JP6799442B2 - Waterproof structure and manufacturing method of waterproof structure - Google Patents

Description

The present invention relates to a waterproof structure and a method for manufacturing the waterproof structure.

Waterproof materials are provided on the rooftops, balconies, balconies, waist walls, parapets, bathroom washrooms, toilets, parking lots, etc. of buildings. Asphalt, rubber sheets, vinyl chloride sheets, urethane resins, acrylic resins and the like have been used as waterproof materials for a long time. In recent years, unsaturated polyester resin and glass fiber have been contained in consideration of wear resistance, adhesion to a base, problems of swelling and cracking due to low strength of the material itself, water resistance and chemical resistance, etc. There is an increasing number of methods of lining a resin composition and coating it with fiber reinforced plastics (FRP) (see, for example, Patent Document 1).

On the other hand, in the method of forming the FRP layer by lining at the construction site, it is easily affected by the skill level of the operator, the dry state of the base, cracks, smoothness, etc., and the resin composition is easily affected when the FRP layer is formed. The styrene inside is volatilized and an odor is generated. In consideration of these points, it has been proposed to use a pre-made FRP sheet. For example, Patent Document 2 proposes a glass fiber reinforced resin molded plate obtained by impregnating glass fibers with a predetermined unsaturated polyester resin syrup and curing the glass fibers. Further, Patent Document 3 proposes a soft FRP sheet formed into a sheet by combining an unsaturated polyester resin containing a predetermined unsaturated polyester and a polymerizable monomer in a predetermined ratio with a reinforcing material. There is.

On the other hand, at a construction site where there is a base to be waterproofed, there are joints and uneven portions between the FRP sheet and the FRP sheet, and it is often necessary to perform FRP lining work at the site. Under such circumstances, a composite waterproofing method that combines an FRP sheet and an FRP lining work has also been proposed (see, for example, Patent Documents 4 and 5).

Japanese Unexamined Patent Publication No. 1-96079 JP-A-1-193329 Japanese Unexamined Patent Publication No. 2000-1433958 Japanese Unexamined Patent Publication No. 5-214791 Japanese Unexamined Patent Publication No. 9-11376

Even with the FRP sheet disclosed in Patent Documents 2 to 5, the flexibility in an environment where the temperature is relatively low, for example, 15 ° C. or lower, cannot be said to be sufficient, and there is room for improvement. The FRP sheet as disclosed in Patent Documents 2 to 5 is provided in the form of a product (FRP sheet wound body) in which a long FRP sheet is wound in a roll shape, and has desired dimensions at a construction site. It is often used after being cut into pieces. However, in an environment where the temperature is relatively low, the hardness of the resin increases, so that when the above-mentioned FRP sheet winding body is spread, the FRP sheet has a habit of winding, or the FRP sheet is adhered to the object to be adhered. It may be difficult to install because it may bounce or rewind when pasted with. Further, since the followability to the base is also lowered, if the base has irregularities, it may be difficult to perform the construction without defects.

Further, in the composite waterproofing method in which the FRP sheet and the FRP lining work are combined, the work man-hours can be reduced as compared with the FRP waterproofing method by the general FRP lining process. However, in the lining work, in consideration of the durability performance of the obtained FRP layer and the like, a resin composition containing a large amount of styrene is often used for its formation, and styrene is volatilized and has an odor when the lining layer is formed. There is still room for improvement in terms of work environment.

Therefore, the present invention has a waterproof structure using an FRP waterproof sheet having sufficient flexibility and good water resistance even in an environment where the temperature is relatively low, and is environmentally friendly with good followability to the substrate. It seeks to provide a type of waterproof structure.

As a result of the studies by the present inventors, in order to increase the flexibility of the FRP waterproof sheet, an unsaturated polyester resin obtained by using a specific glycol component is required, and the water resistance of the FRP waterproof sheet is used. It was found that it depends on the water resistance of the unsaturated polyester resin. Then, the present inventors are sufficient even in a low temperature environment by using an unsaturated polyester resin having a tensile strength and a tensile elastic modulus within a specific range and setting the content of the fibrous reinforcing material within the specific range. It has been found that an FRP waterproof sheet having flexibility and good water resistance can be obtained. Further, the present inventors provide an elastic buffer layer on the base side of the FRP waterproof sheet, and provide a waterproof material layer having a tensile strength and tensile fracture elongation within a specific range on the opposite side. We have found that a waterproof structure having good followability with the above can be obtained, and have completed the present invention.

That is, the present invention is made of a fiber-reinforced plastic containing an elastic buffer layer provided on a base to be subjected to a tarpaulin treatment, an unsaturated polyester resin and a fibrous reinforcing material provided on the elastic buffer layer. The content of the fibrous reinforcing material in the tarpaulin is 18 to 26% by mass, and the unsaturated polyester resin comprises the tarpaulin and the tarpaulin layer provided on the tarpaulin. The tarpaulin layer has a structural unit derived from a glycol containing an ether bond, has a tensile strength of 10 to 30 MPa and a tensile elastic modulus of 700 MPa or less, and is measured in accordance with the provisions of JIS K6911-2006. Is measured in accordance with the above-mentioned regulations, a styrene-free unsaturated polyester resin layer having a tensile strength of 10 MPa or more and a tensile fracture elongation of 400% or less, and JIS A6021-2011. Provided is a waterproof structure including at least one of a urethane resin layer having a tensile strength of 10 MPa or more and a tensile breaking elongation of 400% or less as measured.

According to the present invention, it has a waterproof structure using an FRP waterproof sheet having sufficient flexibility and good water resistance even in an environment where the temperature is relatively low, and is environmentally friendly with good followability to the substrate. A type of waterproof structure can be provided.

It is schematic cross-sectional view which shows an example of the layer structure for demonstrating the waterproof structure of one Embodiment of this invention. It is a schematic diagram for demonstrating the evaluation test method of the followability with a base in a test example, A is a plan view thereof, and B is a cross-sectional view thereof.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

<Waterproof structure>
The waterproof structure of one embodiment of the present invention contains an elastic buffer layer provided on a base to be waterproofed, and an unsaturated polyester resin and a fibrous reinforcing material provided on the elastic buffer layer. It includes a waterproof sheet made of fiber reinforced plastic and a waterproof material layer provided on the waterproof sheet. The content of the fibrous reinforcing material in the fiber-reinforced plastic tarpaulin (hereinafter, may be referred to as "FRP waterproof sheet") used for this waterproof structure is 18 to 26% by mass. Further, the unsaturated polyester resin in the FRP tarpaulin has a structural unit derived from glycol containing an ether bond, has a tensile strength of 10 to 30 MPa, and has a tensile elastic modulus of 700 MPa or less. Further, the waterproof material layer provided on the FRP waterproof sheet comprises at least one of a styrene-free unsaturated polyester resin layer and a urethane resin layer having a tensile strength of 10 MPa or more and a tensile fracture elongation of 400% or less. Including.

The FRP waterproof sheet having the above structure has sufficient flexibility and good water resistance even in an environment where the temperature is relatively low. By using this FRP waterproof sheet, further providing an elastic buffer layer between the FRP waterproof sheet and the base, and providing the above-mentioned specific waterproof material layer on the FRP waterproof sheet, followability with the base can be achieved. A good environment-friendly waterproof structure can be obtained.

FIG. 1 is a schematic cross-sectional view showing an example of the layer structure for explaining the waterproof structure of one embodiment of the present invention. As shown in FIG. 1, the waterproof structure 1 includes an elastic buffer layer 4 provided on the base 2, an FRP waterproof sheet 6 provided on the elastic buffer layer 4, and a waterproof structure provided on the FRP waterproof sheet 6. It includes a material layer 8. The layer structure in the waterproof structure is not limited to the example shown in FIG. For example, as will be described later, an adhesive layer or an adhesive layer is provided between the base 2 and the elastic buffer layer 4, between the elastic buffer layer 4 and the FRP waterproof sheet 6, and between the FRP waterproof sheet 6 and the waterproof material layer 8. It can have another layer such as a primer layer. Further, the waterproof structure may have a plurality of elastic buffer layers 4, an FRP waterproof sheet 6, and a plurality of waterproof material layers 8, respectively. Hereinafter, the waterproof structure according to the embodiment of the present invention will be described with reference to the reference numerals shown in FIG.

[Elastic buffer layer]
The waterproof structure 1 includes an elastic buffer layer 4 provided on the base 2. The elastic buffer layer 4 makes it possible to improve the followability with the base. As the elastic buffer layer 4, for example, a synthetic resin adhesive having high elasticity as disclosed in Patent Document 5, a synthetic resin foamed into a sheet (foamed resin sheet), or the like is used. Can be done. The elastic buffer layer 4 preferably contains a foamed resin sheet. As the foamed resin sheet, one obtained by machine molding, one obtained by spraying a raw material at a construction site and foaming, etc. can be used, but from the viewpoint of film thickness accuracy and workability, machine molding can be used. It is more preferable to use the obtained foamed resin sheet.

Examples of the synthetic resin used as a raw material for the foamed resin sheet include polyester, polyvinyl chloride, polyurethane, polypropylene, polyethylene, and the like, and it is more preferable to use these foam materials. The foaming ratio of the foamed resin sheet is preferably 10 to 40 times from the viewpoint of adhesiveness to the FRP waterproof sheet and laminating at the construction site. The bubbles of the foamed resin sheet may be closed cells or open cells, but it is preferable that there are many closed cells in terms of waterproofness, heat insulation, and the like.

The thickness of the elastic buffer layer 4 is preferably 1 to 40 mm, more preferably 2 to 30 mm, and even more preferably 3 to 10 mm. The elastic buffer layer 4 having a thickness of 1 mm or more can easily secure insulation with the base 2 and can easily or need not adjust the waterproof surface of the base 2, and the elastic buffer layer 4 having a thickness of 40 mm or less. Has good workability.

As the elastic buffer layer 4, it is preferable to use one that is previously bonded to the FRP waterproof sheet 6 provided on the elastic buffer layer 4. That is, it is preferable that the composite waterproof sheet 46 in which the elastic buffer layer 4 and the FRP waterproof sheet 6 are bonded is provided on the base 2 with the elastic buffer layer 4 side as the base 2 side. The elastic buffer layer 4 and the FRP waterproof sheet 6 may be bonded at the construction site, but it is preferable to use the composite waterproof sheet 46 bonded by machine molding from the viewpoint of accuracy and workability.

An adhesive layer (not shown) for bonding them may be provided between the elastic buffer layer 4 and the FRP waterproof sheet 6. For the adhesive layer between the elastic buffer layer 4 and the FRP waterproof sheet 6, for example, an epoxy-based, urethane-based, acrylic-based, rubber-based, or hot-melt-based adhesive can be used. Further, an adhesive layer (not shown) for adhering them can be provided between the base 2 and the elastic buffer layer 4. For the adhesive layer between the base 2 and the elastic buffer layer 4, for example, an epoxy-based, urethane-based, acrylic-based, or modified silicone-based adhesive can be used. Of these, urethane-based adhesives and modified silicone-based adhesives are preferable. The adhesive layer may be provided on the entire surface of the elastic buffer layer 4 on the base 2 side, may be provided on a part of the surface, or may be provided as dots or lines.

[FRP waterproof sheet]
The waterproof structure 1 includes an FRP waterproof sheet 6 provided on the elastic buffer layer 4. As described above, the FRP waterproof sheet 6 is preferably the FRP waterproof sheet 6 which is previously bonded to the elastic buffer layer 4 (composite waterproof sheet 46).

The FRP waterproof sheet 6 contains an unsaturated polyester resin and a fibrous reinforcing material. The FRP waterproof sheet 6 can have a structure in which an unsaturated polyester resin is used as a matrix material and a fibrous reinforcing material is contained in the matrix material. The content of the fibrous reinforcing material in the FRP waterproof sheet 6 is 18 to 26% by mass. The unsaturated polyester resin constituting the FRP tarpaulin 6 has a structural unit derived from glycol containing an ether bond, has a tensile strength of 10 to 30 MPa, and has a tensile elastic modulus of 700 MPa or less.

In the present specification, each value of the tensile strength and the tensile elastic modulus of the unsaturated polyester resin in the FRP tarpaulin is a value measured at 23 ° C. in accordance with the provisions of JIS K6911-2006. These values can also be obtained in accordance with the provisions of JIS K7161-2-2014. Further, in the present specification, each physical property value such as tensile strength and tensile elastic modulus of the unsaturated polyester resin is obtained by obtaining the unsaturated polyester resin itself (curing of the unsaturated polyester resin) without using the fibrous reinforcing material. It means the physical property value of the thing). More specifically, the physical property value of the unsaturated polyester resin is the "casting plate" described in JIS K6919-2009 (a liquid unsaturated polyester resin mixed with a curing agent or a curing agent and an accelerator). It is a physical property value at 23 ° C. of (the one which was put in a mold and cured).

The content of the fibrous reinforcing material in the FRP waterproof sheet 6 is within the above-mentioned specific range, and the FRP waterproof sheet 6 has a structural unit derived from glycol containing an ether bond, and the above-mentioned specific tensile strength and tensile modulus. An unsaturated polyester resin having a modulus is used. Therefore, the FRP waterproof sheet 6 has good water resistance and heat resistance, has the strength required as a waterproof member, and has sufficient flexibility even in an environment where the temperature is relatively low. It is possible to construct. Specifically, for example, even when the FRP preventive sheet wound in a roll shape is used in an environment of, for example, 15 ° C. or lower, the FRP waterproof sheet can be easily attached without leaving a curl. It is possible to do. In the present specification, the "environment with a relatively low temperature" refers to an environment in which the temperature is 15 ° C. or lower (specifically, about 10 to 15 ° C.), and a lower temperature environment such as 10 ° C. or lower. Is sometimes called "low temperature environment".

The tensile strength of the unsaturated polyester resin is 10 to 30 MPa, preferably 10 to 25 MPa, and more preferably 10 to 20 MPa from the viewpoint of having sufficient flexibility even in a low temperature environment. The tensile elastic modulus of the unsaturated polyester resin is 700 MPa or less, preferably 600 MPa or less, more preferably 550 MPa or less, still more preferably 500 MPa or less, from the viewpoint of having sufficient flexibility even in a low temperature environment. is there. Further, from the viewpoint of the strength, water resistance, and heat resistance of the unsaturated polyester resin, its tensile elastic modulus is preferably 150 MPa or more, and more preferably 160 MPa or more.

The tensile fracture strain (elongation) measured in accordance with JIS K6911-2006 of the unsaturated polyester resin is preferably 25% or more, more preferably 30% or more, still more preferably 40% or more and 200%. It is as follows. The bending strength of the unsaturated polyester resin measured in accordance with JIS K6911-2006 is preferably 5 to 30 MPa, more preferably 5 to 25 MPa, still more preferably 10 to 25 MPa.

The tensile strength is 10 to 30 MPa and the tensile strength is 10 to 30 MPa by adjusting the type of monomer such as the acid component (acid and / or its anhydride) and the monomer such as the glycol component and the amount thereof used for the synthesis of the unsaturated polyester resin. , An unsaturated polyester resin having a tensile elastic modulus of 700 MPa or less can be obtained. Hereinafter, preferable monomers and the like from the viewpoint of obtaining an unsaturated polyester resin having the above tensile strength and tensile elastic modulus will be described.

Unsaturated polyester resin can be synthesized by polycondensation of acid or its anhydride and glycol. As the acid, unsaturated polybasic acid and / or saturated polybasic acid can be used. The unsaturated polyester resin has a structural unit derived from recall containing an ether bond, a structural unit derived from unsaturated polybasic acid or its anhydride, and a structural unit derived from saturated polybasic acid or its anhydride. Is preferable.

Examples of the unsaturated polybasic acid or its anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and citraconic acid, among which maleic acid and maleic anhydride are used. Acid is preferred. As the unsaturated polyester resin, one or more of unsaturated polybasic acids and their anhydrides can be used.

Examples of the saturated polybasic acid or its anhydride include phthalic acid (orthophthalic acid), isophthalic acid, terephthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, and hexahydrophthalic acid anhydride. , Cyclohexanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, trimellitic acid, pyromellitic acid and the like. Of these, phthalic acid, isophthalic acid, and terephthalic acid are preferable. Further, from the viewpoint of imparting flexibility to the unsaturated polyester resin, linear saturated dibasic acids such as glutaric acid, adipic acid, pimelic acid, azelaic acid, and sebacic acid are preferable. As the unsaturated polyester resin, one or more of saturated polybasic acids and their anhydrides can be used.

The content ratio of the unsaturated polybasic acid, the saturated polybasic acid, and the structural units derived from their anhydrides is preferably 10 to 50% by mass, more preferably, based on the total mass of the unsaturated polyester resin. Is 20 to 40% by mass, more preferably 25 to 35% by mass.

As the glycol, a glycol containing an ether bond is used from the viewpoint of imparting flexibility to the unsaturated polyester resin. Examples of the glycol containing an ether bond include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol and the like. The glycol containing an ether bond is preferably at least one selected from the group consisting of diethylene glycol, dipropylene glycol, and triethylene glycol. As the unsaturated polyester resin, one or more kinds of glycols containing ether bonds can be used, and one kind or two or more kinds of glycols not containing ether bonds such as ethylene glycol and propylene glycol are used. May be.

The content ratio of the structural unit derived from the glycol containing an ether bond is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, still more preferably 25, based on the total mass of the unsaturated polyester resin. ~ 35% by mass.

As the unsaturated polyester resin, a modified unsaturated polyester resin can also be used in order to improve the curing reactivity and various physical properties. As the modified unsaturated polyester resin, for example, an α, β-unsaturated carboxylic acid ester having an epoxy group or a (meth) acrylate having a hydroxy group is reacted with a carboxy group or a hydroxy group at the molecular end of the unsaturated polyester resin. It is possible to use what is obtained by. Further, a modified unsaturated polyester resin obtained by reacting a hydroxy group at the molecular terminal of an unsaturated polyester resin with a polyisocyanate can also be used. In addition, in this specification, "(meth) acrylate" means that both acrylate and methacrylate are contained, and "(meth) acrylic" means that both acrylic and methacrylic are contained. ..

The unsaturated polyester resin preferably further has a structural unit derived from a polymerizable monomer. By using a polymerizable monomer for the synthesis of the unsaturated polyester resin, a three-dimensionally crosslinked unsaturated polyester resin can be obtained, thereby further enhancing the water resistance and heat resistance of the FRP waterproof sheet 6. Is possible. The unsaturated polyester resin is an unsaturated polyester resin obtained by dissolving unsaturated polyester produced by polycondensation of the above-mentioned acid and glycol containing an ether bond in a polymerizable monomer, diluting the resin, and heat-curing the resin. Saturated polyester resin is more preferred.

The polymerizable monomer is a glycol containing the above-mentioned ether bond, and a polymerizable monomer other than unsaturated polybasic acid, saturated polybasic acid, and their anhydrides. Examples of the polymerizable monomer include (meth) acrylic acid esters such as methyl acrylate and methyl methacrylate, and styrene, α-methylstyrene, divinylbenzene, vinyltoluene, paramethylstyrene, tert-butylstyrene and the like. be able to. Of these, styrene is preferable. As the unsaturated polyester resin, one or more of the polymerizable monomers can be used.

The content ratio of the structural unit derived from the polymerizable monomer is preferably 20 to 60% by mass, more preferably 30 to 50% by mass, still more preferably 35, based on the total mass of the unsaturated polyester resin. ~ 45% by mass.

When synthesizing an unsaturated polyester resin, a resin composition prepared by adding a curing agent to a composition containing the above-mentioned acid or an anhydride thereof and a monomer component such as glycol can be used. An unsaturated polyester resin can be obtained by curing the above-mentioned monomer components with a curing agent. Suitable curing agents include organic peroxides and azo compounds. One type or two or more types of curing agents can be used for the synthesis of the unsaturated polyester resin. The amount of the curing agent used is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass in total of the monomer components forming the unsaturated polyester resin.

As the organic peroxide, hydroperoxide, dialkyl peroxide, diacyl peroxide, ketone peroxide, peroxyester, peroxyketal, peroxydicarbonate and the like can be used. Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, and 1,1-bis (t-butylperoxy)-. 3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumyl peroxide, Dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, and lauryl peroxide And so on. Specific examples of the azo compound include azobisisobutyronitrile, azobiscarboxylicamide, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile and the like.

When synthesizing an unsaturated polyester resin, the resin composition described above may contain an accelerator. Suitable accelerators include metal soaps, metal chelates, amine compounds, β-diketone compounds and the like. One or more accelerators can be used in the synthesis of the unsaturated polyester resin. The amount of the accelerator used is preferably 0.005 to 2 parts by mass with respect to 100 parts by mass in total of the monomer components forming the unsaturated polyester resin.

Examples of metal soaps include cobalt metal salts (for example, cobalt octate, cobalt naphthenate, cobalt octylate, etc.), zinc octylate, vanadium octylate, calcium naphthenate, calcium octate, potassium octate, and naphthenic acid. Examples thereof include copper and barium naphthenate. Examples of the metal chelate include iron acetylacetonate, vanadium acetylacetate, cobalt acetylacetate and the like. Examples of the amine compound include N, N-dimethylaniline, N, N-dimethyl-p-toluidine and the like. Examples of the β-diketone compound include α-acetylbutyrolactone and N, N-dimethylacetacetamide.

When synthesizing an unsaturated polyester resin, various additives may be contained in the above-mentioned resin composition. Additives include, for example, polymerization inhibitors, viscosity modifiers, thixotropy modifiers (swaying agents), pigments, dyes, defoamers, coupling agents, wetting dispersants, leveling agents, fillers, aggregates, antibacterial agents. Agents, fungicides, UV absorbers, antioxidants and the like can be mentioned. It is also possible to blend an unsaturated polyester resin with another resin such as a vinyl ester resin or an acrylic resin to improve durability and curability.

When molding the FRP tarpaulin 6, the resin composition containing the above-mentioned monomer component and the like that forms the unsaturated polyester resin is combined with the fibrous reinforcing material. Examples of the fibrous reinforcing material include glass fibers, amide resin fibers, aramid fibers, vinylon fibers, polyester resin fibers, phenol resin fibers, carbon fibers, metal fibers, and ceramic fibers. The FRP waterproof sheet 6 can contain one kind or two or more kinds of fibrous reinforcing materials. As the fibrous reinforcing material, glass fiber is preferable, glass chopped strand is more preferable, and glass roving chopped strand is further preferable.

As described above, the content of the fibrous reinforcing material in the FRP waterproof sheet 6 needs to be 18 to 26% by mass based on the total mass of the FRP waterproof sheet. If the content of the fibrous reinforcing material is less than 18%, the strength of the FRP waterproof sheet 6 becomes insufficient, and if the content exceeds 26%, the flexibility of the FRP waterproof sheet 6 is insufficient in a low temperature environment. It becomes difficult to construct. From the viewpoint of obtaining the FRP waterproof sheet 6 having appropriate flexibility and strength, the content of the fibrous reinforcing material is preferably 18 to 24% by mass.

The dimensions such as the width, thickness and length of the FRP waterproof sheet 6 are not particularly limited. The width of the FRP waterproof sheet 6 is preferably about 200 to 2000 mm, more preferably about 500 to 1500 mm, and further preferably about 1000 to 1200 mm from the viewpoint of ease of transportation and construction, manufacturing cost, and the like. The thickness of the FRP waterproof sheet 6 is preferably about 0.2 to 2 mm, more preferably 0.4 to 1, from the viewpoint of ensuring the strength as a waterproof member and the flexibility to the extent that it is easy to install. It is about 5 mm, more preferably about 0.6 to 1.2 mm.

Further, the FRP waterproof sheet 6 is preferably in the form of being wound in a roll shape (the form of the FRP waterproof sheet wound body) from the viewpoint of ease of transportation, production cost and the like. In this case, the length of the FRP prevention sheet 6 is preferably about 10 to 20 m from the viewpoint of ease of transportation. By forming the FRP waterproof sheet 6 in the form of a wound body, the FRP waterproof sheet 6 can be used by cutting it to an appropriate length with a cutter, scissors, etc., depending on the object to which the FRP waterproof sheet 6 is provided. It can be used for a wide range of purposes.

The manufacturing method of the FRP waterproof sheet 6 is not particularly limited. For example, a resin composition containing the above-mentioned monomer component forming the unsaturated polyester resin, a fibrous reinforcing material, a curing agent, an accelerator used as necessary, various additives, and the like is prepared, and the resin composition is prepared. Can be mentioned as a method of forming a sheet into a sheet. Further, a step of applying the resin composition before adding the fibrous reinforcing material to the first mold release material, a step of sprinkling the fibrous reinforcing material on the coated resin layer, and a step of sprinkling the fibrous reinforcing material are performed. Examples of the method include a step of covering the added resin layer with a second release material and a step of curing the resin layer to form a sheet. In these methods, it is preferable to continuously mold the FRP waterproof sheet 6 by using a known sheet molding method.

As an example of a method for continuously molding the FRP waterproof sheet 6, for example, "a continuous molding method called a film molding method (sheet molding method)" disclosed in Patent Document 3 can be referred to. As a method for continuously molding the FRP waterproof sheet 6, specifically, first, a first mold release material is continuously fed, and a resin composition is applied onto the first mold release material to form a resin layer. Then, it is preferable to sprinkle the fibrous reinforcing material on the resin layer that is continuously formed. At this time, glass roving is used as a reinforcing material, and chopped strands obtained by continuously cutting the glass roving on the resin layer are uniformly dropped onto the resin layer, and chopped using a roller or the like as necessary. It is preferable to impregnate the strands with resin. In this way, a mixed layer containing the resin composition and the fibrous reinforcing material (chopped strand) can be formed on the first release material. Then, the second mold release material is continuously laminated on the mixed layer, the thickness of the mixed layer is adjusted by using a roller or the like as necessary, and the resin composition is continuously cured in the curing furnace. Is preferable. After that, the first release material and the second release material are peeled off, and if necessary, the FRP waterproof sheet 6 in the form of a product wound up in a roll shape can be obtained through a cutting step of a width dimension.

[Waterproof material layer]
The waterproof structure 1 includes a waterproof material layer 8 provided on the FRP waterproof sheet 6. It is preferable that a primer layer (not shown) is provided between the FRP waterproof sheet 6 and the waterproof material layer 8 to ensure their adhesiveness.

The waterproof material layer 8 includes at least one of a styrene-free unsaturated polyester resin layer and a urethane resin layer having a tensile strength of 10 MPa or more and a tensile fracture elongation of 400% or less. In the present specification, each value of the tensile strength and the tensile fracture elongation of the styrene-free unsaturated polyester resin layer is a value measured in accordance with the provisions of JIS K6911-2006 at 23 ° C., and is a value measured in accordance with JIS K6919-. It can be measured using the casting plate described in 2009. Further, in the present specification, each value of the tensile strength and the tensile fracture elongation of the urethane resin layer is a value measured at 23 ° C. in accordance with the provisions of JIS A6021-2011.

By using at least one of a styrene-free unsaturated polyester resin layer and a urethane resin layer as the waterproof material layer 8, by using the above-mentioned FRP waterproof sheet 6 in combination, an environment-friendly waterproof structure 1 having a small environmental load can be obtained. Obtainable. By using styrene-free unsaturated polyester resin layer and urethane resin layer having a tensile strength of 10 MPa or more and a tensile fracture elongation of 400% or less, they are excellent in water resistance, heat resistance, and durability. It is possible to obtain the waterproof structure 1.

The tensile strength of the styrene-free unsaturated polyester resin layer and the urethane resin layer is preferably 12 MPa or more, more preferably 15 MPa or more. The upper limit of the tensile strength of the styrene-free unsaturated polyester resin layer and the urethane resin layer is not particularly limited, and can be, for example, 30 MPa or less. The tensile fracture elongation of the styrene-free unsaturated polyester resin layer is preferably 20 to 400%, more preferably 40 to 350%, and further preferably 60 to 300%. The tensile fracture elongation of the urethane resin layer is preferably 100 to 400%, more preferably 150 to 400%, and even more preferably 200 to 400%.

From the viewpoint of obtaining the waterproof structure 1 having excellent durability, the waterproof material layer 8 preferably contains a reinforcing material, and reinforces the styrene-free unsaturated polyester resin composition or the urethane resin composition forming the waterproof material layer 8. It is more preferable that the material is impregnated with the material. As the reinforcing material, in addition to the above-mentioned fibrous reinforcing material, a fiber reinforcing material in the form of a sheet, a mat, a mesh, a cloth, or the like can be used. Examples of the material of the fiber reinforcing material include glass fiber, amide resin fiber, aramid fiber, vinylon fiber, polyester fiber, phenol resin fiber, carbon fiber, metal fiber, ceramic fiber and the like. As the reinforcing material, glass fiber is preferable, glass fiber roving cloth, chopped strand mat, and surface mat are more preferable, and roving cloth and glass chopped strand mat are further preferable.

The styrene-free unsaturated polyester resin layer is an unsaturated polyester resin layer obtained without using styrene, and is an unsaturated polyester resin layer that does not contain structural units derived from styrene. The styrene-free unsaturated polyester resin layer is formed by curing a monomer component using a monomer such as an acid component and a glycol component described in the description of the unsaturated polyester resin constituting the FRP waterproof sheet 6, and a curing agent or the like. Can be obtained at. A styrene-free unsaturated polyester resin layer having a tensile strength of 10 MPa or more and a tensile fracture elongation of 400% or less can be obtained by adjusting the types of monomer components and curing agents and the amount used thereof. It is possible. A commercially available product can also be used as the resin composition for forming the styrene-free unsaturated polyester resin layer.

The styrene-free unsaturated polyester resin contains a structural unit derived from at least one selected from the group consisting of benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and phenoxyethyl (meth) acrylate as the polymerizable monomer. It is preferable to have. That is, it is preferable to use the resin composition containing these polymerizable monomers for forming the styrene-free unsaturated polyester resin layer. The resin composition containing these polymerizable monomers has an advantage that it can be easily impregnated into the above-mentioned reinforcing material even if it does not contain styrene.

As the urethane resin composition for forming the urethane resin layer, a commercially available product can be used. Specifically, among commercially available high-strength urethane rubber-based materials specified in JIS A6021: 2011, those satisfying the above-mentioned tensile strength and tensile fracture elongation can be used. By adjusting the types of polyols, polyisocyanates, etc. in the urethane resin composition and the amount used thereof, a urethane resin layer having a tensile strength of 10 MPa or more and a tensile fracture elongation of 400% or less can be obtained. Is possible.

<Manufacturing method of waterproof structure>
The method for manufacturing a waterproof structure according to an embodiment of the present invention includes a step of providing an elastic buffer layer on a base to be waterproofed, and an FRP containing a fibrous reinforcing material and an unsaturated polyester resin on the elastic buffer layer. It includes a step of providing a waterproof sheet and a step of providing a waterproof material layer on the FRP waterproof sheet. The content of the fibrous reinforcing material in the FRP waterproof sheet is 18 to 26% by mass. Further, the unsaturated polyester resin in the FRP tarpaulin has a structural unit derived from glycol containing an ether bond, has a tensile strength of 10 to 30 MPa, and has a tensile elastic modulus of 700 MPa or less. Further, on the FRP waterproof sheet, a waterproof material layer containing at least one of a styrene-free unsaturated polyester resin layer and a urethane resin layer having a tensile strength of 10 MPa or more and a tensile fracture elongation of 400% or less is provided. .. By this manufacturing method, the waterproof structure 1 according to the above-described embodiment can be manufactured. Therefore, the method for manufacturing the waterproof structure described below will also be described with reference to the reference numerals shown in FIG.

In the manufacturing method of the waterproof structure 1 (hereinafter, may be referred to as "waterproof construction method"), the base 2 to be waterproofed is not particularly limited. As the place of the foundation 2, for example, the rooftop of the building, the balcony, the balcony, the waist wall, the parapet, the bathroom washing place, and the toilet, as well as the parking lot, the pool, the sewerage facility, the water purification plant facility, the ozone treatment layer, the water tank, etc. And the floor of a chemical factory. Examples of the material of the base 2 include cement concrete, gypsum, mortar, asphalt concrete, plastic, metal, ceramics, and wood.

In this waterproofing method, since the elastic buffer layer 4 is provided on the base 2, it is possible to make the adjustment of the waterproof surface of the base 2 unnecessary or easy. However, in order to further enhance the adhesion between the base 2 and the elastic buffer layer 4, a base treatment may be performed to smooth the waterproof surface of the base 2 before providing the elastic buffer layer 4 on the base 2.

In this waterproofing method, after the elastic buffer layer 4 is provided on the base 2, the FRP waterproof sheet 6 can be provided on the elastic buffer layer 4. Further, after the elastic buffer layer 4 and the FRP waterproof sheet 6 are bonded together, the elastic buffer layer 4 to which the FRP waterproof sheet 6 is bonded can be provided as a base. For bonding the elastic buffer layer 4 and the FRP waterproof sheet 6, for example, an epoxy-based, urethane-based, acrylic-based, rubber-based, or hot-melt-based adhesive can be used, and if necessary, an adhesive surface can be used. Can also be primed.

Further, in this waterproofing method, a composite waterproof sheet 46 in which the elastic buffer layer 4 and the FRP waterproof sheet 6 are bonded in advance can be used. By providing the composite waterproof sheet 46 on the base 2 with the elastic buffer layer 4 side facing the base 2, the step of providing the elastic buffer layer 4 on the base 2 and the FRP waterproof sheet 6 on the elastic buffer layer 4 It is preferable to carry out the step of providing. By using the composite waterproof sheet 46, it is possible to reduce the number of man-hours as compared with the case where each of the elastic buffer layer 4 and the FRP waterproof sheet 6 is attached at the construction site. It is preferable to use the composite waterproof sheet 46 in the form of a wide long roll roll because it can be cut to a desired size with a cutter, scissors or the like at the construction site.

When the elastic buffer layer 4 is provided on the substrate 2, the elastic buffer layer 4 can be adhered to the substrate 2 by using an adhesive. As the adhesive, for example, epoxy-based, urethane-based, acrylic-based, and modified silicone-based adhesives can be used. Of these, urethane-based adhesives and modified silicone-based adhesives are preferable. For the adhesion between the base 2 and the elastic buffer layer 4, the entire surface of the elastic buffer layer 4 on the base 2 side may be adhered, or the non-adhesive portion may be an air passage by adhering with points or lines. The adhesive can be applied by methods such as brush coating, iron coating, roller coating, and spray coating.

In the step of providing the waterproof material layer 8 on the FRP waterproof sheet 6, the waterproof material layer 8 is formed by applying a liquid resin composition forming the waterproof material layer 8 on the FRP waterproof sheet 6 and curing it. Is preferable. The resin composition for forming the waterproof material layer 8 can be applied to the FRP waterproof sheet 6 by, for example, brush coating, iron coating, roller coating, spray coating, or the like.

When the styrene-free unsaturated polyester resin layer is formed as the waterproof material layer 8, the liquid resin composition contains the monomer component and the curing agent described in the description of the unsaturated polyester resin, and contains styrene. It is possible to use a resin composition that does not. When a urethane resin layer is formed as the waterproof material layer 8, a urethane resin composition containing a urethane prepolymer or a urethane resin composition containing a polyol component and a polyisocyanate component is used as a liquid resin composition. Can be used.

When forming the waterproof material layer 8, it is preferable to further use a reinforcing material. A resin composition containing a fibrous reinforcing material can be applied onto the FRP waterproof sheet 6, or the fibrous reinforcing material can be sprinkled onto the resin composition applied on the FRP waterproof sheet 6. As the reinforcing material, it is preferable to use a fiber reinforcing material in the form of a sheet, a mat, a mesh, a cloth, or the like. In this case, either the fiber reinforced material is arranged on the FRP waterproof sheet 6 and the resin composition is applied onto the FRP waterproof sheet 6, or the fiber reinforced material is arranged on the resin composition applied on the FRP waterproof sheet 6 and the fiber reinforced material is applied. Is impregnated with a resin composition to form a waterproof material layer 8 containing a fiber reinforced material. When a styrene-free unsaturated polyester resin layer is formed as the waterproof material layer 8, from the viewpoint of obtaining a resin composition that can be easily impregnated in the reinforcing material, benzyl (meth) acrylate is used as a polymerizable monomer in the resin composition. It is preferable to contain at least one selected from the group consisting of cyclohexyl (meth) acrylate and phenoxyethyl (meth) acrylate.

Before providing the waterproof material layer 8 on the FRP waterproof sheet 6, the surface of the FRP waterproof sheet 6 is subjected to polishing treatment, primer treatment, etc. in order to ensure the adhesiveness between the FRP waterproof sheet 6 and the waterproof material layer 8. It is preferable to apply a surface treatment. When the waterproof material layer 8 is a urethane resin layer, the urethane resin layer exhibits good adhesiveness to the FRP waterproof sheet 6, and is preferable in that the above-mentioned surface treatment can be omitted.

In the waterproof structure of one embodiment of the present invention described in detail above, a specific FRP waterproof sheet is used, an elastic buffer layer is provided between the FRP waterproof sheet and the base, and a waterproof material layer is provided on the FRP waterproof sheet. By providing it, it is possible to obtain an environment-friendly waterproof structure having good followability to the base. The FRP waterproof sheet used for this waterproof structure contains a fibrous reinforcing material at a content of 18 to 26% by mass, has a structural unit derived from glycol containing an ether bond, and has a tensile strength of 10 to 30 MPa. It contains an unsaturated polyester resin having a tensile elastic modulus of 700 MPa or less. Therefore, this FRP waterproof sheet has good water resistance, has the strength required as a waterproof member, and has sufficient flexibility even in an environment where the temperature is relatively low, and can be easily installed. Is. Further, if the unsaturated polyester resin having a tensile strength of 10 to 25 MPa and a tensile elastic modulus of 600 MPa or less is used, it has good flexibility even in a low temperature environment such as 10 ° C. or lower and further 5 ° C. or lower. It is possible to obtain an FRP tarpaulin having. Therefore, this waterproof structure is also suitable for use in an environment of 15 ° C. or lower, and is also suitable for use in a low temperature environment of 10 ° C. or lower, further 5 ° C. or lower.

As described above, the FRP waterproof sheet is manufactured in a long length from the viewpoint of workability, cost, etc., and the long FRP waterproof sheet is wound in a roll shape, and has the desired dimensions at the construction site. It is preferable to use it after being cut into. In such a usage mode, when a conventional FRP sheet having insufficient flexibility in an environment where the temperature is 15 ° C. or lower is used, a winding habit remains on the FRP sheet when the wound body of the FRP sheet is unfolded. It was sometimes difficult to construct. In addition, when the FRP sheet is attached to an object to be adhered such as a base material with an adhesive, it may bounce or rewind, making it difficult to construct. On the other hand, the FRP waterproof sheet used for the waterproof structure of one embodiment of the present invention has sufficient flexibility even when it is used in the above-mentioned usage mode and in an environment where the temperature is relatively low. Therefore, it can be easily constructed. Further, when the FRP waterproof sheet is attached to an object to be adhered such as a base with an adhesive, the FRP waterproof sheet is less likely to bounce or rewind, and is easy to install.

On the other hand, in the method of directly lining and coating an unsaturated polyester resin and a resin composition containing glass fibers on a base or the like (lining method), it is easily affected by the skill level of the operator, and when the skill level is low. May cause defects in the lining layer. In such a lining method, when there is a problem such as insufficient drying of the base, it may take a lot of time and effort for the base treatment. In addition, in the lining method, due to the influence of the dry state and smoothness of the base, poor adhesion of the lining layer to the base may occur, or if the base cracks, the lining layer may break, causing water leakage. May become. Further, when styrene is contained in the resin composition, there is a problem that styrene is volatilized and an odor is generated when the lining layer is formed. On the other hand, the waterproof structure of one embodiment of the present invention has an advantage that various problems in the lining method as described above are unlikely to occur.

As described above, the waterproof structure of the embodiment of the present invention can have the following configuration.
[1] A waterproof sheet made of a fiber-reinforced plastic containing an elastic buffer layer provided on a base to be waterproofed and an unsaturated polyester resin and a fibrous reinforcing material provided on the elastic buffer layer. And a waterproof material layer provided on the tarpaulin, the content of the fibrous reinforcing material in the tarpaulin is 18 to 26% by mass, and the unsaturated polyester resin has an ether bond. The tarpaulin layer has a structural unit derived from a glycol containing and has a tensile strength of 10 to 30 MPa and a tensile elastic modulus of 700 MPa or less, and is measured in accordance with the provisions of JIS K6911-2006. Measured in accordance with regulations, a styrene-free unsaturated polyester resin layer having a tensile strength of 10 MPa or more and a tensile modulus of 400% or less, and measured in accordance with JIS A6021-2011. , A waterproof structure including at least one of urethane resin layers having a tensile strength of 10 MPa or more and a tensile fracture elongation of 400% or less.
[2] The waterproof structure according to the above [1], wherein the composite waterproof sheet in which the elastic buffer layer and the waterproof sheet are bonded is provided on the base with the elastic buffer layer side as the base side.
[3] The waterproof structure according to the above [1] or [2], wherein the unsaturated polyester resin in the waterproof sheet has a tensile elastic modulus of 600 MPa or less.
[4] The waterproof structure according to any one of the above [1] to [3], wherein the glycol containing an ether bond is at least one selected from the group consisting of diethylene glycol, dipropylene glycol, and triethylene glycol.
[5] The waterproof structure according to any one of [1] to [4] above, wherein the waterproof material layer includes a reinforcing material.
[6] The waterproof structure according to any one of [1] to [5], wherein the elastic buffer layer contains a foamed resin sheet.

Further, as described above, the method for manufacturing the waterproof structure according to the embodiment of the present invention can have the following configuration.
[7] A step of providing an elastic buffer layer on a base to be waterproofed, and a waterproof sheet made of fiber reinforced plastic containing an unsaturated polyester resin and a fibrous reinforcing material are provided on the elastic buffer layer. The step includes a step of providing a waterproof material layer on the tarpaulin, and the content of the fibrous reinforcing material in the tarpaulin is 18 to 26% by mass, and the unsaturated polyester resin is ether. The tarpaulin layer has a structural unit derived from glycol containing a bond, has a tensile strength of 10 to 30 MPa and a tensile elastic modulus of 700 MPa or less, and is measured in accordance with the provisions of JIS K6911-2006. , A styrene-free unsaturated polyester resin layer having a tensile strength of 10 MPa or more and a tensile breaking elongation of 400% or less, measured in accordance with the above regulations, and measured in accordance with JIS A6021-2011. A method for manufacturing a waterproof structure, which comprises at least one of a urethane resin layer having a tensile strength of 10 MPa or more and a tensile fracture elongation of 400% or less.
[8] The elastic buffer layer is provided on the base by providing the composite waterproof sheet in which the elastic buffer layer and the waterproof sheet are bonded on the base with the elastic buffer layer side as the base side. The method for manufacturing a waterproof structure according to the above [7], wherein the step and the step of providing the waterproof sheet on the elastic buffer layer are executed.

Hereinafter, the present invention will be described in more detail with reference to test examples, but the present invention is not limited to the following test examples.

<Test Example 1: Preparation and evaluation of unsaturated polyester resin used for FRP waterproof sheet>
(Preparation of unsaturated polyester resin composition)
As shown in the middle part (unit: mass%) of Table 1, a liquid unsaturated polyester resin composition containing unsaturated acid, saturated acid, glycol, and styrene (hereinafter, simply referred to as "resin composition"). ) A1-9 were prepared. The viscosity of each of the prepared resin compositions at 25 ° C. was measured with a BM type viscometer (rotor: No. 3, rotation speed 30 rpm) in accordance with the provisions of JIS K6901-2008. The results are shown in Table 1. The abbreviations of the components shown in Table 1 are as follows.
MAN: Maleic anhydride IPA: Isophthalic acid TPA: Terephthalic acid OPA: Orthophthalic acid AA: Adipic acid DG: Diethylene glycol DPG: Dipropylene glycol TEG: Triethylene glycol

(Manufacturing of unsaturated polyester resin casting plate)
For each of the prepared resin compositions a1 to 9, test pieces of unsaturated polyester resins b1 to 9 for measuring physical properties were prepared as described below. First, with respect to 100 parts by mass of the resin composition, 1 part by mass of methyl ethyl ketone peroxide (product name "Permec N", manufactured by NOF Corporation) as a curing agent, and cobalt octeneate (Co: 8% by mass, Nippon Kagaku) as an accelerator. (Manufactured by Sangyo Co., Ltd.) 0.05 parts by mass was added and mixed. Next, a resin composition containing a curing agent and an accelerator was poured into a space formed by sandwiching a spacer having a thickness of 3 mm between two glass plates, and the resin composition was first cured at 80 ° C. for 30 minutes. Further, the test piece (casting plate) having a thickness of about 3 mm was prepared by secondary curing under the conditions of 120 ° C. × 60 minutes.

(Tensile test and bending test of unsaturated polyester resin)
Tensile tests and bending tests were performed on each of the prepared casting plates. In the tensile test, the test piece of the No. 1 dumbbell made from each casting plate was subjected to a tensile strength at 23 ° C. using a universal testing machine (manufactured by Shimadzu Corporation) in accordance with the regulations of JIS K6911-2006. Tensile elastic modulus and tensile fracture elongation were measured. In the bending test, a three-point bending test was performed on a test piece with a width of 10 mm and a length of 80 mm prepared from each casting plate at a distance between fulcrums of 46.5 mm, and a digital force gauge (product name "FGJN-50", Japan) was performed. The bending strength at 23 ° C. was measured using (manufactured by Nidec Symposium). These results are shown in Table 1.

(Hot water test of unsaturated polyester resin)
In addition, a hot water test was conducted using each of the prepared casting plates in order to confirm water resistance and heat resistance in a shorter period of time. Specifically, the appearance of the test piece taken out from the hot water after a predetermined time has elapsed by immersing the entire 4 cm square test piece prepared from each casting plate in hot water at 98 ° C. and hot water at 80 ° C. It was confirmed. In the test using hot water at 98 ° C., the appearance change was confirmed 50 hours after the test piece was immersed, and in the test using hot water at 80 ° C., 100 hours after the test piece was immersed. Changes in appearance were confirmed after 168 hours (7 days) and 336 hours (14 days). Then, the heat resistance (water resistance and heat resistance) of each condition was evaluated according to the following evaluation criteria.
A: No crazes, cracks, or blisters occurred on the test piece.
B: There was a craze on the test piece.
C1: The test piece had cracks.
C2: There was blistering on the test piece.
In addition, "cras" (cracks) and "cracks" (cracks) are defined in JIS K6900-1994, respectively. "Craze" is a crack with a structure that contains voids, while "crack" is a crack state in which the inside of the crack is a void, so cracks destroy the product more than craze. It is said that it is easy to connect to and the degree of defects is large. Further, the “blister” represents a state in which the test piece is swollen as if it were swollen.

<Test Example 2: Preparation and evaluation of FRP waterproof sheet>
The above-mentioned resin compositions a1, a2, a4, a7 and a8 were prepared, and FRP waterproof sheets c1, c2, c4, c7 and c8 were prepared for each of the prepared resin compositions as described below. .. Since the physical properties of the cured product (unsaturated polyester resin b3) of the resin composition a3 described above are close to those of the cured products (unsaturated polyester resins b2 and b4) of the resin compositions a2 and a4, the resin composition a3 The production of the FRP waterproof sheet using the above was omitted. Further, since it was confirmed by the hot water test that the cured products (unsaturated polyester resins b5 and b6) of the resin compositions a5 and a6 described above were inferior in water resistance, FRP waterproofing using the resin compositions a5 and a6 was performed. The preparation of the sheet was also omitted. Further, since the cured product (unsaturated polyester resin b9) of the resin composition a9 described above is too hard, when a glass fiber is blended with the cured product (unsaturated polyester resin b9) to prepare an FRP tarpaulin, the FRP tarpaulin is bent and wound. Since it will break, the production of the FRP tarpaulin was also omitted.

(Making FRP tarpaulin)
Specifically, with respect to 100 parts by mass of the resin composition, 1 part by mass of methyl ethyl ketone peroxide (product name "Permec N", manufactured by NOF Corporation) as a curing agent, and cobalt octeneate (Co: 8% by mass) as an accelerator. , Nippon Kagaku Sangyo Co., Ltd.) 0.05 parts by mass, colorant (product name "Tonner Gray", manufactured by Taitai Kako Co., Ltd.), 2 parts by mass, defoaming agent (product name "BYK A-501", manufactured by Big Chemie) 0.2 parts by mass was added to obtain a vacuum defoamed mixture. An aluminum mold with a thickness of 1.0 mm and an inner diameter of 35 cm square was attached onto a 40 cm square glass plate to prepare a molding mold for producing a test piece of an FRP waterproof sheet. The vacuum defoamed mixture was uniformly spread in the mold of the molding die. Glass fibers were sprinkled from a height of about 30 cm onto the mixture in the mold and spread evenly. The glass fiber was impregnated with the mixture while defoaming using a defoaming roller and a screw roller for FRP molding. Next, the mixture was covered with a polyester release film, and a rubber roller was rolled over the release film to smooth the mixture while removing air bubbles. Then, the mixture is first cured in a curing furnace under the condition of 80 ° C. × 20 minutes, then secondarily cured under the condition of 120 ° C. × 20 minutes, air-cooled, and then the glass plate and the release film are peeled off to make the thickness. An FRP waterproof sheet having a thickness of 1 mm ± 0.1 mm was obtained.

The glass fiber is made by cutting a soft type glass roving (product name "RS 240 PU-537", manufactured by Nitto Boseki Co., Ltd.) suitable for a continuous molding method into a length of 1 inch with a roving cutter ( Chopped strand) was used. The amount of glass fiber used is such that the content of glass fiber in the FRP waterproof sheet is the ratio shown in Table 2 below, and the FRP waterproof sheet c1, c2, c4, c7 produced by using each resin composition. For each of c8 and c8, those having different glass fiber contents were prepared.

(Evaluation of flexibility of FRP waterproof sheet)
Each of the obtained FRP waterproof sheets was subjected to a test for confirming the flexibility of the FRP waterproof sheet as described below. First, the obtained FRP waterproof sheet was cut into dimensions having a width of 25 mm and a length of 300 mm to prepare a test piece for evaluating flexibility. In an environment of 25 ° C., the test piece cut to the above dimensions was rolled into a ring, and both ends of the test piece having a width of 25 mm were abutted and fixed with adhesive tape. The test piece in this state was placed in a constant temperature bath at a temperature of −10 ° C. and allowed to stand for 3 hours. Then, at each environmental temperature (-10 ° C, 0 ° C, 5 ° C, 15 ° C, and 25 ° C) shown in Table 2, the adhesive tape was peeled off, the bent test piece was stretched, and a coating amount of 500 g was applied to a plywood base. It was attached with a silicone-based elastic adhesive (product name "SP-300", manufactured by Daitai Kako Co., Ltd.) applied at / m ² . At this time, it can be said that the test piece restrained by the adhesive force of the adhesive had no curl or its degree was small, so it was judged that the flexibility was good, and "○" (passed) in Table 2. Was shown. In addition, the test piece that was not restrained by the adhesive force of the adhesive and bounced off from the end was judged to have poor flexibility because of the remaining curl, and was marked with "x" (failed) in Table 2. Indicated.

As described above, the water resistance of the FRP waterproof sheet depends on the water resistance of the unsaturated polyester resin constituting the FRP waterproof sheet. Therefore, from the results of Test Examples 1 and 2, when the tensile strength of the unsaturated polyester resin having a structural unit derived from glycol containing an ether bond is 10 to 30 MPa and the tensile elastic modulus is 700 MPa or less, it is water resistant. It was confirmed that it is possible to manufacture an FRP waterproof sheet that has both properties and flexibility in an environment at a temperature of 15 ° C. Further, from the viewpoint of obtaining an FRP waterproof sheet having good flexibility even in a low temperature environment, it was confirmed that it is more preferable to set the content of the fibrous reinforcing material in the FRP waterproof sheet to 18 to 24% by mass. Further, from the viewpoint of obtaining an FRP tarpaulin having good flexibility even in a low temperature environment, the FRP tarpaulin is made of an unsaturated polyester resin having a tensile elastic modulus of 600 MPa or less, more preferably 550 MPa or less, still more preferably 500 MPa or less. It was confirmed that it is good to use.

<Test Example 3: Preparation and evaluation of FRP waterproof sheet by actual machine>
(Manufacturing of FRP waterproof sheet and its winding body)
Next, for each of the above-mentioned resin compositions a1, a2, a4, and a7, as described below, the FRP tarpaulin c1, c2, and the glass fiber content of the glass fiber content shown in Table 3 below were subjected to the above-mentioned continuous molding method. c4 and c7 were prepared. Specifically, a first release film made of polyester was continuously fed by a transporter, and a resin composition was applied onto the first release film to continuously form a resin layer. The glass roving is continuously supplied to the roller cutter arranged after the application step of the resin composition, and the chopped strands obtained by the roller cutter are sprinkled onto the resin layer which is sequentially formed to form the glass fiber layer. Formed continuously. A mixed layer containing the resin composition and the glass fiber was formed on the first release film by impregnating the glass fiber layer with the resin layer (resin composition) by a roller arranged in the subsequent step. A second release film made of polyester was layered on the mixed layer, the thickness of the mixed layer was adjusted with a thickness adjusting roller, and the resin composition was continuously cured in a curing furnace. Then, the first release film and the second release film were peeled off, and through a step of cutting the width dimension, an FRP waterproof sheet having a thickness of 1 mm ± 0.1 mm, a length of 1000 mm, and a width of 250 mm was produced. Then, this FRP waterproof sheet was wound into a roll to obtain an FRP waterproof sheet wound body having a diameter of about 300 mm.

(Evaluation of flexibility of FRP waterproof sheet)
The obtained FRP waterproof sheet winder was allowed to stand in each environment of -10 ° C, 0 ° C, 5 ° C, and 15 ° C for 24 hours, and then in that environment, the FRP waterproof sheet was used as a base made of plywood. An FRP waterproof sheet was attached to the entire surface of the above surface via a silicone-based elastic adhesive (product name "SP-300", manufactured by Taitai Kako Co., Ltd.) applied at a coating amount of 500 g / m ² . At this time, it can be said that the FRP waterproof sheet held smoothly on the base by the adhesive force of the adhesive had no curl or a small degree of curl, so it was judged that the flexibility was good, and it was judged in Table 3 It was shown as "○" (passed). In addition, the FRP waterproof sheet that bounced or peeled off from the end was judged to have poor flexibility because it had a habit of curling, and was indicated as "x" (failed) in Table 3.

From the results of Test Example 3, it is more preferable that the content of the fibrous reinforcing material in the FRP waterproof sheet is 24% by mass or less from the viewpoint of obtaining an FRP waterproof sheet having good flexibility in a low temperature environment. Was confirmed. Further, it was confirmed that it is more preferable to use an unsaturated polyester resin having a tensile strength of 10 to 25 MPa and a tensile elastic modulus of 600 MPa or less for the FRP tarpaulin.

<Test Example 4: Preparation and evaluation of waterproof material layer>
Next, plate-shaped waterproof materials d1 to 6 were prepared for the waterproof material layer provided on the FRP waterproof sheet in the waterproof structure, and their evaluation was performed.

(Raw material for waterproof layer)
As the raw materials of the waterproof materials d1 and d2, a commercially available urethane resin composition for a highly stretchable urethane resin specified in JIS A 6021-2011 is used, and the waterproof material d1 and the waterproof material d2 have physical properties of a cured product. Used different raw materials. As the raw materials of the waterproof materials d3 and d4, a commercially available urethane resin composition for the high-strength type urethane resin specified above was used, and the raw materials having different physical properties of the cured product were used between the waterproof material d3 and the waterproof material d4. .. The raw materials for the waterproof materials d5 and d6 are unsaturated polyesters that comply with the standards of "JASS 8 M-101-2007 waterproof polyester resin" in "Architectural Institute of Japan Standard Specifications / Explanation JASS 8 Waterproof Work". A resin composition was used. The raw material of the waterproof material d5 was an unsaturated polyester resin composition containing no styrene, and the raw material of the waterproof material d6 was an unsaturated polyester resin composition containing styrene.

Specifically, the following materials were used as raw materials for the plate-shaped waterproof materials d1 to 6.
Waterproof material d1: Product name "Priadeck 828S" (manufactured by DIC Corporation)
Waterproof material d2: Product name "Perfect 2K Proof" (Main agent: Hardener = 1: 2 (mass ratio) mixed. Made by Nippon Paint Co., Ltd.)
Waterproof material d3: Product name "Priadic EXP2605" (manufactured by DIC Corporation)
Waterproof material d4: Product name "GEX-201" (manufactured by Taitai Kako Co., Ltd.)
Waterproofing material d5: Styrene-free unsaturated polyester resin composition (benzyl methacrylate content: 40% by mass, product name "DK-776", manufactured by Taitai Kako Co., Ltd.) in 100 parts by mass, cobalt octateate as an accelerator ( Co: 8% by mass, manufactured by Nippon Kagaku Sangyo Co., Ltd.) 0.5 parts by mass, and 1.0 part by mass of the product name "328E" (manufactured by Kayaku Akzo Corporation) were added as an organic peroxide-based curing agent. blend.
Waterproof material d6: An unsaturated polyester resin composition containing styrene and an accelerator (styrene content: 50% by mass, product name "DK-633AP", manufactured by Taitai Kako Co., Ltd.), and methyl ethyl ketone peroxide (product) as a curing agent. Name "Permec N", manufactured by NOF CORPORATION) Mixture with 1 part by mass added.

(Making a plate-shaped waterproof material)
For the waterproof materials d1 to d4, a weir frame having a thickness of 2 mm was installed around a 350 mm square glass plate, and a well-stirred raw material was uniformly applied into the formwork. After curing the applied raw material at 25 ° C. for 4 days, the cured product of the raw material was taken out from the mold and further cured at room temperature (25 ° C.) for 3 days to prepare plate-shaped waterproof materials d1 to 4 of the test piece. ..
For the waterproof materials d5 and d6, the raw materials were poured into a mold formed by sandwiching a spacer having a thickness of 3 mm between two glass plates. After curing the raw material at 25 ° C. for 24 hours, the cured product of the raw material was taken out from the mold and further cured at room temperature (25 ° C.) for 3 days to prepare plate-shaped waterproof materials d5 and d6 of the test piece.

(Tensile test of plate-shaped waterproof material)
A test piece for a tensile test was prepared from the prepared plate-shaped waterproof materials d1 to 6. The plate-shaped waterproof materials d1 to 4 were subjected to a tensile test in accordance with the provisions of JIS A6021-2011, and the plate-shaped waterproof materials d5 and d6 were subjected to a tensile test in accordance with the provisions of JIS K6911-2006. .. Table 4 shows the measurement results of the tensile strength (MPa) and the tensile fracture elongation (%) of each plate-shaped waterproof material.

(Tensile performance test after deterioration treatment of plate-shaped waterproof material)
Tensile performance tests after deterioration treatment (heat treatment, alkali treatment, and acid treatment) were performed on the plate-shaped waterproof materials d1 to 6 in accordance with the provisions of JIS A6021-2011, and the tensile strength ratio after each deterioration treatment was performed. (%) And tensile fracture elongation (%) were measured. The results are shown in Table 4.

(Hot water test of plate-shaped waterproof material)
Using the produced plate-shaped waterproof materials d1 to 6, a hot water test was conducted in order to confirm water resistance and heat resistance in a shorter period of time. Specifically, 4 cm square test pieces were prepared from the test bodies for each of the plate-shaped waterproof materials d1 to 6. Then, the entire test piece was immersed in hot water at 80 ° C. and hot water at 98 ° C., and the appearance change of the test piece taken out from the hot water after a lapse of a predetermined time was confirmed. In the test using hot water at 80 ° C., changes in appearance were confirmed 100 hours and 168 hours (7 days) after the test piece was immersed. In the test using hot water at 98 ° C., changes in appearance were confirmed 24 hours and 50 hours after the test piece was immersed. Then, the heat resistance (water resistance and heat resistance) of each condition was evaluated according to the following evaluation criteria, and in this test example, the one with an evaluation of A was accepted. The evaluation results are shown in Table 4.
A: No cracking, blistering, swelling, or dissolution occurred in the test piece.
C1: There was blistering on the test piece.
C2: The test piece was swollen.
C3: The test piece was partially dissolved.

From the results of Test Example 4, a styrene-free unsaturated polyester resin layer having a tensile strength of 10 MPa or more and a tensile fracture elongation of 400% or less as an environment-friendly waterproof material layer having good water resistance and heat resistance. It was confirmed that (see waterproof material d5) and urethane resin layer (see waterproof material d3) can be used.

<Test Example 5: Preparation and evaluation of a laminate of FRP waterproof sheet and waterproof material layer>
Next, a laminate having a waterproof material layer formed on the prepared FRP waterproof sheet was prepared and evaluated. In Test Example 5, the FRP waterproof sheet c2 obtained in Test Example 2 having a glass fiber content of 22% by mass was used as the FRP waterproof sheet. As the waterproof material layer, the raw materials of the plate-shaped waterproof materials d1, d3, d5, and d6 produced in Test Example 4 are used, and the waterproof material layer is formed on the FRP waterproof sheet and laminated as follows. Objects e1 to 7 were produced.

(Preparation of laminate e1)
As a surface treatment, a one-component moisture-curing MDI-based urethane resin primer (product name "Compaq K", manufactured by Daitai Kako Co., Ltd.) is applied to the entire surface of the 300 mm square FRP waterproof sheet to which the waterproof material layer is provided. It was dried for 1 hour and cured. A weir frame with a thickness of 2 mm is installed around the surface of this FRP waterproof sheet, and 180 g of a well-stirred waterproof material d1 raw material is uniformly applied to the mold with a roller brush for 7 days at 25 ° C. After curing, a laminate e1 of the test piece was obtained.

(Preparation of laminate e2)
In the production of the laminate e1, except that one glass cloth (product name "WF230", manufactured by Nitto Boseki Co., Ltd.) was placed on the entire surface of the mold and then the raw material of the waterproof material d1 was applied. The laminate e2 of the test piece was obtained by the same method as in the preparation of the laminate e1.

(Preparation of laminate e3)
The laminated product e3 of the test body was obtained by the same method as in the production of the laminated product e1 except that the raw material of the waterproof material d1 used in the production of the laminated product e1 was changed to the raw material of the waterproof material d3.

(Preparation of laminate e4)
In the production of the laminate e1, except that one glass cloth (product name "WF230", manufactured by Nitto Boseki Co., Ltd.) was placed on the entire surface of the mold and then the raw material of the waterproof material d3 was applied. The laminate e4 of the test piece was obtained by the same method as in the preparation of the laminate e1.

(Preparation of laminate e5)
As a surface treatment, a one-component moisture-curing MDI-based urethane resin primer (product name "Compaq K", manufactured by Daitai Kako Co., Ltd.) is applied to the entire surface of the 300 mm square FRP waterproof sheet to which the waterproof material layer is provided. It was dried for 1 hour and cured. A weir frame having a thickness of 2 mm was installed around the surface of the FRP waterproof sheet, and 120 g of a well-stirred waterproof material d3 raw material was uniformly applied to the mold frame by a roller brush. Next, one glass chopped strand mat (product name "ECM450", manufactured by Central Glass Co., Ltd.) was placed on the coated raw material on the entire surface, and the raw material was impregnated into the mat using an impregnation roller. Further, 100 g of the raw material of the waterproof material d3 was uniformly applied on it with a roller brush, and defoamed and impregnated with an impregnation roller. Then, after curing at 25 ° C. for 7 days, a laminate e5 of the test body was obtained.

(Preparation of laminate e6)
As a surface treatment, a one-component moisture-curing MDI-based urethane resin primer (product name "Compaq K", manufactured by Daitai Kako Co., Ltd.) is applied to the entire surface of the 300 mm square FRP waterproof sheet to which the waterproof material layer is provided. It was dried for 1 hour and cured. After uniformly applying 100 g of the raw material of the waterproof material d5 to the surface of this FRP waterproof sheet, a glass chopped strand mat (product name "ECM450", manufactured by Central Glass Co., Ltd.) is placed on the entire surface of the applied raw material for impregnation. The raw material was impregnated into the mat using a roller. Further, 60 g of the raw material of the waterproof material d5 was applied thereto, defoamed and impregnated with an impregnation roller, and finally smoothed with a metal roller. Then, after curing at 25 ° C. for 7 days, a laminate e6 of the test body was obtained.

(Preparation of laminate e7)
A laminate e7 of a test piece was obtained by the same method as in the production of the laminate e6, except that the raw material of the waterproof material d5 used in the production of the laminate e6 was changed to the raw material of the waterproof material d6.

(Preparation of laminate e8)
As a reference, a laminate e8 using two fiber reinforced materials was prepared without using the FRP waterproof sheet. Specifically, 100 g of the raw material of the waterproof material d6 is uniformly applied to a 300 mm square glass plate, and then one glass chopped strand mat (product name "ECM450", manufactured by Central Glass Co., Ltd.) is applied to the entire surface of the applied raw material. The mat was placed and the mat was impregnated with the raw material using an impregnation roller. Further, 120 g of the raw material of the waterproof material d6 is applied on it, another sheet of the above mat is placed, defoamed and impregnated with an impregnation roller, and then 60 g of the raw material of the waterproof material d6 is uniformly applied, and finally. Smoothed with a metal roller. Then, after curing at 25 ° C. for 7 days, a laminate e8 of the test body was obtained.

(Tensile test of laminate)
For the obtained laminates e1 to 8, test pieces were collected from the laminated portion of each layer, and a tensile test was conducted in accordance with the provisions of JIS K6911-2006 to determine the tensile strength (MPa) and tensile fracture elongation (%). It was measured. The results are shown in Table 5.

(Hot water test of laminate)
For the produced laminates e1 to 8, 4 cm square test pieces were collected from the laminated portion of each layer, and a hot water test was performed using the same method and evaluation criteria as in the above-mentioned "hot water test for plate-shaped waterproof material". , Heat resistance and water resistance (water resistance and heat resistance) were evaluated. The conditions for the hot water test were a condition in which the test piece was immersed in hot water at 80 ° C. for 168 hours and a condition in which the test piece was immersed in hot water at 98 ° C. for 50 hours. The results are shown in Table 5.

From the results of Test Example 5, it was confirmed that the laminate in which the FRP waterproof sheet having good heat resistance and flexibility and the environment-friendly waterproof material layer having good heat resistance also showed good heat resistance. (See laminates e3-6).

<Test Example 6: Fabrication and evaluation of waterproof structure>
Finally, a waterproof structure is prepared using an FRP waterproof sheet having excellent heat resistance and flexibility, a waterproof material layer having excellent heat resistance, etc., and a test is conducted to confirm the followability of the waterproof structure to the base. It was. FIG. 2 shows a schematic diagram for explaining the test method.

(Production of waterproof structure f1 to 3)
First, a polyethylene foam material having a thickness of 3 mm (tensile fracture elongation 110%, foaming magnification 30 times) was used as an elastic buffer layer on the FRP waterproof sheet c2 obtained in Test Example 2 having a glass fiber content of 22% by mass. ) Was bonded with a urethane adhesive to prepare a composite waterproof sheet.
A modified silicone adhesive (product name "SP-300", manufactured by Daitai Kako Co., Ltd.) having a tensile fracture elongation of 70% of the cured product was applied to the entire surface of a 300 mm square slag gypsum plate as a base. The composite tarpaulin was crimped and attached. At this time, the elastic buffer layer in the composite waterproof sheet was adhered to the base. Next, as a surface treatment, 10 g of a one-component moisture-curable MDI-based urethane resin primer (product name "Compack K", manufactured by Daitai Kako Co., Ltd.) was applied to the surface of the FRP waterproof sheet in the composite waterproof sheet. It was dried. A waterproof material layer having the specifications shown in Table 6 was formed on the surface-treated FRP waterproof sheet to prepare waterproof structures f1 to 3. The waterproof material layer was formed according to the method for producing a laminate described in Test Example 5 as conditions for the waterproof material shown in Table 6, the amount used thereof, and the number of glass chopped strand mats used.

(Production of waterproof structure f4)
As a surface treatment, apply 10 g of a one-component moisture-curable MDI urethane resin primer (product name "Compaq K", manufactured by Taitai Kako Co., Ltd.) to the entire surface of a 300 mm square slag gypsum plate as a base and dry it. I let you. A waterproof material layer was formed on the surface-treated substrate to prepare a waterproof structure f4. The waterproof material layer was formed according to the method for producing the laminate e8 described in Test Example 5 as conditions for the waterproof material shown in Table 6, the amount used thereof, and the number of glass chopped strand mats used.

(Evaluation test of followability with the base)
The prepared waterproof structure was cured at 25 ° C. for 3 days. Then, as shown in FIG. 2, the slag gypsum plate (G) and the waterproof structure (f1 to 4) provided on the slag gypsum plate (G) were cut into dimensions of width 50 mm × length 160 mm. The slag gypsum plate (G) from the back surface side of the slag gypsum plate (G) over the entire width of the central position (position 80 mm in length from the edge) in the length direction of the cut waterproof structure (f1 to 4). A cut portion (G1) having a width of about 2 mm was formed by cutting with a cutting tool for the thickness.
Separately, as a jig for evaluation, two steel plates (S) having a length of about 150 mm, a width of about 100 mm, and a thickness of 3 mm were used, and the side surfaces of the two steel plates (S) were butted against each other. The abutting portion (S1) of the two steel plates (S) was processed so as not to have a gap, and the steel plate (S) having a polished surface was used. Further, as the steel plate (S), a steel plate (S) having a through hole (not shown) for attaching to a gripper of a tensile tester was used.
A waterproof structure (f1, f2, f3 or f4) is provided on the jig so that the cut portion (G1) of the slag gypsum plate (G) coincides with the abutting portion (S1) of the jig. The obtained slag gypsum plate (G) was adhered with an adhesive (not shown). In this way, a test body (T) for evaluation of followability was obtained.

The test piece (T) is attached to the tensile tester, and the test piece (T) is cured along the length direction of the test piece (T) under the conditions of a test temperature of 23 ± 2 ° C. and a tensile speed of 1 mm / min (see the arrow in FIG. 2B). I pulled the tool. When this tensile test is performed, a gap is gradually formed in the abutting portion (S1) of the two steel plates (S), and both steel plates (S) move in the direction of separation, and accordingly, they are adhered to the steel plate (S). The slag gypsum plate (G) also moves so that the gap between the cut parts (G1) widens. Then, the gap width between the two steel sheets was measured when a member such as an elastic buffer layer in the waterproof structure was broken or peeled off from the base. Three test pieces were prepared for each waterproof structure, and the average value of the measurement results of the three gap widths was calculated and used as the base follow-up width. The larger the base follow-up width, the more difficult it is for the waterproof structure to peel off or crack, and the better the base followability. Table 6 shows the width of the base and the state of breakage or peeling.

From the results of Test Example 6, by using an FRP waterproof sheet with good heat resistance and flexibility, and an environment-friendly waterproof material layer with good heat resistance, an environment-friendly waterproof sheet with good followability to the base is used. It was confirmed that a waterproof structure can be obtained (see waterproof structures f1 and f2).

1 Waterproof structure 2 Base 4 Elastic buffer layer 6 Tarpaulin 8 Tarpaulin layer 46 Composite waterproof sheet

Claims (8)

An elastic buffer layer provided on the base to be waterproofed,
A tarpaulin made of fiber reinforced plastic containing an unsaturated polyester resin and a fibrous reinforcing material provided on the elastic buffer layer,
A waterproof material layer provided on the waterproof sheet is provided.
The content of the fibrous reinforcing material in the waterproof sheet is 18 to 26% by mass.
The unsaturated polyester resin has a structural unit derived from glycol containing an ether bond, and has a tensile strength of 10 to 30 MPa and a tensile elastic modulus of 700 MPa or less, as measured in accordance with JIS K6911-2006. And
The waterproof material layer is a styrene-free unsaturated polyester resin layer having a tensile strength of 10 MPa or more and a tensile fracture elongation of 400% or less, which is measured in accordance with the above regulations, and JIS A6021-2011. A waterproof structure including at least one of a urethane resin layers having a tensile strength of 10 MPa or more and a tensile fracture elongation of 400% or less, as measured in accordance with the above. The waterproof structure according to claim 1, wherein the composite waterproof sheet in which the elastic buffer layer and the waterproof sheet are bonded is provided on the base with the elastic buffer layer side as the base side. The waterproof structure according to claim 1 or 2, wherein the unsaturated polyester resin in the waterproof sheet has a tensile elastic modulus of 600 MPa or less. The waterproof structure according to any one of claims 1 to 3, wherein the glycol containing an ether bond is at least one selected from the group consisting of diethylene glycol, dipropylene glycol, and triethylene glycol. The waterproof structure according to any one of claims 1 to 4, wherein the waterproof material layer includes a reinforcing material. The waterproof structure according to any one of claims 1 to 5, wherein the elastic buffer layer includes a foamed resin sheet. The process of providing an elastic buffer layer on the base to be waterproofed, and
A step of providing a waterproof sheet made of fiber reinforced plastic containing an unsaturated polyester resin and a fibrous reinforcing material on the elastic buffer layer, and
Including a step of providing a waterproof material layer on the waterproof sheet.
The content of the fibrous reinforcing material in the waterproof sheet is 18 to 26% by mass.
The unsaturated polyester resin has a structural unit derived from glycol containing an ether bond, and has a tensile strength of 10 to 30 MPa and a tensile elastic modulus of 700 MPa or less, as measured in accordance with JIS K6911-2006. And
The waterproof material layer is a styrene-free unsaturated polyester resin layer having a tensile strength of 10 MPa or more and a tensile fracture elongation of 400% or less, which is measured in accordance with the above regulations, and JIS A6021-2011. A method for manufacturing a waterproof structure, which comprises at least one of a urethane resin layers having a tensile strength of 10 MPa or more and a tensile fracture elongation of 400% or less, which is measured in accordance with the above. A step of providing the elastic buffer layer on the substrate by providing the composite waterproof sheet in which the elastic buffer layer and the waterproof sheet are bonded on the substrate with the elastic buffer layer side as the substrate side. The method for manufacturing a waterproof structure according to claim 7, wherein the step of providing the waterproof sheet on the elastic buffer layer is executed.

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