Silane-containing compounds and modified hydrogenated petroleum resins

Abstract

A silane-containing compound having a cyclic structure within the molecular structure; a modified hydrogenated petroleum resin in which the bromine value, the silicon element content, the weight-average molecular weight, and the molecular weight distribution are specific values; a modified hydrogenated petroleum resin obtained by subjecting the modified hydrogenated petroleum resin to a condensation reaction; an adhesive composition that includes the modified hydrogenated petroleum resin; an asphalt composition that contains the silane-containing compound or the modified hydrogenated petroleum resin.

Description

[Technical Field]

[0001] The present invention relates to a silane-containing compound and a modified hydrogenated petroleum resin. [Background technology]

[0002] Silane compounds are used as materials to enhance the affinity between inorganic and organic substances. For example, trialkoxyaminoalkylsilanes are widely used as silane coupling agents, dispersion improvers for dispersing inorganic substances in organic substances such as resins, and adhesion improvers for adhering organic substances to inorganic surfaces.

[0003] In recent years, asphalt peeling, which occurs when rainwater or groundwater penetrates between the asphalt and aggregate, peeling off the asphalt covering the surface of the aggregate, has come to be cited as a major cause of damage to asphalt pavement. This type of asphalt peeling reduces the ability of the aggregate to adhere to each other, potentially making the pavement more susceptible to damage such as cracks and potholes. In order to cope with this asphalt peeling phenomenon, methods have been investigated for suppressing asphalt peeling by mixing fatty acids, such as resin acids such as dimer acid and rosin, saturated fatty acids such as stearic acid, palmitic acid, and myristic acid, and unsaturated fatty acids such as oleic acid, linoleic acid, and ricinolenic acid, into the asphalt as anti-peeling agents (Patent Documents 1 and 2). The technology disclosed in Patent Document 3 is an asphalt composition containing an asphalt base oil and a silane-containing coupling agent. However, the silane-containing coupling agent disclosed in Patent Document 3 is flexible and contains multiple silane atoms in one molecule, which results in low efficiency in function expression. In addition, the amount of silane-containing coupling agent contained in the asphalt composition is large, which increases costs.

[0004] On the other hand, petroleum resins are highly useful as tackifiers for hot-melt adhesives and pressure-sensitive adhesive tapes. These petroleum resins are usually produced by polymerizing unsaturated compounds with 5 to 9 carbon atoms, which are obtained as by-products in the production of olefins by thermal decomposition of naphtha, in a solvent, and then separating and removing the solvent and low-molecular-weight polymers from the resulting polymerization product.

[0005] In order to impart further effects to petroleum resins, modified petroleum resins are being developed. For example, Patent Document 4 discloses a curable petroleum resin that contains repeating units of a ring structure having a specific ethylenically unsaturated group, is copolymerized with silanes, and has a proton content and weight-average molecular weight within a specific range, for the purpose of obtaining a curable petroleum resin. Furthermore, Patent Document 5 discloses a reactive hot melt adhesive composition for interior wrapping of building materials, which is characterized by comprising a graft-modified product obtained by reacting an alkoxysilane compound with an amorphous poly-α-olefin polymer having a specific softening point, and an olefin resin, with the aim of improving coatability, wrap-around property, initial heat resistance, adhesiveness, etc. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-121320 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-143340 [Patent Document 3] Patent No. 6475390 [Patent Document 4] Special Publication No. 2017-523288 [Patent Document 5] Japanese Patent Application Laid-Open No. 2004-176028 Summary of the Invention [Problem to be solved by the invention]

[0007] Although anti-stripping agents such as resin acids and fatty acids are expensive in order to combat the above-mentioned asphalt peeling phenomenon, even if they are added in excess of a certain amount, they do not provide sufficient anti-stripping effect, particularly for acidic rocks such as granite. Therefore, there is a need for technology to suppress asphalt peeling even for these rocks. Therefore, a first object of the present invention is to provide a technology for suppressing asphalt peeling and improving water resistance. On the other hand, hot melt adhesives (hereinafter, in this specification, this includes both reactive hot melt adhesives and non-reactive adhesives) bond objects together by melting and solidifying resin using heat, so the bonded parts are prone to deformation and peeling at high temperatures, and high heat resistance is required, particularly for use in car interiors and woodworking around the kitchen. Although hot melt adhesives and pressure-sensitive adhesives do not require solvents and therefore have little impact on the environment or health, odors resulting from volatile organic compounds contained in the raw materials, such as aromatic compound-based elastomers and low-molecular-weight substances such as tackifiers, have become a problem, and further reduction of odors is required for applications such as disposable diapers and other daily necessities, in addition to the aforementioned applications in automotive interiors and woodworking. Similarly, there is also the problem of adhesives becoming discolored, which deteriorates the appearance, and colorlessness is also required. Although the petroleum resins and hot melt adhesive compositions of Patent Documents 4 and 5 have improved curability and initial heat resistance, further heat resistance, low odor, and high colorlessness are still required. Therefore, a second object of the present invention is to provide a modified hydrogenated petroleum resin that has excellent heat resistance, low odor, and excellent colorlessness. Furthermore, adhesive compositions such as hot melt adhesives are required to have both good applicability and high adhesive strength. Therefore, a third object of the present invention is to provide a modified hydrogenated petroleum resin and an adhesive composition that can achieve both good application properties and high adhesive strength. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have found that the first problem can be solved by setting the bromine number, which indicates the degree of unsaturation of the petroleum resin, to a specific value and by setting the amount of silane modification and the molecular weight within specific ranges.

[0009] That is, the present invention according to the first aspect (hereinafter also referred to as the "first invention") is as follows: <1> ~ <13> Regarding. <1> A silane-containing compound that has a ring structure within its molecular structure. <2> the cyclic structure is a structure in which three or more ring structures of at least one type selected from an aromatic ring and an alicyclic ring having five or more members are linked together; <1> The silane-containing compound according to claim 1. <3> The cyclic structure is a structure represented by any one of the following general formulas (1) to (4): <1> or <2> The silane-containing compound according to claim 1. [ka] (In each formula, l, m, and n each independently represent 1 or 2, and the straight lines represent single or double bonds, provided that the double bonds are not consecutive.) <4> The cyclic structure is a structure represented by any one of the following formulas (5) to (7): <1> ~ <3> 1. The silane-containing compound according to any one of claims 1 to 9. [ka] <5> The cyclic structure is a structure represented by any one of the following structural formulas (8) to (11): <1> ~ <3> 1. The silane-containing compound according to any one of claims 1 to 9. [ka] <6> 1 the integral ratio of aromatic hydrogen in H-NMR measurement [integral value of the peak in the 6.5 to 7.5 ppm region / (sum of integral value of the peak in the 0 to 3.0 ppm region and integral value of the peak in the 6.5 to 7.5 ppm region)] is 70% or less; <1> ~ <5> 1. The silane-containing compound according to any one of claims 1 to 9. <7> The softening point is 90°C or higher. <1> ~ <6> 1. The silane-containing compound according to any one of claims 1 to 9. <8> The viscosity at 40°C is 1 to 1,000 mPa·s. <1> ~ <6> 1. The silane-containing compound according to any one of claims 1 to 9. <9> The glass transition temperature is 30°C or higher. <1> ~ <7> 1. The silane-containing compound according to any one of claims 1 to 9. <10> The ratio of absorbance (ASiO) derived from silicon-oxygen bonds to absorbance (ACH) derived from carbon-hydrogen bonds in IR measurement satisfies the following relational expression: <1> ~ <9> 1. The silane-containing compound according to any one of claims 1 to 9. 0.01 <ASiO / ACH<0.37 <11> 13 the integral ratio of tertiary carbon in C-NMR measurement [integral value of peak in the 35 to 64 ppm region / integral value of peak in the 10 to 64 ppm region] is 2 to 80%; <1> ~ <10> 1. The silane-containing compound according to any one of claims 1 to 9. <12> The aforementioned <1> ~ <11> 1. An asphalt composition comprising the silane-containing compound according to any one of 1 to 8 above and straight asphalt, wherein the content of the straight asphalt is 70.00 to 99.99 mass %. <13> The aforementioned <12> 1. An asphalt mixture comprising the asphalt composition according to claim 1 above and aggregate, wherein the aggregate content is 80 to 99 mass %.

[0010] As a result of extensive research, the present inventors have found that the first and second problems can be solved by setting the bromine number, which indicates the degree of unsaturation of the petroleum resin, to a specific value and by setting the silane modification amount and molecular weight within specific ranges.

[0011] That is, the present invention according to the second aspect (hereinafter also referred to as the "second invention") is as follows: <14> ~ <23> Regarding. <14> A modified hydrogenated petroleum resin that satisfies the following (A1) to (A4): (A1) Bromine number is 0.1 to 10.0 (A2) Contains 0.1 to 10 mass% silicon element in terms of silicon atoms (A3) Weight average molecular weight of 500 to 5,000 (A4) Molecular weight distribution (Mw / Mn) of 1.1 to 3.5 <15> 1 the integral ratio of aromatic hydrogen in H-NMR measurement [integral value of the peak in the 6.5 to 7.5 ppm region / (sum of integral value of the peak in the 0 to 3.0 ppm region and integral value of the peak in the 6.5 to 7.5 ppm region)] is 0 to 15%; <14> The modified hydrogenated petroleum resin according to claim 1. <16> The softening point is 60 to 150°C. <14> or <15> The modified hydrogenated petroleum resin according to claim 1. <17> The volatile content when heated at 150°C for 20 minutes is 1.0% by mass or less. <14> ~ <16> 10. The modified hydrogenated petroleum resin according to any one of the above items. <18> The alkoxysilyl group is bonded to the main chain of the hydrogenated petroleum resin via a bond. <14> ~ <17> 10. The modified hydrogenated petroleum resin according to any one of the above items. <19> A method for producing a modified hydrogenated petroleum resin, comprising reacting a hydrogenated petroleum resin with a compound having a carbon-carbon double bond and an alkoxysilyl group in the presence of a compound that generates radicals. <20> The aforementioned <14> ~ <18> 1. A hot melt adhesive comprising 1 to 70 mass % of the modified hydrogenated petroleum resin according to any one of 1 to 7. <21> The aforementioned <14> ~ <18> 1. A pressure-sensitive adhesive comprising 1 to 70 mass % of the modified hydrogenated petroleum resin according to any one of 1 to 7. <22> The aforementioned <14> ~ <18> 1. An asphalt composition comprising the modified hydrogenated petroleum resin (B) according to any one of 1 to 8 above and straight asphalt, wherein the content of the straight asphalt is 70.00 to 99.99 mass %. <23> The aforementioned <22> 1. An asphalt mixture comprising the asphalt composition according to claim 1 above and aggregate, wherein the aggregate content is 80 to 99 mass %.

[0012] Furthermore, as a result of extensive research, the present inventors have found that the first and third problems can be solved by subjecting the above-mentioned modified hydrogenated petroleum resin to a condensation reaction to satisfy a specific viscosity range. That is, the present invention according to the third aspect (hereinafter also referred to as the "third invention") is as follows: <24> ~ <34> Regarding. <24> A modified hydrogenated petroleum resin (B) obtained by a condensation reaction of a modified hydrogenated petroleum resin (A) that satisfies the following (A1) to (A4), wherein the modified hydrogenated petroleum resin (B) satisfies the following (B1) to (B3): (A1) Bromine number is 0.1 to 10.0 (A2) Contains 0.1 to 10 mass% silicon element in terms of silicon atoms (A3) Weight average molecular weight of 500 to 5,000 (A4) Molecular weight distribution (Mw / Mn) of 1.1 to 3.5 (B1) Viscosity V0.1 measured using a rheometer at an angular velocity of ω = 0.1 rad / s and 190°C is 1,000 to 50,000 mPa·s (B2) Viscosity V100 measured using a rheometer at an angular velocity of ω = 100 rad / s and 190°C is 100 to 1,000 mPa·s (B3) The ratio of the viscosity V0.1 to the viscosity V100 [V0.1 / V100] is 10 or more. <25> The modified hydrogenated petroleum resin (A) 1 the integral ratio of aromatic hydrogen in H-NMR measurement [integral value of the peak in the 6.5 to 7.5 ppm region / (sum of integral value of the peak in the 0 to 3.0 ppm region and integral value of the peak in the 6.5 to 7.5 ppm region)] is 0 to 15%; <24> The modified hydrogenated petroleum resin according to claim 1. <26> The softening point of the modified hydrogenated petroleum resin (A) is 60 to 150°C. <24> or <24> The modified hydrogenated petroleum resin according to claim 1. <27> The modified hydrogenated petroleum resin (A) has a volatile content of 1.0 mass% or less when heated at 150°C for 20 minutes. <24> ~ <26> 10. The modified hydrogenated petroleum resin according to any one of the above items. <28> The modified hydrogenated petroleum resin (A) has an alkoxysilyl group, and the alkoxysilyl group is bonded to the main chain of the hydrogenated petroleum resin via a bonding portion. <24> ~ <27> 10. The modified hydrogenated petroleum resin according to any one of the above items. <29> A method for producing a modified hydrogenated petroleum resin (B) that satisfies the following (B1) to (B3), the method comprising at least the following step (a): (B1) Viscosity V0.1 measured using a rheometer at an angular velocity of ω = 0.1 rad / s and 190°C is 1,000 to 50,000 mPa·s (B2) Viscosity V100 measured using a rheometer at an angular velocity of ω = 100 rad / s and 190°C is 100 to 1,000 mPa·s (B3) The ratio of the viscosity V0.1 to the viscosity V100 [V0.1 / V100] is 10 or more. Step (a): A step of subjecting a modified hydrogenated petroleum resin (A) that satisfies the following (A1) to (A4) to a condensation reaction. (A1) Bromine number is 0.1 to 10.0 (A2) Contains 0.1 to 10 mass% silicon element in terms of silicon atoms (A3) Weight average molecular weight of 500 to 5,000 (A4) Molecular weight distribution (Mw / Mn) of 1.1 to 3.5 <30> The aforementioned <24> ~ <28> The modified hydrogenated petroleum resin (B) according to any one of the above, or <29> 2. An adhesive composition (C) comprising a modified hydrogenated petroleum resin (B) obtained by the production method described in 1., wherein the adhesive composition satisfies the following (C1) to (C3): (C1) Viscosity V0.1 measured using a rheometer at an angular velocity of ω = 0.1 rad / s and 190°C is 20,000 to 800,000 mPa·s (C2) Viscosity V100 measured using a rheometer at an angular velocity of ω = 100 rad / s and 190°C is 1,000 to 5,000 mPa·s (C3) The ratio of the viscosity V0.1 to the viscosity V100 [V0.1 / V100] is 10 or more. <31> The aforementioned <24> ~ <28> The modified hydrogenated petroleum resin (B) according to any one of the above, or <29> The modified hydrogenated petroleum resin (B) obtained by the production method described in the above item (1) is contained in an amount of 1 to 70 mass %. <30> The adhesive composition according to claim 1. <32> Further, the above-mentioned composition contains a base polymer in an amount of 10 to 90% by mass. <30> or <31> The adhesive composition according to claim 1. <33> The aforementioned <24> ~ <28> 1. An asphalt composition comprising the modified hydrogenated petroleum resin (B) according to any one of 1 to 8 above and straight asphalt, wherein the content of the straight asphalt is 70.00 to 99.99 mass %. <34> The aforementioned <33> 1. An asphalt mixture comprising the asphalt composition according to claim 1 above and aggregate, wherein the aggregate content is 80 to 99 mass %. [Effects of the Invention]

[0013] The silane-containing compound according to the first aspect of the present invention inhibits the peeling of asphalt and improves water resistance. The modified hydrogenated petroleum resin according to the second aspect of the present invention has excellent heat resistance, low odor, and colorlessness. It also inhibits asphalt peeling and improves water resistance. Furthermore, the third invention can provide a modified hydrogenated petroleum resin and adhesive composition that can achieve both good application properties and high adhesive strength. In addition, the resin inhibits asphalt peeling and improves water resistance. DETAILED DESCRIPTION OF THE INVENTION

[0014] [First invention] The silane-containing compound, asphalt composition, and asphalt mixture according to one embodiment of the first invention will be described below in order. [Silane-containing compounds] The silane-containing compound according to one embodiment of the first invention has a cyclic structure within its molecular structure. The cyclic structure is preferably a structure in which three or more ring structures of at least one type selected from aromatic rings and alicyclic rings having five or more members are linked together, more preferably a structure in which three or more ring structures of at least one type selected from aromatic rings having four to six members and alicyclic rings having five or six members are linked together, and even more preferably a structure in which three to five ring structures of at least one type selected from aromatic rings having five or six members and alicyclic rings having five or six members are linked together.

[0015] Suitable cyclic structures are specifically described below. The cyclic structure is preferably a structure represented by any one of the following general formulas (1) to (4). [ka] (In each formula, l, m, and n each independently represent 1 or 2, and the straight lines represent single or double bonds, provided that the double bonds are not consecutive.)

[0016] The vertices and intersections of the polygon in each of the above formulas represent carbon atoms. In each of the above formulas, l, m, and n each independently represent 1 or 2. For example, formula (1) represents any one of a 5-membered ring-6-membered ring-5-membered ring, a 5-membered ring-6-membered ring-6-membered ring, a 6-membered ring-6-membered ring-5-membered ring, and a 6-membered ring-6-membered ring. In each of the above formulas, a straight line represents a single bond or a double bond, provided that the double bonds are not consecutive and that no single carbon atom has two or more double bonds.

[0017] Among the structures represented by any one of the general formulae (1) to (4), more preferred structures are shown below. The cyclic structure is more preferably a structure represented by any one of the following formulas (5) to (7). [ka]

[0018] The cyclic structure is more preferably a structure represented by any one of the following formulas (8) to (11). [ka]

[0019] Of the structures represented by any of the formulas (5) to (11), the structure represented by formula (5) is more preferred.

[0020] The silane-containing compound according to one embodiment of the first invention comprises: 1The integral ratio of aromatic hydrogen in H-NMR measurement [integral value of the peak in the 6.5 to 7.5 ppm region / (sum of integral value of the peak in the 0 to 3.0 ppm region and integral value of the peak in the 6.5 to 7.5 ppm region)] is preferably 70% or less, more preferably 40% or less, and even more preferably 20% or less. 1 The integral ratio of aromatic hydrogen in H-NMR measurement is a value indicating the ratio of aromatic moieties in the silane-containing compound, 1 When the integral ratio of aromatic hydrogen in H-NMR measurement is within the above range, compatibility with asphalt is increased, which is preferable. Asphalt contains paraffins, naphthenes, and aromatic components, and generally has fewer aromatic components (aromatic components). Therefore, with regard to this technology, it is expected that fewer aromatic components will result in higher compatibility with asphalt. 1 The integral ratio of aromatic hydrogen in H-NMR measurement can be specifically measured by the method described in the Examples.

[0021] When the silane-containing compound according to one embodiment of the first invention is solid, its softening point is preferably 90°C or higher, more preferably 95°C or higher. The softening point can be measured by the ring and ball method, specifically by the method described in the examples. A softening point within the above range is preferable because it improves the adhesive strength at the interface between the aggregate and the asphalt.

[0022] When the silane-containing compound according to one embodiment of the first invention is a liquid, its viscosity at 40°C is preferably 1 to 1,000 mPa·s, and more preferably 1 to 100 mPa·s. A viscosity within the above range is preferable because compatibility with asphalt is improved and reactivity with the aggregate surface is increased, thereby improving water resistance.

[0023] When the silane-containing compound according to one embodiment of the first invention is a thermoplastic resin, the glass transition temperature thereof is preferably 30°C or higher, more preferably 40°C or higher. The glass transition temperature in the above range is preferable because it increases the interfacial strength between the aggregate and the asphalt.

[0024] In the silane-containing compound, the ratio of the absorbance (ASiO) derived from a silicon-oxygen bond to the absorbance (ACH) derived from a carbon-hydrogen bond in IR measurement preferably satisfies the following relational expression: 0.01 <ASiO / ACH<0.37 The ratio (ASiO / ACH) is preferably greater than 0.01, more preferably greater than 0.03, and is preferably less than 0.37, more preferably less than 0.20. By satisfying the above relational expression, the amount of silane atoms introduced becomes appropriate, and the material of the present technology reacts with the aggregate surface in just the right amount, which is preferable.

[0025] The silane-containing compound according to one embodiment of the first invention comprises: 13 The integral ratio of tertiary carbon in C-NMR measurement [integral value of the peak in the 35 to 64 ppm region / integral value of the peak in the 10 to 64 ppm region] is preferably 2 to 80%, more preferably 2 to 70%, even more preferably 10 to 70%, and still more preferably 40 to 70%. The integral ratio of tertiary carbon is a value indicating the ratio of tertiary carbon in the silane-containing compound, and it is preferable that the integral ratio of tertiary carbon is in the above range because the silane compound has a rigid structure and the interfacial strength between the aggregate and asphalt is improved. The integral ratio of tertiary carbon can be specifically measured by the method described in the Examples.

[0026] The silane-containing compound according to one aspect of the first invention preferably has a cyclic structure in its molecular structure and has the properties described above, but when used as a raw material for an asphalt composition, it preferably has the following properties: Asphalt is a composition with a range of molecular weights of alicyclic, paraffinic, and polycyclic aromatic structures. Furthermore, improving the adhesive strength between the asphalt composition and aggregate not only improves the water resistance of asphalt roads, but also their durability against loads. Therefore, it is extremely important to improve the adhesive strength between the asphalt composition and aggregate. To improve this adhesive strength, it is considered preferable to use an additive that has a silane-containing structure that reacts with and bonds to the hydroxyl groups on the surface of the aggregate, and is also compatible with asphalt. Furthermore, if a hard material is used, the asphalt at the aggregate interface will harden, and even if a load is applied to the interface, the force will be absorbed by the entire interface, which is thought to improve the adhesive strength between the asphalt and the aggregate. Also, in order to be compatible with asphalt, it is preferable that the material has both a polycyclic aromatic and an alicyclic structure. Therefore, the silane-containing compound according to one embodiment of the first invention is preferably a compound having a silane-containing group and further having a rigid polycyclic aromatic and alicyclic structure. Specific examples include partially hydrogenated petroleum resins having a silane-containing group, hydrogenated petroleum resins having a silane-containing group, unhydrogenated petroleum resins having a silane-containing group, cycloolefin copolymers having a silane-containing group, hydrogenated SBS polymers having a silane-containing group, and asphalts having a silane-containing group.

[0027] [Method of producing silane compounds] There are no particular limitations on the method for producing the silane compound according to one embodiment of the first invention, but a method in which silane is introduced into an organic compound having a cyclic structure in the molecular structure is preferred. As a method for producing the silane compound according to one embodiment of the first invention, the following method is preferred from the viewpoint of efficiently introducing silane. The method for producing the silane compound is preferably (A) a method of reacting an organic compound having a cyclic structure with a compound having a carbon-carbon double bond and an alkoxysilyl group in the presence of a compound that generates radicals, or (B) a method of reacting an organic compound having a carbon-carbon double bond and a cyclic structure with a compound having an alkoxysilyl group and a silicon-hydrogen bond in the presence of a metal catalyst or a compound that generates radicals. As a method for introducing an alkoxysilyl group into a compound containing an unsaturated bond, it is preferable to use the hydrosilylation reaction, which is the production method (B).

[0028] The organic compound used as a raw material for the silane compound used in the production method is not limited as long as it has the cyclic structure described above in [Silane Compound]. Examples include hydrogenated SBS polymers, cycloolefin copolymers, asphalt, and petroleum resins, with petroleum resins being preferred. Suitable petroleum resins include hydrogenated petroleum resins, partially hydrogenated petroleum resins, and unhydrogenated petroleum resins, which are used as raw materials in the second invention described below. The organic compound used in the production method (B) has an organic group having a carbon-carbon double bond. Examples of the organic group having a carbon-carbon double bond include vinyl, allyl, butenyl, cyclohexenyl, cyclopentadienyl, and (meth)acryloxypropyl, and the vinyl group, methacryloxy group, and acryloxy group are preferred.

[0029] The compound having a carbon-carbon double bond and an alkoxysilyl group used in the production method (A) is a compound in which one or more organic groups having a carbon-carbon double bond and one or more alkoxy groups are bonded to a silicon atom. Examples of the organic group having a carbon-carbon double bond include vinyl, allyl, butenyl, cyclohexenyl, cyclopentadienyl, and (meth)acryloxypropyl, with vinyl, methacryloxy, and acryloxy groups being preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, and a butoxy group. The number of alkoxy groups bonded to the silicon atom is preferably one or more, more preferably two or more, and even more preferably three. Specific examples of the compound having a carbon-carbon double bond and an alkoxysilyl group include vinyltriethoxysilane, vinyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and methacryloxypropyltriethoxysilane, with vinyltriethoxysilane and vinyltrimethoxysilane being preferred. The amount of the compound having a carbon-carbon double bond and an alkoxysilyl group used in the production method (A) is preferably 0.1 to 10 mass %, more preferably 0.2 to 5 mass %, even more preferably 0.5 to 4 mass %, and even more preferably 1 to 3 mass %, in terms of silicon atoms of the compound having a carbon-carbon double bond and an alkoxysilyl group, relative to the organic compound having a cyclic structure.

[0030] The compound having an alkoxysilyl group and a silicon-hydrogen bond used in the production method (B) is a compound in which one or more hydrogen atoms and one or more alkoxy groups are bonded to a silicon atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, and a butoxy group. The number of alkoxy groups bonded to the silicon atom is preferably one or more, more preferably two or more, and even more preferably three. Specific examples of compounds having an alkoxysilyl group and a silicon-hydrogen bond include methoxysilane, dimethoxysilane, trimethoxysilane, ethoxysilane, diethoxysilane, methylsilane, dimethylsilane, trimethylsilane, phenylsilane, diphenylsilane, and triphenylsilane, with triethoxysilane and trimethoxysilane being preferred. The amount of the compound having an alkoxysilyl group and a silicon-hydrogen bond used in the production method (B) is, in terms of silicon atoms of the compound having an alkoxysilyl group and a silicon-hydrogen bond, preferably 0.1 to 10 mass %, more preferably 0.3 to 8 mass %, even more preferably 0.5 to 5 mass %, and even more preferably 1 to 4 mass %, relative to the organic compound having a cyclic structure.

[0031] The radical-generating compound used in the above production method can be a compound generally known as a radical polymerization initiator. The radical-generating compound can be appropriately selected from, for example, various organic peroxides and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, and among these, organic peroxides are preferred. Examples of organic peroxides include diacyl peroxides such as dibenzoyl peroxide, di-3,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, and di(2,4-dichlorobenzoyl) peroxide; hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, and 2,5-dimethylhexane-2,5-dihydroperoxide; di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, and α,α'-bis(t-butylperoxy). Examples of suitable peroxycarbonates include dialkyl peroxides such as diisopropyl peroxycarbonyl benzene; peroxyketals such as 1,1-bis-t-butylperoxy-3,3,5-trimethylcyclohexane and 2,2-bis(t-butylperoxy)butane; alkyl peresters such as 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, n-butyl 4,4-di(t-butylperoxy)valerate, t-butyl peroxyoctoate, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, and t-butyl peroxybenzoate; and peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, and t-butylperoxyisopropyl carbonate. Among these, dialkyl peroxides are preferred. These may be used alone or in combination of two or more. The amount of the radical-generating compound used is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the organic compound having a cyclic structure.

[0032] The metal catalyst used in the production method (B) is preferably a noble metal catalyst or a transition metal catalyst, more preferably a noble metal catalyst, and even more preferably a platinum catalyst.

[0033] In the production method (A), there are no limitations on the reaction method as long as the reaction proceeds sufficiently. However, (1) a method in which an organic compound having a cyclic structure, a compound having a carbon-carbon double bond and an alkoxysilyl group, and a compound capable of generating radicals are mixed together, and radicals are generated by heating or the like to cause a reaction; and (2) a method in which an organic compound having a cyclic structure, a compound having a carbon-carbon double bond and an alkoxysilyl group, and a compound capable of generating radicals are dissolved in an organic solvent, and radicals are generated by heating or the like to cause a reaction. Methods that do not use an organic solvent are preferred, and therefore (1) a method in which an organic compound having a cyclic structure, a compound having a carbon-carbon double bond and an alkoxysilyl group, and a compound capable of generating radicals are mixed together, and radicals are generated by heating or the like to cause a reaction is more preferred.

[0034] In the case of the method (1) above, it is preferable to mix an organic compound having a cyclic structure with a compound having a carbon-carbon double bond and an alkoxysilyl group, add a compound that generates radicals, and heat the mixture to react the organic compound having a cyclic structure with the carbon-carbon double bond portion of the compound having a carbon-carbon double bond and an alkoxysilyl group, thereby obtaining a silane compound. The reaction temperature is preferably 100 to 300°C, more preferably 100 to 200°C.

[0035] In the case of the method (2) above, it is preferable to obtain a silane compound by dissolving an organic compound having a cyclic structure in an organic solvent, mixing it with a compound having a carbon-carbon double bond and an alkoxysilyl group, adding a compound that generates radicals, and heating the mixture to react the organic compound having a cyclic structure with the carbon-carbon double bond portion of the compound having a carbon-carbon double bond and an alkoxysilyl group. Examples of organic solvents that can be used in this method include hydrocarbon solvents such as pentane, hexane, heptane, cyclohexane, toluene, xylene, and decahydronaphthalene, halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene, and liquefied α-olefins. The reaction temperature is preferably from -50 to 300°C, more preferably from 0 to 300°C, further preferably from 100 to 300°C, and even further preferably from 100 to 200°C.

[0036] In the production method (B), there are no limitations on the reaction method as long as the reaction proceeds sufficiently, but when the reaction is carried out in the presence of a radical-generating compound, the reaction temperature is preferably 0 to 200° C., more preferably 130 to 180° C. When the reaction is carried out in the presence of a metal catalyst, the reaction temperature is preferably 40 to 100° C.

[0037] [Asphalt composition] The asphalt composition which is one embodiment of the first invention contains the silane-containing compound and straight asphalt, and the content of the straight asphalt is preferably 70.00 to 99.99 mass %.

[0038] <Straight asphalt> Straight asphalt is used as an asphalt base oil. The straight asphalt can be asphalt or a mixture thereof specified in JIS K 2207. It is preferable to use straight asphalt having a penetration grade equivalent to 40-60 to 200-300. The content of the straight asphalt in the entire asphalt composition is preferably 70.00 to 99.99 mass %, and more preferably 90 to 99.90 mass %.

[0039] The asphalt composition may use asphalt base oils other than straight asphalt in combination with solvent deasphalted asphalt such as propane deasphalted asphalt, blown asphalt, semi-blown asphalt, and other asphalts, and preferably further contains aromatic heavy mineral oil.

[0040] Solvent deasphalted asphalt is the residue obtained by extracting solvent deasphalted oil (high-viscosity lubricating oil fraction) from vacuum distillation residual oil (see "New Petroleum Dictionary," edited by the Japan Petroleum Institute, 1982, p. 308). It is called propane deasphalted asphalt when propane or propane and butane are used as the solvent. Blown asphalt is, for example, asphalt defined in JIS K 2207. Semi-blown asphalt is, for example, the semi-blown asphalt defined in "Asphalt Pavement Guidelines," published by the Japan Road Association, January 13, 1997, p. 51, Table 3.3.4.

[0041] (Aromatic heavy mineral oil) In the asphalt composition, the aromatic heavy mineral oil can be a solvent-extracted oil obtained by deasphalting the residual oil from vacuum distillation of crude oil with propane or the like, and then subjecting the solvent-deasphalted oil to solvent extraction with a polar solvent such as furfural to obtain bright stock (heavy lubricating oil), i.e., an extract. In particular, in the asphalt composition of one embodiment of the first invention, it is preferable to add an extract as the aromatic heavy mineral oil.

[0042] In the asphalt composition, the role of the extract is to increase the solubility of the thermoplastic elastomer in the asphalt and prevent separation during storage stability. The amount of extract required increases as the amount of thermoplastic elastomer added increases. Furthermore, adding more extract than necessary relative to the amount of thermoplastic elastomer added reduces the elastic modulus of the asphalt composition.

[0043] The content of the extract relative to the entire asphalt composition is determined taking into consideration the penetration, softening point, storage stability, complex modulus indicating strength, dynamic stability (DS) in a wheel tracking test, and bending work and bending stiffness indicating low-temperature properties. Within the range considered in this embodiment, the content of the extract relative to the entire asphalt composition is preferably 2.0 mass% or more and 8.0 mass% or less, but the inclusion of the extract is not particularly essential and it is not necessary for it to be contained.

[0044] (SBS) The asphalt composition may contain, in addition to straight asphalt and other asphalt base oils, SBS (styrene-butadiene-styrene copolymer) as a reinforcing material. SBS is a thermoplastic elastomer used as a reinforcing material. The performance of SBS can be estimated mainly from its molecular weight and styrene content. The styrene content here refers to the mass percentage of styrene contained in the SBS.

[0045] Currently, the weight-average molecular weight of SBS that is easily available industrially is from 120,000 to 250,000.The styrene content of SBS is from 25.0 to 35.0% by mass, and preferably from 27.0 to 33.0% by mass, of the total SBS.

[0046] In addition to the above, SBS with different molecular weights and styrene contents are available, and the molecular weight of these SBS is between 80,000 and 90,000. Furthermore, the styrene content is between 25.0% and 50.0% by mass of the total SBS.

[0047] It is not essential that the asphalt composition contain SBS, and it is not necessary for it to be contained. However, to solve the above-mentioned problems, it is preferable that the SBS content of the entire asphalt composition be 7.0% by mass or less. By setting the SBS content to 7.0% by mass or less, it is possible to maintain the asphalt continuous phase and improve the water resistance of a dense-graded mixture with excellent water impermeability. On the other hand, if it is desired to produce an asphalt mixture with high drainage or permeability by intentionally providing voids within the pavement, by setting the SBS content of the entire asphalt composition of this embodiment to more than 7.0% by mass, it is possible to solve the above-mentioned problems while causing a phase transition of the SBS, thereby producing an asphalt composition with high drainage or permeability.

[0048] The asphalt composition may contain only one type of SBS, or may contain two or more types of SBS having specific molecular structures. Mixing only one type of SBS is preferred because it eliminates the complexity of selecting and mixing two or more types of SBS and reduces the manufacturing labor.

[0049] (Production of asphalt composition) As described above, the asphalt composition contains a silane-containing compound and straight asphalt, and may be produced by any method as long as the straight asphalt content is 70.00 to 99.99 mass%, but is preferably produced by the following method. The straight asphalt is mixed with the extract and stirred and mixed for a predetermined time using a stirring device under conditions such as a temperature of 140°C or higher and a rotation speed of 2,000 rpm to 4,000 ppm, to obtain an asphalt base oil as an asphalt base material. A predetermined amount of SBS may be added simultaneously in this process, or the asphalt composition may be obtained in one process by adding SBS simultaneously. When adding SBS, it is preferable to set the temperature to 180°C or higher. Alternatively, a predetermined amount of SBS may be added after the asphalt base oil is obtained. When SBS is added, the asphalt composition is obtained by stirring and mixing the asphalt base oil for a predetermined time in a stirring device under conditions of, for example, 180°C or higher and a rotation speed of 2,000 rpm or higher and 4,000 ppm or lower. In this production method, the silane-containing compound may be added either in the step of obtaining the asphalt base oil or in the step of mixing SBS, depending on its shape and physical properties, or may be added to the obtained asphalt composition. When the asphalt composition is obtained in a single step, the silane-containing compound may be added simultaneously with the asphalt composition or may be added to the obtained asphalt composition. According to the above method, a homogeneous composition having high water resistance can be obtained efficiently.

[0050] [Asphalt mixture] An asphalt mixture that is one embodiment of the first invention contains the asphalt composition and aggregate, and the aggregate content is 80 to 99 mass %.

[0051] In the asphalt mixture, the content of the aggregate is preferably 80 to 99 mass % and more preferably 90 to 97 mass % based on the total mass of the asphalt mixture. An asphalt mixture having desired properties can be obtained by adding aggregate having a predetermined particle size to the asphalt composition and mixing at a predetermined rotation speed. The temperature when mixing the asphalt composition and aggregate is preferably about 170 to 180°C. The asphalt mixture that is one embodiment of the first invention contains the asphalt composition composed of the component compositions described above, and therefore can improve peeling resistance, inhibit asphalt peeling, and improve water resistance.

[0052] [Second Invention] The modified hydrogenated petroleum resin according to one embodiment of the second invention, the method for producing the modified hydrogenated petroleum resin, and the hot melt adhesive and pressure-sensitive adhesive containing 1 to 70 mass% of the modified hydrogenated petroleum resin will be described below. The asphalt composition and asphalt mixture will also be described. [Modified hydrogenated petroleum resin] The modified hydrogenated petroleum resin according to one embodiment of the second invention satisfies the following (A1) to (A4). (A1) Bromine number is 0.1 to 10.0 (A2) Contains 0.1 to 10 mass% silicon element in terms of silicon atoms (A3) Weight average molecular weight of 500 to 5,000 (A4) Molecular weight distribution (Mw / Mn) of 1.1 to 3.5

[0053] In this specification, the term "petroleum resin" refers to a resin obtained by polymerizing or copolymerizing one or more unsaturated compounds selected from aliphatic olefins and aliphatic diolefins having 4 to 10 carbon atoms, which are obtained as by-products during the production of olefins such as ethylene by thermal decomposition of petroleum such as naphtha, or aromatic compounds having 8 or more carbon atoms and having an olefinically unsaturated bond. Petroleum resins can be broadly classified into, for example, "aliphatic petroleum resins" obtained by polymerizing aliphatic olefins or aliphatic diolefins, "aromatic petroleum resins" obtained by polymerizing aromatic compounds having olefinic unsaturated bonds, and "aliphatic-aromatic copolymer petroleum resins" obtained by copolymerizing aliphatic olefins or aliphatic diolefins with aromatic compounds having olefinic unsaturated bonds.

[0054] Examples of the aliphatic olefins having 4 to 10 carbon atoms include butene, pentene, hexene, and heptene. Examples of the aliphatic diolefins having 4 to 10 carbon atoms include butadiene, pentadiene, isoprene, piperylene, cyclopentadiene, dicyclopentadiene, and methylpentadiene. Examples of aromatic compounds having 8 or more carbon atoms and an olefinically unsaturated bond include styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, vinylxylene, indene, methylindene, and ethylindene. Furthermore, the raw material compounds for this petroleum resin do not all need to be by-products of olefin production by thermal decomposition of petroleum such as naphtha, and chemically synthesized unsaturated compounds may also be used.

[0055] Preferable examples of petroleum resins include dicyclopentadiene-based petroleum resins obtained by polymerizing cyclopentadiene or dicyclopentadiene, dicyclopentadiene-styrene-based petroleum resins obtained by copolymerizing cyclopentadiene or dicyclopentadiene with styrene, C5-based petroleum resins obtained by polymerizing isoprene or piperylene, and C9-based petroleum resins obtained by polymerizing C9 monomers such as indene or vinyltoluene.

[0056] In this specification, the term "hydrogenated petroleum resin" refers to a petroleum resin obtained by adding hydrogen atoms to the above-mentioned petroleum resin. Hydrogenated petroleum resins include fully hydrogenated petroleum resins in which substantially no unsaturated bonds remain and partially hydrogenated petroleum resins in which unsaturated bonds remain, with fully hydrogenated petroleum resins being preferred. The hydrogenated petroleum resin is preferably a hydrogenated aliphatic-aromatic copolymer petroleum resin.

[0057] The modified hydrogenated petroleum resin according to one embodiment of the second invention contains 0.1 to 10 mass % silicon element in terms of silicon atoms. The silicon element is preferably derived from an organosilane structure. The silicon element content can be measured by ICP emission spectrometry, specifically by the method described in the examples. The modified hydrogenated petroleum resin of the present invention contains silicon element in an amount of 0.1 to 10 mass %, preferably 0.3 to 8 mass %, more preferably 0.5 to 5 mass %, and even more preferably 1 to 4 mass %, calculated as silicon atoms. The modified hydrogenated petroleum resin according to one embodiment of the second invention is preferably a silane-modified hydrogenated petroleum resin having an organosilane structure, and more preferably a modified hydrogenated petroleum resin in which an alkoxysilyl group is bonded to the main chain of the hydrogenated petroleum resin via a bonding moiety. Here, the phrase "the alkoxysilyl group is bonded to the main chain of the hydrogenated petroleum resin via a bonding portion" means that, for example, as described above, a bonding portion is directly bonded to a carbon atom contained in a hydrogenated polymer (hydrogenated petroleum resin) obtained by polymerizing aliphatic olefins, aliphatic diolefins, and an aromatic compound having an olefinically unsaturated bond and adding hydrogen atoms, and further, an alkoxysilyl group is bonded to the carbon atom. The alkoxysilyl group is preferably a trialkoxysilyl group having an alkoxy group of 1 to 20 carbon atoms, which may be linear or branched, and more preferably a trialkoxysilyl group having an alkoxy group of 1 to 10 carbon atoms, which may be linear or branched. Specific examples include a trimethoxysilyl group, a triethoxysilyl group, and a tripropoxysilyl group, with a trimethoxysilyl group and a triethoxysilyl group being preferred. The bonding portion may be any organic group having a valence of two or more that can bond to a carbon atom in the main chain of the hydrogenated petroleum resin and to which an alkoxysilyl group can be bonded, and is preferably an alkylene group, more preferably an alkylene group having 2 to 3 carbon atoms.

[0058] <Characteristics of modified hydrogenated petroleum resin> The bromine number (gBr2 / 100g) of the modified hydrogenated petroleum resin that is one embodiment of the second invention is 0.1 to 10.0, more preferably 0.5 to 5.0, and even more preferably 1.0 to 3.0. When the bromine number is within the above range, the resin has low odor and is excellent in colorlessness.

[0059] The modified hydrogenated petroleum resin according to one embodiment of the second invention is 1 The integral ratio of aromatic hydrogen in H-NMR measurement [integral value of peak in the 6.5 to 7.5 ppm region / (sum of integral value of peak in the 0 to 3.0 ppm region and integral value of peak in the 6.5 to 7.5 ppm region)] is preferably 0 to 15%, more preferably 0 to 10%, and even more preferably 0 to 5%. 1 The integral ratio of aromatic hydrogen in H-NMR measurement can be specifically measured by the method described in the Examples. 1The integral ratio of aromatic hydrogen in H-NMR measurement is a value indicating the ratio of aromatic moieties in the modified hydrogenated petroleum resin of the present invention, 1 When the integrated ratio of aromatic hydrogen in H-NMR measurement is within the above range, the composition has low odor and excellent colorlessness.

[0060] The weight average molecular weight (Mw) of the modified hydrogenated petroleum resin according to one embodiment of the second invention is 500 to 5,000, preferably 600 to 3,000, more preferably 700 to 2,000, and even more preferably 800 to 1,500. The weight average molecular weight is an index of fluidity when melted, and the smaller the weight average molecular weight, the greater the fluidity when melted, resulting in better applicability when applied to a hot melt adhesive. By having the weight average molecular weight within the above range, the heat resistance, which is the effect of the present invention, is maintained, and when applied to a hot melt adhesive, excellent applicability is achieved. The weight average molecular weight can be measured specifically by the method described in the Examples.

[0061] The molecular weight distribution (weight average molecular weight / number average molecular weight, Mw / Mn) of the modified hydrogenated petroleum resin according to one embodiment of the second invention is 1.1 to 3.5, preferably 1.3 to 3.0, more preferably 1.5 to 3.0, and even more preferably 2.0 to 2.5. The molecular weight distribution indicates the degree of dispersion of molecular weights, and becomes broad when there are extremely many low molecular weight components or high molecular weight components. The molecular weight distribution can be measured specifically by the method described in the Examples. When the molecular weight distribution is within the above range, the composition has low odor and excellent coatability.

[0062] The number average molecular weight (Mn) of the modified hydrogenated petroleum resin according to one embodiment of the second invention is preferably 100 to 4,500, more preferably 250 to 2,500, and even more preferably 300 to 1,500.

[0063] The softening point of the modified hydrogenated petroleum resin according to one embodiment of the second invention is preferably 60 to 150°C, more preferably 80 to 140°C, and even more preferably 90 to 130°C. The softening point can be measured by the ring and ball method, specifically by the method described in the examples. By having a softening point within the above range, when used in a hot melt adhesive, the adhesive will have an excellent balance between heat resistance and low-temperature applicability. The modified hydrogenated petroleum resin according to one embodiment of the second invention preferably has a volatile content of 1.0 mass % or less when heated at 150° C. for 20 minutes.

[0064] The color depth of the modified hydrogenated petroleum resin according to one embodiment of the second invention when melted is, on the Gardner color scale, preferably 1 to 3, and more preferably 1 to 2. When the color depth is within this range, the resin has excellent colorlessness, and when used as a component of an adhesive, the appearance of the bonded product is improved.

[0065] [Method for producing modified hydrogenated petroleum resin] There are no particular limitations on the method for producing the modified hydrogenated petroleum resin that is one embodiment of the second invention, but the following method is preferred from the viewpoints of efficiently introducing silane into the resin and improving heat resistance. The method for producing the modified hydrogenated petroleum resin is preferably a method in which a hydrogenated petroleum resin is reacted with a compound having a carbon-carbon double bond and an alkoxysilyl group in the presence of a compound that generates radicals.

[0066] The hydrogenated petroleum resin used in the production method is synonymous with the "hydrogenated petroleum resin" described above in the section [Modified Hydrogenated Petroleum Resin], and specifically, is a petroleum resin obtained by adding hydrogen atoms to a petroleum resin. Hydrogenated petroleum resins include fully hydrogenated petroleum resins in which substantially no unsaturated bonds remain, and partially hydrogenated petroleum resins in which unsaturated bonds remain, and the hydrogenated petroleum resin used in the production method of the present invention is preferably a fully hydrogenated petroleum resin. The hydrogenated petroleum resin is preferably a hydrogenated aliphatic-aromatic copolymer petroleum resin.

[0067] The petroleum resin used as a raw material for hydrogenated petroleum resin has the same meaning as the "petroleum resin" explained in the section [Modified hydrogenated petroleum resin] above, and specifically is as follows. Petroleum resins are resins obtained by polymerizing or copolymerizing one or more unsaturated compounds selected from aliphatic olefins and aliphatic diolefins having 4 to 10 carbon atoms, which are obtained as by-products during the production of olefins such as ethylene by thermal decomposition of petroleum such as naphtha, or aromatic compounds having 8 or more carbon atoms and containing olefinically unsaturated bonds. Petroleum resins can be broadly classified into, for example, "aliphatic petroleum resins" obtained by polymerizing aliphatic olefins or aliphatic diolefins, "aromatic petroleum resins" obtained by polymerizing aromatic compounds having olefinic unsaturated bonds, and "aliphatic-aromatic copolymer petroleum resins" obtained by copolymerizing aliphatic olefins or aliphatic diolefins with aromatic compounds having olefinic unsaturated bonds.

[0068] Examples of the aliphatic olefins having 4 to 10 carbon atoms include butene, pentene, hexene, and heptene. Examples of the aliphatic diolefins having 4 to 10 carbon atoms include butadiene, pentadiene, piperylene, isoprene, cyclopentadiene, dicyclopentadiene, and methylpentadiene. Examples of aromatic compounds having 8 or more carbon atoms and an olefinically unsaturated bond include styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, vinylxylene, indene, methylindene, and ethylindene. Furthermore, the raw material compounds for this petroleum resin do not all need to be by-products of olefin production by thermal decomposition of petroleum such as naphtha, and chemically synthesized unsaturated compounds may also be used.

[0069] Preferable examples of petroleum resins include dicyclopentadiene-based petroleum resins obtained by polymerizing cyclopentadiene or dicyclopentadiene, dicyclopentadiene-styrene-based petroleum resins obtained by copolymerizing cyclopentadiene or dicyclopentadiene with styrene, C5-based petroleum resins obtained by polymerizing isoprene or piperylene, and C9-based petroleum resins obtained by polymerizing C9 monomers such as indene or vinyltoluene.

[0070] The compound having a carbon-carbon double bond and an alkoxysilyl group used in the production method is a compound in which one or more organic groups having a carbon-carbon double bond and one or more alkoxy groups are bonded to a silicon atom. Examples of the organic group having a carbon-carbon double bond include vinyl, allyl, butenyl, cyclohexenyl, cyclopentadienyl, and (meth)acryloxypropyl, with vinyl, methacryloxy, and acryloxy groups being preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, and a butoxy group. The number of alkoxy groups bonded to the silicon atom is preferably one or more, more preferably two or more, and even more preferably three. Specific examples of the compound having a carbon-carbon double bond and an alkoxysilyl group include vinyltriethoxysilane, vinyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and methacryloxypropyltriethoxysilane, with vinyltriethoxysilane and vinyltrimethoxysilane being preferred. The amount of the compound having a carbon-carbon double bond and an alkoxysilyl group used in the production method is preferably 0.1 to 10 mass%, more preferably 0.3 to 8 mass%, even more preferably 0.5 to 5 mass%, and even more preferably 1 to 4 mass%, in terms of silicon atoms of the compound having a carbon-carbon double bond and an alkoxysilyl group, relative to the hydrogenated petroleum resin.

[0071] The radical-generating compound used in the above production method can be a compound generally known as a radical polymerization initiator. The radical-generating compound can be appropriately selected from, for example, various organic peroxides and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, and among these, organic peroxides are preferred. Examples of organic peroxides include diacyl peroxides such as dibenzoyl peroxide, di-3,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, and di(2,4-dichlorobenzoyl) peroxide; hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, and 2,5-dimethylhexane-2,5-dihydroperoxide; di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, and α,α'-bis(t-butylperoxy). Examples of suitable peroxycarbonates include dialkyl peroxides such as diisopropyl peroxycarbonyl benzene; peroxyketals such as 1,1-bis-t-butylperoxy-3,3,5-trimethylcyclohexane and 2,2-bis(t-butylperoxy)butane; alkyl peresters such as 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, n-butyl 4,4-di(t-butylperoxy)valerate, t-butyl peroxyoctoate, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, and t-butyl peroxybenzoate; and peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, and t-butylperoxyisopropyl carbonate. Among these, dialkyl peroxides are preferred. These may be used alone or in combination of two or more. The amount of the radical-generating compound used is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the hydrogenated petroleum resin.

[0072] As described above, a suitable method for producing the modified hydrogenated petroleum resin, which is one embodiment of the second invention, is a method of reacting a hydrogenated petroleum resin with a compound having a carbon-carbon double bond and an alkoxysilyl group in the presence of a compound that generates radicals. There are no limitations on the reaction method as long as the reaction proceeds sufficiently, but (1) a method of mixing molten hydrogenated petroleum resin, a compound having a carbon-carbon double bond and an alkoxysilyl group, and a compound that generates radicals, and generating radicals by heating or the like, to cause the reaction, is preferred, and (2) a method of dissolving a hydrogenated petroleum resin, a compound having a carbon-carbon double bond and an alkoxysilyl group, and a compound that generates radicals in an organic solvent, and generating radicals by heating or the like, to cause the reaction, is more preferred. (1) A method of mixing molten hydrogenated petroleum resin, a compound having a carbon-carbon double bond and an alkoxysilyl group, and a compound that generates radicals, and generating radicals by heating or the like, to cause the reaction, is more preferred.

[0073] In the case of the method (1) above, it is preferable to melt the hydrogenated petroleum resin, mix it with a compound having a carbon-carbon double bond and an alkoxysilyl group, add a radical-generating compound, and heat the mixture to react the hydrogenated petroleum resin with the carbon-carbon double bond portion of the compound having a carbon-carbon double bond and an alkoxysilyl group, thereby obtaining a modified hydrogenated petroleum resin. In this method, when the melt viscosity of the hydrogenated petroleum resin is low, it is preferable to carry out the reaction while stirring in a conventional reaction apparatus, and when the melt viscosity of the hydrogenated petroleum resin is high, it is preferable to carry out the reaction while melt-kneading using a roll mill, a Banbury mixer, an extruder, or the like. The reaction temperature is preferably 100 to 300°C, more preferably 100 to 200°C.

[0074] In the case of the method (2) above, it is preferable to obtain a modified hydrogenated petroleum resin by dissolving the hydrogenated petroleum resin in an organic solvent, mixing with a compound having a carbon-carbon double bond and an alkoxysilyl group, adding a radical-generating compound, and heating the mixture to react the hydrogenated petroleum resin with the carbon-carbon double bond portion of the compound having a carbon-carbon double bond and an alkoxysilyl group. Examples of organic solvents that can be used in this method include hydrocarbon solvents such as pentane, hexane, heptane, cyclohexane, toluene, xylene, and decahydronaphthalene, halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene, and liquefied α-olefins. The reaction temperature is preferably from -50 to 300°C, more preferably from 0 to 300°C, further preferably from 100 to 300°C, and even further preferably from 100 to 200°C.

[0075] [Hot melt adhesive] The hot melt adhesive according to one embodiment of the second invention contains 1 to 70 mass % of the modified hydrogenated petroleum resin. That is, the hot melt adhesive contains 1 to 70 mass % of a modified hydrogenated petroleum resin that satisfies the following (A1) to (A4). (A1) Bromine number is 0.1 to 10.0 (A2) Contains 0.1 to 10 mass% silicon element in terms of silicon atoms (A3) Weight average molecular weight of 500 to 5,000 (A4) Molecular weight distribution (Mw / Mn) of 1.1 to 3.5

[0076] The modified hydrogenated petroleum resin can be used as a component having the properties of a tackifier, a component having the properties of a base polymer, or a component having both the properties of a tackifier and a base polymer, among the components constituting a hot melt adhesive, by adjusting its molecular weight, molecular weight distribution, glass transition temperature, etc., but is preferably used as a tackifier. When used as any of these components, the heat resistance of the resulting hot melt adhesive can be improved, and a low-odor, colorless hot melt adhesive can be obtained. When the modified hydrogenated petroleum resin is used as a tackifier, the content of the modified hydrogenated petroleum resin in the hot melt adhesive is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 40% by mass or less.

[0077] The hot melt adhesive may contain a base polymer, a tackifier, a plasticizer, and additives in addition to the modified hydrogenated petroleum resin.

[0078] <Base polymer> The hot melt adhesive preferably further comprises a base polymer. In this specification, the "base polymer" according to the second invention refers to the polymer contained in the largest amount among the polymer components used as components other than the modified hydrogenated petroleum resin. Specific examples of the base polymer include natural rubber, olefin elastomers, styrene elastomers, and olefin plastomers, with olefin elastomers and styrene elastomers being preferred. Other examples of the base polymer used in reactive hot melt adhesives include polymers having silane-containing groups or isocyanate groups that undergo a condensation reaction with moisture. The elastomer is not limited by density as long as it has rubber elastic properties, and may be either chemically crosslinked or not. The plastomer is not limited by density as long as it undergoes plastic deformation, and may be chemically crosslinked or non-chemically crosslinked. These may be used alone or in combination of two or more.

[0079] Examples of the olefin elastomer include ethylene olefin polymers, amorphous olefin polymers, propylene elastomers, ethylene-vinyl acetate copolymers, and ethylene-acrylic acid ester copolymers, with propylene elastomers and ethylene olefin polymers being preferred.

[0080] Ethylene-based olefin polymers are olefin polymers whose main structural unit is ethylene units. Specific examples include polyethylene and copolymers of ethylene and an olefin having 3 to 10 carbon atoms. Here, the term "main structural unit" refers to the structural unit that is most abundant among the structural units constituting the polymer. In this specification, a polymer that contains the most ethylene units but has the same amount of other structural units is referred to as an ethylene-based olefin polymer. While there are no particular limitations on the polymer as long as it can be used as a base polymer for hot melt adhesives, from the viewpoint of adhesiveness of the hot melt adhesive, ethylene-α-olefin copolymers are preferred. Specific examples of α-olefins include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. One or more of these can be used. Among these α-olefins, 1-octene is preferred. From the viewpoint of adhesiveness of the hot melt adhesive, an ethylene-1-octene copolymer is more preferable, and an ethylene-1-octene copolymer containing 5 to 50 mass % of structural units derived from 1-octene is even more preferable. From the viewpoint of heat creep resistance, the melting point of the ethylene-based olefin polymer is preferably 60 to 120°C, more preferably 60 to 90°C. The melting point of the ethylene-based olefin polymer can be measured by differential scanning calorimetry. Among the ethylene-based olefin polymers, amorphous ones belong to the category of amorphous olefin polymers described below.

[0081] The amorphous olefin polymer is one or more homopolymers or copolymers selected from the group consisting of linear or branched α-olefins or dienes having 2 to 24 carbon atoms, and includes, but is not limited to, ethylene-propylene copolymer, atactic polypropylene, polybutene, atactic poly-1-butene, polybutadiene, polyisoprene, and amorphous polyalphaolefin. Examples of polybutene include homopolymers or copolymers of isobutene and normal butene, and hydrogenated products thereof. Examples of polybutadienes include homopolymers or copolymers of 1,2-butadiene or 1,4-butadiene, and hydrogenated products thereof, which may have terminal hydroxyl groups. Examples of polyisoprene include homopolymers or copolymers of isoprene and hydrogenated products thereof, which may have terminal hydroxyl groups. Examples of amorphous polyalphaolefins include homopolymers and copolymers of olefins having 2 to 6 carbon atoms.

[0082] The propylene-based elastomer is an elastomer having propylene units as the main constituent unit, and examples thereof include low-crystalline polypropylene.

[0083] The vinyl acetate content of the ethylene-vinyl acetate copolymer is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass.

[0084] As the styrene elastomer, a styrene block copolymer is preferred. The styrene-based block copolymer is a copolymer in which a styrene-based compound and a conjugated diene compound are block copolymerized, and usually has a styrene-based compound block and a conjugated diene compound block.

[0085] Examples of "styrene-based compounds" include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, and vinylanthracene. Styrene is particularly preferred. These styrene-based compounds can be used alone or in combination. The term "conjugated diene compound" refers to a diolefin compound having at least one pair of conjugated double bonds. Specific examples of the "conjugated diene compound" include 1,3-butadiene, 2-methyl-1,3-butadiene (or isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. 1,3-butadiene and 2-methyl-1,3-butadiene are particularly preferred. These conjugated diene compounds can be used alone or in combination.

[0086] The styrene-based block copolymer may be an unhydrogenated product or a hydrogenated product. Specific examples of "unhydrogenated styrene-based block copolymers" include those in which the blocks based on conjugated diene compounds have not been hydrogenated. Specific examples of "hydrogenated styrene-based block copolymers" include block copolymers in which all or part of the blocks based on conjugated diene compounds have been hydrogenated. The hydrogenation rate of a "hydrogenated styrene block copolymer" can be expressed as the "hydrogenation rate." The "hydrogenation rate" of a "hydrogenated styrene block copolymer" refers to the rate of double bonds that have been hydrogenated and converted to saturated hydrocarbon bonds, based on the total aliphatic double bonds contained in the block based on the conjugated diene compound. This "hydrogenation rate" can be measured using an infrared spectrophotometer, a nuclear magnetic resonance spectrometer, or the like.

[0087] Specific examples of "unhydrogenated styrene block copolymers" include styrene-isoprene-styrene block copolymers (also referred to as "SIS") and styrene-butadiene-styrene block copolymers (also referred to as "SBS"). Specific examples of "hydrogenated styrene block copolymers" include hydrogenated styrene-isoprene-styrene block copolymers (also referred to as "SEPS") and hydrogenated styrene-butadiene-styrene block copolymers (also referred to as "SEBS"). The styrene-based block copolymers can be used alone or in combination.

[0088] From the viewpoint of adhesive strength of the hot melt adhesive, the proportion of styrene blocks contained in the styrene block copolymer (styrene content) is preferably 5 to 50 mass %, more preferably 10 to 40 mass %.

[0089] From the viewpoint of cohesiveness, the content of the base polymer in the hot melt adhesive is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and even more preferably 30% by mass or more, and is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less. The glass transition temperature of the base polymer is preferably from -20 to 100°C, more preferably from -20 to 60°C.

[0090] <Tackifier> The hot melt adhesive preferably further comprises a tackifier. Examples of tackifiers include those that are solid, semi-solid, or liquid at room temperature and are made of rosin derivative resins, polyterpene resins, oil-soluble phenolic resins, etc. Specific examples include natural rosin, modified rosin, hydrogenated rosin, glycerol esters of natural rosin, glycerol esters of modified rosin, pentaerythritol esters of natural rosin, pentaerythritol esters of modified rosin, pentaerythritol esters of hydrogenated rosin, copolymers of natural terpenes, three-dimensional polymers of natural terpenes, hydrogenated derivatives of hydrogenated terpene copolymers, polyterpene resins, and hydrogenated derivatives of phenol-based modified terpene resins. Further examples of the tackifier include unmodified petroleum resins, such as aliphatic petroleum hydrocarbon resins, hydrogenated derivatives of aliphatic petroleum hydrocarbon resins, aromatic petroleum hydrocarbon resins, hydrogenated derivatives of aromatic petroleum hydrocarbon resins, cycloaliphatic petroleum hydrocarbon resins, and hydrogenated derivatives of cycloaliphatic petroleum hydrocarbon resins. The tackifiers may be used alone or in combination of two or more kinds. Of the above tackifiers, hydrogenated products are preferably used in consideration of compatibility with the base polymer.

[0091] Commercially available tackifiers include the following: Examples of tackifiers produced using raw materials obtained during the crude oil and naphtha refining process include "Imarv" (manufactured by Idemitsu Kosan Co., Ltd.), "Alcon" (manufactured by Arakawa Chemical Industries, Ltd.), "Quinton" (manufactured by Zeon Corporation), "T-REZ" (manufactured by ENEOS Corporation), "Escorez", "Oppera" (all manufactured by ExxonMobil Chemical Company), "Eastotac", "Regalite", "Regalrez", "Plastolyn" (all manufactured by Eastman), "Sukorez" (manufactured by Kolon Industries), and "Wingtack" and "Norsolene" (all manufactured by Cray Valley Chemical Industry Co., Ltd.) (all trade names and registered trademarks). Examples of tackifiers produced using essential oils obtained from oranges or the like as raw materials include "Clearon" (manufactured by Yasuhara Chemical Co., Ltd.), "Sylvalite" and "Sylvares" (manufactured by KRATON) (all of which are trade names and registered trademarks). Examples of tackifiers produced using raw materials such as rosin include "Haritack" and "Neotol (registered trademark)" (manufactured by Harima Chemical Co., Ltd.), and "Ester Gum" and "Pensel (registered trademark)" (manufactured by Arakawa Chemical Industries, Ltd.) (all trade names).

[0092] From the viewpoint of improving adhesiveness, the content of the tackifier in the hot melt adhesive is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, and is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less.

[0093] The softening point of the tackifier is preferably −20° C. or higher, more preferably −15° C. or higher, even more preferably −10° C. or higher, and preferably 180° C. or lower, more preferably 170° C. or lower, even more preferably 160° C. or lower.

[0094] <Plasticizer> The hot melt adhesive preferably further contains a plasticizer. The plasticizer is not particularly limited, but is preferably one used in hot melt adhesives, more preferably oil or wax. In addition, phthalates, adipic esters, fatty acid esters, glycols, epoxy polymer plasticizers, etc. can also be used as the plasticizer.

[0095] Examples of oils include paraffinic process oil, naphthenic process oil, isoparaffinic oil, and aromatic oil.

[0096] Commercially available paraffinic process oils include "Diana Process Oil PW-32," "Diana Process Oil PW-90," "Diana Process Oil PW-150," "Diana Process Oil PS-32," "Diana Process Oil PS-90," and "Diana Process Oil PS-430" (all trade names, and "Diana" is a registered trademark) manufactured by Idemitsu Kosan Co., Ltd.; "Kaydol (registered trademark) Oil" manufactured by Sonneborn; and "ParaLux (registered trademark) Oil" manufactured by Chevron USA, Inc. (all trade names).

[0097] Commercially available isoparaffin oils include "IP Solvent 1016," "IP Solvent 1620," "IP Solvent 2028," "IP Solvent 2835," and "IP Clean LX" manufactured by Idemitsu Kosan Co., Ltd.; and the "NA Solvent" series manufactured by NOF Corporation (all trade names).

[0098] Examples of waxes include animal waxes, vegetable waxes, carnauba wax, candelilla wax, Japan wax, beeswax, mineral waxes, petroleum wax, paraffin wax, microcrystalline wax, petrolatum, higher fatty acid waxes, higher fatty acid ester waxes, Fischer-Tropsch wax, polypropylene wax, polyethylene wax, and propylene-ethylene copolymer wax.

[0099] From the viewpoint of improving adhesion and improving application properties, the content of the plasticizer in the hot melt adhesive is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, still more preferably 10% by mass or more, and is preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and still more preferably 20% by mass or less.

[0100] In the hot melt adhesive, the total content of the modified hydrogenated petroleum resin, base polymer, tackifier, and plasticizer is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and preferably 100% by mass or less.

[0101] <Other additives> The hot melt adhesive may further contain optional additives such as inorganic fillers, antioxidants, ultraviolet absorbers, light stabilizers, and lubricants, as needed, within the scope of the second invention.

[0102] Examples of inorganic fillers include talc, calcium carbonate, barium carbonate, wollastonite, silica, clay, mica, kaolin, titanium oxide, diatomaceous earth, urea resins, styrene beads, starch, barium sulfate, calcium sulfate, magnesium silicate, magnesium carbonate, alumina, and quartz powder.

[0103] Antioxidants include trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, "ADEKA STAB (registered trademark) 1178" (manufactured by ADEKA Corporation), "Sumilizer (registered trademark) TNP" (manufactured by Sumitomo Chemical Co., Ltd.), "Irgafos (registered trademark) 168" (manufactured by BASF), and "Sandostab (registered trademark) Examples of antioxidants include phosphorus-based antioxidants such as 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, Sumilizer (registered trademark) BHT (manufactured by Sumitomo Chemical Co., Ltd.), and Irganox (registered trademark) 1010 (manufactured by BASF), and sulfur-based antioxidants such as dilauryl-3,3'-thiodipropionate, pentaerythritol tetrakis(3-laurylthiopropionate), Sumilizer (registered trademark) TPL (manufactured by Sumitomo Chemical Co., Ltd.), DLTP (Yoshitomi (registered trademark)), DSTP (Yoshitomi (registered trademark)), and DMTP (Yoshitomi (registered trademark)) (all manufactured by Mitsubishi Chemical Corporation), and Antiox (registered trademark) L (manufactured by NOF Corporation).

[0104] <Hot melt adhesive manufacturing method and applications> The hot melt adhesive can be produced by dry blending the modified hydrogenated petroleum resin, as well as a base polymer, a tackifier, a plasticizer, and additives, as necessary, using a Henschel mixer or the like, and melt-kneading the mixture using a single-screw or twin-screw extruder, a plastomill, a Banbury mixer, or the like.

[0105] The hot melt adhesive has excellent heat resistance, is colorless, and has little odor, and therefore can be suitably used for, for example, the interior of transportation equipment such as automobiles, trains, ships, and aircraft, sanitary materials, packaging, bookbinding, textiles, woodworking, electrical materials, can making, construction, filters, low-pressure molding, bag making, and the like. Specifically, it can be preferably used as an adhesive for sanitary products such as disposable diapers and sanitary napkins, and as an adhesive for assembly such as automobile floor mats and woodworking applications for kitchens. In particular, since it has little odor, it can be suitably used as an adhesive for automobile interiors and sanitary products.

[0106] [Pressure-sensitive adhesive] A pressure-sensitive adhesive according to one embodiment of the second invention contains 1 to 70 mass % of the modified hydrogenated petroleum resin. That is, the pressure-sensitive adhesive contains 1 to 70 mass % of a modified hydrogenated petroleum resin that satisfies the following (A1) to (A4). (A1) Bromine number is 0.1 to 10.0 (A2) Contains 0.1 to 10 mass% silicon element in terms of silicon atoms (A3) Weight average molecular weight of 500 to 5,000 (A4) Molecular weight distribution (Mw / Mn) of 1.1 to 3.5

[0107] The modified hydrogenated petroleum resin is preferably used as a tackifier among the components constituting the pressure-sensitive adhesive, and may be used in combination with a tackifier other than the modified hydrogenated petroleum resin. When used as either component of the modified hydrogenated petroleum resin, the heat resistance of the resulting pressure-sensitive adhesive can be improved, and a low-odor, colorless pressure-sensitive adhesive can be obtained. When the modified hydrogenated petroleum resin is used as a tackifier, the content of the modified hydrogenated petroleum resin in the pressure-sensitive adhesive is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 40% by mass or less.

[0108] The pressure-sensitive adhesive contains an elastomer and a tackifier as main ingredients. Examples of the elastic body include natural rubber, polyisoprene, butyl rubber, acrylic rubber, urethane rubber, silicone rubber, olefin-based elastomers, acrylic adhesives, and silicone adhesives. Examples of the olefin-based elastomer used as the elastic body include the same olefin-based elastomers as those described in the "Base Polymer" section of the "Hot Melt Adhesive" section above, and the preferred embodiments are also the same. Among these, amorphous olefin polymers are preferred, and examples of the amorphous olefin polymers that are preferred include ethylene-propylene copolymers and atactic polypropylene. As the tackifier, in addition to the modified hydrogenated petroleum resin, the same tackifiers as those in the above-mentioned [Hot melt adhesive] are preferably used.

[0109] The total content of the modified hydrogenated petroleum resin, elastomer, and tackifier in the pressure-sensitive adhesive is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and preferably 100% by mass or less.

[0110] [Asphalt composition and asphalt mixture] An asphalt composition that is one embodiment of the second invention contains the modified hydrogenated petroleum resin and straight asphalt, and the content of the straight asphalt is preferably 70.00 to 99.99 mass %. Suitable straight asphalt, its content, other components, and production method are the same as those for the asphalt composition described in the [Asphalt composition] according to the first invention.

[0111] An asphalt mixture according to one embodiment of the second invention contains the asphalt composition according to one embodiment of the second invention and aggregate, and the aggregate content is preferably 80 to 99 mass %. Suitable aggregates, their contents, and production methods are the same as those for the asphalt composition described in the [Asphalt Mixture] according to the first invention.

[0112] [Third Invention] The modified hydrogenated petroleum resin (B) according to one embodiment of the third invention, a method for producing the modified hydrogenated petroleum resin (B), and an adhesive composition (C) containing the modified hydrogenated petroleum resin (B) will be described below. The asphalt composition and the asphalt mixture will also be described. [Modified hydrogenated petroleum resin (B)] The modified hydrogenated petroleum resin according to one embodiment of the third invention is a modified hydrogenated petroleum resin (B) obtained by a condensation reaction of a modified hydrogenated petroleum resin (A) that satisfies the following (A1) to (A4), and the modified hydrogenated petroleum resin (B) satisfies the following (B1) to (B3): (A1) Bromine number is 0.1 to 10.0 (A2) Contains 0.1 to 10 mass% silicon element in terms of silicon atoms (A3) Weight average molecular weight of 500 to 5,000 (A4) Molecular weight distribution (Mw / Mn) of 1.1 to 3.5 (B1) Viscosity V0.1 measured using a rheometer at an angular velocity of ω = 0.1 rad / s and 190°C is 1,000 to 50,000 mPa·s (B2) Viscosity V100 measured using a rheometer at an angular velocity of ω = 100 rad / s and 190°C is 100 to 1,000 mPa·s (B3) The ratio of the viscosity V0.1 to the viscosity V100 [V0.1 / V100] is 10 or more.

[0113] <Characteristics of modified hydrogenated petroleum resin (B)> The modified hydrogenated petroleum resin (B), one embodiment of the third invention, has a viscosity V0.1 (hereinafter simply referred to as "V0.1") of 1,000 to 50,000 mPa·s, measured using a rheometer at an angular velocity ω of 0.1 rad / s and 190°C (requirement (B1)). When the V0.1 of the modified hydrogenated petroleum resin (B) satisfies the above range, the adhesive composition containing the modified hydrogenated petroleum resin (B) exhibits high cohesive strength and excellent adhesive strength. The V0.1 of the modified hydrogenated petroleum resin (B) is preferably 2,000 to 45,000 mPa·s, more preferably 3,000 to 40,000 mPa·s, and even more preferably 4,000 to 38,000 mPa·s. Furthermore, the modified hydrogenated petroleum resin (B) has a viscosity V100 (hereinafter simply referred to as "V100") of 100 to 1,000 mPa·s, measured using a rheometer at an angular velocity ω of 100 rad / s and 190°C (requirement (B2)). When the V100 of the modified hydrogenated petroleum resin (B) satisfies the above range, the adhesive composition containing the modified hydrogenated petroleum resin (B) has good coatability. The V100 of the modified hydrogenated petroleum resin (B) is preferably 200 to 800 mPa·s, more preferably 250 to 600 mPa·s, and even more preferably 300 to 400 mPa·s. The V0.1 and V100 of the modified hydrogenated petroleum resin (B) can be specifically measured by the method described in the Examples.

[0114] Furthermore, the modified hydrogenated petroleum resin (B) has a ratio [V0.1 / V100] of the viscosity V0.1 to the viscosity V100 (hereinafter simply referred to as "[V0.1 / V100]") of 10 or more (requirement (B3)). When the [V0.1 / V100] of the modified hydrogenated petroleum resin (B) satisfies the above range, the adhesive composition containing the modified hydrogenated petroleum resin (B) achieves both good applicability and high adhesive strength. The modified hydrogenated petroleum resin (B) has a [V0.1 / V100] ratio of preferably 11 or more, more preferably 30 or more, even more preferably 35 or more, and still more preferably 40 or more. The upper limit is preferably 1,000 or less, more preferably 800 or less, even more preferably 500 or less, and still more preferably 300 or less. Specifically, the [V0.1 / V100] of the modified hydrogenated petroleum resin (B) can be calculated from the values of V0.1 and V100 of the modified hydrogenated petroleum resin (B) measured by the method described in the Examples.

[0115] <Modified hydrogenated petroleum resin (A)> The modified hydrogenated petroleum resin (B) is obtained by a condensation reaction of the modified hydrogenated petroleum resin (A). The modified hydrogenated petroleum resin (A) has the same meaning as the [modified hydrogenated petroleum resin] described in the second invention, and preferred embodiments thereof are also the same, so further description thereof will be omitted here.

[0116] The condensation reaction may be exemplified by, for example, a reaction of the modified hydrogenated petroleum resin (A) via a functional group capable of condensation reaction when the modified hydrogenated petroleum resin (A) has such a functional group. The condensation reaction may involve an intramolecular condensation reaction between functional groups present in one molecule of the modified hydrogenated petroleum resin (A), or an intermolecular condensation reaction between two or more molecules of the modified hydrogenated petroleum resin (A) via such a functional group. Among these, an intermolecular condensation reaction is preferred. For example, when the modified hydrogenated petroleum resin (A) has an alkoxysilyl group or the like, the alkoxysilyl group or the like is hydrolyzed by water or the like to generate a silanol group, and the generated silanol groups may then undergo a condensation reaction with each other. Furthermore, when the modified hydrogenated petroleum resin (A) contains a substituent capable of condensation reaction with a silanol group, such as a hydroxyl group, the hydroxyl group or the like may undergo a condensation reaction with the silanol group.

[0117] [Method for producing modified hydrogenated petroleum resin (B)] The method for producing the modified hydrogenated petroleum resin (B) includes at least the following step (a): Step (a): A step of subjecting a modified hydrogenated petroleum resin (A) that satisfies the following (A1) to (A4) to a condensation reaction. (A1) Bromine number is 0.1 to 10.0 (A2) Contains 0.1 to 10 mass% silicon element in terms of silicon atoms (A3) Weight average molecular weight of 500 to 5,000 (A4) Molecular weight distribution (Mw / Mn) of 1.1 to 3.5 As described above, the modified hydrogenated petroleum resin (A) has the same meaning as the modified hydrogenated petroleum resin described in the second invention, and the preferred embodiments thereof are also the same, so further description here will be omitted.

[0118] In the condensation reaction of step (a), the modified hydrogenated petroleum resin (A) preferably has alkoxysilyl groups, and the silanol groups generated by hydrolyzing the alkoxysilyl groups are preferably subjected to a condensation reaction. Therefore, it is preferable to carry out step (a) in the presence of water. The water may be added during step (a) or may be moisture present in the air.

[0119] A catalyst may also be used to carry out the condensation reaction in step (a). Examples of the catalyst include acid catalysts, base catalysts, metal catalysts, etc. Among these, acid catalysts and metal catalysts are preferred, and metal catalysts are more preferred. Examples of the acid catalyst include nitric acid, hydrochloric acid, sulfuric acid, oxalic acid, malonic acid, phosphoric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. Examples of the base catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, dimethylamine, trimethylamine, tetramethylammonium hydroxide, ethylamine, triethylamine, diethylamine, and ethylamine. Examples of metal catalysts include dibutyltin diacetate, bis(acetoxydibutyltin)oxide, bis(lauroxydibutyltin)oxide, dibutyltin bisacetylacetonate, dibutyltin bismaleic acid monobutyl ester, dioctyl bismaleic acid monobutyl ester, dibutyltin dilaurate, diisopropoxytitanium bis(acetylacetonate), titanium tetra(acetylacetonate), dioctanoxytitanium dioctanate, and diisopropoxytitanium bis(ethylacetoacetate). The catalysts may be used alone or in combination of two or more.

[0120] The temperature in step (a) is not particularly limited, but is preferably 0 to 200°C, more preferably 10 to 150°C, and even more preferably 20 to 100°C.

[0121] Step (a) may also be carried out when producing an adhesive composition (C) containing a modified hydrogenated petroleum resin (B) described below. For example, the condensation reaction of the modified hydrogenated petroleum resin (A) may be carried out when the modified hydrogenated petroleum resin (A) is added and mixed with other components such as a base polymer described below.

[0122] [Adhesive composition (C)] The adhesive composition (C) according to one embodiment of the third invention is an adhesive composition (C) containing the modified hydrogenated petroleum resin (B) and satisfies the following (C1) to (C3). (C1) Viscosity V0.1 measured using a rheometer at an angular velocity of ω = 0.1 rad / s and 190°C is 20,000 to 800,000 mPa·s (C2) Viscosity V100 measured using a rheometer at an angular velocity of ω = 100 rad / s and 190°C is 1,000 to 5,000 mPa·s (C3) The ratio of the viscosity V0.1 to the viscosity V100 [V0.1 / V100] is 10 or more.

[0123] The adhesive composition (C) has a viscosity V0.1 of 20,000 to 800,000 mPa·s at an angular velocity ω of 0.1 rad / s and 190°C, as measured using a rheometer (requirement (C1) above). When V0.1 of the adhesive composition (C) satisfies the above range, the adhesive composition (C) has a high cohesive force and excellent adhesive strength. The V0.1 of the adhesive composition (C) is preferably 39,000 to 700,000 mPa·s, more preferably 200,000 to 650,000 mPa·s, and even more preferably 250,000 to 300,000 mPa·s. Furthermore, the adhesive composition (C) has a viscosity V100 of 1,000 to 5,000 mPa·s at an angular velocity ω of 100 rad / s and 190°C, as measured using a rheometer (requirement (C2) above). When the V100 of the adhesive composition (C) satisfies the above range, the adhesive composition (C) has good coatability. The V100 of the adhesive composition (C) is preferably 1,000 to 4,500 mPa·s, more preferably 1,500 to 4,000 mPa·s, and even more preferably 2,000 to 3,500 mPa·s. V0.1 and V100 of the adhesive composition (C) can be specifically measured by the method described in the Examples.

[0124] Furthermore, the adhesive composition (C) has a ratio of the viscosity V0.1 to the viscosity V100 [V0.1 / V100] of 10 or more (requirement (C3)). When [V0.1 / V100] of the adhesive composition (C) satisfies the above range, the adhesive composition (C) achieves both good applicability and high adhesive strength. The adhesive composition (C) has a [V0.1 / V100] ratio of preferably 15 or more, more preferably 50 or more, and even more preferably 150 or more. The upper limit is preferably 1,000 or less, more preferably 500 or less, and even more preferably 250 or less. Specifically, [V0.1 / V100] of the adhesive composition (C) can be calculated from the values of V0.1 and V100 of the adhesive composition (C) measured by the method described in the Examples.

[0125] By including the modified hydrogenated petroleum resin (B), the adhesive composition (C) becomes an adhesive composition that satisfies the requirements (C1) to (C3), and can achieve both good application properties and high adhesive strength. From the viewpoint of making it easier to obtain an adhesive composition that satisfies the requirements (C1) to (C3), the content of the modified hydrogenated petroleum resin (B) in the adhesive composition is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 25% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less.

[0126] The adhesive composition (C) may contain a base polymer in addition to the modified hydrogenated petroleum resin (B), and may further contain one or more additives selected from a plasticizer, a tackifier, and other additives.

[0127] <Base polymer> The adhesive composition (C) preferably further contains a base polymer in addition to the modified hydrogenated petroleum resin (B). In this specification, the "base polymer" according to the third invention refers to the polymer contained in the largest amount among the polymer components used as components other than the modified hydrogenated petroleum resin (B). Specific examples of base polymers include natural rubber, polyisoprene, butyl rubber, acrylic rubber, urethane rubber, silicone rubber, olefin-based elastomers, styrene-based elastomers, olefin-based plastomers, etc. Other base polymers used in reactive hot melt adhesives include polymers having silane-containing groups or isocyanate groups that undergo a condensation reaction with moisture. Among these, when the adhesive composition (C) is used as a hot melt adhesive, natural rubber, olefin-based elastomers, styrene-based elastomers, and olefin-based plastomers are preferred, and olefin-based elastomers and styrene-based elastomers are more preferred. Furthermore, when the adhesive composition (C) is used as a pressure-sensitive adhesive, natural rubber, polyisoprene, butyl rubber, acrylic rubber, urethane rubber, silicone rubber, and olefin-based elastomers are preferred, and natural rubber, polyisoprene, butyl rubber, acrylic rubber, urethane rubber, and olefin-based elastomers are more preferred. When the adhesive composition (C) is used as a pressure-sensitive adhesive, an acrylic adhesive or a silicone adhesive may be used in place of the base polymer. These may be used alone or in combination of two or more.

[0128] Examples of the olefin-based elastomer include the same olefin-based elastomers as those explained in the "Base Polymer" of the [Hot Melt Adhesive] according to the second invention, and the preferred embodiments thereof are also the same. When the adhesive composition (C) is used as a pressure-sensitive adhesive, the olefin-based elastomer is preferably an amorphous olefin polymer, and the amorphous olefin polymer is preferably an ethylene-propylene copolymer or atactic polypropylene. Examples of the styrene-based elastomer include the same styrene-based elastomers as those explained in the <base polymer> of the [hot melt adhesive] according to the second invention, and the preferred embodiments thereof are also the same.

[0129] From the viewpoint of cohesiveness, the content of the base polymer in the adhesive composition (C) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and even more preferably 30% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, still more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0130] <Plasticizer> The adhesive composition (C) preferably further contains a plasticizer. The plasticizer is not particularly limited, but examples thereof include the same plasticizers as those described in <Plasticizer> of the [Hot Melt Adhesive] according to the second invention, and preferred embodiments thereof are also the same.

[0131] From the viewpoint of improving adhesion and improving coatability, the content of the plasticizer in the adhesive composition (C) is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, still more preferably 10% by mass or more, and is preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and still more preferably 20% by mass or less.

[0132] <Tackifier> The adhesive composition (C) preferably further contains a tackifier. Examples of the tackifier include the same tackifiers as those described in the <Tackifier> section of the [Hot Melt Adhesive] according to the second invention, and the preferred embodiments thereof are also the same. The adhesive composition (C) may also contain a modified hydrogenated petroleum resin (A) as a tackifier, to the extent that the effect of the third invention is not impaired.

[0133] From the viewpoint of improving adhesiveness, the content of the tackifier in the adhesive composition (C) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, and is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less.

[0134] In the adhesive composition (C), the total content of the modified hydrogenated petroleum resin (B), base polymer, plasticizer, and tackifier is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and preferably 100% by mass or less.

[0135] <Other additives> The adhesive composition (C) may further contain additives such as inorganic fillers, antioxidants, ultraviolet absorbers, light stabilizers, and lubricants, as needed, within the range that does not impair the effect of the third invention. Examples of inorganic fillers include those similar to the inorganic fillers explained in <Other Additives> of the [Hot Melt Adhesive] according to the second invention. Examples of the antioxidant include the same antioxidants as those explained in <Other Additives> in the [Hot Melt Adhesive] according to the second invention.

[0136] <Production method and uses of adhesive composition (C)> The adhesive composition (C) can be produced by dry blending the modified hydrogenated petroleum resin (B) and, if necessary, a base polymer, a plasticizer, a tackifier, and other additives using a Henschel mixer or the like, and melt-kneading the mixture using a single-screw or twin-screw extruder, a plastomill, a Banbury mixer, or the like.

[0137] The adhesive composition (C) can also be produced by melt-kneading the modified hydrogenated petroleum resin (A), which is the raw material for the modified hydrogenated petroleum resin (B), with a base polymer, a plasticizer, a tackifier, and other additives, as needed, using the method described above, to cause a condensation reaction of the modified hydrogenated petroleum resin (A) to produce the modified hydrogenated petroleum resin (B). The method for condensing the modified hydrogenated petroleum resin (A) can be the same as that described above for step (a).

[0138] The adhesive composition (C) can achieve both good application properties and high adhesive strength, and can therefore be used as an adhesive such as a hot melt adhesive or a pressure-sensitive adhesive.

[0139] The adhesive composition (C) also contains the modified hydrogenated petroleum resin (B), which, as described above, is obtained by subjecting the modified hydrogenated petroleum resin (B) to a condensation reaction. Therefore, the adhesive composition (C) containing the modified hydrogenated petroleum resin (B) is also excellent in heat resistance, colorless, and has little odor, just like the adhesive composition containing the modified hydrogenated petroleum resin (A) of the second invention. Therefore, it can be suitably used for, for example, the interior of transportation equipment such as automobiles, trains, ships, and aircraft, sanitary materials, packaging, bookbinding, textiles, woodworking, electrical materials, can manufacturing, construction, filters, low-pressure molding, and bag manufacturing. Specifically, it can be preferably used as an adhesive for sanitary products such as disposable diapers and sanitary napkins, and as an adhesive for assembly such as automobile floor mats and woodworking applications for kitchens. In particular, since it has little odor, it can be suitably used as an adhesive for automobile interiors and sanitary products.

[0140] [Asphalt composition and asphalt mixture] The asphalt composition which is one embodiment of the third invention contains the modified hydrogenated petroleum resin (B) and straight asphalt, and the content of the straight asphalt is preferably 70.00 to 99.99 mass %. Suitable straight asphalt, its content, other components, and production method are the same as those for the asphalt composition described in the [Asphalt composition] according to the first invention.

[0141] An asphalt mixture according to one embodiment of the third invention contains the asphalt composition according to one embodiment of the third invention and aggregate, and the content of the aggregate is preferably 80 to 99 mass %. Suitable aggregates, their contents, and production methods are the same as those for the asphalt composition described in the [Asphalt Mixture] according to the first invention. [Example]

[0142] Next, the first, second and third inventions according to the present invention will be described in more detail using examples, but the first, second and third inventions according to the present invention are not limited to these examples in any way.

[0143] [Analysis and evaluation of silane compounds and modified hydrogenated petroleum resins] [1. Bromine number] Measurement was carried out in accordance with JIS K 2605.

[0144] [2. Silicon concentration] 0.1 g of the modified hydrogenated petroleum resin, modified petroleum resin, or hydrogenated petroleum resin obtained in the examples and comparative examples was heated in an electric furnace at 550°C for 12 hours, and the ash was dissolved in alkali to prepare a measurement solution. ICP emission spectroscopy was then performed (ICP emission spectroscopy analyzer: 720-ES, manufactured by Agilent Technologies, Inc.) to determine the silicon concentration.

[0145] 3. Molecular Weight and Molecular Weight Distribution The average molecular weight was measured by gel permeation chromatography (GPC) using a GPC measuring device (HLC8220, detector: RI, columns: TSK-GEL GHXL-L, G4000HXL, G2000HXL, tetrahydrofuran as eluent, all manufactured by Tosoh Corporation), and the polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) were determined, and the molecular weight distribution (Mw / Mn) was calculated.

[0146] [4. Integral ratio of aromatic hydrogen] Using a nuclear magnetic resonance (NMR) apparatus (JNM-EX400, manufactured by JEOL Ltd.), the solvent was deuterated chloroform, and the number of accumulations was 256. 1 H-NMR measurements were performed, and the ratio of the integral of the peak in the 6.5-7.5 ppm region (aromatic hydrogen peak) to the sum of the integrals of the peaks in the 0-3.0 ppm region and the 6.5-7.5 ppm region (integral of the peak in the 6.5-7.5 ppm region / (sum of the integrals of the peaks in the 0-3.0 ppm region and the 6.5-7.5 ppm region)) was calculated. When peaks due to raw material additives (antioxidants, etc.) or solvents (chloroform, etc.) were present in the 0-3.0 ppm and 6.5-7.5 ppm regions, standard samples were similarly measured, and the integrals were subtracted from the above integrals to determine the ratio. However, for the resins of Comparative Examples 2-2 to 2-4, silane-modified untreated hydrogenated petroleum resins were similarly measured, and the above integral ratios were calculated.

[0147] [5. Softening point] Measurement was carried out in accordance with JIS K 6863.

[0148] [6. Volatile content] Gas components were generated using a headspace gas chromatograph (instrument name: Agilent 7697A / Agilent 7890B), and the amount of components with a retention time of less than 40 minutes when measured under the conditions below was taken as the amount of volatile matter. (Measurement conditions) Sample heat treatment: 150°C, 20 min, Column: BPX5 30 m x 0.32 m id x 1.0 μm, Injection port: 300°C, Temperature program: 50°C to 300°C, 10°C / min, temperature increase

[0149] [7. Glass transition temperature] The glass transition temperature (Tg) is determined from a melting endothermic curve obtained under the following measurement conditions. Specifically, the intersection of the tangent line at the low-temperature baseline where there is no change in heat quantity and the inflection point (the point where the curve changes from an upward convex to a downward convex curve) or the midpoint of the displacement is taken as the glass transition temperature (Tg). <Measurement conditions> Using a differential scanning calorimeter (DSC) (Perkin-Elmer, "DSC-7"), 10 mg of sample was held at 25°C for 5 minutes under a nitrogen atmosphere, heated to 220°C at 320°C / min and held there for 5 minutes, then cooled to -20°C at 320°C / min, held at -20°C for 5 minutes, and then heated to 220°C at 10°C / min to obtain a melting endothermic curve.

[0150] [8.3 carbon integral ratio] Using the following equipment and conditions: 13 C-NMR spectrum was measured and calculated using the following formula: Equipment: AVANCE III HD manufactured by Bruker BioSpin Co., Ltd. Probe: BBO 10mmφ sample tube compatible Method: Proton complete decoupling method Sample tube diameter: 10mmφ Sample concentration: 220 mg / mL Solvent: deuterated chloroform Observation range: -20 to 220 ppm Observation center: 100 ppm Temperature: room temperature Pulse width: 45° Pulse repetition time: 4 seconds Accumulation: 1000 times <Calculation formula> Tertiary carbon integral ratio (%) = A / B x 100 A: Integrated value of the peak in the 35 to 64 ppm range (integral value of aliphatic tertiary carbon) B: Integral value of the peak in the 10-64 ppm range (integral value of total aliphatic carbon)

[0151] [9. Ratio of absorbance due to silicon-oxygen bonds (ASiO) to absorbance due to carbon-hydrogen bonds (ACH) (ASiO / ACH)] 60 mg of the silane compound was dissolved in 4 mL of dichloromethane, and 10 μL of the solution was dropped onto a KBr plate. The KBr plate was placed on a hot plate at 40°C and dried for 3 minutes. FT-IR analysis was performed under the following conditions, and the ratio of absorbance due to silicon-oxygen bonds (ASiO) to absorbance due to carbon-hydrogen bonds (ACH) (ASiO / ACH) was calculated from the absorbance obtained. The absorbance due to silicon-oxygen bonds (ASiO) is at 1040 cm -1 From 1160cm -1 1091cm when the baseline is -1 The absorbance due to carbon-hydrogen bonds (ACH) is near 2750 cm -1 From 3110cm -1 2925cm when the baseline is -1 The absorbance in the vicinity. Equipment: Fourier transform infrared spectrometer Spectrum One (PerkinElmer) Measurement method: Transmission method Observation range: 450~4000cm -1 Resolution: 4.00cm -1 Number of times accumulated: 4 times

[0152] [10.40℃ viscosity] The viscosity (B-type viscosity) was measured at 40°C using a Brookfield rotational viscometer in accordance with ASTM D3236.

[0153] 11. Smell 1.0 g of the modified hydrogenated petroleum resin, modified petroleum resin, or hydrogenated petroleum resin obtained in the Examples and Comparative Examples was placed in a 20 mL glass sample bottle, sealed, and left at 25°C for 1 hour. The bottle was then opened and subjected to a sensory evaluation. Evaluation was based on the following criteria. The less odor there was, the better. 1: Odorless 2: Almost odorless 3: Has a weak odor 4: Has a strong odor

[0154] [12. Colorlessness] Measurement was carried out in accordance with JIS K 0071-2.

[0155] [13. Temperature-rising creep test (evaluation of heat resistance)] <Preparation of test specimen> The resin compositions (adhesives) obtained in the Examples and Comparative Examples were applied to a Teflon (registered trademark) sheet heated to 140°C to prepare a film of the resin composition (size: 60 mm x 30 mm, thickness: 0.1 mm). The film of the resin composition was placed on cotton canvas (fabric thickness: 13.0 ounces), and a piece of wood (surface in contact with the resin composition: lauan) was placed on top of that, followed by a 500 g weight. The mixture was heated at 150°C for 1 minute (adhesion surface: 60 mm x 30 mm). After cooling, the sample was left to stand for 10 days in an environment of 23°C and 50% humidity to prepare a test specimen. <Temperature-elevated creep test (shear adhesive failure temperature)> In an environment of 30°C and 30% humidity, the end of the wood piece part of the test piece was fixed, and a load of 200 g was applied to the cotton canvas in the shear direction (parallel to the adhesive surface and opposite to the fixed part of the wood piece). (The adhesive surface between the cotton canvas and the resin composition, and between the resin composition and the wood piece was 18 cm.) 2 The temperature was raised from 30°C at a rate of 0.5°C / min, and the temperature at which the cotton canvas of the test piece peeled off was measured and taken as the creep temperature of the resin composition. The higher the creep temperature, the better the heat resistance.

[0156] [14. Viscosity (measurement of V0.1 and V100)] A disk-shaped test piece with a diameter of 25 mm and a thickness of 1 mm was prepared by press molding. Using an Anton Paar rheometer MCR301, the specimen was subjected to a shear rate of 100 s at a temperature of 190 °C under a strain of 5% in a nitrogen atmosphere using the parallel plate method (φ = 25 mm, gap 1 mm). -1 to 0.1 seconds -1 The dynamic viscoelasticity was measured under the conditions of shear rate up to 0.1 s -1 Viscosity (V0.1) at 100s -1 The viscosity (V100) at this time was determined. From the results, the ratio of the viscosity V0.1 to the viscosity V100 [V0.1 / V100] was calculated.

[0157] [Evaluation of asphalt composition] [Water resistance (peeling resistance)] The water resistance was evaluated using a test specimen (asphalt mixture) obtained by mixing an asphalt composition with hard sandstone aggregate of 9.5 mm or more and 13.2 mm or less according to the procedure described below. The test specimens were prepared by adding 5.5g±0.5g of each asphalt composition, which had been heated at 180°C for one hour, to 100g±0.5g of hard sandstone aggregate that had been washed and dried, and stirring for approximately one minute. Ten specimens were then selected from the prepared specimens and placed in 100mL of a 1.0 (mol / L) aqueous solution of sodium carbonate. The specimens were then heated on a hot plate, heated for one minute after reaching 90°C, and cooled, after which the peeling area ratio of the specimens was measured. The peeling area ratios of the upper surface and the lower surface of the test specimen were measured, and the average of the measured peeling area ratios of the upper surface and the lower surface of the test specimen was calculated to determine the peeling resistance. The lower the average peeling rate on the top and bottom surfaces, the better the peeling resistance and water resistance, and the evaluation was based on the following criteria. ○: Average peeling rate on top and bottom surfaces is less than 40% ×: The average peeling rate on the top and bottom surfaces is 40% or more

[0158] [Production of organic compounds having a cyclic structure] Production Example 1-1 (Production of petroleum resin (unhydrogenated)) 180 g of xylene was placed in a 1-liter autoclave and heated to 260°C. Next, a mixture of 100 g of dicyclopentadiene and 100 g of styrene was placed in over 3 hours. This temperature was maintained for an additional 75 minutes to carry out a polymerization reaction, yielding a polymer mixture. Thereafter, xylene was recovered from the obtained polymer mixture, and then the mixture was maintained at 20 mmHg for 2 hours to distill off low boiling point substances, thereby obtaining a petroleum resin having a cyclic structure represented by the above formula (4). The obtained petroleum resin had a softening point of 63.0°C and a bromine number of 58.

[0159] Production Example 1-2 (Production of 9-allylanthracene) Flake magnesium (2.7 g, 110 mmol) was placed in a 300 mL three-neck round-bottom flask equipped with a nitrogen inlet tube and a Dimroth tube, and the mixture was stirred at approximately 100 °C for 10 minutes to activate the magnesium surface. Then, dry tetrahydrofuran (30 mL) was added, followed by the dropwise addition of a tetrahydrofuran solution (50 mL) of 9-bromoanthracene (8.7 g, 55 mmol) and the mixture was slowly refluxed. After 1 hour, a tetrahydrofuran solution (50 mL) of allyl bromide (6.7 g, 55 mmol) was added dropwise in an ice bath. After the addition was complete, the mixture was stirred at room temperature for 8 hours. Approximately 50 mL of tetrahydrofuran was removed by distillation under reduced pressure, and n-heptane (300 mL) was added. The mixture was then separated into a liquid phase and a solid by filtration. The liquid phase was passed through a silica gel column, and 300 mL of n-heptane was passed through the column to obtain a solution. The liquid phase was distilled off under reduced pressure to obtain 9-allylanthracene (5.1 g).

[0160] [Production of silane compounds] Example 1-1 (Production of silane-modified petroleum resin (unhydrogenated)) 50 g of the petroleum resin obtained in Production Example 1-1 and 50 mL of dehydrated toluene were placed in a 300 mL glass container equipped with a nitrogen inlet tube and a stirring blade, and the mixture was dissolved by stirring at 60°C. Subsequently, under a nitrogen atmosphere, trimethoxysilane (1 g) and a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution (0.1 M, 0.1 mL) were added, and the mixture was stirred at 60°C for 3 hours. After the reaction was completed, the mixture was air-dried on a tray and then dried under reduced pressure at 110°C for 2 hours to obtain silane compound P, which is a silane-modified petroleum resin (unhydrogenated) having a cyclic structure represented by formula (4). The analytical and evaluation results of the obtained silane compound P are shown in Table 1.

[0161] Example 1-2 (Production of silane-modified petroleum resin (unhydrogenated)) Silane compound Q, which is a silane-modified petroleum resin (unhydrogenated) having a cyclic structure represented by formula (4), was obtained in the same manner as in Example 1-1, except that Escorez 1310 (manufactured by Exxon Corp.) was used instead of the petroleum resin obtained in Production Example 1-1. The analysis and evaluation results of the obtained silane compound Q are shown in Table 1.

[0162] Example 1-3 (Production of silane-modified anthracene compound) A 300 mL three-necked round-bottom flask equipped with a nitrogen inlet tube was charged with 5.1 g (23.3 mmol) of 9-allylanthracene obtained in Preparation Example 1-2 and 50 mL of dry toluene. Under nitrogen, 2.9 g of trimethoxysilane and a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution (0.1 M, 0.1 mL) were then added. After stirring for 3 hours, the solvent was removed under reduced pressure to obtain Silane Compound S, a silane-modified anthracene compound having a cyclic structure represented by Formula (5). The analytical and evaluation results for the obtained Silane Compound S are shown in Table 1.

[0163] Example 1-4 (Production of silane-modified microcrystalline wax) 100 g of microcrystalline wax Hi-Mic-1080 (manufactured by Nippon Seiro Co., Ltd.) was placed in a 300 mL three-neck round-bottom flask equipped with a nitrogen inlet tube and heated to 160°C in an oil bath under a nitrogen atmosphere to melt. Subsequently, 2.0 g of trimethoxysilane and 1.0 g of organic peroxide (2,5-dimethyl-2,5-di(t-butylperoxy)hexane, trade name "Perhexa (registered trademark) 25B", manufactured by NOF Corporation) were added under nitrogen. After stirring for 1 hour, volatiles were removed under reduced pressure to obtain silane compound T, a silane-modified microcrystalline wax having a cyclic structure represented by formulas (1), (2), and (3). The analytical and evaluation results of the obtained silane compound T are shown in Table 1.

[0164] [Table 1]

[0165] [Production of petroleum resins and hydrogenated petroleum resins] Manufacturing Example 2-1 (Manufacturing petroleum resin) 180 g of xylene was placed in a 1-liter autoclave and heated to 260°C. Next, a mixture of 100 g of dicyclopentadiene and 100 g of styrene was placed in over 3 hours. This temperature was maintained for an additional 75 minutes to carry out a polymerization reaction, yielding a polymer mixture. Thereafter, xylene was recovered from the resulting polymer mixture, and then the mixture was maintained at 20 mmHg for 2 hours to distill off low boiling point materials, yielding a petroleum resin with a softening point of 63.0°C and a bromine number of 58.

[0166] Production Example 2-2 (Production of hydrogenated petroleum resin) 180 g of the petroleum resin obtained in Production Example 2-1, 180 g of ethylcyclohexane, and 4 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 to the autoclave to a pressure of 5 MPa, and the temperature was raised from room temperature to 230°C. Subsequently, a hydrogenation reaction was carried out for 8 hours while maintaining the hydrogen pressure at 5 MPa, yielding a hydrogenated petroleum resin. The resulting hydrogenated petroleum resin had a softening point of 100°C and a bromine number of 2.5. This was designated hydrogenated petroleum resin E.

[0167] [Production of modified petroleum resins and modified hydrogenated petroleum resins] Example 2-1 110 g of the hydrogenated petroleum resin E obtained in Production Example 2-2 was placed in a 500 mL separable flask equipped with a nitrogen inlet tube and a stirring blade, and heated to 140° C. in an oil bath under a nitrogen stream. Once the hydrogenated petroleum resin was dissolved, 12 g of vinyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with stirring, and the mixture was stirred until homogenized. Next, 0.5 g of organic peroxide (2,5-dimethyl-2,5-di(t-butylperoxy)hexane, trade name "Perhexa (registered trademark) 25B", manufactured by NOF Corporation) was added dropwise. After the dropwise addition, the mixture was stirred at an internal temperature (reaction mixture temperature) of 145°C for 1 hour to allow the reaction to proceed. After the reaction was completed, the contents of the flask were transferred to a stainless steel tray and dried under vacuum at 150°C for 1 hour to obtain 102 g of modified hydrogenated petroleum resin A. The analysis and evaluation results of the obtained modified hydrogenated petroleum resin A are shown in Table 2.

[0168] Example 2-2 In Example 2-1, the amount of hydrogenated petroleum resin E was changed to 200 g, the amount of vinyltrimethoxysilane to 33 g, the amount of organic peroxide (2,5-dimethyl-2,5-di(t-butylperoxy)hexane, trade name "PERHEXA (registered trademark) 25B") to 0.8 g, and the reaction time to 3 hours. 210 g of modified hydrogenated petroleum resin B was obtained in the same manner as in Example 2-1. The analysis and evaluation results of the obtained modified hydrogenated petroleum resin B are shown in Table 2.

[0169] Example 2-3 5 kg of the hydrogenated petroleum resin E obtained in Production Example 2-2, 500 g of vinyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 50 g of an organic peroxide (2,5-dimethyl-2,5-di(t-butylperoxy)hexane, trade name "Perhexa (registered trademark) 25B") were mixed in advance at 20°C. The resulting mixture was dropped into the bottom of the hopper of a twin-screw extruder (TEM18SS, Toshiba Machine Co., Ltd.) at a rate of 174 g / hour using a solenoid-driven diaphragm metering pump PW (manufactured by Takumina Corporation), and the mixture was kneaded. The kneading conditions were a temperature of 200°C and a residence time of approximately 70 seconds. The resulting kneaded product was placed on a stainless steel tray and dried under vacuum at 150°C for 1 hour, yielding 450 g of modified hydrogenated petroleum resin C. The analysis and evaluation results of the resulting modified hydrogenated petroleum resin C are shown in Table 2.

[0170] Examples 2-4 A 500 mL separable flask equipped with a nitrogen inlet tube and a stirring blade was charged with 150 g of a hydrogenated petroleum resin trade name "Escorez (registered trademark) 5300" (manufactured by ExxonMobil Chemical Corporation), and heated to 160°C in an oil bath under a nitrogen stream. Once the hydrogenated petroleum resin was dissolved, 6.8 g of vinyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with stirring, and the mixture was stirred until it became homogeneous. Next, 0.34 g of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (trade name "Perhexa (registered trademark) 25B") was added dropwise as an organic peroxide. After the addition, the mixture was stirred at an internal temperature (reaction mixture temperature) of 160°C for 30 minutes to allow the reaction to proceed. After an additional 30 minutes, 0.34 g of Perhexa (registered trademark) 25B was added, and after another 30 minutes, 0.34 g of Perhexa (registered trademark) 25B was added, followed by a reaction for 1 hour. After completion of the reaction, the mixture was dried at 150°C under reduced pressure and stirring for 1 hour to obtain modified hydrogenated petroleum resin F. The analysis and evaluation results of the obtained modified hydrogenated petroleum resin F are shown in Table 2.

[0171] Examples 2-5 In Example 2-4, modified hydrogenated petroleum resin G was obtained in the same manner as in Example 2-4, except that the hydrogenated petroleum resin used was changed from the trade name "Escorez (registered trademark) 5300" to the trade name "Eastotac (registered trademark) C-100W" (manufactured by Eastman Co.). The analysis and evaluation results of the obtained modified hydrogenated petroleum resin G are shown in Table 2.

[0172] Examples 2-6 In Example 2-4, the hydrogenated petroleum resin used was changed from the trade name "Escorez (registered trademark) 5300" to the hydrogenated petroleum resin E obtained in Production Example 2-2, and the same procedure as in Example 2-4 was repeated to obtain modified hydrogenated petroleum resin H. The analysis and evaluation results of the obtained modified hydrogenated petroleum resin H are shown in Table 2.

[0173] Examples 2-7 In Example 2-4, modified hydrogenated petroleum resin I was obtained in the same manner as in Example 2-4, except that the hydrogenated petroleum resin used was changed from the trade name "Escorez (registered trademark) 5300" to the trade name "Arkon (registered trademark) P-100" (manufactured by Arakawa Chemical Industries, Ltd.). The analysis and evaluation results of the obtained modified hydrogenated petroleum resin I are shown in Table 2.

[0174] Examples 2-8 In Example 2-4, modified hydrogenated petroleum resin J was obtained in the same manner as in Example 2-4, except that the hydrogenated petroleum resin used was changed from the trade name "Escorez (registered trademark) 5300" to the trade name "I-MARV (registered trademark) S-100" (manufactured by Idemitsu Kosan Co., Ltd.). The analysis and evaluation results of the obtained modified hydrogenated petroleum resin J are shown in Table 2.

[0175] Examples 2-9 The petroleum resin (110 g) obtained in Production Example 2-1 was placed in a 500 mL separatory flask equipped with a nitrogen inlet tube and a stirring blade and heated in an oil bath (140°C) under a nitrogen stream. Stirring was initiated once the resin was melted, and 12 g of vinyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd.) was added under a nitrogen stream, followed by stirring for 5 minutes under a nitrogen atmosphere. 0.5 g of Perhexa (registered trademark) 25B was added dropwise under a nitrogen atmosphere. The oil bath temperature was raised to 150°C (internal temperature approximately 145°C), and stirring was continued for 1 hour. After the reaction was completed, the reaction product was taken out into a tray and dried at 150°C under vacuum for 1 hour to obtain 98 g of Modified Petroleum Resin D. The analysis and evaluation results of the obtained Modified Petroleum Resin D are shown in Table 3.

[0176] Comparative Example 2-1 As Comparative Example 2-1, the hydrogenated petroleum resin E obtained in Production Example 2-2 was analyzed and evaluated. The results are shown in Table 3.

[0177] Comparative Example 2-2 As Comparative Example 2-2, the hydrogenated petroleum resin used in Example 2-4, trade name "Escorez (registered trademark) 5300" (hereinafter also referred to as "hydrogenated petroleum resin K"), was analyzed and evaluated. The results are shown in Table 3.

[0178] Comparative Example 2-3 As Comparative Example 2-3, the hydrogenated petroleum resin used in Example 2-7, trade name "Arkon (registered trademark) P-100" (hereinafter also referred to as "Hydrogenated Petroleum Resin L"), was analyzed and evaluated. The results are shown in Table 3.

[0179] [Table 2]

[0180] [Table 3]

[0181] [Production of resin composition (adhesive)] Examples 2-10 to 2-17 Each resin composition (adhesive) was obtained by melt-mixing the modified hydrogenated petroleum resins A to C and F to J obtained in Examples 2-1 to 2-8 and low-crystalline polypropylene (product name "L-MODU (registered trademark) S400", manufactured by Idemitsu Kosan Co., Ltd.) at 180°C in the proportions (mass%) shown in Table 4. The evaluation results of each resin composition obtained are shown in Table 4.

[0182] Reference example 2-1 The modified petroleum resin D obtained in Example 2-9 and low-crystalline polypropylene (product name "L-MODU (registered trademark) S400") were melt-mixed at 180°C to obtain a resin composition (adhesive) in the proportions (mass%) shown in Table 4. The evaluation results of the obtained resin composition are shown in Table 4.

[0183] Comparative Example 2-4 A resin composition (adhesive) was obtained by melt-mixing the hydrogenated petroleum resin E obtained in Production Example 2-2 and low-crystalline polypropylene (product name "L-MODU (registered trademark) S400") at 180°C in the proportions (mass%) shown in Table 4. The evaluation results of the obtained resin composition are shown in Table 4.

[0184] Comparative Examples 2-5 to 2-6 Resin compositions (adhesives) were obtained by melt-mixing the hydrogenated petroleum resins K and L used in Comparative Examples 2-2 and 2-3, respectively, with low-crystalline polypropylene (product name "L-MODU (registered trademark) S400") at 180°C in the proportions (mass%) shown in Table 4. Table 4 shows the evaluation results of the obtained resin compositions.

[0185] [Table 4]

[0186] As is clear from the results in Table 2, the modified hydrogenated petroleum resins of the examples have low odor and excellent colorlessness, and as is clear from the results in Table 4, the resin compositions (adhesives) containing the modified hydrogenated petroleum resins have excellent heat resistance.

[0187] [Condensation reaction treatment of modified hydrogenated petroleum resin (A) (production of modified hydrogenated petroleum resin (B)] Example 3-1 5 g of the modified hydrogenated petroleum resin A obtained in Example 2-1 was collected in a 20 mL sample bottle and heated in an oven at 180 ° C. for 3 minutes. Then, 0.04 g of dibutyltin dilaurate was added to the sample bottle removed from the oven and mixed with the modified hydrogenated petroleum resin A. The mixture was stirred with a spatula to cause a condensation reaction of the modified hydrogenated petroleum resin A with moisture in the air, thereby obtaining a modified hydrogenated petroleum resin AR. The evaluation results of the obtained modified hydrogenated petroleum resin AR are shown in Table 5.

[0188] Examples 3-2 to 3-8 The modified hydrogenated petroleum resins BR, CR, and FR to JR shown in Table 5 below were obtained in the same manner as in Example 3-1, except that the modified hydrogenated petroleum resin A before the condensation reaction treatment in Example 3-1 was replaced with the modified hydrogenated petroleum resins B, C, and F to J obtained in Examples 2-2 to 2-8. The evaluation results of the obtained modified hydrogenated petroleum resins BR, CR, and FR to JR are shown in Table 5.

[0189] Example 3-9 and Comparative Examples 3-1 to 3-3 The petroleum resins DR, ER, KR, and LR shown in Table 5 below were obtained in the same manner as in Example 3-1, except that the modified hydrogenated petroleum resin A before the condensation reaction treatment in Example 3-1 was replaced with the modified petroleum resin D obtained in Example 2-9, the hydrogenated petroleum resin E obtained in Production Example 2-2, and the hydrogenated petroleum resins K and L used in Comparative Examples 2-2 and 2-3. The evaluation results of the obtained petroleum resins DR, ER, KR, and LR are shown in Table 6.

[0190] [Table 5]

[0191] [Table 6]

[0192] As is clear from the results in Table 5, it was confirmed that the modified hydrogenated petroleum resins of Examples 3-1 to 3-8 were subjected to the condensation reaction treatment, resulting in modified hydrogenated petroleum resins that had low viscosity at high shear rates and high viscosity at low shear rates. On the other hand, as shown in the results in Table 6, it was confirmed that the hydrogenated petroleum resins of the comparative examples had low viscosities at low shear rates even after the condensation reaction treatment.

[0193] [Production of adhesive composition (C) containing modified hydrogenated petroleum resin after condensation reaction treatment] Examples 3-10 A 50 mL sample bottle was charged with 4.0 g of low-crystalline polypropylene (trade name "L-MODU (registered trademark) S400" manufactured by Idemitsu Kosan Co., Ltd.), 5.0 g of the modified hydrogenated petroleum resin A obtained in Example 2-1, and 1.0 g of a plasticizer "Diana (registered trademark) Process Oil PW-90" manufactured by Idemitsu Kosan Co., Ltd., and left to stand in an oven at 180°C for 10 minutes. The sample bottle was then removed from the oven, and 0.04 g of dibutyltin dilaurate was added to the bottle and stirred and mixed with a spatula. The mixture was then again heated in an oven at 180°C for 5 minutes, removed from the oven, and stirred and mixed with a spatula to obtain an adhesive composition. The evaluation results of the resulting adhesive composition are shown in Table 7. When the mixture was stirred with a spatula, the moisture in the air caused a condensation reaction of the modified hydrogenated petroleum resin A, converting it into the modified hydrogenated petroleum resin AR.

[0194] Examples 3-11 An adhesive composition was obtained in the same manner as in Example 3-10, except that the modified hydrogenated petroleum resin A before the condensation reaction treatment was changed to the modified hydrogenated petroleum resin B obtained in Example 2-2. The evaluation results of the obtained adhesive composition are shown in Table 7. When the mixture was stirred with a spatula, the moisture in the air caused a condensation reaction of the modified hydrogenated petroleum resin B, converting it into the modified hydrogenated petroleum resin BR.

[0195] Example 3-12 An adhesive composition was obtained in the same manner as in Example 3-11, except that the low-crystalline polypropylene (trade name "L-MODU (registered trademark) S400") in Example 3-11 was changed to an olefin-based elastomer (trade name "Affinity (registered trademark) GA1950", manufactured by Dow). The evaluation results of the obtained adhesive composition are shown in Table 7.

[0196] Comparative Example 3-4 An adhesive composition was obtained in the same manner as in Example 3-10, except that the modified hydrogenated petroleum resin A before the condensation reaction treatment was changed to the hydrogenated petroleum resin E obtained in Production Example 2-2. The evaluation results of the obtained adhesive composition are shown in Table 7. When the mixture was stirred with a spatula, the hydrogenated petroleum resin E underwent a condensation reaction due to the moisture in the air. Therefore, in Table 7, this resin is referred to as hydrogenated petroleum resin ER.

[0197] Comparative Example 3-5 An adhesive composition was obtained in the same manner as in Comparative Example 3-4, except that the low-crystalline polypropylene (trade name "L-MODU (registered trademark) S400") was replaced with an olefin-based elastomer (trade name "Affinity (registered trademark) GA1950"). The evaluation results of the obtained adhesive composition are shown in Table 7.

[0198] [Table 7]

[0199] As is clear from the results in Table 7, each adhesive composition in the Examples was prepared by mixing the components and then subjecting the modified hydrogenated petroleum resin A or B to a condensation reaction treatment, resulting in an adhesive composition containing the modified hydrogenated petroleum resin after the condensation reaction treatment (adhesive composition (C) described as the third invention above), and it was confirmed that the adhesive composition had a low viscosity at high shear rates and a high viscosity at low shear rates. That is, the adhesive composition has low viscosity at high shear rates, which allows for good applicability, and also has high viscosity at low shear rates, which increases cohesive force and adhesive strength. On the other hand, as shown in the results of Table 7, it was confirmed that the adhesive composition of the comparative example had a low viscosity at low shear rates even after the condensation reaction treatment with hydrogenated petroleum resin E.

[0200] [Production and evaluation of asphalt compositions] Evaluation Examples 1 to 12 and Comparative Evaluation Examples 1 to 3 Among the silane compounds or modified hydrogenated petroleum resins obtained in the above Examples and Comparative Examples, those shown in Table 8 were used. To 90.5 parts by mass of asphalt (straight asphalt) heated to 180 ° C, 4.0 parts by mass of extract and 4.5 parts by mass of SBS were added and stirred at 3,000 rpm using a homomixer for 1.5 hours. Furthermore, 1.0 part by mass of a silane-containing compound or modified hydrogenated petroleum resin shown in Table 8 was added and stirred at 3,000 rpm for 30 minutes to obtain the asphalt composition shown in Table 8. The asphalt used as the raw material has the following typical properties: penetration of 67 (1 / 10 mm), softening point of 48.0°C, and density of 1,036 kg / m at 15°C. 3 The extract is a petroleum-based solvent-extracted oil, and the SBS has a molecular weight of approximately 150,000 (g / mol) and a styrene content of 30% by mass relative to the total SBS. In the comparative evaluation examples, rosin (Comparative Evaluation Example 2) or dimer acid (Comparative Evaluation Example 3) was used instead of the silane compound or modified hydrogenated petroleum resin of the evaluation examples. Comparative evaluation example 1 did not contain the silane compound or modified hydrogenated petroleum resin of the evaluation examples, and 91.5 parts by mass of asphalt was used instead of 90.5 parts by mass. The rosin was a disproportionated gum rosin with an acid value of 156 (mg KOH / g: JIS K 0070) and a softening point of 77.0°C (JIS K 2207), and the dimer acid was a tall oil fatty acid dimer with 36 carbon atoms and an acid value of 190 to 210 (mg KOH / g: JIS K 0070). The water resistance (peeling resistance) of the obtained asphalt composition was evaluated. The evaluation results are shown in Table 8.

[0201] [Table 8]

[0202] The results in Table 8 show that the silane-containing compound according to the first invention can suppress asphalt peeling and improve water resistance, and that the modified hydrogenated petroleum resin according to the second invention can also suppress asphalt peeling and improve water resistance.

Claims

1. A method for producing a coating composition comprising a silane-containing compound and straight asphalt, The silane-containing compound is at least one selected from the group consisting of a silane-modified petroleum resin having a cyclic structure represented by the following general formula (4), a silane-modified anthracene compound having a cyclic structure represented by the following structural formula (5), and a silane-modified microcrystalline wax having a cyclic structure represented by the following general formulas (1), (2), and (3): The asphalt composition, wherein the content of the straight asphalt is 70.00 to 99.99% by mass. 【Chemical 1】 (In the general formula (4), l, m, and n each independently represent 1 or 2, and the straight line represents a single bond or a double bond, provided that the double bonds are not consecutive.) 【Chemistry 2】 【Chemistry 3】 (In the general formulae (1), (2), and (3), l, m, and n each independently represent 1 or 2, and the straight line represents a single bond or a double bond, provided that the double bonds are not consecutive.)

2. An asphalt composition as described in claim 1, wherein the cyclic structure represented by the general formula (2) is a structure represented by the following structural formula (6): 【Chemistry 4】

3. An asphalt composition according to claim 1, wherein the cyclic structure represented by the general formula (4) is a structure represented by any one of the following structural formulas (8) to (10). 【Chemistry 5】

4. of the silane-containing compound １ The asphalt composition according to any one of claims 1 to 3, wherein the integral ratio of aromatic hydrogen in H-NMR measurement [integral value of the peak in the 6.5 to 7.5 ppm region / (sum of the integral value of the peak in the 0 to 3.0 ppm region and the integral value of the peak in the 6.5 to 7.5 ppm region)] is 70% or less.

5. The asphalt composition according to any one of claims 1 to 4, wherein the softening point of the silane-containing compound is 90°C or higher.

6. The asphalt composition according to any one of claims 1 to 5, wherein the viscosity of the silane-containing compound at 40°C is 1 to 1,000 mPa·s.

7. The asphalt composition according to any one of claims 1 to 6, wherein the glass transition temperature of the silane-containing compound is 30°C or higher.

8. The asphalt composition according to any one of claims 1 to 7, wherein the ratio of the absorbance (ASiO) derived from silicon-oxygen bonds to the absorbance (ACH) derived from carbon-hydrogen bonds in IR measurement of the silane-containing compound satisfies the following relationship: 0.01<ASiO / ACH<0.37

9. of the silane-containing compound １３ The asphalt composition according to any one of claims 1 to 8, wherein the integral ratio of tertiary carbon in C-NMR measurement [integral value of the peak in the 35 to 64 ppm region / integral value of the peak in the 10 to 64 ppm region] is 2 to 80%.

10. An asphalt mixture comprising the asphalt composition according to any one of claims 1 to 9 and aggregate, wherein the aggregate content is 80 to 99 mass%.

11. A modified hydrogenated petroleum resin that satisfies the following (A1) to (A4): (A1) Bromine number is 0.1 to 10.0 (A2) Contains 0.1 to 10 mass% silicon element in terms of silicon atoms (A3) Weight average molecular weight of 500 to 2,000 (A4) Molecular weight distribution (Mw / Mn) of 1.1 to 3.5

12. 1 The integral ratio of aromatic hydrogen in H-NMR measurement [integral value of peak in 6.5 to 7.5 ppm region / (sum of integral value of peak in 0 to 3.0 ppm region and integral value of peak in 6.5 to 7.5 ppm region)] is 0 to 15%. The modified hydrogenated petroleum resin according to claim 11.

13. The modified hydrogenated petroleum resin according to claim 11 or 12, having a softening point of 60 to 150°C.

14. The modified hydrogenated petroleum resin according to any one of claims 11 to 13, wherein the volatile content when heated at 150 ° C. for 20 minutes is 1.0 mass% or less.

15. The modified hydrogenated petroleum resin according to any one of claims 11 to 14, wherein the alkoxysilyl group is bonded to the main chain of the hydrogenated petroleum resin via a bond.

16. A method for producing a modified hydrogenated petroleum resin, comprising reacting a hydrogenated petroleum resin with a compound having a carbon-carbon double bond and an alkoxysilyl group in the presence of a compound that generates radicals to obtain the modified hydrogenated petroleum resin according to claim 11.

17. A hot melt adhesive comprising 1 to 70 mass% of the modified hydrogenated petroleum resin according to any one of claims 11 to 15.

18. A pressure-sensitive adhesive comprising 1 to 70 mass% of the modified hydrogenated petroleum resin according to any one of claims 11 to 15.

19. An asphalt composition comprising the modified hydrogenated petroleum resin according to any one of claims 11 to 15 and straight asphalt, wherein the content of straight asphalt is 70.00 to 99.99% by mass.

20. An asphalt mixture comprising the asphalt composition according to claim 19 and aggregate, wherein the aggregate content is 80 to 99% by mass.

21. A modified hydrogenated petroleum resin (B) obtained by a condensation reaction of a modified hydrogenated petroleum resin (A) that satisfies the following (A1) to (A4), wherein the modified hydrogenated petroleum resin (B) satisfies the following (B1) to (B3): (A1) Bromine number is 0.1 to 10.0 (A2) Contains 0.1 to 10 mass% silicon element in terms of silicon atoms (A3) Weight average molecular weight of 500 to 5,000 (A4) Molecular weight distribution (Mw / Mn) of 1.1 to 3.5 (B1) Viscosity V0.1 measured using a rheometer at an angular velocity ω = 0.1 rad / s and 190°C is 1,000 to 50,000 mPa s (B2) Viscosity V100 measured using a rheometer at an angular velocity ω of 100 rad / s and 190°C is 100 to 1,000 mPa·s (B3) The ratio of the viscosity V0.1 to the viscosity V100 [V0.1 / V100] is 10 or more.

22. The modified hydrogenated petroleum resin (A) １ 22. The modified hydrogenated petroleum resin according to claim 21, wherein the integral ratio of aromatic hydrogen in H-NMR measurement [integral value of the peak in the 6.5 to 7.5 ppm region / (sum of the integral value of the peak in the 0 to 3.0 ppm region and the integral value of the peak in the 6.5 to 7.5 ppm region)] is 0 to 15%.

23. The modified hydrogenated petroleum resin according to claim 21 or 22, wherein the softening point of the modified hydrogenated petroleum resin (A) is 60 to 150 ° C.

24. The modified hydrogenated petroleum resin according to any one of claims 21 to 23, wherein the volatile content of the modified hydrogenated petroleum resin (A) when heated at 150 ° C. for 20 minutes is 1.0 mass% or less.

25. The modified hydrogenated petroleum resin (A) has an alkoxysilyl group, and the alkoxysilyl group is bonded to the main chain of the hydrogenated petroleum resin via a bonding portion. The modified hydrogenated petroleum resin according to any one of claims 21 to 24.

26. A method for producing a modified hydrogenated petroleum resin (B) that satisfies the following (B1) to (B3), the method comprising at least the following step (a): (B1) Viscosity V0.1 measured using a rheometer at an angular velocity ω = 0.1 rad / s and 190°C is 1,000 to 50,000 mPa s (B2) Viscosity V100 measured using a rheometer at an angular velocity ω of 100 rad / s and 190°C is 100 to 1,000 mPa·s (B3) The ratio of the viscosity V0.1 to the viscosity V100 [V0.1 / V100] is 10 or more. Step (a): A step of subjecting a modified hydrogenated petroleum resin (A) that satisfies the following (A1) to (A4) to a condensation reaction. (A1) Bromine number is 0.1 to 10.0 (A2) Contains 0.1 to 10 mass% silicon element in terms of silicon atoms (A3) Weight average molecular weight of 500 to 5,000 (A4) Molecular weight distribution (Mw / Mn) of 1.1 to 3.5

27. An adhesive composition (C) comprising the modified hydrogenated petroleum resin (B) according to any one of claims 21 to 25, or the modified hydrogenated petroleum resin (B) obtained by the production method according to claim 26, wherein the adhesive composition satisfies the following (C1) to (C3): (C1) Viscosity V0.1 measured using a rheometer at an angular velocity ω = 0.1 rad / s and 190°C is 20,000 to 800,000 mPa s (C2) Viscosity V100 measured using a rheometer at an angular velocity ω of 100 rad / s and 190°C is 1,000 to 5,000 mPa·s (C3) The ratio of the viscosity V0.1 to the viscosity V100 [V0.1 / V100] is 10 or more.

28. The adhesive composition according to claim 27, comprising 1 to 70 mass% of the modified hydrogenated petroleum resin (B) according to any one of claims 21 to 25, or the modified hydrogenated petroleum resin (B) obtained by the production method according to claim 26.

29. The adhesive composition according to claim 27 or 28, further comprising 10 to 90 mass % of a base polymer.

30. An asphalt composition comprising the modified hydrogenated petroleum resin (B) according to any one of claims 21 to 25 and straight asphalt, wherein the content of straight asphalt is 70.00 to 99.99% by mass.

31. An asphalt mixture comprising the asphalt composition according to claim 30 and an aggregate, wherein the aggregate content is 80 to 99% by mass.

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