US20050107521A1 - Asphalt composition containing hydrogenated conjugated diene copolymer - Google Patents

Asphalt composition containing hydrogenated conjugated diene copolymer Download PDF

Info

Publication number
US20050107521A1
US20050107521A1 US10/968,241 US96824104A US2005107521A1 US 20050107521 A1 US20050107521 A1 US 20050107521A1 US 96824104 A US96824104 A US 96824104A US 2005107521 A1 US2005107521 A1 US 2005107521A1
Authority
US
United States
Prior art keywords
hydrogenated
copolymer
conjugated diene
weight
monomer units
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/968,241
Other languages
English (en)
Inventor
Masahiro Sasagawa
Toshinori Shiraki
Shigeo Nakajima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Chemicals Corp
Original Assignee
Asahi Kasei Chemicals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Chemicals Corp filed Critical Asahi Kasei Chemicals Corp
Assigned to ASAHI KASEI CHEMICALS CORPORATION reassignment ASAHI KASEI CHEMICALS CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NAKAJIMA, SHIGEO, SASAGAWA, MASAHIRO, SHIRAKI, TOSHINORI
Publication of US20050107521A1 publication Critical patent/US20050107521A1/en
Priority to US11/727,839 priority Critical patent/US7696267B2/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified

Definitions

  • the present invention relates to an asphalt composition containing a hydrogenated conjugated diene copolymer with a specific structure. More particularly, the present invention relates to an asphalt composition comprising 0.5 to 50 parts by weight of a hydrogenated conjugated diene copolymer (a) and 100 parts by weight of asphalt (b), wherein the above described hydrogenated conjugated diene copolymer (a) comprises a polymer block (A) comprising vinyl aromatic monomer units and at least one hydrogenated copolymer block (B) obtained by hydrogenation of a non-hydrogenated random copolymer block comprising conjugated diene monomer units and vinyl aromatic monomer units, the above described hydrogenated conjugated diene copolymer (a) having the following characteristics (1) to (5):
  • the asphalt composition of the present invention has high softening point, modulus and elongation and is excellent in high-temperature storage stability.
  • the asphalt composition has extremely high softening point and modulus even when it contains a low content of the hydrogenated copolymer.
  • the asphalt composition has excellent high-temperature storage stability even when it contains a high content of the hydrogenated copolymer.
  • the asphalt composition of the present invention can be suitably utilized for road pavement, roofings/waterproof sheets and sealants, by making the most of such characteristics.
  • the asphalt composition is very suitable for roofing shingles since it is also excellent in weatherability in addition to the above characteristics.
  • Asphalt compositions have been widely used for applications such as road pavement, waterproof sheets, sound isolation sheets, and roofings.
  • Various attempts have been made to improve the properties by adding various polymers to asphalt.
  • Specific examples of these polymers include ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, rubber latexes, block copolymers consisting of conjugated dienes, and vinyl aromatic hydrocarbons and the like.
  • JP-B-57-24385 (corresponding to U.S. Pat. No. 4,145,322) discloses the use of sulfur
  • JP-A-03-501035 (corresponding to U.S. Pat. No. 5,508,112) discloses the combination of sulfur, a vulcanizing agent and a vulcanization accelerator containing sulfur.
  • improvement methods have not yet provided adequate results and a further improvement has been desired.
  • U.S. Patent No. 2003/0149140 discloses an asphalt composition using a copolymer consisting of a conjugated diene with a special structure and a vinyl aromatic hydrocarbon.
  • the above described composition is inadequate in the balance of the softening point, modulus, and high-temperature storage stability and is poor in weatherability and low-temperature characteristics. Therefore, a further improvement has been desired.
  • U.S. Pat. No. 6,120,913 discloses an asphalt composition for roofing shingles comprising a block copolymer consisting of a vinyl aromatic hydrocarbon and a conjugated diene and fillers.
  • a block copolymer consisting of a vinyl aromatic hydrocarbon and a conjugated diene it is inadequate in high-temperature storage stability and poor in weatherability, therefore, a further improvement has been desired for use in roofing shingles.
  • an asphalt composition containing a hydrogenated conjugated diene copolymer has high softening point, modulus and elongation and is excellent in high-temperature storage stability, wherein the hydrogenated conjugated diene copolymer comprises a polymer block (A) comprising vinyl aromatic monomer units and at least one hydrogenated copolymer block (B) obtained by hydrogenation of a non-hydrogenated random copolymer block comprising conjugated diene monomer units and vinyl aromatic monomer units, the hydrogenated conjugated diene copolymer having the following characteristics: (1) the content of the above described vinyl aromatic monomer units is from 30% to 60% by weight per weight of the above described hydrogenated copolymer; (2) the content of the above described polymer block (A) is from 5% to 50% by weight per
  • an object of the present invention to provide an asphalt composition having high softening point, modulus and elongation and excellent in high-temperature storage stability.
  • the amount of expensive modified polymers to be used can be reduced, since an asphalt composition having extremely high softening point and modulus can be obtained even when it contains a low content of the hydrogenated copolymer.
  • the asphalt composition of the present invention can be applied to roofing shingle applications where suitable polymers have not been found, since this asphalt composition is excellent not only in high-temperature storage stability, but also in heat resistance, weatherability and the like.
  • the present invention provides an asphalt composition comprising from 0.5 to 50 parts by weight of a hydrogenated copolymer (a) and 100 parts by weight of asphalt (b).
  • the above described hydrogenated conjugated diene copolymer (a) includes a polymer block (A) including vinyl aromatic monomer units and at least one hydrogenated copolymer block (B) obtained by hydrogenation of a non-hydrogenated random copolymer block including conjugated diene monomer units and vinyl aromatic monomer units, and it has the following characteristics (1) to (5):
  • An asphalt composition has from 0.5 to 50 parts by weight of a hydrogenated conjugated diene copolymer (a) and 100 parts by weight of asphalt (b), where the hydrogenated conjugated diene copolymer (a) includes a polymer block (A) including vinyl aromatic monomer units and at least one hydrogenated copolymer block (B) obtained by hydrogenation of a non-hydrogenated random copolymer block including conjugated diene monomer units and vinyl aromatic monomer units, and the hydrogenated conjugated diene copolymer (a) has the following characteristics (1) to (5):
  • the hydrogenated conjugated diene copolymer (a) does not substantially have a crystallization peak in the range of from ⁇ 20° C. to 80° C. in the chart of differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the content of the vinyl aromatic monomer units in the hydrogenated conjugated diene copolymer (a) is more preferably more than 40% and not more than 60% by weight per weight of the above described hydrogenated conjugated diene copolymer (a).
  • the hydrogenated copolymer block in the hydrogenated conjugated diene copolymer (a) is preferably a hydrogenated copolymer block obtained by hydrogenation of a non-hydrogenated random copolymer block with a tapered structure.
  • the hydrogenated conjugated diene copolymer (a) may have at least two polymer blocks (A) including vinyl aromatic monomer units.
  • the hydrogenated conjugated diene copolymer (a) preferably has a molecular weight distribution (Mw/Mn) of from 1.1 to 5.
  • the hydrogenated conjugated diene copolymer (a) may be a modified hydrogenated copolymer to which an atomic group having a functional group is bonded.
  • the asphalt composition may be used in a roofing shingle.
  • the hydrogenated conjugated diene copolymer (a) used in the present invention is obtained by hydrogenation of a non-hydrogenated copolymer comprising conjugated diene monomer units and vinyl aromatic monomer units (hereinafter often referred to as “a base non-hydrogenated copolymer”).
  • the hydrogenated conjugated diene copolymer (a) of the present invention comprises a polymer block (A) comprising vinyl aromatic monomer units and at least one hydrogenated copolymer block (B) obtained by hydrogenation of a non-hydrogenated random copolymer block comprising conjugated diene monomer units and vinyl aromatic monomer units.
  • the content of vinyl aromatic monomer units in the hydrogenated conjugated diene copolymer (a) used in the present invention is more than 30% and not more than 60% by weight relative to the hydrogenated copolymer.
  • An asphalt composition excellent in softening point and modulus can be obtained since the content of vinyl aromatic monomer units in the hydrogenated conjugated diene copolymer (a) is in the above-described range.
  • the content of the vinyl aromatic monomer units is preferably more than 35% and not more than 58%, more preferably more than 40% and not more than 55%, most preferably not less than 41% and not more than 53%, by weight.
  • the content of the vinyl aromatic monomer units relative to the hydrogenated conjugated diene copolymer is almost equal to that of the vinyl aromatic monomer units relative to the base non-hydrogenated copolymer, the content of the vinyl aromatic monomer units relative to the hydrogenated copolymer is determined relative to the base-non hydrogenated copolymer.
  • the content of the vinyl aromatic monomer units relative to the hydrogenated conjugated diene copolymer is determined by means of an ultraviolet spectrophotometer using the base non-hydrogenated copolymer as a specimen.
  • the content of the polymer block (A) is from 5% to 50% by weight relative to the hydrogenated copolymer.
  • An asphalt composition excellent in softening point can be obtained since the content of the polymer block (A) in the hydrogenated conjugated diene copolymer (a) is in the above-described range.
  • the content of the polymer block (A) is preferably from 8% to 40%, more preferably from 10% to 35%, even more preferably from 12% to 30%, and most preferably from 14% to 25%, by weight.
  • a higher content of the polymer block (A) is preferred in order to obtain an asphalt composition with a higher softening point by incorporating a high content of the hydrogenated copolymer into the composition.
  • the content of the polymer block (A) relative to the hydrogenated conjugated diene copolymer is almost equal to that of the polymer block (A) relative to the base non-hydrogenated copolymer
  • the content of the polymer block (A) is determined as that of the polymer block (A) relative to the base non-hydrogenated copolymer.
  • the weight of the vinyl aromatic polymer block component is determined by a method for oxidatively decomposing the base non-hydrogenated copolymer with tertiary-butyl hydroperoxide using osmium tetroxide as a catalyst (a method described in I.
  • the content of the polymer block (A) relative to the hydrogenated conjugated diene copolymer (a) can be directly measured by means of a nuclear magnetic resonance apparatus (NMR) using the hydrogenated conjugated diene copolymer as a specimen (a method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY, 54, 685 (1981); hereinafter referred to as the “NMR method”).
  • NMR nuclear magnetic resonance apparatus
  • the Ns value is converted to the Os value.
  • the hydrogenated conjugated diene copolymer (a) used in the present invention has a weight average molecular weight of from 30,000 to 500,000.
  • the weight average molecular weight of the hydrogenated conjugated diene copolymer in the above described range can provide an asphalt composition with good asphalt characteristics such as a softening point and excellent handling properties (low viscosity).
  • the hydrogenated conjugated diene copolymer (a) used in the present invention has a weight average molecular weight of preferably from 50,000 to 400,000, more preferably from 70,000 to 300,000, and most preferably from 80,000 to 250,000.
  • the hydrogenated conjugated diene copolymer (a) used in the present invention has a molecular weight distribution (Mw/Mn) (the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) of preferably 10 or less, more preferably from 1.01 to 8, and most preferably from 1.1 to 5.
  • Mw/Mn molecular weight distribution
  • the ratio is preferably from 1.1 to 5 and more preferably from 1.2 to 5.
  • the weight average molecular weight of the hydrogenated conjugated diene copolymer (a) is almost equal to that of the base non-hydrogenated copolymer, the weight average molecular weight of the hydrogenated conjugated diene copolymer (a) is determined as that of the base non-hydrogenated copolymer.
  • the weight average molecular weight of the base non-hydrogenated copolymer is determined by gel permeation chromatography (GPC) using a calibration curve obtained from a commercially available standard monodisperse polystyrene with a known molecular weight.
  • the number average molecular weight of the hydrogenated conjugated diene copolymer (a) is also determined in the same manner.
  • the molecular weight distribution is determined by calculating a ratio of the weight average molecular weight to the number average molecular weight.
  • the hydrogenated conjugated diene copolymer (a) used in the present invention is obtained by hydrogenation of a non-hydrogenated copolymer (that is, a base non-hydrogenated copolymer) comprising conjugated diene monomer units and vinyl aromatic monomer units.
  • the percentage of hydrogenation of the double bonds in the conjugated diene monomer units of the hydrogenated conjugated diene copolymer (a) is from 60% to 100%.
  • the percentage of hydrogenation of the hydrogenated copolymer is preferably from 70% to 100%, more preferably from 75% to 100%, and most preferably from 90% to 100%, in view of the softening point, modulus and high-temperature storage stability of the asphalt composition.
  • the percentage of hydrogenation of the double bonds in the vinyl aromatic monomer units of the hydrogenated conjugated diene copolymer (a) is not particularly limited, but is preferably 50% or less, more preferably 30% or less, and most preferably 20% or less.
  • the above described percentage of hydrogenation in the hydrogenated conjugated diene copolymer can be determined by means of a nuclear magnetic resonance apparatus.
  • At least one peak of the loss tangent (tan ⁇ ) is present in the range of from ⁇ 40° C. to less than ⁇ 10° C., preferably from ⁇ 38° C. to ⁇ 11° C., and more preferably from ⁇ 30° C. to ⁇ 14° C., in a dynamic viscoelastic spectrum obtained with respect to the hydrogenated conjugated diene copolymer (a) used in the present invention.
  • the loss tangent peak present in the range of from ⁇ 40° C. to less than ⁇ 10° C.
  • the hydrogenated copolymer block (B) (a hydrogenated polymer block obtained by hydrogenation of a non-hydrogenated random copolymer block comprising conjugated diene monomer units and vinyl aromatic monomer units).
  • B hydrogenated copolymer block
  • the presence of the at least one peak of the loss tangent in the range of from ⁇ 40° C. to less than ⁇ 10° C. is necessary for the balance of the softening point, modulus, high-temperature storage stability and the like of an asphalt composition, and it is also important in view of the low temperature characteristics.
  • the presence of the peak of the loss tangent attributable to the polymer block (A) is not particularly limited, but the peak of the loss tangent attributable to the polymer block (A) is generally present in a temperature range of from more than 80° C. to 150° C.
  • the peak of the loss tangent (tan ⁇ ) in the dynamic viscoelastic spectrum is measured by means of a viscoelasticity measurement and analysis apparatus using a frequency of 10 Hz.
  • the hydrogenated copolymer block (B) is obtained by hydrogenation of a non-hydrogenated random copolymer block comprising conjugated diene monomer units and vinyl aromatic monomer units.
  • the weight ratio of the conjugated diene monomer units/vinyl aromatic monomer units in the above described non-hydrogenated random copolymer is not particularly limited. However, taking consideration that at least one peak of the loss tangent needs to be present in the range of from ⁇ 40° C. to less than ⁇ 10° C. as described above, it is recommended that the weight ratio of the conjugated diene monomer units/vinyl aromatic monomer units is preferably from 50/50 to 90/10, more preferably from 53/47 to 80/20, most preferably 56/44 to 75/25.
  • the hydrogenated copolymer block (B) is obtained by hydrogenation of a non-hydrogenated random copolymer block comprising conjugated diene monomer units and vinyl aromatic monomer units.
  • the microstructure (the ratio of cis- and trans-vinyl) of the conjugated diene monomer units in the above described non-hydrogenated random copolymer can be freely changed by using a polar compound or the like to be described below.
  • the vinyl bond content in the conjugated diene monomer units in the non-hydrogenated random copolymer block comprising conjugated diene monomer units and vinyl aromatic monomer units is not particularly limited, but it is recommended to be from 10% to 50%.
  • the sum of the content of the 1,2-vinyl bond and 3,4-vinyl bond (however, the content of the 1,2-vinyl bond when 1,3-butadiene is used as the conjugated diene) is simply referred to as the vinyl bond content.
  • the above described vinyl bond content is determined by means of an infrared spectrophotometer using the base non-hydrogenated copolymer as a specimen.
  • the hydrogenated conjugated diene copolymer (a) with any structure may be used in the present invention.
  • One aspect of the structure of the hydrogenated conjugated diene copolymer (a) of the present invention includes a hydrogenated copolymer comprising at least one hydrogenated copolymer block (B) and at least one polymer block (A).
  • Examples of these hydrogenated copolymers include those with the structures represented by the following formulas: (A-B) n+1 , A-(B-A) n , B-(A-B) n+1 , ((A-B) n ⁇ X, ((B-A) n ⁇ B) n ⁇ X, ((A-B) n -A) n ⁇ X, ((B-A) n+1 ) n ⁇ X (wherein each A independently denotes a polymer block comprising vinyl aromatic monomer units; each B independently denotes a hydrogenated copolymer block obtained by hydrogenation of a non-hydrogenated random copolymer comprising conjugated diene monomer units and vinyl aromatic monomer units; each n independently denotes an integer of 1 or more, preferably an integer of from 1 to 5; each m independently denotes an integer of 2 or more, preferably an integer of from 2 to 11; each X independently denotes a residue of a coupling agent
  • the above described examples preferably have two or more polymer blocks (A), and the A-B-A structure is particularly preferred.
  • the hydrogenated copolymer having two or more polymer blocks (A) will provide an asphalt composition with high softening point and modulus.
  • the vinyl aromatic monomer units in the hydrogenated copolymer block B obtained by hydrogenation of a non-hydrogenated random copolymer may be distributed homogeneously or in a tapered form (tapered structure).
  • the tapered structure means a structure in which the content of the vinyl aromatic monomer units gradually increases along a polymer chain in B.
  • S1 denotes the amount of vinyl aromatics in a copolymer immediately after starting polymerization of the block B
  • S2 denotes the amount of vinyl aromatics in a copolymer in the course of polymerization, for example, when 1 ⁇ 2 of the monomer introduced is polymerized
  • S3 denotes the amount of vinyl aromatics in a copolymer after completion of polymerization.
  • the hydrogenated conjugated diene copolymer with the block B of a tapered structure is preferred
  • the hydrogenated copolymer block B may comprise a plurality of parts where the vinyl aromatic monomer units are homogeneously distributed and/or a plurality of parts where the vinyl aromatic monomer units are distributed in a tapered form.
  • the hydrogenated copolymer block B may comprise a plurality of segments with a different content of the vinyl aromatic monomer units.
  • the hydrogenated conjugated diene copolymer used in the present invention may be any mixture of those having a structure represented by the above described formulas.
  • the hydrogenated conjugated diene copolymer (a) used in the present invention preferably does not substantially have a crystallization peak attributable to the hydrogenated copolymer block (B) in the range of from ⁇ 20° C. to 80° C. in the chart of differential scanning calorimetry (DSC) obtained.
  • DSC differential scanning calorimetry
  • the hydrogenated conjugated diene copolymer which does not substantially have a crystallization peak attributable to the hydrogenated copolymer block (B) in the range of from ⁇ 20° C. to 80° C. in the chart of differential scanning calorimetry (DSC) provides an asphalt composition which is excellent particularly in high-temperature storage stability and elongation.
  • the hydrogenated copolymer which does not substantially have a crystallization peak attributable to the hydrogenated copolymer block (B) in the range of from ⁇ 20° C. to 80° C. as described above is obtained by hydrogenation of a non-hydrogenated copolymer which is obtained by undergoing a polymerization reaction under conditions to be described below using a modifier to be described below for controlling the vinyl bond content and a modifier to be described below for adjusting the random copolymerization between a conjugated diene and a vinyl aromatic compound.
  • the temperature and heat of crystallization peak can be measured by means of a differential scanning calorimeter.
  • the conjugated diene is a diolefin with a pair of conjugated double bonds.
  • the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene (i.e., isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene and 1,3-hexadiene.
  • 1,3-Butadiene and isoprene are most preferable among them. These may be used individually or in combination of two or more.
  • examples of the vinyl aromatic compound include styrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethyl styrene, N,N-diethyl-p-aminoethyl styrene. These may be used individually or in combination of two or more.
  • the hydrogenated conjugated diene copolymer (a) is obtained by hydrogenation of a non-hydrogenated copolymer comprising conjugated diene monomer units and vinyl aromatic monomer units.
  • the method for producing the non-hydrogenated copolymer is not particularly limited, but a known method may be used. For example, it may be produced by anion living polymerization using a polymerization initiator such as an organic alkali metal compound or the like in a hydrocarbon solvent.
  • hydrocarbon solvent examples include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane and n-octane; cycloaliphatic hydrocarbons such as cyclohexane, cycloheptane and methylcycloheptane; and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene.
  • aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane and n-octane
  • cycloaliphatic hydrocarbons such as cyclohexane, cycloheptane and methylcycloheptane
  • aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene.
  • polymerization initiator examples include aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds and organic amino alkali metal compounds, which have the activity of anion polymerization to conjugated dienes and vinyl aromatic compounds.
  • alkali metals include lithium, sodium and potassium.
  • suitable organic alkali metal compounds include aliphatic and aromatic hydrocarbon lithium compounds having from 1 to 20 carbon atoms and including at least one lithium in a molecule (monolithium compounds, dilithium compounds, trilithium compounds, tetralithium compounds and the like).
  • these compounds include n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, a reaction product of diisopropenylbenzene and sec-butyllithium, a reaction product of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene and the like.
  • organic alkali metal compounds disclosed in U.S. Pat. No. 5,708,092, GB Patent No. 2,241,239, U.S. Pat. No. 5,527,753 and the like can also be used.
  • a tertiary amine compound or an ether compound may be added as a modifier for adjusting the content of the vinyl bond (a 1,2-vinyl bond or a 3,4-vinyl bond) derived from conjugated diene monomer units to be incorporated into a polymer or for adjusting the random copolymerization between a conjugated diene and a vinyl aromatic compound.
  • tertiary amine compound examples include compounds represented by the formula: R 1 R 2 R 3 N (wherein R 1 , R 2 and R 3 each independently represent a hydrocarbon group having from 1 to 20 carbon atoms or a hydrocarbon group having a tertiary amino group).
  • these compounds include trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N′,N′-tetramethylethylenediamine, N,N,N′,N′-tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N,N,N′,N′′,N′′-pentamethylethylenetriamine, N,N′-dioctyl-p-phenylenediamine and the like.
  • Examples of the ether compound include straight chain ether compounds and cyclic ether compounds.
  • Examples of the straight chain ether compounds include dimethyl ether, diethyl ether, diphenyl ether; dialkyl ether compounds of ethylene glycol such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol dibutyl ether; and dialkyl ether compounds of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol dibutyl ether.
  • examples of the cyclic ether compounds include tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis(2-oxolanyl)propane and alkyl ethers of furfuryl alcohol.
  • the method for copolymerizing a conjugated diene monomer and a vinyl aromatic monomer using an organic alkali metal compound as a polymerization initiator in the present invention may be by batch polymerization or continuous polymerization or a combination of the two.
  • the polymerization temperature is generally from 0° C. to 180° C., preferably from 30° C. to 150° C.
  • the time required for the polymerization may vary depending on other conditions, but is generally within 48 hours, preferably from 0.1 to 10 hours.
  • the atmosphere of the polymerization system is preferably an inactive gas atmosphere such as nitrogen gas.
  • the polymerization pressure is not particularly limited as long as it is within a range sufficient enough to keep monomers and a solvent in a liquid phase in the above described polymerization temperature range.
  • impurities such as water, oxygen and carbon dioxide
  • a coupling reaction can also be performed using a coupling agent with two or more functionalities at the time of completion of the above described polymerization.
  • the coupling agent with two or more functionalities is not limited, but known ones may be used.
  • Examples of the coupling agents with two functionalities include dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane; and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate and phthalates.
  • multifunctional coupling agents with three or more functionalities include tri- or more hydric polyalcohols; polyepoxy compounds such as epoxidized soybean oils and diglycidyl bisphenol A; and polyhalogen compounds such as halogenated silicon compounds represented by the formula: R 4 ⁇ n SiX n (wherein R each independently denotes a hydrocarbon group having from 1 to 20 carbon atoms; X denotes each independently a halogen atom; and n denotes 3 or 4), for example, methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride, and bromides thereof; and halogenated tin compounds represented by the formula: R 4 ⁇ n SnX n (wherein R each independently denotes a hydrocarbon group having from 1 to 20 carbon atoms; X denotes each independently a halogen atom; and n denotes 3 or 4), for example, methyltin trichloride,
  • a modified hydrogenated conjugated diene copolymer to which at least one atomic group having a functional group is bonded may be used.
  • the atomic group having a functional group includes an atomic group containing at least one functional group selected from, for example, a hydroxy group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxylic acid group, a thiocarboxylic acid group, an aldehyde group, a thioaldehyde group, a carboxylate group, an amide group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphate group, an amino group, an imino group, a nitrile group, a pyridyl group, a quinoline group, an epoxy group,
  • the hydrogenated conjugated diene copolymer is obtained by hydrogenation of the modified conjugated diene copolymer obtained by reacting a compound that forms or contains such a functional group-containing atomic group with a conjugated diene copolymer when polymerization of the conjugated diene copolymer is completed.
  • the modified hydrogenated conjugated diene copolymer that can be used in the present invention is preferably a modified hydrogenated conjugated diene copolymer to which an atomic group having at least one functional group selected from a hydroxy group, an epoxy group, an amino group, a silanol group and an alkoxysilane group is bonded.
  • terminal-treating agents described in JP-B-04-39495 can be used as the compounds with the above described functional groups.
  • the terminal-treating agents include tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ⁇ -caprolactone, 4-methoxybenzophenone, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxybutyltrimethoxysilane, ⁇ -glycidoxypropyltriphenoxysilane, bis( ⁇ -glycidoxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N′-dimethylpropyleneurea, N-methylpyrrolidone and the like.
  • the modified hydrogenated conjugated diene copolymer that can be used in the present invention is obtained in the manner as described below. That is, a modifier that forms or contains a functional group is subjected to an addition reaction to a living terminal of a conjugated diene polymer obtained in the process as described above using an organolithium compound as a polymerization catalyst to obtain a modified conjugated diene copolymer to which at least one atomic group having at least one functional group selected from a hydroxy group, an epoxy group, an amino group, a silanol group and an alkoxysilane is bonded. Hydrogen can be added to the modified conjugated diene copolymer to obtain the modified hydrogenated conjugated diene copolymer.
  • An alternative method for obtaining the modified hydrogenated conjugated diene copolymer includes a method in which a conjugated diene copolymer is allowed to react with an organic alkali metal compound such as an organolithium compound (metalation reaction) and a polymer to which an organic alkali metal is added is allowed to react with a modifier containing a functional group in an addition reaction.
  • an organic alkali metal compound such as an organolithium compound (metalation reaction)
  • a polymer to which an organic alkali metal is added is allowed to react with a modifier containing a functional group in an addition reaction.
  • the modified hydrogenated conjugated diene copolymer can also be obtained by subjecting the conjugated diene copolymer to the metalation reaction followed by reaction with the modifier after obtaining a hydrogenated product of the copolymer.
  • the reaction temperature is preferably from 0° C. to 150° C. and more preferably from 20° C. to 120° C.
  • the time required for the modification reaction may vary depending on other conditions, but is preferably within 24 hours and more preferably from 0.1 hour to 10 hours.
  • a hydroxy group, an amino group or the like may be generally in the form of an organic metal salt at a stage when the modifier has been allowed to react.
  • the salt can be treated with water or a compound having an active hydrogen such as alcohol to form a hydroxy group, an amino group or the like.
  • the hydrogenation catalyst to be used for obtaining the hydrogenated conjugated diene copolymer for use in the present invention is not particularly limited.
  • Catalysts that can be used include previously known catalysts such as (1) supported non-uniform hydrogenation catalysts in which metals such as Ni, Pt, Pd, Ru and the like are supported on carbon, silica, alumina, diatomite and the like, (2) so called Ziegler-type hydrogenation catalysts in which transition metal salts such as organic acid salts or acetylacetone salts of Ni, Co, Fe, Cr and the like in combination with reducing agents such as organic aluminums, and (3) uniform hydrogenation catalysts such as so called organometallic complexes such as organometallic compounds of Ti, Ru, Rh, Zr and the like.
  • Specific hydrogenation catalysts that can be used include those described in JP-B-63-4841, JP-B-01-53851 and JP-B-O 2 -9041.
  • Preferred hydrogenation catalysts include titanocene compounds and/or mixtures of the same with reducing organometallic compounds.
  • Compounds described in JP-A-08-109219 can be used as the titanocene compounds.
  • the same include compounds having at least one ligand with a (substituted) cyclopentadienyl skeleton such as bis(cyclopentadienyl)titanium dichloride, mono(pendamethylcyclopentadienyl)titanium trichloride and the like, an indenyl skeleton or a fluorenyl skeleton.
  • the reducing organometallic compounds include organic alkali metal compounds such as organolithiums, organomagnesium compounds, organoaluminum compounds, organoboron compounds, organozinc compounds or the like.
  • the hydrogenation reaction for obtaining the hydrogenated conjugated diene copolymer for use in the present invention is performed in a temperature range of generally from 0° C. to 200° C. and more preferably from 30° C. to 150° C.
  • the hydrogen pressure used in the hydrogenation reaction is recommended to be from 0.1 MPa to 15 MPa, preferably from 0.2 MPa to 10 MPa, and more preferably from 0.3 MPa to 5 MPa.
  • the duration of the hydrogenation reaction is generally from 3 minutes to 10 hours and preferably from 10 minutes to 5 hours.
  • the hydrogenation reaction may be performed in a batch process or in a continuous process or in combination of the two processes.
  • the hydrogenated polymer can be separated from the solution of the hydrogenated conjugated diene copolymer obtained as described above, catalyst residues being removed if necessary.
  • Methods for separating a solvent can include, for example, a method in which a polymer is recovered by precipitation by adding a polar solvent such as acetone or alcohol, which is a poor solvent to the hydrogenated copolymer, to a reaction solution after the hydrogenation; a method in which a reaction solution is introduced into boiling water under stirring and a solvent is removed by steam stripping to recover a polymer; a method in which a solvent is removed by distillation by directly heating the copolymer solution, or the like.
  • stabilizers such as various phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers and amine stabilizers can be added to the hydrogenated conjugated diene copolymer of the present invention.
  • asphalt examples include byproducts from petroleum refining (petroleum asphalt), those obtained as natural products (natural asphalt), or mixtures thereof with petroleums.
  • the main component of asphalt is a substance called as bitumen.
  • straight asphalt, semi-blown asphalt, blown asphalt, tar, pitch, cutback asphalt to which oil is added, asphalt emulsion and the like can be used. These may be mixed for use.
  • Asphalt that is preferred in the present invention is straight asphalt with a penetration (measured according to JIS-K 2207) of from 30 to 300, preferably from 40 to 200, more preferably from 45 to 150.
  • the hydrogenated conjugated diene copolymer component (a) is mixed in an amount of 0.5 part to 50 parts, preferably from 1 part to 30 parts, and more preferably from 2 parts to 20 parts by weight per 100 parts by weight of asphalt.
  • any additives may be mixed if necessary.
  • Types of additives are not particularly limited as long as the additives are those typically used for compounding thermoplastic resins and rubber polymers.
  • Examples of the additives include those described in “Chemicals for Rubber/Plastics” (by Rubber Digest, Co., Ltd., Japan) and the like such as inorganic fillers such as calcium carbonate, magnesium carbonate, magnesium hydroxide, . . .
  • talc mica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide, slug wool and glass fibers; pigments such as carbon black and iron oxide; lubricants, releasing agents such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate and ethylenebisstearamide; softening agents/plasticizers such as paraffinic process oils, naphthenic process oils, aromatic process oils, paraffins, organic polysiloxanes, mineral oils; antioxidants such as hindered phenol antioxidants and phosphorus heat stabilizers; hindered amine light stabilizers; benzotriazole ultraviolet light absorbers, flame retardants; antistatic agents; reinforcing agents such as organic fibers, glass fibers, carbon fibers and metal whiskers; colorants; and other additives; or mixtures thereof.
  • the amounts of additives are not particularly limited and can be selected appropriately, but are typically 50 parts by weight or less.
  • the method for producing the asphalt composition of the present invention is not particularly limited.
  • conditions for stirring the mixture of the hydrogenated conjugated diene copolymer and asphalt are not particularly limited, but it is preferably performed at a temperature of from 160° C. to 200° C. (generally around 180° C.), and the duration of stirring is preferably from 30 minutes to 6 hours and more preferably from 1 hour to 3 hours.
  • the rate of stirring may be appropriately selected depending on the apparatus to be used, but it is generally from 100 rpm to 8,000 rpm.
  • the content of styrene was determined by means of an ultraviolet spectrophotometer (UV-2450 made by Shimadzu Corporation) using copolymers before hydrogenation.
  • the content of styrene polymer blocks was determined by an osmium tetroxide method described in I. M. Kolthoff, et al., J. Polym. Sci., 1, 429 (1946), using copolymers before hydrogenation.
  • the decomposition of copolymers was performed using an osmic acid solution of 0.1 g/125 ml in tert-butanol.
  • the vinyl bond content was determined by means of an infrared spectrophotometer (name of the apparatus: FT/IR-230; made by JASCO Corporation) by a Hampton technique, using copolymers before hydrogenation.
  • the molecular weight and molecular weight distribution were determined by means of GPC (the apparatus is made by Waters Corporation), using copolymers before hydrogenation. Tetrahydrofuran was used as a solvent, and the measurement was performed at a temperature of 35° C.
  • the molecular weight is the weight average molecular weight (molecular weight in terms of polystyrene), wherein the molecular weight from a peak of a chromatogram was determined by using a calibration curve obtained from the measurement of commercially available standard polystyrenes (prepared by using peak molecular weights of standard polystyrenes).
  • the molecular weight distribution is the ratio of the obtained weight average molecular weight and number average molecular weight.
  • the percentage of hydrogenation was determined by means of a nuclear magnetic resonance apparatus (DPX-400, made by BRUKER Co., Ltd.).
  • the peak temperature of loss tangent was determined by means of a viscoelasticity measurement and analysis apparatus (model DVE-V4 made by Rheology Co., Ltd. is used) by measuring a viscoelastic spectrum, using a frequency of 10 Hz.
  • the crystallization peak and heat of crystallization peak were determined by DSC (DSC 3200S, made by MAC Science Co., Ltd.).
  • the temperature of copolymers was raised from room temperature to 150° C. at a rate of 30° C./minute, and then the temperature was lowered at a rate of 10° C./minute to ⁇ 100° C. measuring a crystallization peak to determine the presence or absence of the crystallization peak.
  • the temperature where the peak occurs was defined as the crystallization peak temperature, and the heat of crystallization peak was determined.
  • the hydrogenation catalyst used for hydrogenation reaction was prepared according to the method as described below.
  • a reaction vessel purged with nitrogen was charged 2 liters of dried, purified cyclohexane, followed by dissolving 40 millimoles of bis( ⁇ 5-cyclopentadienyl)titanium di-(p-tolyl) and 150 grams of 1,2-polybutadiene (a content of 1,2-vinyl bond of about 85%) with a molecular weight of about 11000.
  • To the mixture was added a cyclohexane solution containing 60 millimoles of n-butyllithium for the reaction at room temperature for 5 minutes.
  • 40 millimoles of n-butanol was added to the reaction mixture, which was stirred and then stored at room temperature.
  • Copolymerization was performed according to the following procedure by means of a vessel type reactor with an internal space of 10 L, a stirrer and a jacket.
  • the reactor was charged with 10 parts by weight of cyclohexane. After the cyclohexane was adjusted to a temperature of 70° C., 0.076% by weight of n-butyllithium per weight of all monomers (the total weight of butadiene monomers and styrene monomers charged into the reactor) and 0.4 mole of N,N,N′,N′-tetramethylethylenediamine (hereinafter referred to as TMEDA) per 1 mole of n-butyllithium were added, followed by addition of a cyclohexane solution containing 8 parts by weight of styrene as a monomer (monomer concentration of 22% by weight) over about 3 minutes. Then, the resulting mixture was allowed to react for 30 minutes while adjusting the temperature inside the reactor to about 70° C.
  • TMEDA N,N,N′,N′-tetramethylethylenediamine
  • a cyclohexane solution containing 48 parts by weight of butadiene and 36 parts by weight of styrene (monomer concentration of 22% by weight) was continuously supplied to the reactor at a constant speed over 60 minutes, and the mixture was allowed to react for 30 minutes while adjusting the temperature inside the reactor to about 70° C.
  • Analysis of the polymer solution sampled immediately after the completion of the supply of monomers revealed that the polymerization conversion of butadiene was 90%; the polymerization conversion of styrene was 70%; and the content of styrene in the polymer was 43.6% by weight.
  • the styrene content of the block B part at this time point was 36.8% by weight.
  • a cyclohexane solution containing 8 parts by weight of styrene as a monomer (monomer concentration of 22% by weight) was added over about 3 minutes, and the resulting mixture was allowed to react for 30 minutes while adjusting the temperature inside the reactor to about 70° C., obtaining a copolymer.
  • the resulting copolymer had a styrene content of 52% by weight, a styrene polymer block content of 16% by weight, a content of vinyl bond in the butadiene part of 21% by weight, a weight average molecular weight of 165,000, and a molecular weight distribution of 1.2.
  • a copolymer was obtained in the same manner as in the case of polymer 1 by changing the amount of monomers and the like to be supplied to the reactor.
  • the polymerization was performed in the same manner except that the amount of n-butyllithium to be supplied was changed to 0.07% by weight; the amount of styrene to be supplied at the first stage was changed to 7.5 parts by weight; the amounts of butadiene and styrene to be supplied at the second stage were changed to 59 parts and 26 parts by weight respectively; and the amount of styrene to be supplied at the third stage was changed to 7.5 parts by weight.
  • the resulting copolymer had a styrene content of 41% by weight, a styrene polymer block content of 15% by weight, a content of vinyl bond in the butadiene part of 25% by weight, a weight average molecular weight of 177,000, and a molecular weight distribution of 1.2.
  • Example 2 a hydrogenated copolymer (hereinafter referred to as polymer 2).
  • the percentage of hydrogenation of polymer 2 was 98%.
  • the result of the dynamic viscoelasticity measurement showed that the peak temperature of tan ⁇ was present at ⁇ 25° C.
  • the result of the DSC measurement showed that the crystallization peak was absent.
  • a copolymer was obtained in the same manner as in the case of polymer 1 by changing the amount of monomers and the like to be supplied to the reactor.
  • the polymerization was performed in the same manner except that the amount of n-butyllithium to be supplied was changed to 0.085% by weight; the amount of styrene to be supplied at the first stage was changed to 9.5 parts by weight; the amounts of butadiene and styrene to be supplied at the second stage were changed to 59 parts and 22 parts by weight respectively; and the amount of styrene to be supplied at the third stage was changed to 9.5 parts by weight.
  • the resulting copolymer had a styrene content of 41% by weight, a styrene polymer block content of 19% by weight, a content of vinyl bond in the butadiene part of 26% by weight, a weight average molecular weight of 143,000, and a molecular weight distribution of 1.2.
  • Example 3 a hydrogenated copolymer (hereinafter referred to as polymer 3).
  • the percentage of hydrogenation of polymer 3 was 100%.
  • the result of the dynamic viscoelasticity measurement showed that the peak temperature of tan ⁇ was present at ⁇ 29° C.
  • the result of the DSC measurement showed that the crystallization peak was absent.
  • a copolymer was obtained in the same manner as in the case of polymer 1 by changing the amount of monomers and the like to be supplied to the reactor.
  • the polymerization was performed in the same manner except that the amount of n-butyllithium to be supplied was changed to 0.095% by weight; the amount of styrene to be supplied at the first stage was changed to 12 parts by weight; the amounts of butadiene and styrene to be supplied at the second stage were changed to 44 parts and 36 parts by weight respectively; and the amount of styrene to be supplied at the third stage was changed to 8 parts by weight.
  • the resulting copolymer had a styrene content of 56% by weight, a styrene polymer block content of 24% by weight, a content of vinyl bond in the butadiene part of 23% by weight, a weight average molecular weight of 135,000, and a molecular weight distribution of 1.1.
  • Example 4 a hydrogenated copolymer (hereinafter referred to as polymer 4).
  • the percentage of hydrogenation of polymer 4 was 93%.
  • the result of the dynamic viscoelasticity measurement showed that the peak temperature of tan ⁇ was present at ⁇ 11° C.
  • the result of the DSC measurement showed that the crystallization peak was absent.
  • a copolymer was obtained in the same manner as in the case of polymer 1 by changing the amount of monomers and the like to be supplied to the reactor.
  • the polymerization was performed in the same manner except that the amount of n-butyllithium to be supplied was changed to 0.14% by weight; the amount of styrene to be supplied at the first stage was changed to 18 parts by weight; the amounts of butadiene and styrene to be supplied at the second stage were changed to 56 parts and 9 parts by weight respectively; and the amount of styrene to be supplied at the third stage was changed to 17 parts by weight.
  • the resulting copolymer had a styrene content of 44% by weight, a styrene polymer block content of 35% by weight, a content of vinyl bond in the butadiene part of 33% by weight, a weight average molecular weight of 83,000, and a molecular weight distribution of 1.1.
  • Example 5 a hydrogenated copolymer (hereinafter referred to as polymer 5).
  • the percentage of hydrogenation of polymer 5 was 98%.
  • the result of the dynamic viscoelasticity measurement showed that the peak temperature of tan ⁇ was present at ⁇ 38° C.
  • the result of the DSC measurement showed that the crystallization peak was absent.
  • a copolymer was obtained in the same manner as in the case of polymer 1 by changing the amount of monomers and the like to be supplied to the reactor.
  • the polymerization was performed in the same manner except that the amount of n-butyllithium to be supplied was changed to 0.073% by weight; the amount of styrene to be supplied at the first stage was changed to 9.5 parts by weight; the amounts of butadiene and styrene to be supplied at the second stage were changed to 59 parts and 22 parts by weight respectively; and the amount of styrene to be supplied at the third stage was changed to 9.5 parts by weight.
  • the resulting copolymer had a styrene content of 41% by weight, a styrene polymer block content of 19% by weight, a content of vinyl bond in the butadiene part of 29% by weight, a weight average molecular weight of 168,000, and a molecular weight distribution of 1.2.
  • Example 6 a hydrogenated copolymer (hereinafter referred to as polymer 6).
  • the percentage of hydrogenation of polymer 6 was 75%.
  • the result of the dynamic viscoelasticity measurement showed that the peak temperature of tan ⁇ was present at ⁇ 31° C.
  • the result of the DSC measurement showed that the crystallization peak was absent.
  • a copolymer was obtained in the same manner as in the case of polymer 1 by changing the amount of monomers and the like to be supplied to the reactor.
  • the polymerization was performed in the same manner except that the amount of n-butyllithium to be supplied was changed to 0.075% by weight; the amount of styrene to be supplied at the first stage was changed to 3 parts by weight; the amounts of butadiene and styrene to be supplied at the second stage were changed to 59 parts and 37 parts by weight respectively; and the amount of styrene to be supplied at the third stage was changed to 1 part by weight.
  • the resulting copolymer had a styrene content of 41% by weight, a styrene polymer block content of 4% by weight, a content of vinyl bond in the butadiene part of 27% by weight, a weight average molecular weight of 173,000, and a molecular weight distribution of 1.2.
  • Example 7 a hydrogenated copolymer (hereinafter referred to as polymer 7).
  • the percentage of hydrogenation of polymer 7 was 99%.
  • the result of the dynamic viscoelasticity measurement showed that the peak temperature of tan ⁇ was present at ⁇ 18° C.
  • the result of the DSC measurement showed that the crystallization peak was absent.
  • a copolymer was obtained in the same manner as in the case of polymer 1 by changing the amount of monomers and the like to be supplied to the reactor.
  • the polymerization was performed in the same manner except that the amount of n-butyllithium to be supplied was changed to 0.090% by weight; the amount of styrene to be supplied at the first stage was changed to 5 parts by weight; the amounts of butadiene and styrene to be supplied at the second stage were changed to 71 parts and 19 parts by weight respectively; and the amount of styrene to be supplied at the third stage was changed to 5 parts by weight.
  • the resulting copolymer had a styrene content of 29% by weight, a styrene polymer block content of 10% by weight, a content of vinyl bond in the butadiene part of 30% by weight, a weight average molecular weight of 125,000, and a molecular weight distribution of 1.1.
  • Example 8 a hydrogenated copolymer (hereinafter referred to as polymer 8).
  • the percentage of hydrogenation of polymer 8 was 93%.
  • the result of the dynamic viscoelasticity measurement showed that the peak temperature of tan ⁇ was present at ⁇ 33° C.
  • the result of the DSC measurement showed that the crystallization peak was absent.
  • a non-hydrogenated copolymer was continuously polymerized according to the following procedure by means of two vessel type reactors each with an internal space of 10 liters, a stirrer and a jacket.
  • the continuous polymerization was performed at 90° C. by supplying a cyclohexane solution with a concentration of butadiene of 24% by weight at 4.51 liters/hr, a cyclohexane solution with a concentration of styrene of 24% by weight at 6.47 liters/hr, and a cyclohexane solution of n-butyllithium at 2.0 liters/hr, wherein the concentration of n-butyllithium was adjusted so that the amount of n-butyllithium was 0.077 parts by weight per 100 parts by weight of monomers (the sum of the amounts of butadiene and styrene), each to the bottom of the first reactor, and further supplying a cyclohexane solution of TMEDA at a supply rate such that the amount of THEDA is 0.44 mole per one mole of n-butyllithium.
  • the reaction temperature was adjusted by a jacket temperature.
  • the temperature around the bottom of the reactor was about 88° C.
  • the temperature around the top of the reactor was about 90° C.
  • the average residence time in the polymerization reactor was 45 minutes, and the conversion of butadiene and styrene was almost 100% and 99%, respectively.
  • the polymer solution from the first reactor was supplied to the bottom of the second reactor, and at the same time a cyclohexane solution of a concentration of styrene of 24% by weight was supplied to the bottom of the second reactor at a supply rate of 2.28 liters/hr to continuously polymerize the mixture at 90° C. to obtain a copolymer.
  • the conversion of styrene at the exit of the second reactor was 98%.
  • Polymer 10 was prepared in the same manner as according to the procedures for preparing polymer 3 except that the hydrogenation reaction was not performed.
  • Asphalt compositions were prepared according to the following procedures in Examples 1 to 10 and Comparative Examples 1 to 10
  • a metal can of 750 milliliters was charged with 400 g of straight asphalt 60-80 (available from Nippon Oil Corporation, Japan), and the can was fully immersed in an oil bath at 180° C. Next, a specified amount of a hydrogenated diene copolymer was gradually charged while stirring into the molten asphalt. After the completion of the charge, the mixture was stirred at a rotation speed of 5,000 rpm for 90 minutes to prepare an asphalt composition.
  • the softening point of a composition was determined according to JIS-K 2207.
  • a specimen was filled in a defined ring, which was supported horizontally in a glycerin liquid.
  • a ball of 3.5 g was placed on the specimen at the center thereof, and the temperature of the liquid was raised at a rate of 5° C./minute. The temperature at which the specimen was brought into contact with a bottom plate of a ring base by the weight of the ball was measured.
  • the melt viscosity was measured with a Brookfield viscometer at 160° C.
  • the penetration of a composition was determined according to JIS-K 2207. The length of penetration of a defined needle in 5 seconds into a specimen, which was held at 25° C. in a constant-temperature water bath, was measured.
  • the elongation of a composition was determined according to JIS-K 2207.
  • a specimen was poured into a form and formed into a defined shape, and then held at 15° C. in a constant-temperature water bath. The distance of elongation of the specimen until it broke, when it was elongated at a rate of 5 cm/minute, was measured.
  • the dynamic viscoelasticity was measured with a dynamic shear rheometer.
  • the expression: Modulus G*/tan ⁇ was determined from the complex modulus (G*) and loss tangent (tan ⁇ ) obtained from the measurement as an index for evaluating the performance of a binder to the rutting.
  • the measurement apparatus and measurement conditions are as follows:
  • the asphalt composition was poured into an aluminum can with an inner diameter of 50 mm and a height of 130 mm to the upper limit of the aluminum can and heated for 24 hours in an oven at 180° C. Subsequently, the aluminum can was removed for natural cooling. Next, specimens of the asphalt composition cooled to room temperature were collected each from the lower layer part ranging from the bottom to 4 cm above the bottom and the upper layer part ranging from the top to 4 cm below the top. The softening point each for the upper layer part and the lower layer part was determined, and the difference of the softening point values for the two specimens was adopted as a measure of the high temperature storage stability. The smaller the difference of the softening point values is, the better the high temperature storage stability is.
  • Polymers 1, 2, 3 and 6 were used as the hydrogenated copolymer, and materials and the formulation (copolymer content is 3.5%) described in Table 2-1 were used to obtain asphalt compositions. Characteristics thereof are shown in Table 2-1.
  • Polymers 7 to 11 were used as the hydrogenated copolymer, and materials and the formulation (copolymer content is 3.5%) described in Table 2-2 were used to obtain asphalt compositions. Characteristics thereof are shown in Table 2-2.
  • Polymers 1 to 6 were used as the hydrogenated copolymer, and materials and the formulation (copolymer content is 8.0%) described in Table 2-3 were used to obtain asphalt compositions. Characteristics thereof are shown in Table 2-3.
  • Polymers 7 to 11 were used as the hydrogenated copolymer, and materials and the formulation (copolymer content is 8.0%) described in Table 2-4 were used to obtain asphalt compositions. Characteristics thereof are shown in Table 2-4.
  • the asphalt composition of the present invention has high softening point, modulus and elongation and is excellent in high-temperature storage stability.
  • the asphalt composition has an extremely high softening point and modulus even when it contains a low content of the hydrogenated copolymer. Therefore, the use of expensive modified polymers can be reduced, providing an extremely high industrial utility value.
  • the asphalt composition has excellent high-temperature storage stability even when it contains a high content of the hydrogenated copolymer.
  • the asphalt composition of the present invention can be suitably utilized for road pavement, roofings/waterproof sheets and sealants, by making the most of such characteristics.
  • the asphalt composition is very suitable for roofing shingles since it is also excellent in weatherability in addition to the above characteristics.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Vibration Prevention Devices (AREA)
US10/968,241 2003-10-21 2004-10-20 Asphalt composition containing hydrogenated conjugated diene copolymer Abandoned US20050107521A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US11/727,839 US7696267B2 (en) 2003-10-21 2007-03-28 Asphalt composition containing hydrogenated conjugated diene copolymer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003-360956 2003-10-21
JP2003360956A JP4776155B2 (ja) 2003-10-21 2003-10-21 水添共重合体

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/727,839 Continuation US7696267B2 (en) 2003-10-21 2007-03-28 Asphalt composition containing hydrogenated conjugated diene copolymer

Publications (1)

Publication Number Publication Date
US20050107521A1 true US20050107521A1 (en) 2005-05-19

Family

ID=34567022

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/968,241 Abandoned US20050107521A1 (en) 2003-10-21 2004-10-20 Asphalt composition containing hydrogenated conjugated diene copolymer
US11/727,839 Active US7696267B2 (en) 2003-10-21 2007-03-28 Asphalt composition containing hydrogenated conjugated diene copolymer

Family Applications After (1)

Application Number Title Priority Date Filing Date
US11/727,839 Active US7696267B2 (en) 2003-10-21 2007-03-28 Asphalt composition containing hydrogenated conjugated diene copolymer

Country Status (4)

Country Link
US (2) US20050107521A1 (ja)
JP (1) JP4776155B2 (ja)
CN (1) CN1318511C (ja)
HK (1) HK1078891A1 (ja)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070105986A1 (en) * 2005-11-09 2007-05-10 Kraton Polymers U. S. Llc Blown asphalt compositions
US20090000514A1 (en) * 2007-06-28 2009-01-01 Trumbore David C Method of producing roofing shingle coating asphalt from non-coating grade asphalt
US20090000515A1 (en) * 2007-06-28 2009-01-01 Trumbore David C Process of producing roofing shingle coating asphalt
WO2009110810A1 (de) * 2008-03-03 2009-09-11 Gorniak Wlodzimierz Modifizierungszusatz für asphaltmassen sowie art und weise der asphaltherstellung für die produktion von mineral-asphalt-mischungen mit hohem schermodul
US20090312449A1 (en) * 2006-02-13 2009-12-17 Shigeru Sasaki Hydrogenated block copolymer, resin composition comprising the hydrogenated block copolymer, and crosslinked product and crosslinked foamed product thereof
US7951240B2 (en) 2007-06-28 2011-05-31 Owens Corning Intellectual Capital, Llc Process of producing roofing shingle coating asphalt allowing more material options
US20110197785A1 (en) * 2007-06-28 2011-08-18 Owens Corning Intellectual Capital, Llc Roofing coating asphalt composition
US20130136855A1 (en) * 2011-11-30 2013-05-30 Henry Company Llc Asphalt compositions having improved properties and related coatings and methods
WO2014102152A1 (en) * 2012-12-28 2014-07-03 Shell Internationale Research Maatschappij B.V. Binder composition which can be coloured
EP3147328A1 (en) * 2014-05-19 2017-03-29 Asahi Kasei Kabushiki Kaisha Hydrogenated block copolymer composition and adhesive composition
US9873788B2 (en) 2014-04-08 2018-01-23 Asahi Kasei Kabushiki Kaisha Composition and surface protection film
US10138319B2 (en) 2014-01-17 2018-11-27 Asahi Kasei Kabushiki Kaisha Polymer and asphalt composition
US10189995B2 (en) 2014-05-08 2019-01-29 Asahi Kasei Kabushiki Kaisha Asphalt composition
US10233318B2 (en) 2014-07-01 2019-03-19 Asahi Kasei Kabushiki Kaisha Polyolefin-based resin composition, film, medical bag, and tube
US20190153214A1 (en) * 2014-01-17 2019-05-23 Asahi Kasei Kabushiki Kaisha Polymer and Asphalt Composition
US10414849B2 (en) 2015-07-16 2019-09-17 Asahi Kasei Kabushiki Kaisha Partially hydrogenated block copolymer, viscous adhesive composition, viscous adhesive tape, label, modified asphalt composition, modified asphalt mixture, and paving binder composition
EP3572444A1 (en) * 2016-04-25 2019-11-27 Asahi Kasei Kabushiki Kaisha Hydrogenated block copolymer, polypropylene resin composition, and molded body
US10808066B2 (en) 2016-01-19 2020-10-20 Asahi Kasei Kabushiki Kaisha Hydrogenated copolymer, composition, and molded article
US11912858B2 (en) 2020-07-03 2024-02-27 Asahi Kasei Kabushiki Kaisha Molded bale of rubber-like block copolymer, rubber composition, crosslinking rubber composition, and tread for tire

Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060089430A1 (en) * 2004-10-25 2006-04-27 Kaneka Corporation Curable composition
WO2006088187A1 (ja) * 2005-02-21 2006-08-24 Asahi Kasei Chemicals Corporation 水添ブロック共重合体及びその組成物
JP4919713B2 (ja) * 2005-06-30 2012-04-18 旭化成ケミカルズ株式会社 ブロック共重合体水添物組成物、そのシート・フィルム及び熱収縮性フィルム
JP2007154013A (ja) * 2005-12-05 2007-06-21 Jsr Corp 不織布用共重合体、不織布用共重合体組成物、及び不織布
EP2230265A1 (en) * 2006-08-08 2010-09-22 Asahi Kasei Chemicals Corporation Hydrogenated block copolymers and crosslinking compositions containing the same
JP2009067986A (ja) * 2007-08-22 2009-04-02 Nok Corp ゴム組成物
JP2009249505A (ja) * 2008-04-07 2009-10-29 Cci Corp 制振塗料組成物
US11313127B2 (en) 2009-02-25 2022-04-26 Owens Corning Intellectual Capital, Llc Hip and ridge roofing material
US9151055B2 (en) 2009-02-25 2015-10-06 Owens Corning Intellectual Capital, Llc Hip and ridge roofing material
US20100222464A1 (en) * 2009-02-27 2010-09-02 Semmaterials, L.P. Emulsion of a polymer modified asphalt
US20100239807A1 (en) 2009-03-20 2010-09-23 Grubka Lawrence J Flexible laminated hip and ridge shingle
JP5562573B2 (ja) * 2009-03-31 2014-07-30 旭化成ケミカルズ株式会社 粘着剤用組成物及びこれを具備する表面保護フィルム
JP5620067B2 (ja) * 2009-03-31 2014-11-05 旭化成ケミカルズ株式会社 粘接着剤組成物、粘接着剤組成物の製造方法及びこれを用いた表面保護フィルム
US9097020B2 (en) 2010-03-04 2015-08-04 Owens Corning Intellectual Capital, Llc Hip and ridge roofing shingle
JP5797458B2 (ja) * 2011-05-26 2015-10-21 旭化成ケミカルズ株式会社 アスファルト組成物
JP5797460B2 (ja) * 2011-06-01 2015-10-21 旭化成ケミカルズ株式会社 アスファルト組成物
US9290943B2 (en) 2012-01-05 2016-03-22 Owens Corning Intellectual Capital, Llc Hip and ridge roofing shingle
CN103509355B (zh) * 2012-06-27 2015-12-16 中国石油化工股份有限公司 丁苯胶乳复合改性沥青及其制备方法
US9057163B1 (en) 2013-03-15 2015-06-16 William B. Coe Pavement repair system
EP2971362B1 (en) * 2013-03-15 2018-05-02 William B. Coe Pavement repair system and method
US8992118B2 (en) 2013-03-15 2015-03-31 William B. Coe Pavement repair system utilizing solid phase autoregenerative cohesion
US9758970B2 (en) 2014-02-25 2017-09-12 Owens Corning Intellectual Capital, Llc Laminated hip and ridge shingle
USD755997S1 (en) 2014-02-27 2016-05-10 Owens Corning Intellectual Capital, Llc Shingle
JP6607672B2 (ja) * 2014-04-17 2019-11-20 旭化成株式会社 重合体及びアスファルト組成物
JP2016035037A (ja) * 2014-08-01 2016-03-17 旭化成ケミカルズ株式会社 アスファルト組成物
JP6465599B2 (ja) * 2014-09-18 2019-02-06 旭化成株式会社 ブロック共重合体及び粘接着剤組成物
US11987692B2 (en) * 2015-03-25 2024-05-21 Riken Technos Corporation Thermoplastic resin compositions, adhesive coating materials, and laminates using the same
JP6521696B2 (ja) * 2015-03-30 2019-05-29 旭化成株式会社 アスファルト組成物
JP6504949B2 (ja) * 2015-07-16 2019-04-24 旭化成株式会社 改質アスファルト組成物及び改質アスファルト混合物
CA3047604C (en) 2017-02-14 2024-03-19 William B. Coe Apparatus and method for preparing asphalt and aggregate mixture
JP7105240B2 (ja) * 2017-08-29 2022-07-22 Ｅｎｅｏｓクレイトンエラストマー株式会社 耐摩耗性に優れた感光性印刷版材用ブロック共重合体及びその製造方法
US10961713B2 (en) 2017-12-15 2021-03-30 Owens Coming Intellectual Capital, LLC Polymer modified asphalt roofing material
JP6938026B2 (ja) * 2018-02-22 2021-09-22 北川工業株式会社 難燃高減衰材料
JP2019151808A (ja) * 2018-03-06 2019-09-12 旭化成株式会社 共役ジエン系重合体組成物、及びタイヤ
JP7313167B2 (ja) * 2019-03-19 2023-07-24 旭化成株式会社 水添共重合体、水添共重合体組成物、発泡体及び成形体
JP7304202B2 (ja) * 2019-05-14 2023-07-06 旭化成株式会社 水添ブロック共重合体
KR102382624B1 (ko) * 2021-09-14 2022-04-04 더본드 주식회사 교면 복합방수용 개질 아스팔트 도막방수재 조성물 및 이를 이용한 교면 복합방수 시공방법
WO2023074089A1 (ja) * 2021-10-25 2023-05-04 旭化成株式会社 ブロック共重合体、アスファルト組成物、及び改質アスファルト混合物

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4145322A (en) * 1976-12-28 1979-03-20 Elf Union Process for preparing bitumen-polymer compositions
US5508112A (en) * 1988-09-09 1996-04-16 Elf France Process for the preparation of bitumen-polymer composition
US6120913A (en) * 1998-04-23 2000-09-19 Shell Oil Company Bituminous composition for shingles
US6329459B1 (en) * 1996-09-23 2001-12-11 Bridgestone Corporation Extended syndiotactic polystyrene-elastomeric block copolymers
US6653408B1 (en) * 2002-11-21 2003-11-25 Kraton Polymers U.S. Llc Compositions comprising a functionalized block copolymer crosslinked with aluminum acetylacetonate
US6833411B2 (en) * 2001-08-13 2004-12-21 Japan Elastomer Co., Ltd. Block copolymer compositions

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5724385A (en) 1980-07-17 1982-02-08 Nissan Chem Ind Ltd Theobromine derivative and its preparation
JP3580020B2 (ja) * 1996-04-03 2004-10-20 旭化成ケミカルズ株式会社 ブロック共重合体及びその水添物の製造方法
EP0853102A1 (en) * 1997-01-08 1998-07-15 Fina Research S.A. Bituminous compositions containing coupled copolymers
JP3501035B2 (ja) 1999-09-16 2004-02-23 ミノルタ株式会社 デジタルカメラ
JP2001325476A (ja) * 2000-05-15 2001-11-22 Keiichi Nakao 名簿情報の使用権許諾契約を仲介するための情報処理装置
JP4208176B2 (ja) * 2001-08-10 2009-01-14 旭化成ケミカルズ株式会社 官能基含有ブロック共重合体及びその組成物
US6852806B2 (en) * 2001-10-23 2005-02-08 Asahi Kasei Kabushiki Kaisha Hydrogenated copolymer
US7169848B2 (en) * 2002-02-07 2007-01-30 Kraton Polymers U.S. Llc Block copolymers and method for making same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4145322A (en) * 1976-12-28 1979-03-20 Elf Union Process for preparing bitumen-polymer compositions
US5508112A (en) * 1988-09-09 1996-04-16 Elf France Process for the preparation of bitumen-polymer composition
US6329459B1 (en) * 1996-09-23 2001-12-11 Bridgestone Corporation Extended syndiotactic polystyrene-elastomeric block copolymers
US6120913A (en) * 1998-04-23 2000-09-19 Shell Oil Company Bituminous composition for shingles
US6833411B2 (en) * 2001-08-13 2004-12-21 Japan Elastomer Co., Ltd. Block copolymer compositions
US6653408B1 (en) * 2002-11-21 2003-11-25 Kraton Polymers U.S. Llc Compositions comprising a functionalized block copolymer crosslinked with aluminum acetylacetonate

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7576148B2 (en) 2005-11-09 2009-08-18 Kraton Polymers U.S. Llc Blown asphalt compositions
US20070105986A1 (en) * 2005-11-09 2007-05-10 Kraton Polymers U. S. Llc Blown asphalt compositions
US20090312449A1 (en) * 2006-02-13 2009-12-17 Shigeru Sasaki Hydrogenated block copolymer, resin composition comprising the hydrogenated block copolymer, and crosslinked product and crosslinked foamed product thereof
EP1985641A4 (en) * 2006-02-13 2010-02-10 Asahi Kasei Chemicals Corp HYDROGEN BLOCK COPOLYMER, RESIN COMPOSITION CONTAINING SUCH HYDROGEN BLOCK COPOLYMER, RETICULATED PRODUCT THEREOF, AND RETICULATED FOAM THEREOF
US8753442B2 (en) 2007-06-28 2014-06-17 Owens Corning Intellectual Capital, Llc Roofing coating asphalt composition
US20090000514A1 (en) * 2007-06-28 2009-01-01 Trumbore David C Method of producing roofing shingle coating asphalt from non-coating grade asphalt
US20090000515A1 (en) * 2007-06-28 2009-01-01 Trumbore David C Process of producing roofing shingle coating asphalt
US7857904B2 (en) 2007-06-28 2010-12-28 Owens Corning Intellectual Capital, Llc Process of producing roofing shingle coating asphalt
US7951239B2 (en) 2007-06-28 2011-05-31 Owens Corning Intellectual Capital, Llc Method of producing roofing shingle coating asphalt from non-coating grade asphalt
US7951240B2 (en) 2007-06-28 2011-05-31 Owens Corning Intellectual Capital, Llc Process of producing roofing shingle coating asphalt allowing more material options
US20110197785A1 (en) * 2007-06-28 2011-08-18 Owens Corning Intellectual Capital, Llc Roofing coating asphalt composition
WO2009110810A1 (de) * 2008-03-03 2009-09-11 Gorniak Wlodzimierz Modifizierungszusatz für asphaltmassen sowie art und weise der asphaltherstellung für die produktion von mineral-asphalt-mischungen mit hohem schermodul
US9376565B2 (en) * 2011-11-30 2016-06-28 Henry Company, Llc Asphalt compositions having improved properties and related coatings and methods
US9688883B2 (en) 2011-11-30 2017-06-27 Henry Company Llc Method for making asphalt compositions and substrates coated therewith having improved properties
US20130136855A1 (en) * 2011-11-30 2013-05-30 Henry Company Llc Asphalt compositions having improved properties and related coatings and methods
WO2014102152A1 (en) * 2012-12-28 2014-07-03 Shell Internationale Research Maatschappij B.V. Binder composition which can be coloured
US10640639B2 (en) 2014-01-17 2020-05-05 Asahi Kasei Kabushiki Kaisha Polymer and asphalt composition
US10138319B2 (en) 2014-01-17 2018-11-27 Asahi Kasei Kabushiki Kaisha Polymer and asphalt composition
US20190153214A1 (en) * 2014-01-17 2019-05-23 Asahi Kasei Kabushiki Kaisha Polymer and Asphalt Composition
US9873788B2 (en) 2014-04-08 2018-01-23 Asahi Kasei Kabushiki Kaisha Composition and surface protection film
US10189995B2 (en) 2014-05-08 2019-01-29 Asahi Kasei Kabushiki Kaisha Asphalt composition
EP3147328A4 (en) * 2014-05-19 2017-05-03 Asahi Kasei Kabushiki Kaisha Hydrogenated block copolymer composition and adhesive composition
EP3147328A1 (en) * 2014-05-19 2017-03-29 Asahi Kasei Kabushiki Kaisha Hydrogenated block copolymer composition and adhesive composition
US10233318B2 (en) 2014-07-01 2019-03-19 Asahi Kasei Kabushiki Kaisha Polyolefin-based resin composition, film, medical bag, and tube
US10414849B2 (en) 2015-07-16 2019-09-17 Asahi Kasei Kabushiki Kaisha Partially hydrogenated block copolymer, viscous adhesive composition, viscous adhesive tape, label, modified asphalt composition, modified asphalt mixture, and paving binder composition
US10808066B2 (en) 2016-01-19 2020-10-20 Asahi Kasei Kabushiki Kaisha Hydrogenated copolymer, composition, and molded article
EP3572444A1 (en) * 2016-04-25 2019-11-27 Asahi Kasei Kabushiki Kaisha Hydrogenated block copolymer, polypropylene resin composition, and molded body
US10829632B2 (en) 2016-04-25 2020-11-10 Asahi Kasei Kabushiki Kaisha Hydrogenated block copolymer, polypropylene resin composition, and molded body
US11912858B2 (en) 2020-07-03 2024-02-27 Asahi Kasei Kabushiki Kaisha Molded bale of rubber-like block copolymer, rubber composition, crosslinking rubber composition, and tread for tire

Also Published As

Publication number Publication date
US7696267B2 (en) 2010-04-13
JP4776155B2 (ja) 2011-09-21
CN1318511C (zh) 2007-05-30
HK1078891A1 (en) 2006-03-24
US20070179220A1 (en) 2007-08-02
JP2005126485A (ja) 2005-05-19
CN1621451A (zh) 2005-06-01

Similar Documents

Publication Publication Date Title
US7696267B2 (en) Asphalt composition containing hydrogenated conjugated diene copolymer
US7417081B2 (en) Asphalt composition
US8138270B2 (en) Process for producing block copolymer, and block copolymer or hydrogenated product thereof
JP2549144B2 (ja) 歴青及び熱可塑性エラストマーの配合物から成る歴青組成物
US10138319B2 (en) Polymer and asphalt composition
JP4623246B2 (ja) アスファルト改質用共重合体（組成物）、およびアスファルト組成物
WO2012165120A1 (ja) 水添共役ジエン系共重合体の製造方法
JP2012251040A (ja) アスファルト組成物
KR100626442B1 (ko) 커플링된 스티렌 블록 공중합체 및 이의 제조방법
KR20180044072A (ko) 아스팔트 개질제 및 이를 포함하는 아스팔트 조성물
JP6521696B2 (ja) アスファルト組成物
JP4598534B2 (ja) 共役ジエンブロック（コ）ポリマーとその調製方法
JP4688482B2 (ja) アスファルト組成物
JP3996790B2 (ja) アスファルト組成物
US7166679B2 (en) Conjugated diene polymers and copolymer blocks having high vinyl content prepared using mixed microstructure control agents and process for preparing same
JP2006241289A (ja) ブロック共重合体の製造方法
KR20110062194A (ko) 대칭형 다중가지 비닐 방향족 탄화수소-공액디엔 블록 공중합체, 그의 제조방법, 및 그를 포함하는 아스팔트 조성물
JP2003301112A (ja) 変性重合体含有アスファルト組成物
KR20180057189A (ko) 개질 아스팔트 조성물
JP4656987B2 (ja) アスファルト組成物
JP6917252B2 (ja) アスファルト組成物及び防水シート
JP4672446B2 (ja) アスファルト組成物
JP2008045034A (ja) 新規なブロック共重合体又はその水素添加物
KR20180066448A (ko) 아스팔트 개질제 및 이를 포함하는 개질 아스팔트 조성물
JP2003301113A (ja) アスファルト組成物

Legal Events

Date Code Title Description
AS Assignment

Owner name: ASAHI KASEI CHEMICALS CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SASAGAWA, MASAHIRO;SHIRAKI, TOSHINORI;NAKAJIMA, SHIGEO;REEL/FRAME:015916/0409

Effective date: 20041018

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION