JP2001146551A - Binder for colored pavement - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a binder for colored pavement that is heat-stable upon compounding to a heated mixture for colored pavement, is capable of restricting degradation of the physical properties of the heated mixture for colored pavement and does not generate malodor SOLUTION: An antioxidant comprising at least one of a phenol based antioxidant, an amine based antioxidant, an organic phosphorous acid compound based antioxidant and a sulfur based antioxidant is added in an amount of 0.1-5 pts.wt. to 100 pts.wt. binder for colored pavement. The binder is heat-stable when it is compounded with a heated mixture for colored pavement and can restrain degradation of its properties.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored pavement binder used as a binder for a colored pavement heating mixture used for, for example, roads, sidewalks, parks, plazas, and the like.

[0002]

2. Description of the Related Art Colored pavement binders to be incorporated into a colored pavement heating mixture are disclosed in JP-A-62-189203, JP-A-2135309, and JP-A-2136498. As described above, a hydrocarbon-based resin such as a petroleum resin and a thermoplastic elastomer is added to a mineral oil-based lubricating oil to approximate the physical properties of asphalt. Since the heated mixture for colored pavement is used at 150 to 180 ° C. during storage and use similarly to straight asphalt which is a binder used for heated asphalt pavement, stability to heat is required. However, petroleum resins and thermoplastic elastomers, which are components of the colored pavement binder, are susceptible to deterioration due to oxidation when heated and melted, and have the problem that the physical properties of the colored pavement binder are reduced. Also, the odor during the operation was a problem.

[0003] The present invention has been made in view of such circumstances, and by including an antioxidant, has a good thermal stability when blended into a heated mixture for colored pavement. It is an object of the present invention to provide a colored pavement binder capable of suppressing a decrease in physical properties and generating no odor. Further, the present invention provides an antioxidant, wherein the antioxidant contains at least one of a phenolic antioxidant, an amine antioxidant, an organic phosphite compound antioxidant, or a sulfur antioxidant. Another object of the present invention is to provide a colored pavement binder which has particularly good antioxidant effect and can suppress a decrease in the physical properties of the heated mixture for colored pavement.

The present invention relates to a colored pavement binder 10
By adding 0.1 to 1.5 parts by weight of an antioxidant to 0 parts by weight, it has good thermal stability and does not cause a change in the physical properties of the binder for colored pavement itself. It is intended to provide a binder. Furthermore, the present invention, by adding an antioxidant having a melting point of 110 ° C. or higher, reduces the amount of loss of the antioxidant during heating and mixing,
It is an object of the present invention to provide a colored pavement binder in which good thermal stability is maintained.

[0005]

According to a first aspect of the present invention, there is provided a colored pavement binder comprising a mineral oil lubricating oil, a petroleum resin, and a thermoplastic elastomer, wherein an antioxidant is added. It is characterized by. The colored pavement binder of the second invention is the phenolic antioxidant according to the first invention, wherein the antioxidant is selected from hydroquinone derivative-based, phenol-substituted, bisphenol-based and thiobisphenol-based antioxidants; Aromatic secondary amines,
Amine-based antioxidants selected from imidazole-based and aromatic-amine-based antioxidants, organic phosphite-based antioxidants, or naphthol derivative-based, dithiocarbamate-based, and thiourea-based antioxidants Characterized in that it contains at least one of the sulfur-based antioxidants described above.

[0006] The colored pavement binder of the third invention is the same as the first invention, wherein the colored pavement binder is 100 parts by weight based on the weight of the binder.
The antioxidant is added in an amount of 0.1 to 1.5 parts by weight. The colored pavement bonding material of the fourth invention is the first bonding material of the first aspect.
In the invention, the melting point of the antioxidant is 110 ° C. or more.

[0007] In order to examine the change in physical properties due to heating, a colored pavement binder having the composition shown in the following Table 1 was placed in a closed vessel at 165 ° C under air inflow, or an inert gas (carbon dioxide) inflow. The mixture was stored under stirring for 5 hours, and the physical properties thereafter were measured. Table 2 shows the results.

[0008]

[Table 1]

[0009]

[Table 2]

From Table 2, it can be seen that the physical properties of the colored pavement binder change under the inflow of air, but hardly change under the inflow of carbon dioxide, and the physical properties change by oxidation.

Next, air or an inert gas (carbon dioxide)
Into a 500 ml Erlenmeyer flask filled with
Were collected and heated at 150 ° C. for 1 hour, and the odor was smelled. Equation (1) shows the intensity of the odor at that time. Sample Aromatic mineral oil 40 ° C viscosity 5200 centistokes Flash point 295 ° C Density (15 ° C) 1.007 Naphthenic mineral oil 60 ° C viscosity 110 centistokes Flash point 240 ° C Density (15 ° C) 0.938 C9 petroleum resin manufacturer Japan Petrochemical Co., Ltd. Neopolymer 140 Softening point 145 ° C DCPD petroleum resin manufacturer Maruzen Petrochemical Co., Ltd. Product name M-845A 1345 Softening point 145 ° C C5 petroleum resin manufacturer Tonex Co., Ltd. Product name Escolets 1100 Softening point 100 ℃

C5 + CO ₂ <DCPD + CO ₂ <C9 + CO ₂ <Aromatic mineral oil + CO ₂ ≦ Aromatic mineral oil ≦ Naphthenic mineral oil + CO ₂ ≦ Naphthenic mineral oil <C5 <DCPD <C9 (1) )

According to the formula (1), the one heated with carbon dioxide sealed has a lower odor than the one heated with air sealed, and the tendency is strongly recognized in petroleum resin. It is estimated that is easily oxidized by heating.

The present inventors have conducted intensive studies to solve the above problems. As a result, by adding an antioxidant, a colored pavement binder having stable physical properties can be obtained even when heated and melted. It was found that the odor was also improved. In the first invention, since the colored pavement binder contains an antioxidant, the heat stability is good when blended into the colored pavement heating mixture, and the deterioration of the physical properties of the colored pavement heating mixture is suppressed. And no odor.

In the second invention, the antioxidant contains at least one of a phenol antioxidant, an amine antioxidant, an organic phosphite compound antioxidant, and a sulfur antioxidant. Therefore, the antioxidant effect is particularly good, and it is possible to suppress the deterioration of the physical properties of the heated mixture for colored pavement. In the third invention, the antioxidant is added at 0.1.
Since it is added in an amount of 1 to 1.5 parts by weight, it has good thermal stability and does not change the physical properties of the colored pavement binder itself. In the fourth invention, since an antioxidant having a melting point of 110 ° C. or more is added, the amount of the antioxidant lost during heating and mixing is small, and good thermal stability is maintained.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically based on its embodiments. The colored pavement binder of the present invention contains a mineral oil-based lubricating oil, a petroleum resin that adjusts the hardness of the binder, a thermoplastic elastomer that imparts viscoelasticity to the binder, and an antioxidant. Mineral oil-based lubricating oils are produced during the refining of petroleum, and their component hydrocarbons are classified into paraffinic, naphthenic and aromatic, and depending on the content of the classified composition, paraffinic and naphthenic And aromatic process oils. In addition, a liquid material obtained by polymerizing unsaturated hydrocarbon of a petroleum cracking product can be used. However, the flash point is 220 ° C. or higher, preferably 260 ° C. or higher for use by heating.

The petroleum resin is obtained by polymerizing a diolefin and a monoolefin contained in a cracked oil fraction by-produced from an ethylene plant for producing ethylene, propylene, etc. by steam cracking of petroleum without isolation. , A C5 petroleum resin made from a C5 fraction, a C9 petroleum resin made from a C9 fraction, and a C5 petroleum resin made from both.
There is a 5C9 copolymer resin. In addition, 15 to the naphtha fraction
A DCPD (dicyclopentadiene) -based petroleum resin obtained by thermally dimerizing cyclopentadiene containing 20% can also be used. This DCPD petroleum resin also includes a co-dimer of cyclopentadiene, isoprene, and 1,3-pentadiene. C5 petroleum resin and DCPD
A polymer with a petroleum resin and a polymer with a C9 petroleum resin and a DCPD petroleum resin can also be used. Further, petroleum resins obtained by hydrogenating the double bonds of these resins can also be used, and cumarone-indene resins, terpene resins and the like can also be used.

The thermoplastic elastomer includes random copolymers of SBR and SIR obtained by emulsion polymerization with styrene and butadiene, or isoprene, block copolymers, symmetric block copolymers such as SBS, SIS, styrene and butadiene. SEB which is a polymer with ethylene
Rubber elastomers such as EPM, EPDM obtained by polymerizing S, ethylene, propylene, and dienes with a Ziegler-Natta catalyst, chloroprene rubber obtained by chlorinating acetylene or butadiene, or these rubbers were reduced in molecular weight and liquefied. There are liquid rubber and the like. In addition, EVA which is a polymer of ethylene and vinyl acetate, EEA which is a polymer of ethylene and ethyl acrylate, and ethylene copolymers such as polyethylene can also be used.

The types and melting points of the antioxidants to be added are shown in Tables 3 and 4 below. Phenol antioxidants and amine antioxidants have a free radical chain terminating function, and phosphoric acid antioxidants and sulfur antioxidants have peroxide decomposition and metal deactivation functions. These antioxidants may be used alone, or may be used in combination in consideration of the above functions.

[0020]

[Table 3]

[0021]

[Table 4]

[0022]

Example 1 0.25 parts by weight of the following antioxidant was added to 100 parts by weight of a colored pavement binder having the composition shown in Table 1 above, and each sample obtained was opened at 165 ° C. The mixture was heated and stirred in a container for 18 hours, and the change in physical properties was examined.

Antioxidant 1 Manufacturer Katayama Chemical Co., Ltd. Chemical name BHT (2,6-di-t-butyl-p-cresol) Melting point 69 ° C. or higher Antioxidant 2 Manufacturer Katayama Chemical Co., Ltd. Chemical name phosphorus Triphenyl acid Viscosity (15 ° C) 3000 cp Antioxidant 3 Manufacturer Maruzen Petrochemical Co., Ltd. Chemical name 2,2'-Methylene-bis- (4-ethyl-6-t-butylphenol) Trade name Swanox 425 Melting point 119 ° C or higher

Antioxidant 4 Manufacturer Sanko Chemical Co., Ltd. Chemical name 9,10-Dihydro-9-oxa-10-phosphananthrene-10-oxide Trade name SANKO-HCA Melting point 115-119 ° C Antioxidant 5 Manufacturer Sumitomo Chemical Co., Ltd. Chemical name 4,4'-thiobis- (3-methyl-6-t-butylphenol) Trade name Sumilizer WX-R Melting point 150 ℃ or higher Antioxidant 6 Manufacturer Kawaguchi Chemical Co., Ltd. Chemical name N-phenylene -N'-Isopropyl-P-phenylenediamine Product name Antage 3C Melting point 70 ° C or higher Antioxidant 7 Antioxidant 3 50%, Antioxidant 4
50% mixed

The properties of each sample before and after the heating and stirring are shown in Tables 5 and 6 below.

[0026]

[Table 5]

[0027]

[Table 6]

From Tables 5 and 6, it can be seen that the sample to which the antioxidant was added had a smaller change in properties than the sample without the antioxidant added, and in particular, the sample to which the antioxidant having a melting point of 110 ° C. or higher was added. It can be seen that the amount of change in the properties of the antioxidant 7 was small, and that the antioxidant 7 to which two kinds of antioxidants were added also gave good results.

[0029]

Example 2 The above-described antioxidation was applied to 100 parts by weight of a naphthene-based colored pavement binder (binder) or a paraffin-based colored pavement binder obtained by blending the components shown in the following Table 7 as shown in Table 8. 0.5 part by weight of Agent 6 was added, and the mixture was heated and stirred in the same manner as in Example 1, and the change in properties before and after that was examined. Table 9 shows the results.

[0030]

[Table 7]

[0031]

[Table 8]

[0032]

[Table 9]

From Table 9, it can be seen that the addition of the antioxidant has little change in properties.

[0034]

Example 3 100 parts by weight of the binder for colored pavement shown in Table 1 were blended while changing the amount of the antioxidant 4 added. Each of the obtained samples was subjected to 18 hours at 180 ° C. under the flow of air. The mixture was stirred and the change in properties was examined. Table 10 shows the results.

[0035]

[Table 10]

According to Table 10, the addition amount of the antioxidant is 0.1%.
In the following, there is no effect, and when it is 1.5% or more, the properties of the colored pavement binder greatly change.
It turns out that the range of 1.5% is preferable.

[0037]

Example 4 To 100 parts by weight of the binder for colored pavement shown in Table 1, 0.25 parts by weight of the following antioxidant was added, and this was heated at 80 ° C. for 1 hour. It measured using the Shimadzu Corporation smell discrimination device (brand name FF-1).
1 and 2 show the measurement results. FIG. 1 shows a three-dimensional image, and FIG. 2 shows a two-dimensional image. In the figure, the X axis represents the intensity of the odor, and the Y axis and the Z axis represent the quality of the odor.

Antioxidant manufacturer Asahi Denka Kogyo Co., Ltd. Chemical name n-octadecyl-3- (4′-hydroxy-3 ′, 5 ′)
-Di-t-butylphenyl) propionate Product name ADK STAB AO-50 Melting point 50 ° C According to Fig. 1 and Fig. 2, those with the addition of antioxidants have a lower odor intensity than those without any additives. It can be seen that the quality of the odor was unstimulated, and that the non-added odor had an irritating odor, but the addition of the antioxidant reduced and changed the irritating odor.

As described above, in the present invention, since the antioxidant is added to the binder for colored pavement, the heat stability is good when the antioxidant is added to the heated mixture for colored pavement. The physical properties of the heated mixture for paving can be prevented from deteriorating, and no odor is generated. The antioxidant added to the colored pavement binder is not limited to the antioxidant used in the above embodiment. Then, a plurality of antioxidants may be blended in various ratios.

[0040]

According to the first aspect of the present invention, since the colored pavement binder contains an antioxidant, the heat stability is good when blended into the colored pavement heating mixture, and the physical properties of the colored pavement heating mixture are improved. Can be suppressed, and no odor is generated.

In the case of the second invention, the antioxidant is at least one of a phenolic antioxidant, an amine antioxidant, an organic phosphite compound antioxidant, and a sulfur antioxidant. As a result, the antioxidant effect is particularly good, and a decrease in the physical properties of the heated mixture for colored pavement can be suppressed. In the case of the third invention, since 0.1 to 1.5 parts by weight of the antioxidant is added, it has good thermal stability and does not cause any change in the physical properties of the colored pavement binder itself. In the case of the fourth invention, the melting point is 110 ° C.
Since the above antioxidant is added, the loss of the antioxidant during the heating and mixing is small, and good thermal stability is maintained.

[Brief description of the drawings]

FIG. 1 is a graph showing the results of measuring the odor when the colored pavement binder according to the present invention is heated.

FIG. 2 is a graph showing the results of measuring the odor when the colored pavement binder according to the present invention is heated.

Claims (4)

[Claims] 1. A colored pavement binder comprising a mineral oil-based lubricating oil, a petroleum resin, and a thermoplastic elastomer, wherein an antioxidant is added to the binder. 2. The antioxidant is a phenolic antioxidant selected from hydroquinone derivative-based, phenol-substituted, bisphenol- and thiobisphenol-based antioxidants, aromatic secondary amine-based, imidazole-based, and the like. Amine-based antioxidants selected from aromatic amine-based antioxidants, organic phosphite compound-based antioxidants, or naphthol derivative-based, dithiocarbamate-based, and thiourea-based antioxidants selected from sulfur-based antioxidants 2. The colored pavement binder of claim 1, comprising at least one of an antioxidant. 3. The colored pavement binder according to claim 1, wherein 0.1 to 1.5 parts by weight of the antioxidant is added to 100 parts by weight of the colored pavement binder. 4. The colored pavement binder according to claim 1, wherein the melting point of the antioxidant is 110 ° C. or higher.