JPH0726108A - Bituminous modifier - Google Patents

Abstract

PURPOSE:To obtain an improving material for bitume, composed of a hydrogenated block copolymer containing a vinyl aromatic compound and a conjugated diene, a mixture thereof with a nonopolar polymer, an ethylene-alpha-olefinic copolymer, etc., and capable of providing the bitumen good in thermal stability and durability. CONSTITUTION:This improving material for bitumen is obtained by blending a hydrogenated diene-based copolymer, composed of a block such as a vinyl aromatic compound polymer block, a conjugated diene polymer block, a vinyl aromatic compound-conjugated diene random copolymer block or a vinyl aromatic compound-conjugated diene tapered block in which the content of the vinyl aromatic compound is progressively increased at (5-60)/(95-40) weight ratio of the vinyl aromatic compound/conjugated diene and having >=80% hydrogenated double bond in the conjugated diene part and 50000-600000 number- average molecular weight, a mixture thereof with a nonpolar (co)polymer, an ethylene-3-20C olefin-nonconjugated diene-based copolymer and a butyl-based rubber, etc., as principal components with other components respectively. This improving material is capable of providing the bitumen excellent in thermal stability and durability.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has a high softening point when blended with bitumen such as asphalt and tar, and particularly when used in a bituminous composition for road paving, has a large grasping power (hereinafter referred to as "toughness" to an aggregate. )), Adhesive strength (hereinafter also referred to as “tenacity”), and excellent thermal stability and durability.

[0002]

2. Description of the Related Art Bitumen is widely used for road paving, roofing materials and the like. In recent years, in order to further improve the performance, polymer materials such as rubber and resin have been added to increase the softening point and further increase the gripping force and adhesive force to the aggregate. However, conventional rubbers and resins do not have sufficient performance as described above, and also have insufficient thermal stability and durability.

[0003]

The present invention has been made against the background of the above-mentioned problems of the prior art, and has a high softening point, a large gripping force and an adhesive force to an aggregate, and an excellent thermal stability. An object of the present invention is to provide a bituminous modifier that imparts durability and durability.

[0004]

The present invention provides the following (a)
1), (a-2), (i-3) and (i-4) at least one hydrogenated diene-based (co) polymer (i) selected from the group as a main component The present invention provides a bitumen modifier (hereinafter also referred to as "bituminum modifier (a)").

(A-1); (A)-(B) block copolymer, (A)-(B)-(C) block copolymer or (A)-(B)-(A) block copolymer Polymer [However,
(A) is a vinyl aromatic compound polymer block, (B) is a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene random copolymer block, (C) is a vinyl aromatic compound in which the vinyl aromatic compound is gradually increased. A conjugated diene tapered block, and these block copolymers may have a polymer molecular chain extended or branched via a coupling agent residue], and the vinyl aromatic compound / conjugated diene The ratio is 5 by weight
~ 60 / 95-40, with respect to all monomers constituting the block copolymer,
(A) The content of the vinyl aromatic compound in the block is 3
% By weight, the total vinyl aromatic compound bond content in the blocks (A) and (C) is 50% by weight or less, and the vinyl bond content in the conjugated diene moiety in the block (B) exceeds 30%. A hydrogenated diene-based copolymer having a number average molecular weight of 50,000 to 600,000 in which at least 80% of the double bonds in the conjugated diene moiety are saturated by hydrogenation of the polymer.

(A-2): Polymer block (D),
A block copolymer having one or more of each of (E) and (F) in the molecule (provided that (D) is a polymer block mainly composed of a vinyl aromatic compound containing 90% by weight or more of a vinyl aromatic compound, ( E) has a vinyl bond content of 30 to 70
% Of conjugated diene polymer block, (F) represents a polybutadiene polymer block having a vinyl bond content of less than 25%, and these block copolymers have a polymer molecular chain extended through a coupling agent residue or It may be branched], and the content of the polymer block (D) in the block copolymer is 5 to 50% by weight, and the polymer block (E) is
Content of the polymer block (F) is 30 to 80% by weight, and the content of the polymer block (F) is 5 to 50% by weight [(D) + (E) + (F)
= 100% by weight, the block copolymer is hydrogenated to at least 80% of the double bonds of the conjugated diene moiety.
Saturated hydrogenated diene-based copolymer having a number average molecular weight of 40,000 to 700,000.

(A-3); a block copolymer represented by (G)-(H)-(G) or (G)-(H) (where (G) has a vinyl bond content of 25% or less). And (H) is a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene copolymer block in which the vinyl bond content of the conjugated diene portion is 25 to 95%. Has been hydrogenated to give at least 80 double bonds in the conjugated diene moiety.
% Hydrogenated diene copolymer having a number average molecular weight of 50,000 to 600,000.

(A-4); the conjugated diene polymer is hydrogenated to give at least 80% of the double bonds in the conjugated diene moiety.
Hydrogenated diene-based polymer saturated with.

The present invention also relates to the above hydrogenated diene type (co).
Polymer (a) 5 to 99% by weight, and non-polar (co) polymer (b) 95 to 1% by weight (where (a) + (b) =
The present invention provides a bitumen modifier (hereinafter also referred to as “bitumen modifier (b)”) containing 100% by weight as a main component.

Further, according to the present invention, (a) ethylene is 20
To 90% by weight, (b) 10 to 80% by weight of an α-olefin having 3 to 20 carbon atoms, and (c) an unconjugated diene having an iodine value of 0 to 50, and a Mooney viscosity (ML _{1 + 4} ,
A bituminous modifier (hereinafter, also referred to as "bituminous modifier (ha)"), characterized in that it has an ethylene-α-olefin copolymer (ha) as a main component having a temperature of 100 ° C) of 5 to 350. It is provided.

Furthermore, the present invention is characterized in that butyl rubber (d) is the main component (also referred to as "bituminous modifier (d)" hereinafter, bituminous modifier (b)). To (d) are collectively referred to simply as "bituminous modifier").

The bituminous modifier of the present invention will be described below by dividing it into bitumen modifiers (A) to (D). Bituminous modifier (A) Bituminous modifier (A) is the above (A-1), (A-2),
The main component is at least one hydrogenated diene-based (co) polymer (a) selected from the groups (a-3) and (a-4). Here, the hydrogenated diene-based (co) polymer (i) will be further described by dividing it into (i-1) to (i-4).

(A-1) Hydrogenated diene-based copolymer;
1) The hydrogenated diene-based copolymer (hereinafter, also referred to as “(A-1) component”) includes (A) a vinyl aromatic compound polymer block (hereinafter, also referred to as “(A) block”) and (B). Conjugated diene polymer block or vinyl aromatic compound-conjugated diene random copolymer block (hereinafter also referred to as "(B) block"), and (C) vinyl aromatic compound-conjugated diene taper block in which vinyl aromatic compound gradually increases. (Hereinafter also referred to as “(C) block”) means (A) −
(B), (A)-(B)-(C), or (A)-
It is obtained by hydrogenating a block copolymer arranged as in (B)-(A).

The vinyl aromatic compound used to obtain the component (a-1) is styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenyl. styrene,
N, N-dimethyl-p-aminoethylstyrene, N, N
-Diethyl-p-aminoethyl styrene, vinyl pyridine, etc. are mentioned, and styrene and α-methyl styrene are particularly preferable. Further, as the conjugated diene used to obtain the component (a-1), 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3
-Pentadiene, 2-methyl-1,3-pentadiene,
1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like can be mentioned, but hydrogenated diene-based compounds which can be industrially used and have excellent physical properties. To obtain a copolymer, 1,3
-Butadiene, isoprene and 1,3-pentadiene are preferred, and 1,3-butadiene is more preferred.

In the hydrogenated block copolymer, the ratio of the vinyl aromatic compound and the conjugated diene constituting the same "vinyl aromatic compound / conjugated diene" is 5-60 / 95-40 by weight. , Preferably 7-50 / 93
It should be ˜50. If the bond content of the vinyl aromatic compound is less than 5% by weight, the mechanical properties of the component (A-1) are inferior, and if more than 60% by weight, it becomes resinous and the low temperature elongation of the bituminous composition is inferior. The problem arises.

Further, in the block copolymer to be hydrogenated, the content of the vinyl aromatic compound in the block (A) is 3% by weight or more, preferably at least 3% by weight based on all the monomers constituting the block copolymer. 5 to 15% by weight, and the total content of vinyl aromatic compounds in the (A) block and the (C) block is 50% by weight or less, preferably 5 to 4% with respect to all monomers constituting the block copolymer.
It is 0% by weight, more preferably 5 to 25% by weight.
(A) The content of the vinyl aromatic compound in the block is 3
If it is less than wt%, the mechanical properties of the component (A-1) will be poor.
When the total content of vinyl aromatic compounds in the blocks (A) and (C) exceeds 50% by weight,
Rubbery properties are lost, which is not preferable.

Further, in the block copolymer to be hydrogenated, it is necessary that the content of vinyl bond in the conjugated diene portion in the block (B) exceeds 30%, preferably 35% or more. When the vinyl bond content is 30% or less, the effect of improving flexibility is not sufficiently exhibited even when blended with the resin component.

The above (A)-(B) block copolymer, (A)-(B)-(C) block copolymer, or (A)-(B)-(A) block copolymer. Is represented by the following formulas through a coupling agent residue,
It may be a block copolymer in which the polymer molecular chain is extended or branched. [(A)-(B)] n-X [(A)-(B)-(C)] n-X [(A)-(B)-(A)] n-X (wherein n Is an integer of 2 to 4, and X represents a coupling agent residue.) Examples of the coupling agent at this time include diethyl adipate, divinylbenzene, tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, and butyltrichlorotin. , Dimethylchlorosilicon, tetrachlorogermanium, 1,2-dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4
-Benzene triisocyanate and the like.

The content of the (A) block, (B) block and (C) block in the block copolymer is usually 3 to 20% by weight of the (A) block, preferably 5 to 1%.
5% by weight, (B) block 33 to 95% by weight, preferably 48 to 93% by weight, (C) block 2 to 47% by weight,
Preferably 2 to 37% by weight (however, (A) + (B) +
(C) = 100% by weight]. Also, (A) to (C)
The number average molecular weight of the block is (A) block 5,000 to 150,000, (B) block 25,000 to 400,000, (C).
The number of blocks is preferably in the range of 10,000 to 150,000.

The hydrogenation of the above block copolymer saturates the double bond of the conjugated diene portion of the block copolymer to give a hydrogenated diene copolymer (a-1). ) Component is obtained. Here, the double bond of the conjugated diene moiety is 80% or more, preferably 90% or more.
% Or more, and more preferably 95 to 100% is required to be saturated, and if it is less than 80%, the thermal stability and durability of the bituminous composition will be poor. The number average molecular weight of the component (a-1) is 50,000 to 600,000, preferably 80,000 to 500,000, and if it is less than 50,000, the softening point of the bitumen composition does not become high,
On the other hand, if it exceeds 600,000, it will not be sufficiently dispersed and dissolved in bitumen,
The target bituminous composition of the present invention cannot be obtained. The component (A-1) used in the present invention is, for example, JP-A-3-725.
It can be obtained by the method disclosed in Japanese Patent No.

(A-2) Hydrogenated diene-based copolymer; (A-
2) The hydrogenated diene-based copolymer (hereinafter, also referred to as “(a-2) component”) is a polymer block (hereinafter, referred to as “D)” in which the vinyl aromatic compound is 90 wt% or more as a main component. "(D) block"), (E) vinyl bond content of 30-70% conjugated diene polymer block (hereinafter also referred to as "(E) block"), and (F) vinyl bond content of less than 25%. Is obtained by hydrogenating a block copolymer having one or more of the polybutadiene polymer block (hereinafter also referred to as “(F) block”) in the molecule.

Here, the vinyl aromatic compound and the conjugated diene used for obtaining the component (a-2) are as described in the above (a).
1) The same as that used to obtain the component.
The vinyl aromatic compound is 90% by weight in the block (D) constituting the block copolymer for obtaining the component (A-2).
It is a polymer block mainly composed of the above vinyl aromatic compound, and specifically, the vinyl aromatic compound 90-100.
It is a copolymer block of 10% to 0% by weight of conjugated diene. When the content of the vinyl aromatic compound in the block (D) is less than 90% by weight, the mechanical properties of the component (A-2) are inferior, which is not preferable. (D) Block content is 5 to 50
% By weight, preferably 10-45% by weight, 5% by weight
If it is less than 5, the mechanical properties of the component (A-2) are inferior, while 5
If it exceeds 0% by weight, rubbery properties are lost, which is not preferable.

The block (E) constituting the block copolymer for obtaining the component (a-2) is a conjugated diene polymer block having a vinyl bond content of 30 to 70%, preferably 40 to 70%. is there. When the vinyl bond content is less than 30%, polyethylene chains are formed when hydrogenated and the rubber-like property is lost. On the other hand, when it exceeds 70%, the glass transition temperature becomes high and the rubber-like property is increased when hydrogenated. It is lost and not desirable. Further, the content of the (E) block in the component (A-2) is 30 to 80% by weight, preferably 35 to 70%.
If it is less than 30% by weight, rubbery properties are lost, while if it exceeds 80% by weight, mechanical properties are lost, which is not preferable.

Further, the (F) block constituting the block copolymer for obtaining the (A-2) component is a polybutadiene polymer block having a vinyl bond content of less than 25%, preferably 3 to 20. When the vinyl bond content is 25% or more, the resinous property is lost when hydrogenated and the property of the thermoplastic elastomer as the block copolymer is lost. The content of the (F) block in the block copolymer is 5 to 50% by weight, preferably 5 to 30% by weight.
Is. (F) When the block content is less than 5% by weight,
The mechanical properties of the component (a-2) are inferior. On the other hand, when it exceeds 50% by weight, rubber properties are lost, which is not preferable.

The number average molecular weights of the blocks (D) to (F) are 10,000 to 300,000 for the (D) block, 30,000 to 300,000 for the (E) block, and 5,000 for the (F) block. The range of up to 300,000 is preferable.

Further, the block copolymer constituting the component (a-2) is a polymer having at least one of polymer blocks (D), (E) or (F) via a coupling agent residue. It may be a block copolymer which is bonded to a polymer unit composed of a block and has a polymer molecular chain extended or branched as represented by the following formulas (1) to (4). [(D)-(E)-(F)] n-X [(D)-(E)-(F)] X [(D)-(E)] [-in formula, n is 2-4. An integer, X represents a coupling agent residue, and the coupling agent used is also (a-1).
It is similar to that used in the ingredients. ]

The hydrogenation of the above block copolymer saturates the double bond of the conjugated diene portion of the block copolymer to give a hydrogenated diene copolymer (a-2). ) Component is obtained. Here, the double bond of the conjugated diene needs to be 80% or more saturated, preferably 90% or more, and more preferably 95 to 100%. If the double bond saturation of the conjugated diene moiety is less than 80%, the thermal stability and durability of the bituminous composition will be poor.

The number average molecular weight of the component (a-2) is 40,000 to
It is 700,000, preferably 50,000 to 500,000. When it is less than 40,000, the softening point of the bitumen composition is not high. On the other hand, when it is more than 700,000, it is not sufficiently dispersed and dissolved in the bitumen. A bituminous composition that can be obtained cannot be obtained. The component (a-2) can be obtained, for example, by the method disclosed in JP-A-2-133406.

(A-3) Hydrogenated diene-based copolymer; (A-
3) The hydrogenated diene-based copolymer (hereinafter, also referred to as “(a-3) component”) has (G) a vinyl bond content of 2 and a vinyl bond content of 2).
5% or less of a polybutadiene polymer block (hereinafter, also referred to as “(G) block”) and (H) a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene copolymer block, which comprises a conjugated diene moiety A polymer block having a vinyl bond content of 25 to 95% (hereinafter also referred to as “(H) block”) is (G)-(H)-
It is obtained by hydrogenating a linear or branched block copolymer arranged as in (G) or (G)-(H).

Here, as the vinyl aromatic compound and the conjugated diene used to obtain the component (a-3),
The compound illustrated as what is used for obtaining said (a-1) component can be mentioned. The (G) block in the component (A-3) becomes a crystalline block having a structure similar to that of ordinary low density polyethylene (LDPE) by hydrogenation. The vinyl bond content in the block (G) is 25% or less, preferably 20% or less, more preferably 15% or less.
3) The mechanical properties of the component are inferior, which is not preferable.

Further, the block (H) is a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene copolymer block, and a rubber-like ethylene-butene copolymer block or a vinyl aromatic compound-is obtained by hydrogenation. It becomes a polymer block showing a structure similar to that of the ethylene-butene copolymer. In the (H) block, the vinyl bond content of the conjugated diene portion is 25 to 95%, preferably 25 to 75%, more preferably 25 to 55%.
If the vinyl bond content is less than 25%, the rubber properties are lost, while if it exceeds 95%, the mechanical properties are inferior, which is not preferable.

The amount of the vinyl aromatic compound used in the (H) block is 35% by weight or less, preferably 30% by weight or less, and more preferably 25% by weight of the monomers constituting the (H) block. % Or less, and if it exceeds 35% by weight, the glass transition temperature of the (H) block rises and the rubber-like property is lost, which is not preferable. The vinyl bond content of the butadiene portion of the (H) block is 25 to 95%, preferably 25 to 75%, more preferably 25 to 55%.
When it is less than 25% or more than 95%, after hydrogenation, a polyethylene chain and a polybutene-1 chain-derived crystal structure are exhibited, respectively, and a resin-like property is obtained, and the mechanical properties of the component (A-3) are It is inferior and not preferable.

The number average molecular weight of the (G) block and the (H) block is usually 5,000 or more, preferably 10,000 or more, and more preferably 15,000 or more. In the block copolymer for obtaining the component (a-3), the proportion of the (G) block and the (H) block is usually 5 to 90% by weight, preferably 10 to 10% by weight.
85% by weight, (H) block 95 to 10% by weight, preferably 90 to 15% by weight [(G) + (H) = 10
0% by weight]. (G) Block is less than 5% by weight,
When the content of the (H) block exceeds 95% by weight, the crystalline polymer block is insufficient and the mechanical properties of the component (A-3) are inferior, which is not preferable. Also, the (G) block is 9
When the content of the (H) block is more than 0% by weight and the amount of the (H) block is less than 10% by weight, the hardness of the component (A-3) increases, which is not preferable.

The block copolymer for obtaining the component (A-3) is a block copolymer composed of at least one polymer block of the (G) block and the (H) block via the coupling agent residue. It may be a block copolymer which is bonded to a united unit and whose polymer molecular chain is extended or branched, for example, as represented by the following formulas. [(G)-(H)] n-X [(G)-(H)-(G)] n-X (In the formulas, n and X are the same as above) Further, the coupling agent is also the above ( (A) The same compounds as those used for the component (1) can be mentioned.

By hydrogenating the above block copolymer, the double bond of the conjugated diene portion of the block copolymer is saturated to give a hydrogenated diene copolymer (a-3). ) Component is obtained. Here, the double bond of the conjugated diene needs to be 80% or more saturated, preferably 90% or more, and more preferably 95 to 100%. If the double bond saturation of the conjugated diene moiety is less than 80%, the thermal stability and durability of the bituminous composition will be poor. The number average molecular weight of the component (a-3) is 50,000 to 60.
The softening point of the resulting bitumen composition is not high when it is less than 50,000, while when it exceeds 600,000, it is not sufficiently dispersed and dissolved in the bitumen, and the object of the present invention is to A bituminous composition that can be obtained cannot be obtained. The component (a-3) can be obtained, for example, by the method disclosed in JP-A-3-12895976.

(A-4) Hydrogenated diene polymer; (A-
4) The hydrogenated diene-based polymer (hereinafter, also referred to as “(a-4) component”) is obtained by polymerizing at least one selected from the conjugated dienes, and hydrogenating a polymer of the conjugated diene homopolymer. Obtained. Here, as the conjugated diene, (a-1)
Examples of the component include the compounds, preferably 1,3-
Butadiene and isoprene.

Here, the double bond of the conjugated diene is 8
It is necessary to be 0% or more saturated, preferably 90% or more, and more preferably 95 to 100%.
If the double bond saturation of the conjugated diene moiety is less than 80%,
The bituminous composition is inferior in thermal stability and durability. The number average molecular weight of the component (a-4) is 10,000 to 1,200,000, preferably 30,000 to
If it is less than 10,000, the softening point of the obtained bituminous composition will not be high, while if it exceeds 1 million, it will not be sufficiently dispersed and dissolved in the bitumen, and the bituminous composition aimed at by the present invention will be obtained. Absent. The component (A-3) is, for example, JP-A-3-744.
It can be obtained by the method disclosed in Japanese Patent Publication No. 09.

In the present invention, the object of the present invention is achieved by using the above-mentioned specific hydrogenated diene (co) polymer (a) as a bitumen modifier. Preferred hydrogenated diene-based (co) polymers (i) are (i-1), (i-2) and (i-3), whereby the effects of the present invention which are far superior can be obtained.

Bitumen modifier (b) Bituminous modifier (b) is a non-polar (co) polymer (b) (hereinafter referred to as "(b )
(Also referred to as “component”), it is possible to further impart the peculiar effect of each of the nonpolar (co) polymer (b) to the resulting bituminous composition.

Here, the non-polar (co) polymer (b) is
Polymers obtained by polymerizing without using polar monomers such as vinyl cyanide compounds, acrylic acid, and (meth) acrylic acid esters, such as polyethylene, high molecular weight polyethylene, high density polyethylene, and medium density polyethylene. , Low density polyethylene, LLDPE (linear low density polyethylene), polybutene, polyisobutylene, polypropylene, polystyrene, HIPS (high impact polystyrene), polymethylstyrene, ethylene-α
-Olefin (diene) copolymers, polybutadiene, polyisoprene, styrene-butadiene copolymers and the like can be mentioned, and olefin (co) polymers such as polypropylene and polyethylene are preferable. When the component (b) is an olefin (co) polymer, its melt flow index is usually 0.05 to 100 g / 10.
Min (230 ° C, 2.16 kg load), preferably 0.1
~ 80 g / 10 minutes.

The blending ratio of the above component (a) / component (b) is 5 to 99% by weight of the component (a), preferably 20 to 8%.
0 wt%, (b) component 95 to 1 wt%, preferably 8
0 to 20% by weight (however, (a) + (b) = 100% by weight). If the content of the component (b) is less than 1% by weight, the effect of adding the component (b) cannot be obtained, while if it exceeds 95% by weight, the performance of the component (a) cannot be exhibited.

Bitumen modifier (c) By using the ethylene-α-olefin copolymer (c) (hereinafter also referred to as "(c) component") as a bitumen modifier, the object of the present invention is achieved. To be done. The content of (a) ethylene constituting the component (c) is 20 to 90% by weight,
It is preferably from 30 to 80% by weight, and when it is less than 20% by weight, it is not sufficiently dispersed and dissolved in bitumen, while when it exceeds 90% by weight, a bituminous composition having a high softening point cannot be obtained. Further, the carbon number of the (b) α-olefin constituting the component (C) is 3 to 20, and preferable α-olefins are propylene and butene-1. The content of (b) α-olefin is 10 to 80% by weight, preferably 15 to 7%.
It is 5% by weight, and if it is less than 10% by weight, rubber properties are lost, while if it exceeds 80% by weight, mechanical properties are inferior, which is not preferable. Further, the content of the non-conjugated diene (c) constituting the component (c) is 0 to 50, preferably 0 to 3 in terms of iodine value.
0, and more preferably 0 to 20, and when the iodine value exceeds 50, the thermal stability of the resulting bituminous composition,
Inferior in durability. Examples of the type of the non-conjugated diene (c) include 2-ethylidene-5-norbornene and dicyclopentadiene.

The Mooney viscosity (ML) of the component (C) is
_{1 + 4} , 100 ° C.) is 5 to 350, preferably 20 to 3
For those having a Mooney viscosity of more than 100, the bitumen composition intended by the present invention can be easily obtained by premixing bitumen, oil and / or a plasticizer. If the Mooney viscosity is less than 5,
A high softening point cannot be obtained. On the other hand, when it exceeds 350, it is not sufficiently dispersed / dissolved in bitumen, and the bitumen composition intended by the present invention cannot be obtained. The component (c) may be a copolymer in which the terminal group is modified with maleic anhydride or the like. Further, as a method for obtaining the component (c), a general solution polymerization method or the like is used.

The object of the present invention is achieved by using the bitumen modifier (d) butyl rubber (d) (hereinafter also referred to as "(d) component") as a bitumen modifier. As the component (d), the degree of unsaturation (isoprene mol content%) is 0.2 to 5%, preferably 0.4.
~ 3% can be used. If the degree of unsaturation is less than 0.2%, the mechanical properties will be poor, whereas if it exceeds 5%, the resulting bitumen composition will be poor in thermal stability and durability. As the component (d), halogenated butyl rubber such as chlorinated butyl rubber and brominated butyl rubber may be used. The number average molecular weight of the component (d) is usually 200,000 to 80.
10,000, preferably 400,000 to 600,000. Examples of the method for obtaining the component (d) include a general solution polymerization method.

The bitumen modifier of the present invention can be made into various shapes such as latex, powder, pellets, bales and crumbs in view of solubility and dispersibility in bitumen.
Generally, the bitumen modifiers (a), (b) and (c) are powders, pellets and re-emulsified latex, and the bitumen modifier (d) is a blend of bales, re-emulsified latex and other polymers. Can be used in the form of pellets, etc.

Preparation of Bituminous Composition The bitumen modifiers (A) to (D) of the present invention are mixed with bitumen to be used as a bitumen composition. The bitumen is not particularly limited, and any asphalt such as natural asphalt, petroleum asphalt, or a mixture thereof can be used. Among these, examples of natural asphalt include Gilsonite, grahamite, Trinidat lake asphalt, and the like. Also,
As petroleum asphalt, for example, various penetration grade straight asphalt obtained by distillation of crude oil,
Produces when separating asphalt with a solvent such as propane or n-butane from blown asphalt or semi-blown asphalt produced by blowing air into the presence or absence of a catalyst for straight asphalt and a fraction containing asphalt. Examples include solvent deasphalting asphalt. These petroleum asphalts are
It is also possible to use a mixture of two or more kinds.

In the present invention, the most preferred bitumen is straight asphalt, and the penetration degree at 25 ° C. is 40 to 1 in particular.
Those in the range of 50, preferably 60 to 120 are preferable. The addition amount of the bitumen modifier of the present invention is usually 1 part by weight or more, preferably 2 to 100 parts by weight with respect to 100 parts by weight of bitumen.
Parts by weight. In addition, an inorganic filler such as calcium carbonate, talc, and clay, and other reinforcing agents and softening agents can be added to the bituminous composition obtained by the present invention, if necessary.

The method for producing a bituminous composition using the bituminous modifier of the present invention is not particularly limited, but the following method is adopted. For example, by heating and mixing the bitumen modifier of the present invention with bitumen melted at 140 to 160 ° C.,
Make a uniform bituminous composition. The road paving material, which is the main application of the bitumen modifier of the present invention, is prepared by heating and mixing the above bitumen composition and aggregate at 160 to 180 ° C to prepare an asphalt mixture. Furthermore, the aggregate, asphalt, and the bituminous modifier of the present invention are simultaneously heated at 160 to 190 ° C.
The asphalt mixture may be mixed and prepared all at once.

Examples of the usage form of the bituminous composition using the bituminous modifier of the present invention include a heated bituminous composition (high temperature application), an emulsified bituminous composition (normal temperature application) and a solvent-containing bituminous composition (normal temperature application). However, the bitumen modifier of the present invention is not particularly limited.

[0050]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, parts and% are based on weight unless otherwise specified. In addition, various evaluations in the examples are obtained as follows. Polymer bond
Tylene content and vinyl bond content were measured by infrared absorption method. The number average molecular weight of the polymer was measured by gel permeation chromatography (GPC) in terms of polystyrene.

Hydrogenation rate of polymer Using ethylene tetrachloride as a solvent, 100 MHz, ¹ H--N
It was calculated from the MR spectrum. The ethylene content of the polymer, the propylene content, and the iodine value were measured by the infrared absorption method. Mooney viscosity of polymer (ML _{1 + 4} , 100 ° C.) Measured according to JIS K6300. Dispersion and solubility in bitumen Visually evaluated. ○: Good △: Somewhat bad ×: Poor

Thermal stability of bituminous composition A bituminous composition containing a bituminous modifier was melted at 180 ° C. for 2 hours and then cooled to room temperature, which was repeated 5 times, and the state was visually observed. ○: No change ×: Gelation of polymer or separation of polymer and bitumen Measured according to “Pavement Test Method Handbook” (published by Japan Road Association, November 1988) .

Examples 1 to 5 and Comparative Examples 1 to 12 [Preparation of bituminous composition using bituminous modifier (a)] Straight asphalt having a penetration of 60 to 80 (manufactured by Nippon Oil Co., Ltd., 60 / 80] in Table 1 [bituminous composition using hydrogenated diene copolymer (a-1)] and Table 2 [bituminous composition using hydrogenated diene copolymer (a-2)] ] [Table 3 [[bituminous composition using hydrogenated diene copolymer (a-3)]], Table 4 [[bitumen composition using hydrogenated diene polymer (a-4)] A bituminous composition was obtained by stirring at 400 to 500 rpm with a stirrer (agitating amount of four blades) according to the formulation and conditions. The polymer was added by cutting it into about 5 mm square. The results are shown in Tables 1 to 4.

Examples 1 to 5 are examples in which the bitumen modifier (a) within the scope of the present invention was used. The softening point of the bitumen composition was improved, and the heat resistance, durability, toughness and tenacity were further improved. Is excellent. On the other hand, Comparative Example 1 is an example in which the hydrogenation rate of the polymer is less than the range of the present invention, and the thermal stability and durability of the bituminous composition are poor. Comparative Example 2 is an example in which the number average molecular weight of the polymer is less than the range of the present invention, and the bituminous composition is inferior in thermal stability, durability, toughness and tenacity. Comparative Example 3 is an example in which the number average molecular weight of the polymer exceeds the range of the present invention, and the dispersion / solubility in bitumen is poor.

Comparative Example 4 is an example in which the hydrogenation rate of the polymer is less than the range of the present invention, and the bitumen composition is inferior in thermal stability and durability. Comparative Example 5 is an example in which the number average molecular weight of the polymer is less than the range of the present invention, and the thermal stability, durability, toughness and tenacity of the bituminous composition are inferior. Comparative Example 6 is an example in which the number average molecular weight of the polymer exceeds the range of the present invention, and the dispersion / solubility in bitumen is poor.

Comparative Example 7 is an example in which the vinyl bond content of the (E) block is outside the range of the present invention, and the toughness and tenacity of the bituminous composition are inferior. In Comparative Example 8, the content of the (E) block and the (F) block is out of the range of the present invention, and the toughness and tenacity of the bituminous composition are inferior.

Comparative Example 9 is an example in which the hydrogenation rate of the polymer is less than the range of the present invention, and the bitumen composition is inferior in thermal stability and durability. Comparative Example 10 is an example in which the number average molecular weight of the polymer is less than the range of the present invention, and the thermal stability, durability, toughness and tenacity of the bituminous composition are poor. Comparative Example 11 is an example in which the number average molecular weight of the polymer exceeds the range of the present invention,
Poor dispersion / solubility in bitumen. Comparative Example 12 is an example in which the hydrogenation rate of the polymer is less than the range of the present invention, and the bitumen composition is inferior in thermal stability and durability.

Example 6, Comparative Example 13 [bituminous modifier (b)
Preparation of bituminous composition using the above] Example 1 except that the formulation and conditions shown in Table 5 were followed.
A bituminous composition was obtained in the same manner as in. The results are shown in Table 5. Example 6 is within the scope of the present invention, and the bitumen composition has excellent thermal stability and durability. On the other hand, Comparative Example 13 is an example in which a polymer outside the range of the present invention is blended, and the dispersion / solubility in bitumen is poor, and the thermal stability and durability of the bitumen composition are poor.

Examples 7 to 8 and Comparative Examples 14 to 15 [Preparation of bitumen composition using bituminous modifier (c)] Example 1 except that the formulation and conditions shown in Table 6 were followed.
A bituminous composition was obtained in the same manner as in. The results are shown in Table 6. Examples 7 to 8 are within the scope of the present invention, improve the softening point of the bitumen composition, and are excellent in thermal stability, durability, toughness and tenacity. On the other hand, Comparative Example 1
No. 4 is an example in which the ethylene content of the polymer is less than the range of the present invention, and the dispersion / solubility in bitumen is poor. Comparative Example 15 is an example in which the iodine value of the polymer exceeds the range of the present invention, and the thermal stability and durability of the bituminous composition are poor.

Example 9 [Preparation of bitumen composition using bitumen modifier (d)] Example 1 except that the formulation and conditions shown in Table 7 were followed.
A bituminous composition was obtained in the same manner as in. The results are shown in Table 7. Example 9 is within the scope of the present invention, and the bitumen composition has excellent thermal stability and durability.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

[Table 4]

[0065]

[Table 5]

* 1) Non-polar polymer [Mitsubishi Petrochemical Co., Ltd.
YF-30] * 2) Polar copolymer [N21, manufactured by Nippon Synthetic Rubber Co., Ltd.]
0S]

[0067]

[Table 6]

[0068]

[Table 7]

* 3) Butyl manufactured by Nippon Synthetic Rubber Co., Ltd.
065

The bituminous modifier of the present invention has excellent thermal stability and durability, and can be used in various applications such as road paving, waterproofing, roofing, various coating materials and bonding materials. it can. Especially for road pavement, it has excellent thermal stability and durability, improves the softening point of bitumen, and has a large gripping force (toughness) and adhesive force (tenacity) against aggregates, making it an extremely useful bitumen. It is a modifier.

Front Page Continuation (72) Inventor Akio Hiraharu 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (4)

[Claims] 1. (a) The following (a-1), (a-2),
A bitumen modifier comprising at least one hydrogenated diene-based (co) polymer (a) selected from the groups (a-3) and (a-4) as a main component. (A-1); (A)-(B) block copolymer, (A)
-(B)-(C) block copolymer or (A)-
(B)-(A) block copolymer [where (A) is a vinyl aromatic compound polymer block, (B) is a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene random copolymer block, ( C) shows a vinyl aromatic compound-conjugated diene taper block in which the vinyl aromatic compound is gradually increased, and these block copolymers have a polymer molecular chain extended or branched via a coupling agent residue. Good] and the ratio of vinyl aromatic compound / conjugated diene is 5 by weight.
~ 60 / 95-40, with respect to all monomers constituting the block copolymer,
(A) The content of the vinyl aromatic compound in the block is 3
% By weight, the total vinyl aromatic compound bond content in the blocks (A) and (C) is 50% by weight or less, and the vinyl bond content in the conjugated diene moiety in the block (B) exceeds 30%. A hydrogenated diene-based copolymer having a number average molecular weight of 50,000 to 600,000 in which at least 80% of the double bonds in the conjugated diene moiety are saturated by hydrogenation of the polymer. (A-2): A block copolymer having at least one polymer block (D), (E) and (F) in the molecule [provided that (D) has a vinyl aromatic compound content of 90% by weight or more. A polymer block mainly composed of a vinyl aromatic compound, (E) a conjugated diene polymer block having a vinyl bond content of 30 to 70%, (F) a polybutadiene polymer block having a vinyl bond content of less than 25%, These block copolymers, the polymer molecular chain may be extended or branched via a coupling agent residue],
The content of the polymer block (D) in the block copolymer is 5
˜50 wt%, polymer block (E) content 30˜8
0% by weight, the content of the polymer block (F) is 5 to 50% by weight [(D) + (E) + (F) = 100% by weight]
The hydrogenated diene-based copolymer having a number average molecular weight of 40,000 to 700,000, in which the block copolymer is hydrogenated and at least 80% of the double bonds in the conjugated diene moiety are saturated. (A-3); (G)-(H)-(G) or (G)-
A block copolymer represented by (H) [where (G) is a polybutadiene polymer block having a vinyl bond content of 25% or less, and (H) is a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene copolymer). A polymer block having a vinyl bond content of the conjugated diene portion of 25 to 95.
Hydrogenated diene-based copolymer having a number average molecular weight of 50,000 to 600,000, which is hydrogenated to saturate at least 80% of the double bonds in the conjugated diene moiety. (A-4): A hydrogenated diene polymer in which at least 80% of the double bonds in the conjugated diene moiety are saturated by hydrogenation of the conjugated diene polymer. 2. The hydrogenated diene (co) polymer (a) of 5 to 99% by weight and the nonpolar (co) polymer (b) of 95 to 1% by weight according to claim 1, wherein ) + (B) = 10
0% by weight] as a main component. 3. (a) 20 to 90% by weight of ethylene,
(B) 10 to 80% by weight of α-olefin having 3 to 20 carbon atoms, (c) 0 to 50 of non-conjugated diene having an iodine value, and a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 5
To 350, an ethylene-α-olefin copolymer (C) as a main component, a bituminous modifier. 4. A bituminous modifier comprising butyl rubber (d) as a main component.