JP2003301113A - Asphalt composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an asphalt composition that has a good elongation, flexibility and adhesion and is suitable in use for road pavement. <P>SOLUTION: This asphalt composition consists of 0.5-50 pts.wt. of a composition (1) comprising a modified polymer or its hydrogenated product that is prepared by the addition reaction, using an organolithium compound as a polymerization catalyst, of a functional group-containing modifier with a living terminal of at least one kind of polymer selected from (a) and (b), wherein, (a) is a conjugated diene polymer, (b) is a polymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon, the total amount of the vinyl aromatic hydrocarbon in the polymer (b) is no more than 50 wt.% and the vinyl aromatic hydrocarbon polymer block accounts for no more than 50 wt.% of the total amount of the vinyl aromatic hydrocarbon in the polymer (b), and 100 wt.% of asphalt (2). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an asphalt composition having excellent elongation, flexibility and adhesiveness, and more specifically, it comprises a modified polymer containing a specific functional group or a hydrogenated product thereof and asphalt. It relates to an asphalt composition.

[0002]

2. Description of the Related Art Conventionally, asphalt compositions have been widely used for applications such as road paving, waterproof sheets, sound insulation sheets, and roofing. At that time, many attempts have been made to improve the properties of asphalt by adding various polymers. As specific examples of the polymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, rubber latex, block copolymer composed of conjugated diene and vinyl aromatic hydrocarbon, and the like are used. In particular, it is a general practice to incorporate a rubber-like polymer in applications where elastic properties are required.

[0003]

Under these circumstances, an asphalt composition containing a rubber-like polymer has excellent elongation and flexibility, and is suitable for road paving applications, roofing / waterproof sheet applications, sealant applications, etc. A method of providing a composition has been desired.

[0004]

Means for Solving the Problems The present inventors have excellent elongation, flexibility, and adhesiveness, and are used in applications such as road pavement applications, roofing / waterproof sheet applications, sealant applications, and the like.
As a result of diligent studies on improving the properties of a composition of a rubbery polymer and asphalt, a modified polymer containing a specific functional group or an asphalt composition comprising a hydrogenated product and asphalt effectively solves the above problems. The present invention has been completed and the present invention has been completed.

That is, the present invention is as follows. A component which is a modified polymer obtained by adding a functional group-containing modifier to the living terminal of at least one polymer selected from the following a and b obtained by using an organolithium compound as a polymerization catalyst or a hydrogenated product thereof ( 1) 0.5
˜50 parts by weight a. Conjugated diene polymer b. A polymer comprising a conjugated diene and a vinyl aromatic hydrocarbon, the total vinyl aromatic hydrocarbon content in the polymer is 50% by weight or less, and the total vinyl aromatic hydrocarbon content in the polymer. A polymer having a ratio of vinyl aromatic hydrocarbon polymer blocks to less than 50% by weight, and asphalt (2)
An asphalt composition consisting of 100 parts by weight.

The present invention will be specifically described below.
The component (1) used in the present invention is obtained by adding a functional group-containing modifier to the living terminal of at least one polymer selected from the following a and b obtained by using an organolithium compound as a polymerization catalyst. It is a modified polymer or a hydrogenated product thereof. a. Conjugated diene polymer b. A polymer comprising a conjugated diene and a vinyl aromatic hydrocarbon, the total vinyl aromatic hydrocarbon content in the polymer is 50% by weight or less, and the total vinyl aromatic hydrocarbon content in the polymer. The ratio of the vinyl aromatic hydrocarbon polymer block to the above is less than 50% by weight.

The total vinyl aromatic hydrocarbon content of the modified polymer comprising the conjugated diene and vinyl aromatic hydrocarbon used in the present invention or the hydrogenated product thereof is generally 5 to 50% by weight, more preferably 10 to 45%. % By weight, more preferably 15 to
40 weight. In the present invention, a vinyl aromatic hydrocarbon content of less than 5% by weight is considered to be substantially a conjugated diene polymer. In the present invention, the content of the vinyl aromatic compound in the hydrogenated product may be grasped as the content of the vinyl aromatic compound in the polymer before modification or in the polymer before hydrogenation. The vinyl aromatic hydrocarbon in the modified polymer comprising the conjugated diene and the vinyl aromatic hydrocarbon or the hydrogenated product thereof may be distributed uniformly or in a taper shape. Further, in the polymer, a plurality of portions in which vinyl aromatic hydrocarbons are uniformly distributed and / or a plurality of portions in which taper distribution is formed may coexist.

The modified polymer composed of a conjugated diene and a vinyl aromatic hydrocarbon used in the present invention or a hydrogenated product thereof is a vinyl aromatic hydrocarbon polymer block based on the total vinyl aromatic hydrocarbon content in the polymer. (Hereinafter, the ratio of the vinyl aromatic hydrocarbon polymer block content to the total vinyl aromatic hydrocarbon content in the polymer is referred to as the vinyl aromatic hydrocarbon block ratio) is less than 50% by weight, preferably The polymer is 40% by weight or less, more preferably 20% by weight or less. When the blocking rate is less than 50% by weight, a composition having good flexibility can be obtained.

The content of the vinyl aromatic hydrocarbon polymer block is measured, for example, by oxidatively decomposing the copolymer before hydrogenation with tert-butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLT.
HOFF, et al. J. Polym. Sci. 1,
429 (1946)), using the weight of the vinyl aromatic hydrocarbon polymer block component (provided that the vinyl aromatic hydrocarbon polymer component having an average degree of polymerization of about 30 or less is excluded). Then, it can be obtained from the following equation. Content of vinyl aromatic hydrocarbon polymer block (% by weight) = (weight of vinyl aromatic hydrocarbon polymer block in polymer before hydrogenation / weight of said polymer before hydrogenation)
× 100

In the present invention, the modified polymer before the hydrogenation reaction is obtained by subjecting the living terminal of the polymer obtained by a known method using an organolithium compound as a polymerization catalyst to a reaction with a modifying agent which will be described later. It has a structure represented by the following general formula. (B) _n -X (AB) _n -X, A- (BA) _n -X, B- (AB) _n -X, X- (AB) _n , X- (A -B) _n- X, X-A- (BA) _n- X, X-B- (AB) _n- X, [(B-A) _n ] _m- X, [(A-B ) _N ] _m- X, [(BA) _n- B] _m- X, [(AB) _n- A] _m- X (In the above formula, A is a vinyl aromatic hydrocarbon polymer segment. And B is a conjugated diene polymer or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon, or a conjugated diene polymer segment or a copolymer segment of a conjugated diene and a vinyl aromatic hydrocarbon, n is 1 It is an integer of the above or more, preferably an integer of 1 to 5. m is an integer of 2 or more, preferably an integer of 2 to 11. X is the rest of the modifier to which an atomic group having a functional group described later is bonded. Base When X is added by a metalation reaction described later, it is bonded to the side chains of A and / or B. Further, the structure of the polymer chains bonded to X may be the same or different. Good.) The polymer used in the present invention may be any mixture of the polymers represented by the above general formula.

In the present invention, the microstructure (cis, trans, vinyl ratio) of the conjugated diene moiety in the polymer is
It can be optionally changed by using a polar compound described below, and when 1,3-butadiene is used as the conjugated diene, the 1,2-vinyl bond amount is preferably 5 to 90.
%, More preferably 10 to 80%, when isoprene is used as the conjugated diene or when 1,3-butadiene and isoprene are used in combination, 1,2-vinyl bond and 3,
The total amount of 4-vinyl bonds is preferably 3 to 80%, more preferably 5 to 70%.

However, when the hydrogenated product is used as the polymer, the microstructure is such that when 1,3-butadiene is used as the conjugated diene, the 1,2-vinyl bond content is preferably 10 to 80%, It is more preferably 15 to 75%, particularly preferably 20 to 50%. When isoprene is used as the conjugated diene or 1,3-butadiene and isoprene are used in combination, 1,2-vinyl bond and 3, 4-
It is recommended that the total amount of vinyl bonds is preferably 5-70%, more preferably 10-50%.

In the present invention, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, when 1,3-butadiene is used as the conjugated diene,
-Vinyl bond content) is hereinafter referred to as vinyl bond content. In the present invention, a conjugated diene polymer or a copolymer comprising a conjugated diene and a vinyl aromatic hydrocarbon, or a conjugated diene polymer segment or a copolymer segment comprising a conjugated diene and a vinyl aromatic hydrocarbon has a vinyl bond content of There may be at least one different portion. For example, the vinyl bond content is 25% or less, preferably 10 to 23% and the vinyl bond content is more than 25%, preferably 28.
At least one 80% to 80% portion may be present. Further, in a polymer having two or more segments B, the vinyl bond content of each segment B may be the same or different.

In the present invention, the conjugated diene is a diolefin having a pair of conjugated double bonds, for example, 1,3
-Butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene,
1,3-pentadiene, 1,3-hexadiene and the like, but particularly common ones are 1,3-butadiene,
Examples include isoprene. These may be used not only in one kind but also in two or more kinds in the production of one polymer.
Examples of vinyl aromatic hydrocarbons include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene and vinylanthracene. However, styrene is particularly common. These may be used not only in one kind but also in two or more kinds in the production of one polymer.

In the present invention, when isoprene and 1,3-butadiene are used together as the conjugated diene, the mass ratio of isoprene and 1,3-butadiene is preferably 95/5 to 5/5.
It is 5/95, more preferably 90/10 to 10/90, and further preferably 85/15 to 15/85. In particular, when a composition having good low temperature characteristics is obtained, the mass ratio of isoprene and 1,3-butadiene is preferably 49/51 to
It is recommended to be 5/95, more preferably 45/55 to 10/90, and further preferably 40/60 to 15/85. When isoprene and 1,3-butadiene are used in combination, a composition having good high temperature storage stability can be obtained.

In the present invention, as the solvent used for producing the polymer, butane, pentane, hexane, isopentane, heptane, octane, isooctane and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, Alicyclic hydrocarbons such as ethylcyclohexane, or hydrocarbon solvents such as aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene can be used. These may be used alone or as a mixture of two or more.

The organolithium compound used in the production of the polymer is a compound having one or more lithium atoms bonded in the molecule, such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, Examples include sec-butyllithium, tert-butyllithium, hexamethylenedilithium, butadienyldilithium, and isoprenyldilithium. These may be used alone or as a mixture of two or more.
In addition, the organolithium compound may be dividedly added once or more during the polymerization in the production of the polymer.

In the present invention, the polymerization rate during the production of the polymer is adjusted, the microstructure of the polymerized conjugated diene moiety is changed,
A polar compound or a randomizing agent can be used for the purpose of adjusting the reactivity ratio between the conjugated diene and the vinyl aromatic hydrocarbon. Examples of the polar compound and the randomizing agent include ethers, amines, thioethers, phosphoramide, potassium salt or sodium salt of alkylbenzene sulfonic acid, potassium or sodium alkoxide, and the like.

Examples of suitable ethers are dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether,
It is diethylene glycol dibutyl ether. As amines, tertiary amine, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines can be used. Examples of the phosphine and phosphoramide include triphenylphosphine and hexamethylphosphoramide.

In the present invention, the polymerization temperature for producing the polymer is preferably -10 to 150 ° C, more preferably 30 to 120 ° C. The time required for the polymerization varies depending on the conditions, but it is preferably within 48 hours, particularly preferably 0.5 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within the range of the above-mentioned polymerization temperature and is a pressure sufficient to maintain the monomer and the solvent in the liquid phase. Further, it is preferable that impurities such as water, oxygen, carbon dioxide gas, etc. which inactivate the catalyst and the living polymer are not mixed in the polymerization system.

Component (1), which is a modified polymer obtained by using the organolithium compound used in the present invention as a polymerization catalyst, or a hydrogenated product thereof, is obtained by adding a functional group-containing modifier to the living end of the polymer. , Hydroxyl group, carboxyl group, carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group, Sulfonate group, phosphate group,
Phosphate group, amino group, imino group, nitrile group,
Functional group selected from pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silanol group, alkoxysilane, silicon halide group, tin halide group, alkoxytin group, phenyltin group, etc. A modified polymer in which at least one atomic group having at least one is bonded or a hydrogenated product thereof.

A method for obtaining a modified polymer having an atomic group having such a functional group bonded thereto or a hydrogenated product thereof is selected from the above functional groups in the polymer by an addition reaction with the living end of the polymer. A modified polymer having a functional group forming at least one atomic group having at least one functional group bonded thereto or a hydrogenated product thereof, or an atomic group having the functional group protected by a known method is bonded. It can be obtained by a method in which the modifying agent used is subjected to an addition reaction.

As another method, there is a method in which an organic alkali metal compound such as an organic lithium compound is reacted with the polymer (metalation reaction), and the above modifier is added to the organic alkali metal-added polymer. To be In the latter case, the hydrogenation product of the polymer may be obtained and then the metalation reaction may be carried out to react the above-mentioned modifier. Depending on the type of modifier, the hydroxyl group, amino group, etc. may generally be an organic metal salt at the stage of reaction with the modifier, in which case it should be treated with a compound having active hydrogen such as water or alcohol. Thus, a hydroxyl group or an amino group can be obtained.

In the present invention, when the modifier is reacted with the living end of the polymer, a partially unmodified polymer may be mixed in the modified polymer of the component (1). The proportion of the unmodified polymer mixed in the modified polymer of the component (1) is preferably 70 wt% or less, more preferably 60 w.
It is recommended to be t% or less, and more preferably 50 wt% or less. In the asphalt composition of the present invention,
Since the modified polymer or the atomic group bonded to the hydrogenated product thereof has at least one functional group selected from the above-mentioned functional groups, it has high affinity with asphalt, aggregates, etc. The interaction is effectively expressed by the physical affinity such as chemical bond or hydrogen bond of the compound, and the chemical bond or physical affinity is generated between the agent and the cross-linking agent defined in the present invention. It is possible to obtain a composition having excellent properties which are the objects of the invention.

The modified polymer of the component (1) used in the present invention or a hydrogenated product thereof is particularly preferable to have at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group. It is a modified polymer having at least one atomic group bonded thereto or a hydrogenated product thereof. In the present invention, a preferable atomic group as an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is a general atomic group represented by the following formulas (1) to (14). The atomic groups selected from those represented by the formula are raised.

[0026]

[Chemical 2]

(In the above formula, R ^{1 to} R ⁴ are hydrogen or a carbon number of 1
A hydrocarbon group having 1 to 24 carbon atoms or a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group. R ⁵ has 1 to 1 carbon atoms
A hydrocarbon chain having 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group. Elements such as oxygen, nitrogen, and silicon are bound to the hydrocarbon groups of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ in a bonding mode other than hydroxyl group, epoxy group, silanol group, and alkoxysilane group. It may be. R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms)

In the present invention, at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group is used.
Examples of the modifier used for obtaining the individually bonded modified polymer or the hydrogenated product thereof include the following.

For example, tetraglycidyl metaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane,
Diglycidyl aniline and diglycidyl orthotoluidine. Further, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldisilane Propoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldiethylethoxysilane, γ-glycidoxyp Pyrdimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropylmethyldiisopropeneoxysilane, bis (γ-glycidoxypropyl) dimethoxysilane, It is bis (γ-glycidoxypropyl) diethoxysilane.

Further, bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) dibutoxysilane, bis (γ-glycidoxypropyl) diphenoxysilane, bis (γ-glycid) Xypropyl) methylmethoxysilane, bis (γ-glycidoxypropyl) methylethoxysilane, bis (γ-glycidoxypropyl) methylpropoxysilane, bis (γ-
Glycidoxypropyl) methylbutoxysilane, bis (γ-glycidoxypropyl) methylphenoxysilane, tris (γ-glycidoxypropyl) methoxysilane, γ-methacryloxypropyltrimethoxysilane,
γ-methacryloxypropyltriethoxysilane, γ-
Methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, bis (γ-methacryloxypropyl) dimethoxysilane and tris (γ-methacryloxypropyl) methoxysilane.

Further, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyl-triethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-
Tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β- (3,4
-Epoxycyclohexyl) ethyl-triphenoxysilane, β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyl-ethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldiethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β
-(3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane, β- (3,3
4-epoxycyclohexyl) ethyl-diethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4- Epoxy cyclohexyl) ethyl-
Dimethylbutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylphenoxysilane, β-
(3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane and β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane.

Further, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone,
Examples thereof include N, N'-dimethylpropyleneurea and N-methylpyrrolidone. By reacting the above modifying agent, the residue of the modifying agent to which an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group is bonded is bonded. A modified polymer is obtained. When a functional group-containing modifier is added to the living ends of a polymer having segment A and segment B, the living end of the polymer may be either segment A or segment B, but a composition having an excellent softening point and the like should be used. In order to obtain it, it is preferable that it is bound to the end of segment A.

The amount of the above modifier used is more than 0.5 equivalents and not more than 10 equivalents, preferably more than 0.7 equivalents and not more than 5 equivalents, more preferably 1 equivalent to the living end of the polymer. It is recommended to use more than 1 equivalent and 4 equivalents or less. In the present invention, the amount of the living terminal of the polymer may be calculated from the amount of the organolithium compound used for the polymerization and the number of lithium atoms bonded to the organolithium compound, or the obtained weight. It may be calculated from the number average molecular weight of the coalescence.

In the present invention, the hydrogenated product of the modified polymer is
It is obtained by hydrogenating the modified polymer obtained above. The hydrogenation catalyst is not particularly limited and is a conventionally known (1) supported heterogeneous hydrogenation in which a metal such as Ni, Pt, Pd or Ru is supported on carbon, silica, alumina, diatomaceous earth or the like. Catalyst, (2) Ni, Co, Fe, C
A so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as r or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum, (3) Ti, Ru, Rh, Zr
A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound is used.

As a specific hydrogenation catalyst, Japanese Patent Publication No. 42-
8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-39700,
The hydrogenation catalysts described in JP-B-1-53851 and JP-B-2-9041 can be used. Preferred hydrogenation catalysts include a mixture with a titanocene compound and / or a reducing organometallic compound. As the titanocene compound, compounds described in JP-A-8-109219 can be used, and specific examples thereof include (substituted) biscyclopentadienyl titanium dichloride, monopentamethylcyclopentadienyl titanium trichloride and the like. Examples thereof include compounds having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton or a fluorenyl skeleton. Examples of the reducing organic metal compound include organic alkali metal compounds such as organic lithium, organic magnesium compounds, organic aluminum compounds, organic boron compounds and organic zinc compounds.

The hydrogenation reaction is preferably carried out in the temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used in the hydrogenation reaction is preferably 0.1 to
15 MPa, more preferably 0.2 to 10 MPa, further preferably 0.3 to 5 MPa is recommended. The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction is a batch process,
Either a continuous process or a combination thereof can be used.

In the hydrogenated product of the modified polymer used in the present invention, the total hydrogenation rate of the unsaturated double bond based on the conjugated diene compound can be arbitrarily selected according to the purpose and is not particularly limited. More than 70%, preferably 75% or more, more preferably 85% or more, particularly preferably 90% of the unsaturated double bond based on the conjugated diene compound in the polymer.
The above may be hydrogenated, or only a part thereof may be hydrogenated. When hydrogenating only a part, the hydrogenation rate is 1
0 to 70%, or 15 to 65%, particularly preferably 20 to
It is preferably 60%.

Further, in the present invention, in the hydrogenated polymer, the hydrogenation rate of vinyl bond based on the conjugated diene before hydrogenation is preferably 85% or more, more preferably 9%.
It is recommended to be 0% or more, more preferably 95% or more in order to obtain a composition having excellent thermal stability. here,
The hydrogenation rate of vinyl bonds means the proportion of hydrogenated vinyl bonds in the vinyl bonds based on the conjugated diene before hydrogenation incorporated in the polymer. The hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the polymer is not particularly limited, but is preferably 50.
% Or less, more preferably 30% or less, and further preferably 2
0% or less is recommended. The hydrogenation addition rate can be known by a nuclear magnetic resonance apparatus (NMR).

The modified polymer used in the present invention or the hydrogenated product thereof has a weight average molecular weight of 30,000 or more in view of mechanical strength of the asphalt composition, and 150 in view of solubility in asphalt and viscosity of the composition. It is preferably 10,000 or less, more preferably 40,000 to 1,000,000, and further preferably 5
~ 800,000. The molecular weight distribution is 1.05 to 6, preferably 1.1 to 6, and more preferably 1.55 to 5.
0, particularly preferably 1.6 to 4. Setting the molecular weight distribution within such a range is recommended in terms of compatibility between the component (1) and the component (2), molding processability of the composition, and the like.

In the present invention, the amount of vinyl bond based on the conjugated diene compound in the polymer is determined by the nuclear magnetic resonance apparatus (NM
R) can be used to find out. The hydrogenation rate can also be known using the same device. The weight average molecular weight of the polymer or its hydrogenated product is measured by gel permeation chromatography (GPC), and the molecular weight of the peak of the chromatogram is determined by measuring a commercially available standard polystyrene. The peak molecular weight is used for the calculation). The molecular weight distribution of the polymer can be similarly determined from the measurement by GPC.

A solution of the modified polymer or hydrogenated product thereof obtained as described above is subjected to removal of the catalyst residue if necessary,
The modified polymer or its hydrogenated product can be separated from the solution. As a method for separating the solvent, for example, a method in which a polar solvent that is a poor solvent for the polymer such as acetone or alcohol is added to the solution after polymerization or hydrogenation to precipitate and recover the polymer, a modified polymer or the Examples thereof include a method in which the hydrogenated solution is poured into hot water with stirring, and the solvent is removed by steam stripping to recover the solvent, or a method in which the polymer solution is directly heated to distill off the solvent. still,
The modified polymer or its hydrogenated product used in the present invention includes various phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers,
Stabilizers such as amine stabilizers can be added.

The modified polymer or hydrogenated product thereof particularly preferred in the present invention has a difference between the maximum value and the minimum value of the vinyl bond content in the polymer chain before hydrogenation of less than 10% by weight, preferably 8% by weight. The following modified polymers or hydrogenated products thereof may be mentioned. Further, in the present invention, as a particularly preferred modified polymer or hydrogenated product thereof, a modified polymer or its water whose relation between the molecular weight obtained by GPC / FTIR measurement and the number of terminal methyl carbon atoms satisfies the following formula: An accessory is mentioned. Va-Vb ≧ 0.03 Vc, preferably Va-Vb
≧ 0.05 Vc (where Va is the number of terminal methyl carbon atoms contained in 1000 carbon atoms in the polymer at a molecular weight twice the peak top molecular weight, and Vb is 1/100 of the peak top molecular weight). The same number in the molecular weight of 2 and Vc are the same number in the peak top molecular weight.)

GPC-FTIR is a GPC (Gel Per
FTI as a detector of the Mation Chromatograph
R (Fourier transform infrared spectrophotometer) is used,
The microstructure of each fraction fractionated by molecular weight can be measured. The number of terminal methyl carbon atoms is, the absorbance I (-CH ₂ -) which is attributable to a methylene group <absorption wave numbers: 2925 cm ^-1> to the absorbance I attributed to methyl groups
(-CH ₃₎ <absorption wave numbers: 2960 cm ^-1> ratio, I (-
_{CH 3) / I (-CH 2} - can be obtained from). This method is described in, for example, NICOLET FT-IR CU.
STOMER NEWSLETTER Vol. 2, No
2, 1994 and the like.

Next, the asphalt of the component (2) used in the present invention is a by-product (petroleum asphalt) in refining petroleum. Alternatively, a natural product (natural asphalt), a mixture of these and petroleum, or the like can be used, the main component of which is called bitumen. Specifically, straight asphalt, semi-blown asphalt, blown asphalt, tar, pitch, cutback asphalt to which oil is added, and asphalt emulsion can be used. These may be mixed and used.

Preferred asphalt in the present invention is
Straight asphalt having a penetration of 30 to 300, preferably 40 to 200, and more preferably 45 to 150. In the asphalt composition of the present invention, the blending ratio of the hydrogenated copolymer is 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight, and more preferably 3 to 20 parts by weight with respect to 100 parts by weight of asphalt. is there. Various additives may be added to the asphalt composition of the present invention as required. These additives include, for example, inorganic fillers such as calcium carbonate, magnesium carbonate, talc, silica, alumina, titanium oxide, glass fiber and glass beads,
Organic fibers, organic reinforcing agents such as coumarone indene resin, organic peroxides, cross-linking agents such as inorganic peroxides, titanium white, carbon black, pigments such as iron oxide, dyes, flame retardants, antioxidants, ultraviolet absorbers, Antistatic agents, lubricants, paraffin-based process oils, naphthene-based process oils, aromatic process oils, paraffins, organopolysiloxanes, mineral oils and other softeners / plasticizers, coumarone indene resins, terpene resins, and other tackifying resins. Is.

Further, polyolefin resin such as atactic polypropylene and ethylene-ethyl acrylate copolymer, low molecular weight vinyl aromatic thermoplastic resin, natural rubber, polyisoprene rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber , Isoprene-isobutylene rubber, and styrene-butadiene-based block copolymers other than the present invention or hydrogenated products thereof, styrene-isoprene-based block copolymers or synthetic rubbers such as hydrogenated products thereof, vulcanizing agents such as sulfur, Examples include vulcanization aids, other extenders, and mixtures thereof. In particular, when the asphalt composition of the present invention is used for road paving, it is usually used as a mixture with aggregates such as crushed stone, sand and slag, which are mineral substances. The method of mixing the asphalt composition of the present invention is not particularly limited, and is prepared by heating and melting and kneading with the above-mentioned various additives, if desired, for example, in a hot melt pot, a kneader, a Banbury mixer, an extruder or the like. be able to.

[0047]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. In the following examples, the properties of the polymer and its hydrogenated product were measured as follows. A. Properties of Polymers and Hydrogenated Products (1) Styrene Content Using an ultraviolet spectrophotometer (Hitachi UV200), 262
It was calculated from the absorption intensity at nm. (2) Polystyrene block content Using a polymer before hydrogenation, I. M. Kolthoff, et al. J.
P olym. Sci. It was measured by the method described in 1,429 (1946). (3) Vinyl bond amount and hydrogenation rate Nuclear magnetic resonance apparatus (BRUXER, DPX-400)
Was measured using.

(4) Molecular weight GPC (apparatus: LC10 manufactured by Shimadzu Corporation, column: Shimpac GPC805 + GPC80 manufactured by Shimadzu Corporation)
4 + GPC804 + GPC803). Tetrahydrofuran is used as the solvent, and the measurement condition is a temperature of 35 ° C.
I went there. The molecular weight is a weight average molecular weight obtained by using a calibration curve (prepared by using the peak molecular weight of standard polystyrene) obtained by measuring the standard polystyrene of the chromatogram.

(5) Ratio of unmodified block copolymer A sample solution containing a modified polymer and a low molecular weight internal standard polystyrene was applied by applying the property that a modified component is adsorbed on a GPC column having a silica gel as a packing material. , Above (4)
The ratio of the modified polymer to the standard polystyrene in the chromatogram measured by the method is compared with the ratio of the modified polymer to the standard polystyrene in the chromatogram measured by the silica-based column GPC [the device is Zorbax manufactured by DuPont]. The amount of adsorption to the silica column was measured from the difference of The ratio of the unmodified polymer is the ratio of those not adsorbed on the silica column.

(6) Number of terminal methyl carbon atoms (GPC
/ FTIR) GPC [apparatus manufactured by Waters] was used for measurement, and FT-IR [apparatus manufactured by Perkin-Elmer] was used as a detector. The measurement conditions are as follows.・ Column; AT-807S (1 piece) [Showa Denko KK] and GMH-HT6 (2 pieces) ・ [Tosoh Corporation] connected in series ・ Mobile phase; Trichlorobenzene column temperature; 140 ° C ・ Flow rate; 1.0 ml / min ・ Sample concentration; 20 mg / 20 ml ・ Solution temperature; 140 ° C

B. Preparation of Polymer etc. The hydrogenation catalyst used in the hydrogenation reaction was prepared by the following method. 1) Hydrogenation catalyst Ι A reaction vessel purged with nitrogen was charged with 2 liters of dried and purified cyclohexane, and 40 mmol of bis (η5-cyclopentadienyl) titanium di- (p-tolyl) and a molecular weight of about 1,000 were used. , 2-polybutadiene (1,2-
After dissolving 150 grams of vinyl bond (about 85%), n
A cyclohexane solution containing 60 mmol of -butyllithium was added, and the mixture was reacted at room temperature for 5 minutes. Immediately, 40 mmol of n-butanol was added and stirred, and the mixture was stored at room temperature.

2) Hydrogenation catalyst II 1 liter of dried and purified cyclohexane was charged into a reaction vessel purged with nitrogen, 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride was added, and trimethylaluminum 200 was added with sufficient stirring. An n-hexane solution containing mmol was added, and the mixture was reacted at room temperature for about 3 days.

The polymer and the like used in the present invention were prepared by the following method. a. Polymer 1 A cyclohexane solution having a butadiene concentration of 20% by weight was fed at a feed rate of 6.19 L / hr to a stirrer having an internal volume of 10 L and a tank reactor with a jacket, and n-butyllithium was added to 100 g of butadiene in an amount of 0. The cyclohexane solution adjusted to have a concentration of 25 g was supplied at a feed rate of 2 L / hr, and a cyclohexane solution of N, N, N ′, N′-tetramethylethylenediamine was added to 0.25 to 1 mol of n-butyllithium. Each of them was fed at such a feeding rate as to give a mole, and continuously polymerized at 90 ° C. The reaction temperature is adjusted by the jacket temperature, and the temperature near the bottom of the reactor is about 8
The temperature in the vicinity of the center of the reactor was about 90 ° C, and the temperature in the vicinity of the upper part of the reactor was about 90 ° C. The average residence time in the polymerization reactor was about 45 minutes, and the conversion of butadiene was almost 100%.

The average vinyl bond content of the polymer obtained by continuous polymerization was 27%. In addition, during the polymerization reaction, it was determined from the vinyl bond content of the polymer sampled during the reaction, the butadiene supply amount at that time, and the polymer conversion rate calculated from the reaction rate (conversion rate of the polymer to the total supplied butadiene). The difference in vinyl bond content was less than 5% by weight.

Next, the living polymer obtained by continuous polymerization was treated with tetraglycidyl-1,3-bisaminomethylcyclohexane as a modifier (hereinafter referred to as modifier M1).
Was reacted in 1.1 equivalents with respect to 1 equivalent of n-butyllithium used in the polymerization. Thereafter, 100 ppm of Ti as hydrogenation catalyst I was added to the polymer obtained as described above per 100 parts by weight of the polymer, and the hydrogen pressure was 0.7 MPa,
The hydrogenation reaction was carried out at a temperature of 65 ° C. Methanol was then added, and then octadecyl-3- (3,5-
0.3 parts by weight of di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by weight of the polymer. The polymer obtained had a vinyl bond content of about 27% before hydrogenation, a difference between the maximum and minimum vinyl bond contents of the polymer before hydrogenation of 5% or less, and a hydrogenation addition rate. Of 99%, a molecular weight of 200,000 and a molecular weight distribution of 1.6 were modified hydrogenated polymers (polymer 1).

B. Polymer 2 Continuous polymerization was carried out using two stirrers having an internal volume of 10 L and two tank reactors with jackets. From the bottom of the first unit, add a hexane solution having a butadiene concentration of 30% by weight to 4.
At a feed rate of 6 L / hr, a hexane solution in which n-butyllithium was adjusted to a concentration of 0.097 g per 100 g of butadiene was added at a feed rate of 2 L / hr, and N, N, N ′ and N ′ were further added. -A hexane solution of tetramethylethylenediamine was added to 1 mol of n-butyllithium.
Each of them is fed at a feeding rate such that the amount becomes 06 mol,
It was continuously polymerized at ℃. The reaction temperature was adjusted by the jacket temperature. The temperature near the bottom of the reactor was about 88 ° C and the temperature near the top of the reactor was about 90 ° C. The conversion of butadiene at the outlet of the first unit was almost 100%.

The polymer solution discharged from the first unit was fed from the bottom of the second unit, and at the same time, the butadiene concentration was 30% by weight.
At a feed rate of 6.8 L / hr, and a hexane solution of N, N, N ′, N′-tetramethylethylenediamine was added to 1 mol of n-butyllithium at 0.
Each is fed at a feeding rate of 75 mol,
It was continuously polymerized at ℃. The temperature near the bottom of the second reactor was about 89 ° C and the temperature near the top of the reactor was about 90 ° C. The conversion rate of butadiene at the outlet of the second unit is almost 100.
%Met. The average vinyl bond content of the polymer obtained by continuous polymerization of two groups was 30%.

Next, 1,3-dimethyl-2-imidazolidinone (hereinafter referred to as modifier M2) was used as a modifier in the living polymer obtained by continuous polymerization as a modifier.
-Equimolar reaction to butyllithium. afterwards,
Hydrogenated catalyst II was added to the polymer obtained as described above in an amount of 100 ppm as Ti per 100 parts by weight of the polymer, and hydrogenated at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. Thereafter, methanol was added, and then 0.3 parts by weight of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the polymer. The polymer obtained had a vinyl bond content of about 30% and a hydrogenation addition ratio of 9 before hydrogenation.
8%, molecular weight 220,000, molecular weight distribution 1.8, Va-Vb
Was 15, and 0.03 Vc was 2.6, a modified hydrogenated polymer (Polymer 2).

C. Polymer 3 A n-hexane solution containing a monomer having a weight ratio of butadiene / styrene of 82/18 at a concentration of 16% by weight was supplied to a stirrer having an internal volume of 10 L and a tank reactor with a jacket at a feed rate of 157 g / min. Then, a cyclohexane solution containing 10% by weight of n-butyllithium as a polymerization initiator at a supply rate of 6.5 g / min, and N, N, N ′, N′-tetramethylethylenediamine as a polar substance was further added. An n-hexane solution containing 10% by weight was supplied at a supply rate of 4.5 g / min, and continuous polymerization was performed at 86 ° C.

Next, the living polymer obtained by continuous polymerization was reacted with the modifier M1 in an amount of 0.5 mol per mol of n-butyllithium used in the polymerization. When the obtained polymer was analyzed, the styrene content was 18% by weight and the vinyl bond content in the butadiene part was 30% by weight. From the analysis value of the amount of block styrene, the block of styrene was not present. Next, 100 ppm of Ti was added to the polymer obtained by continuous polymerization as Ti per 100 parts by weight of the polymer, and the hydrogen pressure was 0.7 MPa and the temperature was 6 MPa.
The hydrogenation reaction was carried out at 5 ° C. Then add methanol,
Next, as a stabilizer, octadecyl-3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate was added in an amount of 0.3 part by weight based on 100 parts by weight of the polymer. The resulting modified hydrogenated copolymer (Polymer 3) had a Mooney viscosity of 70, a molecular weight distribution of 1.9, a styrene content of 18% by weight, a vinyl bond content of the butadiene part of 30% by weight, and a hydrogenation rate of 84%. .

C. Preparation of asphalt composition 400 g of straight asphalt 60-80 (manufactured by Nippon Oil Co., Ltd.) was put into a 750 ml metal can, and 1
Thoroughly immerse the metal can in an 80 ° C oil bath. Next, a predetermined amount of polymer or the like is added little by little into the asphalt in a molten state while stirring. After complete addition, the mixture was stirred for 90 minutes at a rotation speed of 5000 rpm to prepare an asphalt composition.

D. Characteristics of asphalt composition (1) Softening point (ring & ball method) According to JIS-K 2207, a sample was filled in a prescribed ring, supported horizontally in a glycerin solution, and at the center of the sample 3.5.
When a g ball was placed and the liquid temperature was raised at a rate of 5 ° C./min, the temperature at which the sample touched the bottom plate of the ring base was measured by the weight of the ball. (2) Elongation According to JIS-K 2207, the sample is poured into a frame,
After being formed into a prescribed shape, the temperature was kept at 15 ° C. in a constant temperature water bath, and then when the sample was pulled at a speed of 5 cm / min, the distance extended until the sample was broken was measured.

(3) Adhesive strength The asphalt composition dissolved in toluene was applied to the canvas with a coater, and the asphalt composition was applied to the canvas and dried at room temperature.
After a period of time, it was dried in a 70 ° C. oven for 7 minutes to completely evaporate the toluene. Next, the canvas coated with the asphalt composition was mixed with the surface of the adherend, which had a smooth granite, at 70 ° C.
Put it in the oven for 1 hour, and immediately take out the load 1kg
The roller was pressed twice. And 180 degreeC peeling test of canvas and granite was performed in a constant temperature room of 23 degreeC, and the adhesive strength was measured.

(4) Storage stability at high temperature (separation property) Immediately after preparation of the asphalt composition, inner diameter 50 mm, height 13
The asphalt composition was poured into a 0 mm aluminum can up to the upper limit of the aluminum can, put in an oven at 180 ° C., taken out after 24 hours and naturally cooled. Next, the asphalt composition cooled to room temperature was sampled from the lower end to 4 cm and from the upper end to 4 cm, and the softening points of the upper and lower layers were measured, and the difference in softening point was used as a measure of high temperature storage stability. .

[0065]

[Examples 1 to 3] Straight asphalt 60-80
8 parts by weight of each of Polymer 1 (Example 1), Polymer 2 (Example 2) and Polymer 3 (Example 3) as a modified polymer was added to 100 parts by weight of [Nippon Oil Co., Ltd.]. The asphalt composition is prepared and its properties are measured. The asphalt composition of the present invention exhibits excellent properties such as elongation, flexibility and adhesiveness.

[0066]

Industrial Applicability The present invention provides an asphalt composition having good elongation, flexibility and adhesiveness. The asphalt composition of the present invention is used for road paving, roofing and
It can be used for applications such as waterproof sheets and sealants.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 AG001 BL012 BL022 BP012                       FD010 FD020 FD090 FD140                       GJ02 GL00                 4J100 AS01P AS02P AS03P AS04P                       CA01 CA27 CA31 HA03 HA55                       HA61 HB02 HC47 HC63 HC77                       HC78 HG02 HG03 JA01 JA67

Claims (7)

[Claims] 1. A modified polymer obtained by adding a functional group-containing modifier to the living end of at least one polymer selected from the following a and b obtained by using an organolithium compound as a polymerization catalyst, or a water thereof. Ingredients (1)
0.5 to 50 parts by weight a. Conjugated diene polymer b. A polymer comprising a conjugated diene and a vinyl aromatic hydrocarbon, the total vinyl aromatic hydrocarbon content in the polymer is 50% by weight or less, and the total vinyl aromatic hydrocarbon content in the polymer. A polymer having a ratio of vinyl aromatic hydrocarbon polymer blocks to less than 50% by weight, and asphalt (2)
An asphalt composition consisting of 100 parts by weight. 2. The polymer constituting the component (1) has at least one bonded atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group. The asphalt composition according to claim 1, which is a modified polymer or a hydrogenated product thereof. 3. The functional group-containing modifier has at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group in the polymer by an addition reaction with the living end of the polymer. The asphalt composition according to any one of claims 1 and 2, which is a modified polymer having a functional group that forms a modified polymer having at least one atomic group that is bonded or a hydrogenated product thereof. 4. A component (1) which is a modified polymer or a hydrogenated product thereof is bound to at least one atomic group having at least one functional group selected from the following formulas (1) to (14). 4. A modified polymer or hydrogenated product thereof.
The asphalt composition according to any one of 1. [Chemical 1] (In the above formula, R ^{1 to} R ⁴ are hydrogen, a hydrocarbon group having 1 to 24 carbon atoms, a hydroxyl group, an epoxy group, a silanol group,
A hydrocarbon group having 1 to 24 carbon atoms having a functional group selected from alkoxysilane groups. R ⁵ is a hydrocarbon chain having 1 to 48 carbon atoms, or 1 carbon atom having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group.
~ 48 hydrocarbon chains. In the hydrocarbon groups of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ , oxygen, in a bonding mode other than a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group,
Elements such as nitrogen and silicon may be bonded. R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms) 5. The asphalt composition for road pavement according to claim 1. 6. An asphalt composition for a roofing / waterproof sheet according to any one of claims 1 to 4. 7. An asphalt composition for a sealant according to claim 1.