JPS5840349A - Bituminous substance-containing composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which is suitable for use in the pavement of roads and has excellent strength, adhesiveness and resistance to wear and weather, etc., by mixing a specified modified block copolymer and/or an ion- crosslinked product of said copolymer with a bituminous substance. CONSTITUTION:A modified block copolymer is prepd. by bonding a carboxyl (derivative) group-contg. molecular unit to a block copolymer which is composed of at least one arom. vinyl compd. polymer block A and at least one olefin compd. polymer block B and in which degree of unsaturation in block B does not exceed 20%. The carboxyl (derivative) groups (as a site to be crosslinked) in said modified block copolymer are ion-crosslinked with a metal ion to obtain an ion-crosslinked product of said copolymer. Then said copolymer and/or said ion- crosslinked product are/is mixed with a bituminous substance to obtain the titled compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention #i relates to a composition in which high temperature heat treatment disease is improved and has excellent processability, workability, weather resistance, and mechanical properties sr. A modified block copolymer and/or Fia modified block copolymer in which a molecular unit containing a carboxylic acid group or its leopard conductor group is bonded to a block copolymer having an aromatic compound polymer block and an olefin compound polymer block. The present invention relates to a composition comprising an ionic crosslinked product.

Conventionally, by mixing natural rubber or synthetic rubber such as Fi-ethylene butadiene rubber or nitrile rubber, bituminous materials are brittle at low temperatures and prone to impact fracture.
It is known that the property of being susceptible to plastic deformation at high temperatures is improved and durability is increased, and it has already been used in road applications, civil engineering, architecture, industrial applications, etc. in Japan and other countries. It is used for.

A method for manufacturing a rubber-containing bituminous composition includes a method in which rubber is mixed with a bituminous material in advance on an oven roll to create a master patch with a high rubber content, and this is poured into a heated and melted bituminous material to dissolve it. A method in which rubber in the form of powder or latex is poured directly into a bituminous material heated and melted, and bitumen obtained by heat-melting block copolymer pellets, crumbs, or powder consisting of a conjugated diene and a vinyl aromatic hydrocarbon. There is a method of dissolving it by adding it to the material. Particularly recently, it has superior solubility during mixing compared to conventionally used bituminous compositions containing natural rubber or synthetic rubber.
There is a tendency for block copolymer-containing bituminous compositions having relatively low viscosity at high temperatures to be used favorably. For example, Japanese Patent Publication No. 47-17319, Japanese Patent Publication No. 47-33058
The publication discloses a composition of nine bituminous materials using a block copolymer of a vinyl aromatic compound and a conjugated diene compound, or a hydrogenated product thereof, as a rubbery material.

However, deep blue compositions containing the above block copolymers are not necessarily sufficient in fields that require superior strength, abrasion resistance, adhesion, etc., and improvements are desired. ing.

The inventors of the present invention have conducted intensive studies on improving the properties of compositions of bituminous materials and block copolymers.

Use of a vinyl aromatic compound-conjugated diene compound block copolymer modified with dicarboxylic acids
It was found that the purpose was achieved by 1% Haraaki 58
- Proposed in No. 16553. As a result of further investigation, the present inventors found that a block copolymer composed of a vinyl aromatized polymer block and an olefin compound polymer block contains a molecular unit containing a carboxylic acid group or its derivative group. modified block copolymer and/or
Alternatively, by using an ionic crosslinked product of the modified block copolymer, not only the above characteristics are improved, but also
The present invention was completed based on the discovery that a composition having excellent high-temperature heat treatment performance and weather resistance can be obtained.

That is, 5 the present invention comprises (1) a bituminous material; (b) at least one vinyl aromatic compound polymer block A and at least one olefin compound polymer block B; A block copolymer which is an olefin compound polymer block with a degree not exceeding 20 As the carboxylic acid group in the block copolymer or its crosslinking position,
Any one of monovalent, divalent or trivalent metal ions
Tane-mamo relates to a composition comprising an ionic cross-linked product of the modified block copolymer which is ionic-cross-linked with two or more types.

The composition of the present invention uses a conventional block copolymer or its hydrogenated product and has mechanical strength (e.g., tensile strength, tear strength, and bending strength) compared to bituminous compositions. , excellent abrasion resistance, adhesive properties, etc.

In the present invention, component (b) is a modified block copolymer in which the degree of unsaturation of the olefin compound polymer block is limited to not exceed 209 and/or an ionic crosslinked product of the modified block copolymer. (hereinafter referred to as modified block copolymers), the degree of unsaturation is low, and the temperature is higher than when using conventional block copolymers, such as styrene-butadiene block copolymers. Excellent heat treatment performance and weather resistance. High temperature heat treatability *I! is 1
This is the performance required when producing Composition O to shorten the dissolution time by raising the dissolution temperature, or to process and construct at high temperatures in order to lower the viscosity and improve workability, and the weather resistance is 1. This is the performance required when the composition is used outdoors relatively permanently.

Hereinafter, one aspect of the present invention will be explained in detail.

The bituminous material used as component (1) in the present invention is as follows.

Straight asphalt, semi-prone asphalt,
Asphalt, lawn asphalt, tar, pitch, and cutback asphalt with added oil may be used, and these may be used in combination.

The modified block copolymer, which is one of the components <b) of the composition of the present invention, comprises at least one vinyl aromatic compound polymer block and at least one olefin compound polymer block whose degree of unsaturation does not exceed 2096. The carboxylic acid group 1+ is bound to the block copolymer consisting of the combined block B (hereinafter referred to as the "basic block copolymer"), and the molecular unit containing the derivative group is bonded to the block copolymer (hereinafter referred to as the "basic block copolymer"). It is a block copolymer. Here, the olefin compound polymer block refers to monoolefins such as ethylene, propylene, 1-butene, isobutylene, etc., or conjugated diolefins such as butadiene, isoprene, 1?3-pentadiene, etc.
Selected from non-conjugated diolefins such as ν4-hexadiene, norbornene, norbornene derivatives &ll! It is a monomer block having a form in which the above olefin compounds are polymerized or copolymerized, and the unsaturation of the block is &Jj20X or less. Therefore, when the above diolefins are used as constituent members of an olefin compound polymer block, the degree of unsaturation in #2 block is 2.
Measures must be taken to reduce the degree of unsaturation by methods such as hydrogenation to an extent that does not exceed 0.05X. Further, the olefin compound 1 combined block KFi vinyl aromatic compound may be randomly copolymerized. In the present invention, examples of the "substrate block copolymer" include hydrogenated block copolymers consisting of a vinyl aromatic compound and a conjugated diene compound, block copolymers of a vinyl aromatic compound and a monoolefin, etc. You can enjoy it. The modified block copolymer used in the present invention can be produced by addition-reacting the above-mentioned "base block copolymer" with a derivative of unsaturated carboxylic acid -t+h.

In the present invention, the most preferable component (b) is the block copolymer #-t, a block copolymer composed of a vinyl aromatic compound polymer block and a polymer block 4 mainly composed of a conjugated diene compound ( From now on, this will be referred to as ``
The block copolymer as a precursor is then selectively hydrogenated to an extent that the degree of unsaturation of the conjugated diene moiety does not exceed 20%.

Unsaturated carvone! or a modified block copolymer obtained by combining derivatives thereof by addition reaction.

"Block copolymer as a precursor" is at least one
4, which contains two or more vinyl aromatic compound polymer blocks and at least one conjugated diene-based polymer block. Here, the polymer block mainly composed of conjugated diene has a weight ratio of vinyl aromatic compound to conjugated diene compound of 0/100 to 50150.
It is a polymer block having a composition range preferably from 0/100 to 30/70, and the distribution of the vinyl aromatic compound in this block is random or tapered (the monomer component increases or decreases along the molecular chain). The partially blocky surface may be any combination of these. 1. In the "block copolymer as a precursor" in the present invention, a vinyl aromatic compound is contained in the transition region between a vinyl aromatic compound polymer block and a polymer block mainly composed of a conjugated diene compound. There may be a copolymer block of a vinyl aromatic compound and a conjugated diene compound in an amount exceeding 50 wt. shall be.

In "Block copolymers as precursors".

The weight ratio of the content of the vinyl aromatic compound to the content of the conjugated diene compound is preferably in the range of tO/90 to '10/10, more preferably in the range of 15/85 to 85/15. Such block copolymers have a content of vinyl aromatic compounds of up to about 60% by weight, preferably 55% by weight.
In the following cases, it exhibits properties as a thermoplastic elastic material, and “
It is suitably used as a block copolymer as a precursor.

As the vinyl aromatic compound constituting the "block copolymer as a precursor", one or more kinds are selected from styrene, 4-methylstyrene, vinyltoluene, etc. Among them, styrene is particularly preferred. As the conjugated diene compound, one or two or more types are selected from butadiene, isoprene, 1#3-pentadiene, etc., and among the butadiene and/or light, isoprene is preferred. The above block copolymer has a number average molecular weight of 20*0
0Q~500tOOOO preferably #i40*000~3
The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) Fi is preferably in the range of 1.05 to 10, and the molecular structure of the block copolymer is
It may be linear, branched, radial, or a combination of these. Furthermore, when butadiene is used as the conjugated diene compound in the block copolymer.

The amount of 192 bonds in the microstructure of the butadiene moiety is 10 to 8.
The range of 09 is preferable, and when it is necessary to impart rubber elasticity to the modified block copolymer, the II2 bond amount F is preferably in the range of 125 to 6596, preferably 1435 to 55%, and 8.

In the case where the block copolymer contains t-2 or more of one combined block of a vinyl aromatic compound or one combined block mainly composed of a conjugated diene compound, each block may have the same structure, The monomer component content, their distribution in the molecular chain, the molecular weight of the block,
This book is good because each structure, such as the microstructure, is different.

For example, Japanese Patent Publication No. 36-19286 discloses a method for producing a "block copolymer as a precursor."

Special Publication No. 43-14979, Special Publication No. 49-3695
Publication No. 7, Special Publication No. 4B-2423, % Special Publication No. 48-
A good method is described in Publication No. 4106 and the like.

All of these methods use an anionic initiator such as an organolithium compound in a hydrocarbon solvent, and if necessary, an ether compound such as diethyl ether, tetrahydrofuran, triethylamine, N? NIN
Using tertiary amines such as 'νN'-tetramethylethylenediamine, Lewis bases such as phosphine compounds such as hexamethylphosphoamide, and polyfunctional compounds such as silicon tetrachloride and epoxidized soybean oil as coupling agents, vinyl A block copolymer having a linear, monobranched or radial structure is obtained by block copolymerization of an aromatic compound and a conjugated diene compound. Any book within the above range may be used. It is possible to use not only one type of block copolymer but also a mixture of two or more types of block copolymers.

By hydrogenating the above-mentioned "block copolymer as a precursor" by a known method 1, for example, the method described in Japanese Patent Publication No. 42-8704, a "block copolymer as a base material" is obtained.
is obtained. "Block copolymer as a base" means that at least 80% of the aliphatic double bonds based on the conjugated diene compound in the polymer block mainly composed of a conjugated diene or compound in the "block copolymer as a precursor" In other words, the degree of unsaturation in the block morphologically converted into the olefin compound polymer block B by hydrogenation of the polymer block mainly composed of a conjugated diene compound is 209. It is necessary not to exceed it. If the degree of unsaturation of the olefin compound polymer block exceeds 20X, it is not preferred because the weather resistance and heat aging resistance of the molded article of the unsaturated polyester resin composition will be poor. On the other hand, the hydrogen of the aromatic double bond based on the vinyl aromatic compound copolymerized in the vinyl aromatic compound in the vinyl aromatic compound polymer block and the vinyl aromatic compound copolymerized in one unitary block mainly composed of a conjugated diene compound as necessary. Although the addition rate cannot be limited to %, it is preferable to keep hydrogen addition II to 20% or less. The degree of unsaturation of the combined floc of olefin compound 1 can be determined by carrier analysis using an infrared spectrophotometer (IR) or gas resonance spectrometer (NMR), or by titration analysis using an iodine titration method.
I can determine.

[The base block copolymer JFi and the unsaturated carvone*1+ are then modified by an addition reaction with a derivative thereof to synthesize the modified block copolymer used in the present invention. Examples of unsaturated carboxylic acids or derivatives thereof include:
Maleic acid, 7ff rulic acid, itaconic acid, halogenated maleic acid, dis-4-cyclohexene-1w2-dicarboxylic acid, endo-cis-bicyclo(2*2tl) 5-
Examples include hebutene-293-dicarboxylic acid and the like, acid anhydrides, esters, amides, and ions of these dicarboxylic acids, acrylic acid, methacrylic acid, and the like, and esters and amides of these monocarboxylic acids. These can be used not only alone but also as a mixture of two or more.

Among these, unsaturated dicarboxylic acids or derivatives thereof are preferred, and Toriwasha's maleic anhydride is preferred.

The modified block copolymer is produced by adding an unsaturated carboxylic acid or its rust conductor (t) to the "base block copolymer" and a solution of "the block copolymer".
1 or in the molten state, with or without the use of a radical initiator.

Regarding the manufacturing method of these modified block copolymers, Fi,
Although not particularly limited in the present invention, production methods in which the resulting modified block copolymer contains undesirable components such as gel, or in which the melt viscosity significantly increases and processability deteriorates are not preferred. A preferred method includes, for example, a method in which a "substrate block copolymer" is reacted with an unsaturated carboxylic acid or a derivative thereof in an extruder in the presence of a radical initiator.

The amount of molecular units containing a carboxylic acid group or its derivative group contained in the modified block copolymer, that is, the amount of unsaturated carboxylic acid or 7-derivative added.

The average value of the entire modified block copolymer used in the present invention is 100 parts by weight of the "base block copolymer", 20 parts by weight, preferably 0.1 to 10 parts by weight. , more preferably 0.3 to 5 parts by weight. When the molecular unit containing a carboxylic acid group or its derivative group is less than 0.05 parts by weight, almost no improvement effect is observed compared to the unmodified block copolymer; The improvement effect is not as remarkable as in the case.

The carboxylic acid group in the modified block copolymer is
The content of molecular units containing conductive groups can be easily determined by methods such as an infrared spectrophotometer and titration. Also, in one aspect of the present invention.

The modified block copolymer used as component <b> contains an unmodified block copolymer within the range in which the amount of the derivative added satisfies the above range as an overall average value. Good too.

In the present invention, the modified block copolymer described above can be mixed in the composition as an ionic bridged product. One ionic crosslinked product of the modified block copolymer is (b) of the present invention.
) It may be used alone as a component, or it may be used as a mixture with a modified block copolymer which is at risk of ionic crosslinking.

In this ionic crosslinked product #i, the modified block copolymer described above was crosslinked with one or a mixture of two or more of monovalent, divalent, and trivalent metal ions through ionic bonding. It is obtained by reacting a modified block copolymer with any one of monovalent, divalent, and trivalent metal compounds or a mixture of two or more metals as a crosslinking agent compound.

In the above ionic crosslinked product, the carboxylic acid groups or derivative groups thereof of the modified block copolymer are ionized by adding a crosslinking agent compound. The amount of ionization can be adjusted by adjusting the amount of crosslinking compound added.
The amount is measured, for example, by an infrared spectrophotometer.

The amount #-i of the crosslinking agent compound is added in such an amount that part or all of the carboxylic acid groups or derivative groups thereof contained in the modified block copolymer are ionized, and the ionization reaction proceeds almost quantitatively. However, in order to obtain the desired amount of ionization, there are cases in which an excess of the crosslinking agent is required compared to the theoretical amount.

In order to effectively obtain an ionic crosslinked product, it is preferable that the molar ratio of Fi, the above metal compound, and the carboxylic acid group or its derivative group contained in the modified block copolymer is 0.1 to 3.0. .

The crosslinking agent compound used to obtain the ionic crosslinked product by adding it to the modified block copolymer is any one of the metal compounds of Group 1, Group 1, and Group 1 of the Periodic Table. Or a mixture of two or more types is preferable, specifically a sodium compound.

Potassium compounds, magnesium compounds, calcium compounds, zinc compounds, aluminum compounds, etc. are available.

What are the preferred metal compounds?

They are hydroxides, alcoholades, and carboxylates.

Specific methods for obtaining ionic crosslinked products of modified block copolymers include adding a crosslinking agent compound to the modified block copolymer in a molten state, or dissolving the modified block copolymer in an appropriate solvent. Examples include a method of adding a crosslinking agent compound to this solution to cause a crosslinking reaction, and a method of using a modified block copolymer as latex and adding a crosslinking agent to it. It can be used as a method to obtain a crosslinked product.

In addition, in the present invention, (Taki) the quality of the component and (b)
A method for forming an ionic crosslinked product by adding a crosslinking agent compound to a mixture consisting of modified block copolymerization of components in a melted state or dissolved in a suitable solvent to cause a crosslinking reaction can.

The ionic crosslinked modified block copolymer used in the present invention is thermoplastic and can be processed at high temperatures, and the ionic crosslinking is reversible. These characteristics differ from crosslinked block copolymers obtained by irreversible crosslinking such as commonly used ionic crosslinking, peroxide crosslinking, or radiation crosslinking, and from ionic crosslinking of modified block copolymers used in the present invention. This is the point in which things are essentially different.

The amount of component (b), such as a block copolymer, contained in a composition containing a bituminous material according to the present invention varies depending on the type of bituminous material to be improved and its use.

Considering the physical properties, workability, and workability, generally (a)
0.5 to 50 oil per 100 parts by weight of bituminous material
Parts by weight, preferably Fi1 to 1001i parts, and more preferably 3 to 70 parts by weight of the needle barrel. In addition, in the present invention, for the purpose of improving the percentage of component (b), 1 part by weight or more and 20 parts by weight or more per 9100 parts by weight of the block copolymer of component (b).
It is also possible to incorporate a (-) component in an amount of 5 to 15 parts by weight, preferably 5 to 15 parts by weight.

The composition of the present invention may contain any additive in any amount as required. Additive 111@toshi”
ctx, clay, merck, calcium carbonate, zinc oxide,
Inorganic fillers such as glass peas, aggregates such as crushed stone, gravel, and sand, fibrous reinforcements such as glass fibers, asbestos, organic reinforcing agents such as carbon black, tackifying resins such as lindenic resins, terpene resins, Paraffinic, naphthenic and aromatic oil softeners, polyolefin resins.

Polystyrene resin, polyvinyl chloride resin, thermoplastic resin, natural rubber, polybutadiene rubber.

Synthetic rubbers such as styrene, butadiene rubber, and nitrile rubber can be used.

In the present invention, the method of mixing component (a) and component (b) is not particularly limited, but a preferred method for mixing the component (b) is to pelletize or powder the component (b).
This is a method in which it is added to the heated and melted component (a) and mixed.

By appropriately selecting the amount of rubber in one composition, the composition according to the present invention can be used for road paving, waterproofing, rust prevention, automobile underlayment, roofing, pipe lining, and joint applications. It can be used for almost all the applications for which bituminous materials are used.

In each application, it can contribute to a decrease in temperature sensitivity, an improvement in resistance to plastic firing, an improvement in impact resistance, and an improvement in durability. Particularly for road paving applications, conventional rubber asphalt has poor workability due to its high viscosity at high temperatures.

(1) The blue composition of the present invention can be applied at a temperature higher than ever before, so by increasing the application temperature (ft-), it is possible to reduce the viscosity and improve the workability. It has excellent characteristics in terms of temperature.

Next, the effects of the composition containing the bituminous material according to the present invention will be shown by examples. It should be noted that these Examples are presented only to demonstrate the excellent effects obtained by the present invention, and are not intended to limit the purpose of the present invention.

The habit block copolymers used in the following examples were prepared as follows.

(υ Preparation of Hydrogenated Block Copolymer Using n-butyllithium as a polymerization catalyst, tetrahedron was reacted in carhexane or cyclohexane solvent.

A block copolymer as shown in Table 1 was synthesized by anionic block copolymerization of butadiene and styrene using Roalane as a vinyl content regulator.

Below, a maleation reaction was carried out at 250°C. From the obtained modified block copolymer, unreacted maleic anhydride was removed under reduced pressure by heating, and 296-sheeter diarybutyl-4-methylphenol (BHT) was added as a stabilizer to the polymer 100.
Add 90.5 parts by weight per part by weight. When this modified block copolymer (referred to as sample B-1) was analyzed, Table 1
The results were obtained.

Next, the same method was used except that the amount of maleic anhydride and the amount of Perhexa 25B added were changed.

Modified block copolymers (samples B-2 to B-4) based on the hydrogenated block copolymers of samples A-2 to A-4 were obtained.

Table 2 (Note 3) The amount of maleic anhydride added was measured by titration with sodium methylate.

(3) Preparation of ionic crosslinked product of modified block copolymer Sample 0-1-(!-3) was obtained according to the procedure shown in Table 3. The ionic crosslinking reaction was carried out in a solvent. In some cases, the solvent was removed by heating after the reaction.It was confirmed by infrared spectroscopy that the acid anhydride groups of Samples 0-1 to 0-3 were ionized by such treatment.

Examples 1 to 6 and Comparative Examples 1 to 3 Below, a composition containing bituminous material of the present invention and a composition as a comparative example were mixed at 200 DEG C. for about 1 hour in accordance with the following procedure.

Composition blending ratio: parts by weight 620/
30 blown asphalt 200 honey block copolymer etc. or not.

Modified block copolymer O heavy calcium carbonate 60
0 Fine powder silica 10
The properties of the obtained composition are shown in Table 4, and it can be seen that the composition of the present invention has superior tensile strength and tear strength compared to the composition of the comparative example. ′! In the present invention, tensile strength and tear strength are further improved by using an ionic crosslinked product of a modified block copolymer.

Next, a weather resistance test (1000 hour weather exposure) of each of the compositions obtained above was carried out, and it was found that the compositions of Examples 1 to 6 had lower tensile strength and tear strength before the weather resistance test. With tensile strength and tear strength of 70% or more. However, the compositions of Comparative Examples 1 to 3 only showed a value of less than 5096.

Next, each composition was prepared using the same formulation method as above except that the temperature at the time of mixing was t-240 DEG C., and the characteristics of each composition were examined to learn about high temperature heat treatment disease. As a result, compositions #'i with the same formulation as Examples 1 to 6 had the same strength as those of Examples 1 to 6! Although the PIC compound treated with the same PIC compound as Examples 1 to 3 had properties of 90% or more of expansion and tear*&, it had properties that were less than 70X of each of Comparative Examples 1 to 3. Didn't show it.

From the above results, it has become clear that the composition containing the blue-green pigment of the present invention has excellent weather resistance and high-temperature heat treatment performance.

Margins below Example 7s8 and Comparative Example 4y5 To 95 parts by weight of 60780 straight asphalt heated to 240°C, 51 parts by weight of the modified or unmodified block copolymer shown in Table 5 was added, Rubber asphalt was prepared by dissolving for 1 hour at a stirring speed of about 15 Or, pom.

Next, each of the above-mentioned rubber asphalt and aggregate were mixed using a small asphalt plant at a temperature of 240° C. for about 1 hour to prepare an asphalt mixture for road paving. Incidentally, the aggregate was blended so that the content of the above-mentioned rubber asphalt mixture as a pinter was about 6 weight X.

The properties of each composite material obtained are shown in Table 5.1 The composite material containing the composition of the present invention has excellent heat resistance, stability, low temperature properties, and abrasion resistance, and is suitable for use as an asphalt mixture for road paving. It has become clear that it can be suitably used as

Margin below the particle size of the aggregate used in the pot Examples 9 to 13 and Comparative Examples 6 to 9 According to the formulation shown in Table 6, asphalt-containing compositions were prepared by mixing at 200° C. for 1 hour. The obtained nine asphalt-containing compositions were sandwiched between a cotton canvas and a steel plate, and after being pressed together at 150°C, the peel strength was determined.

The results are shown in Table 6.1 The composition of the present invention had superior adhesiveness compared to the composition of the comparative example.

Margin below

Claims (1)

[Scope of Claims] (a) a bituminous material; (b) at least one vinyl aromatic compound polymer block and at least one olefin compound; A modified block copolymer and/or a modified block copolymer in which a molecular unit containing a carboxylic acid group and a conductor group thereof is bonded to a block copolymer that is an olefin compound polymer block of not more than 20%. Monovalent % with the carboxylic acid group or its fermentation conductor group as the crosslinking position
A composition consisting of an ionic crosslinked product of a modified block copolymer that is ionicly crosslinked with any one of divalent or trivalent metal ions or two or more types of Fi.