KR102218411B1 - Multifunctional asphalt modifier composition with excellent dissolution and dispersibility and drainable modify asphalt using the same - Google Patents

Abstract

The present invention relates to a multifunctional asphalt modifier composition having improved solubility and dispersibility, and modified drainage asphalt using the same. In order to solve the problem of degradation of a modification effect of asphalt, caused by insufficient solubility and dispersibility to matrix straight asphalt, which is a disadvantage of an asphalt modifier based on the conventional plant mix method, the multifunctional asphalt modifier composition adopts optimized management of a dispersion-controlling agent by introducing the solubility parameter concept and aniline point concept precisely to rubber materials as main ingredients of a modifier so that the solubility and dispersibility to matrix straight asphalt may be improved. When an asphalt mixture is prepared in a plant by using the modifier for plant mix obtained by the present invention, the solubility and dispersibility are improved significantly upon the introduction to and mixing with straight asphalt as a matrix, unlike the conventional plant mix modifier, thereby providing modified asphalt which is homogeneous and has an excellent modification effect. In this manner, it is possible to realize an excellent modification effect, including excellent co-dissolution properties, and thus to improve the duration of a paved body and to minimize the cost required for repairing and maintaining a paved body.

Description

Multifunctional asphalt modifier composition with excellent dissolution and dispersibility and drainable modify asphalt using the same}

The present invention relates to a multifunctional asphalt modifier composition having excellent dispersibility in dissolution and to a drainage modified asphalt using the same, and more particularly, to the base material straight asphalt, which is a disadvantage of the existing plant mix type asphalt modifier. In order to dramatically improve the deterioration of the asphalt modification effect due to insufficient dissolution and dispersibility, the concept of soluble parameter and aniline point to improve dissolution and dispersibility when mixing rubber, the main component of asphalt modifier, into straight asphalt base material. ) It relates to a multifunctional asphalt modifier composition excellent in dissolution and dispersibility by the use of an optimal dispersion control agent incorporating the concept, and a drainage modified asphalt using the same.

In general, the drainage pavement method is an asphalt pavement having a porosity of about 20%, and it is a method of draining through the lower impermeable layer through the air gap in case of rain.This drainage function improves rain slip resistance, water film phenomenon, and spray phenomenon. It not only improves visibility by reducing the number of road surfaces and reducing the number of road surfaces at night, but also exhibits a noise reduction function due to the formed voids.

These drainage pavement methods were first introduced as open wear layers in Arizona or Nevada in the United States in 1959, and since they were first tested on the Gyeongbu Expressway in 1997 in Korea, this drainage pavement method was designated as a new technology by the Ministry of Construction and Transportation. Until now, many types of drainage asphalt have been operated.

First, looking at the physico-chemical properties of asphalt, which is a binder in the drainage pavement method, the grain size composition of the aggregate to maintain the voids of the drainage pavement is about 20%, and the part of the aggregate that is mainly thicker than the aggregate grain size composition of the general density asphalt concrete. Because there are many, in the case of drainage pavement, the contact area ratio between aggregate and aggregate is theoretically lower than that of dense pavement, so that the binder has a large resistance against the load shear stress caused by the vehicle wheel load, namely, toughness (toughness) and tenacity (toughness, 强靭性). Larger and high viscosity binders must be used.

Therefore, in order to develop high toughness & tenacity and high viscosity binder, various kinds of water-repellent asphalt are manufactured and operated by adding rubbers, which are the main components of the asphalt modifier, to neat asphalt.

In addition, modified asphalt is a rubber such as SBR (styrene-butadiene rubber) or SBS (Styrene) for the purpose of improving the shortcomings of severe change in physical properties due to temperature change, which is the large temperature sensitivity of straight asphalt. -Thermoplastic elastomers such as Butadiene-Styrene Copolymer), Styrene-Isoprene-Styrene Copolymer (SIS), Styrene-Ethylene-Butadiene-Styrene copolymer (SEBS), and thermoplastic resins such as EVA (Ethylene Vinyl Acetate), PE, PP, etc. It refers to a so-called polymer modified asphalt that has been added to improve physical and chemical properties.

In the manufacturing method of these modified asphalt, usually, straight asphalt is put into the reactor in advance at a separate plant, and various rubbers and auxiliary agents are heated, dissolved and dispersed at about 180 to 200°C for 4 to 5 hours using a high-speed shear mixer. As a result, there is a Pre-Mix method in which the modified asphalt prepared by dissolving and dispersing-integrated rubbers in advance is mixed with aggregates at the asphalt concrete factory.Semi-finished products manufactured in granular form of only rubbers and auxiliary agents through an extruder (hereinafter referred to as'plant Plant mix (Plant-Mix) that transforms rubber into asphalt during the process of mixing with aggregate by separately adding particulate plant mix modifier while adding straight asphalt to aggregate at Ascon factory. It is largely distinguished in a way.

In the manufacturing method of such modified asphalt, the Pre-Mix method as described above is sufficient shear mixing in advance of various rubbers and thermoplastic elastomers, etc. of which the modified asphalt has poor dispersibility in the straight asphalt, which is the base material. And since the mixture was homogeneously dissolved and dispersed for a long time, the quality variation of the prepared mixture is small, whereas the plant-mix method of the existing technology separates the modifier for plant mix on straight asphalt, which is the base material, at the Ascon factory. In the case of post-adding, the mixing time is very short, about 45 to 60 seconds, so the time required to completely homogeneously dissolve and mix the particulate plant mix modifier to be post-added is insufficient. There is a drawback that is likely to cause deviation.

These reforming polymers are a polystyrene block corresponding to A (hereinafter referred to as'PS Block') at both ends of a molecular structure having good compatibility with relatively straight asphalt, and a polybutadiene block corresponding to B (hereinafter referred to as'PB). Block'), polyisoprene block (hereinafter referred to as'PI Block'), polyethylene-butadiene block (hereinafter referred to as'PEB Block'), so-called ABA-type tri-block chemical structure Thermoplastic elastomers dominate.

In particular, SBS (Styrene-Butadiene-Styrene Copolymer) is used as the main modified polymer, and a typical molecular structure is as shown in [Fig. 1].

These SBSs are classified into linear SBS (Linear SBS), in which PS Block and PB Block are linearly connected, and radial SBS (Radial SBS), in which these blocks are radially connected to each other. And the weight average molecular weight (Mw) of the radially structured SBS is usually 10,000 to 1,000,000 g/mol, and the linear structure or radial structure chains of various molecular weights are entangled with each other to form a single thread (Entanglement state). It is a well-known fact that it has characteristics.

In the process of modifying by adding these SBSs as a modifying polymer to straight asphalt, which is a base material, these SBSs and thermoplastic elastomers are completely dissolved in water as a solvent like sugar, so that sugar is completely dissolved. A chain in which chains of various lengths (molecular weight) are entangled with each other, rather than being solutionized from a solid state to a completely liquid state. A chain of molecules twisted together by straight asphalt as a solvent in an entanglement state ) SBS and thermoplastic elastomers are twisted with chains of small molecular weight, which are easy to disperse on straight asphalt, during the process of swelling while the entire molecule is swelled by increasing the volume of about 5-7 times as the structure is gradually released from the edge of the thread. It has a mechanism in which these modified polymers are gradually dispersed from a small degree of chain and are modified through the process of converting these modified polymers into chain dispersions in the concept of morphology.

However, among the molecular structural components of SBS and thermoplastic elastomers, PS Block has a high solubility parameter, whereas Maltene, the main component of straight asphalt, has a medium solubility parameter, so mutual affinity due to the difference in solubility parameters between the positive components. Because it is difficult to disperse due to lack, in fact, these SBSs and thermoplastic elastomers are not pretreated, that is, they are very strong over a long period of about 4 hours or more to disperse them at 180 to 210°C on straight asphalt, which is a base material by itself. There is a problem in that it is difficult to obtain a homogeneous modified asphalt unless agitation is performed with a shearing force.

Therefore, many related companies, including many modified asphalt researchers, have applied rubber-type modified asphalt since 1950 and researched and developed thermoplastic elastomer-type modified asphalt including SBS since the mid-1980s, and these SBS and thermoplastic elastomers are very suitable for straight asphalt. In order to homogeneously disperse into a small dispersion, various process oils and tackifiers have been introduced as dispersion control agents, and the addition amounts of these dispersion control agents are also specified, and many compositions and preparation methods have been applied to this day.

In the case of most modified asphalt so far, polymers used for modification are usually synthetic rubbers such as SBS, SIS, SEBS or EVA, Tire-CRM (Crumb Rubber Modified), regardless of the premix method or the plant mix method. These rubbers have been used alone or in combination to add 4 to 25% by weight to asphalt. As a dispersion control agent, paraffinic oil, naphthenic oil or aromatic oil is used, and petroleum resins are used as tackifiers. Most of all the so-called modifier compositions for modified asphalt by using them together are composed of three components: SBS and thermoplastic elastomers, various process oils and tackifier resins.

However, the so-called plant mix modifier of the present invention, in which the modified asphalt mixture of the present invention is manufactured by simultaneously inputting the reforming material while simultaneously inputting straight asphalt into the aggregate while stirring directly at the on-site asphalt mixture manufacturing plant (factory for hot mixing aggregate/asphalt binder) is mixed on-site. In the process, the modifier must be homogeneously dispersed in straight asphalt within 1 minute within a short period of time, so that a high-dispersibility property of solid solution is particularly required.

Accordingly, the investigation and analysis of the prior art are as follows.

In WO 2007/051703 A1, 2 to 8 weight of a Styrene-Butadiene copolymer having a Styrene content of 20 to 40% by weight and a molecular weight of 120,000 to 200,000 g/mol among copolymers of Styrene and Polybutadiene in 85 to 97.5 parts by weight of asphalt (bitumen) In addition, it relates to a technology to provide a binder for open asphalt and drainage asphalt consisting of 0 to 5 parts by weight of Diblock copolymers of Styrene-Butadiene or Styrene-Isoprene and 0.5 to 3 parts by weight of EVA, but the example technology is specific to the composition. There was no information on the specific manufacturing method.

In Japanese Patent Laid-Open No. Hei 9 (1997)-25416, a process oil containing 10 to 300 parts by weight of a tackifying resin and 0 to 40% by weight of an aromatic component is 0 to 100 parts by weight of a vinyl aromatic hydrocarbon-conjugated diene block copolymer. It is a technology for producing a composition containing 300 parts by weight in extrusion-granular form through an extruder. In the vinylaromatic hydrocarbon-conjugated diene block copolymer, the vinylaromatic hydrocarbons are styrene, α-methyl styrene, and the like, and the conjugated diene blocks are Butadiene, Isoprene, and the like, and the copolymers thereof are Styrene-Butadien copolymers, Styrene-Butadiene-Styrene copolymer. Ryu, Styrene-Isoprene and Styrene-Isoprene-Styrene copolymers were specified, and coumaron-indene resin, phenolic resin, Para-tertiary Butylphenol acetylene resin, terpene phenolic resin, polyterpene resin, xylene-form as tack imparting resins. Among the aldehyde resins, C5 petroleum resins, C9 petroleum resins and DCPD resins, and rosin and rosin ester resins, in particular, the use of C5 petroleum resins, C9 petroleum resins and DCPD petroleum resins was specified, and moreover, C9 petroleum resins were specified. I did.

In the process oil, which is a compound operated by being called process oil in the sense that the purpose of use is to facilitate processing of the rubber polymers, that is, to facilitate processing in the processing process, the aromatic hydrocarbon content is 0 to 40% by weight. Phosphorus, in particular, was specified as a low aromatic petroleum hydrocarbon oil having an aromatic hydrocarbon content of 0 to 10% by weight and a naphthenic hydrocarbon and paraffinic hydrocarbon content of 60 to 100% by weight so that there is no blocking between particles of the produced extrusion-grain type. . Its technology is a technology to provide a plant mix-type asphalt modifier produced by specifying the composition and raw materials and then extruding them at about 100 to 250°C through an extruder to form a particle size of 0.5 to 50 mm.

Republic of Korea Patent No. 0422896 (2004) is a technology related to the manufacturing method of a plant mix method of water-repellent asphalt modifier, and the weight average molecular weight (Mw) is in the range of 70,000 to 110,00 Styrene-Butadiene-Styrene linear copolymer 60 to 65 weight. % To 2 to 3% aromatic hydrocarbons, 60 to 64% paraffinic hydrocarbons, and 33 to 36% naphthenic hydrocarbons. C9-based petroleum resin 23-27 parts by weight of 90-125°C, 0.3-0.5 parts by weight of antioxidant, 0.1-0.3 parts by weight of UV stabilizer are well mixed, and a plant mix method manufactured in a vertical form at 160-180°C through an extruder. It is a technology that provides an asphalt modifier.

Republic of Korea Patent No. 0655635 (2006) relates to a method for manufacturing a high-viscosity drainage asphalt modifier. Radial Styrene-Butadiene-Styrene copolymer having 2 to 6 branches is 40 to 100% by weight, and linear Styrene-butadiene-styrene copolymer is 0. ~40% by weight, Multi Block Styrene-butadiene-styrene copolymer 0-30% by weight, prepared by kneading with 0-10% by weight of Styrene-butadiene diblock copolymer, and a styrene content of 15-50% by weight and a molecular weight of 50,000-300,000. Based on 100 parts by weight of styrene-butadiene-styrene copolymer, it is composed of 10 to 60 parts by weight of a tackifying resin, 5 to 70 parts by weight of a processing aid selected from mineral process oil, liquid resin, liquid butadiene rubber, polybutene, and polyisobutylene. In addition, 5-20 parts by weight of Ethylene-α-olefine copolymer with 2-20 carbon atoms, 5-30 parts by weight of Acrylonitrile resin, and 5-20 parts by weight of EVA are mixed and extruded at 100-220℃ through an extruder to form granularity. It relates to the provision of an anticorrosive asphalt modifier. In the process oil, it was specified that the aromatic hydrocarbon content was 0 to 30% by weight, the naphthenic hydrocarbon content was 20 to 50% by weight, and the paraffinic hydrocarbon content was 40 to 80% by weight.

Korean Patent No. 1778150 (2017) relates to a multi-layered low noise drainage asphalt composition using a plant mix modifier for asphalt pavement and a premix modifier, and is a high molecular weight Styrene-butadiene-styrene copolymer 25 with a molecular weight of 250,000-350,000. ~35% by weight, 10-30% by weight of low molecular weight Styrene-butadiene-styrene copolymer having a molecular weight of 30,000-120,000, 3-10% by weight of Portland cement, 3-15% by weight of brown asphalt, 2-12% by weight of Gilsonite And a plant mix modifier composition consisting of 1 to 4% by weight of grahamite, 5 to 20% by weight of petroleum resin, and 0.1 to 3% by weight of an antioxidant, and high molecular weight Styrene-butadiene-styrene having a molecular weight of 250,000 to 350,000. 5 to 20% by weight of copolymer, 40 to 55% by weight of low molecular weight Styrene-butadiene-styrene copolymer with molecular weight of 30,000 to 120,000, 5 to 15% by weight of sulfide, 3 to 15% by weight of brown asphalt, 2 to 12 by weight of Gilsonite %, 5 to 20% by weight of petroleum resin, and 3 to 20% by weight of a mixture composed of 0.1 to 3% by weight of an antioxidant was mixed with 80 to 95% by weight of asphalt (bitumen), but the composition was not specified. There was no information about its manufacturing method and characteristic values.

Republic of Korea Patent No.1956562 (2019) is a technology related to an asphalt reforming material, a modified asphalt concrete composition containing the same, and a low noise drainage asphalt concrete composition.Styrene-butadiene-styrene copolymer 40-60% by weight, process oil 15-25% by weight , 10 to 30% by weight of organic polymer, 1 to 6% by weight of phthalate-based plasticizer, 1 to 5% by weight of gilsonite, 1 to 5% by weight of latex, 0.1 to 3% by weight of sulfur, 0.5 to 2% by weight of a separate plasticizer It is a technology for providing a granular plant mix modifier through an extruder through a composition consisting of 0.5 to 2% by weight of aromatic phosphate and 0.1 to 3% by weight of calcium carbonate.

As a result of reviewing the technology to which the present invention belongs and the prior art in the same field as described above, most of the conventional patented technologies are Styrene on straight asphalt to secure High Toughness (toughness) and High Tenacity (toughness) of the mixture. The molecular weight of tri-block type copolymers such as butadiene-styrene copolymers and styrene-isoprene-styrene copolymers, and the choice of chain entanglements such as linear or radial, and styrene-butadiene It can be seen that the type and composition of rubber compounds, such as whether or not Di-Block copolymers such as copolymer or styrene-isoprene copolymer are introduced, and whether or not components such as EVA are introduced, are largely different.

However, in terms of the operating method of the modifier, it is known that there is only a difference in the amount of addition and whether the process oil is introduced as a material to help the extrusion process in order to produce the plant-mix method and the pre-mix method modifier in terms of production, and whether or not an adhesion enhancer is introduced to improve adhesion. I can.

In other words, a problem in which a specific technology for the optimum plant mix modifier composition and optimization based on the study of the influence of major factors on the solubility and high dispersibility of straight asphalt, the base material of the plant mix modifier, is not specified. There was this.

In order to solve the above-described problem, the object of the present invention is to implement multifunctional modified asphalt such as PG 76-22 and PG 82-22 in a plant by post-adding a modifier in various amounts to straight asphalt as a base material, and in a short time, high solubility and Solubility parameter as a dissolution dispersion correlation index between the chemical components of the modified polymer, SBS and thermoplastic elastomer, and the constituents of straight asphalt to dissolve and disperse them, and the dissolution dispersion correlation index with dispersion regulators to exhibit excellent dispersibility and excellent modifying effect. It is intended to obtain a multifunctional asphalt modifier composition with excellent solubility and dispersibility more precisely and effectively by introducing and analyzing the concept of Anilin Point as an index of solubility of a new concept and applying it.

Another object of the present invention is to obtain a drainage modified asphalt using the multifunctional asphalt modifier composition excellent in solubility and dispersibility.

Another object of the present invention is to obtain a method of manufacturing a water-repellent modified asphalt using the multifunctional asphalt modifier composition having excellent solubility and dispersibility in a plant mix (Plant-Mix) method.

The present invention is a means to achieve the object of the present invention to obtain a multi-functional asphalt modifier composition with excellent solubility and dispersibility more precisely and effectively, and a drainage modified asphalt using the same,

15 to 35% by weight of linear SBS (Styrene-Butadiene-Styrene Copolymer) having a Styrene content of 25 to 35% by weight and a weight average molecular weight (Mw) of 200,000 to 400,000 g/mol of the present invention; 30-35% by weight of linear SBS having a styrene content of 25 to 35% by weight and a weight average molecular weight (Mw) of 50,000 to 200,000 g/mol; SIS (Styrene-Isoprene-Styrene Copolymer) 5 to 9 wt% containing 15 to 25 wt% of Diblock (Styrene-Isoprene Copolymer) content by adjusting the Styrene content of 10 to 20 wt% and the coupling rate (%); 10 to 15% by weight of petroleum resin with a Hilderbrand solubility parameter of 8.2 to 9.6 (J/cm 3) ^1/2 ; It is characterized in that it is a plant mix (Plant-Mix) asphalt modifier composition containing 20 to 25% by weight of a high boiling point oil having an aniline point of 30 to 45 ℃ and a flash point of 250 ℃ or more.

In the asphalt modifier composition of the present invention, the petroleum resin is an aromatic C9 petroleum resin having a Hilderbrand solubility parameter of 8.2 to 9.6 (J/cm 3) ^1/2 , an alicyclic C5 petroleum resin, and a C5-C9 alicyclic-aromatic aerial It is characterized in that at least one selected from the group consisting of total petroleum resin.

In addition, the asphalt modifier composition of the present invention is characterized in that the high boiling point oil having the aniline point of 30 to 45°C is a combination oil in which the aniline point is adjusted to 30 to 45°C by combining two or more high boiling point oils.

Another aspect of the present invention is characterized by a high viscosity water drainage modified asphalt using the asphalt modifier composition.

Another aspect of the present invention is characterized in that the water-repellent modified asphalt of PG (Performance Grade) 76-22 grade or higher using the asphalt modifier composition.

Another aspect of the present invention is a method of manufacturing a water-repellent modified asphalt, characterized in that the high-viscosity water-repellent modified asphalt is produced in a plant-mix method.

Another aspect of the present invention is a method for producing a water-repellent modified asphalt, characterized in that the water-repellent modified asphalt of a PG (Performance Grade) 76-22 grade or higher is manufactured by a plant-mix method.

The present invention is also characterized in that the asphalt is straight asphalt (Straight Asphalt).

Accordingly, when manufacturing a modified asphalt by mixing it with asphalt in a plant using the modifier composition for plant mix obtained through the solution of the present invention, unlike the existing plant mix modifier, it is solubility in the case of input and mixing into straight asphalt as the base material. And the dispersibility was remarkably improved to express the modified asphalt which is homogeneous and excellent in the effect of reforming.

In the present invention, when manufacturing a modified asphalt by mixing with asphalt in a plant by using the modifier composition for plant mix obtained through the solution of the above problem, when mixing it into straight asphalt as a base material unlike the existing plant mix modifier The improved solubility and dispersibility is remarkably improved, resulting in a homogeneous and excellent reforming effect, and the resulting modified asphalt exhibits excellent remodeling effects with excellent common properties, and thus the durability life and maintenance of the pavement. It has the effect of minimizing maintenance costs.

1 is a schematic diagram of a molecular structure of a typical SBS (Styrene-Butadiene-Styrene Copolymer).
2 is a view showing the composition of straight asphalt.
3 is a diagram showing the solubility relationship between marten and asphaltene of PS Block and PB Block of SBS versus straight asphalt.
4 is a Cp, Cn, Ca Portion distribution diagram of a typical process oil.
5 is a graph of the difference (%) of the modified asphalt at 180°C holding time versus 90°C Vertical Flow.
6 is a regression analysis graph of the modified asphalt at 180°C holding time versus 90°C Vertical Flow difference (%).
7 is a view showing a Hilderbrand solubility parameter positioning map of reforming polymers and various petroleum resins.

Hereinafter, the present invention will be described in detail.

Prior to this, terms or words used in the description and claims of the present invention should not be construed as being limited to their usual or dictionary meanings, and the inventors have devised the concept of terms in order to explain their own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that it can be properly defined.

The present invention includes 15 to 35% by weight of a linear SBS (Styrene-Butadiene-Styrene Copolymer) having a Styrene content of 25 to 35% by weight and a weight average molecular weight (Mw) of 200,000 to 400,000 g/mol; 30 to 35% by weight of linear SBS having a styrene content of 25 to 35% by weight and a weight average molecular weight (Mw) of 50,000 to 200,000 g/mol; Consisting of 5 to 9% by weight of SIS (Styrene-Isoprene-Styrene Copolymer) containing 15 to 25% by weight of DiBlock (Styrene-Isoprene Copolymer) content by adjusting the Styrene content of 10 to 20% by weight and coupling rate (%) The high solubility parameter of straight asphalt, the base material to dissolve and disperse, improves the dissolution-dispersibility of the modified polymers and PS Block, the high solubility parameter of both ends of these modified polymers. Aromatic C9 petroleum resin, cycloaliphatic C5 petroleum resin and C5-C9 alicyclic in a range similar to those of these high solubility parameters in order to improve the dissolution-dispersion of asphaltene components. -10-15% by weight of at least one of the aromatic copolymer petroleum resins, the medium solubility parameter of PB and PI Block, the soft segment of the center of the modified polymer, and the straight asphalt as the base material. 20 to 25% by weight of a high-boiling oil with an aniline point of 30 to 45°C and a flash point of 250°C or higher, similar to the solubility parameter of Malten, the main component, the medium solubility parameter. It features a composition comprising a.

Hereinafter, the configuration, operation and specific embodiments of the present invention will be described.

First, in the development of a multifunctional asphalt modifier with excellent dissolution and dispersibility, which is the object of the present invention, among the modifier components, SBS and thermoplastic elastomers, which are the main components of viscoelastic properties, are dissolved in asphalt. The dissolution and dispersibility of modified polymers from the viewpoint of chemical and histological morphology and the influence of factors on the homogeneous distribution of these dispersed particles will be examined.

As is well known, modified asphalt is a mixture prepared by heating and dispersing 4 to 25% by weight of various rubbers in 75 to 96% by weight of straight asphalt, which is a base material, and is interpreted in terms of the histological morphology of the dispersion. In other words, it is a fine rubber particle dispersion in which rubbers are only physically dispersed as a dispersion phase in an asphalt continuous phase, which is a solvent.

Looking at the dissolution and dispersing process of modified asphalt, which is a dispersion of these fine rubber particles, when SBS and thermoplastic elastomers are heated and mixed with the parent material, Maltene, which is a medium-soluble parameter component, among the straight asphalt components. It is absorbed by these rubbers and swells about 5 to 7 times, and from a chain of low molecular weight that is easy to disperse and a chain with small molecular twist, diffuses and disperses into the straight asphalt, which is a solvent, and has a secondary sufficient shear force. ) And over time it is converted into a stable rubber dispersion.

However, the higher the content of asphaltene, which is a high-solubility parameter component, among the straight asphalt components, the slower the dissolution and dispersion rate with SBS and thermoplastic elastomers.

At this time, when the content of SBS and thermoplastic elastomers is less than 10% by weight, these rubbers exist in a dispersion phase, but when they are more than 10% by weight, these rubbers are phase shifted to a continuous phase due to an increase in volume due to swelling. The (phase transition) is formed and the straight asphalt becomes a dispersion phase, so that the physicochemical properties of the modifier are remarkably changed into a liquid rubber state.

In the present invention, the composition of straight asphalt as the parent material is broadly classified as shown in FIG. 2, and the maltene component dissolved in n-Heptane, which is a saturated hydrocarbon solvent, and toluene, an aromatic hydrocarbon, is not dissolved in n-Heptane. It is composed of asphaltene, which is dissolved in ).

Maltene (Maltene) is a polycyclic structure of low molecular weight, a solid or semi-solid viscous material containing a large amount of oil components, and contains about 77 to 88% by weight of straight asphalt. Maltene is composed of three components: saturated hydrocarbons, aromatic hydrocarbons and resin components.

Asphaltene is a brittle, high molecular weight black solid, containing 11 to 23% by weight of straight asphalt, and the higher the asphaltene content, the higher the viscosity of the asphalt and the higher the softening point. .

Therefore, looking at the structural analysis of the base material, straight asphalt, in general, asphaltenes in asphalt are easily associated with each other, so they aggregate to form a micelle structure. Asphaltene on micelles by aggregation has low affinity with maltenes, but the resin component of malten adsorbed on the surface of asphaltene micelles acts as a deflocculating agent. (Maltene) and low affinity asphaltene (Asphaltene) component is structurally considered to be dispersed in a colloidal form in the malten (Maltene) component, and when the SBS and thermoplastic elastomers of the present invention are heated and dispersed, these straight It can be seen that among the asphalt components, the intrinsic content ratio of the maltene component and the asphaltene component is a large factor in the influence of the dissolution and dispersion rate.

On the other hand, SBS and thermoplastic elastomers used as conventional modified polymers have PS Blocks at both ends and PB, PI, PEB Blocks, etc., which are soft segments between them as shown in FIG. The chemical structure of these modified polymers is as shown in FIG. 3 when referring to the research paper on the dissolution relationship between each block and straight asphalt components, Maltene and Asphaltene.

That is, the PS Blocks at both ends of the modified polymers are insoluble with the PB Blocks bonded to them, and are not soluble with Maltene of straight asphalt as the base material, but are soluble with asphaltenes, PB Block, on the contrary, indicates that it is insoluble with asphaltene and soluble with maltene.

As described above, it has been reported that the solubility relationship between PS Block and PB Block of SBS and thermoplastic elastomers, and Maltene and asphaltene of straight asphalt as a base material is correlated with the solubility parameter of each of the components. .

In other words, the determination of the possibility of dissolution and dispersion between substances to be mixed is a concept of “Like Dissolve Like” that has similar solubility proposed by Hilderbrand and Scott, and it is reasonable to interpret it as a traditional indicator of compatibility that the more similar solubility parameters are, the higher the compatibility. I think it will do. These solubility parameters are classified into Hilderbrand solubility parameter values and Hansen solubility parameter values and used.

According to Kamiya & Yang, the Hansen solubility parameter of Maltene of asphalt is ≤ 16.4 (J/cm3) ^1/2 , and the Hansen solubility parameter of Asphaltene is 16.4 ~ 20.4 (J/cm3) ^1/2 of asphalt. The Hansen solubility parameter of PS Block was reported as 18.6 ~ 19.8(J/cm3) ^1/2 , and the Hansen solubility parameter of PB Block was reported as 16.6 ~ 17.6(J/cm3) ^1/2 .

That is, when analyzing the Hansen solubility parameter index, the solubility parameter of PS Block and Asphaltene is almost similar, and it is predicted that the compatibility with PS Block and Asphaltene will be excellent. Maltene)'s solubility parameter is large, so poor compatibility is predicted.

On the other hand, in the case of PB Block, which is a soft segment, the solubility parameter of Maltene is similar, so it has good solubility in Maltene and the solubility is very different from the solubility parameter of Asphaltene. Fall is predicted.

Here, it is characterized in that the optimum range of the Hilderbrand solubility parameter of the petroleum resin according to the solubility parameter concept of the present invention is 8.2 to 9.6 (J/cm 3) ^1/2 .

In conclusion, when SBS and thermoplastic elastomers are heated and dispersed in straight asphalt, which is the base material, they are not simply dissolved and dispersed as substance-to-material, but in the end, individual blocks such as PS Block and PB Block of modified polymers It can be seen that a selective dissolve dispersion occurs due to the respective components of Maltene and Asphaltene of the base material, straight asphalt, and the values of the similar solubility parameters.

That is, when polymer modifiers such as SBS and thermoplastic elastomers, which are the object of the present invention, are heated and dispersed in straight asphalt as a base material, in order to exhibit easy dissolution and dispersibility, it is necessary to adjust the composition so that the unique solubility parameters of each component are similar. You can see that there is.

However, from the perspective of users of modified asphalt, in the reality that the composition ratio of maltene and asphaltene of straight asphalt used industrially cannot be arbitrarily adjusted, malten is used to maximize compatibility with SBS and thermoplastic elastomers. As a method to control the ratio of saturated hydrocarbons/aromatic hydrocarbons among (Maltene) components, there is a conventional technique for controlling by adding paraffinic, naphthenic and aromatic process oils in a composition ratio, but these process oils are also Cp (paraffinic hydrocarbon weight). %), Cn (naphthenic hydrocarbon weight%), Ca (aromatic hydrocarbon weight%) as a mixed oil mixed at a certain ratio, typically, as shown in Table 1 and Figure 4 below, by classification and figure. As the paraffinic, naphthenic, and aromatic ranges of Cp, Cn, and Ca are overlapped, it is difficult to accurately classify them, so in the present invention, the conventional technology that regulates and operates the portion ratios of these Cp, Cn and Ca There is a limitation in specifying the technology by the process oil classification as described above.

[Table 1] Classification by composition of Cp, Cn, and Ca of common process oil

Paraffinic wt% (Cp) Naphthenic wt% (Cn) Aromatic wt% (Ca) Paraffinic Oil 60 to 74 20 to 35 0 to 10 Naphthenic Oil 35 ~ 59 30 to 45 10 to 30 Aromatic Oil 20 to 35 20 to 40 35-50

Rather, as in the present invention, the concept of aniline point, which is already used as an indicator of the dissolution performance of various solvents used in the adhesive industry and adhesion theory, was introduced in the field of asphalt research for process oil in the present invention. As a result of a long study, it was judged that it was more rational and effective to reflect the purpose of the invention in the design of the modifier composition for excellent improvement in solubility and dispersibility.

As is well known, Aniline Point is a pure aromatic single substance, aniline, which is used in the same volume of oil and solvents to be used. The temperature at which the phase separation is formed while cooling is referred to as the aniline point.

In other words, it means the lowest temperature at which any oil or solvent is completely mixed with aniline, and the meaning of the aniline point value is, for example, when the aniline point is 90℃, aniline and any oil Or, it means that the temperature required for complete mixing of the solvent is 90℃, which means that there is no compatibility between room temperature and 89℃, so that phase separation is formed. If the aniline point is 20℃, any oil or It means that the solvent is mixed with aniline at 20°C (room temperature) to maintain a completely transparent solution. In general, the aniline point of any oil or solvent can be easily measured in a laboratory, and any oil or solvent It is an effective technique that has a very high utility as an index of solubility determination of, and has the characteristic that it is possible to easily adjust the aniline point because the mixed aniline points of a plurality of oils or solvents represent the arithmetic mean value of each aniline point.

Therefore, in the present invention, the existing technology from the perspective of users of modified asphalt that cannot arbitrarily control the composition ratio of Cp, Cn and Ca of process oils used for controlling the solubility of straight asphalt, which is a base material to be used as a solvent for SBS and thermoplastic elastomers. By newly introducing the concept of aniline point as an index of solubility performance that can solve the limitations of the present invention, it can be achieved effectively by introducing and operating a technique that can easily optimize and control the composition of oils as a dispersion control agent for excellent improvement of solubility and dispersibility, which is the object of the present invention. Became possible.

In the modified polymers of the asphalt modifier composition of the present invention, the optimum content of asphaltene (Asphaltene) component of straight asphalt as a base material and Styrene (PS Block) having good selective dissolution and dispersibility is 25 to 35% by weight, and marten ( Maltene) is a linear SBS with a relatively low weight average molecular weight (Mw) of 50,000 to 200,000 g/mol and 30 to 35% by weight of linear SBS with a relatively low molecular twist. Linear SBS 15 with an optimal content of Styrene (PS Block) of 25 to 35% by weight and a weight average molecular weight (Mw) of 200,000 to 400,000 g/mol so that the asphaltene component and selective dissolution and dispersion rate can be quickly achieved. SIS 5 to 9 containing ~35% by weight and good soluble Styrene (PS Block) content of 10 to 20% by weight and 15 to 25% by weight of Diblock (Styrene-Isoprene Copolymer) content by adjusting the coupling rate (%) Consisting of weight percent, one type or two or more types can be used.

In the constitutional composition of the modified polymers of the present invention, the selection of linear SBS leads to an improvement in the dissolution and dispersion rate of the base material, straight asphalt, which is the object of the present invention, because the twist of the molecular chain is lower than that of the radial SBS with many branches. In addition, linear SBS having a weight average molecular weight (Mw) of 50,000 to 200,000 g/mol and a linear SBS having a weight average molecular weight (Mw) of 200,000 to 400,000 g/mol are in the same composition range as above. SIS containing 15 to 25% by weight of Diblock content is combined with and blended by adjusting the coupling rate (%) to improve the dissolution and dispersing speed, as well as the workability and PG of the modified asphalt using these. I was able to satisfy the grade.

In terms of their composition ratio, below the lower limit of each composition range, the high temperature grade 76°C, which is the minimum PG grade of the modified asphalt, could not be satisfied, and above the upper limit, the PG grade could be satisfied, but the modified asphalt using these It was not preferable because the compaction temperature could be high.

In the high boiling point oil of the asphalt modifier composition of the present invention, the medium solubility parameter of the PB and PI block, which is a soft segment in the center of the modified polymers, and the medium solubility parameter as the main component of straight asphalt as the base material Characterized by a composition consisting of 20 to 25% by weight of a high boiling point oil having an aniline point of 30 to 45°C and a flash point of 250°C or higher, similar to the solubility parameter of the Malten component, which is the (Medium Solubility Parameter). To do. The high boiling point oil of the present invention can be used by adjusting the aniline point by combining two or more high boiling point oils.

In the high boiling point oil composition ratio of the present invention, when the composition ratio is below the lower limit value, the dissolution and dispersing rate of the straight asphalt, which is the base material of the modified polymer, is slow, and thus the object of the present invention cannot be satisfied. However, it was not preferable because the viscosity of the modified asphalt using this was lowered and the minimum PG grade of PG 76°C could not be obtained.

In the petroleum resins of the asphalt modifier composition of the present invention, the solid solution of straight asphalt, the base material to dissolve and disperse them, while trying to improve the dissolution and dispersibility of the PS Block, a high solubility parameter at both ends of the modified polymer. In order to improve the dissolution-dispersion of asphaltene, which is a component of the high solubility parameter, the solubility parameter is similar to those of the high solubility parameters as shown in Fig.7. One of resin or alicyclic C5 petroleum resin and C5-C9 alicyclic-aromatic copolymer petroleum resin may be selected or used in combination of two or more, and the addition amount thereof is configured to be 10 to 15% by weight.

In the composition ratio of the aromatic C9 petroleum resin or alicyclic C5 petroleum resin and the C5-C9 alicyclic-aromatic copolymer petroleum resin of the present invention, when the amount of these added is less than the lower limit, the dissolution and dispersion rate of the modified polymer is slow, and the upper limit or more Although the dissolution and dispersion rate is satisfactory, it was not preferable because the low-temperature stability of the modified asphalt using the same was poor.

Hereinafter, the present invention will be described in more detail through examples. These examples are for illustrative purposes only, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not construed as being limited by these examples.

For evaluation of the performance of the present invention, the modifier of the present invention was carried out as follows.

In order to evaluate the dissolution and dispersibility performance of the modified material of the present invention on the base material straight asphalt, which is the object of the present invention, based on the manual of pavement test method established by Japan Road Association [Sample Preparation of Modified Asphalt] For each of the added amounts 8% by weight, 12% by weight and 16% by weight, samples were collected at 10 minute intervals while heating and stirring and dispersing at 2,500 rpm for about 90 minutes at Shear 2,500 rpm, and each softening point (℃) was measured by ASTM D36. By measuring the vertical melt flow value at a 75 degree angle for 30 minutes at 90℃, the inflection point was found, and the minimum dissolution time of the sample sample was calculated by regression analysis to evaluate the dissolution and dispersing performance. It was carried out after dispersing and stabilizing.

Toughness (toughness, 靭性) and Tenacity (toughness, 强靭性), which are indicators of the adhesion performance (grasp strength) with the aggregates of the modifier examples and comparative examples of the present invention and the bonding strength (caking strength) between binders, were determined by ASTM D5801 Method. Analyzed.

In addition, in order to evaluate the heat resistance of the binder, that is, heat and fluid resistance, the kinematic viscosity at 60°C and the softening point (°C) of each sample were measured by ASTM D36 by ASTM D2171, and by AASHTO T315, Dynamic Shear Rheometer (DSR ) To measure the complex shear modulus (G*) and phase angle δ values and obtain the G*/sinδ values at 76°C and 82°C to determine the permanent deformation performance. , To evaluate the oxidation resistance by analyzing the fatigue crack property due to long-term aging with the G*×Sin δ value of each sample by PAV (Pressure Aging Vessel) treatment.

In addition, by measuring BBR (bending beam reometer) by AASHTO T313, the actual creep stiffness (S), creep stiffness, and the slope of the loading time curve at -12℃ (corresponding to PG -22℃) low temperature m -Value was measured to analyze the low temperature crack generation and fatigue crack characteristics.

<Modifier Example 1>

A linear SBS=20% by weight with 31.5% by weight of Styrene, a weight average molecular weight (Mw) of 320,000 g/mol, and a linear with 31.5% by weight of Styrene, with a weight average molecular weight (Mw) of 750,000 g/mol SBS=34% by weight, SIS=8% by weight with 12% by weight of Styrene and 16.7% by weight of Diblock, high-boiling oil with an aniline point of 42°C=23% by weight, and Hilderbrand solubility parameter of 8.8 (J/ C5-C9 alicyclic-aromatic copolymer petroleum resin = 14% by weight, calcium-stearate = 0.5% by weight and antioxidant I-1010 = 0.5% by weight with a ^1/2 and a softening point (℃) of 108°C After homogeneous agitation for about 20 minutes, slowly put it into the Bus-Co kneader set in the temperature range of 180℃~200℃, and the residence time is homogeneous compounding at a rate of about 20~30 minutes, while a 2mm diameter T -Pick Strands through Die. The modified compound strands homogeneously mixed in this way were cooled through a water bath controlled to a temperature of 10° C. or lower, cut to a pellet length of about 2 mm with a pelletizer, and dried to prepare a sample of the modified compound Example 1.

<Modifier Examples 2 to 4 and Comparative Example 1 to Comparative Example 3>

Samples of the modified material Examples 2 to 4 and Comparative Example 1 to Comparative Example 3 were prepared by performing the same method as in Example 1 of the modified material with the composition as specified in [Table 2] below.

[Table 2] Formulation composition of modifier Examples 1 to 4 and Comparative Example 1 to Comparative Example 3

<Modified Asphalt Example 1>

150 g of straight asphalt AP-5 was added to a clean 250 ml stainless beaker, and the temperature was raised while stirring at 180° C. at a stirring speed of about 400 rpm, and then 12 g (8 wt%) of the sample sample of Modifier Example 1 was added to increase the stirring speed. Increase to 2,500rpm and start the stopwatch while stirring. Thereafter, samples are taken every 10 minutes to prepare a sample for measuring a softening point (℃) and a vertical flow of 90℃ and 75 degrees. After 30 minutes elapsed, the remaining amount was taken out and used as a sample of Example 1 of the modified asphalt of the present invention.

<Modified Asphalt Examples 2 to 6 and Comparative Example 1 to Comparative Example 3>

Modified asphalt samples of Examples 2 to 6 and Comparative Examples 1 to 3 of modified asphalt were prepared by carrying out the same method as in Example 1 of modified asphalt with the composition specified in [Table 3] below. I did.

[Table 3] Mixing configuration of modified asphalt examples 1 to 6 and comparative examples 1 to 3

Summarizing the dissolution and dispersion performance evaluation results for the modified asphalt Examples 1 to 6 and Comparative Examples 1 to 3 are shown in [Table 4] below.

[Table 4] Results of evaluation of dissolution and dispersion performance of modified asphalt examples 1 to 6 and comparative examples 1 to 3

As can be seen in Table 4 and FIGS. 5 and 6, in the case of the modified asphalt examples 1 to 6 of the present invention, it was found that the dissolution and dispersing time was very good within about 10 minutes, whereas the modified asphalt comparative example In the case of 1 to Comparative Example 3, it was found that the dissolution and dispersion time was very slow, such as about 40 minutes or more.

Considering these results, the molecular structure of SBS uses a radial structure with a large chain twist (Comparative Example 1) and Cp = 35 to 55 wt%, Cn = 30 to 45 wt%, Ca = 10 to 30 wt. The use of a typical process oil consisting of% (Comparative Example 2) and an aliphatic C5 petroleum resin having a Hilderbrand solubility parameter of 8.1, which is different from the solubility parameter of SBS (Comparative Example 3) as the petroleum resin, is clearly the present invention. As the dissolution and dispersing rate is much slower than the examples of, it suggests that the problem solving means of the present invention is very meaningful.

In addition, as described above, the results of evaluation of the application properties performance for the modified asphalt Examples 1 to 6 and Comparative Examples 1 to 3 are summarized in [Table 5] below.

[Table 5] Results of application property performance evaluation of modified asphalt examples 1 to 6 and comparative examples 1 to 3

As can be seen in Table 5, the results of the performance evaluation of the embodiments of the present invention, in the case of modified asphalt Examples 1 to 4, in which 12g (8% by weight) of the modifier of the present invention was modified on straight asphalt as a base material, Toughness And Tenacity value, softening point expression value, and G*/sinδ expression values in DSR analysis showed that PG was 76℃, satisfactory heat and fluid resistance sufficiently, and in BBR evaluation, which is a low-temperature crack property index, all -12℃ (PG -22℃ grade) satisfies the Stiffness(S) value and m-Value value, and as a result of PG Grade evaluation, it was found that the PG 76-22 grade could be implemented.

As can be seen in Table 5 above, modified asphalt example 5-modified asphalt of 18g (12% by weight)-24g (16% by weight) of the present invention on straight asphalt as a base material. In the case of Example 6, when analyzing the Toughness and Tenacity values, the softening point expression values, and G*/sinδ expression values in DSR analysis, PG was 82°C, sufficiently satisfying the heat and fluid resistance, and in the evaluation of BBR, which is a low-temperature crack resistance index, All of them satisfies the Stiffness(S) value and m-Value value at -12℃ (PG -22℃ grade). As a result of PG Grade evaluation, it was found that PG 82-22 grade could be realized.

On the other hand, in the case of Comparative Examples 1 to 3, most of the PG 82 and PG 76 were satisfied, except that Comparative Example 3 using the radial SBS had poor cold resistance at -12°C.

However, the evaluation of the application properties performance of the comparative examples is a result of sufficiently dissolving, dispersing and stabilizing the modifiers of these comparative examples at 180° C. for 90 minutes. Since the dissolution rate is about 4 times slower than that of the modifier, it is judged that it will change to a much inferior side than the above application properties.

In conclusion, as a result of the performance evaluation, the modifying material of the present invention will have excellent dissolution and dispersibility, which is the object, when applied in a plant mix method than that of the prior art, so that the modification effect will be excellent. In the case of weight% modification, not only can the modified asphalt of PG 76-22 grade be manufactured, but also when 12 wt% to 16 wt% is modified, application to PG 82-22 grade drainage asphalt and high viscosity drainage asphalt will be sufficiently possible. It is possible to provide a multifunctional asphalt modifier composition excellent in dissolution and dispersibility, which is an object of the present invention, and a modified asphalt for drainage using the same.

As described above, specific parts of the present invention have been described in detail, and for those of ordinary skill in the art, it is obvious that these specific techniques are only preferred embodiments, and the scope of the present invention is not limited thereby. something to do. Therefore, it will be said that the substantial scope of the present invention is defined by the claims of the appended claims and their equivalents.

Claims (9)

15-35% by weight of linear SBS (Styrene-Butadiene-Styrene Copolymer) having a Styrene content of 25 to 35% by weight and a weight average molecular weight (Mw) of 200,000 to 400,000 g/mol; 30 to 35% by weight of linear SBS having a styrene content of 25 to 35% by weight and a weight average molecular weight (Mw) of 50,000 to 200,000 g/mol; SIS (Styrene-Isoprene-Styrene Copolymer) 5 to 9 wt% containing 15 to 25 wt% of Diblock (Styrene-Isoprene Copolymer) content by adjusting the Styrene content of 10 to 20 wt% and the coupling rate (%); 10 to 15% by weight of petroleum resin with a Hilderbrand solubility parameter of 8.2 to 9.6 (J/cm 3) ^1/2 ; A plant mix (Plant-Mix) asphalt modifier composition containing 20 to 25% by weight of high-boiling oil having an aniline point of 30 to 45°C and a flash point of 250°C or higher.
The method according to claim 1,
The petroleum resin is selected from the group consisting of an aromatic C9 petroleum resin, an alicyclic C5 petroleum resin, and a C5-C9 alicyclic-aromatic copolymer petroleum resin having a Hilderbrand solubility parameter of 8.2 to 9.6 (J/cm 3) ^1/2 Asphalt modifier composition of the plant mix (Plant-Mix) method, characterized in that the.
The method according to claim 1,
Plant-Mix, characterized in that the high boiling point oil having an aniline point of 30 to 45°C is a combination oil in which the aniline point is adjusted to 30 to 45°C by combining two or more high boiling point oils. Anticorrosive asphalt modifier composition.
High viscosity water drainage modified asphalt using the asphalt modifier composition of any one of claims 1 to 3.
PG (Performance Grade, publicity grade) 76-22 grade or higher drainage modified asphalt using the asphalt modifier composition of any one of claims 1 to 3.
A method for producing a water-repellent modified asphalt, characterized in that the high-viscosity water-removable modified asphalt of claim 4 is manufactured in a plant-mix method.
A method for producing a water-repellent modified asphalt, characterized in that the water-repellent modified asphalt of PG (Performance Grade) 76-22 or higher of claim 5 is manufactured by a plant-mix method.
The method of claim 6,
The asphalt is straight asphalt (Straight Asphalt), characterized in that the manufacturing method of the water-repellent modified asphalt.
The method of claim 7,
The asphalt is straight asphalt (Straight Asphalt), characterized in that the manufacturing method of the water-repellent modified asphalt.

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