KR101227739B1 - Asphalt composition having improved mechanical property and anti-aging property and Method of preparing the Same - Google Patents

Abstract

The present invention relates to an asphalt composition having improved mechanical properties and aging resistance, and a method for manufacturing the same, and more particularly, by mixing a specific polymer in asphalt or bitumen at a predetermined ratio, and optionally using an additive, such as penetration or elongation. The present invention relates to a method for providing asphalt cement having excellent mechanical properties and improved storage stability.

Asphalt, free sulfur, aromatic hydrocarbon compounds, styrene polymers, ethylene polymers, isoprene polymers, stabilizers

Description

Asphalt composition having improved mechanical property and anti-aging property and Method of preparing the Same}

1 is a schematic diagram showing a method of measuring the penetration of asphalt cement,

2 is a schematic diagram showing a method of measuring the elongation of asphalt cement,

3 is a schematic diagram showing a method for evaluating the aging degree of asphalt cement.

The present invention relates to an asphalt composition having improved mechanical properties and aging resistance, and a method of manufacturing the same, and more particularly, by mixing a polymer in asphalt or bitumen at a predetermined ratio and optionally using a specific additive, such as penetration or elongation. The present invention relates to a method for providing an asphalt cement having excellent mechanical properties and improved storage stability.

As a general rule, asphalt is classified into various types according to production methods and production regions. However, asphalt may be largely classified into natural asphalt directly produced from nature and petroleum asphalt produced from crude oil. Most asphalt currently produced and used in Korea is petroleum-based asphalt or intermittently imported natural asphalt. In general, petroleum-based asphalt is a oxidized bituminous material obtained from the bottom of a reduced pressure distillation column during the refining process of crude oil or oxidized such bituminous materials, and is mainly used for road paving, building materials, coatings and other industries. Since the quality of such asphalt is greatly influenced by the characteristics of the crude oil, poor quality asphalt is obtained by using improper crude oil. In addition, asphalt is very sensitive to temperature changes, so it must be manufactured and used to suit the climatic characteristics of the region to be used. For example, it is very important to select and use asphalt suitable for regional climatic conditions because asphalt showing good quality at high temperature (60 ° C) may have poor quality at room temperature (15 ° C) or low temperature (4 ° C). can do. On the other hand, in order to improve the quality of asphalt, many additives such as hydrocarbons have been utilized, but did not obtain a satisfactory improvement effect.

Recently, studies have been actively conducted to improve asphalt quality by adding materials such as polymer modifiers. In US Pat. Nos. 3,985,694 and 4,130,516, polymers such as polyolefin and styrene-butadiene rubber were added to asphalt to improve physical properties, but there was a problem in that the adhesion at room temperature (15 ° C.) was not improved. U. S. Patent No. 5,221, 703 also discloses a method for preparing asphalt / polymer compositions with improved properties by adding polymer modifiers such as oil and styrene-butadiene rubber. In this patent, the physical properties such as viscosity have been improved by adding the polymer modifier and oil, and in particular, the properties at low temperatures (4 ° C) have been improved, but the adhesiveness at room temperature (15 ° C) or the quality can be maintained when stored at high temperatures. The effect of improving the aging resistance was insignificant or not achieved at all. In other words, the polymer modifiers such as styrene-butadiene series cause oxidation or deterioration when stored for a long time at high temperature, which can cause deterioration of physical properties. Doing so is a very important task.

The present invention has been made to solve the above problems and to provide an asphalt composition which is excellent in adhesion at room temperature and in particular significantly improved aging resistance.

One aspect of the present invention for achieving the above object is 100 ~ 1,000,000Poise viscosity (@ 60 ℃), 5 ~ 400dmm (1 / 10mm) of penetration (@ 25 ℃) asphalt or bitumen (component A) 90 ~ 99.9 weight %; And a styrene polymer having a weight average molecular weight of 50,000 to 2,000,000 and a styrene content of 20 to 50 wt% in the polymer, an ethylene methacrylate, an ethylene propylene rubber having a weight average molecular weight of 50,000 to 1,000,000, and an ethylene content of 40 to 99.7 weight percent, or It is prepared by mixing 0.1 to 10% by weight of at least one polymer (component B) selected from the group consisting of ethyl vinyl acetate random copolymer and isoprene polymer having a weight average molecular weight of 50,000 to 1,000,000 at 110 to 220 ° C. The present invention relates to a method for preparing an asphalt composition having improved mechanical properties and aging resistance.

Another aspect of the present invention for achieving the above object is 100 ~ 1,000,000Poise viscosity (@ 60 ℃), 5 ~ 400dmm (1 / 10mm) penetration (@ 25 ℃) asphalt or bitumen (component A) 90 ~ 99.9 weight%; And a styrene polymer having a weight average molecular weight of 50,000 to 2,000,000 and a styrene content of 20 to 50 wt% in the polymer, an ethylene methacrylate, ethylene propylene rubber having a weight average molecular weight of 50,000 to 1,000,000, and an ethylene content of 40 to 99.7 weight percent, or Improved mechanical and aging resistance characteristics, characterized in that it comprises 0.1 to 10% by weight of at least one polymer (component B) selected from the group consisting of ethyl vinyl acetate random copolymer and isoprene polymer having a weight average molecular weight of 50,000 to 1,000,000. Related to asphalt composition.

Hereinafter, the present invention will be described in more detail.

As already mentioned above, the asphalt composition according to the present invention is characterized by mixing and using at least one polymer (component B) in asphalt or bitumen (component A). In addition, if necessary, one or more of a) free sulfur, b) aromatic hydrocarbon compound having an aromatic content of 80% by weight or more, and c) stabilizer may be additionally included.

Asphalt (component A), which is the main component of the asphalt composition according to the present invention, has a viscosity (@ 60 ° C.) of 100 to 1,000,000 Poise, and an invasion rate (@ 25 ° C.) of 5 to 400 dmm (1/10 mm) according to ASTM standards. It is not particularly limited as long as it falls within the range of, and various types of straight-run asphalt produced from crude oil and those diluted with a hydrocarbon oil such as paraffin, aromatic, and naphthic, respectively, or diluted with them It can be configured as. In addition, special asphalts other than petroleum-based asphalt such as coal tar pitch and Trinidad asphalt may also be included. More preferably, the asphalt has a flash point of at least 230 ° C. or higher (COC method, ASTM D-92) and accordingly, the asphaltene content (analytical method ASTM D 4142) is 2 to 40% by weight.

In addition, the asphalt is included in the composition according to the invention 90 to 99.9% by weight, because the performance improvement effect is insignificant or the fluidity may be reduced if it is out of this range.

The polymer, which is a second component of the asphalt composition according to the present invention, is added to improve the quality of asphalt as a polymer modifier. Generally, polymer modifiers can be classified into (1) thermoplastic polymers, (2) natural and synthetic rubbers, (3) thermoplastic rubbers, and (4) thermosetting polymers. Different modifiers may be applied. That is, the polyolefin resin series is used to improve the quality at high temperature, while the rubber series is used to improve the quality at the high temperature and low temperature at the same time. In this case, in particular, styrene is excellent in compatibility with asphalt. Many polymers are used.

More specifically, the polymer used in the present invention is a styrene polymer having a weight average molecular weight of 50,000 to 2,000,000 and a styrene content of 20 to 50% by weight in the polymer, an ethylene having a weight average molecular weight of 50,000 to 1,000,000 and an ethylene content of 40 to 99.7% by weight. Methacrylate, ethylene propylene rubber, or ethyl vinyl acetate random copolymer or isoprene polymer having a weight average molecular weight of 50,000 to 1,000,000 may be used, each of which may be used alone or in combination of two or more thereof.

Preferably the polymer can be used in 0.1 to 10% by weight in the composition according to the present invention, because the performance improvement effect may be insignificant or there is no additional improvement effect outside this range.

On the other hand, the polymer may be used in any form of solid or latex type, but in order to simultaneously improve the mechanical properties and aging resistance of the object of the present invention, it is more preferable that the particles are mixed with asphalt in a very small state.

Specifically, when using a polymer in a solid state, the polymer is added to the asphalt, and then a high-speed shear stirrer such as a homogenizer is used to grind into very small particles. Mixing with asphalt after grinding can save mixing time.

On the other hand, in the case of the polymer in the latex state, since the polymer having a very fine size is already mixed with water, it is only necessary to remove the water after mixing with asphalt. At this time, the water can be removed by various methods known in the art, and in particular, when mixing the styrene-based polymer and asphalt in the latex state may be removed by evaporating the water while heating.

In the present invention, in the case of using the styrenic polymer in the latex state, the solid content is 5 to 70% by weight, the molecular weight is preferably 50,000 to 2,000,000 g / mol, and in the case of using the isoprene polymer in the latex state It is preferable that solid content is 30 to 70 weight%, and molecular weight is 50,000 to 1,000,000 g / mol.

The mixing of the asphalt or bitumen (component A) and the polymer (component B) is preferably carried out at a temperature of 110-220 ° C., because of the consideration of the mixing and oxidizing properties of the two components.

Meanwhile, in the present invention, in order to further improve the mechanical properties of the asphalt / polymer composition, 1-10% by weight of hydrocarbons having 0.01% or more by weight and 0.01-5% by weight of free sulfur may be added at the same time or before or after polymer addition. have. Preferably, the mixing thereof is performed at a temperature range of 110 to 220 ° C, more preferably at a temperature of 130 to 200 ° C, and the mixing time in each step is 10 minutes to 10 hours as necessary. It can stir while adjusting.

In addition, when mixing the latex polymer and asphalt mixed with water and solid content, water may evaporate and break during the mixing process. That is, in this case, since too much amount of the latex state of the polymer is mixed within a short time to boil over phenomenon occurs, it is necessary to control the amount of the polymer mixture. Preferably it is effective to adjust the mixing ratio to 0.1 to 1.0% by weight per hour, more preferably 0.1 to 0.5% by weight relative to asphalt.

On the other hand, the additive may include a stabilizer in addition to the free sulfur and aromatic hydrocarbon compounds. That is, when the asphalt / polymer composition according to the present invention is stored at a high temperature may result in a decrease in physical properties due to oxidation and deterioration, the composition according to the present invention is solved by using a suitable stabilizer. Specifically, examples of the stabilizer include N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (N- (1,3-Dimethylbutyl) -N'-phenyl-p-phenylenediamine) as an amine compound. ) Or N-isopropyl-N-phenyl-p-phenylenediamine, tris (2,4-di-t-butylphenyl) as a phosphite compound Phosphite ([tris (2,4-di-t-butylphenyl) phospite]), 2-methyl-4,6-bis-[(octylthio) -methyl] phenol (2-Methyl-4, 6-bis-[(octylthio) -methyl] phenol) and propionate compounds include pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate] These compounds may be used alone or in combination of two or more thereof.

The preferred amount of the stabilizer is 0.001 to 1% by weight relative to the asphalt or bitumen, because if it is out of this range, the aging improvement effect is insignificant and there is no further improvement.

Physical properties of the asphalt composition prepared above can be evaluated through the existing standard test, the evaluation items are shown in Table 1 below.

Evaluation items Test Items Test equipment Test Methods Test purpose Mechanical
Properties Trespassing Invasion Pottery ASTM
D-5 Simulates crack and plastic deformation resistance by measuring the hardness of asphalt at room temperature Softening point Ring & Ball Tester ASTM
D-36 Simulation of plastic deformation resistance at high temperatures by measuring the temperature at which asphalt begins to flow Temperature sensitivity Invasion Pottery ASTM
D-5 Evaluation of temperature sensitivity according to temperature by measuring invasiveness by temperature flash point Flash tester ASTM
D-92 Simulate safety by measuring instantaneous temperature Viscosity Thermostat and
Capillery tube ASTM
D-4402 Simulation of plastic deformation resistance and workability by measuring the resistance to the flow of asphalt Shinto Thermostat and elongation gauge ASTM
D-113 Simulation of crack resistance and cohesion by measuring tensile length when tension is applied Thin Film Heating Test Thin Film Oven ASTM
D-1754 Simulates the aging state of asphalt generated during asphalt production and asphalt mixing of asphalt and aggregate

In the present invention, the degree of improvement in aging resistance was evaluated by measuring physical properties before and after storage, in particular, elongation properties after thin film heating. That is, when the difference in physical properties before and after storage is small, it can be said that the aging resistance is excellent.

Asphalt / polymer / stabilizer composition comprising the asphalt / polymer composition or stabilizer according to the present invention can be applied directly to the road paving, further reprocessed in an emulsion state using the composition as a raw material, and then to the road paving or industrial waterproofing Can be applied.

Hereinafter, the present invention will be described in more detail with reference to Examples, but this is for illustrative purposes only and is not intended to limit the scope of the present invention. In the following examples and comparative examples, the content of each material is expressed as weight relative to the total amount of asphalt / polymer / stabilizer.

Comparative Example 1

Penetration degree, softening point, viscosity, PI (penetration index), and room temperature elongation before and after heating for 100% composition of asphalt having 70% penetration (@ 25 ° C) according to ASTM standards produced by conventional methods using crude oil from Middle East Was measured and shown in Table 2 below.

Comparative Example 2

The same physical properties as those of Comparative Example 1 were measured for asphalt 100% compositions having an invasion (@ 25 ° C.) of 72 according to ASTM standards, which were produced by conventional methods using crude oil instead of Middle Eastern crude oil, and are shown in Table 2 below. It was.

Comparative Example 3

The same physical properties as those of Comparative Example 1 were measured for asphalt 100% compositions having a penetration rate (@ 25 ° C.) of 85 according to ASTM standards produced by a conventional method using Chinese crude oil, and are shown in Table 2 below.

Comparative Example 4

The same physical properties as those of Comparative Example 1 were measured for the asphalt 100% composition having a penetration of 35 ° C. (@ 25 ° C.) according to the ASTM standard produced by a conventional method using Chinese crude oil, and are shown in Table 2 below.

Comparative Example 5

Asphalt composition was prepared by adding 1% by weight of natural asphalt to 99% by weight of asphalt produced according to Comparative Example 3 in a reactor maintained at 180 ° C, and then stirring for 1 hour.

Comparative Example 6

Asphalt composition was prepared by adding 9% by weight of a hydrocarbon having an aromatic content of 91% to 91% by weight of asphalt produced according to Comparative Example 4 in a reactor maintained at 150 ° C, followed by stirring for 1 hour.

Comparative Example 7

Asphalt composition was prepared by adding 9% by weight of hydrocarbon having an aromatic content of 82% to 91% by weight of asphalt produced according to Comparative Example 4 in a reactor maintained at 150 ° C, followed by stirring for 1 hour.

Comparative Example 8

Asphalt composition was prepared by adding 9% by weight of hydrocarbon having 66% aromatic content to 91% by weight of asphalt produced according to Comparative Example 4 in a reactor maintained at 150 ° C, followed by stirring for 1 hour.

Example  One

An asphalt composition according to the present invention was prepared by adding 0.5% by weight of ethylene methacrylate having an average molecular weight of 150,000 g / mol to 99.5% by weight of asphalt produced according to Comparative Example 1, and then stirring at 150 ° C for 2 hours.

Example 2

99.5 wt% of the asphalt produced according to Comparative Example 1, 0.5 wt% of ethylene propylene rubber having an average molecular weight of 200,000 g / mol was mixed at 150 ° C., and stirred for 2 hours to prepare an asphalt composition according to the present invention.

Example 3

99.5 wt% of the asphalt produced according to Comparative Example 1 was mixed with 0.5 wt% of ethylene vinyl acetate having an average molecular weight of 350,000 g / mol, and stirred at 150 ° C. for 2 hours to prepare an asphalt composition according to the present invention.

Example 4

To 99.6% by weight of asphalt produced according to Comparative Example 1, 0.4% by weight of styrene-butadiene polymer having a weight average molecular weight of 1,000,000 g / mol and a styrene content of 23% was added, and stirred for 1 hour in a reactor maintained at 180 ° C. To prepare an asphalt composition according to the present invention.

Example  5

0.4% by weight of a styrene-butadiene polymer having a weight average molecular weight of 50,000 g / mol and a styrene content of 23% was added to 99.6% by weight of asphalt produced according to Comparative Example 1 in a reactor maintained at 180 ° C for 1 hour. By stirring, an asphalt composition according to the present invention was prepared.

Example  6

In a reactor maintained at 180 ° C, 0.4.9% of a styrene-butadiene polymer having a weight average molecular weight of 1,000,000 g / mol and a styrene content of 23.48% by weight of asphalt produced according to Comparative Example 1 was stirred for 1 hour. After adding 0.02% by weight of free sulfur and stirring for 30 minutes, 0.1% by weight of pentaerythryl tetrakis [3- (3,5-di-tert.butyl-4-hydroxyphenyl) Propionate] was added to 1 Mixing over time produced an asphalt composition according to the present invention.

Example 7

Asphalt according to the present invention was added to 99% by weight of asphalt prepared according to Comparative Example 2 by adding 1% by weight of a styrene-butadiene polymer having a weight average molecular weight of 400,000 g / mol and a styrene content of 23%, and stirring at 130 ° C. for 1 hour. The composition was prepared.

Example 8

To 98.99% by weight asphalt prepared according to Comparative Example 2, 1% by weight of a styrene-butadiene polymer having a weight average molecular weight of 400,000 g / mol and a styrene content of 23% and 0.01% of free sulfur were added and stirred at 140 ° C. for 1 hour. After preparing the asphalt composition according to the present invention.

Example 9

97% by weight of asphalt according to Comparative Example 2 was mixed with 2% by weight of a styrene-butadiene polymer having a weight average molecular weight of 400,000 g / mol and a styrene content of 23%, stirred for 1 hour, and then 1% by weight of free sulfur was added After stirring for 1 hour at 130 ℃ prepared asphalt composition according to the present invention.

Example 10

To 99.2 wt% of the asphalt composition prepared according to Comparative Example 6, 0.8 wt% of a styrene-butadiene polymer having a weight average molecular weight of 400,000 g / mol and a styrene content of 23% was added thereto, and stirred at 130 ° C. for 1 hour. Asphalt compositions were prepared.

Example 11

The asphalt composition according to the present invention was prepared by adding 2% by weight of an isoprene-based polymer having a weight average molecular weight of 100,000 g / mol to 98% by weight of the asphalt composition prepared according to Comparative Example 6, followed by stirring at 120 ° C for 1 hour.

Example 12

Asphalt composition according to the present invention was prepared by adding 1% by weight of an isoprene polymer having a weight average molecular weight of 700,000 g / mol to 99% by weight of the composition prepared according to Comparative Example 6, and then stirring the mixture at 150 ° C for 1 hour.

Example 13

0.39.6% by weight of a styrene-butadiene polymer having a weight average molecular weight of 1,000,000 g / mol and a styrene content of 23% was added to 99.6% by weight of asphalt according to Comparative Example 1, followed by stirring at 180 ° C for 1 hour. Asphalt composition according to the present invention was prepared by further mixing 0.1% by weight of isoprene-based polymer which is g / mol.

Example 14

To 99.59% by weight asphalt according to Comparative Example 1, 0.4% by weight of a styrene-butadiene polymer having a weight average molecular weight of 1,000,000 g / mol and a styrene content of 23% was stirred at 180 ° C for 1 hour, and then 0.01% by weight of phenylene Asphalt according to the present invention by adding N-isopropyl-N'-phenyl-P-phenylenediamine of phenylene diamine series and mixing for 30 minutes The composition was prepared.

Example 15

To the 99.58% by weight of asphalt according to Comparative Example 1, the weight average molecular weight of 1,000,000g / mol and 0.3% by weight of styrene-butadiene polymer having a styrene content of 23% was added and stirred at 180 ° C for 1 hour, and then the weight average molecular weight was 300,000g 0.1% by weight of isoprene-based polymer / mol was further mixed, and then 0.02% by weight of N-isopropyl-N'-phenyl-pi-phenylenediamine (N-Isopropyl-N) based on phenylene diamine After the addition of '-phenyl-p-phenylene diamine) was mixed for 30 minutes to prepare an asphalt composition according to the present invention.

Example 16

99% by weight of asphalt according to Comparative Example 1 was added at a rate of 0.5% by weight of a styrene-butadiene polymer in a latex state having a weight average molecular weight of 1,000,000 g / mol and a styrene content of 23% at a rate of 0.5% by weight for 1 hour at 200 ° C. After stirring for a while, 0.1% by weight of isoprene-based polymer having a weight average molecular weight of 300,000 g / mol was further mixed, and again, 0.1% by weight of phenylene diamine-based N-isopropyl-N'-phenyl- An asphalt composition according to the present invention was prepared by adding p-phenylenediamine (N-Isopropyl-N'-phenyl-p-phenylene diamine) and then mixing for 30 minutes.

Example 17

After adding 8% by weight of a styrene-butadiene polymer having a weight average molecular weight of 400,000 g / mol and a styrene content of 23% to 90% by weight of asphalt having 350 degrees of penetration of Chinese crude oil, the mixture was stirred at 200 ° C. for 2 hours, and then An additional 1% by weight of isoprene-based polymer having an average molecular weight of 200,000 g / mol is further mixed, and again 0.5% by weight of N-isopropyl-N'-phenyl-p-phenylenediamine (N-Isopropyl-N'-phenyl-p- Phenylene diamine) and 0.5% by weight of trisphosphite [tris (2,4-di-t-butylphenyl) phospite] were added and then mixed for 30 minutes to prepare an asphalt composition according to the present invention.

Example 18

To 98% by weight asphalt according to Comparative Example 1, 1.3% by weight of a styrene-butadiene polymer having a weight average molecular weight of 400,000 g / mol and a styrene content of 23% was added thereto, stirred at 180 ° C for 2 hours, and then the weight average molecular weight was 200,000. An additional 0.3% by weight of isoprene-based polymer g / mol is further mixed, and again 0.1% by weight of N-isopropyl-N'-phenyl-p-phenylene diamine 0.1 weight percent trisphosphite [tris (2,4-di-t-butylphenyl) phospite], 0.1 weight percent 2-methyl-4,6-bis-[(octylthio) -methyl] phenol and 0.1 weight percent Asphalt composition according to the present invention was prepared by mixing% pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate].

Example 19

90.5% by weight of hydrocarbons having an aromatic content of 82% was added to 90.5% by weight of asphalt produced according to Comparative Example 4, and stirred at 180 ° C. for 1 hour, and then an average molecular weight of 1,000,000 g / mol and a styrene content of 23% by weight of styrene-butadiene. 0.5% by weight of polymer was added again and stirred for 1 hour to prepare an asphalt composition.

The asphalt compositions prepared according to Comparative Examples 1-8 and 1-19 were measured and shown in Table 2 by measuring physical properties such as penetration, softening point, and elongation before and after heating the thin film.

Penetration (25 ℃), dmm Softening point, ℃ Viscosity
(60 ℃), P * PI Room temperature elongation (15 ℃), cm before thin film heating Room temperature elongation (15 ℃), cm after thin film heating Comparative Example 1 70 48.2 1908 -1.61 > 150 71 Comparative Example 2 72 51.0 2599 -0.3 12 5 Comparative Example 3 85 48.4 2385 -0.4 137 13 Comparative Example 4 35 59.6 - - 6 4 Comparative Example 5 70 50.3 2735 -0.25 136 9 Comparative Example 6 72 49.0 2490 -0.44 142 10 Comparative Example 7 73 49.2 2590 -0.54 123 7 Comparative Example 8 75 48.8 2310 -0.7 90 5 Example 1 74 49.1 2215 -0.9 > 150 > 150 Example 2 75 49.3 2108 -1.5 > 150 142 Example 3 78 48.8 2006 -1.4 > 150 133 Example 4 69 48.7 2028 -1.3 > 150 > 150 Example 5 69 48.6 1990 -1.0 > 150 50 Example 6 70 49.0 2108 -1.2 > 150 140 Example 7 70 51.5 2650 -0.25 > 150 125 Example 8 69 51.8 2660 -0.22 > 150 80 Example 9 67 52.4 2762 -0.14 > 150 145 Example 10 72 49.0 2082 -1.2 > 150 > 150 Example 11 73 48.6 2002 -1.3 > 150 > 150 Example 12 69 49.4 2246 -0.8 > 150 > 150 Example 13 73 48.8 1998 -1.2 > 150 > 150 Example 14 72 49.0 2062 -1.3 > 150 > 150 Example 15 73 48.9 2010 -1.2 > 150 > 150 Example 16 71 49.0 2230 -0.2 > 150 > 150 Example 17 78 72.1 4406 0.6 > 150 > 150 Example 18 70 49.9 2406 -0.8 > 150 > 150 Example 19 72 49.5 2620 -0.50 > 150 > 150

* PI (Penetration Index): An index that evaluates temperature sensitivity. It measures and measures penetration at 15 ℃, 25 ℃ and 30 ℃. The larger the value, the lower the temperature sensitivity (the lower the value, the better the quality).

PI = [20 * (1-25A)] / (1+ 50A), where A is the slope indicated in relation to each temperature and penetration

Asphalt standard that is widely applied at home and abroad is an invasion standard, and it measures asphalt hardness at 25 ℃ and classifies 60 ~ 80 as AP-5 and 80 ~ 100 as AP-3 according to the invasion. In this case, since the quality of asphalt is greatly affected by the characteristics of crude oil, the quality of asphalt produced from specific crude oil is inevitably limited. That is, the asphalt having a low penetration has a high viscosity but poor elongation and quality, and the asphalt having a high penetration has good viscosity while having a low viscosity. Therefore, the penetration of asphalt produced from crude oil has a limit of quality improvement. ·

However, in the present invention, as shown in Table 2, by using a polymer and optionally a stabilizer, while improving the penetration degree of the softening point and the temperature sensitivity index, as well as the viscosity of the various crude oils while maintaining the same penetration grade, especially thin film It was confirmed that the elongation before and after heating was significantly improved. In addition, the composition added with free sulfur showed that the softening point and viscosity were improved, but the elongation was not improved, compared to the composition before the addition, and the quality was improved by adding ethylene vinyl acetate, but the styrene-based polymer and the isoprene-based polymer were used separately or in combination. It was confirmed that the effect of improving Shinto is less than when.

In particular, by using a stabilizer suitable for a composition mixed with asphalt and a polymer can improve the resistance to aging, the results can be confirmed through the following Comparative Examples and Examples. In order to evaluate the aging resistance, the physical properties before and after storage, especially after elongation of thin film heating, were measured after long-term storage at high temperature (120 ° C.), and the results are shown in Table 3.

Before saving 3 days after storage 10 days after storage Trespassing Room temperature elongation after thin film heating Trespassing Room temperature elongation after thin film heating Trespassing Room temperature elongation after thin film heating Comparative Example 1 70 71 66 50 62 28 Example 4 69 > 150 65 > 150 62 90 Example 6 70  140 67 130 66 125 Example 15 73 > 150 69 > 150 66 > 150 Example 16 71 > 150 68 > 150 66 > 150

As shown in Table 3, in the case of Comparative Example 1, which is an asphalt-only composition, elongation after storage was drastically decreased compared to before storage, when stored at 120 ° C. for 10 days. In the case of 4, 6, 15, and 16, there was no significant change in elongation quality even after 10 days of storage at high temperature, indicating that the aging resistance and storage stability were significantly improved.

From the above results, according to the manufacturing method of the present invention, it is possible to improve the quality of various kinds of asphalt, and in particular, the adhesiveness evaluated by measuring the elongation (@ 15 ° C, ASTM D113) has been proved to be remarkably improved. In addition, it was confirmed that the mechanical properties of asphalt, such as penetration, softening point, and PI, were improved along with elongation.

Asphalt composition prepared by adding a specific polymer to the existing asphalt according to the present invention is excellent in mechanical properties such as viscosity, softening point, elongation, and the change in elongation is small even at high temperature storage, so the aging resistance and storage stability are remarkably improved. Can provide an effect. Therefore, the asphalt composition may not only be directly applied to the pavement but also may be widely applied as a pavement or industrial waterproofing material after reprocessing the composition into an emulsion state using the composition as a raw material.

Claims (9)

(A) 90 to 99.9 weight percent of asphalt or bitumen (component A) having a viscosity (@ 60 ° C.) of 100 to 1,000,000 Poise and a penetration (@ 25 ° C.) of 5 to 400 dmm (1/10 mm); And (B) a styrene polymer having a weight average molecular weight of 50,000 to 2,000,000 and a styrene content in the polymer of 20 to 50% by weight; Ethylene methacrylate, ethylene propylene rubber or ethyl vinyl acetate random copolymer having a weight average molecular weight of 50,000 to 1,000,000 and an ethylene content of 40 to 99.7 weight%; And isoprene polymer having a weight average molecular weight of 50,000 to 1,000,000; at 0.1 to 10% by weight of at least one polymer (component B) selected from the group consisting of: (C) N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (N- (1,3-Dimethylbutyl) -N'-phenyl-p-phenylenediamine), tris (2,4 -Di-t-butylphenyl) phosphite ([tris (2,4-di-t-butylphenyl) phospite]), 2-methyl-4,6-bis-[(octylthio) -methyl] phenol (2- Methyl-4,6-bis-[(octylthio) -methyl] phenol) and pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate] Adding at least one stabilizer in an amount of 0.001 to 1% by weight relative to the asphalt or bitumen (component A), and mixing at 110 ~ 220 ℃, mechanical properties and aging resistance is improved Method for producing asphalt composition. The asphalt composition according to claim 1, further comprising (D) free sulfur in an amount of 0.01 to 5% by weight relative to the asphalt or bitumen (component A). Manufacturing method. The method of claim 1, wherein the styrene polymer is mixed in a solid state by adding a predetermined compounding amount at a time, thereby improving mechanical properties and aging resistance. The asphalt according to claim 1, wherein the styrene polymer is mixed at a mixing rate of 0.1 to 1.0% by weight per hour compared to asphalt or bitumen (component A) in a latex state, and has improved mechanical properties and aging resistance. Method of Preparation of the Composition. delete delete The method of claim 2, wherein asphalt or bitumen (component A), polymer (component B) and free sulfur are added at a temperature of 110 to 220 ° C. and stirred for 0.5 to 10 hours, and then a stabilizer is added and 0.5 to 10 hours. Method for producing an asphalt composition, characterized in that the mixing, mechanical properties and aging resistance is improved. (A) 90 to 99.9 wt% of asphalt or bitumen (component A) having a viscosity (@ 60 ° C.) of 100 to 1,000,000 Poise and a penetration (@ 25 ° C.) of 5 to 400 dmm (1/10 mm); And (B) Styrene polymer having a weight average molecular weight of 50,000 to 2,000,000, polymer having a styrene content of 20 to 50% by weight, ethylene methacrylate having an average weight of 50,000 to 1,000,000, and an ethylene content of 40 to 99.7% by weight, ethylene 0.1 to 10% by weight of at least one polymer (component B) selected from the group consisting of propylene rubber or ethyl vinyl acetate random copolymer and isoprene polymer having a weight average molecular weight of 50,000 to 1,000,000; As an asphalt composition comprising: (C) N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (N- (1,3-Dimethylbutyl) -N'phenyl-p-phenylenediamine), tris (2,4- Di-t-butylphenyl) phosphite ([tris (2,4-di-t-butylphenyl) phospite]), 2-methyl-4,6-bis-[(octylthio) -methyl] phenol (2-Methyl 1 selected from the group consisting of -4,6-bis-[(octylthio) -methyl] phenol) and pentaerythryl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate] Asphalt or more stabilizer is characterized in that it further comprises an amount of 0.001 to 1% by weight relative to the asphalt or bitumen (component A), asphalt composition with improved mechanical properties and aging resistance. The asphalt composition according to claim 8, further comprising (D) free sulfur in an amount of 0.01 to 5% by weight relative to the asphalt or bitumen (component A).

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