure asphalt, the asphalt composition may contain various additives to an extent that does not impair the effect of the present invention. Examples of additives include antioxidants, adhesion promoters, emulsifiers, chemical modifiers, fibers, pigments, rubber-based additives, tackifiers, and regeneration additives.

[0218] If an additive is used, its content in the asphalt composition is preferably 20% by mass or less, more preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 3% by mass or less. <Verfahren zur Herstellung einer Asphaltzusammensetzung>

[0219] The method for producing the asphalt composition is not particularly restricted, and, for example, the asphalt composition is preferably produced as follows: the hydrogenated petroleum resin (C) is pulverized to a predetermined diameter or less; the pulverized hydrogenated petroleum resin (C) and the pure asphalt are then placed in a stainless steel container in a predetermined ratio; and heating, stirring, and mixing are carried out under predetermined conditions.

[0220] The stirring and mixing time can be reduced by pulverizing the hydrogenated petroleum resin (C) to a diameter of preferably 10 mm or less, more preferably 7 mm or less, or more preferably 5 mm or less, before stirring and mixing the hydrogenated petroleum resin (C) and the pure asphalt.

[0221] The predetermined conditions for stirring and mixing are not particularly restricted, and the heating condition is preferably 80 °C or more, more preferably 100 °C or more, more preferably 150 °C or more, the stirring condition is preferably 500 rpm to 8000 rpm, more preferably 700 rpm to 7000 rpm, more preferably 1000 rpm to 5000 rpm, and the stirring and mixing time is preferably 3 minutes to 60 minutes, more preferably 5 minutes to 45 minutes, more preferably 10 minutes to 30 minutes. <asphaltmischung>

[0222] An asphalt mixture according to one aspect of the third invention comprises the asphalt composition containing the hydrogenated petroleum resin (C) of the third invention and aggregate. The content of the asphalt composition is preferably 0.1 wt% to 30 wt%, more preferably 1 wt% to 20 wt%, more preferably 1 wt% to 15 wt%, more preferably 1 wt% to 10 wt%, and more preferably 2 wt% to 7 wt%.

[0223] Regarding the asphalt mixture, an asphalt mixture with a desired property is obtained by adding aggregate with a predetermined particle diameter to the asphalt composition and mixing the materials at a predetermined rotational speed. The temperature at the time of mixing the asphalt composition and the aggregate is preferably about 150 °C to about 200 °C. Examples

[0224] Next, the first, second and third inventions will be described in more detail using examples, although the first, second and third inventions are by no means limited to these examples. [Concentration of silicon element]

[0225] 0.1 grams of a petroleum resin or hydrogenated petroleum resin prepared in each example were heated in an electric furnace at 550 °C for 12 hours, and a sample solution was prepared by alkali fusion of an ash content. ICP emission spectroscopy was performed using an ICP emission spectrometer 720-ES (manufactured by Agilent Technologies, Inc., "720-ES") to determine the silicon element concentration. [Weight average molecular weight (Mw)]

[0226] The weight-mean molecular weight (Mw) of the petroleum resin or hydrogenated petroleum resin produced in each example was determined by gel permeation chromatography (GPC). The weight-mean molecular weight (Mw) was measured using the following apparatus and conditions and determined as the molecular weight relative to polystyrene. <GPC-Messgerät> Device: “HLC-8321GPC / HT” from Tosoh Corporation Detector: RI detector Pillar: 2 pillars “TOSOH GMHHR-H(S) HT” from Tosoh Corporation <messbedingungen> Solvent: 1,2,4-Trichlorobenzene Measurement temperature: 145 °C Flow rate: 1.0 ml / min Sample concentration: 0.5 mg / ml Injection volume: 300 µl Calibration curve: created using a standard PS substance Molecular weight conversion: calculated using a universal calibration method Analysis program: 8321GPC-WS [Softening point]

[0227] The softening point of the petroleum resin or hydrogenated petroleum resin produced in each example was measured according to JIS K 6863:1994. [Bromine number]

[0228] The bromine number of the petroleum resin or hydrogenated petroleum resin produced in each example was measured according to JIS K 2605:1996. [Evaluation of the asphalt composition]

[0229] Crushed hard gravel No. 6 was washed with water and dried at 170 °C for at least 1 hour. Then, 5.5 g ± 0.5 g of an asphalt composition was added to 100 g ± 0.5 g of the dried hard gravel aggregate. While the mixture was dried on a hot plate at a temperature of 160 °C to 180 °C, it was mixed and stirred for approximately 2 to 3 minutes. An asphalt mixture was thus prepared, from which 10 samples were selected. Next, the selected asphalt mixture was added to 100 ml of a 1.0 mol / l aqueous sodium carbonate solution. The aqueous solution was then heated on the hot plate, and heating was continued for 1 minute after the temperature reached 90 °C. After cooling to room temperature, the surface of the asphalt mixture was visually inspected.The proportion of the detached asphalt surface covering the surface of the aggregate was calculated, and the asphalt composition was evaluated based on the following criteria. A: The proportion of the area removed was 50% or less. B: The proportion of the area removed was more than 50% and less than 70%. C: The proportion of the area removed was more than 70%.

[0230] The asphalt composition can be evaluated as follows: The smaller the proportion of the detached surface of the top of the asphalt mixture, the more the detachment of the asphalt is suppressed and the better the water resistance of the asphalt mixture. Comparative manufacturing example 1: Hydrogenated petroleum resin

[0231] 180 g of xylene were placed in a 1-liter autoclave and the temperature was raised to 260 °C. A mixture of 100 g of dicyclopentadiene and 100 g of styrene was then added over a period of 3 hours. The polymerization reaction was carried out while maintaining the temperature for a further 75 minutes. A polymer mixture was thus obtained.

[0232] Xylene was then recovered from the resulting polymer mixture, and the mixture was held at 20 mmHg for 2 hours, causing a low-boiling-point product to evaporate. This yielded a petroleum resin.

[0233] 180 grams of the obtained petroleum resin, 180 g of ethylcyclohexane, and 4 g of a nickel-based catalyst (series N110) from JGC Catalysts and Chemicals Ltd. were placed in a 1-liter autoclave. Hydrogen was added until a pressure of 5 MPa was reached. The temperature in the autoclave was increased from room temperature to 230 °C. Subsequently, a hydrogenation reaction was carried out for 8 hours at a hydrogen pressure of 5 MPa. This yielded a hydrogenated petroleum resin. Production example 1: Petroleum resin (A1)

[0234] 180 g of xylene were placed in a 1-liter autoclave, and 236 g of dicyclopentadiene, 108 g of styrene, and 72 g of vinyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. After purging with nitrogen, the autoclave pressure was set to 0.15 MPa. The autoclave temperature was raised to 278 °C, and a polymerization reaction was carried out while maintaining the temperature for 3 hours. This resulted in the formation of a polymer mixture.

[0235] Subsequently, xylene was recovered from the resulting polymer mixture, and the mixture was held at 20 mmHg for 2 hours, causing a low-boiling-point product to evaporate. This yielded a petroleum resin (A1). Production example 2: Hydrogenated petroleum resin (A2)

[0236] 180 grams of the petroleum resin obtained in Production Example 1, 180 g of ethylcyclohexane, and 8 g of a nickel-based catalyst (N110 series) from JGC Catalysts and Chemicals Ltd. were placed in a 1-liter autoclave. Hydrogen was added until a pressure of 5 MPa was reached. The temperature in the autoclave was increased from room temperature to 230 °C. Subsequently, a hydrogenation reaction was carried out for 8 hours at a hydrogen pressure of 5 MPa. This yielded a hydrogenated petroleum resin (A2). Production example 3: Petroleum resin (A3)

[0237] 180 g of xylene were placed in a 1:1 autoclave, and 236 g of dicyclopentadiene, 108 g of styrene, and 11 g of vinyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. After purging with nitrogen, the autoclave pressure was set to 0.15 MPa. The autoclave temperature was raised to 278 °C, and a polymerization reaction was carried out while maintaining the temperature for 3 hours. A polymer mixture was thus obtained.

[0238] Subsequently, xylene was recovered from the resulting polymer mixture, and the mixture was held at 20 mmHg for 2 hours, causing a low-boiling-point product to evaporate. This yielded a petroleum resin (A3). Production example 4: Hydrogenated petroleum resin (A4)

[0239] 180 g of the petroleum resin (A3) obtained in Preparation Example 3, 180 g of ethylcyclohexane, and 8 g of a nickel-based catalyst (N110 series) manufactured by JGC Catalysts and Chemicals Ltd. were placed in a 1-liter autoclave. Hydrogen was added until a pressure of 5 MPa was reached. The temperature in the autoclave was increased from room temperature to 230 °C. Subsequently, a hydrogenation reaction was carried out for 8 hours at a hydrogen pressure of 5 MPa. This yielded a hydrogenated petroleum resin (A4). [Production of an asphalt mixture]Example 1

[0240] The petroleum resin (A1) obtained in Production Example 1 was pulverized to a diameter of 5 mm or less. The petroleum resin (A1) and the pure asphalt (manufactured by Idemitsu Kosan Co., Ltd., penetration grade: 72) were then mixed in a 200 ml stainless steel cylindrical container in the ratio specified in Table 1, resulting in a total quantity of 50 g. The materials were stirred and mixed for approximately 15 minutes using a stirrer with a heating jacket at temperatures of 160 °C or higher and rotational speeds of 2,000 rpm or higher and 4,000 rpm or lower. This process yielded an asphalt composition. Example 2

[0241] An asphalt composition was obtained in the same way as in Example 1, except that the petroleum resin (A1) obtained in Production Example 1 was replaced by the hydrogenated petroleum resin (A2) obtained in Production Example 2. Example 3

[0242] An asphalt composition was obtained in the same way as in Example 1, except that the petroleum resin (A1) obtained in Production Example 1 was replaced by the petroleum resin (A3) obtained in Production Example 3. Example 4

[0243] An asphalt composition was obtained in the same way as in Example 1, except that the petroleum resin (A1) obtained in Production Example 1 was replaced by the hydrogenated petroleum resin (A4) obtained in Production Example 4. Comparative example 1

[0244] An asphalt composition was obtained in the same way as in Example 1, except that the petroleum resin (A1) obtained in Production Example 1 was replaced by the hydrogenated petroleum resin obtained in Comparative Production Example 1 and the mixing ratio was changed to that given in Table 1. Comparative example 2

[0245] An asphalt composition was obtained in the same way as in Example 1, except that no petroleum resin was used.

[0246] The evaluation results of the asphalt composition produced in each example according to the first invention are listed in Table 1.

[0247] The evaluation results of the petroleum resin (B) produced in each example according to the second invention are listed in Table 2.

[0248] The evaluation results of the hydrogenated petroleum resin (C) according to the third invention, which was produced in each example, are listed in Table 3. [Table 1] Table 1: Asphalt composition according to the first invention Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Petroleum resin or hydrogenated petroleum resin Art Production example 1: Petroleum resin Production example 2: Hydrogenated petroleum resin Production example 3: Petroleum resin Production example 4: Hydrogenated petroleum resin Comparative manufacturing example 1: Hydrogenated petroleum resin - Silicon element concentration (mass %) 3,0 2,9 0,5 0,5 0 - Weight-average molecular weight (Mw) 1.400 1.900 1.600 2.400 1.100 - Molecular weight distribution (Mw / Mn) 2,3 2,8 2,8 3,9 2,1 Bromine value (g / 100 g) 14,3 2,5 16,5 2,5 2,5 - Softening point (°C) 100,9 136,6 94,9 119,2 102,5 Salary (mass %) 0,5 0,5 0,5 0,5 1 - asphalt Art Pure Asphalt Pure Asphalt Pure Asphalt Pure Asphalt Pure Asphalt Pure Asphalt Salary (mass %) 99,5 99,5 99 99,5 99 100 Assessment of asphalt composition Percentage of area removed (%) 20 50 4 50 95 100 Result A A A A C C

[0249] The results in Table 1 showed that each of the asphalt compositions according to the first invention of Examples 1 to 4 suppressed the detachment of the asphalt from the aggregate and improved the water resistance of the asphalt mixture compared to each of the asphalt compositions of Comparative Examples 1 and 2. [Table 2] Table 2: Petroleum resin (B) according to the second invention Example 3 Example 4 Comparative example 1 Comparative example 2 Petroleum resin or hydrogenated petroleum resin Art Production example 3: Petroleum resin Production example 4: Hydrogenated petroleum resin Comparative manufacturing example 1: Hydrogenated petroleum resin - Silicon element concentration (mass %) 0,5 0 0 - Weight-average molecular weight (Mw) 1.600 2.400 1.100 - Molecular weight distribution (Mw / Mn) 2,8 3,9 2,1 Bromine value (g / 100 g) 16,5 2,5 2,5 - Softening point (°C) 94,9 119,2 102,5 Salary (mass %) 0,5 0,5 1 - asphalt Art Pure Asphalt Pure Asphalt Pure Asphalt Pure Asphalt Salary (mass %) 99,5 99,5 99 10 Assessment of the asphalt composition Percentage of area removed (%) 40 50 95 10 Result A A C C

[0250] The results in Table 2 showed that each of the asphalt compositions containing the petroleum resin (B) according to the second invention of Examples 3 and 4 suppressed the detachment of the asphalt from the aggregate and improved the water resistance of the asphalt mixture compared to each of the asphalt compositions of Comparative Examples 1 and 2. [Table 3] Table 3: Hydrogenated petroleum resin (C) according to the third invention Example 2 Example 4 Comparative example 1 Comparative example 2 Petroleum resin or hydrogenated petroleum resin Art Production example 2: Hydrogenated petroleum resin Production example 4: Hydrogenated petroleum resin Comparative manufacturing example 1: Hydrogenated petroleum resin - Silicon element concentration (mass %) 2,9 0 0 - Weight-average molecular weight (Mw) 1.900 2.400 1.100 - Molecular weight distribution (Mw / Mn) 2,8 3,9 2,1 Bromine value (g / 100 g) 2,5 2,5 2,5 - Softening point (°C) 136,6 119,2 102,5 Salary (mass %) 0 0,5 1 - asphalt Art Pure Asphalt Pure Asphalt Pure Asphalt Pure Asphalt Salary (mass %) 99,5 99,5 99 10 Assessment of the asphalt composition Percentage of area removed (%) 50 50 95 100 Result A A C C

[0251] The results in Table 3 showed that each of the asphalt compositions containing the hydrogenated petroleum resin (C) according to the third invention of Examples 2 and 4 suppressed the detachment of the asphalt from the aggregate and improved the water resistance of the asphalt mixture compared to each of the asphalt compositions of Comparative Examples 1 and 2. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] WO 2021 / 161672 A1

[0004] < / messbedingungen> < / asphaltmischung> < / asphaltzusammensetzung> < / asphaltmischung> < / asphaltzusammensetzung> < / asphaltmischung> < / asphaltzusammensetzung> < / begriffsbestimmungen>

Claims

[1] Asphalt composition, comprising: a petroleum resin (A); and pure asphalt, wherein the petroleum resin (A) is a petroleum resin obtained by copolymerization of: a monomer containing at least one type of cyclic olefin with an ethylene unsaturated group selected from a C5 fraction, a C8 fraction and a C9 fraction of cracked naphtha, and a cyclopentadiene-based compound; and a silane, and wherein the petroleum resin (A) satisfies the following conditions (a1) and (a2): (a1) the petroleum resin (A) contains 0.1 wt% or more and 10 wt% or less silicon element, expressed in silicon atoms; and (a2) the petroleum resin (A) has a weight-average molecular weight (Mw) of 500 or more and 3,000 or less. [2] The asphalt composition according to claim 1, wherein the petroleum resin (A) satisfies the following condition (a3): (a3) the petroleum resin (A) has a softening point of 70 °C to 150 °C. [3] The asphalt composition according to claim 1 or 2, wherein the silane has a structure represented by the following formula (1): CH2=CR-(COO) x (C n H 2n ) y SiR'3 Formula (1): where in formula (1) represents a pure hydrogen atom or a methyl group, “x” and “y” each represent 0 or 1, provided that if “x” represents 1, “y” represents 1, “n” represents an integer from 1 to 12, and R’s each independently represent an alkoxy group with 1 to 12 carbon atoms, an aryloxy group, an aralkyloxy group, an aliphatic acyloxy group with 1 to 12 carbon atoms, an amino or substituted amino group, or a lower alkyl group with 1 to 6 carbon atoms, provided that two or fewer of the three R’ groups are each an alkyl group. [4] The asphalt composition according to any one of claims 1 to 3, wherein the silane is at least one type selected from vinyltrimethoxysilane, vinyltriethoxysilane and 3-(trimethoxysilyl)propyl methacrylate. [5] The asphalt composition according to any one of claims 1 to 4, wherein the monomer comprises dicyclopentadiene. [6] The asphalt composition according to any one of claims 1 to 5, wherein the petroleum resin (A) is a hydrogenated product. [7] Asphalt composition according to any one of claims 1 to 6, wherein the content of petroleum resin (A) in the asphalt composition is 0.1 wt% or more and 5 wt% or less. [8] Asphalt mixture, comprising: the asphalt composition according to any one of claims 1 to 7; and Aggregate, where the asphalt composition content is 1% by mass to 20% by mass. [9] A petroleum resin (B) obtained by copolymerization of: a monomer containing at least one type of cyclic olefin with an ethylene-unsaturated group selected from a C5 fraction, a C8 fraction and a C9 fraction of cracked naphtha, and a cyclopentadiene-based compound; and a silane wherein the petroleum resin (B) satisfies the following conditions (b1) and (b2): (b1) the petroleum resin (B) contains 0.1 wt% or more and 10 wt% or less silicon element, expressed in silicon atoms; and (b2) the petroleum resin (B) has a weight-average molecular weight (Mw) of 500 or more and 3,000 or less. [10] Petroleum resin (B) according to claim 9, wherein the petroleum resin (B) satisfies the following condition (b3): (b3) the petroleum resin (B) has a softening point of 70 °C to 150 °C. [11] The petroleum resin (B) according to claim 9 or 10, wherein the silane has a structure represented by the following formula (1): CH2=CR-(COO) x (C n H 2n ) y SiR'3 Formula (1): where in formula (1) R represents a hydrogen atom or a methyl group, “x” and “y” represent 0 or 1 respectively, provided that if “x” represents 1, “y” represents 1, “n” represents an integer from 1 to 12, and R' independently represents an alkoxy group with 1 to 12 carbon atoms, an aryloxy group, an aralkyloxy group, an aliphatic acyloxy group with 1 to 12 carbon atoms, an amino or substituted amino group, or a lower alkyl group with 1 to 6 carbon atoms, provided that two or fewer of the three R' groups are each an alkyl group. [12] The petroleum resin (B) according to any one of claims 9 to 11, wherein the silane is at least one type selected from vinyltrimethoxysilane, vinyltriethoxysilane and 3-(trimethoxysilyl)propyl methacrylate. [13] The petroleum resin (B) according to any one of claims 9 to 12, wherein the monomer comprises dicyclopentadiene. [14] The petroleum resin (B) according to any one of claims 9 to 13, wherein the petroleum resin (B) is a hydrogenated product. [15] Asphalt composition, comprising: the petroleum resin (B) according to any one of claims 9 to 14; and pure asphalt. [16] The asphalt composition according to claim 15, wherein the content of petroleum resin (B) in the asphalt composition is 0.1 wt% or more and 5 wt% or less. [17] Asphalt mixture comprising: the asphalt composition according to claim 15 or 16; and Aggregate, where the content of the asphalt composition is 1% by mass to 20% by mass. [18] A hydrogenated petroleum resin (C) obtained by copolymerization of: a monomer containing at least one type of cyclic olefin with an ethylene-unsaturated group selected from a C5 fraction, a C8 fraction and a C9 fraction of cracked naphtha, and a cyclopentadiene-based compound; and a silane wherein the hydrogenated petroleum resin (C) satisfies the following conditions (c1) and (c2): (c1) the hydrogenated petroleum resin (C) contains 0.1 wt% or more and 10 wt% or less silicon element, expressed in silicon atoms; and (c2) the hydrogenated petroleum resin (C) has a weight-average molecular weight (Mw) of 500 or more and 3,000 or less. [19] The hydrogenated petroleum resin (C) according to claim 18, wherein the hydrogenated petroleum resin (C) satisfies the following condition (c3): (c3) The hydrogenated petroleum resin (C) has a softening point of 70 °C to 150 °C. [20] The hydrogenated petroleum resin (C) according to claim 18 or 19, wherein the silane has a structure represented by the following formula (1): CH2=CR-(COO) x (CnH 2n ) y SiR'3 Formula (1): where in formula (1) R represents a hydrogen atom or a methyl group, “x” and “y” represent 0 or 1 respectively, provided that if “x” represents 1, “y” represents 1, “n” represents an integer from 1 to 12, and R’s each independently represent an alkoxy group with 1 to 12 carbon atoms, an aryloxy group, an aralkyloxy group, an aliphatic acyloxy group with 1 to 12 carbon atoms, an amino or substituted amino group, or a lower alkyl group with 1 to 6 carbon atoms, provided that two or fewer of the three R’ groups are each an alkyl group. [21] The hydrogenated petroleum resin (C) according to any one of claims 18 to 20, wherein the silane is at least one type selected from vinyltrimethoxysilane, vinyltriethoxysilane and 3-(trimethoxysilyl)propyl methacrylate. [22] The hydrogenated petroleum resin (C) according to any one of claims 18 to 21, wherein the monomer comprises dicyclopentadiene. [23] Asphalt composition, comprising: the hydrogenated petroleum resin (C) of any one of claims 18 to 22; and pure asphalt. [24] The asphalt composition according to claim 23, wherein the content of hydrogenated petroleum resin (C) in the asphalt composition is 0.1 wt% or more and 5 wt% or less. [25] An asphalt mixture comprising: the asphalt composition according to claim 23 or 24; and Aggregate, where the content of the asphalt composition is 1% by mass to 20% by mass.