KR101169757B1 - Thermosetting polymer resin and load paving method with thin layer by using - Google Patents

Abstract

PURPOSE: A thermosetting polymer resin is provided to have excellent early strength revelation, high strength, high adhesion, and excellent elongation, and to have low fracture rate, thereby maintaining the appearance of a road. CONSTITUTION: A thermosetting polymer resin comprises: 5-70 weight% of a polymer resin consisting of o-phthal-based unsaturated polyester; 5-40 weight% of a flexible resin consisting of iso-phthal-based unsaturated polyester; 15-21 weight% of vinyl toluene; 0.2-1 weight% of a cocatalyst consisting of cobalt naphthenate, dimethylaniline, and an initiator consisting of methyl ethyl ketone which is aqueous solution of 6% mineral sprit; 5-26 weight% of filler in which silicon dioxide with the grain size of 30-40 micron, and a silica or silica fume based mixture with the grain size of 0.1-1000 nm are mixed; and 0.05-3 weight% of fiber selected from carbon nanofiber, and carbon nanotubes, with the grain size of 10-200 nm.

Description

Thermosetting polymer resin and load Paving method with thin layer by using}

The present invention relates to a thermosetting polymer resin and an ultra-thin layer road paving method using the same. More specifically, the thermosetting polymer resin exhibits exothermic phenomenon by curing after dilution of an initiator and a promoter, and early strength to be cured within 1 to 2 hours. By using the material properties of the expression, high strength properties, and high adhesion and excellent elongation (4-9%), ultra thin layer packaging of 1.5 to 3.0mm is possible, and high strength can be secured in a short time, minimizing traffic congestion due to construction. It can be applied to both cement concrete and asphalt concrete at the same time to improve the workability, which can be prevented from deterioration of concrete due to salt or calcium chloride by the ultra thin layer paving, which can prolong road life, and not promote it. In polymer resins composed of allophthalic unsaturated polyesters It is possible to increase flexural strength and tensile strength by increasing the tensile modulus by mixing a flexible resin composed of isophthalic unsaturated polyester having a high tensile strength.As a result, the breakage rate of the construction part is low after completion of construction to maintain a clean and beautiful road. , Dilution of polymer resin and flexible resin with vinyltoluene, a monomer that has little effect on mechanical properties, improves workability by reducing styrene smell of polymer resin and flexible resin, and improves fracture toughness by reducing shrinkage during construction. Not only is it effective for reinforcing microcracking, but it is also possible to improve the overall mechanical properties by using carbon nanotubes with cylindrical graphene nanofibers with graphene layers and carbon nanotubes with graphene sheets similar to honeycombs with hexagonal holes. Of course, thermosetting polymer resins When spraying mixed silica after spraying or roller coating, the rough surface is maintained to increase the sliding resistance, and additional maintenance is easy when the thermosetting polymer resin and mixed silica are sprayed. The present invention relates to a thermosetting polymer resin that is easy to maintain and to an ultra-thin layer road paving method using the same.

Until now, the representative cement-based material of concrete, which is widely used as a structural material in construction sites, has been widely used as a major constituent material of construction structures because of its excellent compressive strength, economical efficiency and durability, but it is harmful to cracks due to its low tensile and bending strength and low deformation capacity. It has a problem of brittle material in which stress and durability sharply decrease after generation.

On the other hand, with the development of construction technology, many concrete structures are being made today, causing a number of problems, the most representative of which is the occurrence of cracks.

In general, concrete and repair mortars are used to generate microcracks such as initial cracking and dry shrinkage cracking before and after curing, which is one of the general cracks in concrete structures.

In addition to these cracks, they can be classified into two types: structural cracks such as cracks and port holes due to external loads such as vehicle loads, and nonstructural cracks due to corrosion and freeze-thawing of reinforcing bars. Once cracks occur, they can lead to fatal damage to the concrete's lifespan due to reduced durability, damage to the exterior, and corrosion of the rebar.

In addition, when the environment is polluted and carbon dioxide is combined with water in the atmosphere emitted from many vehicles or factories, the carbon dioxide enters the concrete and is neutralized by destroying the strong alkaline protective film (floating layer) that surrounds the reinforcement in the reinforced concrete. Corrosion easily occurs. Formula 1 shows the chemical reaction of carbon dioxide and water in the concrete.

This reinforcing bar leads to about seven times the volume expansion, and this expansion pressure pushes the concrete into serious defects. In addition, the cross-sectional area of the rebar is reduced, which results in a severe impact on the concrete structure due to a drop in tensile strength.

<Formula 1>

Ca (OH) ₂ + CO ₂ -------- → CaCO ₃ + 2H ₂ O

                 ↑

H ₂ O

When H ₂ O generated after the chemical reaction evaporates from the concrete surface, tensile stress is generated due to shrinkage of the concrete, and when this exceeds the tensile strength, surface cracking occurs.

Aggregate used in the manufacture of concrete is mainly silicic acid system, the volume is expanded by the reaction of aggregate containing cement alkali component (Na, K) and alkali soluble silicic acid, which causes crack of concrete. Alkali is contained not only in cement but also in sea sand, admixtures and snow removing agents. Aggregates containing silicic acid include opal, agate, phosphorus, volcanic glass, silver-crystal quartz and silicate, and limestone containing dolomite, the most sensitive being opal and relatively less reactive volcanic glass, silicate and dolomite One limestone. Alkali aggregate reaction is a chemical reaction as shown in formula (2) in the wet state.

<Formula 2>

SiO ₂ ㆍ nH ₂ O + ₂ NaOH ------> Na ₂ SiO ₂ ㆍ (n + 1) H ₂ O

At this time, the silicic acid reacts with the hydroxide to make a gel around the aggregate, and when the gel contacts with moisture, it expands and causes a tensile crack around the aggregate. When an alkali aggregate reaction occurs on unconstrained concrete, there are dangerous signs such as turtle cracks on the exposed part of the surface. Once a crack occurs, the moisture is easily penetrated, and the alkali aggregate reaction is further promoted. It may cause damage. These reactions can occur for months or years depending on climatic conditions, causing whitening, peeling, and deterioration damage. Fine lattice-like cracks can be initiated and, in the worst case, concrete completely destroyed.

In addition, since seawater and groundwater contain a large amount of sulfate salts, and plant wastewater, clay soil, and plant exhaust gas also contain sulfate salts, and cracks are generated by the biological reaction of sewage sludge. Of _{ettringite; (3CaO Al 2 O 3 6H} 2 O aluminate Hydrate??) And the needle-like crystal structure in response (ettringite if the SO ₄ ^-2 ions, soluble in water penetration through concrete pores cement hydrate aluminate hydrate; 3CaO-Al ₂ O ₃ -3CaSO ₄ -32H ₂ O), and the volume increases by about 227%, applying a compressive force to the pore walls, causing tensile cracking in the concrete. As the crack width increases due to the reaction result of Ca (OH) ₂ and SO ₄ ^-2 gypsum (CaSO _{4 2} 2H ₂ O), the ettringite-producing surface continues into the concrete and consequently the concrete is destroyed. Will be.

One method of maintaining and repairing such concrete defects is to use inorganic cement patching repair materials. Conventional repair methods have been used to remove deteriorated areas of reinforced concrete structures and to simply remove inorganic cement-based patch repair agents, or to increase rigidity by increasing the cross-section of existing reinforced concrete structures.

The cement-based patching repair material is repaired and reinforced through partial repair or partial overlay of the packaging layer.

However, in general, in order to satisfy the maintenance of the pavement layer of a concrete structure, high strength is required as well as early strength development. Such cement-based patching repair materials are required to obtain a result of low strength and a certain strength at the time of strength development. The disadvantage is that the time required is long.

On the other hand, in order to solve this problem, instead of a cement binder, a polymer concrete including a polymer-based binder and silica sand, aggregate and the like used in general concrete has been developed.

The polymer concrete is frequently used as a repair material for decks, pavements, warehouses and factory floors of bridges. Typical polymer binders are used based on epoxy, polyester resins, acrylic monomers, and polyurethanes and polyurea resins.

In particular, the polymer concrete is widely used not only for patching but also for continuous overlay (overlaying of asphalt, concrete, etc. on a broken road).

However, the polymer concrete as described above has excellent adhesion to the concrete matrix, but requires a separate primer coating to secure more sufficient adhesion.

The design of the primer is related to the chemical properties of the resin binder used in the polymer concrete.

For example, acrylic binders are used with methyl methacrylate binder and styrene or urethane binders are used with polyester polymer concrete. In addition, epoxy or improved epoxy resins are commonly used as a binder for general polymer concrete overlay.

In the case of the polyester resin, there is a problem that brittleness is too strong to be used as an overlay or patch repair material.

In addition, polyurethane and polyurea resins can provide high rigidity, whereas the isocyanate (-NCO) group has high reactivity with moisture, and moisture generated in concrete pavement or dew point temperature where moisture is absorbed inside. There is a problem that there is a lot of room for structural defects when constructing concrete or concrete pavement layer remaining on this surface.

The thermosetting polymer resin of the present invention for solving the above problems is a condensation polymer produced by the reaction of a polyol is prepared by the condensation of 35 to 70% by weight of a polymer resin consisting of allophthalic unsaturated polyester, polyol and isophthalic acid 5 to 40% by weight of flexible resin composed of isophthalic unsaturated polyester, 15 to 21% by weight of vinyl toluene, initiator of methyl ethyl ketone in 6% mineral split solution and promoter of cobalt naphthenic acid and dimethyl aniline 0.2 to 1 Carbon nanofibers, carbon with a particle size of 10 to 200 nm and a filler of 5 to 26% by weight of a mixture of one or more mixtures of silicon dioxide having a particle size of 30 to 40 µm and silica or silica fume having a particle size of 0.1 to 1000 nm. It comprises 0.05 to 3% by weight of fibers consisting of any one selected from nanotubes or mixtures thereof It characterized.

delete

delete

delete

delete

delete

Ultra-thin layer road paving method using the thermosetting polymer resin of the present invention comprises a ground surface cleaning step of removing foreign matter, paint and contaminants with a high pressure washing or a high pressure air gun to form a healthy ground surface on a concrete road; Applying a primer to the surface of the base surface arranged in the base surface cleaning step using a spray or a roller to apply a primer to cure in a dry state; Condensation polymer produced by the reaction of a polyol, 35 to 70% by weight of a polymer resin consisting of allophthalic unsaturated polyester, 5 to 40% by weight of a flexible resin consisting of isophthalic unsaturated polyester prepared by condensation of polyol and isophthalic acid , 15% to 21% by weight of vinyl toluene, 6% aqueous solution of mineral split, initiator of methyl ethyl ketone, and 0.2 to 1% by weight of cobalt naphthenic acid and dimethyl aniline, and silicon dioxide having a particle size of 30 to 40㎛ 5 to 26% by weight of a filler containing one or more mixtures of silica or silica fume mixtures of 0.1 to 1000 nm, carbon nanofibers having a particle size of 10 to 200 nm, carbon nanotubes, or any combination thereof. Apply a thermosetting polymer resin consisting of 3% by weight to a thickness of 1.5 to 3.0mm using a spray gun or roller. The thermosetting polymer resin coating step; A mixed silica spraying step of spraying the mixed silica having a particle size of 0.05 to 1 mm and a thickness of 3 to 5 mm after applying the thermosetting polymer resin; Curing the thermosetting polymer resin after the step of spraying the mixed silica, and curing the thermosetting polymer resin for 30 to 50 minutes at room temperature (20 ° C.) and 60 to 90 minutes for the low temperature (10 ° C. or less); After the curing step, the completion of the step of inhaling and cleaning the remaining silica by using the air gun or vacuum suction device is not bonded to the base surface by the thermosetting polymer resin; consisting of the step of applying the thermosetting polymer resin (S30) and Mixing silica spraying step (S40) is characterized in that made at the same time.

delete

The thermosetting polymer resin of the present invention exhibits early strength development, high strength, high adhesion, and excellent elongation characteristics, and can be used for ultra-thin road paving of 1.5 to 3.0 mm.

In addition, it is possible to increase the tensile strength by increasing the tensile modulus by mixing a flexible resin composed of flexible isophthalic unsaturated polyester with a polymer resin composed of non-promoting, non- thixotropic unsaturated polyester, thereby increasing bending strength and tensile strength. After the completion of the construction, the damage rate of the construction part is low, so it is possible to maintain the beautiful road.

In addition, the polymer resin and the flexible resin are diluted with vinyl toluene, a monomer which has little influence on the mechanical properties, thereby reducing the styrene odor of the polymer resin and the flexible resin, thereby improving the workability and reducing the shrinkage during construction, thereby improving the fracture toughness. Efficient for fine crack reinforcement.

In addition, it is possible to improve the overall mechanical properties by using a carbon nanofiber of cylindrical nanostructure having a graphene layer and carbon nanotubes formed with graphene sheets similar to barbed wire with hexagonal holes.

In addition, when the thermosetting polymer resin is applied to the surface by spraying or roller method, and then the mixed silica is sprayed, the rough surface is maintained on the surface, so the slip resistance is significant.

In addition, when the thermosetting polymer resin and the mixed silica are installed through a spray method, there is an advantage of easy maintenance due to easy maintenance.

1 is a block diagram showing the construction procedure of the ultra-thin road paving method using a thermosetting polymer resin according to the present invention.
Figure 2 is a side view schematically showing the mechanical coating step of the thermosetting polymer resin according to the present invention.

Hereinafter, the configuration of the present invention will be described in detail with reference to the accompanying drawings.

First, the present invention provides a thermosetting polymer resin.

The thermosetting polymer resin in the present invention includes 35 to 80% by weight of polymer resin, 5 to 40% by weight of flexible resin, 0.001 to 0.1% by weight of vinyl toluene, 0.2 to 1% by weight of initiator and promoter, and 5 to 26% by weight of filler. It is configured by.

The polymer resin is a condensation polymer produced by the reaction of a polyol, and is a polymer compound belonging to a thermosetting plastic, and a primary resin having a polymerizable double bond having a molecular weight of 1,000 to 3,000 is formed by using a vinyl unit such as styrene. It is a material formed by curing. Since the resin is generally reinforced with glass fibers, it is also called fiber reinforced plastics (FRP). In addition to glass fibers, fibers such as nylon and teflon are also used and are widely used as industrial plastics.

Herein, the polymer resin is an allophthalic unsaturated polyester and has chemical resistance at 80 ° C. and pH 10 or less.

Therefore, the polymer resin in the present invention is used to improve the mechanical strength, when it is mixed below the threshold value, it is difficult to express a certain mechanical strength or higher, and when used above the threshold value, it is not suitable because it forms high brittleness.

Meanwhile, in the present invention, a flexible resin made of isophthalic unsaturated polyester is mixed to impart flexibility to the polymer resin made of allophthalic unsaturated polyester to improve fracture toughness by improving tensile elongation and lowering viscosity to enhance brittleness. do.

The flexible resin is an isophthalic unsaturated polyester prepared by the condensation of polyol and isophthalic acid to react with the polymer resin to lower the viscosity to act to liquidate the polymer resin early.

In particular, the polymer resin of the initial liquid reacted with the flexible resin is converted into a solid by the free group crosslinking reaction.

This is achieved by free groups in the unsaturated bonds and propagates in a chain reaction to other unsaturated bonds in the surrounding molecule.

Such a flexible resin is produced by condensation of polyol and isophthalic acid, and forms a direct tensile elongation of 50 to 60%.

Therefore, it is possible to obtain a result of significantly improving the overall fracture toughness of the polymer resin used for repair, reinforcement and construction of concrete structures used for roads, bridges, and the like.

When the flexible resin in the present invention is mixed below the threshold value, the flexibility to impart flexibility to the polymer resin is low, so that it is difficult to express a constant strength of tensile elongation and fracture toughness. There is a concern, and if the mixing exceeds the threshold, there is a problem that leads to an increase in the overall cost.

In the present invention, vinyl toluene as a monomer is mixed.

In general, the monomer is combined with the polyester resin to act to lower the overall viscosity of the polymer resin.

The most common of these monomers, styrene is suitable from the economical point of view, but the styrene generates a very strong odor resulting in a problem that causes the inconvenience of the constructor during construction.

In the present invention, vinyl toluene is used, which can reduce the odor of the polymer resin and the flexible resin without causing a change in the mechanical properties of the polymer resin.

Of course, the vinyl toluene has a limited effect on elongation compared to styrene, but when the polymer resin and the flexible resin are mixed, the shrinkage amount is reduced to improve the overall fracture toughness and thereby to obtain a significant effect on the reinforcement of microcracks. do.

On the other hand, in this invention, the initiator and the promoter are included and comprised.

The initiator typically used in the free group, crosslinked polymerization of the unsaturated polyester resin is methylethylketone.

The initiator may also use other compounds such as free radical initiators based on nitrated compounds such as benzoyl peroxide or AIBN (α, α'-azoisobutyronitrile).

Unsaturated polyester resins are generally supplied in the form of accelerated, non-promoted.

The accelerated unsaturated polyester resin is a free group, crosslinked polymerization promoter which already contains a catalyst. This is easy to use resin, but because the storage life of the resin is relatively short, long-term storage is not suitable for practical use.

That is, the thermosetting polymer resin in the present invention may be stored for a long time before use.

Therefore, it is suitable to use a non-promoted unsaturated polyester that does not contain a catalyst. At this time, the initiator, which is a curing compound, acts to promote the non-promoted unsaturated ester to achieve a certain strength of strength.

The initiator in the present invention is used to control the setting time and strength expression of the thermosetting polymer resin by using a mixture of an organic amine such as dimethyl aniline cobalt naphthenic acid solution of 6% mineral split.

Meanwhile, in the present invention, fillers having various particle size sizes are used.

The filler in the present invention may utilize a general extender based on calcium carbonate, magnesium silicate and silicon dioxide for partial filling of polymer resins and flexible resins. Fillers of this type are generally micron-sized granules, which can be used in the order of a few microns, from very fine fillers to 30-40 μm medium fillers, including large concretes such as silica sand and aggregates. Size fillers may be used in combination with medium size fillers.

The filler serves to reduce shrinkage during curing and increase fracture toughness.

In such a filler, the viscosity of the polymer resin and the flexible resin changes depending on the type and the mixing amount.

In particular, the present invention includes a filler in the form of nanoparticles (0.1 ~ 1,000nm) based on clay minerals because there is a possibility that the space is not filled through the polymer resin and the flexible resin.

The fillers of these nanoparticles can achieve breakdown toughness as compared to the addition of micron-sized fillers even when a small amount is mixed with the thermosetting polymer resin including the reactive monomer.

In addition, the present invention may further comprise a fiber.

In general, fiber reinforcement is a very important factor. In other words, it increases the fracture toughness (impact resistance) and improves the tensile and bending strengths required in concrete structures by a certain amount.

In particular, the fiber can reduce the amount of expensive flexible resin required to improve the fracture toughness.

Typically, milled glass, polyester fibers, cellulose fibers, natural fibers such as wollastonite and carbon pitch fibers and the like.

The fibers used in the present invention are carbon nanofibers and carbon nanotubes.

Carbon nanofibers consist of cylindrical nanostructures with layers of graphene arranged like stacked cone cups or plates.

Carbon nanotubes consist of a multi-walled carbon structure that resembles a graphene sheet that resembles a honeycomb with hexagonal holes joined into a cylindrical tube. The multi-walled carbon nanotubes are composed of many tubes inside each other.

The carbon nanotubes are stronger than steel, and when applied to a thermosetting polymer resin, fracture toughness, strength modulus, and fatigue resistance may be increased.

The carbon nanofibers and carbon nanotubes may be included in a thermosetting polymer resin and used to improve mechanical properties.

However, in the present invention, carbon nanofibers, which are cheaper than carbon nanotubes, are more suitable.

The above-described carbon nanofibers and carbon nanotubes are hollow and have a size of nanometers. Carbon nanotubes generally have a diameter of 10 to 30 nm, and carbon nanofibers are in the range of 50 to 200 nm depending on the type.

These nanomaterials vary in length from hundreds of micrometers, and because of their small size, van der Waals' strength is strong in carbon nanotubes, and the use of sonic technology to help or maintain chemical dispersants or dispersions. This is necessary.

However, carbon nanofibers are less susceptible to van der Waals' forces and tend to be dispersed and maintained for a long time.

Therefore, when the carbon nanofibers are mixed with the polymer resin and the flexible resin, the carbon nanofibers can be mechanically dispersed so that the mixing can be performed smoothly.

[Example 1]

79.5% by weight of allophthalic unsaturated polyester diluted with styrene and vinyl toluene as polymer resin, 20% by weight of isophthalic unsaturated polyester which is a flexible resin, 0.1% by weight of cobalt naphthenic acid as a promoter, and 0.3% by weight of dimethyl aniline as a promoter % And methyl ethyl ketone 0.1% by weight were mixed to prepare a thermosetting polymer resin.

Polymer resin liquid properties of Example 1 summary Product Specifications Appearance-Color 100 (max) Viscosity @ 25 ℃, LV # 3 @ 60rpm (cps) 2,900 SPI gelation time (1% BPO @ 82.2 ℃) min 3 SPI Lyrics Hour-Minute 2 Heat generation (℃) 182 Density (g / cm 3) 1.13 ～ 1.15 Nonvolatile Mass (% NVM) 72.0

Polymer resin mechanical properties of Example 1 summary Test Methods result Fracture Toughness (㎏f? Cm) ASTM D-790 800 ～ 900 Flexural strength (MPa) ASTM D-790 60 to 70 Flexural Modulus (GPa) ASTM D-790 3.62 Tensile Strength (MPa) ASTM D-638 30 to 35 Tensile Modulus (GPa) ASTM D-638 3.9 Tensile Elongation (%) ASTM D-638 7 ～ 9 Barcol Hardness (934.1) ASTM D-2583 46

Flexible resin liquid properties of Example 1 summary Product Specifications Appearance-Color Light yellow Viscosity @ 25 ℃, LV # 3 @ 60rpm (cps) 750 ～ 900 SPI gelation time (1% BPO @ 82.2 ℃) min 5 to 7 SPI Lyrics Hour-Minute 2.5 to 4.5 Heat generation (℃) 146 ～ 168 Density (g / cm 3) 1.13 ～ 1.15 Nonvolatile Mass (% NVM) 69.0 ～ 72.0 PH, mg / g 8.5 to 11.5

Flexible resin mechanical properties of Example 1 summary Test Methods result Flexural strength (MPa) ASTM D-790 Deformation without breakage Flexural Modulus (GPa) ASTM D-790 Deformation without breakage Tensile Strength (MPa) ASTM D-638 13.8 Tensile Modulus (GPa) ASTM D-638 Deformation without breakage Tensile Elongation (%) ASTM D-638 50 SD hardness ASTM D-2240 74

[Comparative Example 1]

79.5% by weight of allophthalic unsaturated polyester diluted with styrene as polymer resin, 20% by weight of isophthalic unsaturated polyester as flexible resin, 0.1% by weight of cobalt naphthenic acid as promoter, 0.3% by weight of dimethyl aniline as promoter, methyl 0.1 wt% of ethyl ketone was mixed to prepare a thermosetting polymer resin.

Polymer resin liquid properties of Comparative Example 1 summary Product Specifications Appearance-Color Light yellow Viscosity (cps) Brookfield (RVT # 3 @ 50 rpm) 120 SPI gelation time (1% BPO @ 82.2 ℃) min 3.5 SPI Lyrics Hour-Minute 3.0 Heat generation (℃) 204 Density (g / cm 3) 1.09 Nonvolatile Mass (% NVM) 54

Polymer resin mechanical properties of Comparative Example 1 summary Test Methods result Fracture Toughness (㎏f? Cm) ASTM D-790 700-780 Flexural strength (MPa) ASTM D-790 110 Flexural Modulus (GPa) ASTM D-790 3.61 Tensile Strength (MPa) ASTM D-638 55 Tensile Modulus (GPa) ASTM D-638 3.74 Tensile Elongation (%) ASTM D-638 2.0 Thermal deflection temperature (℃) ASTM D-648 71

Looking at Example 1 and Comparative Example 1, in Example 1, the polymer resin was used styrene and vinyl toluene, but in Comparative Example 1 was diluted using only styrene.

In addition, the flexible resin in Example 1 and the comparative example 1 used the same product.

Looking at the results of Tables 1 to 2 in Examples 1 and Tables 5 to 6 in Comparative Example 1, the monomers based on vinyl toluene at the viscosity and gelling time of the polymer resin, It can be seen that the time in Example 1 used was shortened.

In particular, the mechanical properties show the better results in Example 1 in flexural strength, flexural modulus, tensile strength, tensile modulus and barcol hardness.

This is understood to have a limiting effect on elongation when vinyl toluene is used instead of styrene, but this is to improve the overall fracture toughness of the binder.

[Example 2]

55.68% by weight of allophthalic unsaturated polyester diluted with styrene as polymer resin, 18.37% by weight of vinyl toluene as monomer, 11.13% by weight of isophthalic unsaturated polyester as flexible resin, 0.04% by weight of cobalt naphthenic acid as promoter, cocatalyst A thermosetting polymer resin was prepared by mixing 0.01% by weight of dimethyl aniline, 0.85% by weight of methyl ethyl ketone, and 13.92% by weight of silica fume having increased density.

In Example 2, silica fume having a higher density is further included.

The silica fume was incorporated in the polymer resin and the flexible resin to increase the fracture toughness as a filler and to be mixed to provide improved workability while reducing the use of expensive flexible resin.

[Example 3]

48.5% by weight of allophthalic unsaturated polyester diluted with styrene as polymer resin, 16% by weight of vinyl toluene as monomer, 9.7% by weight of isophthalic unsaturated polyester as flexible resin, 0.04% by weight of cobalt naphthenic acid as promoter, cocatalyst Thermosetting polymer by mixing 0.01% by weight of dimethyl aniline, 0.74% by weight of methyl ethyl ketone, 0.19% by weight of silica fume in microparticles and nanoparticles, 5.96% by weight of aluminum silicate (Minex # 4), 18.86% by weight of amorphous silicon dioxide Resin was prepared.

In Example 3, it can be used in combination with other micro fillers such as aluminum silicate, it is also possible to use a general filler used in the coating industry. In particular, the micro-unit filler may be replaced with carbon particles to improve the UV resistance of the polymer resin and the flexible resin.

Example 4

50.17% by weight of allophthalic unsaturated polyester diluted with styrene as polymer resin, 16.56% by weight of vinyl toluene as monomer, 7.53% by weight of isophthalic unsaturated polyester as flexible resin, 0.04% by weight of cobalt naphthenic acid as promoter, cocatalyst 0.01% by weight phosphorus dimethyl aniline, 0.77% by weight methyl ethyl ketone, 0.2% by weight silica fume in microparticles and nanoparticles, 6.16% by weight aluminum silicate (Minex # 4), 16.05% by weight amorphous silicon dioxide, 2.51% by weight glass fiber It was mixed to prepare a thermosetting polymer resin.

In Example 4, microfiber glass is further added and used.

The overall flexibility is determined according to the ratio of the polymer resin and the flexible resin in the present invention, if the mixing ratio of the flexible resin is lowered, the fracture toughness is reduced due to the decrease in flexibility. In the present invention, it is included to increase the fracture toughness using the milled glass fiber or wollastonite fiber.

[Example 5]

54.10% by weight of allophthalic unsaturated polyester diluted with styrene as polymer resin, 17.85% by weight of vinyl toluene as monomer, 8.12% by weight of isophthalic unsaturated polyester as flexible resin, 0.04% by weight of cobalt naphthenic acid as promoter, cocatalyst A thermosetting polymer resin was prepared by mixing 0.01% by weight of dimethyl aniline, 0.83% by weight of methyl ethyl ketone, 4.87% by weight of aluminum silicate (Minex # 4), 14.07% by weight of amorphous silicon dioxide, and 0.11% by weight of carbon nanofibers.

In Example 5, carbon nanofibers, which have excellent dispersibility and can increase fracture toughness, were applied.

[Example 6]

52.68% by weight of allophthalic unsaturated polyester diluted with styrene as polymer resin, 17.38% by weight of vinyl toluene as monomer, 7.90% by weight of isophthalic unsaturated polyester as flexible resin, 0.04% by weight of cobalt naphthenic acid as promoter, cocatalyst Thermosetting polymer by mixing 0.01% by weight of phosphorus dimethyl aniline, 0.81% by weight of methyl ethyl ketone, 4.74% by weight of aluminum silicate (Minex # 4), 13.70% by weight of amorphous silicon dioxide, 0.11% by weight of carbon nanofiber, and 2.63% by weight of micro glass fiber. Resin was prepared.

In Example 6, carbon toughness and microfiber glass are applied to improve fracture toughness.

That is, all the cracks start with a nano-size that cannot be reinforced with microfiber glass, and micro cracks are generated, and carbon nanofibers in the present invention are very efficient for such cracks.

Thus, the mixing of nanofibers and microfibers improves fracture toughness within the micro-sized crack range while improving crack resistance.

Comparative Table of Mechanical Properties According to Examples Fracture toughness
(Kgf? Cm) Elongation
(%) Flexural strength
(MPa) The tensile strength
(MPa) Example 1 800-900 7-9 60-70 30-35 Example 2 800-1,000 4-6 80-85 41-43 Example 3 850-1,050 4-6 85-97 42-48 Example 4 1,200-1,400 4-6 95-100 50-55 Example 5 1,350-1,500 4-6 93-95 45-50 Example 6 2,000-2,200 4-6 93-95 55-60

In Comparative Example 2, it can be seen that the elongation rate decreases as the amount of the flexible resin decreases in comparison with Example 1.

However, it can be seen that the fracture toughness, tensile strength and flexural strength are increased due to the application of silica fume. This is because the silica fume with higher density serves to fill the micropores, thereby improving the overall strength.

In addition, in Example 3, the addition of micro particles and nano particles of silica fume, aluminum silicate (Minex # 4), and amorphous silicon dioxide filled the pores and improved the overall mechanical strength.

In particular, in Example 4, glass fiber was applied to improve the fracture toughness by reducing the ratio of the polymer resin and the flexible resin to reduce the overall fracture toughness.

In addition, in Example 5, carbon nanofibers made of cylindrical nanostructures having graphene layers aligned like stacked cone cups or plates were applied to further improve fracture toughness, tensile strength, and bending strength.

In addition, in Example 6, carbon nanofibers and microfiber glass are simultaneously applied to improve a considerable amount of fracture toughness.

In general, all cracks start with a nano size that cannot be reinforced with microfiber glass, and micro cracks are generated. The carbon nanofibers of the present invention are very efficient for such cracks.

Therefore, it can be seen that the mixing of the nanofibers and the microfibers improves the fracture toughness within the micro-sized crack range while improving the crack resistance.

On the other hand, in the present invention, it is possible to form a base surface of a healthy state of the surface of the concrete road by using the thermosetting polymer resin as described above.

If you look at it in detail,

Remove foreign substances, paint and contaminants with high pressure washing or high pressure air gun to form a healthy ground surface on cement concrete road or asphalt concrete road to be repaired.

Then, the primer is applied to the surface of the surface of the base surface cleaned in step S10, using a spray or roller, to cure in a dry contact state. (Primer application step-S20)

In this case, the primer is preferably applied to the entire base surface area to increase the adhesion.

On the other hand, when the application of the primer is completed as described above, 35 to 80% by weight of the polymer resin consisting of allophthalic unsaturated polyester, 5 to 40% by weight of the flexible resin consisting of isophthalic unsaturated polyester, 0.001 to 0.1% by weight of vinyl toluene, A thermosetting polymer resin consisting of 0.2 to 1% by weight of initiator and cocatalyst, 5 to 26% by weight of filler, and 0.05 to 3% by weight of fiber is applied to a thickness of 1.5 to 2.0 mm using a spray gun or roller. Application step-S30)

Here, the thermosetting polymer resin may be applied by spraying the thermosetting polymer resin on a concrete road to which a primer is applied through a material injector by mixing the thermosetting polymer resin in a material mixer mounted on a vehicle as shown in FIG. 2.

At this time, the thermosetting polymer resin stored in the material injector can be sprayed in the form of an ultra-thin layer (t = 1.5 ~ 3.0mm) with a thin coating thickness on the concrete road through a conventional air compressor.

Then, after the thermosetting polymer resin is applied, the mixed silica sand having a particle size of 0.05 to 1 mm is sprayed to have a thickness of 3 to 5 mm. (Mixed silica sand spraying step-S40)

In other words, this step is to apply more than the amount of mixed silica that can be adhered through the primer and the thermosetting polymer resin to attach the maximum amount of mixed silica to the concrete road surface.

In particular, the spraying method of the mixed silica sand spraying step (S40) may be applied to the surface of the concrete road to which the thermosetting polymer resin is applied through a silica tube in which the mixed silica sand mounted on the vehicle is stored as shown in FIG. 2.

At this time, the mixed silica can be applied to the concrete road surface by spraying in various forms, in the present embodiment, the concrete road through the natural flow (using the fluid in the upper flows down by gravity.) Using gravity. It is good to apply to the surface.

Next, the thermosetting polymer resin is cured after the mixed silica sand spraying step (S40), but at room temperature (20 ° C.), for 30 to 50 minutes, and at low temperature (10 ° C. or less), for 60 to 90 minutes. Thermosetting Polymer Resin Curing Step-S50)

In addition, after the curing step (S50) of the mixed silica sprayed in the spraying step (S40) of the silica sand that is not bonded to the base surface by the thermosetting polymer resin using the air gun or vacuum suction device to suck and clean the remaining silica By (construction completion step-S60) it is possible to complete the construction.

Since the construction site is constructed using thermosetting polymer resin with excellent mechanical properties, it prevents deterioration of the concrete surface and has excellent effects in reinforcing microcracking as well as failure rate after construction. It is possible to increase the sliding resistance without hindering the road beautiful appearance and even to some breakages in the future.

In particular, the above-mentioned thermosetting polymer resin coating step (S30) and mixed silica sand spraying step (S40) can be performed simultaneously by using a vehicle as shown in Figure 2 it is also possible to obtain the effect of shortening the working time.

Although the above-described embodiments have been described with respect to the most preferred embodiments of the present invention, it is noted that the present invention can be modified in various forms without departing from the technical spirit of the present invention.

Claims (8)

Condensation polymer produced by the reaction of a polyol, 35 to 70% by weight of a polymer resin consisting of allophthalic unsaturated polyester, 5 to 40% by weight of a flexible resin consisting of isophthalic unsaturated polyester prepared by condensation of polyol and isophthalic acid , 15% to 21% by weight of vinyl toluene, 6% aqueous solution of mineral split, initiator of methyl ethyl ketone, and 0.2 to 1% by weight of cobalt naphthenic acid and dimethyl aniline, and silicon dioxide having a particle size of 30 to 40㎛ 5 to 26% by weight of a filler containing one or more mixtures of silica or silica fume mixtures of 0.1 to 1000 nm, carbon nanofibers having a particle size of 10 to 200 nm, carbon nanotubes, or any combination thereof. A thermosetting polymer resin characterized by comprising 3% by weight.
delete delete delete delete delete A base surface cleaning step (S10) of removing foreign matter, paint and contaminants with a high pressure washing or high pressure air gun to form a sound surface on a concrete road;
Primer application step (S20) for curing in a dry contact state by applying a primer using a spray or roller on the surface of the base surface cleansing step (S10);
Condensation polymer produced by the reaction of a polyol, 35 to 70% by weight of a polymer resin consisting of allophthalic unsaturated polyester, 5 to 40% by weight of a flexible resin consisting of isophthalic unsaturated polyester prepared by condensation of polyol and isophthalic acid , 15% to 21% by weight of vinyl toluene, 6% aqueous solution of mineral split, initiator of methyl ethyl ketone, and 0.2 to 1% by weight of cobalt naphthenic acid and dimethyl aniline, and silicon dioxide having a particle size of 30 to 40㎛ 5 to 26% by weight of a filler containing one or more mixtures of silica or silica fume mixtures of 0.1 to 1000 nm, carbon nanofibers having a particle size of 10 to 200 nm, carbon nanotubes, or any combination thereof. Apply a thermosetting polymer resin consisting of 3% by weight to a thickness of 1.5 to 3.0mm using a spray gun or roller. The thermosetting polymer resin applying step (S30);
A mixed silica spraying step (S40) of spraying the mixed silica having a particle size of 0.05 to 1 mm to have a thickness of 3 to 5 mm after applying the thermosetting polymer resin;
Curing the thermosetting polymer resin after the spraying step (S40) of the mixed silica, thermosetting polymer resin curing step of curing for 30 to 50 minutes at room temperature (20 ℃), 60 to 90 minutes at low temperature (10 ℃ or less) : (S50);
After the curing step (S50), the construction completion step (S60) of inhaling and cleaning the remaining silica using an air gun or a vacuum suction device is not bonded to the base surface by the thermosetting polymer resin;
The thermosetting polymer resin coating step (S30) and mixed silica spraying step (S40) is an ultra-thin layer road paving method using a thermosetting polymer resin characterized in that at the same time. delete

Images