WO2006080123A1

WO2006080123A1 - Color binder composition

Info

Publication number: WO2006080123A1
Application number: PCT/JP2005/020246
Authority: WO
Inventors: Yoshikazu Nakamura; Toru Tsukagoshi; Tatsuya Ito; Sadaharu Ueno
Original assignee: Nippon Oil Corporation; Nichireki Co., Ltd.
Priority date: 2005-01-31
Filing date: 2005-10-28
Publication date: 2006-08-03
Also published as: JPWO2006080123A1; JP5059595B2

Abstract

A color binder composition that is low in the content of polycyclic aromatic hydrocarbons hazardous to a human body, excelling in the compatibility of binder composition raw materials, hue, durability, water resistance and cracking preventing performance at low temperature (low temperature performance). There is provided a color binder composition produced by heating/mixing of a heavy mineral oil having a polycyclic aromatic hydrocarbon content reduced, a petroleum resin, a thermoplastic elastomer, an ethylene copolymer and an antistripping agent.

Description

Specification Color Pineda Composition Technical Field

The present invention relates to a composition for a color binder. More specifically, the present invention relates to a binder composition for color pavement that has a low content of polycyclic aromatic hydrocarbons harmful to the human body and is excellent in safety and low-temperature performance. Background art

Kara pavement is intended for harmony with the environment, color classification and attention, etc. It is paved on roadways, sidewalks, parks and open spaces.

Color pavement types include asphalt mixture pavement using colored (colored) aggregates, colored concrete pavement, block pavement, and pavement using petroleum resin or epoxy resin. Among these, in the binder for color pavement using petroleum resin, the binder composition used for it is a composition containing petroleum resin, aromatic mineral oil and styrene / conjugated gen type block copolymer. A thing (patent document 1) is already known. These binder compositions are light in color and can be colored by adding colored materials, pigments, and dyes, and when road paving aggregates are added, a mixture similar to ordinary asphalt mixtures is obtained. . However, the aromatic mineral oil used here is an aromatic mineral oil for improving the solubility and dispersibility of styrene / conjugated gen type block copolymers and the like. Recently, the toxicity of polycyclic aromatic hydrocarbons (PCA) contained in this highly aromatic mineral oil has become a problem. In view of this problem, a pavement binder composition (Patent Document 2) has been devised that contains a mineral oil with reduced polycyclic aromatic hydrocarbons, a hydrogenated petroleum resin, and a block copolymer of styrene and butadiene. However, there were problems such as high price, or insufficient compatibility between the raw materials of the binder composition, and the color pavement surface after construction was sticky. Also, conventional color paving binder composition However, there are problems such as cracking due to thermal stress at the pavement in areas where the minimum temperature in winter is below -3 in severe weather conditions.

Patent Document 1: Japanese Patent Laid-Open No. 4-1258

Patent Document 2: Japanese Patent Laid-Open No. 20 03-3-30 1 1 1 1 Disclosure of Invention

Problems to be solved by the invention

In view of such circumstances, the present invention has a low content of polycyclic aromatic hydrocarbons harmful to the human body, compatibility of the binder composition raw materials, hue, durability, water resistance, and crack prevention performance at low temperatures. The object is to provide a color binder composition excellent in (low temperature performance).

Means for solving the problem

As a result of intensive research, the present inventors have confirmed that specific non-aromatic heavy mineral oils, specific petroleum resins, specific thermoplastic elastomers, specific ethylene copolymers, and specific bipolar polymer compounds are prevented from peeling. The present invention has been completed by finding that a color binder composition obtained by heating and mixing a specific amount of an agent can solve the above problems. That is, the first of the present invention is: (A) the content of polycyclic aromatic hydrocarbons is less than 3% by mass, the content of aromatic hydrocarbons (% CA) is 4 to 15%, the kinematic viscosity (100 at) is ^{1 0~ 5 0 mm 2 / s} , a flash point of 2 3 0 or more, nonaromatic initial boiling point by Gasukuroma Bok graph method distillation test is more than 280 heavy mineral oil 2 0 - 6 0 mass %,

(B) a softening point of 80 to 140, a viscosity (at 200) of 200 to 400 mPa's, an aromatic content of 40 to 85 mass% of a petroleum resin of 30 to 90 mass%,

(C) Melt melt □ —Rate (190 ° C, 2 1.2 N) is 10 (gZ 10 minutes) or less, and weight average molecular weight is 10 0 X 10 ³ to 30 0 X 1 0 ³ 3-20% by mass of thermoplastic elastomer,

(D) Melt flow rate (19, 0, 2 1.2 N) is less than 10 (g / 10 min), and ethylene copolymer with a comonomer content of 10-30% by mass is 0.1 ~ 1 0 quality amount%,

and

(E) 0.05 to 1.0% by mass of an anti-peeling agent that is a bipolar polymer compound with a softening point of 100 to 140 and a penetration (25 mm) of 10 to 15 (1/10 mm) (For the total amount of (A), (B), (C) and (D)),

This is an invention of a color binder composition obtained by heating and mixing. A second aspect of the present invention is a color binder composition according to the first aspect of the present invention, wherein the petroleum resin is a C5 / C9 copolymer type petroleum resin. According to the third aspect of the present invention, the penetration (25) is 30 to 80 (1/1 Omm), the softening point is 30 to 100 T: the kinematic viscosity (18 o) is 90 to 600 mm ² Zs In addition, the transition temperature obtained by heating and mixing the first color pine composition according to the present invention and the aggregate having a transition temperature of 1 11 ^ or less is −30 to 1 This is a pavement mixture. The invention's effect

The color binder composition of the present invention has a low content of polycyclic aromatic hydrocarbons harmful to the human body, compatibility of the binder composition raw material, hue, durability, water resistance, and crack prevention performance at low temperatures It is a color binder composition excellent in (low temperature performance). BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

(Non-aromatic heavy mineral oil monopoly aromatic)

The content of polycyclic aromatic hydrocarbon (PCA) in the non-aromatic heavy mineral oil used in the color binder composition of the present invention must be less than 3% by mass. A PCA content of 3% by mass or more in mineral oil is not preferable because it may increase the load on the environment and the human body. For this reason, PCA is preferably 2.8% by mass or less, more preferably 2.5% by mass or less. The polycyclic aromatics (PCA) here refers to “The Institute of Petroleum” IP346 / 92 Determination of polycyclic aromatics m unused lubricating base oils and asphaltene free petroleum fractions-Dimethyl sulphoxide extraction refractive index method. It means the content (% by mass) of the polycyclic aromatic hydrocarbon compound obtained according to the method.

(Non-aromatic heavy mineral oil, one aromatic component)

The aromatic hydrocarbon content (% CA) of the non-aromatic heavy mineral oil used in the color binder composition of the present invention needs to be 4% or more and 15% or less. If the aromatic hydrocarbon content (% CA) in the mineral oil is less than 4%, the thermoplastic elastomer cannot be uniformly swelled / dispersed and the desired binder performance cannot be obtained. . On the other hand, when the content of aromatic hydrocarbons in mineral oil exceeds 15%, the content of polycyclic aromatic hydrocarbons (PCA) in mineral oil may be 3% by mass or more. Absent. For this reason, the lower limit of the content of aromatic hydrocarbon in the non-aromatic heavy mineral oil needs to be 4% or more, preferably 5% or more. The upper limit is required to be 15% or less, more preferably 12% or less, and still more preferably 10% or less.

The aromatic hydrocarbon content (% CA) here is the total carbon measured by ASTM D3238 Standard Test Method ior Calculation of Carbon Distribution and Structural Group Analysis of Petroleum Oils by the nd-M Method. It means the percentage (%) of the number of aromatic ring carbons relative to the number.

(Non-aromatic heavy mineral oil dynamic viscosity)

The kinematic viscosity at 100 of the non-aromatic heavy mineral oil used in the color binder composition of the present invention needs to be 10 to 50 mm ² s. If the kinematic viscosity at 100 is less than 10 mm ² , s, it contains a lot of light components, which is not preferable because it tends to cause white smoke during the production, paving and construction of color binders. . On the other hand, if the kinematic viscosity at 100 is more than 50 mm ² / s, the ratio of aromatic components is high and PCA may be 3% by mass or more, which is not preferable. For this reason, the lower limit of the kinematic viscosity at 100 is preferably 15 mm ² Z s or more, more preferably 20 mm ² / s or more. The upper limit is preferably 45 mm ² / s or less, and more preferably 40 mm ² Z s or less.

The kinematic viscosity here means the kinematic viscosity (mm ² s) measured by JISK 2283 Γ Crude oil and petroleum product kinematic viscosity test method and viscosity index calculation method ”.

(Aromatic heavy mineral oil flash point)

The flash point of the non-aromatic heavy mineral oil used in the composition of the color binder of the present invention needs to be 2 30 or more. When the flash point of mineral oil is less than 230, mixing with thermoplastic elastomer is performed at around 200, which is not preferable because safety at the time of production is reduced. For this reason, the flash point is preferably 24 Ot: or more, more preferably 250 or more.

The flash point here means the flash point measured by the Cleveland open-type flash point test method of J I S K 2265 “Crude oil and petroleum products one flash point test method”.

(Non-aromatic heavy mineral oil GC)

The initial boiling point of a non-aromatic heavy mineral oil used in the color binder composition of the present invention by gas chromatography distillation test (hereinafter abbreviated as GC distillation) must be 280 or more. If the initial boiling point by GC distillation is less than 280, it contains a lot of light components, which is not preferable because white smoke and the like are likely to occur during the production and construction of a color pinder mixture. For this reason, the initial boiling point by GC distillation is preferably 300 or more, more preferably 3 10 or more, further preferably 330 or more, and more preferably 350 ° C. or more.

Here, the initial boiling point by GC distillation means the initial boiling point measured by the gas chromatographic distillation test method of JISK 22 54 “Petroleum product single distillation test method”. (Non-aromatic heavy mineral oil-production method)

The crude oil used when producing the non-aromatic heavy mineral oil used in the color binder composition of the present invention is not particularly limited. For example, Pennsylvania crude oil, Mineral crude oil, Daqing crude oil, etc. Preferred are mixed base crude oils such as zone special crude oil, foot crude oil, Kuwait crude oil, Lattaway crude oil, Allian crude oil, Yeosin crude oil, and Solyushu crude oil. The non-aromatic heavy mineral oil used in the color binder composition of the present invention is not particularly limited, but is usually obtained by atmospheric distillation of crude oil such as paraffin base crude oil, naphthene base crude oil, mixed base crude oil and the like. It is preferable to distill the pressure residue and use the resulting fraction. The fraction obtained from the vacuum distillation process is solvent-removed, typically propane-removed, solvent-extracted, such as furfural extraction, and MEK (Methylethylketone) to remove wax. It is further preferable that the purification is performed by appropriately combining treatments such as solvent dewaxing, hydrocracking solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment. In particular, the lubricating oil fraction obtained by distilling crude oil under reduced pressure is treated with furfural to remove the aromatic compounds and resin from the lubricating oil fraction.・ Refined raffinate obtained by combining MEK dewaxing, etc., PDA extract, PDA obtained by evacuation of bread pan for the purpose of extracting lubricating oil fraction from vacuum distillation residue oil The PDA furfural extract obtained by full-fractal extraction of the extract and the PDA furfural rough-fat obtained by furfural extraction of the PDA extract are treated with a combination of MEK dewaxing, hydrorefining, etc. The resulting high-viscosity high-grade lubricating oil component (bright stock) is preferably used.

The use of a high-viscosity high-grade lubricating oil component (brightstock) is particularly preferred in that a color binder composition having a lower temperature performance than conventional products can be obtained.

The non-aromatic heavy mineral oil with the above physical properties is a commercially available product as shown in the examples below. W

Is available.

(Petroleum resin one softening point)

The softening point of the petroleum resin used in the color binder composition of the present invention needs to be 80 to 14 Ot :. If the softening point is less than 80, the proportion of the C5 resin is increased, the melted / dispersed state of the thermoplastic elastomer is deteriorated, and the predetermined binder property cannot be obtained. On the other hand, if it exceeds 140, the proportion of the C 9 resin increases, the compatibility with the non-aromatic heavy mineral oil deteriorates and becomes cloudy, and this is not preferable because a predetermined binder property cannot be obtained. For this reason, the lower limit is preferably 85 t: or more, more preferably 90 or more. Also. The upper limit is preferably 1 30 t or less, and more preferably 120 20 c or less.

The softening point here is a value measured according to JISK 22 07 “Petroleum asphalt one softening point test method”. (Petroleum resin one viscosity)

The viscosity (200) of the petroleum resin used in the color binder composition of the present invention needs to be 200 to 400 mPa · s. If the viscosity (200 ° C) is less than 20 Om Pa · s, the proportion of the C5 resin will increase and the melted / dispersed state of the thermoplastic elastomer will deteriorate and the specified binder properties will not be obtained. It is not preferable for the reason. On the other hand, when the viscosity (200) exceeds 400 mPa · s, the proportion of C 9 resin increases and compatibility with non-aromatic mineral oil deteriorates and becomes cloudy and the desired binder properties are obtained. Not preferred for no reason. For this reason, the lower limit of the viscosity (2 00 ^) is preferably 2 30 mPa · s or more, and more preferably 250 mPa · s or more. Further, the upper limit is preferably 380 mPa ′s or less, and more preferably 3500 mPa * s or less. The viscosity here was measured according to the “viscosity test method using a rotational viscometer” described in the “Pavement Test Method Handbook” (published by the Japan Road Association, published by Maruzen Co., Ltd.).

(Petroleum resin-aromatic content) The aromatic content of the petroleum resin used in the color binder composition of the present invention needs to be 40 to 85% by mass. When the aromatic content is less than 40% by mass, it is not preferable because the melted and dispersed state of the thermoplastic elastomer is deteriorated and a predetermined binder property cannot be obtained. On the other hand, if it exceeds 85% by mass, it is not preferable because of the deterioration of compatibility with non-aromatic heavy mineral oil, the cloudiness of the color binder composition, and the predetermined properties cannot be obtained. For this reason, the lower limit of the aromatic content is preferably 45% by mass or more, and more preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, and more preferably 75% by mass or less.

The aromatic content here refers to the aromatic content (mass) measured in accordance with the composition analysis method by column chromatography of asphalt of “JPI — 5 S— 2 2— 8 3” of the Japan Petroleum Institute Standard. %).

(Petroleum resin—type)

The petroleum resin used in the color binder composition of the present invention is composed of 1,3-pentagen as the main raw material for reasons such as compatibility of raw materials during the production of the color binder composition, improvement of the hue of the binder composition and low temperature performance, etc. It is particularly preferable to use a C5Z C9 copolymer petroleum resin produced by copolymerization from the C 5 fraction and C 9 fraction not containing cyclopentagen, dicyclopentene and the like.

The C5ZC9 copolymer petroleum resin having the above-mentioned physical properties can be obtained as a commercial product as shown in the examples below.

The petroleum resin used in the color binder composition of the present invention has the above-mentioned predetermined properties, so that the hue of the petroleum resin changes during heating and in service without hydrogenating the petroleum resin to obtain a low bromine number. It is possible to provide a color binder composition that prevents the disadvantages associated with the use of hydrogenated petroleum resins such as an increase in the size of the binder composition and the hue of the binder composition itself.

(Thermoplastic elastomer, melt point rate)

The thermoplastic elastomer used in the color binder composition of the present invention must have a melt opening (1 90 :, 2 1.2 N) of 10 (g 10 minutes) or less. It is important. The lower limit of the melt flow rate is preferably 1 (g / 10 minutes) or more, more preferably 2 (g / 10 minutes) or more, from the viewpoint of compatibility with petroleum resin. On the other hand, the upper limit is preferably 8 (gZl 2 O min) or less, more preferably 6 (gZl 2 O min) or less from the viewpoint of improving the dynamic stability of the color binder mixture.

The melt flow rate here (1 90, 2 1.2 N) is measured according to AS TMD 1 238 "Test Me forod for Flows of Thermo plastics by Extrusion P lasto me ter" The value at a test temperature of 190 and a load of 2 1.2 N. That is, a numerical value representing the flow rate in 10 minutes when the asphalt modifier melted at a constant temperature of 1 90 is extruded from a circular die of a specified length and diameter at a constant load of 21.2 N in terms of the number of drums. It is.

(Weight average molecular weight of thermoplastic elastomer)

Further, the weight average molecular weight (Mw) of the thermoplastic elastomer used in the color binder composition of the present invention is required to be 10 0 X 10 ^{3 to} 300 X 10 ³ . The lower limit of the weight average molecular weight is preferably 1 2 5 X 10 ³ or more, more preferably 1 40 X 10 ³ or more, from the viewpoint of improving the dynamic stability of the color binder mixture. Meanwhile, the upper limit is, in terms of compatibility with the petroleum resin is preferably 2 60 X 1 0 ³ or less, 2 ³ 0 X 1 0 3 or less is more preferable.

The weight average molecular weight here refers to the value of the weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC).

(Thermoplastic elastomer)

The thermoplastic elastomer used in the color binder composition of the present invention is not particularly limited as long as it has the above-mentioned properties, and examples thereof include a block copolymer of styrene and conjugated gen or a hydride thereof. Preferably, thermoplastic elastomer such as styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (S EB S), etc. Tomah is suitable for use with these thermoplastic elastomers. It is possible to combine one or two kinds of toma as appropriate. Of these, styrene-butadiene-styrene block copolymer (SBS) is more preferably used.

A preferable styrene-butadiene-styrene block copolymer has a styrene content of 5 to 40% by mass. The lower limit of the styrene content is poor in improving the toughness and tenacity, which are predetermined properties of the color binder composition, and further reduces the performance of the color binder mixture using the composition. From the point of view, it is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more. On the other hand, the upper limit is compatibility with petroleum resin and non-aromatic mineral oil mixture. Is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

The thermoplastic elastomer having the above physical properties can be obtained as a commercial product as shown in the examples below. (Ethylene copolymer one melt mouth rate)

The melt flow rate (190 "C, 21.2N) of the ethylene copolymer used in the color binder composition of the present invention must be 10 (gZlO content) or less. The lower limit is preferably 1 (gZ 10 minutes) or more, more preferably 3 (gZ 10 minutes) or more, from the viewpoint of compatibility with petroleum resin, while the upper limit is the 6 Ot viscosity of the color binder composition. 8 (gZ 10 minutes) or less is preferable, and 7 (gZ 10 minutes) or less is more preferable from the viewpoint that the improvement effect to be increased is reduced.

The melt flow rate here (1 90, 2 1.2 N) means that the test temperature measured by AS TMD 1 2 3 8 “Test Method for Flow Rates of Thermoplastics by Extrusion Plastometer” is 1 90 The value at load 2 1.2 N is taken. That is, the flow rate in 10 minutes when extruding asphalt modifier melted at a constant temperature of 1 90 from a circular die of specified length and diameter with a constant load of 21.2 N is expressed in grams. is there.

(Ethylene copolymer-comonomer content) The comonomer content of the ethylene copolymer used in the color binder composition of the present invention needs to be 10 to 30% by mass. The lower limit of the comonomer content is preferably 15% by mass or more, more preferably 18% by mass or more, from the viewpoint of improving the durability of the color binder composition 6 O: suppressing the decrease in viscosity. On the other hand, the upper limit is preferably 25% by mass or less, more preferably 22% by mass or less, from the viewpoint of compatibility with the petroleum resin and the mineral oil mixture.

Here, the content of cocoon monomer means a value obtained in accordance with the IR method described in IS 0 8 9 85. (Ethylene copolymer)

The ethylene copolymer used in the color binder composition of the present invention is not particularly limited as long as it has the above properties. For example, the comonomer may be an olefin such as propylene or butene, but the preferred comonomer is a polar comonomer such as vinyl acetate or (meth) acrylic acid ester.

Accordingly, preferred ethylene copolymers include ethylene monopolar monomer copolymers, such as ethylene-ethyl acrylate copolymer (EEA), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (EMA). Etc. More preferably, ethylene copolymers such as ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer can be used, and these ethylene copolymers can be suitably combined by combining one or more of them. Of these, ethylene-ethyl acrylate copolymer is particularly preferably used.

The ethylene copolymer having the above physical properties can be obtained as a commercial product as shown in Examples and the like described later.

(Anti-peeling agent one softening point)

The softening point of the release inhibitor used in the color binder composition of the present invention is required to be 10 0 to 1.4 0. If the softening point is less than 100, the flash point is low, which is unfavorable because it hinders handling. On the other hand, when exceeding 1 4 0 It is not preferable because the solubility of the release inhibitor is lowered and the function is not sufficiently exhibited. For this reason, the lower limit is preferably 1 10 or more, and more preferably 1 15 or more. Also. The upper limit is preferably 1 3 5 X: or less, and more preferably 1 30 or less. The softening point here is a value measured according to JISK 2207 “Petroleum Asphalt—Softening Point Test Method”.

(Permeation of one anti-peeling agent)

The penetration (2 5 "C) of the release inhibitor used in the color binder composition of the present invention needs to be from 10 to 15 (1/10 mm). 5) is less than 10 (1/10 mm) for reasons of softening the color binder composition and lowering the properties of the composition, while exceeding 15 is not preferred in the color binder composition. For this reason, the lower limit is preferably 11 or more, more preferably 1 2 or more, and the upper limit is 14. The following is preferable, and further 13 or less is preferable.

The penetration here is the penetration at 25 X measured according to JIS K 2 20 7 “Petroleum asphalt penetration test method”.

(Anti-peeling agent)

The anti-peeling agent used in the color binder composition of the present invention is blended for improving the adhesion to the aggregate. Conventionally, inorganic compounds such as slaked lime, acidic organic phosphorus compounds, maleic anhydride, maleic Anion compounds such as higher fatty acids or metal salts of higher fatty acids typified by halogenated organic compounds, cationic compounds typified by amine organic compounds, etc. Single molecules typified by fatty acid salts of aliphatic amin Bipolar polymer compounds having both cations and anions are used. Considering the fact that aggregates used in color binder pavements have extremely weak affinity with color binders, and many aggregates are easy to peel off, affecting the durability of color pavements. In the present invention, since this cause is due to the uneven distribution of aggregate ions, it is necessary to use an ambipolar polymer compound that can improve adhesion without being influenced by the ionic state of the aggregate surface. is there. In addition, the above peeling agent having physical properties can be obtained as a commercial product as shown in Examples below.

(Other ingredients)

Further, the color binder composition of the present invention can contain various additives in addition to the above constituent materials. Additives that can be blended include antioxidants (such as hindered phenolic antioxidants), UV absorbers (such as benzotriazole ultraviolet absorbers), and light stabilizers (such as hindered amine light stabilizers). Examples of such additives are those that suppress the deterioration of the binder.

(Mixing ratio of color binder composition)

The color binder composition of the present invention comprises 20 to 60% by mass of non-aromatic heavy mineral oil having the above-mentioned specific properties, and 30 to 90% by mass of petroleum resin having the above-mentioned specific properties. 3 to 20% by mass of the thermoplastic elastomer having the above-mentioned specific properties, 0.1 to 10% by mass of the ethylene copolymer having the above-mentioned specific properties, and a peeling inhibitor having the above-mentioned specific properties Is obtained by heating and mixing 0.05 to 1.0 mass% with respect to the total amount of each base material of non-aromatic heavy mineral oil, petroleum resin, thermoplastic elastomer, and ethylene copolymer. is there. The blending ratio of non-aromatic heavy mineral oil must be 20% by mass or more in that the penetration of the color binder composition is small and the softening point becomes too high to deteriorate the workability of color paving. On the other hand, non-aromatic heavy mineral oil and thermoplastic elastomer are poorly compatible, so they can be melted and dispersed sufficiently. In order to secure the blending amount of the petroleum resin to be blended, it is necessary that it is 60% by mass or less, preferably 45% by mass or less, and more preferably 40% by mass or less.

The blending ratio of the petroleum resin is required to be 30% by mass or more in order to improve the compatibility of the thermoplastic elastomer added to improve the performance of the color binder composition. % Or more is preferable, and 50% by mass or more is more preferable. Meanwhile, Kara —90% by mass or less is required, 65% by mass or less is preferable, and 60% by mass or less is more preferable in terms of suppressing breakage due to brittleness of the binder pavement. The blending ratio of the thermoplastic elastomer must be 3% by mass or more in order to improve the 60 viscosity of the color binder composition and improve the flow resistance of the color pavement. Preferably, 4 mass% or more is more preferable. On the other hand, 20% by mass or less is necessary in terms of the softening point of the color binder composition, the high kinematic viscosity at high temperatures and the increase in the construction temperature of the color pavement. 5 mass% or less is preferable and 10 mass% or less is more preferable. The blending ratio of the ethylene copolymer is 60 in the color binder composition, and is required to be 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 0.8% by mass or more in terms of improving the viscosity. . On the other hand, when the color binder composition is stored at a high temperature for a long period of time, 10 mass% or less is necessary, and 5 mass% or less is required in order to prevent the difference in properties between the upper and lower parts of the tank. 4% by mass or less is more preferable. The blending ratio of the peeling preventive agent is required to be not less than 0.05% by mass with respect to the color binder composition so that the adhesion is not impaired even with the color binder composition and poor aggregate. % Or more is preferable, and 0.2% by mass or more is more preferable. On the other hand, 1.0% by mass or less is necessary, 0.8% by mass or less is preferable, and 0.5% by mass or less is preferable in that it does not affect the binder properties such as viscosity and toughness / tenacity of the color binder composition. The following is more preferable. (Physical properties of color binder composition)

The physical property value of the color binder composition of the present invention preferably takes the following values. In particular, the following physical property values are preferred for use in color paving mixtures.

The penetration (25 ° C.) of the color binder composition of the present invention is preferably 30 to 80 (1/10 mm). Lower limit improves brittle fracture of color binder pavement 40 or more is more preferable, and 45 or more is more preferable. The upper limit is more preferably 75 or less, and more preferably 70 or less, in terms of preventing the pavement from being destroyed due to early flow rutting of the color binder pavement. .

The penetration here is the penetration value at 25 measured according to J I S K 2 2 07 “Petroleum asphalt penetration test method”.

The softening point of the color binder composition of the present invention is preferably 30 to: L 00. The lower limit is 35 or more, more preferably 40 or more, in consideration of cracking due to the temperature of the color binder pavement, and 40 or more is more preferable. In this respect, 95 ° C or less is more preferable, and 90 or less is more preferable.

The softening point mentioned here is a value measured by JISK 2207 “Petroleum asphalt one softening point test method”. The kinematic viscosity at 18 Ot: of the color binder composition of the present invention is preferably 90 to 600 mm ² / s. The lower limit is more preferably 100 mm ² Z s or more, more preferably 110 mm ² / s or more in terms of improving the environmental deterioration due to the generation of white smoke during the construction of the glass binder binder with light fractions. The upper limit is more preferably 5 50 mm ² Z s or less, and more preferably SO Omrr ^ Zs or less, in terms of improving white smoke generation due to superheat when the construction temperature is high.

Here, the kinematic viscosity is a value of kinematic viscosity at 180 measured according to JISK 2207 “Petroleum Asphalt One High Temperature Kinematic Viscosity Test Method”. The flash point of the color binder composition of the present invention is preferably 111 ° C. or lower. More preferably, it is 1 12 or less from the viewpoint of improving cracks caused by temperature changes of the color binder pavement.

The frusto-saturation temperature mentioned here is a temperature measured by JISK 22 0 7 “Petroleum tofra-sulphiation point test method”.

(Method for producing color binder composition) The color binder composition of the present invention comprises a non-aromatic heavy mineral oil and a specific amount of a petroleum resin, a thermoplastic elastomer, an ethylene copolymer, and an anti-peeling agent, and has a temperature of 130 to 200: Preferably, it can be prepared by mixing at a temperature of 170 to 190, usually 30 minutes to 20 hours, preferably 2 to 10 hours. The blending method of each component is not particularly limited, but the non-aromatic heavy mineral oil previously heated to a predetermined temperature of 130 to 200 is added to petroleum resin, thermoplastic elastomer, ethylene copolymer and release. A method of adding an inhibitor is desirable. In addition, each of the blended components can be mixed with various stirrers such as a propeller stirrer and a homogenizer, but can be mixed in a relatively short time when stirred with a high shear mixer.

(Use of color binder composition)

The main use of the color binder composition of the present invention is pavement such as sidewalk pavement, roadway pavement, water permeable, drainage pavement, pavement such as park and open space, but as other uses, civil engineering structure as a general binder It can also be used for waterproofing of objects, etc., and for corrosion protection of metal surfaces and painted surfaces. In addition, since the color binder composition of the present invention reduces components harmful to the human body, has no health and safety problems, and is excellent in hue, it is appropriately blended with a colorant or the like as a paint application, and has a light or colored color. It can also be used for anti-corrosion / water-resistant coatings that can form coatings. (Mixture for color paving)

The color pavement mixture of the present invention can be obtained by heating and mixing the aforementioned color binder composition of the present invention and aggregates. Colored pavement mixture is used for color pavement such as sidewalk pavement, road pavement, permeable / drainage pavement, pavement of parks / open spaces.

In addition, since the color binder composition of the present invention is light in color, the color expression due to the natural coloring of the colored material is remarkable even when no colored aggregate or colorant is added, in contrast to the black fascia 卜. . Therefore, the color pavement referred to in the present application includes a pavement that expresses the color of a natural material without particularly incorporating colored aggregates or colorants. Preferably, color pavements such as pigments, Aggressive color by blending colored aggregates It is a pavement that gives

The color paving mixture of the present invention used for the use of the color paving and the like is preferably produced by the following method. In a conventional asphalt mixture production plant, it is possible to produce a color paving mixture by mixing the color binder composition and heated aggregate, and then apply the mixture with conventional construction machines. Colored aggregates are also possible as aggregates. A pigment can be added and used to color the mixture. As the pigment, ordinary inorganic pigments such as iron oxide, chromium oxide, iron hydroxide, and titanium oxide can be used. The order of adding the pigment is not particularly limited, but it is preferably added when the binder, the aggregate and the filler are mixed in the asphalt mixture manufacturing plant. The added amount of the pigment is usually 2 to 3% by mass of the composition. The binder composition for color pavement of the present invention can be applied not only to the production of ordinary dense particle mixture, but also to the production of water-permeable mixture and drainage mixture having a porosity of about 20%.

(Mixture for color paving)

The transition point of the color paving mixture of the present invention is preferably 1 15 to −1. The lower limit of the transition point does not impair the flow resistance of the color binder composition and is caused by temperature change. In terms of improving cracks, it is more preferably 1 13 ^ or more, and more preferably _ 1 2 or more. On the other hand, the upper limit is more preferably 12 ° C or less, and even more preferably 13 or less, in terms of improving cracks caused by temperature changes in the color binder pavement.

Here, the transition point (the limit temperature at which the stress relaxation state disappears) was determined by a temperature stress test of a color pavement mixture comprising a color binder composition and an aggregate.

Thermal Stress Test is a summary of the 3rd Annual Conference of the Japan Society of Civil Engineers, Part 5, P 2 6 7 “Study on fracture of asphalt mixture (5th report), Moriyoshi, Sugawara, 3rd 5th Civil Engineering Annual Scientific Lecture Meeting Summary, Part 5, P 3 8 9 “Studies on the Destruction of Asphalt Mixtures (6th Report), Moriyoshi, Sugawara, 3rd Annual Conference of Japan Society of Civil Engineers W

Summary Collection, Part 5, P 4 2 9 “Study on Fracture of Asphalt Mixtures (7th Report), Thermal Stress Test described in Moriyoshi and Sugawara.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[Examples 1 to 6 and Comparative Examples 1 to 7]

The physical property values of the base materials used in Tables 1 to 5 are shown in Table 7.

-The physical property values of the binder composition were described.

Examples 1 to 6 and Comparative Examples 1 to 7 show non-aromatic heavy mineral oil with petroleum resin, thermoplastic elastomer, ethylene copolymer, and release inhibitor in Table 7 (Table 7—Example, Table 7 Comparison) Example) was mixed at the ratio described in the above, and the mixture was stirred at a temperature of 170 to 190 for about 3 hours with a high-frequency mixer. The physical properties of the obtained color binder composition are also shown in Table 7 (Table 7—Examples, Table 7_Comparative Examples).

The mineral oil, petroleum resin, thermoplastic elastomer, ethylene copolymer, and anti-peeling agent used to produce the color binders are as follows, and their properties are shown in Table 1 to Table 5, respectively. Mineral oil A: Super Oil N 4 60 manufactured by Nippon Oil Corporation

Mineral oil B: Nippon Oil Co., Ltd. Co-Molex 7 0 0

Petroleum resin A: Quinton G 1 1 5 manufactured by Nippon Zeon Co., Ltd.

Petroleum resin B: Idemitsu Kosan Co., Ltd. P— 1 4 0

Petroleum resin C: Neo-Nippon Petrochemical Co., Ltd. Neopolymer N P 1 2 0 Petroleum resin D: Mitsui Petrochemical Co., Ltd. T 1 1 0 0 X

Thermoplastic elastomer: Toughprene T 3 1 5 manufactured by Asahi Kasei Corporation

Ethylene Copolymer: Nippon Polyolefin Co., Ltd., Giei Rex E E A Viscosity Control Material; Mitsui Chemicals, Inc. High Wax N P 0 5 5

Peeling preventive agent; Neogard S— 1 0 0, manufactured by Toho Chemical Industry Co., Ltd. The physical properties of mineral oil, petroleum resin, thermoplastic elastomer, ethylene copolymer, and release inhibitor were measured by the following methods.

Polycyclic aromatics (PCA) conforms to “The Institute of Petroleum” IP346 / 92 “Determination of polycyclic aromatics in unused lubricant base oils and asphaltene free petroleum fractions-Dimethyl sulphoxide extraction refractive index method”. It was measured.

Aromatic (% CA), naphthene (% CN), and paraffin (% CP) are ASTM D3238 Standard Test Method for Calculation of Carbon Distribution and Structural Group Analysis of Petroleum Oils by the n'd'M Method " It was measured by.

The kinematic viscosity (40 t: at 100) was measured by JISK 2 28 3 “Crude oil and petroleum products kinematic viscosity test method and viscosity index calculation method”.

The flash point (CO C) was measured by the clear brand open-type flash point test method of J I S K 2 2 6 5 “Crude oil and petroleum products – flash point test method”.

The initial boiling point by GC distillation was measured by the gas chromatographic distillation test method of J I S K 2 2 54 “Petroleum products—distillation test method”.

The softening point was measured by J I S K 2 2 0 7 “Petroleum asphalt one softening point test method”.

The flash point was measured by J I S K 2 2 0 7 “Petroleum Asphalt 1 Full Point Change Test Method”. Viscosity (200 TC) was measured in accordance with “Viscosity Test Method Using Rotational Viscometer” described in “Handbook of Pavement Test Methods, Separate Volume” published by Maruzen Co., Ltd. The aromatic content was measured in accordance with the composition analysis method by the column chromatography method of asphalt of the Japan Petroleum Institute standard “JP I-5 S-2 2-8 3”.

The melt flow rate (190: 21.2 N) was measured by ASTM D 1 2 3 8 “Test Method for Flow Rates of Thermoplastics” by Extrusion Plastometer.

The weight average molecular weight was determined by gel permeation chromatography (GPC). The comonomer content was measured according to the IR method described in ISO 8 9 85. The penetration (1 Z 10 mm) was measured according to JISK 2 2 0 7 “Petroleum oil-penetration test method”. The physical property values of the color binder composition were measured by the following method.

Hue was measured according to JISK 5400 Gardener method. The smaller the number of colors, the lighter the color.

The penetration was measured according to JI S K 2 2 0 7 “Petrole oil-penetration test method”.

Toughness tenacity was measured by the test method described in “Handbook of Pavement Test Methods” (published by Japan Road Association, published by Maruzen Co., Ltd.).

The 60 viscosity was measured according to the “60 ° C. Viscosity Test Method” described in “Handbook of Pavement Test Method” (edited by Japan Road Association, published by Maruzen Co., Ltd.).

The kinematic viscosity was measured according to JI S K 2 2 0 7 “Petroleum asphalt one high temperature kinematic viscosity test method”.

(Preparation of color pavement mixture test specimen and mixture test)

A color pavement mixture was produced using the above color binder composition and aggregates shown in Table 6. The production method and the test of the resulting pavement mixture are shown below.

(Manufacture of color paving mixture)

Using a bag mill mixer, add 5.9% by mass of the aggregates shown in Table 6 and the color binder composition shown in Table 7 (Table 7—Examples, Table 7—Comparative Examples) to the aggregates, A color pavement mixture was produced by stirring and mixing for 1 minute. The obtained mixture was subjected to wheel tracking test <durability>, temperature stress test <low temperature performance evaluation> and water immersion marshall test <water resistance evaluation> by the following methods. The results are shown in Table 8. (Wheel tracking test) High durability>

Japan Road Association “Pavement Test Method Handbook” 3-7 — 3 “Wheel Tracking Test Method”

A small specimen with a specified load (6 8 6 Sat 10 N) in a constant temperature room at 60 ° C. The specimen was molded by putting the mixture for color paving into a predetermined formwork (3 0 0 X 3 0 0 X 50 mm). Move the wheel back and forth, measure the deformation (rubbing amount) at 45 minutes and 60 minutes, determine the dynamic stability (times / mm), and evaluate the resistance of the color paving mixture to rutting. The larger the value of Dynamic Stability (D S), the better the rutting resistance of the pavement mixture at high temperatures. The results are shown in Table 8.

(Temperature stress test) Low temperature performance evaluation>

Thermal stress test is an evaluation of low temperature cracks. Summary of performances of the 34th Annual Conference of Japan Society of Civil Engineers, Part 5, P2 6 7 “Study on fracture of asphalt mixture (5th report), Moriyoshi, Sugawara, 3rd Annual Meeting of the Japan Society of Civil Engineers, Summary of Performances, Part 5, P 3 8 9 “Study on the Destruction of Asphalt Mixtures (6th Report), Moriyoshi, Sugawara, 3rd Annual Engineering Society of Japan Academic Lecture Performance Summary Collection, Part 5, P4 29 “Study on the Destruction of Asphalt Mixtures (7th report), Moriyoshi, Sugawara, conducted in accordance with the thermal stress test described.

In other words, a 6 × 3 X 3 × 27 Cm rod-shaped specimen is cut from the wheel tracking test specimen. Attach the specified fixtures to both ends, set in a low temperature thermostatic chamber, and cool with liquid nitrogen at a speed of 1 O ^ Zh. The load generated on the specimen fixed at both ends during cooling was measured for each unit. The critical temperature (transition point) was determined from the relationship between temperature and tensile stress.

A lower transition point means that cracks due to temperature stress are less likely to occur at low temperatures, indicating superior low-temperature performance. The results are shown in Table 8. (Water immersion marshall test) Water resistance evaluation>

Japan Road Association “Pavement Test Method Handbook” 3-7-1 “Water immersion marshall test method”

Place the side surface of the test specimen (inner diameter 10 1.6 height 63.5 mm) into which the colored pavement mixture was placed in a predetermined form (inner diameter 10 1.6 height 63.5 mm). The maximum load (until the specimen is damaged) is measured by sandwiching the two arc-shaped loading plates, applying a load in the diametric direction at a specified temperature (60) and a specified loading speed (about 50 mm per minute). Stability) to obtain the standard Marshall stability.

The water immersion marshall test is a method of evaluating water resistance based on the Marshall stability after 48 hours of water immersion and the residual stability (%) obtained from the standard marshall stability based on the following formula. The higher the residual stability, the better the water resistance. The results are shown in Table 8.

Residual stability (%) = (6 o, 48 Marshall stability after 8 hours immersion Standard marshall stability) X 1 0 0 Table 7 (Table 7—Examples, Table 7—Comparative) and Table 8 Evaluation of the results of:

About Examples 1-6

Examples 1-6 Color binder compositions of the present invention, and the polycyclic aromatics of the color binder composition obtained from the values listed in Table 7 (Table 7—Examples, Table 7—Comparative Examples) It can be seen that the content (PCA) is small, the compatibility and hue of each base material are excellent, and the physical properties as a color paving binder are satisfied. In addition, Examples 1 to 6 in Table 8 are examples of tests and evaluations of color pavement mixtures manufactured using the color binder composition of the present invention. In both cases, the dynamic stability value has the durability required for paving, results in a low transition point, excellent low-temperature performance, high residual stability, and excellent water resistance. . About Comparative Examples 1-7

In Comparative Example 1, the proportion of mineral oil is high and the proportion of petroleum resin is low. As a result, the desired color binder composition cannot be obtained.

In Comparative Example 2, the proportions of thermoplastic elastomer and ethylene copolymer are high, and in Comparative Example 3, the proportions of mineral oil, petroleum resin, thermoplastic elastomer, and ethylene copolymer are all outside the scope of claims. Thus, the desired color binder composition could not be obtained.

Comparative Example 4 is a binder composition using a hydrogenated petroleum resin, which is not preferable because the low-temperature performance and water resistance of the color pavement mixture are inferior while the coloration point of the color binder composition deteriorates.

Since Comparative Examples 5 and 6 use C9 aromatic petroleum resin, the PCA content in the binder composition is increased, and the hue and the flash point of the binder composition are deteriorated. In addition, the color pavement mixture durability, low temperature performance, and water resistance are inferior, which is not preferable.

Comparative Example 7 is an example of using a mixture of C5 aliphatic and C9 aromatic petroleum resins. The hue deteriorates and the flashing point also deteriorates. It is inferior in performance and not preferable. Industrial applicability

The color binder composition of the present invention has a low content of polycyclic aromatic hydrocarbons harmful to the human body, compatibility of the binder composition raw materials, hue, durability, water resistance, and crack prevention performance at low temperatures It is a color binder composition excellent in (low temperature performance). Therefore, it is useful as a binder for color pavements such as roads.

table 1

Mineral oil A Mineral oil Type B Paraffin type Aromatic type Polycyclic aromatic component (PCA) Mass% 0.1 11.0 Kinematic viscosity (40 ° C) 2 1

mm / s 472.9 4830

(At 100) mm ² / s 31.58 64.76 Flash point (COC) X 316 310

The first boiling point of GC distillation. C 410 305 Density (at 15) g / cm 0.9002 1.0097 Aromatic content (% CA)% 8.8 34.6 Naphthene content: (% CN)% 22.9 4.1 Paraffin content (% CP)% 68.3 61.3

Table 2 Petroleum resin A Petroleum resin B Petroleum resin C Petroleum resin D

C5 / C9 copolymer system

Type C5 / C9 copolymer C9 aromatic C5 aliphatic

Hydrogenated products

Softening point ° C 115 140 130 100 Viscosity (200 ° C) mPa * s 350 360 320 310

Is3 Aromatic content Member / o 76 3 92 5 Oxidized mgKOH / g <0.1 0 0.0 <0.1 Bromination g / 100g 30 0 25 35 Number average molecular weight (GPC) 1,150 930-1,250 Weight average molecular weight (GPC)-- 1,800 3,350

Table 3

Table 4

* EEA: ethylene-ethyl acrylate copolymer 6

Table 6

Aggregate name Mixing ratio

G No. crushed stone mass ^_0/0 37

No.7 crushed stone mass% 15

Coarse sand Mass% 34

Fine sand Mass% 7

Stone powder Mass% 7

No. 6 meteorite, No. 7 crushed stone ... Specified in JIS A5001 “Crumble for road” Table 7—Examples

* Blended with 100% by mass of mineral oil, petroleum resin, thermoplastic elastomer, ethylene copolymer, and viscosity modifier.

Table 7—Comparative Examples

Table 8

Color paving mixture evaluation results

Dynamic stability Transition point Residual stability Times / mm ° C% Example 1 1050 -18.0 95 Example 2 7875 -17.0 95 Example 3 850 -14.0 90 Example 4 6800 -22.0 90 Example 5 980 -12.0 89 Actual 6 8700 -24.0 96 Comparative Example 1

Comparative example 2

Comparative Example 3

Comparative Example 4 980-8.0 75 Comparative Example 5 600 -9.0 85 Comparative Example 6 5250 -7.0 80 Comparative Example 7 1100 -4.0 90

Claims

The scope of the claims

1.

(A) Polycyclic aromatic hydrocarbon content less than 3% by mass, aromatic hydrocarbon content

(% CA) is 4 to 15%, kinematic viscosity (at 100) is 10 to 50 mm ² / s, flash point is 230 or more, and initial boiling point by gas chromatography distillation test is 280 or more 20-60% by mass of aromatic heavy mineral oil,

(B) Softening point 80 ~: 1 40, viscosity (200) is 200 ~ 400111? 3'5, petroleum resin with aromatic content 40-8 5 mass% 30-90 mass%,

(C) Thermoplastic elastomer with a melt flow rate (190, 21.2 N) of 10 (g / 10 min) or less and a weight average molecular weight of 100 X 10 ^{3 to} 300 X 10 ³ 3-20% by mass of Tomaichi,

(D) Melt flow rate (190, 21.2 N) is 10 (gZlO min) or less. Copolymer content is 10 to 30% by mass. 0% by mass,

and .

(E) An anti-peeling agent that is a bipolar polymer compound having a softening point of 100 to 140 tons and a penetration (25X :) of 10 to 15 (1/10 mm) is 0.0 5 ~ 1.0% by weight (based on the total amount of (A), (B), (C) and (D)),

A color binder composition obtained by heating and mixing.

2.

The color binder composition according to claim 1, wherein the petroleum resin is a C 5 / C 9 copolymer petroleum resin.

3.

Penetration (25 ° C) is 30 ~ 80 (1/1 0 mm), softening point is 30 ~ 1 0 0, kinematic viscosity (at 1 80) is 90 ~ 600 mm ² / s Yes, and there is a single point of flagging The color pavement characterized by having a transition point of 1 30 to 1 obtained by heating and mixing aggregates with a color binder composition according to claim 1 which is 1 1 "C or less. blend.