KR20040025057A - Asphalt Sealant Composition Containing Waste Edible Oil - Google Patents

Abstract

PURPOSE: Provided is an asphalt sealer composition using waste edible oil, which is environmental-friendly, has excellent low-temperature adhesion, low-temperature flexibility and heat resistance, and is suitable to a zone in which a change in temperature is great. CONSTITUTION: The asphalt sealer composition using waste edible oil comprises 10-90 wt% of asphalt, 0.5-40 wt% of a styrene-conjugated diene block copolymer, 0.5-50 wt% of a petroleum resin and 0.5-40 wt% of waste edible oil. In particular, the asphalt is straight asphalt having a softening point of 30-100 deg.C and a penetration of 30-195. Further, the styrene-conjugated diene block copolymer is selected from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butadiene-styrene block copolymer and a styrene-butadiene block copolymer and a mixture thereof.

Description

Asphalt Sealant Composition Containing Waste Edible Oil

The present invention relates to an asphalt sealing material composition using waste cooking oil, and more specifically, to crack and filler (joint filler), joint material, expansion joint sealing material for the construction and construction of asphalt or concrete pavement, bridges or various structures ( It relates to an asphalt sealant composition using waste cooking oil that can be used for joint sealant or filler, binder, primer, waterproof sealant, waterproof membrane, bridge waterproof coating or hot melt adhesive.

Asphalt sealants generally have excellent adhesion to concrete or asphalt concrete at room temperature, but exhibit viscous behavior that flows down at high temperatures, and brittle fracture at low temperatures below 0 ° C may cause cracks in the sealant itself. When the adhesive force is poor, there is a problem in that the desorption from the substrate (base) when the tensile force is applied.

Therefore, there is a need for an asphalt sealant composition having sufficient heat resistance at high temperatures in summer and having flexibility and adhesion even in winter.

Japanese Laid-Open Patent Publication No. 57-98559 discloses asphalt containing an aromatic and / or naphthenic oil (or mineral oil) and a thermoplastic rubber as a rubber additive for asphalt modification.

Mineral oil gives plasticity effect to the asphalt to give flexibility, thermoplastic rubber to create a three-dimensional network structure in the asphalt matrix to increase the softening point and give toughness, but these compositions also have a problem that the adhesiveness and flexibility at low temperatures are not sufficient.

In addition, U.S. Patent No. 4,485,201 discloses an antioxidant that provides heat resistance to blends containing waste tire rubber powder and styrene-butadiene-styrene block copolymers (linear or branched) in asphalt, and hydrogenated rosin-based adhesives to increase adhesion. Disclosed is an asphalt composition mixed between 149 ° C. and 204 ° C. by adding processing oil as a tackifying agent, plasticizer or softener.

Since the composition has high cohesion and adhesion at high temperatures, high flexibility at high and low temperatures, and excellent elasticity, the composition is applied to a crack filler, a concrete expansion joint sealer or a filler, and an upper part of a building. It says that it can be used as a sealant.

However, the product made of the composition has a problem that the flow and plastic deformation occurs when exposed to high temperatures in the summer, prolonged to a small impact at low temperatures, there is a disadvantage that there is little tensile elongation very hard.

In addition, the amount of the tackifier is used in a small amount of 0.02 to 0.5 parts by weight with respect to 100 parts by weight of asphalt has a disadvantage in that the adhesion is particularly poor at low temperatures.

In addition, Korean Patent Publication No. 94-5188, a thermoplastic elastomer (TPE), is used to dissolve in asphalt to which plasticizer is added using styrene-butadiene-styrene block copolymer, and then add coumarone-indene resin and rubber powder to give strength. And a method for producing a rubberized asphalt coating waterproofing material having high hardness, as well as increased adhesive strength and solid content.

The composition is increased by 10 to 25 parts by weight of the coaron indene resin as a tackifier with respect to 100 parts by weight of asphalt, but the low-temperature adhesiveness and flexibility is not enough, there is a risk of desorption in winter.

On the other hand, the waste cooking oil is known as a raw material for the regeneration industrial paint as in Korean Patent Application No. 2001-8058 or as a fuel oil composition as in Korean Patent Application No. 1999-49548. Recycling is being limitedly used due to problems such as physical properties, and the current waste cooking oil is mainly used to make soap.

Therefore, in the present invention, as a result of extensive research in order to solve the above problems, by applying waste cooking oil to the asphalt sealing material composition as a softener or plasticizer, the adhesion and flexibility at low temperature, but also excellent heat resistance and four seasons temperature change It has been found that it can be used even in a large and severe crossover area, the present invention was completed based on this.

Accordingly, an object of the present invention is to recycle waste cooking oil, which is not only environmentally friendly, but also excellent in low temperature adhesiveness and low temperature flexibility, and excellent in heat resistance, thereby providing an asphalt sealing material composition using waste cooking oil suitable for four season temperature change and severe crossover areas. It is.

Asphalt sealant composition using waste cooking oil of the present invention for achieving the above object is 10 to 90% by weight of asphalt, 0.5 to 40% by weight of styrene-conjugated diene block copolymer, 0.5 to 50% by weight of petroleum resin and 0.5 to 40 weight percent.

Looking at the present invention in more detail as follows.

Asphalt sealant composition of the present invention comprises asphalt, styrene-conjugated diene block copolymer, petroleum resin and waste cooking oil.

The amount of the asphalt used in the present invention is preferably 10 to 90% by weight. If the amount of the asphalt is less than 10% by weight, the compatibility with Ascon is poor, and the adhesion is poor. And heat resistance worsens and elasticity tends to disappear.

As the asphalt, any asphalt can be used, such as straight asphalt, cutback asphalt, goose asphalt, blown asphalt, emulsified asphalt, Fiji (PG) grade asphalt, but it is preferable to use straight asphalt.

It is further more preferable that the straight asphalt has a softening point of 30 to 100 ° C and a penetration of 30 to 195, and a softening point of 40 to 60 ° C and a penetration of 80 to 180.

Examples of the straight asphalt include AP-5, AP-3, and AP-2.5 provided by SK Oil and LG Caltex Oil. More preferable asphalt content is 20 to 60% by weight.

The asphalt sealant composition of the present invention comprises a styrene-conjugated diene block copolymer to increase the modulus and strength. As the styrene-conjugated diene block copolymer included in the asphalt sealant composition of the present invention, styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-ethylene-butadiene-styrene (SEBS), styrene-butadiene Block copolymers, such as (SB), can be used, and these can also be used in mixture of 1 or more types.

In addition, when using the same type of block copolymer, the molecular weight and styrene content of each block may be changed and used. In particular, styrene-butadiene-styrene triblock copolymer is most suitable, and it is more preferable to use a triblock copolymer having a styrene content of 20 to 60 mol%, and the most preferable styrene content is 25 to 40 mol. %to be.

The form of the block copolymer can be either linear or branched. The number average molecular weight of the block copolymer is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 300,000.

SBS triblock copolymers are thermoplastic rubbers that are provided in pellet, powder, and powder form. For example, KOSYN KTR-101, 101P, 201, 401, 401P, etc. manufactured by Kumho Petrochemical Co., Ltd. Chemical products and Shell's Kraton products. The product form of the block copolymer is preferred because the powder form has a short dissolution time.

Styrene-butadiene-styrene block copolymers, one of thermoplastic rubbers, are fully dispersed in the asphalt matrix by high-speed mixing at high temperatures (between 150 ° C and 200 ° C) by means of high shear mixers or ordinary impeller mixers. Forming a network structure of the form and its content increases as its content increases, but the disadvantage is relatively expensive compared to asphalt.

Therefore, it is necessary to appropriately control the content of such a block copolymer, and at the same time, when the high concentration of petroleum resin, which is a tackifier included in the sealant composition of the present invention, prevents the decrease in elasticity and increase in brittleness of the asphalt sealant composition, In consideration of the aspect, the content of the styrene-conjugated diene block copolymer is 0.5 to 40% by weight, but is preferably as low as 2 to 15% by weight, and it is more preferable to add 15 to 25% by weight to maintain elasticity at low temperature. Used.

Petroleum resin included in the asphalt sealant composition of the present invention serves as a tackifying agent, aromatic petroleum resin, coumarone indene resin, aliphatic petroleum resin, hydrogenated dicyclopentadiene resin (hydrogenated dicyclopentadiene hydrocarbon At least one selected from hydrocarbon resin or petroleum resin can be used. In particular, it is most preferable to use the hydrogenated dicyclopentadiene type resin which is excellent in adhesive force and low brittleness.

In addition, one or more selected from commonly used tackifiers such as rosin, hydrogenated rosin, hydrogenated rosin ester, modified rosin, shellac, copal, fatty acid, phenolic resin, polyamide, and polyester resin can be used in combination with petroleum resin. have.

Such petroleum resins work well to adhere to substrates such as asphalt or concrete even when the polymer modified asphalt composition is used as a waterproofing material, a sealing material, a sealing material, a road crack repair agent or a filling material in cold regions.

The content of the petroleum resin is 0.5 to 50% by weight, more preferably 10 to 40% by weight. If the content of the petroleum resin is less than 0.5% by weight, there is almost no additive effect, and if the content of the petroleum resin exceeds 50% by weight, the elasticity of the sealing material composition is lowered and brittleness easily broken at low temperature occurs.

The waste cooking oil contained in the asphalt sealant composition of the present invention is simply filtered and purified waste cooking oil using room temperature or 60 ° C. or less using various filtration materials such as cotton wool, glass wool, quartz wool, filter paper or filter cloth. Removes suspended solids, food dregs, carbonaceous substances, etc., and the filtration apparatus may use a pressurized or pumped method to increase the filtration rate.

In addition, waste cooking oil includes both vegetable oils obtained from soybeans, castors, sesame seeds, cottonseeds, palms, corn, etc., and animal and animal wastes discarded after use, such as various animal oils such as various kinds of tallow, pork and fish oils.

The amount of the waste cooking oil used is 0.5 to 40% by weight, preferably 5 to 20% by weight. If the amount of use is less than 0.5% by weight, there is almost no effect of addition, and if the amount is more than 40% by weight, plasticization is severe and undesirable. In special cases, cooking oil may be used instead of waste cooking oil.

On the other hand, the asphalt sealant composition of the present invention may further comprise less than 50 parts by weight of the waste tire rubber powder with respect to 100 parts by weight of the sealing material composition in order to improve the hardness, softening point and the original recovery rate.

The waste tire rubber powder is a powder obtained by crushing the discarded tire at room temperature or low temperature, and includes styrene-butadiene rubber (SBR) and / or natural rubber and carbon black.

The average particle size of the waste tire rubber powder is preferably 200 mesh or less, more preferably between 10 and 80 mesh. The finer the waste tire rubber powder is, the better the physical properties such as elongation and adhesiveness are used. Therefore, it is preferable to use as fine a powder as possible.

By using the waste tire rubber powder in the asphalt sealant composition of the present invention, the manufacturing cost can be further lowered, and the problems of environmental pollution due to waste tire disposal and incineration can be solved.

Asphalt sealant composition according to the present invention may further include an inorganic filler to 200 parts by weight or less with respect to 100 parts by weight of the sealing material composition in order to increase the softening point.

As inorganic fillers, talc (talc), silica, dolomite, magnesium hydroxide, alumina hydroxide, kaolin (white clay), mica, barium sulfate, calcium carbonate, asbestos, aggregate, stone powder, steel slag, etc. can be used alone or in combination. Can be.

Among the inorganic fillers, talc, calcium carbonate or silica is most preferably used alone, and two or more of talc, calcium carbonate or silica may be used in combination depending on the intended use. The smaller the average particle size of talc, calcium carbonate or silica, the better, but between 20 and 2,000 mesh is suitable.

In the asphalt sealant composition according to the present invention, a plasticizer or a softener is further added in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the sealant composition in order to further increase the penetration, low temperature adhesion and low temperature elongation of the asphalt sealant composition. can do.

As a plasticizer or a softener, heavy oil (bunker A, B, C oil), lubricating oil, various process oils (paraffin type, naphthenic type, aromatic type). Phthalate plasticizers (DOP, DINP, DBP, DIBP, DHP, etc.), aromatic carbonic acid ester plasticizers (TOTM, DEDB, etc.), aliphatic dibasic acid ester plasticizers (DOS, DOA, DIDA, DOZ, etc.), phosphate (phosphate ester) plasticizers (TCP, TOF, TPP, etc.), epoxy plasticizer (epoxidized soy bean oil or epoxidized linseed oil), chlorinated paraffin, phosphorus-chlorine-containing plasticizer (TCPP, TCEP, etc.) alone or in combination thereof Can be used.

Plasticizers mainly used in the asphalt composition of the present invention include bunker-C oil, dioctylphthalate (DOP), tricresyl phosphate (TCP), naphthene or aromatic process oil, etc. There is this. Among these, it is particularly preferable to use aromatic and naphthenic process oils alone or in parallel.

The addition of process oil greatly increases the elongation of the asphalt sealant composition but slightly reduces the softening point, slightly increasing the penetration and making it very good at low temperature flexibility and adhesion. Therefore, it is particularly suitable for various uses such as joints, sealants, sealing materials, crack repair agents, waterproofing materials or filling materials in cold regions.

Suitable process oils according to the present invention include naphthenic process oils produced by unchanged petroleum, N-1, N-2 and N-3, aromatic process oils A-2 and A-3, of which A-3 is used. Most preferably, it is contained in the asphalt composition because it dissolves SBS rubber well and compatibility with asphalt greatly increases the flexibility.

In the asphalt sealant composition of the present invention, antioxidants, light stabilizers (ultraviolet absorbers or HALS-based light stabilizers), thermal stabilizers, and the like may be further added to prevent physical property degradation, and colorants and antibacterial agents such as dyes and pigments may be added depending on the application. Anti-slip agent, anti-wear agent, etc. may be added.

In addition, it may contain various reinforcing agents such as glass fibers, glass flakes, carbon fibers and silicon carbide fibers, and may contain polymers such as rubber or polyethylene, ethylene-based copolymers and / or plastics such as polypropylene, or wastes discarded using these. It may be.

Polymeric wastes include various crushed rubber products, polyethylene wastes such as agricultural waste vinyl, styrene waste plastics (for example, yogurt bottles or styrofoams of high impact polystyrene), and the like.

Asphalt sealant composition of the present invention can be produced regardless of the type and mixing order of the mixer, such as an impeller mixer, high shear mixer. It is preferable here to use high shear or high viscosity mixers in order to obtain a more uniformly dispersed composition and to mix in less time.

Hereinafter, the asphalt sealing material composition of the present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.

Example 1

Melted asphalt (SK-5 from SK), SBS block copolymer (KOSYN KTR-101P from Kumho Petrochemical), Petroleum resin (Sukorez SU-120 from Kolon Oil), Waste cooking oil, Antioxidant (Songnox from Songwon Industries) , HALS-based light stabilizer, waste tire rubber powder (Korea Resources Recycling Corporation) and talc (Hanjung Talc Co., Ltd. KCN325) is put in the impeller mixer according to the contents given in Table 1 below and stirred for at least 4 hours while maintaining 160 ~ 190 ℃ Ash compositions were prepared.

Examples 2-5

It was prepared in the same manner as in Example 1 except for changing to the composition and content shown in Table 1.

Comparative Example 1

Except for using bunker C oil (LG Caltex essential oil) instead of waste cooking oil was prepared in the same content and method as in Example 2.

Comparative Example 2

It was prepared in the same amount and method as in Example 2 except for using A-3 (unchanged petroleum), an aromatic oil, as a process oil instead of waste cooking oil.

For the asphalt sealant compositions of Examples 1 to 5 and Comparative Examples 1 and 2 produced by the above method, the penetration, softening point, elongation and tensile adhesion length were measured as follows, and the results are shown in Table 1 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Composition of Composition (wt%) Asphalt AP-5 34 35 34 49 31 35 35 SBS KTR-101P 18 20 22 10 18 20 20 Petroleum resin 35 30 28 28 28 30 30 Waste Cooking Oil 12 14 15 10 12 - - Antioxidant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Light stabilizer 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Waste Tire Rubber Powder - - - 2 - - - Talc - - - - 10 - - Bunker C oil - - - - - 14 - Process oil - - - - - - 14 Properties Breakthrough (dmm) ¹⁾ 73 88 85 87 65 47 64 Softening Point (℃) ²⁾ 103 102 106 93 108 112 110 Elongation (cm) ³⁾ 76 66 64 70 62 87 70 Tensile Adhesion Length (mm) ⁴⁾ 65 86 80 41 49 14 20

The final physical properties of the asphalt sealant compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were measured by the methods given below.

1) Penetration Degree: KS M 2252 (Load 150g)

2) Softening point: KS M 2250

3) Shinto: KS F 4052

4) Tensile Adhesion Length: KS F 2368 (However, the measured temperature is measured by using a low temperature chamber at -20 ℃ instead of room temperature)

Referring to Table 1, it can be seen that the composition to which the waste cooking oil is added as a composition according to the present invention not only has good heat resistance but also has a very large tensile adhesive length indicating low temperature (-20 ° C.) adhesion.

In particular, when the same content as in Example 2 where the low-temperature tensile adhesion length was greatest was used, and Bunker C oil was used instead of the waste cooking oil (Comparative Example 1), the penetration was greatly reduced and the heat resistance and elongation increased, but The adhesion was significantly worse.

In addition, when A-3, which is a process oil instead of waste cooking oil, was used (Comparative Example 2), the penetration was slightly decreased and the softening point was increased. However, the low temperature adhesiveness was very bad as in Bunker C oil.

Therefore, when the waste cooking oil is used in place of the process oil or bunker C oil, it can be seen that the adhesiveness at the low temperature is greatly increased due to the excellent low temperature flexibility while reducing the heat resistance.

In addition, the compositions given in Examples 1-3 show excellent low temperature adhesion that meets US standard ASTM D-1190, which is a specification for melt-injection sealants for expansion joints.

As described above, the asphalt sealing material composition of the present invention is very good low-temperature adhesiveness by using a suitable amount of waste cooking oil, while also suitable for physical properties such as penetration and heat resistance. Therefore, the present invention is to apply the waste cooking oil discarded or recycled only as a soap to the sealing material to have excellent physical properties.

Asphalt sealant composition of the present invention is used in the construction and repair of pavement, buildings, bridges and structures according to various construction methods using various equipment even in the region of high temperature change, crack repair agent, joint material, expansion joint sealing material Alternatively, it can be used as a filling material, a sealing material, a waterproofing material, a waterproofing film, an index film, a geomembrane, an intermediate layer of a shock absorbing film, an upper coating material of various structures, an underbody coating of military vehicles and equipment, a packaging repair film, a dustproof material, etc. Or it can be used for more applications, such as a binder for the reinforcing agent.

Therefore, it is possible to contribute to environmental protection by securing the technology for obtaining the asphalt sealing material composition having excellent physical properties by recycling the waste cooking oil discarded.

Claims (10)

Asphalt sealant composition using waste edible oil, comprising 10 to 90% by weight of asphalt, 0.5 to 40% by weight of styrene-conjugated diene block copolymer, 0.5 to 50% by weight of petroleum resin and 0.5 to 40% by weight of waste cooking oil. . The asphalt sealant composition according to claim 1, wherein the asphalt is straight asphalt having a softening point of 30 to 100 ° C and a penetration of 30 to 195. The method of claim 1, wherein the styrene-conjugated diene block copolymer is a styrene-butadiene-styrene (SBS) block copolymer, a styrene-isoprene-styrene (SIS) block copolymer, a styrene-ethylene-butadiene-styrene (SEBS) block Asphalt sealant composition using waste cooking oil, characterized in that one or more selected from the group consisting of a copolymer and a styrene-butadiene (SB) block copolymer. The method of claim 1, wherein the petroleum resin is selected from the group consisting of hydrogenated dicyclopentadiene hydrocarbon resin (hydrogenated dicyclopentadiene hydrocarbon resin), aromatic petroleum resin, coumaroneindene resin and aliphatic petroleum resin Asphalt sealing material composition using waste cooking oil. The method of claim 1, wherein the petroleum resin further comprises one or more components selected from the group consisting of rosin, hydrogenated rosin ester, modified rosin, shellac, copal, fatty acid, phenol resin, polyamide resin, polyester resin Asphalt sealing material composition using waste cooking oil characterized in that. The composition of claim 1, wherein the composition is a heavy oil, a lubricating oil, a process oil, a phthalate plasticizer, an aromatic carbonic acid ester plasticizer, an aliphatic dibasic acid ester plasticizer, a phosphate (phosphate ester) plasticizer, an epoxy plasticizer, a chlorine-containing plasticizer and a phosphorus-chlorine. Asphalt sealant composition using waste cooking oil, characterized in that it further comprises one or more plasticizers or softeners selected from the group consisting of containing plasticizers. The asphalt sealing material composition using waste cooking oil according to claim 1, wherein the composition further comprises waste tire rubber powder. The method of claim 1, wherein the composition is selected from one or more selected from the group consisting of talc, silica, calcium carbonate, magnesium hydroxide, kaolin, mica, barium sulfate, asbestos, asbestos, aggregate, glass fiber, carbon fiber and silicon carbide fiber. Asphalt sealant composition using waste cooking oil, characterized in that it further comprises an inorganic filler. The lung according to claim 1, wherein the composition further comprises one or more components selected from the group consisting of light stabilizers, heat stabilizers, antioxidants, reinforcing agents, anti-slip agents, colorants, matting agents, lubricants and anti-wear agents. Asphalt sealant composition using cooking oil. The method of claim 1, wherein the composition further comprises any one or more components selected from the group consisting of one or more polymers, rubbers or their waste selected from the group consisting of polyethylene, ethylene-based copolymers and polypropylene. Asphalt sealant composition using waste cooking oil.