JP2018080528A - Waterproof construction and method of manufacturing waterproof construction - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a waterproof construction using an FRP waterproof sheet having sufficient flexibility even under the environment with comparatively low temperature and having an excellent water-resistant property, and an environment-responsive waterproof construction having excellent followability to a base material.SOLUTION: A waterproof construction provided with an elastic cushioning layer provided on a base material to be an object of waterproofing treatment, a waterproof sheet made of fiber-reinforced plastic containing an unsaturated polyester resin and a fibrous reinforcement material that is provided on the elastic cushioning layer, and a waterproof material layer provided on the waterproof sheet. The content rate of fibrous reinforcement material in the waterproof sheet is 18 to 26 mass%. The unsaturated polyester resin in the waterproof sheet has a structural unit originating from glycol containing ether bonds, and a tensile strength is 10 to 30 MPa and a tensile elastic modulus is 700 MPa or less. The waterproof material layer includes at least one of a styrene non-containing unsaturated polyester resin later and an urethane resin layer having a tensile strength of 10 MPa or more, and a tensile breaking elongation of 400% or less.SELECTED DRAWING: Figure 1

Description

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

  Waterproof materials are provided on the rooftops of buildings, verandas, balconies, waist walls, parapets, bathroom washes, toilets, and parking lots. As a waterproof material, asphalt, rubber sheet, vinyl chloride sheet, urethane resin, acrylic resin and the like have been used for a long time. In recent years, it contains unsaturated polyester resin and glass fiber in consideration of wear resistance, adhesion to the substrate, problems of blistering and cracking due to low strength of the material itself, water resistance and chemical resistance, etc. A method of lining a resin composition to coat fiber reinforced plastics (FRP) is increasing (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 at the time of forming the FRP layer The styrene inside is volatilized and odor is generated. In consideration of these points, it has been proposed to use a pre-manufactured FRP sheet. For example, Patent Document 2 proposes a glass fiber reinforced resin molded plate obtained by impregnating glass fiber with a predetermined unsaturated polyester resin syrup and curing. Patent Document 3 proposes a soft FRP sheet formed by combining a reinforcing material with an unsaturated polyester resin containing a predetermined unsaturated polyester and a polymerizable monomer in a predetermined ratio and molding the sheet into a sheet shape. Yes.

  On the other hand, in a construction site where there is a base to be subjected to waterproofing processing, the FRP sheet has a joint portion or an uneven portion of the FRP sheet, and an FRP lining work on the site is often required. Under such circumstances, a composite waterproofing method combining an FRP sheet and an FRP lining work has also been proposed (see, for example, Patent Document 4 and Patent Document 5).

JP-A-1-96079 JP-A-1-193329 JP 2000-143958 A JP-A-5-214791 JP-A-9-11376

  Even in the FRP sheet disclosed in Patent Documents 2 to 5, flexibility in an environment where the temperature is relatively low, such as 15 ° C. or less, is not 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 a desired dimension at a construction site. It is often used after being cut into pieces. However, in an environment where the temperature is relatively low, since the hardness of the resin increases, when the above-mentioned FRP sheet winding body is expanded, curling flaws remain on the FRP sheet or the FRP sheet is attached to the object to be adhered. It may be difficult to perform the work due to rebounding or rewinding when sticking with. Furthermore, since the followability to the ground is also lowered, it may be difficult to perform a defect-free construction when the ground is uneven.

  Moreover, in the composite waterproofing method combining the FRP sheet and the FRP lining work, the number of work steps can be reduced as compared with the FRP waterproofing method using a general FRP lining process. However, in the lining operation, in consideration of the durability performance of the obtained FRP layer, etc., a resin composition containing a large amount of styrene is often used for the formation thereof. There is still room for improvement in terms of working environment.

  Therefore, the present invention is 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 compatible with the environment with good followability with the ground. It is intended to provide a waterproof structure for the mold.

  As a result of the study 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 necessary, and the water resistance of the FRP waterproof sheet is used. It has been found that this depends on the water resistance of the unsaturated polyester resin. And, the present inventors use an unsaturated polyester resin having a tensile strength and a tensile modulus within a specific range, and by making the content of the fibrous reinforcing material within a specific range, it is sufficient even in a low temperature environment. It has been found that an FRP waterproof sheet having flexibility and good water resistance can be obtained. Furthermore, 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 a tensile breaking elongation within a specific range on the opposite side, thereby providing the base It was found that a waterproof structure with good followability was obtained, and the present invention was completed.

  That is, the present invention is an elastic buffer layer provided on a base to be waterproofed, and a 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, the content of the fibrous reinforcing material in the waterproof sheet is 18 to 26% by mass, and the unsaturated polyester resin is The waterproofing material layer having a structural unit derived from glycol containing an ether bond, having a tensile strength of 10 to 30 MPa and a tensile elastic modulus of 700 MPa or less, as measured in accordance with the provisions of JIS K6911-2006 Is a styrene-free unsaturated polyester having a tensile strength of 10 MPa or more and a tensile breaking elongation of 400% or less, measured in accordance with the above rules. Resin layer, and is measured according to the standards of JIS A6021-2011, a tensile strength of more than 10 MPa, and a tensile breaking elongation at least one of a urethane resin layer is not more than 400%, to provide a waterproof structure.

  According to the present invention, it is 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 has good followability with the ground. A waterproof structure of the mold can be provided.

It is a schematic sectional drawing showing 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 the foundation | substrate in a test example, A is the top view, B is the sectional drawing.

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

<Waterproof structure>
A waterproof structure according to an embodiment of the present invention includes an elastic buffer layer provided on a base to be waterproofed, an unsaturated polyester resin and a fibrous reinforcing material provided on the elastic buffer layer. A waterproof sheet made of fiber reinforced plastic and a waterproof material layer provided on the waterproof sheet are provided. The content of the fibrous reinforcing material in the waterproof sheet made of fiber reinforced plastic (hereinafter sometimes referred to as “FRP waterproof sheet”) used in this waterproof structure is 18 to 26 mass%. The unsaturated polyester resin in the FRP waterproof sheet has a structural unit derived from glycol containing an ether bond, has a tensile strength of 10 to 30 MPa, and a tensile elastic modulus of 700 MPa or less. Furthermore, 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 breaking elongation of 400% or less. Including.

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

  FIG. 1 is a schematic cross-sectional view showing an example of a layer structure for explaining a waterproof structure according to an 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 provided on the FRP waterproof sheet 6. And a material layer 8. In addition, the layer structure in a waterproof structure is not limited to the example shown in FIG. For example, as 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. The waterproof structure may include a plurality of elastic buffer layers 4, FRP waterproof sheets 6, and waterproof material layers 8. Hereinafter, the waterproof structure of one embodiment of the present invention will be described using 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 can 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 and a foamed synthetic resin sheet (foamed resin sheet) are used. Can do. The elastic buffer layer 4 preferably includes a foamed resin sheet. The foamed resin sheet can be obtained by mechanical molding, or obtained by blowing a raw material at the construction site and foamed, but from the viewpoint of film thickness accuracy and workability, It is more preferable to use the obtained foamed resin sheet.

  Examples of the synthetic resin that is a raw material for the foamed resin sheet include polyester, polyvinyl chloride, polyurethane, polypropylene, and polyethylene. 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 with the FRP waterproof sheet and the construction surface for bonding at the construction site. The foamed resin sheet may have closed cells or open cells, but it is preferable that there are many closed cells from the viewpoint of waterproofness and heat insulation.

  The thickness of the elastic buffer layer 4 is preferably 1 to 40 mm, more preferably 2 to 30 mm, and still more preferably 3 to 10 mm. The elastic buffer layer 4 having a thickness of 1 mm or more can easily ensure insulation from the base 2 and can make adjustment of the waterproof surface of the base 2 unnecessary or easy, 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 a layer bonded in advance to the FRP waterproof sheet 6 provided thereon. 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. Although the elastic buffer layer 4 and the FRP waterproof sheet 6 may be bonded together at the construction site, it is preferable to use a composite waterproof sheet 46 bonded by mechanical molding in terms of accuracy and workability.

  Between the elastic buffer layer 4 and the FRP waterproof sheet 6, an adhesive layer (not shown) for bonding them may be provided. For the adhesive layer between the elastic buffer layer 4 and the FRP waterproof sheet 6, for example, an epoxy, urethane, acrylic, rubber, or hot melt adhesive can be used. Moreover, between the base | substrate 2 and the elastic buffer layer 4, it can have an adhesive bond layer (not shown) for bonding them together. For the adhesive layer between the base 2 and the elastic buffer layer 4, for example, an epoxy, urethane, acrylic, or modified silicone adhesive can be used. Of these, urethane adhesives and modified silicone adhesives are preferred. 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 thereof, or may be provided with 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 that is bonded to the elastic buffer layer 4 in advance (composite waterproof sheet 46).

  The FRP waterproof sheet 6 contains an unsaturated polyester resin and a fibrous reinforcing material. This FRP waterproof sheet 6 can take a configuration 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 rate of the fibrous reinforcement in this FRP waterproof sheet 6 is 18-26 mass%. The unsaturated polyester resin constituting the FRP waterproof sheet 6 has a structural unit derived from glycol containing an ether bond, has a tensile strength of 10 to 30 MPa, and a tensile modulus of 700 MPa or less.

  In this specification, each value of the tensile strength and the tensile elastic modulus of the unsaturated polyester resin in the FRP waterproof sheet is a value measured at 23 ° C. in accordance with the provisions of JIS K6911-2006. Those values can also be obtained in accordance with the provisions of JIS K7161-24-2. Moreover, in this specification, each physical property value such as tensile strength and tensile elastic modulus of the unsaturated polyester resin is obtained by using the unsaturated polyester resin itself (curing of the unsaturated polyester resin) obtained without using a fibrous reinforcing material. This means the physical property value of the material. More specifically, the physical property value of the unsaturated polyester resin is “casting plate” described in JIS K6919-2009 (a liquid unsaturated polyester resin blended with a curing agent or a curing agent and an accelerator. It is a physical property value at 23 ° C. of a product cured in a mold.

  The content of the fibrous reinforcing material in the FRP waterproof sheet 6 is within the above specific range, and the FRP waterproof sheet 6 has a structural unit derived from glycol containing an ether bond, and the above specific tensile strength and tensile elasticity. An unsaturated polyester resin having a rate is used. Therefore, this 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 and easily. It is possible to construct. Specifically, for example, even when the FRP prevention sheet wound in the form of a roll is used in an environment of, for example, 15 ° C. or less, it is easy to attach the FRP waterproof sheet without any curl remaining. Is possible. In this specification, the “environment having a relatively low temperature” means an environment having a temperature of 15 ° C. or lower (specifically, about 10 to 15 ° C.), and a lower temperature environment such as 10 ° C. or lower. Is sometimes referred to as a “low temperature environment”.

  The tensile strength of the unsaturated polyester resin is 10 to 30 MPa, and preferably 10 to 25 MPa, 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, and preferably 600 MPa or less, more preferably 550 MPa or less, and further preferably 500 MPa or less, from the viewpoint of 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, the 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 according to JIS K6911-2006 is preferably 5 to 30 MPa, more preferably 5 to 25 MPa, and still more preferably 10 to 25 MPa.

  By adjusting the acid component (acid and / or anhydride thereof) used for the synthesis of the unsaturated polyester resin and the type and amount of monomers such as glycol component, the tensile strength is 10-30 MPa, and 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.

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

  Examples of the unsaturated polybasic acid or anhydride thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and citraconic acid. Among these, maleic acid and maleic anhydride Acid is preferred. As the unsaturated polyester resin, one or more of unsaturated polybasic acids and anhydrides thereof can be used.

  Examples of the saturated polybasic acid or its anhydride include, for example, phthalic acid (orthophthalic acid), isophthalic acid, terephthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride , Cyclohexanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, trimellitic acid, and pyromellitic acid. Of these, phthalic acid, isophthalic acid, and terephthalic acid are preferred. 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 anhydrides thereof can be used.

  The content ratio of the unsaturated polybasic acid, the saturated polybasic acid, and the structural units derived from the anhydrides thereof 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, and polypropylene glycol. 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 of glycols containing an ether bond can be used, and one or more of glycols not containing an ether bond such as ethylene glycol and propylene glycol are used. It may be.

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

  As the unsaturated polyester resin, a modified unsaturated polyester resin can be used for improving 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 which is a molecular terminal of the unsaturated polyester resin. What is obtained can be used. Moreover, the modified | denatured unsaturated polyester resin obtained by making polyisocyanate react with the hydroxyl group of the molecular terminal of unsaturated polyester resin can also be used. In the present specification, “(meth) acrylate” means that both acrylate and methacrylate are included, and “(meth) acryl” means that both acrylic and methacryl are included. .

  The unsaturated polyester resin preferably further has a structural unit derived from a polymerizable monomer. By using a polymerizable monomer in the synthesis of the unsaturated polyester resin, it is possible to obtain a three-dimensionally crosslinked unsaturated polyester resin, thereby further improving the water resistance and heat resistance of the FRP waterproof sheet 6. Is possible. As this unsaturated polyester resin, an unsaturated polyester obtained by polycondensation of the aforementioned acid and a glycol containing an ether bond, dissolved in a polymerizable monomer and diluted, is heated and cured. Saturated polyester resins are more preferred.

  The polymerizable monomer is a polymerizable monomer other than the above-described glycol containing an ether bond, and unsaturated polybasic acid, saturated polybasic acid, and anhydrides thereof. Examples of the polymerizable monomer include (meth) acrylic acid esters such as methyl acrylate and methyl methacrylate, and styrene, α-methyl styrene, divinyl benzene, vinyl toluene, paramethyl styrene, and tert-butyl styrene. be able to. Of these, styrene is preferred. 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, and still more preferably 35 based on the total mass of the unsaturated polyester resin. It is -45 mass%.

  When synthesizing the unsaturated polyester resin, a resin composition prepared by adding a curing agent to a composition containing monomer components such as the acid or anhydride thereof and glycol described above can be used. An unsaturated polyester resin can be obtained by a curing reaction of the monomer component described above with a curing agent. Suitable curing agents include organic peroxides and azo compounds. For the synthesis of the unsaturated polyester resin, one or more curing agents can be used. It is preferable that the usage-amount of a hardening | curing agent is 0.5-5 mass parts with respect to a total of 100 mass parts of the monomer component which forms 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-butyl peroxybenzoate, 1,1-bis (t-butylperoxy)- 3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, Dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, and lauryl peroxide Mention may be made of earth or other. Specific examples of the azo compound include azobisisobutyronitrile, azobiscarbonamide, and 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile.

  When synthesizing the unsaturated polyester resin, an accelerator may be contained in the resin composition described above. Suitable accelerators include metal soaps, metal chelates, amine compounds, and β-diketone compounds. One or more accelerators can be used in the synthesis of the unsaturated polyester resin. It is preferable that the usage-amount of an accelerator is 0.005-2 mass part with respect to a total of 100 mass parts of the monomer component which forms unsaturated polyester resin.

  Examples of metal soaps include cobalt metal salts (such as cobalt octenoate, cobalt naphthenate, and cobalt octylate), zinc octylate, vanadium octylate, calcium naphthenate, calcium octenoate, potassium octenoate, and naphthenic acid. Examples thereof include copper and barium naphthenate. Examples of metal chelates include iron acetylacetonate, vanadium acetylacetate, and cobalt acetylacetate. Examples of amine compounds include N, N-dimethylaniline and N, N-dimethyl-p-toluidine. Examples of the β-diketone compound include α-acetylbutyrolactone and N, N-dimethylacetoacetamide.

  In addition, when synthesizing the unsaturated polyester resin, the above-described resin composition may contain various additives. Examples of the additives include polymerization inhibitors, viscosity modifiers, thixotropy modifiers (thixotropic agents), pigments, dyes, antifoaming agents, coupling agents, wetting and dispersing agents, leveling agents, fillers, aggregates, antibacterial agents. Agents, fungicides, ultraviolet absorbers, antioxidants and the like. It is also possible to improve durability and curability by blending unsaturated polyester resin with other resins such as vinyl ester resin and acrylic resin.

  When the FRP waterproof sheet 6 is molded, a resin composition containing the above-described monomer component or the like that forms an unsaturated polyester resin is combined with a fibrous reinforcing material. Examples of the fibrous reinforcing material include glass fiber, amide resin fiber, aramid fiber, vinylon fiber, polyester resin fiber, phenol resin fiber, carbon fiber, metal fiber, and ceramic fiber. The FRP waterproof sheet 6 can contain one type or two or more types 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 more 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. When the content of the fibrous reinforcing material is less than 18%, the strength of the FRP waterproof sheet 6 is insufficient, and when 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 waterproofing 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 still more preferably about 1000 to 1200 mm from the viewpoints 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.mm, from the viewpoint of ensuring the strength as a waterproof member and the flexibility that allows easy construction. It is about 5 mm, more preferably about 0.6 to 1.2 mm.

  Moreover, it is preferable that the FRP waterproof sheet 6 is a form wound in the shape of a roll (form of FRP waterproof sheet wound body) from the viewpoints of ease of transport, 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 easy transportation. By using the FRP waterproof sheet 6 in the form of a wound body, the FRP waterproof sheet 6 can be used by cutting it with an appropriate length with a cutter or a scissors according to the object on which the FRP waterproof sheet 6 is provided. Applications can be expanded.

  The manufacturing method of the FRP waterproof sheet 6 is not particularly limited. For example, a resin composition prepared by blending the above-described unsaturated polyester resin-forming monomer component, fibrous reinforcing material, curing agent, and accelerators and various additives used as necessary is prepared. The method of shape | molding can be mentioned to a sheet form. In addition, a step of applying the resin composition before adding the fibrous reinforcing material to the first release material, a step of scraping the fibrous reinforcing material on the coated resin layer, and a fibrous reinforcing material A method including a step of covering the added resin layer with a second release material and a step of curing the resin layer and forming it into a sheet can be mentioned. In these methods, it is preferable to continuously form the FRP waterproof sheet 6 using a known sheet forming method.

  As an example of a method for continuously forming the FRP waterproof sheet 6, for example, a “continuous forming method called a film forming method (sheet forming method)” disclosed in Patent Document 3 can be referred to. Specifically, as a continuous molding method of the FRP waterproof sheet 6, first, a first release material is continuously fed, and a resin composition is applied on the first release material to form a resin layer. However, it is preferable to scrape the fibrous reinforcing material on the resin layer that is continuously formed. At this time, glass roving is used as a reinforcing material, and the chopped strand obtained by continuously cutting the glass roving on the resin layer is uniformly dropped on the resin layer, using a roller or the like as necessary. It is preferable to impregnate the strand with resin. In this manner, a mixed layer containing the resin composition and the fibrous reinforcing material (chopped strand) can be formed on the first release material. And the 2nd mold release material is piled up continuously on the mixed layer, the thickness of a mixed layer is adjusted using a roller etc. as needed, and the resin composition is continuously hardened in a hardening furnace. It is preferable. Thereafter, the first release material and the second release material are peeled off, and the FRP waterproof sheet 6 in the form of a product wound in a roll shape can be obtained through a width dimension cutting step as necessary.

[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 in order to ensure the adhesiveness thereof.

  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 tensile strength and tensile breaking elongation of the styrene-free unsaturated polyester resin layer is a value measured at 23 ° C. according to the provisions of JIS K6911-2006, and JIS K6919- It can be measured using a casting plate described in 2009. Moreover, in this specification, each value of the tensile strength and tensile fracture elongation of a urethane resin layer is a value measured at 23 degreeC based on prescription | regulation of JISA6021-2011.

  By using at least one of a styrene-free unsaturated polyester resin layer and a urethane resin layer as the waterproof material layer 8, the environmentally friendly waterproof structure 1 with a small environmental load can be obtained by using the FRP waterproof sheet 6 together. Can be obtained. And, as a styrene-free unsaturated polyester resin layer and a urethane resin layer, excellent in water resistance, heat resistance, and durability by using one having a tensile strength of 10 MPa or more and a tensile breaking elongation of 400% or less. The waterproof structure 1 can be obtained.

  The tensile strength of the styrene-free unsaturated polyester resin layer and the urethane resin layer is preferably 12 MPa or more, and 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 elongation at break of the styrene-free unsaturated polyester resin layer is preferably 20 to 400%, more preferably 40 to 350%, still more preferably 60 to 300%. Moreover, it is preferable that the tensile fracture elongation of a urethane resin layer is 100 to 400%, More preferably, it is 150 to 400%, More preferably, it is 200 to 400%.

  From the viewpoint of obtaining a waterproof structure 1 having excellent durability, the waterproof material layer 8 preferably includes a reinforcing material, and reinforces the styrene-free unsaturated polyester resin composition or urethane resin composition that forms the waterproof material layer 8. What was formed by impregnating the material is more preferable. As the reinforcing material, a fiber reinforcing material in the form of a sheet, a mat, a mesh, and a cloth can be used in addition to the above-described fibrous reinforcing material. 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, and ceramic fiber. As the reinforcing material, glass fiber is preferable, roving cloth made of glass fiber, chopped strand mat, and surface mat are more preferable, and roving cloth and glass chopped strand mat are more 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 a structural unit derived from styrene. The styrene-free unsaturated polyester resin layer is a monomer component 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 reaction of the monomer component. Can be obtained at By adjusting the types of monomer components, curing agents, etc. and the amount of use thereof, 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 can be obtained. Is possible. A commercial item can also be used for the resin composition which forms this styrene non-containing unsaturated polyester resin layer.

  The styrene-free unsaturated polyester resin has 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 a polymerizable monomer. It is preferable to have. That is, it is preferable to use the resin composition containing those polymerizable monomers for forming a styrene-free unsaturated polyester resin layer. Resin compositions containing these polymerizable monomers have the advantage that they can be easily impregnated into the reinforcing material even if they do not contain styrene.

  A commercial item can be used as a urethane resin composition which forms a urethane resin layer. Specifically, among the commercially available high-strength urethane rubber materials specified in JIS A6021: 2011, those satisfying the above-described tensile strength and tensile elongation at break can be used. In addition, by adjusting the types of polyols and polyisocyanates in the urethane resin composition and the amount of use thereof, a urethane resin layer having a tensile strength of 10 MPa or more and a tensile breaking elongation of 400% or less is obtained. Is possible.

<Method for manufacturing waterproof structure>
A 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. 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. The unsaturated polyester resin in the FRP waterproof sheet has a structural unit derived from glycol containing an ether bond, has a tensile strength of 10 to 30 MPa, and a tensile elastic modulus of 700 MPa or less. Furthermore, a waterproof material layer including 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 on the FRP waterproof sheet. . With this manufacturing method, the waterproof structure 1 according to the above-described embodiment can be manufactured. Therefore, the manufacturing method of the waterproof structure described below will also be described using the reference numerals shown in FIG.

  In the manufacturing method of the waterproof structure 1 (hereinafter sometimes referred to as “waterproofing method”), the base 2 to be subjected to waterproofing treatment is not particularly limited. Examples of the ground 2 are, for example, rooftops of buildings, balconies, balconies, waist walls, parapets, bathroom washes, and toilets, as well as parking lots, pools, sewerage facilities, water purification facilities, ozone treatment layers, water tanks, And chemical factory floors. Examples of the material of the base 2 include cement concrete, gypsum, mortar, asphalt concrete, plastic, metal, ceramics, and wood.

  In this waterproof construction method, since the elastic buffer layer 4 is provided on the base 2, the adjustment of the waterproof surface of the base 2 can be made unnecessary or easy. However, in order to further improve the adhesion between the base 2 and the elastic buffer layer 4, a base treatment for finishing the waterproof surface of the base 2 smoothly may be performed before the elastic buffer layer 4 is provided on the base 2.

  In this waterproof construction method, after providing the elastic buffer layer 4 on the base 2, the FRP waterproof sheet 6 can be provided on the elastic buffer layer 4. Alternatively, the elastic buffer layer 4 and the FRP waterproof sheet 6 may be bonded together, and then the elastic buffer layer 4 to which the FRP waterproof sheet 6 is bonded may be provided on the base. For bonding the elastic buffer layer 4 and the FRP waterproof sheet 6, for example, an epoxy, urethane, acrylic, rubber, or hot melt adhesive can be used. Primer treatment can also be applied.

  Further, in this waterproof construction 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. The composite waterproof sheet 46 is provided on the base 2 with the elastic buffer layer 4 side on the base 2 side, and the FRP waterproof sheet 6 is provided on the elastic buffer layer 4. It is preferable to execute 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 the attaching work for each of the elastic buffer layer 4 and the FRP waterproof sheet 6 is performed at the construction site. As the composite waterproof sheet 46, it is preferable to use a wide, long roll-shaped one because it can be cut into a desired size with a cutter, scissors or the like at the construction site.

  When the elastic buffer layer 4 is provided on the base 2, the elastic buffer layer 4 can be adhered to the base 2 using an adhesive. Examples of the adhesive that can be used include epoxy, urethane, acrylic, and modified silicone adhesives. Of these, urethane adhesives and modified silicone adhesives are preferred. The base 2 and the elastic buffer layer 4 may be bonded by bonding the entire surface of the elastic buffer layer 4 on the base 2 side, or by bonding with dots or lines or the like to make the non-adhesive part an air passage. The adhesive can be applied by, for example, techniques such as brush coating, trowel 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 and curing a liquid resin composition that forms the waterproof material layer 8 on the FRP waterproof sheet 6. It is preferable. Application of the resin composition for forming the waterproof material layer 8 to the FRP waterproof sheet 6 can be performed by techniques such as brush coating, trowel coating, roller coating, and spray coating.

  When forming a styrene-free unsaturated polyester resin layer 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. Moreover, when forming a urethane resin layer as the waterproof material layer 8, as a liquid resin composition, a urethane resin composition containing a urethane prepolymer, or a urethane resin composition containing a polyol component and a polyisocyanate component. Can be used.

  When forming the waterproof material layer 8, it is preferable to use a reinforcing material. A resin composition in which a fibrous reinforcing material is blended can be applied on the FRP waterproof sheet 6, or the fibrous reinforcing material can be scraped off on 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, or a cloth. In this case, a fiber reinforcement is disposed on the FRP waterproof sheet 6 and a resin composition is applied thereon, or a fiber reinforcement is disposed on the resin composition applied on the FRP waterproof sheet 6 and the fiber reinforcement is provided. It is preferable to impregnate a resin composition to form a waterproof material layer 8 containing a fiber reinforcement. In the case of forming a styrene-free unsaturated polyester resin layer as the waterproof material layer 8, from the viewpoint of obtaining a resin composition that can be easily impregnated into the reinforcing material, benzyl (meth) acrylate, It is preferable to contain at least one selected from the group consisting of cyclohexyl (meth) acrylate and phenoxyethyl (meth) acrylate.

  Before the waterproof material layer 8 is provided on the FRP waterproof sheet 6, in order to ensure adhesion between the FRP waterproof sheet 6 and the waterproof material layer 8, the surface of the FRP waterproof sheet 6 is subjected to polishing treatment, primer treatment, etc. It is preferable to perform a surface treatment. When the waterproof material layer 8 is a urethane resin layer, the urethane resin layer is preferable in that the surface treatment described above can be omitted because the urethane resin layer exhibits good adhesion to the FRP waterproof sheet 6.

  The waterproof structure of one embodiment of the present invention described in detail above uses a specific FRP waterproof sheet, 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 is possible to obtain an environmentally-friendly waterproof structure with good followability with 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, and a structural unit derived from glycol containing an ether bond, and a tensile strength of 10 to 30 MPa and An unsaturated polyester resin having a tensile modulus of 700 MPa or less is contained. Therefore, this FRP waterproof sheet has good water resistance, has the strength required as a waterproof member, and can be easily constructed with sufficient flexibility even in a relatively low temperature environment. It is. In addition, if the unsaturated polyester resin has a tensile strength of 10 to 25 MPa and a tensile modulus of 600 MPa or less, it has good flexibility even in a low temperature environment such as 10 ° C. or less and further 5 ° C. or less. It is possible to obtain an FRP waterproof sheet having Therefore, this waterproof structure is suitable for use in an environment of 15 ° C. or less, and is also suitable for use in a low temperature environment of 10 ° C. or less, and further 5 ° C. or less.

  As described above, the FRP waterproof sheet is manufactured in a long form from the viewpoint of workability, cost, etc., and the long FRP waterproof sheet is formed into a product form wound in a roll shape, and has a desired dimension at the construction site. It is preferable to be cut into pieces. When using a conventional FRP sheet that is insufficiently flexible in an environment having a temperature of 15 ° C. or less in such a use mode, curling folds remain on the FRP sheet when the wound body of the FRP sheet is spread. It was difficult to construct. In addition, when the FRP sheet is attached to an adherend such as a base with an adhesive, rebounding or rewinding may occur, 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-described manner and in an environment where the temperature is relatively low. Therefore, it can be easily constructed. In addition, when the FRP waterproof sheet is attached to an adherend such as a base with an adhesive, the FRP waterproof sheet does not easily bounce or rewind, and is easy to construct.

  On the other hand, in the method (lining method) in which the resin composition containing the unsaturated polyester resin and the glass fiber is directly lined and coated on the ground or the like (lining method), it is easily affected by the skill level of the worker, and the skill level is low. May cause defects in the lining layer. In such a lining method, when the substrate has a problem such as insufficient drying, the substrate processing may take a lot of trouble. Also, in the lining method, due to the dryness and smoothness of the base, poor adhesion of the lining layer to the base may occur, or if the base cracks, the lining layer will break, causing water leakage. May be. Furthermore, when styrene is contained in the resin composition, when forming the lining layer, there is a problem that styrene is volatilized and odor is generated. On the other hand, the waterproof structure according to the embodiment of the present invention has an advantage that the problems in the lining method as described above hardly occur.

In addition, as above-mentioned, the waterproof structure of one Embodiment of this invention can take the following structures.
[1] A waterproof sheet made of 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 waterproof sheet, wherein the content of the fibrous reinforcing material in the waterproof sheet is 18 to 26% by mass, and the unsaturated polyester resin has an ether bond. Having a structural unit derived from a glycol containing and having 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, Styrene-free unsaturated polyester resin layer having a tensile strength of 10 MPa or more and a tensile elongation at break of 400% or less, measured according to the regulations, and J A waterproof structure comprising 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, which is measured in accordance with the regulations of ISA 6021-2011.
[2] The waterproof structure according to [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 [1] or [2], wherein the tensile elastic modulus of the unsaturated polyester resin in the waterproof sheet is 600 MPa or less.
[4] The waterproof structure according to any one of [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], 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 includes a foamed resin sheet.

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

  Hereinafter, although a test example is given and this invention is demonstrated further more concretely, this invention is not limited by the following test examples.

<Test Example 1: Production and evaluation of unsaturated polyester resin used for FRP waterproof sheet>
(Preparation of unsaturated polyester resin composition)
As shown in the middle part of Table 1 (unit: mass%), an unsaturated acid, a saturated acid, glycol, and styrene are blended, and a liquid unsaturated polyester resin composition (hereinafter simply referred to as “resin composition”). A1-9 were prepared. The viscosity at 25 ° C. of each prepared resin composition was measured with a BM viscometer (rotor: No. 3, rotation speed: 30 rpm) in accordance with JIS K6901-2008. The results are shown in Table 1. 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 DEG: diethylene glycol DPG: dipropylene glycol TEG: triethylene glycol

(Preparation 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 octenoate (Co: 8% by mass, Nippon Chemical Co., Ltd.) as an accelerator. 0.05 part by mass) was added and mixed. Next, after pouring a resin composition containing a curing agent and an accelerator into a space formed by sandwiching a spacer having a thickness of 3 mm between two glass plates, the resin composition is primarily cured at 80 ° C. for 30 minutes. Furthermore, secondary curing was performed under the conditions of 120 ° C. × 60 minutes to prepare a test piece (casting plate) having a thickness of about 3 mm.

(Tensile test and bending test of unsaturated polyester resin)
About each produced casting board, the tension test and the bending test were done. In the tensile test, about the test piece of No. 1 dumbbell produced from each casting plate, using a universal testing machine (manufactured by Shimadzu Corporation), the tensile strength at 23 ° C. in accordance with the provisions of JIS K6911-2006, Tensile modulus and tensile elongation at break were measured. In the bending test, a test piece having a width of 10 mm and a length of 80 mm made from each casting plate was subjected to a three-point bending test at a distance between fulcrums of 46.5 mm, and a digital force gauge (product name “FGJN-50”, Japan) The bending strength at 23 ° C. was measured using Denshin Shinpo Co., Ltd. These results are shown in Table 1.

(Hot water test of unsaturated polyester resin)
Moreover, in order to confirm water resistance and heat resistance in a shorter time using each produced casting board, the hot water test was done. Specifically, changes in the appearance of the test piece taken out from the hot water after a predetermined time had elapsed by immersing the entire 4 cm square test piece prepared from each casting plate in hot water of 98 ° C. and 80 ° C. It was confirmed. In the test using hot water at 98 ° C., the change in appearance 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, Appearance changes were confirmed after 168 hours (7 days) and after 336 hours (14 days). And the hot water resistance (water resistance and heat resistance) of each condition was evaluated according to the following evaluation criteria.
A: None of crazing, cracking, and swelling was generated on the test piece.
B: Crazing occurred in the test piece.
C1: The test piece had cracks.
C2: A swelling occurred on the test piece.
“Craze” (crack) and “crack” (crack) are respectively defined in JIS K6900-1994. “Craze” is a crack with a structure that contains voids, whereas “crack” is a cracked state with voids in the cracks, so cracks are more disruptive to products than crazes. It is said that the degree of defects is large. Further, the “fluff” represents a state where the test piece is swollen as if swollen.

<Test Example 2: Production and evaluation of FRP waterproof sheet>
The resin compositions a1, a2, a4, a7, and a8 described above were prepared, and the FRP waterproof sheets c1, c2, c4, c7, and c8 were prepared as described below for each of the prepared resin compositions. . In addition, since the physical property of the hardened | cured material (unsaturated polyester resin b3) of the resin composition a3 mentioned above is near the physical property of each hardened | cured material (unsaturated polyester resin b2 and b4) of resin composition a2 and resin composition a3. The production of the FRP waterproof sheet using was omitted. Moreover, since it was confirmed that each hardened | cured material (unsaturated polyester resin b5 and b6) of resin composition a5 and a6 mentioned above was inferior in water resistance by the hot water test, FRP waterproofing using resin composition a5 and a6 The production of the sheet was also omitted. Furthermore, since the cured product (unsaturated polyester resin b9) of the resin composition a9 described above is too hard, when an FRP waterproof sheet is prepared by blending glass fiber therein, the FRP waterproof sheet is bent and wound. The FRP waterproof sheet was also omitted because it would break.

(Preparation of FRP waterproof sheet)
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 octenoate (Co: 8% by mass) as an accelerator. , Manufactured by Nippon Kagaku Sangyo Co., Ltd.) 0.05 parts by mass, colorant (product name “Toner Gray”, manufactured by Taitai Kako Co., Ltd.), defoamer (product name “BYK A-501”, manufactured by BYK Chemie) 0.2 parts by mass was added to obtain a vacuum degassed mixture. An aluminum mold having a thickness of 1.0 mm and an inner diameter of 35 cm was pasted on a 40 cm square glass plate to prepare a mold for preparing a test piece of FRP waterproof sheet. The vacuum degassed mixture was spread uniformly in the mold of the mold. The glass fiber was sprinkled from a height of about 30 cm on the mixture in the mold and spread uniformly. Using a defoaming roller and a screw roller for FRP molding, the glass fiber was impregnated with the mixture while defoaming. Next, the top of the mixture was covered with a release film made of polyester, a rubber roller was rolled from above the release film, and smoothed while removing air bubbles. The mixture was first cured in a curing oven under conditions of 80 ° C. × 20 minutes, and then secondarily cured under conditions of 120 ° C. × 20 minutes. After air cooling, the glass plate and the release film were peeled off to obtain a thickness. An FRP waterproof sheet having a thickness of 1 mm ± 0.1 mm was obtained.

  The glass fiber is a soft type glass roving (product name “RS 240 PU-537”, manufactured by Nitto Boseki Co., Ltd.) suitable for a continuous molding method, cut to a length of 1 inch with a roving cutter ( Chopped strand) was used. Moreover, the usage-amount of glass fiber shall be the quantity used as the ratio which the content rate of the glass fiber in a FRP waterproofing sheet shows in postscript Table 2, and FRP waterproofing sheet c1, c2, c4, c7 produced using each resin composition And c8 were prepared with different glass fiber contents.

(Flexibility evaluation 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 a size of 25 mm wide × 300 mm long to prepare a test piece for flexibility evaluation. In a 25 ° C. environment, the test piece cut to the above dimensions was rolled into a ring, both ends of the test piece having a width of 25 mm were butted and fixed with an adhesive tape. The test piece in this state was placed in a thermostatic bath at a temperature of −10 ° C. and allowed to stand for 3 hours. Thereafter, 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 and the bent test piece was stretched, and the coating amount was 500 g on the base made of plywood. It was affixed with a silicone-based elastic adhesive (product name “SP-300”, manufactured by Taitai Kako Co., Ltd.) applied at / m ² . At this time, the test piece constrained by the adhesive strength of the adhesive was judged to have good flexibility since it could be said that there was no curl or its degree was small. It showed. Moreover, the test piece which was not restrained by the adhesive strength of the adhesive and bounced off from the end portion was judged to be inflexible because of the curl remaining, and “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, 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 from the results of Test Examples 1 and 2, It has been confirmed that it is possible to manufacture an FRP waterproof sheet that has both the properties and flexibility in an environment at a temperature of 15 ° C. Moreover, it was confirmed that it is more preferable to make the content rate of the fibrous reinforcement in a FRP waterproof sheet into 18-24 mass% from a viewpoint of obtaining the FRP waterproof sheet which has favorable softness | flexibility also in a low temperature environment. Furthermore, from the viewpoint of obtaining an FRP waterproof sheet having good flexibility even in a low temperature environment, the FRP waterproof sheet includes an unsaturated polyester resin having a tensile elastic modulus of 600 MPa or less, more preferably 550 MPa or less, and even more preferably 500 MPa or less. It was confirmed that it was good to use.

<Test Example 3: Production and evaluation of FRP waterproof sheet using actual machine>
(Production of FRP waterproof sheet and wound body thereof)
Next, as described below, for each of the resin compositions a1, a2, a4, and a7 described above, the glass fiber content FRP waterproof sheets c1, c2, shown in Table 3 below, by the continuous molding method described above, c4 and c7 were produced. Specifically, a first release film made of polyester was continuously fed by a transporter, and a resin composition was applied on the first release film to continuously form a resin layer. The glass roving is continuously supplied to the roller cutter disposed after the coating process of the resin composition, and the chopped strand obtained by the roller cutter is scraped off on the resin layer that is sequentially formed to form the glass fiber layer. Formed continuously. The glass fiber layer was impregnated with the resin layer (resin composition) with a roller disposed in the subsequent process, thereby forming a mixed layer containing the resin composition and the glass fiber on the first release film. A second release film made of polyester was stacked 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. Thereafter, the first release film and the second release film were peeled off, and 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 through a width dimension cutting step. And this FRP waterproofing sheet was wound up in roll shape, and the FRP waterproofing sheet winding body about 300 mm in diameter was obtained.

(Flexibility evaluation of FRP waterproof sheet)
The obtained FRP waterproof sheet wound body was allowed to stand for 24 hours in each environment at −10 ° C., 0 ° C., 5 ° C., and 15 ° C. An FRP waterproof sheet was attached to the entire surface of the film through a silicone elastic adhesive (product name “SP-300”, manufactured by Taitai Kako Co., Ltd.) applied at an application amount of 500 g / m ² . At this time, it was determined that the FRP waterproof sheet, which was held smoothly on the base due to the adhesive strength of the adhesive, had no curl or its degree was small, and therefore, it was determined that the flexibility was good. “O” (passed). Further, the FRP waterproof sheet that bounced off or peeled off from the end portion was judged to be inflexible due to the presence of curling flaws, and indicated as “x” (failed) in Table 3.

  Also from the result 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. Moreover, 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 modulus of 600 MPa or less for the FRP waterproof sheet.

<Test Example 4: Production and evaluation of waterproof material layer>
Next, for the waterproof material layer provided on the FRP waterproof sheet in the waterproof structure, plate-shaped waterproof materials d1 to 6 were produced and evaluated.

(Raw material layer raw material)
As a raw material for the waterproof materials d1 and d2, a commercially available urethane resin composition for urethane resin of high elongation type specified in JIS A 6021-2011 is used. The waterproof material d1 and the waterproof material d2 have physical properties of cured products. Different raw materials were used. As the raw materials for the waterproof materials d3 and d4, commercially available urethane resin compositions for the above-specified high-strength urethane resin were used, and the waterproof material d3 and the waterproof material d4 used raw materials having different physical properties of the cured product. . The material for the waterproofing material d5 and d6 is unsaturated polyester corresponding to the standard of “JASS 8 M-101-2007 waterproofing polyester resin” in the Architectural Institute of Japan, “Building Construction Standard Specification / Explanation JASS 8 Waterproofing Work”. A resin composition was used. The raw material for the waterproof material d5 was an unsaturated polyester resin composition not containing styrene, and the raw material for the waterproof material d6 was an unsaturated polyester resin composition containing styrene.

Specifically, the following were used as raw materials for the plate-shaped waterproofing materials d1 to d6.
Waterproof material d1: Product name “Priadec 828S” (manufactured by DIC)
Waterproof material d2: Product name “Perfect 2K Proof” (mixed with main agent: curing agent = 1: 2 (mass ratio), manufactured by Nippon Paint Co., Ltd.)
Waterproof material d3: Product name “Priadick EXP2605” (manufactured by DIC)
Waterproof material d4: Product name “GEX-201” (manufactured by Taitai Kako Co., Ltd.)
Waterproof material d5: styrene-free unsaturated polyester resin composition (benzyl methacrylate content: 40% by mass, product name “DK-776”, manufactured by Taitai Kako Co., Ltd.) Co: 8% by mass, manufactured by Nippon Kagaku Sangyo Co., Ltd.) and 0.5 parts by mass and 1.0 part by mass of the product name “328E” (manufactured by Kayaku Akzo Co., Ltd.) as an organic peroxide curing agent blend.
Waterproof material d6: unsaturated polyester resin composition containing styrene and an accelerator (styrene content: 50% by mass, product name “DK-633AP”, manufactured by Taitai Kako Co., Ltd.), methyl ethyl ketone peroxide (product) Name “Permec N” (manufactured by NOF Corporation).

(Preparation of sheet-like waterproof material)
About waterproofing material d1-4, the 2 mm-thick sill frame was installed in the circumference | surroundings of the 350 mm square glass plate, and the raw material stirred well was uniformly apply | coated in the formwork. After the applied raw material was cured at 25 ° C. for 4 days, the cured material was taken out of the mold and further cured at room temperature (25 ° C.) for 3 days to prepare plate-like waterproof materials d1 to 4 as test specimens. .
For the waterproofing materials d5 and d6, the raw material was poured into a mold formed by sandwiching a 3 mm thick spacer between two glass plates. The raw material was cured at 25 ° C. for 24 hours, and then the cured material was removed from the mold and further cured at room temperature (25 ° C.) for 3 days to prepare test sheet waterproof materials d5 and d6.

(Tensile test of sheet waterproof material)
Test pieces for tensile tests were produced from the produced waterproof sheet materials d1-6. For the sheet-shaped waterproofing materials d1 to 4, a tensile test was conducted in accordance with the provisions of JIS A6021-2011, and for the sheet-like waterproofing materials d5 and d6, a tensile test was conducted in accordance with the provisions of JIS K6911-2006. . Table 4 shows the measurement results of the tensile strength (MPa) and tensile breaking elongation (%) of each waterproof sheet.

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

(Hot water test of sheet waterproofing material)
In order to confirm water resistance and heat resistance in a shorter time using the produced waterproof sheet materials d1 to d6, a hot water test was performed. Specifically, 4 cm square test pieces were produced from the test specimens for each of the sheet-shaped waterproofing materials d1 to d6. And the whole test piece was immersed in hot water of 80 degreeC and hot water of 98 degreeC, and the external appearance change of the test piece taken out from hot water after predetermined time progress was confirmed. In the test using hot water at 80 ° C., the appearance change after 100 hours and 168 hours (7 days) after the test piece was immersed was confirmed. 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. And according to the following evaluation criteria, the hot water resistance (water resistance and heat resistance) of each condition was evaluated, and in this test example, the evaluation was A. The evaluation results are shown in Table 4.
A: Neither cracking, swelling, swelling, nor dissolution occurred in the test piece.
C1: Dandruff occurred on the test piece.
C2: The test piece was swollen.
C3: The test piece was partially dissolved.

  From the results of Test Example 4, as an environmentally friendly waterproof material layer having good water resistance and heat resistance, 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. It was confirmed that (waterproof material d5) and a urethane resin layer (waterproof material d3) can be used.

<Test Example 5: Production and evaluation of 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 having a glass fiber content of 22% by mass obtained in Test Example 2 was used as the FRP waterproof sheet. For the waterproof material layer, the respective raw materials of the plate-like waterproof materials d1, d3, d5, and d6 prepared in Test Example 4 are used, and the waterproof material layer is formed on the FRP waterproof sheet as follows and laminated. Things e1-7 were produced.

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

(Preparation of laminate e2)
In the production of the laminate e1, the glass cloth (product name “WF230”, manufactured by Nitto Boseki Co., Ltd.) is placed on the entire surface in the mold, and then the waterproof material d1 is applied as a raw material. A laminate e2 of the test specimen was obtained by the same method as the production of the laminate e1.

(Preparation of laminate e3)
A laminate e3 of a test specimen was obtained by the same method as that for the laminate e1, except that the raw material for the waterproof material d1 used in the production of the laminate e1 was changed to the raw material for the waterproof material d3.

(Preparation of laminate e4)
In the production of the laminate e1, the glass cloth (product name “WF230”, manufactured by Nitto Boseki Co., Ltd.) is placed on the entire surface in the mold, and then the waterproof material d3 is applied as a raw material. By a method similar to the production of the laminate e1, a laminate e4 of the test body was obtained.

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

(Preparation of laminate e6)
As a surface treatment, a one-component moisture-curing MDI urethane resin primer (product name “Compak K”, manufactured by Taitai Kako Co., Ltd.) is applied to the entire surface of the 300 mm square FRP waterproof sheet on which the waterproof material layer is provided. It was dried for 1 hour and cured. After uniformly applying 100 g of the waterproof material d5 on the surface of the 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 material was soaked into the mat using a roller. Further, 60 g of the waterproof material d5 was applied thereon, defoamed and impregnated with an impregnation roller, and finally smoothed with a metal roller. Then, after curing for 7 days at 25 ° C., a laminate e6 of the test specimen was obtained.

(Preparation of laminate e7)
A test specimen laminate e7 was obtained in the same manner as in the production of the laminate e6 except that 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 reinforcements was prepared without using the FRP waterproof sheet. Specifically, 100 g of waterproof material d6 is uniformly applied to a 300 mm square glass plate, and then a glass chopped strand mat (product name “ECM450”, manufactured by Central Glass Co., Ltd.) is applied to the entire surface of the applied material. The material was soaked into the mat using an impregnation roller. Further, 120 g of the waterproof material d6 is applied thereon, and another mat is placed, defoamed and impregnated with an impregnation roller, and then 60 g of the waterproof material d6 is uniformly applied. Smoothed with a metal roller. Then, after curing for 7 days at 25 ° C., a laminate e8 of the test specimen was obtained.

(Laminate tensile test)
With respect to the obtained laminates e1 to 8, a test piece was collected from the laminated portion of each layer and subjected to a tensile test in accordance with the provisions of JIS K6911-2006, and the tensile strength (MPa) and tensile elongation at break (%) were obtained. It was measured. The results are shown in Table 5.

(Hot water test of laminate)
About the produced laminates e1-8, a 4 cm square test piece was collected from the laminated portion of each layer, and a hot water test was performed using the same method and evaluation criteria as the above-mentioned “hot water test for sheet waterproofing material”. The hot water resistance (water resistance and heat resistance) was evaluated. The conditions of 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 a laminate obtained by combining an FRP waterproof sheet having good hot water resistance and flexibility and an environmentally friendly waterproof material layer having good hot water resistance also shows good hot water resistance. (See laminates e3-6).

<Test Example 6: Production and evaluation of waterproof structure>
Finally, using a FRP waterproof sheet with excellent hot water resistance and flexibility, and a waterproof material layer with excellent hot water resistance, etc., a waterproof structure is produced, and a test to confirm the followability of the waterproof structure with respect to the ground is performed. It was. FIG. 2 is a schematic diagram for explaining the test method.

(Preparation of waterproof structure f1-3)
First, a 3 mm thick polyethylene foam material (tensile elongation at break 110%, foaming ratio 30 times) was used as an elastic buffer layer on the FRP waterproof sheet c2 having a glass fiber content of 22% by mass obtained in Test Example 2. ) Were bonded with a urethane adhesive to produce a composite waterproof sheet.
A modified silicone adhesive (product name “SP-300”, manufactured by Taitai Kako Co., Ltd.) having a tensile elongation at break of 70% is applied to the entire surface of a 300 mm square slag gypsum plate as a base, and the above A composite waterproof sheet was bonded by pressure. 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 urethane resin primer (product name “Compak K”, manufactured by Taitai Kako Co., Ltd.) is applied to the surface of the FRP waterproof sheet in the composite waterproof sheet. Dried. A waterproof material layer having the specifications shown in Table 6 was formed on the surface-treated FRP waterproof sheet, and waterproof structures f1 to 3 were produced. The waterproof material layer was formed in accordance with the method for producing a laminate described in Test Example 5 as the conditions of the waterproof material shown in Table 6 and the amount of the waterproof material used and the number of used glass chopped strand mats.

(Production of waterproof structure f4)
As a surface treatment, 10g of 1-component moisture-curing MDI urethane resin primer (product name "Compak K", manufactured by Taitai Kako Co., Ltd.) is applied to the entire surface of the 300mm square slag gypsum board as the base and dried. I let you. A waterproofing material layer was formed on the surface-treated substrate to produce a waterproof structure f4. The waterproof material layer was formed in accordance with the method for producing the laminate e8 described in Test Example 5 as the conditions of the waterproof material shown in Table 6, the amount of the waterproof material used, and the number of used glass chopped strand mats.

(Evaluation test of followability with the ground)
The produced waterproof structure was cured at 25 ° C. for 3 days. Then, as shown in FIG. 2, the waterproof structure (f1-4) provided on the slag gypsum board (G) and the slag gypsum board (G) was cut into a dimension of width 50 mm × length 160 mm. The slag gypsum board (G) extends in the thickness direction from the back side of the slag gypsum board (G) over the entire width of the center position (position of length 80 mm from the end) in the length direction of the cut waterproof structure (f1 to 4). A cut was made with a blade for the thickness, and a cut part (G1) having a width of about 2 mm was formed.
Separately, 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 as evaluation jigs, and the side surfaces of the two steel plates (S) were butted together. The butted portion (S1) of the two steel plates (S) was processed so as not to have a gap, and the surface of the steel plate (S) was polished. Moreover, the steel plate (S) used what the through-hole (not shown) for attaching to the holding tool of a tensile tester was formed.
A waterproof structure (f1, f2, f3 or f4) is provided on the jig so that the cut part (G1) of the slag gypsum plate (G) is aligned with the abutting part (S1) of the jig. The obtained slag gypsum board (G) was bonded with an adhesive (not shown). Thus, the test body (T) for followability evaluation was obtained.

  A specimen (T) is attached to a tensile tester, and cured along the length direction of the specimen (T) (see the arrow in FIG. 2B) under the conditions of a test temperature of 23 ± 2 ° C. and a tensile speed of 1 mm / min. I pulled the tool. When this tensile test is performed, a gap is gradually formed in the butt portion (S1) of the two steel plates (S) and the steel plates (S) move in a direction away from each other, and accordingly, the two steel plates (S) are bonded to the steel plate (S). The slag gypsum plate (G) also moves so that the gap between the cut portions (G1) increases. And the clearance gap width | variety of both the steel plates when the fracture | rupture of members, such as an elastic buffer layer in a waterproof structure, or peeling with a foundation | substrate produced was measured. Three test specimens were prepared for each waterproof structure, and the average value of the measurement results of the three gap widths was obtained, and this was used as the base following width. The larger the background tracking width is, the harder it is to peel off or break the waterproof structure, and the better the tracking performance with the base. Table 6 shows the base following width and the state of breakage or peeling.

  From the results of Test Example 6, by using an FRP waterproof sheet with good hot water resistance and flexibility, and an environmentally friendly waterproof material layer with good hot water resistance, It was confirmed that a waterproof structure was obtained (see waterproof structures f1 and f2).

DESCRIPTION OF SYMBOLS 1 Waterproof structure 2 Base 4 Elastic buffer layer 6 Waterproof sheet 8 Waterproof material layer 46 Composite waterproof sheet

Claims (8)

An elastic buffer layer provided on a base to be waterproofed;
A waterproof sheet made of a 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,
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 a 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 layer is 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, as measured in accordance with the above rules, and the rules of JIS A6021-2011. A waterproof structure comprising 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, measured in accordance with the above.   The waterproof structure according to claim 1, wherein a 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 tensile elastic modulus of the unsaturated polyester resin in the waterproof sheet is 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 claim 1, 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. A step of providing an elastic buffer layer on a base to be waterproofed;
Providing a waterproof sheet made of fiber-reinforced plastic containing an unsaturated polyester resin and a fibrous reinforcing material on the elastic buffer layer;
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 a 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 layer is 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, as measured in accordance with the above rules, and the rules of JIS A6021-2011. A method for producing a waterproof structure, comprising at least one urethane resin layer having a tensile strength of 10 MPa or more and a tensile elongation at break of 400% or less, measured in accordance with the above.   A step of providing the elastic buffer layer on the base by providing the composite waterproof sheet in which the elastic buffer layer and the waterproof sheet are bonded together on the base with the elastic buffer layer side as the base side; and The manufacturing method of the waterproof structure of Claim 7 which performs the process of providing the said waterproof sheet on the said elastic buffer layer.

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