Waterproofing methods, waterproofing layers for floor slabs, laminates and structures

Abstract

To provide a waterproofing method that can suppress the occurrence of blistering between the waterproofing layer and the adhesive layer formed on top of it, as well as within the adhesive layer, and that exhibits excellent adhesive strength between the layers. [Solution] A waterproofing method comprising forming a waterproof layer on a substrate and then forming an adhesive layer on the waterproof layer, wherein the waterproof layer is formed by applying a two-component waterproofing material to the substrate, the material comprising a first agent containing a compound having an isocyanate group and a second agent containing a compound having an active hydrogen-containing group, and the molar ratio of the isocyanate group to the active hydrogen-containing group is 0.75 or more and 0.95 or less.

Description

[Technical Field]

[0001] This invention relates to a waterproofing method, a waterproofing layer for a floor slab, a laminate, and a structure. [Background technology]

[0002] On concrete decks used in road bridges and other structures, a waterproof layer is sometimes formed prior to the formation of the asphalt layer to prevent rainwater and snowmelt that seep through the asphalt layer from directly contacting the deck or penetrating into the deck. Furthermore, a layer of adhesive may be provided between the waterproof layer and the asphalt layer to enhance their adhesion. One method for forming a waterproof layer is to form a coating of waterproofing material such as polyurethane resin or polyurea resin (Patent Documents 1-3). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2003-49445 [Patent Document 2] Japanese Patent Publication No. 2003-166209 [Patent Document 3] Japanese Patent Publication No. 2014-95284 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, according to the inventor's research, conventional methods can cause blistering between the waterproofing coating and the adhesive layer formed on top of it, or within the adhesive layer itself. When blistering occurs, the adhesive strength between the layers decreases, reducing the waterproofing performance and thus the durability of the structure.

[0005] The present invention provides a waterproofing method that can suppress the occurrence of blistering between the waterproofing layer and the adhesive layer formed thereon, as well as within the adhesive layer, and that exhibits excellent adhesive strength between the layers; a waterproofing layer for floor slabs that can suppress the occurrence of blistering between the waterproofing layer and the adhesive layer formed thereon, as well as a laminate and structure using the same. [Means for solving the problem]

[0006] The present invention has the following aspects. [1] A waterproofing method comprising forming a waterproof layer on a substrate, and then forming an adhesive layer on the waterproof layer, A waterproofing method wherein the waterproof layer is formed by applying a two-component waterproofing material, comprising a first agent containing a compound having an isocyanate group and a second agent containing a compound having an active hydrogen-containing group, onto the substrate, and the molar ratio of the isocyanate group to the active hydrogen-containing group is 0.75 or more and 0.95 or less. [2] The waterproofing method according to [1], wherein the first agent comprises an isocyanate group-terminated prepolymer obtained by reacting a polyol with a polyisocyanate. [3] The waterproofing method according to [2], wherein the polyisocyanate comprises at least one selected from the group consisting of aliphatic polyisocyanates, aromatic polyisocyanates, alicyclic polyisocyanates, and modified forms thereof. [4] The waterproofing method according to any one of [1] to [3], wherein the compound having the active hydrogen group comprises at least one selected from the group consisting of polyols and polyamines. [5] The waterproofing method according to any one of [1] to [4], wherein the adhesive comprises asphalt and a thermoplastic resin. [6] The waterproofing method according to [5], wherein the proportion of the thermoplastic resin is 1 to 90 parts by mass per 100 parts by mass of asphalt. [7] The waterproofing method according to any one of [1] to [6], wherein the two-component waterproofing material is applied by spraying. [8] A waterproofing method according to any one of [1] to [7], wherein an asphalt layer is further formed on the layer of adhesive. [9] A waterproofing method according to any one of [1] to [8], wherein a primer layer is formed on the substrate before forming the waterproofing layer.

[10] The waterproofing method according to any one of [1] to [9], wherein the thickness of the waterproofing layer is 0.5 mm to 5.0 mm.

[11] The waterproofing method according to any one of [1] to

[10] , wherein the thickness of the adhesive layer is 0.5 mm to 5.0 mm.

[12] The waterproofing method according to any one of [1] to

[11] , wherein the base material is a floor slab.

[13] A waterproof layer for a deck slab, A waterproof coating for floor slabs, comprising a two-component waterproofing material comprising a first agent containing a compound having an isocyanate group and a second agent containing a compound having an active hydrogen-containing group, wherein the molar ratio of the isocyanate group to the active hydrogen-containing group is 0.75 or more and 0.95 or less.

[14] The waterproof layer for floor slabs according to

[13] , wherein the first agent comprises an isocyanate-terminated prepolymer obtained by reacting a polyol with a polyisocyanate.

[15] The waterproof layer for a floor slab according to

[14] , wherein the polyisocyanate comprises at least one selected from the group consisting of aliphatic polyisocyanates, aromatic polyisocyanates, alicyclic polyisocyanates, and modified forms thereof.

[16] The waterproof layer for a floor slab according to any one of

[13] to

[15] , wherein the compound having the active hydrogen group comprises at least one selected from the group consisting of polyols and polyamines. A laminate comprising a waterproofing layer for floor slabs as described in any of

[17] ,

[13] , to

[16] , and a layer of adhesive.

[18] The laminate according to

[17] , wherein the adhesive comprises asphalt and a thermoplastic resin.

[19] The laminate according to

[18] , wherein the proportion of the thermoplastic resin is 1 to 90 parts by mass per 100 parts by mass of asphalt.

[20] A laminate according to any one of

[17] to

[19] , further comprising an asphalt layer.

[21] The laminate according to any one of

[17] to

[20] , wherein the thickness of the waterproof layer for the floor slab is 0.5 mm to 5.0 mm.

[22] The laminate according to any one of

[17] to

[21] , wherein the thickness of the layer of the adhesive material is 0.5 mm to 5.0 mm.

[23] A structure including a floor slab and the laminate according to any one of

[17] to

[22] .

Advantages of the Invention

[0007] According to the present invention, there are provided a waterproofing method capable of suppressing the occurrence of blisters between the waterproof layer and the layer of the adhesive material formed thereon and within the layer of the adhesive material, and exhibiting excellent adhesive strength between the layers; a waterproof layer for a floor slab capable of suppressing the occurrence of blisters between the layer of the adhesive material formed thereon and within the layer of the adhesive material, and exhibiting excellent adhesive strength between the layers; a laminate using the same; and a structure.

Brief Description of the Drawings

[0008] [Figure 1] It is a process diagram showing an example of the waterproofing method. [Figure 2] It is a cross-sectional view showing an example of the structure.

Embodiments for Carrying Out the Invention

[0009] In this specification, the number average molecular weight is the polystyrene-reduced molecular weight obtained by measurement using gel permeation chromatography (GPC) with a calibration curve prepared using standard polystyrene with a known molecular weight. The viscosity is measured by a B-type viscometer. "~" indicating a numerical range means including the numerical values described before and after it as the lower limit value and the upper limit value. Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the scales of each part in the drawings may be different from the actual ones for convenience of explanation.

[0010] 〔Waterproofing Method〕 As shown in FIG. 1, the waterproofing method according to an embodiment of the present invention has the following steps (a), (b), (c), and (d). Step (a): A step of forming a primer layer 2 on a base material 1. Step (b): A step of forming a waterproof layer 3 on a substrate 1 on which a primer layer 2 has been formed. Step (c): A step of forming an adhesive layer 4 on a substrate 1 on which a primer layer 2 and a waterproof layer 3 have been formed. Step (d): A step of forming an asphalt layer 5 on a substrate 1 on which a primer layer 2, a waterproof layer 3, and an adhesive layer 4 have been formed. As a result, a laminate is constructed on the substrate 1 in which a primer layer 2, a waterproofing layer 3, an adhesive layer 4, and an asphalt layer 5 are sequentially layered. Steps (a), (c), and (d) are not necessarily required. For example, step (a) may be omitted, and in step (b), the waterproof layer 3 may be formed on the substrate 1 on which the primer layer 2 has not been formed.

[0011] <Base material> The base material 1 is preferably one on which a waterproof layer is to be constructed, such as a deck slab. The deck slab may be any type of deck slab used in road bridges, such as concrete deck slabs, prestressed concrete (PC) deck slabs, or steel deck slabs. However, the base material to which the waterproofing method of this embodiment is applied is not limited to deck slabs.

[0012] <Process (a)> The primer layer 2 can be formed by applying a primer onto the substrate 1. Any primer that can adequately bond the substrate 1 and the waterproof layer 3 is acceptable, and examples include epoxy resin primers, urea resin primers, and urethane resin primers. The method of applying the primer is not particularly limited, and any known application method can be used.

[0013] <Process (b)> The waterproof layer 3 is formed by applying a two-component waterproofing material onto the substrate 1, the material comprising a first agent containing a compound having an isocyanate group (hereinafter also referred to as an isocyanate compound) and a second agent containing a compound having an active hydrogen-containing group (hereinafter also referred to as an active hydrogen compound). In other words, the waterproof layer 3 is a coating film of a two-component waterproofing material. The coating film constituting the waterproof layer 3 may consist of one layer or two or more layers.

[0014] The first component, an isocyanate compound, functions as the main component of the two-component waterproofing material. Isocyanate compounds typically have two or more isocyanate groups. As for the isocyanate compound, isocyanate-terminated prepolymers obtained by reacting a polyol with a polyisocyanate are preferred from the viewpoint of the reactivity of the main component and storage stability.

[0015] Examples of polyols that constitute the isocyanate group-terminated prepolymers include those similar to the polyols used in the active hydrogen-containing compounds described later. As for the polyol, polyether polyols obtained by addition polymerization of propylene oxide or propylene oxide and ethylene oxide to an initiator having two or three active hydrogen atoms per molecule are preferred, as they allow for lower viscosity and ensure flexibility of the prepolymer. The number average molecular weight of the polyether polyol is preferably 800 to 8,000, and more preferably 1,000 to 5,000. One type of polyol may be used, or two or more types may be used in combination.

[0016] Polyisocyanates that constitute the isocyanate-terminated prepolymer include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, lysine diisocyanate, and 2-methylpentane-1,5-diisocyanate. Aliphatic polyisocyanates such as 3-methylpentane-1,5-diisocyanate; tolylene diisocyanate (TDI), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, polymethylene polyphenylene polyisocyanate, xylylene Examples include aromatic polyisocyanates such as isocyanate (XDI), α,α,α',α'-tetramethylxylylene diisocyanate, 4,4'-dibenzyle diisocyanate, tolidine diisocyanate, and 1,5-naphthalene diisocyanate; alicyclic polyisocyanates such as norbornane diisocyanate (NBDI), isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexyl diisocyanate, 1,3-bis(isocyanate-methyl)cyclohexane, and dicyclohexylmethane diisocyanate (H12MDI); aromatic aliphatic polyisocyanates such as dialkyldiphenylmethane diisocyanate and tetraalkyldiphenylmethane diisocyanate, and modified versions of these polyisocyanates. Examples of modified compounds include biuret modified compounds, isocyanurate modified compounds, adduct modified compounds (e.g., trimethylolpropane adducts), allophanate modified compounds, uretdione modified compounds, and carbodiimide modified compounds. The polyisocyanate is preferably at least one selected from the group consisting of aliphatic polyisocyanates, aromatic polyisocyanates, alicyclic polyisocyanates, and modified forms of these polyisocyanates. Examples of these modified forms of polyisocyanates are the same as those described above. Among these, aromatic polyisocyanates are preferred in that they can impart mechanical strength and rapid curing properties to the waterproofing material, and XDI and MDI are more preferred in that they shorten the curing time and thus shorten the construction period. One type of polyisocyanate may be used, or two or more types may be used in combination.

[0017] When synthesizing isocyanate-terminated prepolymers by reacting a polyol with a polyisocyanate, the molar ratio of NCO / OH is preferably 1.1 to 100, more preferably 4 to 50. For XDI, 4 to 15 is even more preferable. For MDI, 10 to 50 is even more preferable. The NCO group content is preferably 1.0 to 50% by mass relative to the total mass of the isocyanate-terminated prepolymer. For XDI, 1.0 to 45% by mass is more preferred, and 5 to 20% by mass is even more preferred. For MDI, 1.0 to 34% by mass is more preferred, and 5 to 20% by mass is even more preferred. The number-average molecular weight of the isocyanate-terminated prepolymer is preferably 1,000 to 10,000, and more preferably 1,500 to 5,000. The isocyanate-terminated prepolymer is preferably liquid at 23°C. The viscosity of the liquid isocyanate-terminated prepolymer at 23°C is preferably 10,000 mPa·s or less, and more preferably 5,000 mPa·s or less. The lower limit of the viscosity is not particularly limited, but for example, it is 300 mPa·s. When the viscosity is below the upper limit, the spraying temperature of the first and second components becomes lower, making it easier to apply by spraying.

[0018] The second active hydrogen compound functions as a curing agent. The number of active hydrogen-containing groups in an active hydrogen compound is typically two or more. An active hydrogen-containing group is a group containing a hydrogen atom that can react with an isocyanate group. Examples include hydroxyl groups, carboxyl groups, amino groups, monovalent functional groups obtained by removing one hydrogen atom from a primary amine, and mercapto groups, all of which are bonded to a carbon atom. Amino groups and hydroxyl groups are preferred as active hydrogen-containing groups. An active hydrogen compound may have two or more active hydrogen-containing groups. As the active hydrogen compound used in the second agent, at least one selected from the group consisting of polyols and polyamines is preferred because it can react stably with the isocyanate group.

[0019] The polyol is not particularly limited as long as it has two or more hydroxyl groups, but examples include polyether polyols, polyester polyols, polytetramethylene glycol, dipropylene glycol, diethylene glycol, 1,4-butanediol, propylene glycol, ethylene glycol, and flame-retardant polyols (e.g., phosphorus-containing polyols). These may be used individually or in combination of two or more.

[0020] As for the polyol, a polyether polyol (hereinafter also referred to as polyether polyol A) obtained by addition polymerization of propylene oxide or propylene oxide and ethylene oxide to an initiator having two or three active hydrogen atoms in one molecule is preferred in order to ensure the flexibility of the waterproofing material. The number average molecular weight of polyether polyol A is preferably 800 to 8,000, and more preferably 1,000 to 5,000.

[0021] Polyether polyol A may be used in combination with other polyols. By using other polyols in combination, the physical properties of the isocyanate-terminated prepolymer (viscosity, isocyanate content, NCO / OH molar ratio, etc.) can be adjusted. Other polyols preferred include diols with a molecular weight of 500 or less (hereinafter also referred to as short-chain diols), as they can improve the mechanical strength of the waterproofing material. The lower limit of the molecular weight of short-chain diols is not particularly limited, but is, for example, 62. Examples of short-chain diols include dipropylene glycol, diethylene glycol, 1,4-butanediol, propylene glycol, and ethylene glycol. The mass ratio of polyether polyol A to short-chain polyol (polyether polyol A / short-chain polyol) is preferably 100 / 0 to 20 / 80, and more preferably 99 / 1 to 50 / 50.

[0022] The polyamine is not particularly limited as long as it has two or more amino groups, but examples include aromatic polyamines and aliphatic polyamines. Specifically, examples include diethyltoluenediamine, dimethylthiotoluenediamine, 4,4'-methylenebis(N-(1-methylpropyl)aniline), diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, dialkyl-4,4'-methylenedianiline, tetraalkyl-4,4'-methylenedianiline, 4,4'-methylenebis(2-chloroaniline), 4,4'-methylenebis(3-chloro-2,6-diethylaniline), bis(methylthio)toluenediamine, metaxylylenediamine, ethylenediamine, polyoxyalkylenediamine, isophoronediamine, etc. These may be used individually or in combination of two or more. As for the polyamine, aromatic polyamines are preferred in that they can impart mechanical strength to the waterproofing material, and diethyltoluenediamine, dimethylthiotoluenediamine, 4,4'-methylenebis(N-(1-methylpropyl)aniline), diaminodiphenylmethane, and 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane are more preferred.

[0023] When polyamines are used as the active hydrogen compounds, urea bonds are formed by the reaction between the isocyanate compound and the active hydrogen compound. When polyols are used, urethane bonds are formed by the reaction between the isocyanate compound and the active hydrogen compound. When a waterproofing layer contains urea bonds, it tends to have superior mechanical strength compared to when it does not. Therefore, it is preferable that the active hydrogen compound contains a polyamine, and more preferably a polyamine alone, or a mixture of a polyol and a polyamine. When the active hydrogen compound contains a polyamine, the polyamine content is preferably 50 to 500, and more preferably 100 to 400, when converted to the amine value of the second agent. The amine value represents the amount of perchloric acid and the equivalent amount of potassium hydroxide (in mg) required to neutralize all basic nitrogen contained in 1 g of sample, and is measured in accordance with JIS K 7237. The mass ratio of polyol to polyamine (polyol / polyamine) is preferably 100 / 0 to 0 / 100, and more preferably 90 / 10 to 0 / 100.

[0024] In a two-component waterproofing material, the molar ratio of isocyanate groups of the isocyanate compound to the active hydrogen-containing groups of the active hydrogen compound (hereinafter also referred to as the NCO ratio) is 0.75 or more and 0.95 or less, and preferably 0.80 or more and 0.95 or less. A NCO ratio of 0.75 or higher suppresses the retention of large amounts of unreacted active hydrogen compounds in the waterproofing layer 3, improving the durability of the waterproofing layer 3 and the adhesion between the waterproofing layer 3 and the layers formed on top of it (adhesive layer 4, asphalt layer 5). If large amounts of unreacted active hydrogen compounds remain in the coating, there is a risk of reduced coating strength and bleeding. When the NCO ratio is 0.95 or less, the residual isocyanate groups in the waterproof layer 3 can be suppressed, and the occurrence of blistering between the waterproof layer 3 and the adhesive layer 4, as well as within the adhesive layer 4, can be suppressed. By suppressing the occurrence of blistering, which is a cause of poor adhesion, the adhesive strength between the waterproof layer 3 and the layer formed on top of it is improved.

[0025] The two-component waterproofing material may further contain other components besides isocyanate compounds and active hydrogen compounds, if necessary. Other components that can be used include those known as additives for waterproofing materials, such as curing catalysts (lead octoate, etc.), weather stabilizers, defoamers, plasticizers, flame retardants, silane coupling agents, dispersants, and pigments. These may be used individually or in combination of two or more. Other ingredients may be included in the first agent, the second agent, or both.

[0026] A known method can be used for applying the two-component waterproofing material. Since a curing reaction proceeds rapidly when the isocyanate compound of the first component and the active hydrogen compound of the second component come into contact, the first and second components are usually mixed immediately before application. For two-component waterproofing materials, spray application is preferred due to the rapid curing properties achieved by heating the material. In the spray application method, the first and second components are mixed using a special machine and sprayed onto the application surface. The amount of two-component waterproofing material to be applied can be appropriately set according to the thickness of the waterproof layer 3 to be formed, for example, 0.5 to 6.0 kg / m 2 That is the case. After applying the two-component waterproofing material, curing may be performed as needed. Curing conditions include, for example, 0 to 40°C for 4 to 48 hours.

[0027] The thickness of the waterproof layer 3 is preferably 0.5 to 5.0 mm, and more preferably 1.0 to 3.0 mm. If the thickness of the waterproof layer 3 is above the lower limit, the waterproof performance is excellent. If the thickness of the waterproof layer 3 is below the upper limit, the cost-effectiveness is excellent.

[0028] <Process (c)> The adhesive layer 4 can be formed by applying the adhesive onto the waterproof layer 3. As an adhesive, an adhesive containing asphalt and thermoplastic resin (hereinafter also referred to as an asphalt-based adhesive) is preferred because it provides excellent adhesion between the waterproof layer 3 and the asphalt layer 5. The adhesive can be appropriately changed depending on the layer provided on top of the adhesive layer 4.

[0029] Any type of asphalt may be used, but it is preferable to use one that has good affinity with the asphalt contained in the asphalt mixture forming the asphalt layer 5. For example, straight asphalt, artificial asphalt, or a mixture of both is preferred. Artificial asphalt is a mixture of petroleum resin and oil in a mass ratio of petroleum resin:oil = 80:20 to 20:80, preferably 50:50. Examples of oils include aromatic oils, naphthenic oils, and paraffinic oils. Examples of petroleum resins include aromatic, aliphatic, aliphatic aromatic, coumarone, indene, styrene, coumarone-indene-styrene, alicyclic, terpene, terpene phenol, and rosin-based petroleum resins.

[0030] Examples of thermoplastic resins include SEBS (styrene-ethylene-butylene-styrene block copolymer), SBS (styrene-butadiene block copolymer), SBR (styrene-butadiene rubber), SEPS (styrene-ethylene-propylene-styrene block copolymer), EVA (ethylene-vinyl acetate copolymer), PE (polyethylene), EPDM (ethylene-propylene-diene terpolymer), TPU (thermoplastic polyurethane), and PA (polyamide). These can be used individually or in combination of two or more. At least a portion of the thermoplastic resin contained in the asphalt-based adhesive may have functional groups that can react with active hydrogen groups (hereinafter also referred to as reactive functional groups). When the thermoplastic resin has reactive functional groups, the reactive functional groups react with unreacted active hydrogen groups in the waterproof layer 3, thereby increasing the adhesive strength between the waterproof layer 3 and the adhesive layer 4. Examples of reactive functional groups include epoxy groups and carboxyl groups.

[0031] In asphalt-based adhesives, the ratio of thermoplastic resin to 100 parts by mass of asphalt is preferably 1 to 90 parts by mass, and more preferably 1 to 40 parts by mass. When the ratio of thermoplastic resin is above the lower limit, the adhesive strength between the waterproof layer 3 and the layer formed thereon is excellent, and when it is below the upper limit, the application workability is excellent.

[0032] As for the method of applying the adhesive, known methods such as brush application can be used. The amount of adhesive to be applied can be appropriately set according to the thickness of the adhesive layer 4 to be formed, for example, 0.5 to 5.0 kg / m 2 That is the case. After applying the adhesive, curing may be performed as needed. Curing conditions include, for example, 0 to 40°C for 1 to 48 hours.

[0033] The thickness of the adhesive layer 4 is preferably 0.5 to 5.0 mm, and more preferably 1.0 to 3.0 mm. If the thickness of the adhesive layer 4 is greater than or equal to the lower limit, the adhesive strength between the waterproof layer 3 and the layer formed on top of it is improved. If the thickness of the adhesive layer 4 is less than or equal to the upper limit, the adhesive strength between the waterproof layer 3 and the layer formed on top of it, and the flow resistance (resistance to plastic deformation due to traffic load) of the asphalt mixture formed on top of layer 4 are excellent.

[0034] After the formation of the adhesive layer 4, and before forming the asphalt layer 5 in the next step, sand such as silica sand may be scattered on top of the adhesive layer 4.

[0035] <Process (d)> The asphalt layer 5 can be formed by laying an asphalt mixture on top of the adhesive layer 4. Asphalt mixtures typically consist of asphalt and aggregate. Any asphalt mixture can be used as long as it hardens to form an asphalt pavement, and any type of asphalt mixture, such as dense-graded or open-graded, can be used. A heat-activated asphalt mixture is preferred because it heat-welds with the asphalt components contained in layer 4 of the adhesive. The method of paving the asphalt mixture is not particularly limited, and known paving methods can be adopted depending on the asphalt mixture used. The thickness of the asphalt layer 5 is, for example, 30 to 50 mm.

[0036] According to the waterproofing method of this embodiment, the waterproofing layer 3 is formed by applying a two-component waterproofing material having a first agent containing an isocyanate compound and a second agent containing an active hydrogen compound. Since the molar ratio (NCO ratio) of isocyanate groups of the isocyanate compound to the active hydrogen-containing groups of the active hydrogen compound is 0.75 or more and 0.95 or less, the occurrence of blistering between the waterproofing layer 3 and the adhesive layer 4 formed on top of it, and within the adhesive layer 4, can be suppressed. By suppressing the occurrence of blistering, which is a cause of poor adhesion, the adhesive strength between the waterproofing layer 3 and the layer formed on top of it is improved, and a structure with excellent physical properties such as tensile strength and shear strength can be formed. If even a small amount of isocyanate groups from the isocyanate compound remain in the waterproof layer 3, these groups will react with the adhesive layer 4 during or after its formation, generating gas and causing the blistering described above. By keeping the NCO ratio of the waterproofing material to 0.95 or less, the remaining isocyanate groups in the waterproof layer 3 can be suppressed, thereby preventing the occurrence of the blistering described above.

[0037] [Structure] As shown in Figure 2, a structure 10 according to one embodiment of the present invention comprises a floor slab 1A and a laminate 6. The laminate 6 is provided on top of the floor slab 1A. The laminate 6 includes, in order from the floor slab 1A side, a primer layer 2, a waterproof layer 3A for the floor slab, an adhesive layer 4, and an asphalt layer 5.

[0038] As for the floor slab 1A, the same type as the floor slab listed in base material 1 can be used. The primer layer 2, the waterproofing layer 3A for the deck slab, the adhesive layer 4, and the asphalt layer 5 are the same as the primer layer 2, waterproofing layer 3, adhesive layer 4, and asphalt layer 5 described above.

[0039] According to the structure of this embodiment, the waterproof layer 3A for the deck slab is a coating film formed from a two-component waterproofing material having a first agent containing an isocyanate compound and a second agent containing an active hydrogen compound. The molar ratio (NCO ratio) of isocyanate groups of the isocyanate compound to the active hydrogen-containing groups of the active hydrogen compound is 0.75 or more and 0.95 or less. Therefore, the occurrence of blistering between the waterproof layer 3A for the deck slab and the adhesive layer 4 formed thereon, and within the adhesive layer 4, can be suppressed. By suppressing the occurrence of blistering, which causes poor adhesion, the adhesive strength between the waterproof layer 3A for the deck slab and the layer formed thereon is improved, and the structure 10 becomes superior in physical properties such as tensile strength and shear strength.

[0040] Although embodiments of the present invention have been described above, the configurations and combinations thereof in the above embodiments are merely examples, and additions, omissions, substitutions, and other modifications to the configurations are possible without departing from the spirit of the present invention.

[0041] For example, in the laminate 6, the primer layer 2 and the asphalt layer 5 are not essential and may be omitted. The laminate 6 may further include other layers besides the primer layer 2, the waterproof layer 3A for the floor slab, the adhesive layer 4, and the asphalt layer 5. The surface of the base material 1 or the floor slab 1A does not have to be flat. For example, it may have a railing, as shown in Figure 2 of Japanese Patent Publication No. 2014-95284. [Examples]

[0042] The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. "Parts" means "parts by mass". Examples 4-8 and 14-20 are examples, and Examples 1-3 and 9-13 are comparative examples.

[0043] (Asphalt mixture) Crushed stone mastic asphalt (SMA) was used as the asphalt mixture. The composition of SMA is shown in Table 1.

[0044] [Table 1]

[0045] (First drug) For the first agent, we used agents 1 to 4 synthesized in the following synthesis examples 1 to 4.

[0046] <Synthesis Example 1: Agent 1> In a reaction vessel equipped with a stirrer, thermometer, nitrogen sealing tube, and heating / cooling device, 453.0 parts of exenol 2020 (polyether polyol, number of functional groups = 2, hydroxyl value 56 mg KOH / g, number average molecular weight 2000, manufactured by AGC Inc.) were charged as a polyol while flowing nitrogen gas. While stirring, 467.4 parts of myrionate NM (diphenylmethane diisocyanate, NCO content 33.6% by mass, manufactured by Tosoh Corporation) and 79.6 parts of myrionate MTL (carbodiimide-modified diphenylmethane diisocyanate, NCO content 28.9% by mass, manufactured by Tosoh Corporation) were charged as polyisocyanates, and the reaction was carried out with stirring at 75-85°C for 2 hours. After that, analysis was performed, and the reaction was terminated when the isocyanate (NCO) content fell below the theoretical value (theoretical value of NCO content is 16.1% by mass), and the mixture was cooled to obtain an isocyanate group-containing urethane prepolymer. The obtained isocyanate group-containing urethane prepolymer was a transparent liquid at room temperature, and its viscosity at 23°C was 600 mPa·s. This was designated as Component 1. Table 2 shows the mass ratio of the materials used in the synthesis of Component 1.

[0047] <Synthesis Example 2: First Agent 2> In a reaction vessel equipped with a stirrer, thermometer, nitrogen sealing tube, and heating / cooling device, 584.6 parts of exenol 2020 (polyether polyol, number of functional groups = 2, hydroxyl value 56 mg KOH / g, number average molecular weight 2000, manufactured by AGC Inc.) were charged as a polyol while flowing nitrogen gas. While stirring, 415.4 parts of Takenate 500 (m-xylylene diisocyanate, NCO content 44.7% by mass, manufactured by Mitsui Chemicals Inc.) were charged as a polyisocyanate, and the reaction was carried out with stirring at 75-85°C for 2 hours. After that, analysis was performed and the reaction was terminated when the isocyanate (NCO) content fell below the theoretical value (theoretical value of NCO content is 16.1% by mass), and the mixture was cooled to obtain an isocyanate group-containing urethane prepolymer. The obtained isocyanate group-containing urethane prepolymer was a transparent liquid at room temperature, and its viscosity at 23°C was 500 mPa·s. This was designated as the first agent 2. Table 2 shows the mass ratio of the materials used in the synthesis of Agent 1 2.

[0048] <Synthesis Example 3: First Agent 3> In a reaction vessel equipped with a stirrer, thermometer, nitrogen sealing tube, and heating / cooling device, 515.5 parts of JEFFAMINE D-2000 (polyether polyamine, 2 functional groups, amine value 56 mg KOH / g, number average molecular weight 2000, manufactured by HUNTSMAN) were charged as a polyamine while flowing nitrogen gas. While stirring, 484.5 parts of Desumodul I (isophorone diisocyanate, NCO content 37.7% by mass, manufactured by Covestro) were charged as a polyisocyanate, and the reaction was carried out at 110-120°C with stirring for 2 hours. After analysis, the reaction was terminated when the isocyanate (NCO) content fell below the theoretical value (theoretical NCO content is 16.1% by mass), and the mixture was cooled to obtain an isocyanate-containing urea prepolymer. The obtained isocyanate-containing urea prepolymer was a transparent liquid at room temperature, and its viscosity at 23°C was 450 mPa·s. This was designated as Agent 13. Table 2 shows the mass ratio of the materials used in the synthesis of Agent 13.

[0049] <Synthesis Example 4: First Agent 4> Duranate TLA-100 (hexamethylene diisocyanate isocyanurate modified, NCO content 23.3% by mass, manufactured by Asahi Kasei Corporation), a commercially available polyisocyanate, was a transparent liquid at room temperature, and its viscosity at 23°C was 480 mPa·s. This was designated as Agent 4.

[0050] [Table 2]

[0051] (Second drug) For the second component, we used components 1 to 16 prepared according to the following manufacturing examples 1 to 16.

[0052] <Manufacturing Example 1: Second Agent 1> In a container equipped with a stirrer, 513.3g of Exenol 2020 (polyether polyol, manufactured by AGC Inc.) and 272.7g of dipropylene glycol (manufactured by AGC Inc.) were charged. While stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by Arcsada Inc.), 8.0g of Nikka Octix Lead 24% (lead octoate, manufactured by Nippon Chemical Industrial Co., Ltd.), 5.0g of HS Ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed and the amine value was measured to determine the second agent 1. The amine value was measured in accordance with JIS K 7237 using a potentiometric titrator COM-A19S manufactured by HIRANUMA Co., Ltd. (the same applies below).

[0053] <Manufacturing Example 2: Second Agent 2> In a container equipped with a stirrer, 551.3g of Exenol 2020 (polyether polyol, manufactured by AGC Inc.) and 234.7g of dipropylene glycol (manufactured by AGC Inc.) were charged. While stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by Arcsada Inc.), 8.0g of Nikka Octix Lead 24% (lead octoate, manufactured by Nippon Chemical Industrial Co., Ltd.), 5.0g of HS Ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed to measure the amine value, and this was designated as Agent 2.

[0054] <Manufacturing Example 3: Second Agent 3> In a container equipped with a stirrer, 583.7g of Exenol 2020 (polyether polyol, manufactured by AGC Inc.) and 202.3g of dipropylene glycol (manufactured by AGC Inc.) were charged. While stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by Arcsada Inc.), 8.0g of Nikka Octix Lead 24% (lead octoate, manufactured by Nippon Chemical Industrial Co., Ltd.), 5.0g of HS Ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed to measure the amine value, and the result was designated as Agent 3.

[0055] <Manufacturing Example 4: Second Agent 4> In a container equipped with a stirrer, 611.5g of Exenol 2020 (polyether polyol, manufactured by AGC Inc.) and 174.5g of dipropylene glycol (manufactured by AGC Inc.) were charged. While stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by Arcsada Inc.), 8.0g of Nikka Octix Lead 24% (lead octoate, manufactured by Nippon Chemical Industrial Co., Ltd.), 5.0g of HS Ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed to measure the amine value, and the result was identified as Agent 4.

[0056] <Manufacturing Example 5: Second Agent 5> In a container equipped with a stirrer, 636.0g of Exenol 2020 (polyether polyol, manufactured by AGC Inc.) and 150.0g of dipropylene glycol (manufactured by AGC Inc.) were charged. While stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by Arcsada Inc.), 8.0g of Nikka Octix Lead 24% (lead octoate, manufactured by Nippon Chemical Industrial Co., Ltd.), 5.0g of HS Ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed to measure the amine value, and the result was determined to be Agent 5.

[0057] <Manufacturing Example 6: Second Agent 6> In a container equipped with a stirrer, 657.8g of Exenol 2020 (polyether polyol, manufactured by AGC Inc.) and 128.2g of dipropylene glycol (manufactured by AGC Inc.) were charged. While stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by Arcsada Inc.), 8.0g of Nikka Octix Lead 24% (lead octoate, manufactured by Nippon Chemical Industrial Co., Ltd.), 5.0g of HS Ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed to measure the amine value, and the second agent was determined to be 6.

[0058] <Manufacturing Example 7: Second Agent 7> In a container equipped with a stirrer, 676.8g of Exenol 2020 (polyether polyol, manufactured by AGC Inc.) and 109.2g of dipropylene glycol (manufactured by AGC Inc.) were charged. While stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by Arcsada Inc.), 8.0g of Nikka Octix Lead 24% (lead octoate, manufactured by Nippon Chemical Industrial Co., Ltd.), 5.0g of HS Ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed to measure the amine value, and the second agent was determined to be 7.

[0059] <Manufacturing Example 8: Second Agent 8> In a container equipped with a stirrer, 694.2g of Exenol 2020 (polyether polyol, manufactured by AGC Inc.) and 91.8g of dipropylene glycol (manufactured by AGC Inc.) were charged. While stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by Arcsada Inc.), 8.0g of Nikka Octix Lead 24% (lead octoate, manufactured by Nippon Chemical Industrial Co., Ltd.), 5.0g of HS Ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed to measure the amine value, and the second agent was determined to be 8.

[0060] <Manufacturing Example 9: Second Agent 9> In a container equipped with a stirrer, 709.6g of Exenol 2020 (polyether polyol, manufactured by AGC Inc.) and 76.4g of dipropylene glycol (manufactured by AGC Inc.) were charged. While stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by Arcsada Inc.), 8.0g of Nikka Octix Lead 24% (lead octoate, manufactured by Nippon Chemical Industrial Co., Ltd.), 5.0g of HS Ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed and the amine value was measured, resulting in the second agent being 9.

[0061] <Manufacturing Example 10: Second Agent 10> In a container equipped with a stirrer, 723.6g of Exenol 2020 (polyether polyol, manufactured by AGC Inc.) and 62.4g of dipropylene glycol (manufactured by AGC Inc.) were charged. While stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by Arcsada Inc.), 8.0g of Nikka Octix Lead 24% (lead octoate, manufactured by Nippon Chemical Industrial Co., Ltd.), 5.0g of HS Ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed to measure the amine value, and the second agent was determined to be 10.

[0062] <Manufacturing Example 11: Second Agent 11> In a container equipped with a stirrer, 736.2g of Exenol 2020 (polyether polyol, manufactured by AGC Inc.) and 62.4g of dipropylene glycol (manufactured by AGC Inc.) were charged. While stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by Arcsada Inc.), 8.0g of Nikka Octix Lead 24% (lead octoate, manufactured by Nippon Chemical Industrial Co., Ltd.), 5.0g of HS Ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed to measure the amine value, and the second agent was determined to be 11.

[0063] <Manufacturing Example 12: Second Agent 12> In a container equipped with a stirrer, 748.0g of Exenol 2020 (polyether polyol, manufactured by AGC Inc.) and 38.0g of dipropylene glycol (manufactured by AGC Inc.) were charged. While stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by Arcsada Inc.), 8.0g of Nikka Octix Lead 24% (lead octoate, manufactured by Nippon Chemical Industrial Co., Ltd.), 5.0g of HS Ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed to measure the amine value, and the second agent was determined to be 12.

[0064] <Manufacturing Example 13: Second Agent 13> In a container equipped with a stirrer, 758.6g of Exenol 2020 (polyether polyol, manufactured by AGC Inc.) and 27.4g of dipropylene glycol (manufactured by AGC Inc.) were charged. While stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by Arcsada Inc.), 8.0g of Nikka Octix Lead 24% (lead octoate, manufactured by Nippon Chemical Industrial Co., Ltd.), 5.0g of HS Ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed to measure the amine value, and the second agent was determined to be 13.

[0065] <Manufacturing Example 14: Second Agent 14> In a container equipped with a stirrer, 514.4g of JEFFAMINE D-2000 (polyether polyamine, manufactured by HUNTSUMAN) was charged, and while stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by ARCSADA), 279.6g of ETHACURE 420 (4,4'-methylenebis[N-(1-methylpropyl)aniline], manufactured by ALBEMARLE), 5.0g of HS ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed to measure the amine value, and the second agent was determined to be 14.

[0066] <Manufacturing Example 15: Second Agent 15> In a container equipped with a stirrer, 530.6g of Exenol 2020 (polyether polyol, manufactured by AGC Inc.) and 255.4g of dipropylene glycol (manufactured by AGC Inc.) were charged. While stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by Arcsada Inc.), 8.0g of Nikka Octix Lead 24% (lead octoate, manufactured by Nippon Chemical Industrial Co., Ltd.), 5.0g of HS Ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed to measure the amine value, and the second agent was determined to be 15.

[0067] <Manufacturing Example 16: Second Agent 16> In a container equipped with a stirrer, 138.0g of JEFFAMINE D-2000 (polyether polyamine, manufactured by HUNTSUMAN) was charged, and while stirring, 200.0g of LONZACURE DETDA80 (diethyltoluenediamine, manufactured by ARCSADA), 656.0g of ETHACURE 420 (4,4'-methylenebis[N-(1-methylpropyl)aniline], manufactured by ALBEMARLE), 5.0g of HS ester 292 (weather stabilizer, manufactured by Toyokuni Oil Co., Ltd.), and 1.0g of Disparon P-467 (defoaming agent, manufactured by Kusumoto Chemical Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. After that, analysis was performed to measure the amine value, and the second agent was determined to be 16.

[0068] (Example 1) Nominal strength as a floor slab: 27 N / mm 2 We prepared concrete slabs (standard slabs with nominal size 300, abbreviated as N, as specified in JIS A 5371). The surface of the deck slab was cleaned, and an epoxy resin primer (manufactured by Nichireki Co., Ltd.: AU Primer) was applied to the surface of the deck slab using a roller at a rate of 1.2 kg / m². 2 The primer layer was formed by applying the specified amount and curing it at 20°C for 2 hours. Next, a waterproofing material is applied to the primer layer using a special machine at a rate of 1.5 kg / m². 2 The waterproof layer was formed by spraying the material in the specified amount and curing it at 20°C for 4 hours. The waterproofing material used was prepared by mixing 100 parts each of component 1 and component 2. The thickness of the formed waterproof layer was 1.4 mm. Next, modified asphalt (manufactured by Nichireki Co., Ltd.: HQ Coat AU, a mixture of asphalt and thermoplastic resin (SEBS), with a ratio of 30 parts thermoplastic resin to 100 parts asphalt) is applied to the waterproof layer as an adhesive at a temperature of 240°C using a brush at a rate of 1.2 kg / m². 2 The adhesive was applied in the specified amount and cured at 20°C for one day to form a layer. The thickness of the formed adhesive layer was 1.1 mm. Furthermore, an asphalt mixture heated to 140°C was laid on top of that to a pavement thickness of 40 mm to create a test pavement (test specimen 1). The following evaluation tests were conducted on the test pavement samples that were prepared. The results are shown in Table 3.

[0069] <Tensile bonding test, shear bonding test> Three circular tensile test specimens with a diameter of 100 mm in plan view and three rectangular shear test specimens measuring 100 mm x 100 mm in plan view were cut from the test pavement. Using these specimens, tensile and shear adhesion tests were performed in accordance with the test methods in the Road Bridge Slab Waterproofing Handbook (Japan Road Association, 2007), and the tensile adhesion strength and shear strength were measured. All tests were conducted in a thermo-hygrostat chamber at 23°C and 50% RH. In the tensile test, metal fixtures were attached to both sides of the specimen using epoxy adhesive, and these fixtures were pulled in a direction where the distance between them increased using a tensile testing machine (INSTRON 5969). The tensile adhesion strength was defined as the strength at the time when the specimen broke. The measured values of three specimens for each test were averaged to obtain the tensile adhesion strength and shear adhesion strength of each test paving. In the tensile adhesion test, a tensile adhesion strength of 0.6 N / mm 2 or more was considered as passing, and a tensile adhesion strength of less than 0.6 N / mm 2 was considered as failing. In the shear adhesion test, a shear adhesion strength of 0.6 N / mm 2 or more was considered as passing, and a shear adhesion strength of less than 0.6 N / mm 2 was considered as failing.

[0070] <Visual Blister Confirmation Test> The test paving before asphalt mixture paving was used as the specimen. The specimen was cured at 50°C for 7 days in a thermo-hygrostat chamber with adjustable temperature. After curing, the waterproof layer, adhesive layer, and the interface between these layers of the specimen were visually observed. If no blisters were confirmed on the specimen, it was evaluated as ○; if 1 to 10 blisters were confirmed, it was evaluated as △; if 11 or more blisters were confirmed, it was evaluated as ×.

[0071] <Microscopic Blister Confirmation Test> Three specimens after the shear adhesion test were used as specimens for microscopic blister confirmation. The fracture surfaces (waterproof layer, adhesive layer, or the interface between these layers) of these specimens were observed using a microscope (manufactured by KEYENCE CORPORATION: Digital Microscope VHX-6000). If no blisters were confirmed on all fracture surfaces, it was evaluated as ○; if blisters were confirmed on one fracture surface, it was evaluated as △; if blisters were confirmed on two or more fracture surfaces, it was evaluated as ×.

[0072] <Comprehensive Blister Evaluation> If the evaluations of both the visual blister confirmation test and the microscopic blister confirmation test were ○ or △, it was considered as passing; if there was an evaluation of ×, it was considered as failing.

[0073] (Examples 2-13) Except for changing the second agent 1 of the waterproofing material used in Example 1 to second agents 2-13, test pavement specimens (specimens 2-13) were prepared in the same manner as in Example 1, and evaluation tests were conducted. The results are shown in Table 3.

[0074] (Examples 14, 16, 18) Except for mixing the first agent and the second agent 14 shown in Table 4 in the mass ratio shown in Table 4 to produce the waterproofing material, test pavement specimens (specimens 14, 16, and 18) were prepared in the same manner as in Example 1, and evaluation tests were conducted. The results are shown in Table 4.

[0075] (Examples 15, 17) Except for mixing the first agent and the second agent 7 shown in Table 4 in the mass ratio shown in Table 4 to produce the waterproofing material, test pavement specimens (specimens 15 and 17) were prepared in the same manner as in Example 1, and evaluation tests were conducted. The results are shown in Table 4.

[0076] (Examples 19, 20) Except for mixing Agent 4 and Agent 15 or 16 in the mass ratio shown in Table 4 to produce the waterproofing material, test pavement specimens (specimens 15 and 17) were prepared in the same manner as in Example 1, and evaluation tests were conducted. The results are shown in Table 4.

[0077] Tables 3 and 4 show the composition and properties of the waterproofing material. In Tables 3 and 4, "EL2020" refers to Exenol 2020, "DPG" refers to dipropylene glycol, "D-2000" refers to JEFFAMINE D-2000, "DETDA" refers to LONZACURE DETDA80, "E-420" refers to ETHACURE 420, "DP467" refers to Disparon P-467, "HSE292" refers to HS ester 292, and "Lead octylate" refers to Nikka Octix lead 24%. "Number of NCO groups" indicates the number of isocyanate groups per 100g of the first component. "Total number of OH and NH2 groups" indicates the total number of hydroxyl and amino groups per 100g of the second component. "Main component density" indicates the density of the first component. "Hardener density" indicates the density of the second component. The "molar ratio" indicates the ratio of the number of isocyanate groups in the first component to the number of active hydrogen-containing groups in the second component (NCO ratio), and was calculated as (number of NCO groups × density of main component) / (total number of OH groups and NH2 groups × density of curing agent). The "amine value" indicates the amine value of the second component.

[0078] [Table 3]

[0079] [Table 4]

[0080] In examples 4-8 and 14-20, both the tensile and shear adhesion tests passed. Furthermore, the overall evaluation for blistering confirmation also passed. Examples 1-3, where the molar ratio of isocyanate groups in the first agent to active hydrogen-containing groups in the second agent was less than 0.75, failed the shear adhesion test. Examples 1-2, in particular, also failed the tensile adhesion test. Examples 9-13, where the molar ratio of isocyanate groups in the first agent to active hydrogen-containing groups in the second agent was greater than 0.95, failed the comprehensive evaluation based on blister confirmation. In particular, examples 11-13 showed 11 or more blisters upon visual inspection and also failed the shear adhesion test. Furthermore, example 13 also failed the tensile adhesion test. [Explanation of Symbols]

[0081] 1…Base material, 1A…Down slab, 2…Primer layer, 3…Waterproofing layer, 3A…Waterproofing layer for down slab, 4…Adhesive layer, 5…Asphalt layer, 6…Laminate, 10…Structure

Claims

1. A waterproofing method comprising forming a waterproof layer on a substrate, and then forming an adhesive layer on top of the waterproof layer, The waterproofing method is characterized in that the waterproofing layer is formed by applying a two-component waterproofing material, comprising a first agent containing a compound having an isocyanate group and a second agent containing a compound having an active hydrogen-containing group, onto the substrate, wherein the molar ratio of the isocyanate group to the active hydrogen-containing group is 0.75 or more and 0.95 or less.

2. The waterproofing method according to claim 1, wherein the first agent comprises an isocyanate-terminated prepolymer obtained by reacting a polyol with a polyisocyanate.

3. The waterproofing method according to claim 2, wherein the polyisocyanate comprises at least one selected from the group consisting of aliphatic polyisocyanates, aromatic polyisocyanates, alicyclic polyisocyanates, and modified forms thereof.

4. The waterproofing method according to claim 1, wherein the compound having the active hydrogen group comprises at least one selected from the group consisting of polyols and polyamines.

5. The waterproofing method according to claim 1, wherein the adhesive comprises asphalt and a thermoplastic resin.

6. The waterproofing method according to claim 5, wherein the proportion of the thermoplastic resin is 1 to 90 parts by mass per 100 parts by mass of the asphalt.

7. The waterproofing method according to claim 1, wherein the two-component waterproofing material is applied by spraying.

8. The waterproofing method according to any one of claims 1 to 7, further comprising forming an asphalt layer on the adhesive layer.

9. A waterproofing method according to any one of claims 1 to 7, wherein a primer layer is formed on the substrate before forming the waterproofing layer.

10. The waterproofing method according to any one of claims 1 to 7, wherein the thickness of the waterproofing layer is 0.5 to 5.0 mm.

11. The waterproofing method according to any one of claims 1 to 7, wherein the thickness of the adhesive layer is 0.5 to 5.0 mm.

12. The waterproofing method according to any one of claims 1 to 7, wherein the base material is a floor slab.

13. A waterproof layer for deck slabs, A waterproof coating for floor slabs, comprising a two-component waterproofing material comprising a first agent containing a compound having an isocyanate group and a second agent containing a compound having an active hydrogen-containing group, wherein the molar ratio of the isocyanate group to the active hydrogen-containing group is 0.75 or more and 0.95 or less.

14. The waterproof layer for a floor slab according to claim 13, wherein the first agent comprises an isocyanate-terminated prepolymer obtained by reacting a polyol with a polyisocyanate.

15. The waterproof layer for a floor slab according to claim 14, wherein the polyisocyanate comprises at least one selected from the group consisting of aliphatic polyisocyanates, aromatic polyisocyanates, alicyclic polyisocyanates, and modified forms thereof.

16. The waterproof layer for a floor slab according to claim 13, wherein the compound having the active hydrogen group comprises at least one selected from the group consisting of polyols and polyamines.

17. A laminate comprising a waterproof layer for a floor slab as described in claim 13 and a layer of adhesive.

18. The laminate according to claim 17, wherein the adhesive comprises asphalt and a thermoplastic resin.

19. The laminate according to claim 18, wherein the proportion of the thermoplastic resin is 1 to 90 parts by mass per 100 parts by mass of the asphalt.

20. The laminate according to claim 17, further comprising an asphalt layer.

21. The laminate according to claim 17, wherein the thickness of the waterproof layer for the floor slab is 0.5 to 5.0 mm.

22. The laminate according to claim 17, wherein the thickness of the adhesive layer is 0.5 to 5.0 mm.

23. A structure comprising a floor slab and a laminate according to any one of claims 17 to 22.

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