JP2021046731A - Concrete structure and its manufacturing method, and tile structure - Google Patents

Abstract

To provide a concrete structure capable of exhibiting sufficient load bearing capacity from a low temperature range to a high temperature range.SOLUTION: One aspect of the present disclosure provides a concrete structure comprising a structure containing concrete and a coating layer provided on the structure. The coating layer has an adhesive layer and a reinforcing layer provided on the side of the adhesive layer opposite to the structure side. The storage elastic modulus E' at 50°C of the adhesive layer is 4.0×108 Pa or more.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to concrete structures, manufacturing methods thereof, and tile structures.

In recent years, the fall of concrete pieces from structures including concrete such as tunnel inner walls, highway piers, railway piers, and bridges has become a problem. Further, even in a building in which tiles are attached to an outer wall surface, there is a problem that the tiles fall due to deterioration over time. Examples of the fall of the concrete piece include the case where the surface of the concrete deteriorates due to some deterioration factor and the small concrete piece peels off from the mother body, and the case where the peeling progresses as described above and the relatively large concrete piece falls off from the mother body. And so on.

In order to prevent the structure containing concrete from being peeled off, various methods of providing a reinforcing layer made of a cured resin layer such as urethane resin on the surface of the structure have been studied. Generally, before the reinforcing layer is provided, the surface of the structure containing concrete is impregnated with fine irregularities on the surface layer of the structure having a low viscosity, and the adhesive force is exhibited by the anchoring effect. A method of providing an adhesive layer with an epoxy resin or the like is adopted.

Regarding structure construction management, for example, the NEXCO standard is known. Construction that meets this standard is known to be highly reliable, but its required characteristics are very high. Therefore, in order to obtain an anti-scraping structure that satisfies the NEXCO standard, generally, a means such as providing a net-like anti-scraping material such as a mesh layer woven with synthetic fibers such as vinylon in the anti-scraping structure is used. Has been done.

For example, Patent Document 1 is a peeling prevention method including a step of applying an adhesive and a step of attaching a reinforcing olefin fiber sheet, wherein the surface wet tension of the reinforcing olefin fiber sheet is 25 mN / m or more and 45 mN. An exfoliation prevention method characterized by being less than / m has been proposed.

Further, Patent Document 2 is a concrete piece peeling prevention method in which a net-like peeling prevention material is adhered to the surface side of the concrete skeleton to prevent the concrete pieces from peeling off, and a primer is layered on the surface of the concrete skeleton. A step of applying (X1), a step of arranging a net-like anti-flood material in a layer on the surface of the applied primer layer (X3), and a step of arranging the surface of the arranged anti-scrap material by a curing reaction. A method for preventing the peeling of concrete pieces has been proposed, which comprises a step (X4) of applying a layered impregnating material composed of at least a two-component mixed resin composition for forming a urea bond.

JP-A-2007-146588 Japanese Unexamined Patent Publication No. 2011-052457

It is an object of the present disclosure to provide a concrete structure capable of exhibiting sufficient load bearing capacity from a low temperature region to a high temperature region. The present disclosure is also intended to provide a method for manufacturing the concrete structure described above. It is also an object of the present disclosure to provide a tile structure capable of exhibiting sufficient load bearing capacity from a low temperature region to a high temperature region.

One aspect of the present disclosure is a concrete structure including a structure containing concrete and a coating layer provided on the structure, and the coating layer is an adhesive layer and the structure side of the adhesive layer. the and a reinforcing layer provided on the opposite side, the storage modulus E at 50 ° C. of the adhesive layer 'is 4.0 × 10 8 ^Pa or more, to provide a concrete structure.

By adopting a layer in which the storage elastic modulus E'at 50 ° C. is equal to or higher than a predetermined value as the adhesive layer, the concrete structure has sufficient load resistance from the low temperature range to the high temperature range, and has excellent peeling prevention performance. Excellent.

The reinforcing layer may contain at least one selected from the group consisting of particles and fibers, and the average particle size of the particles and the average major axis length of the fibers may be 10 μm or less. When the particles and fibers contained in the reinforcing layer are both smaller than a predetermined size, the transparency of the coating layer is also more excellent. In this case, the concrete structure can be easily visually observed through the coating layer on the surface of the structure.

The concrete structure may have a maximum punching load of 1.5 kN or more at 50 ° C. When the maximum load of the concrete structure is within the above range, the load bearing capacity in a high temperature environment is improved.

The concrete structure may have a maximum punching load at 23 ° C. and a maximum punching load at −30 ° C. of 1.5 kN or more. When all of the above maximum loads of the concrete structure are within the above range, more sufficient load bearing capacity can be exhibited from the low temperature region to the high temperature region, so that the concrete structure's peeling prevention performance is more reliable. It can be excellent in sex.

The haze of the reinforcing layer may be 30 or less, and the total light transmittance of the reinforcing layer may be 80% or more. When the haze of the reinforcing layer and the total light transmittance are within the above ranges, the transparency of the coating layer is excellent.

The haze of the coating layer may be 40 or less, and the total light transmittance of the coating layer may be 70% or more. When the haze of the coating layer and the total light transmittance are within the above ranges, the transparency is excellent. The excellent transparency of the coating layer makes it easy to visually recognize the surface of the structure containing concrete, and it becomes easy to visually confirm the occurrence of deterioration such as cracks in the structure containing concrete.

The reinforcing layer may have a storage elastic modulus at −30 ° C. as a ratio of 1 to 20 to a storage elastic modulus at 50 ° C. Since the storage elastic modulus of the reinforcing layer at 50 ° C. and -30 ° C. has the above-mentioned relationship, the change in load bearing capacity from the low temperature range to the high temperature range is suppressed, so that the concrete structure can be prevented from falling off. It can be made more reliable.

The thickness of the adhesive layer may be 0.05 to 0.50 mm. When the thickness of the adhesive layer is within the above range, it is possible to have sufficient adhesiveness to a structure containing concrete and the like, and it is possible to shorten the construction time.

The adhesive layer may contain at least one selected from the group consisting of a cured product of an acrylic resin, a cured product of a urethane resin, and a cured product of an epoxy resin. When the adhesive layer contains the above-mentioned resin, the adhesiveness to the surface of the structure containing concrete becomes excellent, and the peeling prevention performance of the concrete structure can be further improved.

The concrete structure may further have a top coat layer on the side of the coating layer opposite to the structure side. By further having the top coat layer in the concrete structure, it is possible to have the performance corresponding to the top coat layer. Thereby, the concrete structure can exhibit, for example, weather resistance and landscape.

The concrete structure may be used as a peeling prevention structure. The anti-scraping structure may be for preventing the peeling of a structure containing concrete, for protecting a structure containing concrete, or for preventing the falling of tiles. Since the concrete structure described above can exhibit sufficient load bearing capacity from a low temperature region to a high temperature region, it may be used as a peeling prevention structure and is suitable for the above-mentioned applications.

One aspect of the present disclosure, the first resin composition layer on a structure comprising a concrete provided by curing, the adhesive layer is the storage elastic modulus E at 50 ° C. 'is 4.0 × 10 8 ^Pa or more The present invention provides a method for producing a concrete structure, which comprises a step of forming a reinforcing layer by providing a second resin composition layer on the adhesive layer and curing the layer.

The method for manufacturing a concrete structure includes a step of providing an adhesive layer having a storage elastic modulus E'at a predetermined value or more at 50 ° C. on a structure containing concrete, and a step of providing a reinforcing layer on the adhesive layer. From, the concrete structure mentioned above can be manufactured.

The reinforcing layer may contain at least one selected from the group consisting of particles and fibers, and the average particle size of the particles and the average major axis length of the fibers may be 10 μm or less. When the particles and fibers contained in the reinforcing layer are all smaller than a predetermined size, a concrete structure can be easily manufactured. The protective layer formed is also more transparent. In this case, in the concrete structure, the surface of the structure containing concrete can be visually observed through the coating layer.

One aspect of the present disclosure is a tile structure including a structure having tiles and a coating layer provided on the structure, wherein the coating layer is an adhesive layer and the structure side of the adhesive layer. the and a reinforcing layer provided on the opposite side, the storage modulus E at 50 ° C. of the adhesive layer 'is 4.0 × 10 8 ^Pa or more, to provide a tile structure.

The tile structure has sufficient load resistance from a low temperature range to a high temperature range by adopting a layer having a storage elastic modulus E'at 50 ° C. or higher as an adhesive layer, and has excellent peeling prevention performance. Excellent.

According to the present disclosure, it is possible to provide a concrete structure capable of exhibiting sufficient load bearing capacity from a low temperature region to a high temperature region. According to the present disclosure, it is also possible to provide the above-mentioned method for manufacturing a concrete structure. According to the present disclosure, it is also possible to provide a tile structure capable of exhibiting sufficient load bearing capacity from a low temperature region to a high temperature region.

FIG. 1 is a schematic cross-sectional view showing an example of a concrete structure.

Hereinafter, embodiments of the present disclosure will be described with reference to the drawings as the case may be. However, the following embodiments are examples for explaining the present disclosure, and are not intended to limit the present disclosure to the following contents. Unless otherwise specified, the positional relationship such as up, down, left, and right shall be based on the positional relationship shown in the drawings. The dimensional ratio of each element is not limited to the ratio shown in the drawings.

Unless otherwise specified, the materials exemplified in the present specification may be used alone or in combination of two or more. The content of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component in the composition are present, unless otherwise specified. ..

[Concrete structure]
FIG. 1 is a schematic cross-sectional view showing an example of a concrete structure. The concrete structure 50 includes a structure 10 containing concrete, an adhesive layer 20 provided on the structure 10 containing concrete, and reinforcement provided on the side of the adhesive layer 20 opposite to the structure 10 side containing concrete. It has a layer 30 and. That is, the concrete structure 50 has a structure 10 including concrete, an adhesive layer 20, and a reinforcing layer 30 in this order. The adhesive layer 20 and the reinforcing layer 30 are collectively referred to as a coating layer 40. FIG. 1 shows an example in which the structure 10 including concrete and the adhesive layer 20, and the adhesive layer 20 and the reinforcing layer 30 are in direct contact with each other. Another layer may be provided.

The concrete structure 50 may be used as a peeling prevention structure. The above-mentioned anti-scraping structure can be suitably used for preventing flaking of concrete structures, protecting concrete structures, or preventing tiles from flaking. The tile peeling prevention is to prevent the tile from falling when the concrete structure 50 further has tiles.

The structure 10 including concrete may be, for example, an inner wall of a tunnel, a highway pier, a railway pier, a bridge, or the like.

(Adhesive layer)
The adhesive layer 20 is a layer that adheres the reinforcing layer 30 to the surface of the structure 10 including concrete and improves the peeling prevention performance in the concrete structure. The lower limit of the storage elastic modulus E'of the adhesive layer 20 at 50 ° C. is 4.0 × 10 ⁸ Pa or more, and for example, 4.5 × 10 ⁸ Pa or more, 5.0 × 10 ⁸ Pa or more, 5. 5 × 10 ⁸ Pa or more, 6.0 × 10 ⁸ Pa or more, 7.0 × 10 ⁸ Pa or more, 8.0 × 10 ⁸ Pa or more, 10.0 × 10 ⁸ Pa or more, or 20 × 10 ⁸ Pa or more It may be. When the lower limit of the storage elastic modulus E'of the adhesive layer 20 at 50 ° C. is within the above range, it is superior to the load capacity of the concrete structure. The upper limit of the storage elastic modulus E'of the adhesive layer 20 at 50 ° C. may be, for example, 80 × 10 ⁸ Pa or less, or 50 × 10 ⁸ Pa or less. When the upper limit of the storage elastic modulus E'at 50 ° C. of the adhesive layer 20 is within the above range, it is difficult to be deformed and torn when a load is applied, so that highly reliable peeling prevention performance can be exhibited. Can be done.

The storage elastic modulus E'of the adhesive layer 20 at 50 ° C. can be adjusted within the above range, for example, 4.0 × 10 ⁸ to 80 × 10 ⁸ Pa, or 4.5 × 10 ⁸ to 50 × 10. It may be ^{8 Pa.} The storage elastic modulus E'of the adhesive layer 20 at 50 ° C. can be controlled by, for example, adjusting the component composition of the resin composition when forming the adhesive layer 20 described later, the curing conditions, and the like.

The storage elastic modulus E'at 50 ° C. in the present specification means a value obtained by dynamic viscoelasticity measurement. For the dynamic viscoelasticity measurement of the adhesive layer 20, the adhesive layer 20 can be sampled from the concrete structure 50 and used as a test body, or a cured film of only the adhesive layer used for manufacturing the concrete structure 50. Can be prepared in advance and used as a test body (the same applies to a test body to be subjected to a loss tangent, thickness, and other characteristic tests of the adhesive layer 20). The dynamic viscoelasticity of the adhesive layer 20 is measured by the method described in the examples of the present application.

The lower limit of the maximum value (peak temperature) at the loss tangent (tan δ) measured by the dynamic viscoelasticity measurement of the adhesive layer 20 is, for example, 55 ° C. or higher, 60 ° C. or higher, 65 ° C. or higher, or 70 ° C. or higher. It's okay. The upper limit of the maximum value (peak temperature) at the loss tangent (tan δ) measured by the dynamic viscoelasticity measurement of the adhesive layer 20 may be, for example, 100 ° C. or lower, 90 ° C. or lower, or 80 ° C. or lower. The maximum value (peak temperature) at the loss tangent (tan δ) of the adhesive layer 20 can be adjusted within the above range, and may be, for example, 55 to 100 ° C. or 60 to 80 ° C. Within this range, the adhesive layer does not soften at 50 ° C, and the maximum punching load at 50 ° C is excellent.

The lower limit of the thickness of the adhesive layer 20 may be, for example, 0.05 mm or more, 0.07 mm or more, 0.10 mm or more, or 0.15 mm or more. When the lower limit of the thickness of the adhesive layer 20 is within the above range, the adhesiveness between the structure 10 including concrete and the reinforcing layer 30 can be improved, and the load bearing capacity of the concrete structure can be further improved. it can. The upper limit of the thickness of the adhesive layer 20 may be, for example, 0.50 mm or less, 0.40 mm or less, 0.30 mm or less, or 0.25 mm or less. When the upper limit of the thickness of the adhesive layer 20 is within the above range, the construction time can be shortened. The thickness of the adhesive layer 20 can be adjusted within the above range, and may be, for example, 0.05 to 0.50 mm or 0.10 to 0.30 mm.

The adhesive layer 20 is also referred to as a primer layer because it is formed by applying a first resin composition serving as a primer on a structure 10 containing concrete and curing the adhesive layer 20. The adhesive layer 20 may contain at least one selected from the group consisting of, for example, a cured product of an acrylic resin, a cured product of a urethane resin, and a cured product of an epoxy resin, and preferably contains a cured product of an epoxy resin. It preferably consists of a cured product of epoxy resin. The adhesive layer 20 can be strongly adhered to the structure 10 containing concrete by impregnating the fine irregularities and cracked portions existing on the surface of the structure 10 containing concrete with the resin and then hardening the resin. .. When the adhesive layer 20 contains the above-mentioned resin, the adhesiveness to the surface of the structure 10 including concrete becomes excellent, and the peeling prevention performance of the concrete structure 50 can be further improved.

(Reinforcement layer)
The reinforcing layer 30 is a layer for preventing the peeling of concrete pieces and the like generated from the structure 10 containing concrete in the concrete structure 50. The reinforcing layer 30 may have a ratio of the storage elastic modulus at −30 ° C. to the storage elastic modulus at 50 ° C., for example, 1 to 20, 1 to 15, 1 to 10, or 1 to 8. Since the storage elastic modulus of the reinforcing layer 30 at 50 ° C. and −30 ° C. has the above-mentioned relationship, the change in load bearing capacity is suppressed from the low temperature region to the high temperature region. Can be made more reliable. The ratio of the storage elastic modulus of the reinforcing layer 30 can be controlled by adjusting the component composition, curing conditions, thickness, and the like of the resin composition when forming the reinforcing layer 30, which will be described later.

The loss tangent (tan δ) measured by the dynamic viscoelasticity measurement of the reinforcing layer 30 does not have to have a maximum value in the temperature range of −10 to 30 ° C. The loss tangent measured by the dynamic viscoelasticity measurement of the reinforcing layer 30 does not have to have a maximum value in the temperature range of -30 to 50 ° C, and has a maximum value in the temperature range of -50 to 80 ° C. You don't have to. The fact that the reinforcing layer 30 does not have the maximum value of the loss tangent within the above-mentioned temperature range means that the changes in breaking strength and breaking elongation in the above-mentioned temperature range (the temperature range having no maximum loss tangent) are small. However, it means that the reinforcing layer 30 is excellent in reliability of toughness and load bearing capacity even in an environment such as a cold region and a high temperature region.

As the test body to be used for the dynamic viscoelasticity measurement of the reinforcing layer 30 in the present specification, for example, the reinforcing layer 30 can be collected from the concrete structure 50 and used as a test body, or the concrete structure 50 can be manufactured. It is also possible to prepare a cured film of the reinforcing layer 30 to be used in advance and use it as a test body (the same applies to the haze of the reinforcing layer 30, the total light transmittance, and other test bodies to be used for characteristic tests). Specifically, the dynamic viscoelasticity of the reinforcing layer 30 can be measured by the method described in Examples. The maximum value of the loss tangent is the ratio of the loss modulus (E ″) and the storage modulus (E ′) measured by dynamic viscoelasticity measurement (the value of the loss modulus divided by the value of the storage modulus). Value: E'' / E') can be obtained from the graph showing the temperature dependence.

The reinforcing layer 30 may be slightly colored or slightly turbid, but is preferably colorless and transparent from the viewpoint of improving the appearance such as glare. The appearance of the reinforcing layer 30 can be controlled by adjusting the composition of the second resin composition described later or the reinforcing layer forming agent containing the second resin composition and the solvent.

The upper limit of the haze of the reinforcing layer 30 may be, for example, 30 or less, 28 or less, 25 or less, 23 or less, or 20 or less. When the upper limit of the haze of the reinforcing layer 30 is within the above range, the transparency of the coating layer 40 can be further improved. The lower limit of the haze of the reinforcing layer 30 is not particularly limited, but may be usually 1 or more, or 3 or more. The haze of the reinforcing layer 30 can be adjusted within the above range and may be, for example, 1-30, or 3-20.

The haze in the present specification means a value obtained in accordance with JIS K 7136: 2000 “How to obtain a haze of a plastic-transparent material”. Specifically, the haze can be measured using a turbidity meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: NDH4000).

The minimum value of the total light transmittance of the reinforcing layer 30 may be 80% or more, 85% or more, or 90% or more. When the minimum value of the total light transmittance of the reinforcing layer 30 is within the above range, the transparency of the coating layer 40 can be further improved.

The total light transmittance in the present specification means a value obtained in accordance with JIS K 7375: 2008 "Plastic-How to obtain total light transmittance and total light reflectance". Specifically, the total light transmittance can be measured using a turbidity meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: NDH4000).

It is desirable that the reinforcing layer 30 has a low haze and a high total light transmittance. Specifically, for example, the haze of the reinforcing layer 30 may be 30 or less and the total light transmittance of the reinforcing layer 30 may be 80% or more, and the haze of the reinforcing layer 30 is 20 or less and the reinforcing layer 30. The total light transmittance may be 90% or more.

The reinforcing layer 30 is also referred to as a resin cured layer because it is formed by applying a second resin composition on the adhesive layer 20 and curing the reinforcing layer 30. The reinforcing layer 30 may contain, for example, an acrylic resin, an epoxy resin, a urea resin, a polyurethane resin, a polyurethane urea resin, or the like, or may be made of a polyurethane urea resin.

The lower limit of the thickness of the reinforcing layer 30 may be, for example, 0.3 mm or more, 0.4 mm or more, or 0.5 mm or more. When the lower limit of the thickness of the reinforcing layer 30 is within the above range, the load bearing capacity of the concrete structure 50 can be further improved. The upper limit of the thickness of the reinforcing layer 30 may be, for example, 5 mm or less, 4 mm or less, 3 mm or less, or 2 mm or less. When the upper limit of the thickness of the reinforcing layer 30 is within the above range, the construction cost can be reduced and the anti-scraping performance can be improved (for example, the load resistance can be improved). The thickness of the reinforcing layer 30 can be adjusted within the above range, and may be, for example, 0.3 to 5 mm or 0.5 to 2 mm.

In the above-mentioned concrete structure, it is not always necessary to mix a mesh made of continuous fibers, a sheet made of continuous fibers, and a reinforcing material such as short fibers with the reinforcing layer 30. Even when it does not contain, it can exhibit sufficient anti-stripping performance. The reinforcing layer 30 does not have to include a sheet composed of a reinforcing mesh and continuous fibers. Here, the continuous fiber means a long fiber bundle composed of a single fiber. Examples of the single fiber include carbon fiber, aramid fiber, glass fiber and the like.

The reinforcing layer 30 may include the above-mentioned reinforcing material or the like as long as the gist of the present disclosure is not impaired. When the reinforcing layer 30 contains at least one selected from the group consisting of particles and fibers, the average particle size of the particles and the average major axis length of the fibers may be 10 μm or less. More specifically, both the average particle size of the particles contained in the reinforcing layer 30 and the average major axis length of the short fibers are preferably 10 μm or less, more preferably 1 μm or less, and further preferably. Is 0.1 μm or less. In the case of a material in which the particles can form secondary particles, the average particle size means the average particle size of the primary particles.

The "average particle size" in the present specification means a value measured according to the method described in JIS Z 8825: 2013 "Particle size analysis-laser diffraction / scattering method". The "average major axis length" in the present specification is measured according to the method described in JIS P 8226: 2011 "Pulp-Fiber length measurement method by optical automatic analysis method-Part 2: Non-polarization method". Means the value.

The material of the above-mentioned particles is not particularly limited. Examples of the material of the particles include inorganic materials such as silica, alumina, titanium oxide, barium sulfate, talc, calcium carbonate, glass, and quartz, as well as epoxy resin, melamine resin, urea resin, guanamine resin, polyester resin, and polyamide. Examples thereof include organic materials such as resin, rubber, and silicone. Among these materials, since the haze of the reinforcing layer 30 is low and the total light transmittance is excellent, the material of the particles preferably contains at least one material selected from the group consisting of silica and glass, and is more preferable. Is silica or glass.

The mesh composed of continuous fibers and the sheet composed of continuous fibers refer to those in which continuous fibers are knitted in a mesh shape and those in which continuous fibers are bonded or joined to form a sheet. Reinforcing materials such as short fibers refer to fibers having an average major axis length of 30 mm or less. The material of these fibers is not particularly limited. Examples of the fiber include vinylon fiber, glass fiber, carbon fiber and the like.

When the reinforcing layer 30 contains at least one selected from the group consisting of particles having an average particle size of 10 μm or less and fibers having an average major axis length of 10 μm or less, the transparency of the coating layer 40 From the viewpoint of more sufficiently suppressing the decrease, the total content of the above-mentioned predetermined particles and the predetermined fibers is preferably less than 20% by mass, more preferably 10% by mass, based on the total amount of the reinforcing layer 30. It is less than, more preferably less than 5% by mass, and even more preferably less than 3% by mass. The reinforcing layer 30 preferably does not contain particles having an average particle size of more than 10 μm and fibers having an average major axis length of more than 10 μm.

(Coating layer: Lamination including adhesive layer and reinforcing layer)
The upper limit of the haze of the coating layer 40 may be, for example, 40 or less, 35 or less, or 30 or less. When the upper limit of the haze of the coating layer 40 is within the above range, the transparency of the coating layer 40 is high, the surface of the structure 10 including concrete in the concrete structure 50 is easily visible, and cracks in the structure are easily recognized. It becomes easy to visually confirm the occurrence of deterioration of concrete. The lower limit of the haze of the coating layer 40 may be, for example, 1 or more, or 3 or more.

The minimum value of the total light transmittance of the coating layer 40 may be, for example, 70% or more, 75% or more, or 80% or more. When the minimum value of the total light transmittance of the coating layer 40 is within the above range, the transparency of the coating layer 40 is high, and the surface of the structure 10 including concrete in the concrete structure 50 can be easily visually recognized. It becomes easy to visually confirm the occurrence of deterioration such as cracks in the concrete.

It is desirable that the coating layer 40 has a low haze and a high total light transmittance. Specifically, for example, the haze of the coating layer 40 may be 40 or less and the total light transmittance of the coating layer 40 may be 70% or more, and the haze of the coating layer 40 is 30 or less and the coating layer 40. The total light transmittance of the light may be 80% or more.

Since the above-mentioned coating layer 40 is excellent in weather resistance and breaking strength and can be excellent in transparency, the concrete structure 50 has excellent blocking property against deterioration factors without impairing the appearance of the structure 10 including concrete. For example, it may have salt-shielding property, oxygen permeation blocking property, water vapor permeation blocking property, and neutralization blocking property).

(Performance of concrete structure)
Since the concrete structure 50 is excellent in load resistance, it is excellent in peeling prevention performance. The lower limit of the maximum punching load of the concrete structure 50 at 50 ° C. can be, for example, 1.5 kN or more, 1.6 kN or more, 1.8 kN or more, or 2.0 kN or more. The upper limit of the maximum punching load of the concrete structure 50 at 50 ° C. is not particularly limited, but is usually 3.5 kN or less, and from the viewpoint of reducing the manufacturing cost, it is 3.2 kN or less, or 3. It may be 0 kN or less.

The lower limit of the displacement in the punching test of the concrete structure 50 is, for example, because it is possible to easily detect an abnormality by the deformation while preventing the concrete piece (tile, etc. in the case of the tile structure) to be peeled off. It can be 10 mm or more, 30 mm or more, 50 mm or more, or 70 mm or more. The upper limit of the displacement of the concrete structure 50 in the punching test may be, for example, 100 mm or less, 90 mm or less, or 80 mm or less from the viewpoint of suppressing excessive deformation.

The maximum load and displacement of the concrete structure 50 in the punching test are preferably within the above ranges at 23 ° C, and within the above ranges at the temperatures of −10 ° C, 23 ° C, and 50 ° C. More preferably, it is within the above range at each temperature of −30 ° C., 23 ° C., and 50 ° C. When the maximum load and displacement in the punching test of the concrete structure 50 are within the above ranges, it is possible to suitably prevent the concrete pieces (tiles and the like in the tile structure) from falling off. Further, when the maximum load and displacement in the punching test of the concrete structure 50 are within the above ranges, the load capacity is superior to that of the conventional concrete structure, so that the concrete structure 50 is not easily torn even when a load is applied and is reliable. Can demonstrate high anti-scraping performance.

The punching test in the present specification means a test performed in accordance with JSCE-K 533-2013 (Japan Society of Civil Engineers punching test method for surface covering material applied to prevent concrete pieces from falling off).

Since the concrete structure 50 includes an adhesive layer 20 and a reinforcing layer 30, a punching test method (JSCE-K 533-2013) of a surface covering material applied to prevent peeling of concrete pieces of the Japan Society of Civil Engineers, and structure construction management. The performance described in the fall prevention measures of the procedure (East Nippon Expressway Co., Ltd., Central Nippon Expressway Co., Ltd., West Nippon Expressway Co., Ltd., July 2017) can be exhibited.

The concrete structure 50 may further have other layers in addition to the adhesive layer 20 and the reinforcing layer 30 described above. Examples of other layers include a top coat layer and the like. The concrete structure 50 may further have a top coat layer on the side of the coating layer 40 opposite to the side of the structure 10 including the concrete. The top coat layer can impart weather resistance, landscape, and the like to the concrete structure 50, for example.

The above description of the concrete structure 50 has been described by taking the structure 10 including concrete as an example, but it can also be applied to the case where a structure having tiles is used instead of the structure 10 containing concrete.

[Manufacturing method of concrete structure]
The concrete structure 50 described above can be manufactured, for example, by the following method. An embodiment of a method of producing a concrete structure, the first resin composition layer on a structure comprising a concrete provided by curing, the storage elastic modulus E at 50 ° C. 'is 4.0 × 10 ⁸ Pa It includes a step of forming the adhesive layer as described above, and a step of forming a reinforcing layer by providing a second resin composition layer on the adhesive layer and curing the layer.

(First resin composition layer)
In the method for manufacturing a concrete structure, the thickness of the first resin composition layer can be adjusted according to the thickness of the adhesive layer after curing. The lower limit of the thickness of the first resin composition layer may be, for example, 0.05 mm or more, 0.07 mm or more, 0.10 mm or more, or 0.15 mm or more. When the lower limit of the thickness of the first resin composition layer is within the above range, the adhesiveness between the structure containing concrete and the reinforcing layer can be improved, and the load resistance of the concrete structure is further improved. be able to. The upper limit of the thickness of the first resin composition layer may be, for example, 0.50 mm or less, 0.40 mm or less, 0.30 mm or less, or 0.25 mm or more. When the upper limit of the thickness of the first resin composition layer is within the above range, it is possible to have sufficient adhesive strength for a structure containing concrete and shorten the construction time. The thickness of the first resin composition layer can be adjusted within the above range, and may be, for example, 0.05 to 0.50 mm or 0.10 to 0.30 mm.

The first resin composition layer can be formed, for example, by applying a first resin composition or a primer solution containing the first resin composition and a solvent onto a structure containing concrete. it can. The coating can be performed by, for example, a method using a trowel, a spatula, a brush, a roller, a spray, or the like. When the primer solution is applied by hand, a coating film having a desired thickness can be easily formed outdoors. The application of the primer solution may be performed in a plurality of times.

The first resin composition may contain, for example, a resin such as an epoxy resin, an acrylic resin, and a urethane resin, and a curing agent corresponding to the resin, preferably an epoxy resin and a curing agent corresponding to the resin. Including. Since the first resin composition forms a primer layer, it is also called a primer. That is, as the primer, for example, an epoxy-based primer, an acrylic-based primer, a urethane-based primer, or the like can be used.

Examples of the epoxy resin include epoxy resins such as glycidyl ether type, glycidyl amine type, glycidyl ester type, and olefin oxidation type. The epoxy resin preferably contains a glycidyl ether type epoxy resin. Examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, and alkyldiphenol type epoxy resin. Of these, from the viewpoint of increasing the storage elasticity E'of the adhesive layer, the epoxy resin preferably contains at least one of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin, and more preferably a bisphenol A type epoxy resin. , And more preferably a bisphenol A type epoxy resin. The epoxy resin may have other functional groups. Examples of other functional groups include hydroxyl groups. The epoxy resin is preferably liquid.

The epoxy equivalent of the epoxy resin (the number of grams of epoxy resin containing 1 gram equivalent of epoxy groups) can be selected to adjust the storage modulus E'of the adhesive layer. That is, in order to improve the storage elastic modulus E'of the adhesive layer, an epoxy resin having a small epoxy equivalent may be used. The lower limit of the epoxy equivalent of the epoxy resin may be, for example, 150 or more, 160 or more, or 180 or more. The upper limit of the epoxy equivalent of the epoxy resin may be, for example, 250 or less, 230 or less, or 200 or less. In order to adjust the storage elastic modulus E'of the adhesive layer, a plurality of epoxy resins having different epoxy equivalents may be mixed and used. For example, as the resin constituting the first resin composition, a bisphenol A type diglycidyl ether having an epoxy equivalent of 180 to 195 and an alkyldiphenol type epoxy resin having an epoxy equivalent of 200 to 250 are mixed and used. You may.

When the first resin composition contains an epoxy resin, as the curing agent, a compound having active hydrogen capable of reacting with an epoxy group, a compound capable of producing active hydrogen capable of reacting with an epoxy group, or the like can be used. Examples of such a curing agent include amines, dibasic acids, acid anhydrides, and the like. The epoxy resin curing agent preferably contains an amine because it has excellent curability at room temperature. The amine may be any of a primary amine, a secondary amine, and a tertiary amine. The amine may also be a polyamine.

When the first resin composition contains an epoxy resin, the curing agent preferably contains an aromatic polyamine and a modified product (A) thereof from the viewpoint of increasing the storage elastic modulus E'of the adhesive layer. Examples of the aromatic polyamine used here include aromatic compounds having two or more amino groups, aromatic compounds having one or more amino groups and imino groups, and the like. The aromatic compound having one or more amino groups and one or more imino groups each preferably contains an aromatic compound having a primary amino group from the viewpoint of excellent curability at room temperature, and more preferably the amino group is an alkylene group. Includes aromatic compounds attached to the aromatic ring via.

Examples of the aromatic polyamine as described above include metaxylylenediamine and paraxylylenediamine. The aromatic polyamine preferably contains m-xylylenediamine, and more preferably m-xylylenediamine. The aromatic polyamine preferably contains a modified product, and is more preferably a modified product. The modified product is not particularly limited, but for example, amine adduct, modified polyamine, polyamide amine and the like can be used. Amine adduct is a compound obtained by adding an epoxy resin to polyamine. Examples of the modified polyamine include polyamine-ethylene oxide adduct, polyamine-propylene oxide adduct, Mannich-type curing agent, and cyanoethylated polyamine. Examples of the polyamide amine include a reaction product of a polyamine and a dimer acid, a reaction product of a polyamine and a polycarboxylic acid, and the like.

When the first resin composition contains an epoxy resin, the curing agent preferably contains an alicyclic polyamine and a modified product (B) thereof from the viewpoint of increasing the storage elastic modulus E'of the adhesive layer. Examples of the alicyclic polyamine used here include a compound having an alicyclic structure having two or more amino groups, a compound having an alicyclic structure having one or more amino groups and an imino group, and the like. Of these, from the viewpoint of increasing the glass transition temperature (maximum value in tan δ), the alicyclic polyamine is preferably an alicyclic polyamine having an amino group directly bonded to the alicyclic structure and a modified product thereof (B-1). )including. Examples of the alicyclic polyamine used here include isophorone diamine (IPDA) and bis (aminocyclohexyl) methane (H-MDA). The alicyclic polyamine preferably contains a modified product, and is more preferably a modified product. The modified product is not particularly limited, and for example, amine adduct, modified polyamine, polyamide amine and the like can be used. Amine adduct is a compound obtained by adding an epoxy resin to polyamine. Examples of the modified polyamine include polyamine-ethylene oxide adduct, polyamine-propylene oxide adduct, Mannich-type curing agent, and cyanoethylated polyamine. Examples of the polyamide amine include a reaction product of a polyamine and a dimer acid, a reaction product of a polyamine and a polycarboxylic acid, and the like.

When the first resin composition contains an epoxy resin, the curing agent preferably contains a modified aliphatic polyamine (C) from the viewpoint of improving adhesiveness and increasing the maximum punching load. The modified aliphatic polyamine is a modified version of the aliphatic polyamine, and examples thereof include polyamine-ethylene oxide adduct, polyamine-propylene oxide adduct, Mannig-type curing agent, and cyanoethylated polyamine. Examples of the aliphatic polyamine used here include an aliphatic compound having two or more amino groups, an aliphatic compound having one or more amino groups and an imino group, and the like. Aliphatic polyamines include aliphatic diamines such as hexamethylenediamine (HMD), octamethylenediamine (OMD), and nonanediamine (NDA) and their structural isomers; ethylenediamine (EDA), diethylenetriamine (DETA), triethylene. High amines such as tetramine (TETA), tetraethylenepentamine (TEPA), diproprendiamine (DPDA), and diethylaminopropylamine (DEAPA) and their derivatives; polyoxyalkylamines and their derivatives and their structural isomers, etc. Can be mentioned. Examples of the polyoxyalkylamine include Jeffamine manufactured by Huntsman Co., Ltd. and polyetheramine manufactured by Mitsui Kagaku Fine Co., Ltd.

When the first resin composition contains an epoxy resin, the curing agent preferably contains a polyamide amine (D) from the viewpoint of improving the flexibility of the adhesive layer and increasing the maximum punching load. Examples of the polyamide amine include a reaction product of a polyamine and a dimer acid, a reaction product of a polyamine and a polycarboxylic acid, and the like. The polyamine used here preferably includes the above-mentioned aromatic polyamine, the above-mentioned alicyclic polyamine, the above-mentioned aliphatic polyamine, and the like.

When the first resin composition contains an epoxy resin, the curing agent preferably contains an aliphatic polyamine (E) from the viewpoint of improving adhesiveness and increasing the maximum punching load. The polyamine used here preferably contains the above-mentioned aliphatic polyamine.

The above-mentioned curing agent preferably contains an aromatic polyamine and a derivative thereof (A), and an alicyclic polyamine and a modified product thereof (B) from the viewpoint of increasing the storage elastic modulus E'of the adhesive layer. From the viewpoint of increasing the storage elasticity E'of the adhesive layer and increasing the glass transition temperature, the above-mentioned curing agent is preferably an aromatic polyamine and its derivative (A), and an amino directly bonded to an alicyclic structure. An alicyclic polyamine having a group and a modified product thereof (B-1), more preferably an aromatic polyamine and a derivative thereof (A), and an alicyclic polyamine having an amino group directly bonded to the alicyclic structure and It does not contain the alicyclic polyamine and its derivative (B-2), which contains the modified product (B-1) and does not have an amino group directly bonded to the alicyclic structure.

From the viewpoint of increasing the storage elasticity E'of the adhesive layer, enhancing the adhesiveness, and improving the maximum punching load, the above-mentioned curing agent is preferably an aromatic polyamine and its derivative (A), and a modified fat. An alicyclic polyamine containing a group polyamine (C), more preferably an aromatic polyamine and a derivative thereof (A), a modified aliphatic polyamine (C), and having no amino group directly bonded to the alicyclic structure, and an alicyclic polyamine. It does not contain the derivative (B-2).

From the viewpoint of increasing the storage elasticity E'of the adhesive layer, enhancing the adhesiveness, and improving the maximum punching load, the above-mentioned curing agent is preferably an aromatic polyamine and its derivative (A), an alicyclic. More preferably, an aromatic polyamine and its derivative (A), including the formula polyamine and its modified product (B), and the modified aliphatic polyamine (C), an alicyclic polyamine having an amino group directly bonded to the alicyclic structure. And a modified product thereof (B-1), and a modified aliphatic polyamine (C), more preferably an aromatic polyamine and a derivative thereof (A), an alicyclic polyamine having an amino group directly bonded to the alicyclic structure. And its modified product (B-1), and the alicyclic polyamine and its derivative (B-2), which contain a modified aliphatic polyamine (C) and do not have an amino group directly bonded to the alicyclic structure.

When the first resin composition contains an epoxy resin, the equivalent ratio of the number of epoxy groups in the first resin composition to the number of active hydrogen contained in the curing agent (molar equivalent of epoxy group / molar of active hydrogen). The lower limit of (equivalent) may be, for example, 0.8 or more, or 0.9 or more. By setting the corresponding amount ratio within the above range, the adhesiveness between the structure including concrete and the reinforcing layer by the adhesive layer can be made more sufficient. The upper limit of the equivalent ratio between the number of epoxy groups in the first resin composition and the number of active hydrogens contained in the curing agent may be, for example, 1.2 or less, or 1.1 or less. By setting the corresponding amount ratio within the above range, it is possible to suppress the decrease in the storage elastic modulus E'of the adhesive layer due to the influence of environmental moisture during curing.

The first resin composition may contain other components in addition to the above-mentioned resin and the curing agent corresponding to the resin. Examples of other components include a reactive diluent, a shake denaturing agent and the like.

As the reactive diluent, for example, a low molecular weight compound having at least two glycidyl groups can be used. The low molecular weight compound having at least two glycidyl groups can reduce the viscosity of the first resin composition and improve the workability. The molecular weight of the low molecular weight compound having at least two glycidyl groups may be, for example, 500 or less, or 250 or less. Examples of the low molecular weight compound having at least two glycidyl groups include alkyl diglycidyl ether and the like. Examples of the alkyl diglycidyl ether include 1,6-hexanediol diglycidyl ether and glycerin diglycidyl ether.

When the first resin composition contains a low molecular weight compound having at least two glycidyl groups, the upper limit of the content of the low molecular weight compound is, for example, 20% by mass or less based on the total amount of the first resin composition. , Or 15% by mass or less. By setting the upper limit of the content of the low molecular weight compound within the above range, it is possible to suppress a decrease in the storage elastic modulus E'of the adhesive layer. The lower limit of the content of the low molecular weight compound may be, for example, 10% by mass or more, or 11% by mass or more based on the total amount of the first resin composition. By setting the lower limit of the content of the low molecular weight compound within the above range, the workability of the first resin composition can be further improved.

As the rocking denaturing agent, those described as being usable in the second resin composition described later can be used in the same manner.

When the first resin composition contains a urethane resin, it may contain a curing agent corresponding to the resin, and may be a one-component curing type in which the resin such as moisture in the air reacts and cures. The polyisocyanate component contained in the urethane resin preferably contains an aliphatic polyisocyanate from the viewpoint of increasing the storage elastic modulus E'of the adhesive layer, enhancing the adhesiveness, and improving the maximum punching load, and more preferably. Includes alicyclic polyisocyanates.

(Second resin composition layer)
In the method for manufacturing a concrete structure, the thickness of the second resin composition layer can be adjusted according to the thickness of the reinforcing layer after curing. The lower limit of the thickness of the second resin composition layer may be, for example, 0.3 mm or more, 0.4 mm or more, or 0.5 mm or more. When the lower limit of the thickness of the second resin composition layer is within the above range, the load bearing capacity of the concrete structure can be further improved. The upper limit of the thickness of the second resin composition layer may be, for example, 5 mm or less, 4 mm or less, 3 mm or less, or 2 mm or more. When the upper limit of the thickness of the second resin composition layer is within the above range, the construction cost can be reduced and the peeling prevention performance can be improved (for example, the load resistance can be improved). The thickness of the second resin composition layer can be adjusted within the above range, and may be, for example, 0.3 to 5 mm or 0.5 to 2 mm.

The second resin composition layer can be formed, for example, by applying a second resin composition or a reinforcing layer forming agent containing the second resin composition and a solvent onto the adhesive layer. As the coating method and the like, the description of coating the first resin composition layer can be applied.

As the second resin composition, a coating resin composition or the like can be used. As the second resin composition, for example, a resin composition containing a prepolymer (a) having an isocyanato group and a curing agent (b) can be used. The prepolymer (a) may have a structure derived from polyisocyanate and a structure derived from polyol. The second resin composition can be dissolved in the solvent (c) and used as a reinforcing layer forming agent.

The second resin composition contains a prepolymer (a) having an isocyanato group (hereinafter, also simply referred to as a prepolymer (a)). The prepolymer (a) has, for example, a structure derived from polyisocyanate and a structure derived from polyol. The structure derived from polyisocyanate may include an aliphatic polyisocyanate structure. The structure derived from the aliphatic polyisocyanate may include an alicyclic structure. The aliphatic polyisocyanate may have, for example, 6 or more, 10 or more, or 13 or more carbon atoms. The polyol may be, for example, an aliphatic polyol. The prepolymer (a) may have a structure derived from other components in addition to the structure derived from polyisocyanate and the structure derived from polyol. The prepolymer (a) may have an isocyanato group at the end of the prepolymer (a) or may have a side chain. The prepolymer (a) has, for example, a structural unit represented by the following general formula (1) as a terminal structure.

In the above general formula (1), R ¹ represents a functional group having 4 or more carbon atoms, 8 or more carbon atoms, or 11 or more carbon atoms. The functional group may be linear, branched or cyclic, and may contain a heteroatom. The functional group may be, for example, an aliphatic group. The carbon number of the aliphatic group may be 6 or more, 12 or more, or 13 or more, and may be 30 or less, or 20 or less. In the above general formula (1), R ² may have a structure represented by the following general formulas (2) to the following general formulas (6), for example.

In the above general formulas (2) to (6), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are independently alkyl groups and alkylene groups, respectively. And at least one functional group selected from the group consisting of aryl groups. R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different from each other. The alkyl group and the alkylene group may be linear, branched or cyclic. The aryl group may have a substituent on the aromatic ring.

R ³ may be a functional group having 4 to 18 carbon atoms, a functional group having 5 to 9 carbon atoms, or a functional group having 5 to 6 carbon atoms. R ⁴ and R ⁵ may be a functional group having 2 to 20 carbon atoms, a functional group having 2 to 14 carbon atoms, or a functional group having 2 to 10 carbon atoms. R ⁶ may be a functional group having 2 to 9 carbon atoms, a functional group having 3 to 6 carbon atoms, or a functional group having 3 to 4 carbon atoms. R ⁷ and R ⁸ may be a functional group having 2 to 20 carbon atoms, a functional group having 2 to 14 carbon atoms, or a functional group having 2 to 10 carbon atoms. R ⁹ and R ¹⁰ may be a functional group having 2 to 18 carbon atoms, a functional group having 2 to 10 carbon atoms, or a functional group having 4 to 6 carbon atoms. In the general formulas (2) to (6), p, q, r, s, t, u and v may be independently integers of 1 or more.

The content of the isocyanato group in the prepolymer (a) may be 0.1 to 15% by mass, 1 to 12% by mass, or 3 to 10% by mass based on the total mass of the prepolymer (a). .. When the content of the isocyanato group in the prepolymer (a) is 0.1% by mass or more, the number average molecular weight and the viscosity of the prepolymer (a) can be made appropriate, and the second resin composition It is possible to suppress a decrease in workability due to an increase in the viscosity of the polymer. Further, when the content of the isocyanato group in the prepolymer (a) is within the above range, the cross-linking point can be increased when the prepolymer (a) is cured, and the reinforcing layer (for example, a cured film) can be increased. And the adhesiveness with the adhesive layer can be improved. When the content of the isocyanato group in the prepolymer (a) is 15% by mass or less, the ratio of the rigid components such as urethane bond and ring structure in the reinforcing layer is made appropriate, and the flexibility of the reinforcing layer is lowered. It can be suppressed.

The viscosity of the prepolymer (a) at 23 ° C. may be 1,000 to 150,000 mPa · s, 3,000 to 100,000 mPa · s, or 10,000 to 50,000 mPa · s. When the viscosity of the prepolymer (a) at 23 ° C. is within the above range, the workability of the obtained second resin composition can be further improved. The viscosity of the prepolymer (a) can be appropriately adjusted by adding a solvent, a plasticizer, or the like.

The "viscosity" in the present specification is the kinematic viscosity measured according to the method described in the cone-plate type rotational viscometer and the single cylindrical rotational viscometer in JIS Z 8803: 2011 "Method for measuring the viscosity of liquid". Means.

The number average molecular weight of the prepolymer (a) may be 500 or more, 700 to 10,000, or 1,000 to 10,000. When the number average molecular weight of the prepolymer (a) is within the above numerical range, the mechanical strength of the obtained reinforcing layer can be improved.

The "number average molecular weight" in the present specification indicates a value measured by gel permeation chromatography (GPC) and is expressed in polystyrene-equivalent molecular weight. If appropriate, the isocyanato group may be derivatized as a pretreatment for the measurement using GPC.

As the prepolymer (a), for example, one prepared by the following method can be used. As a method for preparing the prepolymer (a), for example, a polyfunctional isocyanate containing an aliphatic polyisocyanate having two or more isocyanato groups and an aliphatic polyol having two or more hydroxyl groups are heated and stirred at 50 to 130 ° C. A method comprising reacting, or a polyisocyanate containing an aliphatic polyisocyanate having two or more isocyanato groups, an aliphatic polyol having two or more hydroxyl groups, and an active hydrogen compound having two or more functional groups capable of reacting with an isocyanato group. And a method including heating and stirring at 50 to 130 ° C. to cause a reaction.

In the above-mentioned method for preparing the prepolymer (a), a urethanization catalyst such as an organic tin compound, an organic bismuth and an amine may be further used, if necessary.

In the method for preparing the prepolymer (a) described above, the content of the isocyanato group in the polyisocyanate is 0.1 to 60% by mass, 5 to 50% by mass, or 10 to 40 based on the total mass of the polyisocyanate. It may be% by mass. When the content of the isocyanato group in the polyisocyanate is within the above range, excellent curability can be obtained by mixing with a curing agent.

In the method for preparing the prepolymer (a) described above, the aliphatic polyisocyanate may have 6 or more carbon atoms, 10 or more, 13 or more, 14 or more, or 15 or more carbon atoms. When the lower limit of the carbon number of the aliphatic polyisocyanate is within the above range, the boiling point of the aliphatic polyisocyanate is high and the saturated vapor concentration can be reduced. Therefore, even if polyisocyanate, which is a raw material of the prepolymer (a), remains in the second resin composition, the influence on the working environment in which the second resin composition is used is reduced. can do. The aliphatic polyisocyanate may have 30 or less carbon atoms or 20 or less carbon atoms. When the upper limit of the carbon number of the aliphatic polyisocyanate is within the above range, the viscosity of the obtained prepolymer (a) becomes appropriate, and the viscosity of the second resin composition increases, making construction difficult. Can be suppressed.

The aliphatic polyisocyanate used in the above-mentioned preparation method of the prepolymer (a) preferably has a ring structure, and more preferably has two or more ring structures. The ring structure may be a polycyclic or fused ring alicyclic, or may be a heterocycle containing an element other than carbon. When the aliphatic polyisocyanate has a ring structure (for example, an alicyclic structure), the weather resistance (low yellowing) of the cured product and the breaking strength can be compatible at a higher level.

The number of isocyanato groups contained in the aliphatic polyisocyanate used in the above-mentioned preparation method of the prepolymer (a) may be, for example, 2-9, 2-6, or 2-3. There may be two. When the number of isocyanato groups contained in the aliphatic polyisocyanate is within the above numerical range, the prepolymer (a) in which gelation is sufficiently suppressed can be produced.

Examples of the aliphatic polyisocyanate used in the method for preparing the prepolymer (a) include dicyclohexylmethane diisocyanate (hydrogenated diphenylmethane diisocyanate), hexamethylene diisocyanate, or isocyanurate compound derived from isophorone diisocyanate, hexamethylene diisocyanate, or the like. Examples thereof include an allophanate compound derived from isophorone diisocyanate, a bullet compound derived from hexamethylene diisocyanate or isophorone diisocyanate, and an adduct compound derived from hexamethylene diisocyanate or isophorone diisocyanate.

In the method for preparing the prepolymer (a) described above, the polyisocyanate may contain an aromatic polyisocyanate compound in addition to the aliphatic polyisocyanate as long as the properties are not impaired.

In the above-mentioned method for preparing the prepolymer (a), the above-mentioned aliphatic polyisocyanate and the above-mentioned other polyisocyanate compound may be modified, and uretdione bond, isocyanurate bond, allophanate bond, bullet bond, uretonimine bond, carbodiimide. It may have at least one bond selected from the group consisting of a bond, a urethane bond, and a urea bond, and preferably has an isocyanurate bond.

Examples of the polyol used in the above-mentioned preparation method of the prepolymer (a) include polycarbonate polyol, polyester polyol, polycarbonate polyester polyol, polyoxyalkylene-based polyol, polyesteramide polyol, polyether ester polyol, and poly (meth). Examples thereof include acrylic polyols and (hydrogenated) polybutadiene-based polyols. The polyol preferably contains at least one selected from the group consisting of polycarbonate polyols, polyester polyols, polyether polyols, and polycarbonate polyester polyols.

The above-mentioned polyol is at least one selected from the group consisting of polycarbonate polyol, polyester polyol, polyoxypropylene polyol, and polytetramethylene ether polyol from the viewpoint of improving the strength of the coating film and the weather resistance of the obtained reinforcing layer. It is preferable to include it. The above-mentioned polyol preferably contains a polyoxyalkylene-based polyol from the viewpoint of reducing the viscosity of the obtained prepolymer (a). The polyoxyalkylene-based polyol preferably contains a polyoxypropylene polyol or a polytetramethylene polyol, and particularly preferably contains a polytetramethylene polyol. In addition to the above-mentioned polyols, polyols exemplified as the polyols used as the curing agent (b) described later can be preferably used.

Examples of the above-mentioned polycarbonate polyol include polycarbonate polyols obtained by copolymerizing 1,6-hexanediol and dimethyl carbonate (ETERNACOLL UH series manufactured by Ube Kosan Co., Ltd .; UH-50, UH-100, UH-200, and UH. -300 etc.), Polycarbonate polyol obtained by copolymerizing 1,5-pentanediol, 1,6-hexanediol and dimethyl carbonate (manufactured by Ube Kosan Co., Ltd., ETERNAL COLL PH series; PH-50, PH-100, and PH -200 etc.), Polycarbonate polyol obtained by copolymerizing 1,4-cyclohexanedimethanol and dimethyl carbonate (ETERNACOLL; UC-100 etc., manufactured by Ube Kosan Co., Ltd.), 1,4-Cyclohexanedimethanol and 1,6- Polycarbonate polyol obtained by copolymerizing hexanediol and dimethyl carbonate (ETERNACOLL manufactured by Ube Kosan Co., Ltd .; UM-90 (3/1), UM-90 (1/1), UM-90 (1/3), etc. ), Duranol series manufactured by Asahi Kasei Co., Ltd., Nippon series manufactured by Toso Co., Ltd., Clare Polycarbonate C series manufactured by Clare Co., Ltd., and Praxel CD series manufactured by Daicel Co., Ltd.

Examples of the polytetramethylene polyol include polytetramethylene ether glycol manufactured by Mitsubishi Chemical Co., Ltd. (PTMG series; PTMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000, PTMG3000, etc.), and TERATHANE series manufactured by INVISTA. , Poly THF series manufactured by BASF Japan Co., Ltd., PTG and PTG-L series manufactured by Hodoya Chemical Industry Co., Ltd., and polytetramethylene polyol obtained by copolymerizing tetrahydrofuran and neopentyl glycol (manufactured by Asahi Kasei Co., Ltd., PTXG-1800 etc.) and the like.

The number average molecular weight of the polyol used in the method for preparing the prepolymer (a) described above may be 100 to 10,000, 300 to 5,000, or 500 to 2,000.

The active hydrogen compound having two or more functional groups capable of reacting with an isocyanato group used in the above-mentioned method for preparing the prepolymer (a) includes, for example, aromatic polyols, aromatic polyamines, aliphatic polyamines, and alkanols. It may contain at least one selected from the group consisting of amines and silane compounds. As the active hydrogen compound, the compound exemplified as the curing agent (b) described later can be used.

In the above-mentioned method for preparing the prepolymer (a), when the prepolymer (a) is prepared by reacting the polyisocyanate with an aliphatic polyol, the molar ratio of the isocyanato group of the polyisocyanate to the hydroxyl group of the polyol ( The molar equivalent of the isocyanate group / the molar equivalent of the hydroxyl group) may be 1.3 to 8.0, 1.5 to 3.5, or 1.7 to 3.0. When the molar ratio of the isocyanato group of the polyisocyanate to the hydroxyl group of the polyol is within the above range, the viscosity of the prepolymer is appropriately controlled, and the workability of the second resin composition is excellent.

The second resin composition contains a curing agent (b). As the curing agent (b), for example, a compound having active hydrogen capable of reacting with the isocyanato group contained in the prepolymer (a), a latent curing agent, and the like can be used. As the latent curing agent, a compound or the like that can react with water and react with the isocyanato group of the prepolymer (a) to generate active hydrogen can be used.

The curing agent (b) may contain an aromatic curing agent. As the aromatic curing agent, an aromatic compound having an active hydrogen capable of reacting with an isocyanato group can be used, and for example, an aromatic compound having a total of two or more amino groups and hydroxyl groups can be used. Can be done. Examples of the aromatic compound having two or more amino groups and hydroxyl groups in total include aromatic polyamines and aromatic polyols, and aromatic polyamines are particularly preferable because the curing time is short. The aromatic curing agent may be a mixture of two or more compounds. However, from the viewpoint of economical efficiency, curability, and suitable control of pot life, the aromatic curing agent is preferably composed of one kind of compound. The curing agent (b) may further contain, for example, an aliphatic polyamine, an alkanolamine, an aliphatic polyol, an oxazolidine compound, a bisoxazolidine compound, a silane compound, or the like, in addition to the aromatic curing agent.

When the curing agent (b) contains an aromatic curing agent, the content of the aromatic curing agent in the curing agent (b) is preferably 25% by mass based on the total amount of the curing agent (b). It is more preferably 40% by mass or more, further preferably 80% by mass or more, and it may be 100% by mass. When the content of the aromatic curing agent is 100% by mass, it means that the curing agent (b) is composed of the aromatic curing agent. In this case, the aromatic curing agent may contain an aromatic polyamine or may consist of an aromatic polyamine. When the ratio of the content of the aromatic curing agent in the curing agent (b) is increased, the tensile elastic modulus and the breaking strength at 50 ° C. can be further improved. Further, when the ratio of the content of the aromatic curing agent in the curing agent (b) is increased, the punching performance of the concrete structure at high temperature (for example, 50 ° C.) to prevent peeling can be further improved. When the aromatic curing agent is a mixture of two or more compounds, the "content of the aromatic curing agent" means the total content of each aromatic curing agent.

The content of the aromatic curing agent in the second resin composition is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably, based on the total amount of the second resin composition. Is 10% by mass or more. When the ratio of the content of the aromatic curing agent in the second resin composition is increased, the tensile elastic modulus and the breaking strength at 50 ° C. can be further improved. Further, when the ratio of the content of the aromatic curing agent in the second resin composition is increased, the punching performance for preventing peeling at a high temperature (for example, 50 ° C.) can be further improved. When the aromatic curing agent is a mixture of two or more compounds, the "content of the aromatic curing agent" means the total content of each aromatic curing agent.

Examples of the aromatic polyamine include an aromatic compound having two or more amino groups, an aromatic compound having one or more amino groups and one or more imino groups, and the like. Examples of the aromatic polyamine include methylene dianiline (MDA), 4,4'-methylenebis (3-chloro-2,6-diethylaniline) (MCDEA), diethyltoluenediamine (DETDA), and 4,4'-methylenebis. (2-Ethyl-6-methylaniline) (MMEA), 4,4'-methylenebis (2,6-diethylaniline) (MDEA), 4,4'-methylenebis (2-isopropyl-6-methylaniline) (MMIPA) ), 4,4'-bis (sec-butylamino) diphenylmethane, phenylenediamine, methylenebis (о-chloroaniline) (MBOCA), 4,4'-methylenebis (2-methylaniline) (MMA), 4,4' -Methylenebis (2-chloro-6-ethylaniline) (MCEA), 1,2-bis (2-aminophenylthiol) ethane, N, N'-dialkyl-p-phenylenediamine, 4,4'-methylenebis (2) , 6-Diisopropylaniline) (MDIPA), dimethylthiotoluenediamine (DMTDA), alkylene glycol bis (para-aminobenzoate), and aminobenzoate terminal compounds such as polyalkylene glycol bis (p-aminobenzoate). As the aromatic diamine having one aromatic ring, for example, diethyl toluenediamine (DETDA) is preferable.

Examples of the aromatic polyol include aromatic compounds having two or more hydroxyl groups. Examples of the aromatic polyol include aromatic polyols having phenolic hydroxyl groups such as catechol, resorcinol, hydroquinone, and phenol resin; aromatic polyols having alcoholic hydroxyl groups such as benzenedimethanol and benzenediethanol; and aromatics. Examples thereof include polycarbonate polyols containing a skeleton, polyester polyols containing an aromatic skeleton, polyether polyols containing an aromatic skeleton, and polymer aromatic polyols such as castor oil-based modified polyols containing an aromatic skeleton. The aromatic polyol is preferably an aromatic polyol having an alcoholic hydroxyl group or a polymer-based aromatic polyol because the curing time of the second resin composition or the reinforcing layer forming agent can be shortened.

The curing agent (b) may further contain, for example, an aliphatic polyamine, an alkanolamine, an aliphatic polyol, an oxazolidine compound, a bisoxazolidine compound, a silane compound, or the like, in addition to the aromatic curing agent. The curing agent (b) may contain an aromatic polyamine and at least one selected from the group consisting of an aliphatic polyamine, an aliphatic polyol, and a silane compound from the viewpoint of obtaining a sufficient pot life. preferable. Further, the curing agent (b) is selected from the group consisting of aromatic polyamines, aliphatic polyamines, and aliphatic polyols because the obtained resin cured layer is excellent in low temperature characteristics (for example, breaking strength). It is more preferable to include at least one kind. Of these, it is particularly preferable to include aromatic polyamines and aliphatic polyamines.

Examples of the aliphatic polyamine include an aliphatic compound having two or more amino groups, an aliphatic compound having one or more amino groups and an imino group, and the like. The aliphatic polyamines include aliphatic diamines such as hexamethylenediamine (HMD), octamethylenediamine (OMD), and nonanediamine (NDA) and their structural isomers; ethylenediamine (EDA), diethylenetriamine (DETA), triethylene. High amines such as tetramine (TETA), tetraethylenepentamine (TEPA), diproprenedamine (DPDA), and diethylaminopropylamine (DEAPA) and their derivatives; N-aminoethylpyverazine (NAEP), mensendiamine ( Diamines having an alicyclic structure such as MDA), isophoronediamine (IPDA), and 1,3-bisaminomethylcyclohexane (1,3-BAC) and their structural isomers; polyoxyalkylamines and derivatives thereof and these. Structural isomers of Examples of the polyoxyalkylamine include Jeffamine manufactured by Huntsman Co., Ltd. and polyetheramine manufactured by Mitsui Kagaku Fine Co., Ltd. In addition, examples of the latent curing agent include ketimine compounds, oxazolidine compounds, bisoxazolidine compounds, and aldimine compounds of the above aliphatic polyamines.

The aliphatic polyamine includes at least one selected from the group consisting of linear aliphatic polyamines, branched aliphatic polyamines, and alicyclic polyamines having one or more primary amino groups among the above-mentioned amines. Is preferable. In other words, as the aliphatic polyamine, it is preferable to use at least one selected from the group consisting of an aliphatic polyamine having no alicyclic structure and an aliphatic polyamine having one or more primary amine structures, and the alicyclic. An aliphatic polyamine having no structure and having one or more primary amine structures is more preferable, and an aliphatic polyamine having no alicyclic structure and having two or more primary amine structures is more preferable. Aliphatic polyamines having no structure and having three or more primary amine structures are particularly preferable.

The number average molecular weight of the aliphatic polyamine may be 1,000 or more or 3,000 or more, and may be 7,000 or less or 10,000 or less. When the number average molecular weight of the aliphatic polyamine is within the above range, the characteristics of the obtained reinforcing layer at low temperature (for example, breaking strength) can be improved. The aliphatic polyamine preferably contains, for example, a polyoxyalkylene polyamine. The number average molecular weight of the polyoxyalkylene polyamine may be 1,000 or more or 3,000 or more. By using a polyoxyalkylene polyamine having a number average molecular weight within the above range, the characteristics of the obtained reinforcing layer at low temperature (for example, breaking strength) can be further improved.

Examples of the alkanolamine include a compound having an alcoholic hydroxyl group and an amino group, a compound having an alcoholic hydroxyl group, an amino group and an imino group, and the like. Examples of the alkanolamine include diethanolamine, dipropanolamine, N- (2-hydroxyethyl) -N- (2-hydroxypropyl) amine and the like.

As the aliphatic polyol, a relatively low molecular weight aliphatic polyol or a relatively high molecular weight aliphatic polyol can be used. Examples of the aliphatic polyol having a relatively low molecular weight include ethylene glycol (EG), diethylene glycol (DEG), propylene glycol (PG), dipropylene glycol (DPG), and 1,3-butanediol (1,3-BD). , And dihydric alcohols such as 1,4-butanediol (1,4-BD), trihydric alcohols such as glycerin, 1,1,1-trimethylolpropane (TMP), and 1,2,5-hexanetriol. , Pentaerythritol, glucose, shoe cloth, and sorbitol and other polyhydric alcohols having a valence of 4 or more. As the aliphatic polyol having a relatively high molecular weight, for example, the compound exemplified as the polyol used for the preparation of the prepolymer (a) can be preferably used.

The silane compound is a compound that produces active hydrogen that can react with the isocyanato group of the prepolymer (a) by being hydrolyzed or the like. Examples of the silane compound include an alkoxysilane derivative and a silane-based coupling agent. Examples of the silane compound include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, ethyltrimethoxysilane, diethyldiethoxysilane, n-butyltrimethoxysilane, and n-hexyltriethoxysilane. , N-Octil dimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane and other hydrocarbon-bonded alkoxysilanes; Xysilanes; 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimailmethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyl Methyldiisopropenoxysilane, 3-glycidoxypropylethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3- (aminopropylmethyldimethoxysilane, N-2- (aminoethyl) ) -3-Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, and N-phenyl Examples thereof include alkoxysilanes having a functional group such as -3-aminopropyltrimethoxysilane.

As the silane compound, among the above-mentioned compounds, a silane compound having an amino group is preferable because the reactivity with the prepolymer (a) can be easily controlled. Examples of the silane compound having an amino group include N-2- (aminoethyl) -3- (aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyl. More preferred are trimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane and the like.

The molecular weight of the silane compound may be, for example, 500 or less or 400 or less. The silane compound may be at least one partially hydrolyzed condensate selected from the group consisting of the above-mentioned silane compound and these silane-based coupling agents. The molecular weight of the partially hydrolyzed condensate may be 200-3,000.

In the second resin composition, the content of the curing agent (b) is the ratio (R) of the molar equivalent of the isocyanate group of the prepolymer (a) to the molar equivalent of the reactive active hydrogen of the curing agent (b). Value: For example, the molar ratio of NCO group / OH group or NCO group / NH group) can be adjusted to be within a predetermined range. The R value may be, for example, 0.5 to 2.0, 0.8 to 1.2, or 0.9 to 1.1. When the content of the curing agent (b) in the second resin composition is within the above range, the number average molecular weight of the resin in the reinforcing layer is increased, and the breaking elongation of the reinforcing layer can be improved. Further, when the content of the curing agent (b) in the second resin composition is within the above range, yellowing of the reinforcing layer can be suppressed, and the weather resistance of the reinforcing layer can be further improved.

The second resin composition can be dissolved in the solvent (c) and used as a reinforcing layer forming agent. As the solvent (c), for example, aromatic compounds, aliphatic compounds and the like can be used. The aliphatic compound may contain, for example, an aliphatic compound having at least one molecular structure selected from a linear structure, a ring structure, a branched structure, an ester structure, a ketone structure, and an ether structure. More specifically, the aliphatic compound includes an aliphatic compound having a linear structure, an aliphatic compound having a ring structure, an aliphatic compound having a branched structure, an aliphatic compound having an ester structure, and a fat having a ketone structure. Examples thereof include group compounds and aliphatic compounds having an ether structure.

As the aromatic compound, for example, an aromatic compound having 6 to 12 carbon atoms and a mixture thereof can be used. Examples of aromatic compounds include toluene, xylene, trimethylbenzene, methylethylbenzene, propylbenzenes, propylbenzene, butylbenzene, tetramethylbenzene, methylpropylbenzene, dimethylethylbenzene, diethylbenzene and the like. When the aromatic compound is a mixture, aromatic naphtha having 6 to 12 carbon atoms (for example, Solvent # 100 and Solvent # 150 manufactured by Sankyo Chemical Co., Ltd., Swazole 1000, Swazole 1500 and Swazole 1800 manufactured by Maruzen Petrochemical Co., Ltd.) , Ipsol 100 and Ipsol 150 manufactured by Idemitsu Kosan Co., Ltd., T-SOL 100 FLUID and T-SOL 150 FLUID manufactured by JXTG Energy Co., Ltd.), and aromatic compounds having 6 to 12 carbon atoms and fats having 6 to 12 carbon atoms. Mineral spirits (for example, mineral spirits A and A solvents manufactured by JXTG Energy Co., Ltd.) and tarpen (LS tarpen manufactured by Suzuka Fine Co., Ltd.), which are mixtures with group compounds, can be used.

Examples of the aliphatic compound having a ring structure include naphthenic hydrocarbons having 7 to 15 carbon atoms and a mixture thereof (for example, Swaclean 150 manufactured by Maruzen Petrochemical Co., Ltd. and Daika Eco Thinner manufactured by Daisho Kasei Co., Ltd.). Etc.) etc. can be used. Examples of the aliphatic compound having a linear structure include hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane and the like. Examples of the aliphatic compound having a branched structure include 2,4-dimethylpentane, 2-methylhexane, 3-methylhexane, 3,4-dimethylheptane, 2-methyloctane, 3-methyloctane, 2-methylnonane, and the like. Examples thereof include 3-methylnonane, 3-ethyloctane, and dimethyloctanes. Examples of the mixture of aliphatic compounds include isoparaffinic hydrocarbons having 7 to 15 carbon atoms and mixtures thereof (for example, IP solvent manufactured by Idemitsu Kosan Co., Ltd., IP clean, and NA solvent manufactured by Nissui Co., Ltd., JXTG Energy. (Naftezol and Isosol manufactured by Co., Ltd.), turpentine oil (Turpentine oil manufactured by Yasuhara Chemical Co., Ltd., turpentine oil manufactured by Osaka Paint Industry Co., Ltd., and turpentine oil manufactured by Arakawa Chemical Industry Co., Ltd.) can be used.

The aniline point of the solvent (c) is preferably 85 ° C. or lower, more preferably 60 ° C. or lower, and further preferably 15 ° C. or lower. When the aniline point of the solvent (c) is within the above range, the solubility of the curing agent can be improved, and the storage stability of the reinforcing layer forming agent can be improved. When the aniline point of the solvent (c) is within the above range, the storage stability of the reinforcing layer forming agent is excellent particularly at a low temperature (for example, 5 ° C.). When the aniline point of the solvent (c) is within the above range, even when the reinforcing layer forming agent contains inorganic particles, the dispersibility of the inorganic particles can be excellent. That is, in order to improve the workability (particularly, sagging prevention property) of the reinforcing layer forming agent, for example, when trying to increase the content of fine powder silica or the like described later, a solvent having an aniline point within the above range. Can be preferably used. In other words, the workability of the reinforcing layer forming agent can be improved by using a solvent in which the aniline point is within the above range. The solvent (c) may be a mixture. In the case of a mixture, those having an aniline point in the state of the mixture within the above range can be preferably used.

The “aniline point” in the present specification means a numerical value obtained according to the method described in JIS K 2256: 2013 “Petroleum products-How to obtain an aniline point and a mixed aniline point”.

The content of the solvent (c) is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass, based on the total amount of the reinforcing layer forming agent. The content of the solvent (c) may be, for example, 50% by mass or less, 40% by mass or less, or 30% by mass or less based on the total amount of the reinforcing layer forming agent. When the content of the solvent (c) is within the above range, the viscosity of the reinforcing layer forming agent can be made appropriate, and the workability when applying the second resin composition layer on the adhesive layer can be improved. Excellent. Further, when the content of the solvent (c) is within the above range, it becomes easy to defoam the bubbles generated in the coating film of the reinforcing layer forming agent, and the occurrence of defects in the obtained reinforcing layer is sufficiently suppressed. be able to.

In the second resin composition, in addition to the prepolymer (a) and the curing agent (b), for example, a weather resistance imparting agent (d), a shaking modification imparting agent (e), a curing catalyst (f) and other additions are added. The agent (g) and the like may be further contained. In addition to the prepolymer (a), the curing agent (b) and the solvent (c), the reinforcing layer forming agent includes, for example, a weather resistance imparting agent (d), a shaking modification imparting agent (e), and a curing catalyst (f). ) And other additives (g) and the like may be further contained.

The weather resistance imparting agent (d) may contain, for example, at least one selected from the group consisting of hydroxyphenyltriazine derivatives and hindered amine-based derivatives. When an aromatic polyamine is used as the curing agent (b), the tensile strength of the reinforcing layer and the weather resistance can be achieved at a higher level by using the weather resistance imparting agent (d) in combination.

The hydroxyphenyltriazine derivative can improve the weather resistance of the cured product by absorbing ultraviolet rays in sunlight. The hydroxyphenyltriazine derivative has the property of being less likely to bleed out from the cured product than general benzophenone-type UV absorbers and benzotriazole-type UV absorbers, so that the weather resistance of the reinforcing layer can be improved over a long period of time. Can be maintained.

Examples of the hydroxyphenyltriazine derivative include 2- [4- (2-hydroxy-3-dodecyloxy-propyl) oxy-2-hydroxyphenyl] -4,6- [bis (2,4-dimethylphenyl) -1, 3,5-Triazine and 2- [4- (2-hydroxy-3-tridecyloxy-propyl) oxy-2-hydroxyphenyl] -4,6- [bis (2,4-dimethylphenyl) -1,3,5 -A mixture of triazine (manufactured by BASF Japan Co., Ltd., trade name: TINUVIN400), 2- [4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl] -4,6- [bis (2,4-) Dimethylphenyl)] -1,3,5-triazine (manufactured by BASF Japan Co., Ltd., trade name: TINUVIN479), and tris [2,4,6- [2- {4- (octyl-2-methylethanoate) oxy) -2-Hydroxyphenyl}]-1,3,5-triazine (manufactured by BASF Japan Co., Ltd., trade name: TINUVIN777) and the like. As the hydroxyphenyltriazine derivative, TINUVIN400 is preferable because it has excellent dispersibility.

The hindered amine derivative is a 2,2,6,6-tetraalkylpiperidine derivative having a substituent at the 4-position. Examples of the substituent at the 4-position include an alkyl group, an ester group, an alkoxy group, an alkylamino group, and various other substituents. Further, the N-position may be substituted with an alkyl group, an oxy radical or the like. In particular, when used in combination with a hydroxyphenyltriazine derivative, the weather resistance of the reinforcing layer is further improved. Therefore, an ester group as the substituent at the 4-position and an alkyl group as the substituent at the N-position are preferable.

Examples of the hindered amine derivative include TINUVIN292, TINUVIN123, TINUVIN144, TINUVIN765, Chimasolve 119FL, Chimasorve 2020FDL, Chimasorve 944, Chimasorve 622LD (all of which are manufactured by BASF Japan Ltd., trade name), Sumitomo Chemical Co., Ltd., etc. Made by the company, product name), ADEKA STAB LA-52, ADEKA STAB LA-57, ADEKA STAB LA-62, ADEKA STAB LA-67, ADEKA STAB LA-63P, ADEKA STAB LA-68LD, ADEKA STAB LA-82, ADEKA STAB LA-87, ADEKA STAB LA- 503, ADEKA STAB LA-601, etc. (all manufactured by ADEKA Corporation, trade name), and Sanol LS-2626, Sanol LS-744, Sanol LS-440, etc. (all manufactured by Sankyo Co., Ltd., trade name). ) And so on. As the hindered amine derivative, TINUVIN292 is particularly preferable.

The content of the weather resistance imparting agent (d) may be 0.01 to 10 parts by mass or 0.05 to 1 part by mass with respect to 100 parts by mass of the prepolymer (a). By setting the lower limit of the content of the weather resistance imparting agent (d) within the above range, the weather resistance of the reinforcing layer can be further improved. Further, by setting the upper limit of the content of the weather resistance imparting agent (d) within the above range, it is possible to prevent the weather resistance imparting agent from bleeding out from the reinforcing layer, and the reinforcing layer provided with the weather resistance imparting agent (d) can be prevented from bleeding out. Discoloration can be suppressed. Further, by setting the content of the weather resistance imparting agent (d) within the above range, the effect of imparting weather resistance to the reinforcing layer and the economic efficiency can be more desirablely balanced.

The rocking modification imparting agent (e) may contain at least one selected from the group consisting of, for example, fine powder silica, a polyhydroxycarboxylic acid ester derivative, a polycarboxylic acid amide derivative, and a polyether phosphoric acid ester derivative. When the reinforcing layer forming agent further contains the shaking modification imparting agent (e), it is possible to suppress sagging when the reinforcing layer forming agent is applied to the slope and the vertical surface.

The rocking modification imparting agent (e) may be used in combination with hydrophilic fine powder silica and at least one selected from the group consisting of polyhydroxycarboxylic acid ester derivatives and polycarboxylic acid amide derivatives, or hydrophobic fine powders. It is preferable to use a silica in combination with at least one selected from the group consisting of a polyhydroxycarboxylic acid ester derivative and a polycarboxylic acid amide derivative. When the rocking denaturing agent (e) is used in the above combination, the amount of finely powdered silica added can be reduced and the transparency of the reinforcing layer can be improved.

Specific surface area determined by the BET method of finely divided silica, for ^{example, 130~300m} 2 / ^g, may be 200 to 300 m ² / g, or 180~250m ² / g. When the specific surface area of the fine powder silica is within the above range, the fine powder silica is excellent in dispersibility in the reinforcing layer forming agent, so that the reinforcing layer forming agent can be sufficiently subjected to shaking modification.

The fine powder silica may be, for example, hydrophilic fine powder silica. The hydrophilic fine powder silica can be used in combination with a polyhydroxycarboxylic acid ester derivative, a polycarboxylic acid amide derivative, or the like, and the amount of fine powder silica added can be reduced. The fine powder silica may be hydrophobized. The hydrophobization treatment is preferably carried out with an alkylsilyl compound, more preferably with dimethylsilyl or trimethylsilyl.

The content of the fine silica is 100 parts by mass in total of the prepolymer (a), the curing agent (b) and the solvent (c) from the viewpoint of excellent workability (difficult to drip) of the reinforcing layer forming agent on the vertical surface. On the other hand, 1.0 part by mass or more is preferable. In addition to the above, the content of fine powdered silica is based on 100 parts by mass of the total amount of the prepolymer (a), the curing agent (b) and the solvent (c) from the viewpoint of excellent workability even when thickly applied. More than 1.9 parts by mass is more preferable. The content of finely divided silica is 2.5 with respect to 100 parts by mass of the total amount of the prepolymer (a), the curing agent (b) and the solvent (c) from the viewpoint of being excellent in workability at a lower viscosity. More than parts by mass is particularly preferable. The content of the fine silica is, for example, 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass with respect to 100 parts by mass of the total amount of the prepolymer (a), the curing agent (b) and the solvent (c). It may be: By setting the upper limit of the amount of finely powdered silica added within the above range, the transparency of the reinforcing layer can be improved. By appropriately selecting a solvent having a low aniline point, the fine powder silica can be dispersed regardless of the content of the fine powder silica, and a reinforcing layer forming agent can be easily produced.

As the polyhydroxycarboxylic acid ester derivative, for example, BYK-R 606 (manufactured by Big Chemie Japan Co., Ltd., trade name) and the like can be used. As the polycarboxylic acid amide derivative, for example, BYK-405, BYK-R 605, etc. (manufactured by Big Chemie Japan Co., Ltd., trade name) and the like can be used. As the polyether phosphate derivative, for example, Disparon 3500 (manufactured by Kusumoto Kasei Co., Ltd., trade name) and the like can be used.

Examples of the curing catalyst (f) include organometallic compounds and amines. The curing catalyst (f) preferably contains an organic tin compound having an excellent crosslinking rate. Organic tin compounds include, for example, stanas octate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate, dioctyltin dilaurate, and Dioctyl tin diversate and the like can be mentioned. Among these organic lead compounds, dibutyltin dilaurate is particularly preferable because it is a liquid having an excellent crosslinking rate and relatively low toxicity and volatility. The blending amount of the curing catalyst (f) is 0 with respect to 100 parts by mass of the prepolymer (a) from the viewpoints of excellent cross-linking speed, shorter tack-free time, excellent breaking strength of the reinforcing layer, and the like. .001 to 3 parts by mass is preferable, and 0.01 to 0.1 parts by mass is more preferable.

Other additives (g) include, for example, defoaming agents, wet dispersants, surfactants, pigments, dyes, inorganic fillers, antioxidants, curability modifiers, metal deactivators, and ozone deterioration inhibitors. , Lubricants, anti-termites, and additives such as antifungal agents can be used.

As the defoaming agent, for example, a silicone-based defoaming agent, a fluorine-modified silicone-based defoaming agent, an acrylic polymer-based defoaming agent, a vinyl ether polymer-based defoaming agent, or the like can be used. The content of the defoaming agent may be, for example, 0.05 to 5 parts by mass or 0.1 to 3 parts by mass with respect to 100 parts by mass of the prepolymer (a). When the content of the defoaming agent is within the above range, the foaming that may occur due to the reaction of the prepolymer (a) can be more sufficiently suppressed, so that the defects of the obtained reinforcing layer can be sufficiently suppressed. The appearance and tensile strength of the reinforcing layer can be improved.

The above-mentioned second resin composition and reinforcing layer forming agent contain liquid A (main agent composition) and liquid B (hardener composition) because they are not easily affected by external factors such as weather during curing. It may be a two-component mixed type second resin composition or a reinforcing layer forming agent composed of. In the case of the two-component mixed type, the solution A contains the prepolymer (a) and the solution B contains the curing agent (b). In the case of the two-component mixed type, either one of the A solution and the B solution may contain the solvent (c), and both the A solution and the B solution may contain the solvent (c). The above-mentioned weather resistance imparting agent (d), shaking modification imparting agent (e), curing catalyst (f) and other additive (g) may be blended in either liquid A or liquid B, but the liquid B may be blended. It is preferable to mix. The above-mentioned second resin composition and reinforcing layer forming agent may be composed of a third component other than the liquid A and the liquid B.

The second resin composition and the reinforcing layer forming agent may be a one-component mixed type second resin composition or the reinforcing layer forming agent because a mixing operation is not required and the workability can be improved. In the case of the one-component mixed type, the curing agent (b) contains a latent curing agent (for example, an oxazolidine compound, a bisoxazolidine compound, a ketimine compound, an aldimine compound, a silane compound, etc.).

The above-mentioned second resin composition and reinforcing layer forming agent may contain an aliphatic polyisocyanate which is a raw material of the prepolymer (a). When the second resin composition and the reinforcing layer forming agent contain an aliphatic polyisocyanate, the content of the aliphatic polyisocyanate is 25 based on the total amount of the second resin composition or the total amount of the reinforcing layer forming agent. It may be 10% by mass or less, or 7% by mass or less. When the content of the aliphatic polyisocyanate is within the above range, safety can be improved, and the breaking strength of the coating film of the second resin composition or the reinforcing layer forming agent is also excellent.

The second resin composition and the reinforcing layer forming agent are also expected to be used in a closed place such as in a tunnel. Therefore, it is desirable to suppress the use of highly volatile aliphatic diisocyanate in the second resin composition and the reinforcing layer forming agent from the viewpoint of safety during work. The aliphatic polyisocyanate that can be contained in the second resin composition and the reinforcing layer forming agent preferably has a saturated vapor concentration of 300 ppb or less, 100 ppb or less, or 50 ppb or less at 25 ° C. and atmospheric pressure. By using the prepolymer (a) using such an aliphatic polyisocyanate as a raw material, the safety of the second resin composition and the reinforcing layer forming agent can be further improved.

The viscosity of the second resin composition and the reinforcing layer forming agent may be, for example, 0.1 to 100 Pa · s, or 1 to 50 Pa · s. When the viscosities of the second resin composition and the reinforcing layer forming agent are within the above ranges, construction with a trowel, a spatula, or the like becomes easy. The viscosity of the second resin composition and the reinforcing layer forming agent can be adjusted, for example, by adjusting the concentration of the prepolymer (a), the content of the solvent (c), and the like.

The thixotropy index (TI) (viscosity of 5 rpm / viscosity of 50 rpm) of the second resin composition and the reinforcing layer forming agent may be, for example, 1.0 or more, 1.1 or more, or 1.2 or more. When the TI of the second resin composition and the reinforcing layer forming agent is within the above range, the second resin composition and the reinforcing layer forming agent are excellent in rock denaturation (thixotropic property), and the second resin is placed on the primer layer. It is possible to suppress the occurrence of liquid dripping when applying the composition and the reinforcing layer forming agent.

As used herein, the "thixotropy index (TI)" means a value calculated using the viscosity measured by the following dynamic viscosity measurement. That is, after mixing the second resin composition or the reinforcing layer forming agent until uniform, JIS Z 8803: 2001 “Method for measuring viscosity of liquid:” using an E-type viscometer TVE25H manufactured by Toki Sangyo Co., Ltd. The measurement is carried out according to the method described in "Conical-Flat plate type rotational viscometer". As the cone rotor, 3 ° × R9.7 is used, the sample volume at this time is 0.2 mL, and the measurement temperature is 23 ° C. For the measurement, the viscosity is measured with the rotation speeds of 5 rpm and 50 rpm, and the viscosity when the rotation speed is 5 rpm is divided by the viscosity when the rotation speed is 50 rpm to calculate the thixotropy index.

The above-mentioned second resin composition and reinforcing layer forming agent can be prepared, for example, as follows. The second resin composition and the reinforcing layer forming agent (the two-component mixed type second resin composition or the reinforcing layer forming agent of the liquid A (main agent composition) and the liquid B (curing agent composition)) are each described above. The components can be prepared by mixing them with a mixer to prepare solutions A and B, respectively. Usually, the liquid A and the liquid B are mixed immediately before applying the second resin composition and the reinforcing layer forming agent. Examples of the mixer include a disper, a ball mill, and S.I. G. Mills, roll mills, planetary mixers and the like can be used.

The above-mentioned method for manufacturing a concrete structure may further include other steps in addition to the above-mentioned steps. Other steps include, for example, a step of polishing the surface of the structure containing concrete before coating the first resin composition, and after forming a reinforcing layer, further providing a layer of topcoat paint, and the like. A step of forming a layer of the above can be mentioned. Examples of the topcoat paint include a fluorine-based topcoat agent, a silicone-based topcoat agent, and an acrylic urethane-based topcoat agent.

Although some embodiments have been described above, the present disclosure is not limited to the above embodiments. In addition, the contents of the description of the above-described embodiments can be applied to each other.

Hereinafter, the contents of the present disclosure will be described in more detail with reference to Examples and Comparative Examples. However, the present disclosure is not limited to the following examples.

[Synthesis and evaluation of adhesive layer]
<Primer for forming an adhesive layer (first resin composition)>
The following primers E1 to E7 were used as primers.

[Primer E1]
A primer in which the following main agent and curing agent were mixed so as to have a ratio of 100:50 (mass ratio) was used.
Main agent: Epoxy resin containing bisphenol A type epoxy resin as the main component (viscosity: 1,230 mPa · s)
Hardener: A mixture containing an aromatic polyamine and its modified product (A), an alicyclic polyamine having an amino group directly bonded to the alicyclic structure and its modified product (B-1), and a modified aliphatic polyamine (C). (Viscosity: 220 mPa · s)

[Primer E2]
A primer in which the following main agent and curing agent were mixed so as to have a ratio of 100:50 (mass ratio) was used.
Main agent: Epoxy resin containing bisphenol A type epoxy resin as the main component (viscosity: 760 mPa · s)
Hardener: Aromatic polyamine and its modified product (A), alicyclic polyamine having an amino group directly bonded to the alicyclic structure and its modified product (B-1), and an amino group directly bonded to the alicyclic structure. A mixture containing alicyclic polyamines and their modified products (B-2), modified aliphatic polyamines (C), polyamideamines (D), and aliphatic polyamines (E) (viscosity: 180 mPa · s).

[Primer E3]
A primer in which the following main agent and curing agent were mixed so as to have a ratio of 100:50 (mass ratio) was used.
Main agent: Epoxy resin containing bisphenol A type epoxy resin as the main component (viscosity: 760 mPa · s)
Hardener: Aromatic polyamine and its modified product (A), alicyclic polyamine having an amino group directly bonded to the alicyclic structure and its modified product (B-1), and an amino group directly bonded to the alicyclic structure. No alicyclic polyamines and mixtures thereof (B-2), modified aliphatic polyamines (C), and mixtures containing aliphatic polyamines (E) (viscosity: 300 mPa · s)

[Primer E4]
A primer in which the following main agent and curing agent were mixed so as to have a ratio of 100:40 (mass ratio) was used.
Main agent: Epoxy resin containing bisphenol A type epoxy resin as the main component (viscosity: 500 mPa · s)
Hardener: Aromatic polyamine and its modified product (A), alicyclic polyamine having an amino group directly bonded to the alicyclic structure and its modified product (B-1), modified aliphatic polyamine (C), polyamideamine ( D) and a mixture containing the aliphatic polyamine (E) (viscosity: 300 mPa · s)

[Primer E5]
Urethane-based primer: 1-component urethane resin, ethyl acetate, and butyl acetate (viscosity 10 mPa · s)

[Primer E6]
A primer in which the following main agent and curing agent were mixed so as to have a ratio of 100:50 (mass ratio) was used.
Main agent: Epoxy resin containing bisphenol A type epoxy resin as the main component (viscosity: 550 mPa · s)
Hardener: A mixture containing an aromatic polyamine and its modified product (A), and an aliphatic polyamine (E) (viscosity: 500 mPa · s).

[Primer E7]
A primer in which the following main agent and curing agent were mixed so as to have a ratio of 100:50 (mass ratio) was used.
Main agent: Epoxy resin containing bisphenol A type epoxy resin as the main component (viscosity: 600 mPa · s)
Hardener: A mixture containing an alicyclic polyamine having an amino group directly bonded to the alicyclic structure and a modified product thereof (B-1), and a modified aliphatic polyamine (C) (viscosity: 500 mPa · s).

<Evaluation of cured film as an adhesive layer>
A cured film was formed using each of the above-mentioned primers E1 to E7, and the performance as an adhesive layer was evaluated. Specifically, the above-mentioned primer was applied onto a substrate and cured for 7 days in an environment of temperature: 23 ° C. and humidity: 50% to form a cured film having a thickness of 0.15 mm. The performance of the cured film as an adhesive layer was evaluated.

[Measurement of maximum storage elastic modulus E'and loss tangent (tan δ)]
The cured film obtained above was cut into strips to make test pieces, and dynamic viscoelasticity measurements were performed using a solid viscoelasticity analyzer RSA-G2 manufactured by TA Instruments. The maximum value of tan δ) was determined. The conditions for dynamic viscoelasticity measurement are as follows. The results are shown in Table 1.

[Conditions for dynamic viscoelasticity measurement]
Measurement mode: Pull mode Dynamic measurement sweep TYPE: Temperature step 3 ° C / min Sok time: 0.5 min Frequency: 1 Hz (6.28 rad / sec)
Strain: 0.2 to 3% (AUTO setting)
Temperature range: -100 ° C to 200 ° C
Atmosphere: In a nitrogen stream

The maximum value of the loss tangent (tan δ) is the ratio of the loss elastic modulus (E ″) and the storage elastic modulus (E ′) measured by dynamic viscoelasticity measurement (the value of the loss elastic modulus is the storage elastic modulus. It is a value obtained from a graph showing the temperature dependence of (value divided by the value of: E'' / E'), and the temperature showing the maximum value in the graph was defined as the peak temperature.

[Preparation and evaluation of reinforcing layer]
<Preparation of solution A (main component composition)>
A prepolymer having an isocyanato group at the end was synthesized as follows. 24.5 parts by mass of polyisocyanate (H12-MDI) and 4.4 parts by mass of solvent (solvent) while flowing nitrogen gas through a stirrer, thermometer, nitrogen seal tube, and reaction vessel with heating / cooling device. # 100) and was measured. Next, 46.2 parts by mass of polyol (PTMG1000) was measured and added while stirring the inside of the container. Here, as a curing catalyst, DBTDL was further added so as to be 10 ppm based on the total amount of H12-MDI and PTMG1000. Then, the reaction was carried out with stirring at 70 to 80 ° C. When the content of isocyanato groups determined by neutralization titration according to the procedure of JIS K 1603-1: 2007 "How to determine the isocyanate group content" becomes less than the theoretical value (about 2 hours), the reaction is carried out. The prepolymer was synthesized by finishing and cooling. The obtained prepolymer had an isocyanato group content determined by titration of 5.1% by mass based on the total amount of the prepolymer. The obtained prepolymer was a transparent liquid at room temperature and had a viscosity at 23 ° C. of 32,000 mPa · s.

<Preparation of solution B (curing agent composition)>
In a container, 7.2 parts by mass of aromatic amine (diethyltoluenediamine: DETDA) and 12.8 parts by mass of solvent (solvent # 100) were measured as a curing agent and kneaded until uniform. Next, a weather resistance imparting agent, a rock denaturing imparting agent, and other additives were added, and the mixture was further stirred and mixed to prepare a curing agent composition (solution B).

<Preparation of reinforcing layer forming agent (second resin composition and solvent)>
A reinforcing layer forming agent was produced by adding the above-mentioned solution A and the above-mentioned solution B to the container and stirring and mixing them until they became uniform. Table 2 shows the compounding ratio (mass ratio) of each raw material.

<Evaluation of cured film as a reinforcing layer>
A cured film having a thickness of 1.6 mm was formed by applying the reinforcing layer forming agent prepared as described above onto a substrate and curing it in an environment of temperature: 23 ° C. and humidity: 50% for 7 days. .. The performance of the cured film as a reinforcing layer was evaluated.

[Measurement of storage elastic modulus]
The cured film obtained above was cut into strips to obtain test pieces, and dynamic viscoelasticity measurements were performed using a solid viscoelasticity analyzer RSA-G2 manufactured by TA Instruments to determine the storage elastic modulus E'. The conditions for the dynamic viscoelasticity measurement were the same as those described in "Evaluation of the cured film as an adhesive layer". The results are shown in Table 2.

[Transparency evaluation 1: Haze measurement]
For the cured film obtained as described above, a haze conforming to JIS K 7136: 2000 (How to obtain a haze of a plastic-transparent material) was measured using NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd. The results are shown in Table 2.

[Transparency evaluation 2: Measurement of total light transmittance]
For the cured film obtained as described above, NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd. was used, and all the cured films were obtained in accordance with JIS K 7375: 2008 (Plastic-How to determine total light transmittance and total light reflectance). The light transmittance was measured. The results are shown in Table 2.

(raw materials)
The raw materials listed in Table 2 are as follows.

[Polyisocyanate]
H12-MDI: Dicyclohexylmethane-4,4'-diisocyanate (manufactured by Evonik Japan, VESTANAT H12MDI, aliphatic polyisocyanate having 13 or more carbon atoms)

[Polycarbonate]
PTMG1000: Polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, hydroxyl value: 115.6 mgKOH / g)

[Curing agent (b)]
Aromatic polyamine DETDA: Diethyl toluenediamine (manufactured by Mitsui Kagaku Fine Co., Ltd., ETHACURE 100 PLUS)

[Solvent (c)]
Solvent # 100: Aromatic fragrant hydrocarbons, manufactured by Sankyo Chemical Co., Ltd., aniline point: 13 ° C)

[Weather resistance imparting agent (d)]
Hydroxyphenyltriazine derivative TINUVIN 400: 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hydroxyphenyl and oxylane [(C10-C16, mainly) Reaction product with C12-C13 alkyloxy) methyl] oxylane, 15% 1-methoxy-2-propanol (manufactured by BASF Japan Co., Ltd.)
Hindered amine derivative TINUVIN 292: 70-80% bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 20-30% methyl 1,2,2,6,6-pentamethyl-4-piperidyl Mixture with sebacate (manufactured by BASF Japan Ltd.)

[Sway denaturing agent (e)]
Fused silica (hydrophilic)
Aerosil 200: Made by Nippon Aerosil Co., Ltd., specific surface area 200m ² / g
Polyhydroxycarboxylic acid ester derivative BYK-R 606: Polyhydroxycarboxylic acid ester (manufactured by Big Chemie Japan Co., Ltd.)

[Other additives (g)]
Dispersant DISPERBYK 111: Copolymer having an acid group (polyester phosphate) (manufactured by Big Chemie Japan Co., Ltd.)

(Example 1)
A concrete structure was produced using the primer E1 and the reinforcing layer forming agent prepared as described above. Specifically, primer E1 is applied onto a concrete base material (structure containing concrete) so that the thickness of the coating film is 0.15 mm, and this is cured to obtain a thickness of 0.15 mm. Adhesive layer was formed. Next, a reinforcing layer forming agent was applied onto the adhesive layer so that the thickness of the coating film was 2.0 mm, and this was cured to form a reinforcing layer having a thickness of 1.6 mm. In this way, the concrete structure was manufactured.

<Evaluation as a coating layer (laminated body of adhesive layer and reinforcing layer)>
The transparency of the coating layer constituting the concrete structure manufactured as described above was evaluated. Transparency was evaluated by haze and total light transmittance. The haze and total light transmittance were measured by the same method as described in "Evaluation of the cured film as a reinforcing layer" above. The results are shown in Table 3.

<Evaluation of load resistance as a concrete structure>
The load bearing capacity was evaluated by measuring the maximum load at each temperature of 50 ° C., 23 ° C., and -30 ° C. for the concrete structure manufactured as described above. The maximum load was measured by a punch test.

Specifically, among the "upper lid type U-shaped side grooves" specified in Annex 5 of JIS A 5372: 2010 "Precast Reinforced Concrete Products", the classification by strength is "Type 1" and the name is "300 (400 x 600 x)". Thickness 60 mm) ”top lid type U-shaped side groove (hereinafter, simply referred to as“ U-shaped lid ”) is coated with primer E1 on a concrete plate and cured under the conditions of temperature 23 ° C. and humidity 50%. A 0.15 mm adhesive layer was formed. The reinforcing layer forming agent was applied onto the adhesive layer and cured under the conditions of a temperature of 23 ° C. and a humidity of 50% to form a reinforcing layer having a thickness of 1.6 mm.

Next, a punching test was performed at a temperature of 50 ° C. according to JSCE-K 533-2013 (Japan Society of Civil Engineers punching test method for surface covering material applied to prevent peeling of concrete pieces). The maximum load at a displacement of 10 mm or more in the load-displacement measurement was defined as the maximum load (kN) in the punching test. The results are shown in Table 3.

(Example 2)
A concrete structure was produced in the same manner as in Example 1 except that the primer E2 was used instead of the primer E1. With respect to the obtained concrete structure, the transparency of the coating layer and the load bearing capacity of the concrete structure were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 3)
A concrete structure was produced in the same manner as in Example 1 except that the primer E3 was used instead of the primer E1. With respect to the obtained concrete structure, the transparency of the coating layer and the load bearing capacity of the concrete structure were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 4)
A concrete structure was produced in the same manner as in Example 1 except that the primer E4 was used instead of the primer E1. With respect to the obtained concrete structure, the transparency of the coating layer and the load bearing capacity of the concrete structure were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 5)
A concrete structure was produced in the same manner as in Example 1 except that the primer E5 was used instead of the primer E1. With respect to the obtained concrete structure, the transparency of the coating layer and the load bearing capacity of the concrete structure were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Comparative Example 1)
A concrete structure was produced in the same manner as in Example 1 except that the primer E6 was used instead of the primer E1. With respect to the obtained concrete structure, the transparency of the coating layer and the load bearing capacity of the concrete structure were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Comparative Example 2)
A concrete structure was produced in the same manner as in Example 1 except that the primer E7 was used instead of the primer E1. With respect to the obtained concrete structure, the transparency of the coating layer and the load bearing capacity of the concrete structure were evaluated in the same manner as in Example 1. The results are shown in Table 3.

According to the present disclosure, it is possible to provide a concrete structure capable of exhibiting sufficient load bearing capacity from a low temperature region to a high temperature region. According to the present disclosure, it is also possible to provide the above-mentioned method for manufacturing a concrete structure.

10 ... Structure containing concrete, 20 ... Adhesive layer, 30 ... Reinforcing layer, 40 ... Coating layer, 50 ... Concrete structure.

Claims (15)

A concrete structure including a structure containing concrete and a coating layer provided on the structure.
The coating layer has an adhesive layer and a reinforcing layer provided on the side of the adhesive layer opposite to the structure side.
The storage modulus at 50 ° C. of the adhesive layer E 'is 4.0 × ¹⁰ 8 Pa or more, the concrete structure. The concrete structure according to claim 1, wherein the reinforcing layer contains at least one selected from the group consisting of particles and fibers, and the average particle size of the particles and the average major axis length of the fibers are 10 μm or less. The concrete structure according to claim 1 or 2, wherein the maximum punching load at 50 ° C. is 1.5 kN or more. The concrete structure according to any one of claims 1 to 3, wherein the maximum punching load at 23 ° C. and the maximum punching load at −30 ° C. are both 1.5 kN or more. The concrete structure according to any one of claims 1 to 4, wherein the haze of the reinforcing layer is 30 or less, and the total light transmittance of the reinforcing layer is 80% or more. The concrete structure according to any one of claims 1 to 5, wherein the haze of the coating layer is 40 or less, and the total light transmittance of the coating layer is 70% or more. The concrete structure according to any one of claims 1 to 6, wherein the reinforcing layer has a ratio of the storage elastic modulus at −30 ° C. to the storage elastic modulus at 50 ° C. of 1 to 20. The concrete structure according to any one of claims 1 to 7, wherein the thickness of the adhesive layer is 0.05 to 0.50 mm. The concrete structure according to any one of claims 1 to 8, wherein the adhesive layer contains at least one selected from the group consisting of a cured product of an acrylic resin, a cured product of a urethane resin, and a cured product of an epoxy resin. .. The concrete structure according to any one of claims 1 to 9, further comprising a top coat layer on the side of the coating layer opposite to the structure side. The concrete structure according to any one of claims 1 to 10, which is used as a peeling prevention structure. The concrete structure according to claim 11, wherein the anti-scraping structure is for preventing the falling of a structure containing concrete, for protecting the structure containing concrete, or for preventing the falling of tiles. A first resin composition layer provided on the structure including the concrete, by curing, a step of storage elastic modulus E at 50 ° C. 'to form an adhesive layer is 4.0 × 10 8 ^Pa or more,
A method for producing a concrete structure, comprising a step of forming a reinforcing layer by providing a second resin composition layer on the adhesive layer and curing the layer. The production method according to claim 13, wherein the reinforcing layer contains at least one selected from the group consisting of particles and fibers, and the average particle size of the particles and the average major axis length of the fibers are 10 μm or less. A tile structure including a structure having tiles and a coating layer provided on the structure.
The coating layer has an adhesive layer and a reinforcing layer provided on the side of the adhesive layer opposite to the structure side.
The storage modulus at 50 ° C. of the adhesive layer E 'is the 4.0 × ¹⁰ 8 Pa or more, the tile structure.

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