JPH08311299A - Bitumen modifier and bitumen composition - Google Patents

Abstract

PURPOSE: To obtain a bitumen modifier which can give a bitumen composition excellent in bitumen solubility and binder properties and improved in low-temp. properties and storage stability by using a specific block copolymer and a specific oil-soluble polyester as active ingredients. CONSTITUTION: 100 pts.wt. block copolymer which has at least one polymer block (A) consisting mainly of vinylaromatic hydrocarbon units (a) and at least one polymer block (B) consisting mainly of conjugated diene units (b) and in which the contents of the units (a) and the units (b) are 5-95wt.% and 95-5wt.%, respectively, is compounded as an active ingredient with 1-200 pts.wt. oil-soluble polyester, as another active ingredient, obtained by condensation-polymerizing at least one higher carboxylic acid comprising at least 50wt.% 10C or higher dicarboxylic acid with at least one polyhydric alcohol comprising 60-100wt.% dihydric alcohol to obtain a bitumen modifier. This modifier is incorporated into bitumen to obtain a bitumen composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a bituminous modifier and a bituminous composition, and more specifically, it has excellent solubility in bitumen, excellent binder properties such as toughness and tenacity, and low temperature characteristics and storage stability. The present invention relates to a bituminous modifier capable of giving an excellent bituminous composition, and to such a bituminous composition.

[0002]

2. Description of the Related Art In recent years, the need for drainage pavement has become stronger from the viewpoint of noise and safety during vehicle running, but the open-grain size asphalt mixture used for these pavements is Since there is little biting and adhesion area between the aggregates, it is required to blend a binder having a higher gripping force between the aggregates than in the case of the dense-grained asphalt mixture.

In response to these requirements, bitumen and styrene-
A technique of adding a butadiene block copolymer and a petroleum resin for improvement is disclosed (JP-A-6-107953). However, this method improves the binder properties such as toughness and tenacity of bitumen. In particular, it has a drawback that properties such as storage stability and low temperature properties are deteriorated.

Further, JP-A-62-205150 discloses a method of adding a styrene-butadiene block copolymer and an aromatic process oil to bitumen, but this method improves the low temperature characteristics. However, there is a problem that the binder properties such as toughness and tenacity and the storage stability are impaired.

[0005]

An object of the present invention is to provide a bituminous composition having excellent solubility in bitumen, excellent toughness and tenacity, and improved low temperature characteristics and storage stability. An object of the present invention is to provide a bitumen modifier which can be obtained, and a bitumen composition containing the bitumen modifier.

The present inventors have conducted extensive studies to overcome the above-mentioned problems of the prior art, and as a result, have obtained a block copolymer obtained by polymerizing a vinyl aromatic compound and a conjugated diene, and a polyvalent higher carboxylic acid. A modifier containing an oil-soluble polyester obtained by polycondensation of an acid and a polyhydric alcohol as an active ingredient, has excellent solubility in bitumen, and,
Excellent binder properties such as toughness and tenacity,
It has also been found to provide a bituminous composition having excellent low-temperature properties and storage stability. The present invention has been completed based on these findings.

[0007]

Thus, according to the present invention, at least one polymer block (A) mainly composed of vinyl aromatic hydrocarbon and a polymer block (B) mainly composed of conjugated diene are provided. A block copolymer containing at least one and having a vinyl aromatic hydrocarbon content of 5 to 95% by weight and a conjugated diene content of 95 to 5% by weight,
Provided is a bituminous modifier containing an oil-soluble polyester obtained by polycondensing a polyvalent higher carboxylic acid and a polyhydric alcohol as an active ingredient. Further, according to the present invention, there is provided a bitumen and a bituminous composition containing the bitumen modifier.

The present invention will be described in detail below. Block Copolymer The block copolymer used in the present invention is a polymer having a conjugated diene as a main component and at least one polymer block (A) having a vinyl aromatic hydrocarbon as a main component and preferably 2 or more. It is a block copolymer having at least one block (B). The polymer block (A) mainly composed of vinyl aromatic hydrocarbon means that vinyl aromatic hydrocarbon is 50
% By weight, preferably 60 to 100% by weight, more preferably 70 to 100% by weight, still more preferably 80% by weight.
The polymer block is contained in a proportion of ˜100% by weight, and is a vinyl aromatic hydrocarbon homopolymer or a polymer block composed of a vinyl aromatic hydrocarbon and a conjugated diene. The distribution of the conjugated diene in the polymer block (A) is
It may be random, tapered, partially block-shaped, or a combination thereof. The polymer block (B) containing a conjugated diene as a main component means that the conjugated diene is more than 50% by weight, preferably 60 to 100% by weight, more preferably 70 to 100% by weight, further preferably 80 to 1%.
It is a polymer block contained at a ratio of 00% by weight, and is a homopolymer of a conjugated diene or a polymer block composed of a conjugated diene and a vinyl aromatic hydrocarbon. The distribution of the vinyl aromatic hydrocarbon in the polymer block (B) may be random, tapered, partially block-shaped, or a combination thereof.

The block copolymer used in the present invention may have either a linear structure or a branched structure, and preferably has a structure represented by the following general formulas (a) to (e). (A) (B-A) m (b) (B-A) m-B (c) (A-B) n-A (d) (A-B) p-X (e) (B-A) p-X In these general formulas, A is a polymer block (A) mainly containing a vinyl aromatic hydrocarbon, and B is a polymer block (B) mainly containing a conjugated diene. X is the residue of the coupling agent. m and n are each an integer of 1 or more, preferably m is an integer of 2 or more, and n is 1. p is an integer of 2-6.

The composition ratio of the vinyl aromatic hydrocarbon and the conjugated diene in the block copolymer used in the present invention is 5:95 to 95: 5 by weight, preferably 10:90 to.
70:30, more preferably 15:85 to 50:50. If the vinyl aromatic hydrocarbon content is too low, the toughness, tenacity, etc. are not sufficient, and conversely,
If the amount is too large, the low-temperature characteristics will be insufficient, and neither is preferable.

The amount of vinyl bond in the conjugated diene moiety of the block copolymer of the present invention is not particularly limited, but is usually 90.
% Or less, preferably 1 to 60%, more preferably 5 to
It is in the range of 30%. If the vinyl bond content is excessively large, the penetration of the bitumen composition may decrease.

The molecular weight of the block copolymer used in the present invention is not particularly limited, but the solubility in bitumen and the binder properties such as penetration, toughness, tenacity and low temperature properties are highly balanced. Therefore, the polystyrene-converted weight average molecular weight measured by GPC is 1
The range of 10,000 to 1,000,000 is preferable, and 2
The range of 50,000 to 800,000 is more preferable, and 5
The range of 50,000 to 500,000 is the most preferable.

The block copolymer used in the present invention can be prepared by a known method, for example, in JP-B-36-19286, JP-B-43-17979, and JP-B-45-31.
In accordance with the method described in Japanese Patent Publication No. 951 and Japanese Patent Publication No. S46-32415, etc., it is produced by polymerizing a vinyl aromatic hydrocarbon and a conjugated diene using an organic lithium compound as an initiator in a hydrocarbon solvent. You can At the time of polymerization, a polar compound can be used for the purpose of adjusting the reactivity ratio of vinyl aromatic hydrocarbon and conjugated diene, changing the microstructure of the polymerized conjugated diene portion, adjusting the polymerization rate, and the like.

Examples of vinyl aromatic hydrocarbons include:
Styrene, α-methylstyrene, o-methylstyrene,
p-methylstyrene, pt-butylstyrene, 1,3
-Dimethylstyrene, vinyltoluene, vinylnaphthalene, vinylanthracene and the like. Of these, styrene is particularly preferable. The vinyl aromatic hydrocarbons may be used alone or in combination of two or more.

As the conjugated diene, for example, 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3
-Dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like. Among these, 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is particularly preferable. The conjugated dienes can be used alone or in combination of two or more.

The hydrocarbon solvent used for producing the block copolymer includes, for example, butane, pentane, hexane, isopentane, heptane, octane, isooctane and other aliphatic hydrocarbons; cyclopentane, methylcyclopentane, cyclohexane, Methylcyclohexane,
Alicyclic hydrocarbons such as ethylcyclohexane; aromatic hydrocarbons such as benzene, ethylbenzene, xylene and the like can be used, and these can be used alone or in admixture of two or more. The amount of hydrocarbon solvent used is
Usually, it is used so that the monomer concentration is 1% by weight to 50% by weight.

Examples of polar compounds include ethers such as tetrahydrofuran, diethyl ether, anisole, dimethoxybenzene, and ethylene glycol dimethyl ether; amines such as triethylamine, tetramethylenediamine, N-dimethylaniline, and pyridine; thioethers, Examples include phosphines, phosphoramides, alkylbenzene sulfonic acids, and alkoxides such as potassium and sodium, which are appropriately selected according to the required performance. The amount of the polar compound used is appropriately determined according to the type of compound and the required properties,
Usually, 0.001 to 1 mol of the organic lithium compound
It is in the range of 1 molar amount, preferably 0.01 to 0.5 molar amount.

As the organic lithium compound, an organic monolithium compound, an organic dilithium compound, etc. are used.
Specific examples thereof include n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-hexyl lithium, iso-hexyl lithium, phenyl lithium, naphthyl lithium, hexamethylene dilithium,
Examples include butadienyldilithium and isoprenyldilithium. Generally, organic monolithium compounds are used, and these are used alone or in combination of two or more kinds. The amount used is appropriately selected depending on the molecular weight of the target polymer and the type of the organolithium compound, but is usually 0.0 per 1 mol of the organolithium compound.
It is in the range of 01 to 1 mol, preferably 0.01 to 0.5 mol.

The polymerization reaction may be an isothermal reaction or an adiabatic reaction, and is usually 0 to 150 ° C., preferably 20 to 12
It is carried out in the polymerization temperature range of 0 ° C.

As the block copolymer, a block copolymer produced by adding a coupling agent after the above polymerization reaction can also be used. The coupling agent is not particularly limited as long as it is usually used in anionic polymerization using an organolithium compound as an initiator, and examples thereof include tin tetrachloride, tin dichloride, tin tetrabromide, silicon tetrachloride and tetrachloride. Silicon bromide, silicon tetraiodide, germanium tetrachloride, lead dichloride, methyltrichlorosilane, dimethyldichlorosilane, butyltrichlorosilane, dibutyldichlorotin,
Bistrichlorosilylethane, bistrichlorostannylethane, tetramethoxysilicon, tetramethoxytin,
Metal compounds such as tetraethoxysilicon, tetraethoxytin, tetrabutoxysilicon and tetrabutoxytin;
Unsaturated nitriles such as ethyl acrylonitrile; dihalogenated hydrocarbons such as dibromobenzene, dichlorobenzene, dibromoethylene; dimethyl adipate, diethyl adipate, ethyl benzoate, dimethyl terephthalate, diethyl terephthalate, dimethyl phthalate, isophthalate Carboxylic acid esters such as acid dimethyl; carboxylic acid halides such as terephthalic acid dichloride, phthalic acid dichloride, isophthalic acid dichloride, adipic acid dichloride; carbon tetrachloride and the like.

These coupling agents may be used alone or in admixture of two or more, and the amount thereof is usually 0.25 to 2 equivalents, preferably 0.30 to the organic lithium compound. The range is 1.5 equivalents, and more preferably 0.35 to 1 equivalents. The coupling reaction is usually performed at 0 to 150 ° C. for 0.1 to 20 hours.

As the block copolymer, it is possible to use a block copolymer produced by adding a modifier after the polymerization reaction. As the modifier, for example, Japanese Patent Publication No. 62-6
Unsaturated carboxylic acids such as maleic anhydride disclosed in Japanese Patent No. 1615, and imino compounds, cyanamide compounds, aziridinyl compounds, amide compounds and the like disclosed in Japanese Patent Publication No. 4-387770.

Polyester The polyvalent higher carboxylic acid used in the synthesis of the oil-soluble polyester of the present invention is a carboxylic acid having 10 or more carbon atoms, preferably 15 or more carbon atoms, more preferably 20 or more carbon atoms. A carboxylic acid having a valency of 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more is used. If the carbon number in the carboxylic acid is too small, the oil solubility is poor and the compatibility with the bitumen to be modified is poor.

The polyvalent higher carboxylic acid may be a single acid or a mixture. More specifically, the divalent carboxylic acid accounts for 50 to 100% by weight, preferably 60 to 100% by weight, more preferably 70 to 100% by weight, and the trivalent or higher carboxylic acid accounts for 50 to 0% by weight, preferably Is 40 ~
Those which occupy 0% by weight, more preferably 30 to 0% by weight are used.

As examples of the polyvalent higher carboxylic acid, examples of the divalent carboxylic acid include linear, branched, cyclic and aromatic divalent carboxylic acids, which may be used alone or in combination. A combination of two or more species can be used. Specific examples of the polyvalent higher carboxylic acid, sebacic acid, brassic acid, polyalkylene succinic acid, polymerized fatty acid dimer acid and the like are exemplified, among these, at least selected from polyalkylene succinic acid and polymerized fatty acid dimer acid It is preferably one type. Examples of the trivalent or higher carboxylic acid include a trivalent or higher polymerized fatty acid obtained by polymerizing a higher fatty acid, and particularly a trimer acid of the polymerized fatty acid. The most preferable polycarboxylic acid component is 60
A purified polymerized fatty acid or a hydride thereof containing a dimer acid component in an amount of at least wt% can be used.

The polymerized fatty acid is obtained by polymerizing a higher fatty acid, and usually has 8 to 24 carbon atoms, preferably 16 to 2 carbon atoms.
It is a general term for polymerized acids obtained by polymerizing a fatty acid having 0 saturated or at least one unsaturated bond or a fatty acid ester derivative thereof. Commercially available polymerized fatty acids are those obtained by polymerizing oleic acid, linoleic acid, ricinoleic acid, eleostearic acid, etc., containing dimer acid as the main component, and polymer acid and monomer acid of trimer acid or more as sub-components. Is what you are doing. Structural analysis of polymerized fatty acids is described in D. H. McMahon et al. (J. Am. Oil. Chem. Soc., 5
1 , 522 (1974)). The polymerized product can be separated into polymerized fatty acids having different contents of each component by a distillation method or a solvent extraction method. Further, hydrogenated polymerized fatty acids having good thermal oxidation stability can be obtained by hydrogenating the unsaturated carbon-carbon bonds remaining in these polymerized fatty acids. In the present invention, any of unpurified polymerized fatty acid, purified polymerized fatty acid or hydrogenated polymerized fatty acid can be used, and preferably purified polymerized fatty acid containing 60% by weight or more of a dimer acid component or its hydride is used. It

Polyalkylene succinic acid has the general formula It is represented by. R in the formula is a polymer chain of lower alkylene, and the lower alkylene is preferably at least one selected from ethylene, propylene and butylene, and the degree of polymerization thereof is in the range of 10 to 300.

If necessary, a small amount of other carboxylic acid (usually 30% based on the total weight of carboxylic acid) is used as long as the intended purpose of modification as a bituminous modifier is not impaired.
Wt% or less, preferably 20 wt% or less) can be used together. Specific examples of the carboxylic acid that can be used in combination with the polyvalent higher carboxylic acid include succinic acid, glutaric acid, adipic acid, suberic acid, maleic acid, itaconic acid, pimelic acid, azelaic acid, methylmalonic acid, and dimethylmalon. Aliphatic lower dicarboxylic acids such as acids; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and methylisophthalic acid; other divalent lower carboxylic acids such as alkylene succinic acid; trimellitic acid, tricarballylic acid (1, 2, 3-propanetricarboxylic acid), camphoronic acid (2,3-dimethylmethane-1,2,3-tricarboxylic acid), trimesic acid (1,3,5-benzenetricarboxylic acid) and other lower carboxylic acids having a valence of 3 or more; And 2
-Saturated fatty acids such as methylpropanoic acid, isooctylic acid, isononanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid or unsaturated fatty acids such as linoleic acid, oleic acid and elaidic acid. Examples include lower and higher monocarboxylic acids.

The polyhydric alcohol component used in the synthesis of the oil-soluble polyester of the present invention is not particularly limited,
What is used for usual reaction of polyester can be used. Generally, dihydric alcohol is 60 to 100
It is used in an amount of 70% by weight, preferably 70 to 100% by weight, more preferably 80 to 100% by weight, and the balance consisting of trivalent or more alcohol.

Examples of the dihydric alcohol include alkane diol, polyoxyalkylene glycol, hindered glycol and polyester diol. The alkanediol usually has 2 to 50 carbon atoms.
Individual ones are used, specifically, ethylene glycol, propylene glycol, 1,2-butanediol,
1,4-butanediol, 1,6-hexanediol,
Examples thereof include 3-methyl-1,5-pentanediol and 1,9-nonanediol. As the polyoxyalkylene glycol, polyethylene glycol including oligooxyalkylene glycol such as diethylene glycol, dipropylene glycol, and triethylene glycol, polypropylene glycol, polyoxyethylene-polypropylene glycol, etc., having an alkylene group having 2 to 5 carbon atoms, are polymerized. Those having a degree of 2 to 100 are exemplified.
As a hindered glycol, 2,2-dimethyl-
1,3-propanediol, 2,2-diethyl-1,3
-Propanediol, 2,2-dipropyl-1,3-propanediol, 2,2-diisopropyl-1,3-propanediol, 2,2-diisobutyl-1,3-propanediol, 2-methyl-2-dodecyl -1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-propyl-2-pentyl-1,3
-Propanediol and the like are exemplified. Among these, hindered glycols and alkane diols are particularly preferable.

As the dihydric alcohol, N-methyldimethanolamine, N-butyldiethanolamine, N-butyldimethanolamine, N-isopropyldimethanolamine, N-ethyldiethanolamine,
2,6-pyridinedimethanol, 2- (2-pyridyl)
-1,3-propanediol, 2-hydroxymethyl-
Nitrogen-containing alcohols such as 2- (4-pyridyl) -1,3-propanediol; and polycaprolactanediol may be used.

The trihydric or higher alcohol is not particularly limited, and examples thereof include trimethylolethane, trimethylolpropane, trimethylolbutane, glycerol,
Pentaerythritol, dipentaerythritol, sorbitol, glucose, mannitol, sucrose, glucose and the like can be mentioned, and preferably trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol and the like can be mentioned. it can.

In addition to the polyhydric alcohol component, a monohydric alcohol may be used in combination as long as the object of the present invention is not impaired. Examples of the monohydric alcohol used in combination include neopentyl alcohol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, 2,3,3-trimethyl-2-butanol, 1-decanol, nonyl alcohol and the like. Is mentioned. In general, the permissible amount of monohydric alcohol is usually 10 mol% or less based on all alcohol components.

The polycondensation reaction for synthesizing the oil-soluble polyester may be carried out by a conventional method. The polycondensation reaction is usually 100 to 300 ° C., preferably 150 to 28.
It is particularly preferred to work at a reaction temperature of 0 ° C. and in the presence of an inert gas. If necessary, a water-insoluble organic solvent that is azeotropic with water such as toluene or xylene may be used, or the reaction may be performed under reduced pressure. In the esterification polycondensation reaction, usually, as an esterification catalyst, paratoluenesulfonic acid, sulfuric acid, boron trifluoride complex, phosphoric acid, hydrochloric acid, potassium acetate, zinc stearate, zinc,
Various metal oxides such as titanium, tin and butyltin oxide, and titanium oxide are used, but it is preferable to use the metal oxide from the viewpoint of the oxidation resistance stability of the obtained polyester.

The ratio of the carboxylic acid component and the alcohol component may be appropriately selected according to the type of each component or the desired molecular weight of the polyester, but is usually 0.5 to 2.0 in terms of OH / COOH (equivalent) ratio. , Preferably 0.8-
The range is 1.5.

The molecular weight of the polyester of the present invention is not particularly limited, but is 1,000 to 1,000,000, more preferably a weight average molecular weight of standard polystyrene measured by gel permeation chromatography (GPC). Is 2,000 to 500,000, and more preferably 3,000 to 150,000. When the molecular weight is within this range, binder properties such as toughness and tenacity and processability such as solubility in bitumen are highly balanced, which is preferable.

The acid value and hydroxyl value of the polyester of the present invention are not particularly limited, but the acid value is usually 100 mgKO.
H / g or less, preferably 30 mgKOH / g or less, and a hydroxyl value of usually 100 mgKOH / g or less, preferably 5
It is 0 mgKOH / g or less.

Optional Components In the present invention, a bituminous modifier composed of the block copolymer and the polyester is used, but if necessary, a softening agent and a tackifier may be added as long as the intended purpose is not impaired. Agents, anti-blocking agents, etc. can be added to the bitumen modifier.

Examples of softening agents include petroleum-based softening agents,
Paraffin, vegetable oil-based softeners, plasticizers and the like can be mentioned. The amount of the softening agent used is usually 0 to 200 parts by weight, preferably 20 to 15 parts by weight, per 100 parts by weight of the block copolymer.
0 parts by weight.

Examples of the tackifier include coumarone / indene resin, phenol resin, pt-butylphenol / acetylene resin, phenol / formaldehyde resin, terpene / phenol resin, polyterpene resin, xylene / formaldehyde resin, C5 petroleum oil. Examples thereof include resins, C9 petroleum resins, dicyclopentadiene resins, polybutene, rosin, and the like, and hydrogenated products thereof or modified products thereof with maleic anhydride and the like.
The amount of the tackifier used is usually 0 to 200 parts by weight, preferably 20 to 1 per 100 parts by weight of the block copolymer.
50 parts by weight.

Examples of anti-blocking agents include talc, calcium carbonate, clay, silica, barium sulfate,
Examples thereof include zinc oxide. The amount of the anti-blocking agent used is usually 0 to 5 per 100 parts by weight of the block copolymer.
It is 0 part by weight, preferably 0.1 to 20 parts by weight.

The bitumen modifier of the present invention may further contain, if necessary, an antioxidant such as a hindered phenol type, a sulfur type, a phosphoric acid type, an ultraviolet absorber such as a benzophenone type, or a light stabilizer such as a hindered amine type. Natural rubber, polyisoprene rubber, polybutadiene rubber, random styrene-butadiene rubber, nitrile rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, isoprene-
Rubber such as isobutyl rubber; thermoplastic elastomers such as block copolymers other than the above block copolymers used in the present invention; ethylene ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene / alkyl acrylate copolymer, etc. A thermoplastic resin such as a polyolefin resin, a polystyrene resin, or a polyvinyl chloride resin; an inorganic filler such as glass beads, silica, or carbon black;

Bituminous modifier The bitumen modifier of the present invention is a mixture of the block copolymer and the polyester, further mixed with various additives, if desired, in advance, to obtain powder, pellets, porous pellets, A latex or the like may be used, or each component may be independently added to the bitumen.

The proportion of polyester in the bitumen modifier of the present invention is usually 1 to 100 parts by weight of the block copolymer.
200 parts by weight, preferably 10 to 100 parts by weight, more preferably 20 to 80 parts by weight.

The bitumen to be modified by bitumen is not particularly limited, and a conventional asphalt, for example, straight asphalt, semi-blown asphalt, blown asphalt, asphalt emulsion, tar, pitch, oil or the like is added. Back Alfalto, playback Alfalto, etc. can be used. These can be used alone or in combination of two or more. The bitumen may be decolorized asphalt.

Bitumen Composition The bitumen modifier of the present invention is, as described above, a mixture of a specific block copolymer, a specific polyester and, if desired, various additives. The bitumen composition of the present invention is a mixture of bitumen and the above-mentioned bitumen modifier.

The method for preparing the bituminous composition of the present invention is not particularly limited, and for example, each component may be heated in a hot melting pot,
A method of heating, melting and kneading with a wet mill, a high shear mixer, a roll, a kneader, a Banbury mixer, an extruder or the like can be adopted. In particular, a method in which the block copolymer is pelletized or powdered, polyester is heated to a liquid having a high fluidity, and the liquid is added to the bitumen that has been heated and melted is preferable in view of solubility.

The mixing ratio of the bitumen modifier varies depending on the purpose of use and the type of bitumen, but is based on 100 parts by weight of bitumen.
Usually, it is in the range of 0.5 to 500 parts by weight, preferably 1 to 100 parts by weight, more preferably 3 to 50 parts by weight.

Various additives can be added to the bituminous composition. The additive to be blended is not particularly limited, and is appropriately selected from the additives generally used in bitumen compositions. Specific examples of the additive include crushed stone, crushed stone, gravel,
Aggregates such as sand and recycled aggregates; fillers such as stone powder, talc and calcium carbonate; anti-stripping agents such as slaked lime, amines and amides; fibrous reinforcing materials such as methyl cellulose and polyvinyl alcohol; elasticity improvers, viscosity A reducing agent, a viscosity improver, a filler, a pigment, a softening agent, a tackifier, an antioxidant, an ultraviolet absorber, a light stabilizer, rubber, other thermoplastic elastomer, a thermoplastic resin, etc. can be used. .

When the bituminous composition of the present invention is used for road paving, it is usually used as a bituminous mixture by mixing an aggregate and a filler. As aggregates and fillers (hereinafter, both are referred to as "aggregates"), for dense particle size, fine particle size or coarse particle size mixture used for general road pavement, water permeable pavement, drainage pavement, Aggregates and fillers for open particle size mixtures such as those used for sound absorbing pavements are used. The composition of the bitumen mixture is usually 98-85% by weight of aggregates and 2-15% by weight of bitumen. Block copolymers and polyesters, which are bitumen modifiers, are usually
It is used within the range of the above-mentioned mixing ratio with respect to bitumen. The above-mentioned additives can be added to the bitumen mixture, if necessary.

The mixing method is not particularly limited, and the premix method of kneading the bituminous composition containing the bitumen and the bitumen modifier prepared in advance and the aggregate, the bituminous modifier, the bitumen and the aggregates are used. A plant mix method of kneading can be used. As the plant mix method, for example, (a) a filler, a heated aggregate, and a heated bitumen are kneaded in advance, and then a bituminous modifier is added and kneaded, and (b) a filler, a heated aggregate, a heated bitumen, and a bitumen. There are a method of kneading the modifier at the same time, a method of previously kneading the filler (c), the heated aggregate, and the bituminous modifier, and then a method of adding heated bitumen and kneading.

[0052]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Parts and% in these examples are by weight unless otherwise specified.

The physical property measuring methods are as follows. (1) Weight average molecular weight The weight average molecular weights of the block copolymer and the polyester were measured as standard polystyrene equivalents according to the GPC method. (2) Amount of bound styrene The amount of bound styrene (% by weight) of the block copolymer was calculated by the Hampton method using an infrared spectrophotometer.

(3) Acid Value and Hydroxyl Value The acid value and hydroxyl value of the polyester were measured according to the following described in "Standard oil and fat analysis test method" (Japan Oil Chemistry Association). Acid value 2,4,1-83 Hydroxyl value 2,4,9,2-83

(4) Solubility The solubility of the bituminous modifier in bitumen is 160 ° C according to the "preparation of modified asphalt sample" method described in the Pavement Test Method Handbook established by the Japan Road Association. The block copolymer and the polyester were added to the heated Alfalto and stirred, and the time (hr) until the undissolved material disappeared was determined.

(5) Penetration Penetration (1/10 mm) of the bituminous composition is JIS K2.
It measured according to 207. (6) The 60 ° C. viscosity was measured according to the method described in the Japan Asphalt Association Standard.

(7) Storage Stability The melted bituminous composition was poured into a tin can having a diameter of 15 mm and a height of 100 mm, and left standing in a constant temperature bath at 150 ° C. for 3 days. Thereafter, the cylindrical can was returned to room temperature, and the cylindrical can was cut into three parts (upper layer, middle layer, lower layer), and the binder properties (penetration and 60 ° C. viscosity) of the upper layer and the lower layer were measured. Those having no difference in binder properties between the upper layer and the lower layer have excellent storage stability.

(8) Toughness and tenacity The toughness (kgf · cm) and tenacity (kgf · cm) of the bituminous composition are measured according to the method described in “Handbook of Pavement Test Methods” edited by Japan Road Association. did. (9) Low temperature characteristics The 7 ° C elongation was measured according to JIS K2207. The higher this value, the better the low temperature characteristics.

Production Example 1 Production of Block Copolymer A A 15-liter stainless steel reaction vessel equipped with a jacket and a stirrer was sufficiently replaced with nitrogen, and then cyclohexane 6 was added.
kg, first stage styrene 200 g and butadiene 40
g, and tetramethylethylenediamine (0.05 times mol of n-butyllithium added later) were charged, and warm water was passed through the jacket to bring the content to 60 ° C. Then, 6 ml of a cyclohexane solution containing 14 mmol of n-butyllithium was added to initiate polymerization. The temperature was raised to 80 ° C. at a rate of 1 ° C./min to proceed the polymerization reaction. After the completion of the polymerization, 1560 g of the second-stage butadiene was added to continue the polymerization, and after the polymerization was almost completely completed, styrene of the third-stage was further added.
In the same manner, 00 g was added to effect almost complete polymerization. After the completion of the polymerization, methanol was added in an amount twice that of n-butyllithium, and the mixture was stirred for 10 minutes. Remove the contents from the reactor,
After adding 10 g of 2,6-di-t-butylphenol, the solvent was removed by steam stripping and vacuum drying, and the powder was pulverized to obtain a block polymer A which passed through a 20-mesh sieve. Polymer A
Had a weight average molecular weight of 250,000 and a bound styrene content of 21% by weight.

Production Example 2 Production of Block Copolymer B The amount of monomer charged was 300 g of styrene in the first stage, 10 mmol of n-butyllithium, and 1360 g of butadiene in the second stage.
Further, a block copolymer B was produced by carrying out polymerization in the same manner as in Production Example 1 except that 300 g of the third stage styrene was used. The block copolymer B had a weight average molecular weight of 360,000 and a bound styrene content of 31% by weight.

Production Example 3 Production of Polyester 1 A 1000 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water diversion tube and a nitrogen gas introduction tube was charged with polymerized fatty acid halider 200 (acid value 192 mgKOH / g,
Monomer acid 8.0%, dimer acid 75.0%, trimer acid 17.0%; manufactured by Harima Kasei Co., Ltd.) 420.0 g, 2-butyl-2-ethyl-1,3-propanediol 11
9.1 g and catalyzed monobutyltin oxide 0.
26g was charged. (OH / COOH = 1.03)

Stirring is performed while introducing nitrogen gas to 100
The temperature was raised to ° C. Then, while removing water and unreacted diol generated during the reaction, 100 to 260 ° C.
It took 6 hours to raise the temperature. After that, the reaction was continued for 10 hours while dehydrating at 260 ° C. The obtained polyester 1 has a weight average molecular weight of 12,600 and an acid value of 0.7 m.
It had a gKOH / g and a hydroxyl value of 9.2 mgKOH / g.

Production Example 3 Production of Polyester 2 A 1000 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water diversion tube and a nitrogen gas introduction tube was charged with polymerized fatty acid halider 270S (acid value 192 mgKOH /
g, monomer acid 0.5%, dimer acid 80.5%, trimer acid 17.5%; manufactured by Harima Chemicals Co., Ltd.) 454.0 g, 3
73.4 g of -methyl-1,5-propanediol and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / COOH = 1.05)

Stirring is performed while introducing nitrogen gas to 100
The temperature was raised to ° C. Then, while removing water and unreacted diol generated during the reaction, 100 to 260 ° C.
It took 6 hours to raise the temperature. After that, the reaction was continued for 10 hours while dehydrating at 260 ° C. The obtained polyester 2 has a weight average molecular weight of 14,800 and an acid value of 0.2 m.
It had a gKOH / g and a hydroxyl value of 7.9 mgKOH / g.

Examples 1-2 Heat 6 parts of block copolymer B and 3 parts of each of polyester 1 or polyester 2 to 160 ° C. in a 1 liter dissolution tank with a jacket and a three-stage propeller stirring blade. Straight asphalt 60/80 (penetration 7
0, softening point 49 ° C.) to 91 parts, and stirring was continued until completely dissolved to prepare each binder. The properties of each of the obtained binders were measured, and the results are shown in Table 1.

Comparative Examples 1 to 3

As comparative examples, an aromatic process oil (Comparative Example 1), an aromatic petroleum resin (Comparative Example 2) were used in place of the polyester, and no polyester was used (Comparative Example 3). The same operation was performed. The results are shown in Table 1.

[0068]

[Table 1]

The results shown in Table 1 show that the composition of the present invention has improved solubility and storage stability, higher viscosity at 60 ° C., and higher penetration as compared with the prior art. You can see that

Examples 3 to 4 4 parts of block copolymer A and 4 parts of polyester 1 or polyester 2 were heated to 160 ° C. in a 1 liter dissolution tank equipped with a jacket and equipped with three-stage propeller stirring blades. Straight asphalt 60/80 (penetration 7
0, softening point 49 ° C.) to 92 parts, and stirring was continued until completely dissolved to prepare each binder. The toughness, tenacity, and low temperature characteristics (15 ° C. elongation) of each of the obtained binders were measured, and the results are shown in Table 2.

Comparative Examples 4 to 6 As comparative examples, aromatic process oil (Comparative Example 4), aromatic petroleum resin (Comparative Example 5) were used in place of polyester, and polyester was not used (Comparative Example 6). ,
The same operation as in Example 3 was performed, and the results are shown in Table 2.

[0072]

[Table 2]

From the results shown in Table 2, the composition of the present invention has a higher gripping power (toughness / tenacity) of the aggregate than the prior art.
It can be seen that the low temperature characteristics are well balanced.

[0074]

Embodiments Preferred embodiments of the bitumen modifier and the bitumen composition of the present invention are shown below. (1) The block copolymer has the following general formula (A) to
It has a structure shown in (f). (A) (B-A) m (b) (B-A) m-B (c) (A-B) n-A (d) (A-B) p-X (e) (B-A) p-X However, A is a polymer block (A) which has a vinyl aromatic hydrocarbon as a main component, and B is a polymer block (B) which has a conjugated diene as a main component. X is the residue of the coupling agent. m and n are each an integer of 1 or more,
p is an integer of 2-6.

(2) In the above item (1), m is an integer of 2 or more. (3) In the above (1), n is 1. (4) The block copolymer has an A ₁ -BA ₂ type structure. (A ₁ and A ₂ are polymer blocks mainly composed of vinyl aromatic hydrocarbon, and both may be the same or different.) (5) Vinyl aromatic carbon in the block copolymer The composition ratio of hydrogen and conjugated diene is preferably 10: 9 by weight.
0-70: 30, more preferably 15: 85-50: 5
0.

(6) The vinyl aromatic hydrocarbon is styrene and the conjugated diene is 1,3-butadiene or isoprene. (7) The weight average molecular weight of the block copolymer is 10,0.
00 to 1,000,000, preferably 20,000 to
800,000, more preferably 50,000-50
It is 10,000. (8) The polyvalent higher carboxylic acid contains at least 50% by weight of a divalent higher carboxylic acid.

(9) The polyvalent higher carboxylic acid is composed of only a divalent carboxylic acid, or is a mixture of a divalent higher carboxylic acid and a trivalent or higher carboxylic acid. (10) The carbon number of the higher carboxylic acid is 10 or more. (11) The divalent higher carboxylic acid is at least one selected from polyalkylene succinic acid and dimer acid of polymerized fatty acid. (12) The polyvalent higher carboxylic acid is a purified polymerized fatty acid containing 60% by weight or more of dimer acid or a hydride thereof.

(13) The polyhydric alcohol is composed of only dihydric alcohol, or the dihydric alcohol is 60% by weight or more and 3
It is a mixture with 40% by weight or less of an alcohol having a valency or more. (14) The dihydric alcohol is at least one selected from alkane diol, polyoxyalkylene glycol, hindered glycol and polyester diol. (15) The weight average molecular weight of the polyester is 1,000
~ 1,000,000, more preferably 2,000-5
0,000, more preferably 3,000 to 150,
000.

(16) A bituminous modifier containing 100 parts by weight of a block copolymer and 1 to 200 parts by weight of polyester, more preferably 10 to 100 parts by weight. (17) Bitumen modifier 0.5 per 100 parts by weight of bitumen
A bituminous composition containing 500 parts by weight, more preferably 1 to 100 parts by weight. (18) The bitumen composition is for road paving.

[0080]

Since the bitumen modifier of the present invention has excellent solubility in bitumen, it can be easily and uniformly dispersed in the bitumen. The bituminous composition obtained by blending the bitumen modifier of the present invention with the bitumen has excellent binder properties such as penetration, 60 ° C. viscosity, toughness, tenacity, and 7 ° C. elongation, and also excellent storage stability. There is. Therefore, the bitumen composition of the present invention, depending on its composition and properties, for example, road pavement,
It can be used for applications such as waterproofing, rust prevention, automobile undercoating, roofing, pipe coating, joint material, etc. By incorporating the bituminous modifier of the present invention, the resistance to plastic deformation is improved and the impact resistance is improved. The effects of improving durability, imparting flexibility, and the like are exhibited.

Claims (2)

[Claims] 1. A vinyl aromatic carbonized product containing at least one polymer block (A) mainly composed of vinyl aromatic hydrocarbons and at least one polymer block (B) mainly composed of conjugated dienes. Hydrogen content of 5 to 95% by weight,
Bituminous modifier containing, as an active ingredient, a block copolymer having a conjugated diene content of 95 to 5% by weight, and an oil-soluble polyester obtained by polycondensing a polyvalent higher carboxylic acid and a polyhydric alcohol. . 2. A bituminous composition comprising bitumen and the bituminous modifier according to claim 1.