Water stoppage material and laminate

Abstract

The first problem addressed by the present invention is to provide a water stoppage material which is excellent in terms of embedding and removability. The second problem is to provide a laminate including the water stoppage material.　This water stoppage material is of a non-foam type and has predetermined physical properties.

Description

Water-stopping material and laminate

[0001] The present invention relates to a waterproof material and a laminate.

[0002] Various water-stopping technologies have been investigated to mitigate damage caused by flooding or water leakage. One example of such a water-stopping technology is a method of covering water inlets or outlets with a water-stopping material. Flooding damage to buildings occurs, for example, when water enters through gaps in windows, doors, etc. A method of sealing the gaps and preventing water intrusion using a water-stopping material is effective in addressing such flooding damage. One example of a water-stopping material is a water-stopping material made of a water-absorbent material that can absorb and expand. The water-stopping material is placed in gaps in windows, doors, etc. that could serve as a water intrusion route. Upon contact with water, the water-stopping material absorbs water and expands (swells), thereby reducing the size of the gap and preventing water intrusion. For example, Patent Document 1 discloses a water-stopping material that includes a substrate and a water-expanding member that is attached to the substrate and expands upon absorbing water.

[0003] Japanese Patent Application Laid-Open No. 2022-127273

[0004] In recent years, there has been an increasing demand for water-stopping materials that can be easily used in various shapes, and excellent embeddability is required. In this specification, embeddability refers to the ability to embed the material into corners without leaving any gaps. Furthermore, when a water-stopping material is placed in gaps in windows, doors, etc. that could serve as water intrusion routes to prevent flooding damage to a building, there are cases where the water-stopping material that was not used to stop flooding is peeled off from the gap and removed without causing flooding damage. In such cases, the water-stopping material is also required to be easily peeled off from the gap (in other words, to have excellent peelability). The present inventors have studied the water-stopping material described in Patent Document 1 and found that there is room for further improvement in embeddability and peelability.

[0005] Therefore, an object of the present invention is to provide a waterproofing material that has excellent embeddability and peelability. Another object of the present invention is to provide a laminate including the waterproofing material.

[0006] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0007] [1] A non-foaming water-stop material, wherein when the water-stop material is compressed to obtain a stress-strain curve with stress on the vertical axis and strain on the horizontal axis, and the vertical axis of the obtained stress-strain curve is logarithmically transformed to obtain a conversion curve, a first approximation line obtained by the least squares method of the curve in a 30 to 50% strain range in the conversion curve intersects with a second approximation line obtained by the least squares method of the curve in a 75 to 100% strain range in the conversion curve, and the stress value H1 at the intersection H is 1.00 MPa or less; When the storage modulus G' and loss modulus G'' of the waterstop material are measured at a temperature of 25°C, a frequency of 1 Hz, and a strain of 0.001 to 100%, the strain at which the storage modulus G' and the loss modulus G'' become equal is 50% or more, or the storage modulus G' is greater than the loss modulus G'' over the entire range of strain, and the ratio of the storage modulus G' to the loss modulus G'' at the strain value H2 at the intersection H of the transformation curve is 3.0 or less. [2] The waterstop material according to [1], which has a compressive modulus of 20 kPa or more in a strain range of 20 to 30%. [3] The waterstop material according to [1] or [2], which swells upon contact with water. [4] A laminate comprising a long substrate and a waterstop material layer made of the waterstop material according to any one of [1] to [3], arranged on the substrate.

[0008] According to the present invention, a waterproofing material having excellent embeddability and peelability can be provided. Furthermore, according to the present invention, a laminate including the waterproofing material can also be provided.

[0009] FIG. 1 is a schematic diagram of a stress-strain curve (transformed curve) obtained by logarithmically transforming the vertical axis of the stress-strain curve of a waterstop material measured using a compression tester. FIG. 2 is a schematic diagram showing an example of the form of an evaluation sample for performing embeddability evaluation. FIG. 3 is a schematic cross-sectional view for explaining embeddability evaluation. FIG. 4 is a schematic cross-sectional view for explaining embeddability evaluation. FIG. 5 is a schematic cross-sectional view for explaining embeddability evaluation. FIG. 6 is a side view of a waterstop material of one embodiment. FIG. 7 is a side view of a waterstop material of one embodiment.

[0010] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Furthermore, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In this specification, in a numerical range described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in a numerical range described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0011] In this specification, the term "(meth)acrylic" refers to a concept that includes either or both of acrylic and methacrylic, and the term "(meth)acrylate" refers to a concept that includes either or both of acrylate and methacrylate, and the same applies to the terms "(meth)acryloyl" and "(meth)acryloxy."

[0012] In addition, the term "organic group" used herein refers to a group containing at least one carbon atom.

[0013] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (also referred to as "molecular weight distribution") (Mw / Mn) are defined as polystyrene equivalent values ​​measured by GPC (Gel Permeation Chromatography) using a GPC apparatus (HLC-8120GPC, manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M (manufactured by Tosoh Corporation), column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector). In this specification, unless otherwise specified, measurements of various physical properties are carried out at 25°C. Furthermore, when measuring various physical properties, unless otherwise specified, the measurement object shall be left in the test environment (25°C unless otherwise specified) for 12 hours or more before the measurement is carried out.

[0014] [Waterstop Material] The waterstop material of the present invention is a non-foaming waterstop material, and has the following first to third characteristic points: [First Characteristic Point] When the waterstop material is compressed to obtain a stress-strain curve with stress on the vertical axis and strain on the horizontal axis, and the vertical axis of the obtained stress-strain curve is logarithmically transformed to obtain a converted curve, the stress value H1 at the intersection H where a first approximate straight line obtained by the least squares method of the curve in the 30 to 50% strain range of the converted curve intersects with a second approximate straight line obtained by the least squares method of the curve in the 75 to 100% strain range of the converted curve is 1.00 MPa or less.

[0015] [Second Feature] When the storage modulus G' and loss modulus G'' of the water-stopping material are measured at a temperature of 25°C, a frequency of 1 Hz, and strains ranging from 0.001 to 100%, the strain at which the storage modulus G' and the loss modulus G'' become equal is 50% or more, or the storage modulus G' is greater than the loss modulus G'' over the entire range of strain.

[0016] [Third Feature] When the storage modulus G' and loss modulus G'' of the water-stopping material are measured at a temperature of 25°C, a frequency of 1 Hz, and strains varied from 0.001 to 100%, the ratio of the storage modulus G' to the loss modulus G'' (storage modulus G' / loss modulus G'', hereinafter also referred to as "G' ratio") is 3.0 or less at a strain value H2 at the intersection H of the conversion curve.

[0017] While the reason why the waterstop material having the above configuration can solve the problem of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. By having the first and third characteristic points, the waterstop material has excellent embeddability. In the first characteristic point, the intersection of the first approximate line and the second approximate line in the conversion curve corresponds to the stress change point when the waterstop material is compressed. By having the first characteristic point, the waterstop material can be embedded into the corner without gaps even with pressure equivalent to finger pressure when pressed into the corner. Furthermore, by having the third characteristic point, when the waterstop material is pressed into the corner, elastic rebound is unlikely to occur even when the pressure is released (for example, when the finger is pressed and then released), and good adhesion to the corner can be maintained. In other words, a good embedding state can be maintained. Furthermore, by having the second characteristic point, the waterstop material has excellent peelability. Specifically, when water-stopping material that has been placed in a gap but has not contributed to water-stopping is peeled off and removed from the gap, the water-stopping material is less likely to tear and can be easily peeled off.

[0018] Hereinafter, the superior embeddability and / or superior peelability of the water-stopping material of the present invention will also be referred to as "the superior effect of the present invention." The water-stopping material of the present invention will be described in detail below.

[0019] The waterstop material of the present invention is a non-foaming waterstop material. Typically, a foaming waterstop material refers to a waterstop material in which a foaming reaction is carried out by adding a foaming agent or the like during the manufacturing process, while a non-foaming waterstop material refers to a waterstop material obtained through a manufacturing process that does not involve a foaming reaction. When a cross-section of a foaming waterstop material in which a foaming reaction is carried out during the manufacturing process is observed under a microscope, it contains many relatively uniform bubbles, whereas a non-foaming waterstop material typically contains no bubbles or only a small number of bubbles generated due to insufficient defoaming treatment or the like. In this specification, a non-foaming waterstop material refers to a waterstop material obtained through a manufacturing process that does not involve a foaming reaction, and when the waterstop material is observed using the following methods, the number of bubbles confirmed in each observation is within the following range. When 10 random cross sections of the water-stopping material were observed using a microscope (VHS-5000, manufactured by Keyence Corporation) with an objective lens magnification of 1, a lens body magnification of 500, and an observation field of view of 500 μm × 500 μm, the arithmetic mean number of bubbles observed in each cross section was 1 bubble / μm. ２ The following is the result.

[0020] Next, a first characteristic feature of the waterstop material of the present invention will be described. FIG. 1 is a schematic diagram of a stress-strain curve (vertical axis: stress (MPa), horizontal axis: strain (%); hereinafter also referred to as the "conversion curve") obtained by logarithmically transforming the vertical axis of the stress-strain curve of the waterstop material of the present invention measured using a compression tester. The waterstop material of the present invention has a stress value H1 (hereinafter also referred to as the "stress value H1") at the intersection H of a first approximate straight line A (dashed line in FIG. 1) obtained by the least squares method of the curve in the 30 to 50% strain interval of the conversion curve and a second approximate straight line B (dashed line in FIG. 1) obtained by the least squares method of the curve in the 75 to 100% strain interval of the conversion curve) of 1.00 MPa or less. The stress value H1 is preferably 0.70 MPa or less, and more preferably 0.40 MPa or less, in that the effects of the present invention are more excellent. The lower limit of the stress value H1 is not particularly limited, but is preferably 0.10 MPa or more, and more preferably 0.20 MPa or more. As described above, the intersection of the first approximate line and the second approximate line on the conversion curve is the point of stress change when the water-stopping material is compressed. The smaller the stress value at this intersection, the easier it is for the water-stopping material to undergo plastic deformation with a small stress, and the better its embeddability.

[0021] In the above-mentioned conversion curve of the water-stopping material of the present invention, it is preferable that the slope of the second approximate straight line B is greater than the slope of the first approximate straight line A, in order to obtain a more excellent effect of the present invention.

[0022] Furthermore, in the above-mentioned conversion curve of the water-stopping material of the present invention, in order to obtain a better effect of the present invention, the strain value H2 at the intersection H where the first approximate line A and the second approximate line B intersect is preferably in the range of 60 to 90%, and more preferably in the range of 70 to 80%.

[0023] The stress-strain curve of the water-stop material is obtained by using a compression tester (e.g., Strograph VE20D, Toyo Seiki Seisakusho Co., Ltd.) to measure strain dispersion at a strain of 0 to 100% at a compression speed of 0.5 mm / min, with a compression element (a 30 mm stainless steel disk surface) positioned at the center of the water-stop material test sample. For the measurement, the water-stop material test sample is preferably in the form of a plate measuring 50 mm in length, 50 mm in width, and 4 mm in thickness. The measurement environment is preferably 25°C. The strain dispersion measurement is performed after the test sample has been left in the test environment (preferably 25°C) for 12 hours or more.

[0024] Next, a second characteristic of the waterstop material of the present invention will be described. When the storage modulus G' and loss modulus G" of the waterstop material of the present invention are measured at a temperature of 25°C, a frequency of 1 Hz, and a strain of 0.001 to 100%, the strain at which the storage modulus G' and loss modulus G" become the same is 50% or greater, or the storage modulus G' is greater than the loss modulus G" throughout the entire strain range. Note that "the storage modulus G' is greater than the loss modulus G" throughout the entire strain range means that the storage modulus G' > the loss modulus G" is satisfied at all strains (%) in the strain range of 0.001 to 100%. When the waterstop material becomes such that the storage modulus G' and loss modulus G" become the same in the strain range of 0.001 to 100% (i.e., an intersection exists), the strain corresponding to the intersection is preferably 60% or greater, more preferably 70% or greater, and even more preferably 80% or greater. In the waterstop material of the present invention, the storage modulus G' is preferably greater than the loss modulus G'' over the entire range of strain. The storage modulus G' and loss modulus G'' are obtained by performing strain dispersion measurements at a temperature of 25°C and a measurement frequency of 1 Hz over a strain range of 0.001 to 100% using a rheometer (MCR302, manufactured by Anton Paar Co., Ltd.). The strain dispersion measurements are performed after the measurement object has been placed in a test environment at 25°C for 12 hours or more.

[0025] Next, a third characteristic of the waterstop material of the present invention will be described. When the storage modulus G' and loss modulus G" of the waterstop material of the present invention are measured at a temperature of 25°C, a frequency of 1 Hz, and strains varying from 0.001 to 100%, the G' ratio (storage modulus G' / loss modulus G") is 3.0 or less at the strain value H2 (hereinafter sometimes abbreviated as "strain value H2") (%) at the intersection H of the first approximate line A and the second approximate line B in the conversion curve described above. From the viewpoint of the superior effect of the present invention, the G' ratio is preferably 2.8 or less, and more preferably 2.6 or less. The lower limit is not particularly limited, but is often 1.0 or more. The G' ratio of a waterstop material at a temperature of 25°C, a frequency of 1 Hz, and a strain value H2 (%) can be calculated from the values ​​of the storage modulus G' and loss modulus G" at a strain (%) corresponding to the strain value H2 in the measurement results obtained by performing strain dispersion measurements at a temperature of 25°C and a measurement frequency of 1 Hz at strains of 0.001 to 100% using a rheometer (MCR302, manufactured by Anton Paar Co., Ltd.). That is, for example, if the strain value H2 at the intersection H of the first approximate line A and the second approximate line B in the above-mentioned conversion curve is 60%, the G' ratio is calculated from the values ​​of the storage modulus G' and loss modulus G" at a strain of 60% in the strain dispersion measurement results obtained using the rheometer. The strain dispersion measurement is performed after the measurement object has been placed in a test environment at 25°C for 12 hours or more.

[0026] The storage modulus G' of the water-stopping material at a temperature of 25°C, a frequency of 1 Hz, and a strain value H2 (%) is preferably 500 to 50,000 Pa, more preferably 1,000 to 30,000 Pa, and even more preferably 1,000 to 20,000 Pa. The loss modulus G'' of the water-stopping material at a temperature of 25°C, a frequency of 1 Hz, and a strain value H2 (%) is preferably 500 to 50,000 Pa, more preferably 1,000 to 30,000 Pa, even more preferably 1,000 to 20,000 Pa, and particularly preferably 1,000 to 12,000 Pa.

[0027] Furthermore, the compressive elastic modulus of the waterstop material of the present invention is preferably 20 kPa or more, more preferably 50 kPa or more, and even more preferably 100 kPa or more in the 20 to 30% strain range, in order to easily suppress shape deformation due to water pressure when used for watertight sealing (excellent water pressure resistance). There is no particular upper limit, but it is preferably 300 kPa or less, and more preferably 250 kPa or less. The compressive modulus of the water-stop material is measured using a compression tester (e.g., Strograph VE20D, manufactured by Toyo Seiki Seisakusho Co., Ltd.) with a compression element (φ30 mm stainless steel disk surface) placed in the center of the water-stop material test sample. A strain dispersion measurement is performed at a compression rate of 0.5 mm / min from 0 to 100% strain. The slope of the obtained stress-strain curve (vertical axis: stress, horizontal axis: strain) in the 20 to 30% strain range is linearly approximated using the least squares method, and this is the compressive modulus (unit: kPa). For measurement, the water-stop material test sample is preferably in the form of a plate measuring 50 mm in length, 50 mm in width, and 4 mm in thickness. The measurement environment is preferably 25°C. The strain dispersion measurement is performed after the test sample has been left in the test environment (preferably 25°C) for 12 hours or more.

[0028] The tensile modulus of the waterstop material of the present invention is preferably anisotropic (preferably orthogonal anisotropic) in terms of superior workability. The anisotropy of the tensile modulus of the waterstop material means, for example, that in the case where the waterstop material is long, the tensile modulus is different between the long direction and the width direction (the direction perpendicular to the long direction). Note that orthogonal anisotropy means that the tensile modulus is different in directions perpendicular to each other, such as the long direction and the width direction. In terms of superior workability, the tensile modulus of the waterstop material of the present invention is preferably different in the longitudinal and width directions of the gap in which the waterstop material is placed, and in particular, the tensile modulus corresponding to the longitudinal direction of the gap is preferably greater than the tensile modulus corresponding to the width direction of the gap. Examples of methods for imparting anisotropy in the tensile modulus of the waterstop material include a method of laminating a substrate (e.g., a nonwoven fabric) having an anisotropic tensile modulus of the waterstop material with the waterstop material, and a method of adding a filler to the waterstop material.

[0029] The waterstop material of the present invention is preferably a waterstop material that expands (swells) upon contact with water. The waterstop material expands upon contact with water, filling gaps and providing superior waterstop properties. The swelling ratio (absorption ratio) of the waterstop material after immersion for one hour is preferably 1.1 to 5.0, more preferably 2.0 to 4.0, and even more preferably 2.0 to 3.0, in terms of providing superior waterstop properties. The swelling ratio (absorption ratio) after immersion for one hour can be calculated by dividing the mass of the waterstop material immersed for one hour in water adjusted to 25°C by the mass of the waterstop material before immersion.

[0030] [Composition of Waterstop Material] The composition of the waterstop material will be described below. The above-mentioned various physical properties of the waterstop material of the present invention can be adjusted by the composition of the waterstop material.

[0031] <<Polymer>> The water-stopping material preferably contains a polymer. The polymer may be either water-absorbent or non-water-absorbent, but is preferably water-absorbent. That is, the water-stopping material preferably contains a water-absorbent polymer. The water-absorbent polymer is preferably a polymer that swells upon contact with water, and known water-absorbent polymers can be used. Here, "water-absorbency" means that the water absorption rate measured in accordance with Method A described in JIS K 7209:2000 (ISO 62:1999) is 12% or more. The water absorption rate is the percentage of mass change relative to the initial mass. For example, the water absorption rate is preferably 15% or more, more preferably 20% or more. Furthermore, from the viewpoint of durability, the upper limit is preferably 500% or less, more preferably 400% or less. Note that the water-absorbent polymer is a component different from the water-absorbent resin particles.

[0032] The polymer is preferably polyurethane, since the waterproofing material is likely to satisfy the predetermined physical properties. Examples of polyurethane include polyurethanes formed from polyols and polyisocyanates, and among these, polyurethanes formed from polyols containing a polyoxyalkylene structure and polyisocyanates are more preferred.

[0033] The equivalent ratio of the isocyanate groups (NCO groups) of the polyisocyanate to the hydroxyl groups (OH groups) of the polyol is preferably 0.50 to 1.00, more preferably 0.70 to 0.90, even more preferably 0.75 to 0.80, and particularly preferably 0.75 to 0.79, in terms of making it easier for the water-stopping material to satisfy the predetermined physical properties.

[0034] The polyurethane preferably has a cross-linked structure in order to prevent dissolution of the waterproofing material. The cross-linked structure may be either a physical cross-link or a chemical cross-link, but a chemical cross-link is preferred in terms of durability. That is, the polyurethane preferably has a three-dimensional cross-linked structure formed by covalent bonds.

[0035] (Polyol (polyhydric alcohol compound)) The number of hydroxyl groups possessed by the polyol is not limited as long as it is 2 or more, but is preferably 3 or more, more preferably 3 or 4, and even more preferably 3. The molecular weight of the polyol is preferably 1,000 to 10,000, more preferably 2,000 to 8,000, and even more preferably 3,000 to 6,000, in terms of excellent flexibility of the waterstop material and better effects of the present invention. When the polyol has a molecular weight distribution, it is preferable that the number average molecular weight falls within the above range. As the polyol, a polyol containing a polyoxyalkylene structure is preferred.

[0036] The polyoxyalkylene structure is -(O-AL) ｎ- is a structural moiety represented by the formula (I). AL represents an alkylene group. The alkylene group may be linear, branched, or cyclic, and is preferably linear or branched, and more preferably linear. The number of carbon atoms in the alkylene group represented by AL is preferably 1 to 6, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. Specific examples of the alkylene group represented by AL include a methylene group, an ethylene group, and a propylene group (specifically, an n-propylene group and a 2-methylethylene group), and an ethylene group or a 2-methylethylene group is preferred, and an ethylene group is more preferred. n represents the number of repetitions. The number of repetitions represented by n may be any number equal to or greater than 2, and is, for example, preferably 2 to 300, more preferably 10 to 200, even more preferably 15 to 100, and particularly preferably 20 to 50.

[0037] In the polyoxyalkylene structure, AL may be one type or two or more types. In addition, the polyol may have only one polyoxyalkylene structure in the molecule, or two or more polyoxyalkylene structures.

[0038] The polyoxyalkylene structure preferably contains an oxyethylene structural unit, since the polyurethane has better water absorption.When the polyol contains an oxyethylene structural unit in the molecule, the content of the oxyethylene structural unit in the molecule is preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 50 mol% or more, particularly preferably 60 mol% or more, and most preferably 70 mol% or more, based on the total oxyalkylene structural units in the molecule.The upper limit is 100 mol% or less.

[0039] The polyol is preferably a polyoxyalkylene polyol obtained by polymerizing an oxirane compound containing at least ethylene oxide using a low-molecular-weight polyol as an initiator. Examples of the low-molecular-weight polyol include low-molecular-weight diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, and diethylene glycol, and low-molecular-weight triols such as glycerin and trimethylolpropane, with low-molecular-weight triols being preferred. Examples of the oxirane compound include the above-mentioned ethylene oxide, as well as propylene oxide, butylene oxide, and tetrahydrofuran.

[0040] As the polyol, a compound represented by the following formula (PO1) is preferred, since it is easy to obtain the desired physical properties of the water-stopping material. １ - [(O-AL) ｎ -OH] ｍ Formula (PO1) In formula (PO1), M １ represents an m-valent linking group. AL represents an alkylene group. n is the number of repeating groups and is a number of 2 or more. m represents an integer of 2 or more.

[0041] M １ The m-valent linking group represented by the formula (I) is not particularly limited, and examples thereof include m-valent aliphatic groups and m-valent aromatic groups, with m-valent aliphatic groups being preferred. Examples of the m-valent aliphatic groups include m-valent aliphatic hydrocarbon groups and groups in which one or more carbon atoms of an m-valent aliphatic hydrocarbon group are substituted with heteroatoms, with m-valent aliphatic hydrocarbon groups being preferred. Examples of the heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom, with an oxygen atom being preferred. The number of carbon atoms in the m-valent linking group is preferably 1 to 20, more preferably 3 to 12, even more preferably 3 to 6, particularly preferably 3 or 4, and most preferably 3.

[0042] AL represents an alkylene group. The alkylene group may be linear, branched, or cyclic, preferably linear or branched, and more preferably linear. The number of carbon atoms in the alkylene group represented by AL is preferably 1 to 6, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. Specific examples of the alkylene group represented by AL include a methylene group, an ethylene group, and a propylene group (specifically, an n-propylene group and a 2-methylethylene group), with an ethylene group or a 2-methylethylene group being preferred, and an ethylene group being more preferred. AL may be one type, or two or more types.

[0043] n represents the number of repetitions. The number of repetitions represented by n may be any number as long as it is 2 or more, and is, for example, preferably 2 to 300, more preferably 10 to 200, still more preferably 15 to 100, and particularly preferably 20 to 50.

[0044] The structure represented by -(O-AL)n- in formula (PO1) includes -(O-C ２ H ４ ) n Ａ -(O-C ３ H ６ ) n Ｂ It is also preferable that the structure is represented by n Ａ and n Ｂ represents the number of repetitions, each independently representing a number of 2 or more. Ａ and Ｂ The total number is, for example, preferably 2 to 300, more preferably 10 to 200, even more preferably 15 to 100, and particularly preferably 20 to 50.

[0045] m represents an integer of 2 or more, preferably an integer of 2 to 8, more preferably 3 or 4, and even more preferably 3.

[0046] In the compound represented by formula (PO1), the oxyethylene structural unit in the molecule (—O—C ２ H ４The content of the oxyalkylene structural units represented by -O-AL-) relative to the total oxyalkylene structural units in the molecule (the sum of oxyalkylene structural units represented by -O-AL- in the molecule) is preferably 10 mol % or more, more preferably 30 mol % or more, even more preferably 50 mol % or more, particularly preferably 60 mol % or more, and most preferably 70 mol % or more, in that the polyurethane has better water absorption properties. The upper limit is 100 mol % or less.

[0047] Examples of polyols include Sannix FA103, Newpol 80-4000, Newpol PE-64, and Sannix FA195 (all manufactured by Sanyo Chemical Industries, Ltd.), and Exenol 840 (manufactured by AGC Inc.).

[0048] The polyol may be used alone or in combination of two or more. The content of the structure derived from the polyol in the polyurethane is preferably 20 to 45 mass %, more preferably 20 to 40 mass %, and still more preferably 25 to 40 mass %, based on the total mass of the waterstop material.

[0049] (Polyisocyanate) Polyisocyanate is a compound having two or more isocyanate groups (NCO groups). The number of isocyanate groups in the polyisocyanate is not particularly limited as long as it is two or more, but is preferably 3 to 6, and more preferably 3. The molecular weight of the polyisocyanate is preferably 100 to 1,000, more preferably 150 to 500, and even more preferably 200 to 300. When the polyisocyanate has a molecular weight distribution, it is preferable that the number average molecular weight falls within the above range.

[0050] The polyisocyanate may be any known polyisocyanate, such as a chain aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, or a complex thereof, such as an isocyanurate, a biuret, an allophanate, or an adduct.

[0051] Examples of the linear aliphatic polyisocyanates include linear aliphatic diisocyanates such as methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate, and branched aliphatic diisocyanates such as trimethylhexamethylene diisocyanate. Examples of the alicyclic polyisocyanates include isophorone diisocyanate (IPDI), 4,4-dicyclohexylmethane diisocyanate, 1,4-cyclohexylene diisocyanate, and hydrogenated tolylene diisocyanate. Examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, p- or m-phenylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, toluene diisocyanate (TDI), phenylene diisocyanate, toluidine diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, triisocyanate toluene, triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and 4,4',4"-triphenylmethane triisocyanate.

[0052] The polyisocyanate is preferably a complex of a linear aliphatic diisocyanate or a triisocyanate, more preferably a complex of HDI.

[0053] Examples of polyisocyanates that can be used include Duranate D101, Duranate D201, Duranate TKA-100, Duranate E402-100, Duranate AE700-100, and Duranate TUL-100 (all manufactured by Asahi Kasei Corporation).

[0054] The polyisocyanate may be used alone or in combination of two or more. The content of the polyisocyanate-derived structure in the polyurethane is preferably 1 to 10 mass%, more preferably 1 to 5 mass%, and even more preferably 2 to 4 mass%, relative to the total mass of the waterstop material. The mass ratio of the polyisocyanate-derived structure to the polyol-derived structure in the polyurethane is preferably 0.01 to 0.20, more preferably 0.05 to 0.15, and even more preferably 0.05 to 0.11.

[0055] The polymer may be used alone or in combination of two or more. The content of the polymer is preferably 20 to 50 mass %, more preferably 20 to 40 mass %, still more preferably 20 to 35 mass %, and particularly preferably 20 to 32 mass %, based on the total mass of the water-stopping material.

[0056] <<Water-absorbent resin particles>> The water-stopping material may contain water-absorbent resin particles. The water-absorbent resin particles are resin particles that absorb water and swell when they come into contact with water. The water absorption rate of the water-absorbent resin particles is preferably 20% or more, and from the viewpoint of more excellent water-stopping ability, more preferably 50% or more, and even more preferably 100% or more. From the viewpoint of durability, the upper limit of the water absorption rate of the water-absorbent resin particles is preferably 10,000% or less, and more preferably 8,000% or less.

[0057] The shape of the water-absorbent resin particles is not particularly limited as long as it is particulate, and examples thereof include spherical, polygonal, scaly, tabular, and irregular shapes. The median particle size of the water-absorbent resin particles is not particularly limited, but is preferably 1 to 100 μm, more preferably 1 to 50 μm, in terms of being able to suppress detachment of the water-absorbent resin particles. The median particle size can be measured using a laser diffraction / scattering particle size distribution measuring device.

[0058] Examples of the water-absorbent resin constituting the water-absorbent resin particles include resins obtained by polymerizing at least one selected from polymerizable monomers having an ionic group and polysaccharides with a crosslinking agent.

[0059] The polymerizable monomer having an ionic group includes a polymerizable monomer having an acid group. The acid group includes a carboxy group, a sulfo group, and a phosphate group, with a carboxy group being preferred. The acid group may form a salt. Examples of the salt include alkali metal salts (e.g., sodium salts and potassium salts), alkaline earth metal salts (e.g., calcium salts and magnesium salts), amine salts, and ammonium salts. Examples of the polymerizable monomer having a carboxy group include (meth)acrylic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, sorbic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, cinnamic acid, citraconic acid, citraconic acid monoalkyl esters, and anhydrides thereof. Examples of polymerizable monomers having a sulfo group include vinyl sulfonic acid, allyl sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, 2-hydroxy-3-(meth)acryloxypropyl sulfonic acid, (meth)acrylalkyl sulfonic acids (e.g., sulfoethyl (meth)acrylate and propyl (meth)acrylate), and (meth)acrylamidoalkyl sulfonic acids (e.g., 2-acrylamido-2-methylpropane sulfonic acid). Examples of polymerizable monomers having a phosphoric acid group include (meth)acrylic acid hydroxyalkyl phosphoric acid monoesters (e.g., 2-hydroxyethyl (meth)acryloyl phosphate and phenyl-2-acryloyloxyethyl phosphate).

[0060] The polysaccharides are a general term for substances in which multiple monosaccharide molecules are polymerized through glycosidic bonds, and examples thereof include agarose, dextran, carrageenan, alginic acid, hyaluronic acid, chitin, chitosan, starch, and cellulose-based compounds.

[0061] Examples of the crosslinking agent include polymerizable monomers having two or more polymerizable groups, compounds having a polymerizable group and a reactive group (e.g., a hydroxyl group) that reacts with an acid group, and compounds having two or more reactive groups that react with an acid group. Examples of polymerizable monomers having two or more polymerizable groups include N,N'-methylenebis(meth)acrylamide, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane triacrylate, triallylamine, triallyl cyanurate, triallyl isocyanurate, tetraallyloxyethane, and pentaerythritol triallyl ether. Examples of compounds having a polymerizable group and a reactive group that reacts with an acid group include hydroxyethyl (meth)acrylate, N-methylol (meth)acrylamide, and glycidyl (meth)acrylate. Examples of compounds having two or more reactive groups that react with an acid group include ethylene glycol, diethylene glycol, glycerin, propylene glycol, trimethylolpropane, alkanolamines (e.g., diethanolamine), and polyamines (e.g., polyethyleneimine).

[0062] Examples of water-absorbent resins include crosslinked polyacrylic acid, crosslinked acrylic acid-vinyl alcohol copolymers, crosslinked starch-acrylic acid graft copolymers, crosslinked acrylic acid-acrylamide copolymers, crosslinked polysulfonic acid, crosslinked polyacrylic acid-polysulfonic acid copolymers, crosslinked isobutylene-maleic anhydride copolymers, crosslinked polyvinylpyrrolidone, crosslinked carboxylic acid-modified polyvinyl alcohol, hydrolyzed starch-acrylonitrile graft copolymers, hydrolyzed cellulose-acrylonitrile graft copolymers, crosslinked carboxymethyl cellulose, crosslinked polyaspartic acid, and salts and partial salts thereof. Note that the partial salt of a polymer refers to an embodiment in which some acid groups of repeating units contained in the polymer form a salt; for example, a crosslinked partial sodium salt of polyacrylic acid refers to a crosslinked polyacrylic acid-polyacrylic acid sodium salt copolymer. Among these, in terms of durability, crosslinked polyacrylic acid, crosslinked starch-acrylic acid graft copolymer, and salts or partial salts thereof are preferred, with crosslinked polyacrylic acid partial salts being more preferred.

[0063] Commercially available water-absorbent resin particles can also be used, such as Sunfresh ST-500MPSA, ST-500DC, ST-500MPS, ST-100, and ST-100MPS (all manufactured by Sanyo Chemical Industries, Ltd.).

[0064] The water-absorbent resin particles may be used alone or in combination of two or more. When the water-stopping material contains water-absorbent resin particles, the content of the water-absorbent resin particles is preferably 5% by mass or more, more preferably 20% by mass or more, and even more preferably 40% by mass or more, relative to the total mass of the water-stopping material, in order to achieve a more excellent effect of the present invention. Furthermore, the content of the water-absorbent resin particles is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less, relative to the total mass of the water-stopping material, in order to achieve a more excellent effect of the present invention.

[0065] <<Polysaccharide Particles>> The water-stopping material preferably contains polysaccharide particles. When the water-stopping material contains polysaccharide particles, it can have plastic deformability. The shape of the polysaccharide particles is not particularly limited, and examples thereof include spherical, polygonal, scaly, flat, and irregular shapes. The average particle diameter of the polysaccharide particles is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more, in order to facilitate the water-stopping material to satisfy predetermined physical properties. The upper limit is not particularly limited, and is, for example, preferably 100 μm or less, more preferably 50 μm or less. The average particle diameter of the polysaccharide particles can be determined by measuring the particle diameters of any 10 polysaccharide particles within the field of view during SEM (Scanning Electron Microscope) observation and calculating the arithmetic mean value of the measured values.

[0066] An example of a polysaccharide particle is a starch particle. Examples of starch particles include corn starch, potato starch, wheat starch, tapioca starch, waxy corn starch, rice starch, and sweet potato starch. The starch particle may also be chemically modified. Modification methods for obtaining modified starch particles include esterification such as acetylation, etherification such as carboxyalkylation, phosphorylation, oxidation, sulfation, phosphate cross-linking, adipic acid cross-linking, enzyme treatment, moist heat treatment, and combinations thereof. Among these, phosphate cross-linking and / or moist heat treatment are preferred. The starch particle may also be cross-linked. The cross-linking method is not particularly limited, and examples include a cross-linking method using a cross-linking agent, and a cross-linking method using radiation (e.g., gamma rays, X-rays, and electron beams) and / or heat.

[0067] The polysaccharide particles may be used alone or in combination of two or more. When the water-stopping material contains polysaccharide particles, the lower limit of the content of the polysaccharide particles is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, relative to the total mass of the water-stopping material, in order to facilitate the water-stopping material to satisfy the predetermined physical properties. The upper limit of the content of the polysaccharide particles is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less, relative to the total mass of the water-stopping material, in order to facilitate the water-stopping material to satisfy the predetermined physical properties.

[0068] <<Plasticizer>> The water-stopping material preferably contains a plasticizer, since this makes it easier to obtain the desired physical properties of the water-stopping material. It is also preferable that the plasticizer does not have a crosslinked structure.

[0069] The plasticizer is not particularly limited as long as it is compatible with the polymer, and examples thereof include polycarboxylic acid ester-based plasticizers, polyether ester-based plasticizers, glycerin-based plasticizers, phosphate ester-based plasticizers, epoxy-based plasticizers, polyester-based plasticizers, and acrylic acid ester-based plasticizers. Of these, polycarboxylic acid ester-based plasticizers or polyether ester-based plasticizers are preferred because they make it easier to obtain the desired physical properties of the water-stopping material.

[0070] Examples of polycarboxylic acid ester-based plasticizers include aromatic dicarboxylic acid esters, aliphatic dicarboxylic acid esters, trimellitic acid esters, and citrate esters. Examples of the esters include alkyl esters, phenyl esters, and benzyl esters. The number of carbon atoms in the alkyl group in the alkyl esters is preferably 1 to 30, more preferably 1 to 22, and even more preferably 3 to 16. The alkyl group may have a phenyl group as a substituent, or may have a divalent linking group represented by -O- between the carbon-carbon bonds of the alkyl group.

[0071] Examples of the aromatic dicarboxylic acid esters include phthalic acid esters (e.g., dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, heptyl phthalate, diisononyl phthalate, benzyl phthalate, and butyl benzyl phthalate) and terephthalic acid esters (e.g., dimethyl terephthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, heptyl phthalate, diisononyl phthalate, benzyl phthalate, and butyl benzyl phthalate). Examples of the aliphatic dicarboxylic acid esters include adipic acid esters (e.g., diisodecyl adipate, di-n-octyl adipate, and di-n-decyl adipate), azelaic acid esters (e.g., di-2-ethylhexyl azelate), and sebacate esters (e.g., dibutyl sebacate and di-2-ethylhexyl sebacate). Examples of trimellitic acid esters include trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, triamyl trimellitate, trihexyl trimellitate, triheptyl trimellitate, tri-n-octyl trimellitate, tri-2-ethylhexyl trimellitate, trinonyl trimellitate, triisononyl trimellitate, tris(decyl) trimellitate, tris(dodecyl) trimellitate, tris(tetradecyl) trimellitate, tris(C8-C12 mixed alkyl) trimellitate, tris(C7-C9 mixed alkyl) trimellitate, and trilauryl trimellitate. Commercially available products include Adeka Cizer C-8, C-880, C-79, C810, C-9N, and C-10 manufactured by ADEKA Corporation. Examples of citrate esters include acetyl triethyl citrate and acetyl tributyl citrate.

[0072] Examples of polyether ester plasticizers include organic acid esters of polyalkylene glycols and compounds represented by the following formula (PP1). Examples of the polyalkylene glycols include polyethylene glycol, polypropylene glycol, polybutylene glycol, poly(ethylene oxide-propylene oxide) block copolymers, poly(ethylene oxide-propylene oxide) random copolymers, and polytetramethylene glycol. The polyether chain may contain an aromatic unit such as a bisphenol. Examples of the organic acids include monocarboxylic acids (e.g., benzoic acid, butanoic acid, isobutanoic acid, 2-ethylbutyric acid, 2-ethylhexyl acid, and decanoic acid).

[0073] R １ -(O-AL) ｐ -O-CO-R ２ Formula (PP1) In formula (PP1), R １ represents a hydrogen atom or a monovalent organic group. ２ represents a monovalent organic group. AL represents an alkylene group. p represents an integer of 2 or more. R １Examples of the monovalent organic group represented by the formula (I) include an alkyl group, an aryl group, an aralkyl group, and an acyl group. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 18, and even more preferably 1 to 10. The aryl group includes an aryl group having 6 to 18 carbon atoms. The aryl group may be either monocyclic or polycyclic. The aralkyl group includes the above-mentioned alkyl group in which one hydrogen atom is substituted with the above-mentioned aryl group. The number of carbon atoms in the aralkyl group is preferably 7 to 18. Examples of aralkyl groups include a benzyl group and a phenethyl group. Examples of acyl groups include an alkylcarbonyl group and an arylcarbonyl group. The alkyl group portion in the alkylcarbonyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 20, more preferably 2 to 18, and even more preferably 2 to 10. The aryl group moiety in the arylcarbonyl group may be either a monocyclic or polycyclic aryl group, and examples thereof include aryl groups having 6 to 18 carbon atoms.

[0074] R ２ Examples of the monovalent organic group represented by the formula (I) include an alkyl group, an aryl group, and an aralkyl group. The alkyl group, the aryl group, and the aralkyl group include the above-mentioned R ２ Examples of the alkyl group, aryl group, and aralkyl group include those similar to those represented by the following formula:

[0075] AL represents an alkylene group. The alkylene group may be linear, branched, or cyclic, preferably linear or branched, and more preferably linear. The number of carbon atoms in the alkylene group represented by AL is preferably 1 to 6, more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2. Specific examples of the alkylene group represented by AL include a methylene group, an ethylene group, and a propylene group (specifically, an n-propylene group and a 2-methylethylene group), with an ethylene group or a 2-methylethylene group being preferred, and an ethylene group being more preferred.

[0076] AL may be one type or two or more types.

[0077] p represents the number of repetitions. The number of repetitions represented by p may be any number as long as it is 2 or more, and is, for example, preferably 2 to 50, more preferably 3 to 10, and even more preferably 4 or 5.

[0078] Commercially available polyether ester plasticizers include, for example, Sunflex EB-200 and Sunflex EB-400 (both manufactured by Sanyo Chemical Industries, Ltd.), and Adeka Cizer RS-1000, RS-735, and RS-700 (all manufactured by ADEKA Corporation).

[0079] The plasticizer may be used alone or in combination of two or more. The content of the plasticizer is preferably 15 to 40 mass %, more preferably 15 to 35 mass %, and even more preferably 20 to 35 mass %, based on the total mass of the water-stopping material.

[0080] <<Catalyst>> The water-stopping material may contain a catalyst for polymer synthesis (for example, a catalyst such as a polyaddition catalyst for polyurethane synthesis). Known catalysts can be used as the catalyst, including organometallic compounds and tertiary amine compounds. Specific examples that can be used include organotin catalysts such as dibutyltin dilaurate and dibutyltin dioctoate, organolead catalysts such as lead octoate, and tertiary amine compounds such as triethylenediamine, N,N'-dimethylhexamethylenediamine, and N,N'-dimethylbutanediamine.

[0081] The catalyst may be used alone or in combination of two or more. When the water-stopping material contains a catalyst, the content of the catalyst is preferably 0.01 to 1.0 mass %, more preferably 0.05 to 0.3 mass %, based on the total mass of the water-stopping material.

[0082] <<Other Components>> The water-stopping material may contain components other than the components described above. Examples of the other components include an adhesive component and a pigment that can be contained in the adhesive layer, which will be described later.

[0083] [Method for manufacturing waterstop material] The method for manufacturing the waterstop material is not particularly limited, and the waterstop material can be manufactured by a known method. For example, a method can be used in which polymer raw materials (e.g., polyol and polyisocyanate, which are raw materials for polyurethane) and other optional components (e.g., polysaccharide particles, water-absorbent resin particles, plasticizer, catalyst, and pigment) are mixed together as needed, and the waterstop material is manufactured while polymerizing the polymer. The mixing may be performed in the air or in an inert gas atmosphere. The mixing may also be performed under normal pressure or reduced pressure. During polymer polymerization, polymerization treatments such as heating and light irradiation may be performed as needed. One or more selected from the raw materials, the mixture, and the polymer before mixing may also be subjected to a drying treatment as needed.

[0084] [Shape of Waterstop Material] The shape of the waterstop material is not particularly limited, and examples include a plate shape. Other examples of the shape of the waterstop material include a cross-sectional shape in which at least a portion protrudes away from the bottom. Here, the bottom refers to a portion that includes at least the bottom surface. The waterstop material (waterstop material layer) disposed on the substrate (nonwoven fabric) in the laminate sample C10 shown in FIG. 2 (described later) has a flat portion 14A and a triangular protruding portion 14B in cross-sectional view that protrudes from the flat portion 14A. The bottom portion of the waterstop material included in the laminate sample C10 corresponds to the flat portion 14A, including the bottom surface that contacts the substrate. The shape of the waterstop material is preferably tapered, with the width decreasing away from the bottom, for superior workability. The width may decrease continuously or discontinuously, preferably continuously. Furthermore, a portion in which the width does not change away from the bottom may be included. The waterproofing material contained in laminate sample C10 has a triangular cross-sectional shape whose width continuously decreases in the direction away from the bottom. The thickness of flat portion 14A is not particularly limited, but is typically 1 to 2 mm. The maximum height (maximum thickness) of protruding portion 14B is not particularly limited, but is typically 10 to 20 mm.

[0085] Furthermore, the shape of the water-stopping material may also be a convex shape in cross section, etc. A water-stopping material having a convex shape in cross section corresponds to a water-stopping material included in a laminate sample C10 shown in Fig. 2, which will be described later, in which the shape of the protrusion 14B in cross section is a square shape in cross section.

[0086] When the water-stopping material has a cross-sectional shape in which at least a portion of the material protrudes in a direction away from the bottom, the protruding portion of the water-stopping material can be inserted into a gap in an object such as a door. If the water-stopping material has the function of expanding (swelling) upon contact with water, the water-stopping material swells when it comes into contact with water, thereby enabling it to fill the gap more effectively. It is also preferable that the water-stopping material be in a long shape.

[0087] One embodiment of a water-stopping material will be described with reference to the drawings. FIG. 7 is a side view of one embodiment of the water-stopping material. In FIG. 7, the water-stopping material 10A extends in the X direction, which corresponds to the front-to-back direction of the paper. The water-stopping material 10A has a bottom surface 32 and a pair of inclined surfaces 34, each consisting of an inclined surface 34A and an inclined surface 34B, whose spacing narrows in a direction away from the bottom surface 32. In the water-stopping material 10A shown in FIG. 7, the pair of inclined surfaces 34 form a tip portion located away from the bottom surface. In the water-stopping material 10A shown in FIG. 7, the pair of inclined surfaces 34 extend from the edge (end) of the bottom surface 32.

[0088] As shown in FIG. 7 , the elongated water-stopping material preferably has a shape that extends in one direction and includes a bottom surface and a pair of inclined surfaces at a tip located away from the bottom surface, the distance between which narrows in the direction away from the bottom surface. This shape has a cross-sectional view with a protrusion having a pair of oblique sides whose distance narrows continuously in the direction away from the base. In particular, a shape in which the acute angle between at least one of the pair of inclined surfaces and the bottom surface (the acute angle φ1 between one inclined surface 34A and the bottom surface 32 in FIG. 7 ) is 65° or greater (hereinafter also referred to as a "specific shape") is preferred in terms of excellent water flow resistance. The water-stopping material described above refers to the property of the water-stopping material being less likely to detach from the gap under flowing water conditions when applied to a gap by inserting the tip of the water-stopping material into the gap. It is presumed that a water-stopping material with a specific shape has excellent water flow resistance because it is less susceptible to water currents that act in a direction that would peel the water-stopping material under flowing water conditions. In the specific shape, the acute angle between at least one of the inclined surfaces and the bottom surface is 65° or more, and preferably 70° or more in terms of better water resistance. The upper limit of the acute angle is less than 90°, and preferably 75° or less in terms of ease of application to gaps. The acute angle between the other inclined surface and the bottom surface is preferably 65 to 75°, and more preferably 70 to 75°.

[0089] As shown in FIG. 7 , the pair of inclined surfaces spaced apart from the bottom surface may extend from the edge of the bottom surface, or may extend from a position spaced apart from the edge of the bottom surface via another surface. For example, a preferred embodiment includes a pair of vertical surfaces extending from the edge of the bottom surface in a direction perpendicular to the bottom surface, with the inclined surfaces extending from the edge of the vertical surfaces on the opposite side from the bottom surface. This embodiment will be described below with reference to FIG. 8 . FIG. 8 is a side view of one embodiment of a water-stopping material. In FIG. 8 , the water-stopping material 10B extends in the X direction, which corresponds to the front-to-rear direction of the page. The water-stopping material 10B includes a bottom surface 32 and a pair of inclined surfaces 34, each consisting of an inclined surface 34A and an inclined surface 34B, whose spacing narrows in a direction away from the bottom surface 32. In the water-stopping material 10B shown in FIG. 8 , the pair of inclined surfaces 34 form a tip portion spaced apart from the bottom surface. The water-stopping material 10B of embodiment 2 shown in Fig. 8 includes a pair of vertical surfaces 36 extending from the edge of the bottom surface 32 in a direction perpendicular to the bottom surface, and a pair of inclined surfaces 34 extend from the edge of the vertical surfaces 36 on the side opposite to the bottom surface 32. In Fig. 8 as well, it is preferable that the acute angle φ1 formed between one inclined surface 34A and the bottom surface 32 is 65° or more. In other words, it is preferable that the water-stopping material 10B also has the above-mentioned specific shape.

[0090] In Figures 7 and 8, the width of the bottom surface 32 is typically 10 to 15 mm. In Figures 7 and 8, the width of the pair of inclined surfaces 34 is typically 15 to 25 mm. In Figures 7 and 8, the height from the bottom surface 32 to the apex of the tip is typically 15 to 25 mm. The apex of the tip refers to the position of the tip that is farthest from the bottom surface. In Figure 8, the width of the pair of vertical surfaces 36 is typically 2 to 5 mm. The width of each surface refers to the length in a direction perpendicular to the extension direction of the water-stopping material of a specific shape.

[0091] In Figures 7 and 8, the inclined surfaces 34A and 34B are shown intersecting each other at the apex of the tip portion, but they may also be connected via other surfaces (e.g., a surface parallel to the bottom surface 32 and a surface having a curvature).

[0092] It should be noted that even if a water-stopping material does not have at least one of the first to third characteristic features described above and has the specific shape described above, it will still have excellent resistance to running water.

[0093] [Uses] The waterstop material of the present invention can be used for various waterstop applications. The waterstop material of the present invention is preferably applied, in particular, to applications for preventing flooding damage to buildings. The waterstop material of the present invention can be used, for example, by being placed in gaps between windows and window frames, between doors and door frames, or between doors when doors (automatic doors and manual doors) and windows are closed, to prevent or reduce water leakage from the above gaps. The waterstop material may be applied from either the water inflow side or the water outflow side, but is preferably applied from the water inflow side. Furthermore, the mode of use of the waterstop material of the present invention is not particularly limited; the waterstop material may be placed alone at the waterstop location, or may be used in the form of a laminate described below.

[0094] [Laminate] The laminate of the present invention includes a long substrate and a waterstop layer formed on the substrate and comprising the waterstop material of the present invention. Each component of the laminate of the present invention will be described in detail below.

[0095] [Substrate] The substrate may be long, and the length and width are not particularly limited. The term "length" refers to the length of the substrate in the longitudinal direction, and the term "width" refers to the length of the substrate in the direction perpendicular to the longitudinal direction. The thickness of the substrate is not particularly limited, and is, for example, 15 to 200 μm. It is also preferable that the tensile modulus of elasticity of the substrate differs between the longitudinal direction and the width direction.

[0096] The substrate is preferably made of a material capable of supporting the water-stopping layer, such as a resin, for example, cellulose, polyester, rayon, polyolefin, poly(meth)acrylate, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), cycloolefin polymer (COP), and acrylonitrile / butadiene / styrene copolymer (ABS).

[0097] The substrate is also preferably a water-permeable substrate. "Water-permeable" means the property of allowing liquid water to pass through. Specific examples of water-permeable substrates include substrates having pores through which water can pass. When the substrate is a water-permeable substrate, water passes through the water-permeable substrate and is absorbed into the water-stopping material layer, thereby enabling efficient water blocking. The water-permeable substrate is preferably a layer containing fibers, in terms of better water permeability, and more preferably a layer containing cellulose fibers, rayon fibers, polyolefin fibers, or polyester fibers. Furthermore, the water-permeable substrate is preferably a nonwoven fabric, cloth, or paper, in terms of better water permeability, and more preferably a nonwoven fabric.

[0098] When the water-stopping material has the above-mentioned specific shape, the substrate is preferably laminated on the bottom side of the water-stopping material.

[0099] [Waterstop Layer] The laminate has a waterstop layer made of a waterstop material. The waterstop material and its shape are as described above. For example, when the waterstop material has a cross-sectional shape in which at least a portion protrudes in a direction away from the bottom, as described in the upper section, it is preferable that the bottom is disposed so as to face the substrate. The method for forming the waterstop layer is not particularly limited, and examples include a method of forming a waterstop layer on a substrate by laminating a waterstop material and a substrate together, a method of forming a waterstop layer on a substrate by applying a necessary treatment (e.g., a curing treatment such as heating treatment and light irradiation treatment) to a waterstop material-forming composition applied to the substrate, and a method of forming a waterstop layer on a substrate by contacting the waterstop material layer-forming composition introduced into a mold with the substrate and applying a necessary treatment (e.g., a curing treatment such as heating treatment and light irradiation treatment). An example of the water-stopping material-forming composition is a composition containing polymer raw materials (e.g., polyol and polyisocyanate, which are raw materials for polyurethane) and other optional components (e.g., polysaccharide particles, absorbent resin particles, plasticizers, catalysts, and pigments).

[0100] [Adhesive layer] The laminate may further have an adhesive layer on the side opposite to the substrate side of the water-stopping material layer. The adhesive layer is a layer that has at least one of the functions of adhesion and cohesion to members (e.g., glass, resin, metal, and ceramics). By having the adhesive layer in the laminate, the laminate can be easily maintained in the water-stopping location. The adhesive layer is preferably a water-absorbent adhesive layer. A water-absorbent adhesive layer is a layer that absorbs water when it comes into contact with water and thereby exhibits or increases adhesiveness or cohesion. By using a water-absorbent adhesive layer, the adhesive layer can exhibit excellent adhesion even in wet locations.

[0101] As the component of the adhesive layer, known adhesives and pressure sensitive adhesives can be used, such as vinyl resins, silicones, poly(meth)acrylates, polyurethanes, polyamides, polyesters, polyolefins, and rubbers.

[0102] Examples of vinyl resins include polyvinyl alcohol and polyvinylpyrrolidone.

[0103] Examples of silicones include addition reaction type silicones, peroxide curing type silicones, and condensation type silicones.

[0104] Examples of poly(meth)acrylates include homopolymers of (meth)acrylic acid ester monomers and copolymers of acrylic acid ester monomers with other monomers. Examples of acrylic acid ester monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, and glycidyl methacrylate. Examples of other monomers include vinyl acetate, (meth)acrylonitrile, (meth)acrylamide, styrene, methacrylic acid, acrylic acid, itaconic acid, methylol acrylamide, and maleic anhydride.

[0105] Polyurethanes include, for example, polyester polyurethanes and polycarbonate polyurethanes.

[0106] Examples of polyamides include polyamide (amide 11) obtained by ring-opening polycondensation of undecane lactam and polyamide (amide 12) obtained by ring-opening polycondensation of lauryllactam.

[0107] Examples of polyesters include condensation polymers of polycarboxylic acids and polyhydric alcohols, and specific examples thereof include polyethylene terephthalate and polybutylene terephthalate.

[0108] Examples of polyolefins include olefin homopolymers and copolymers of olefins with other monomers. The olefin is preferably an olefin having 2 to 6 carbon atoms. Examples of olefins include ethylene, propylene, butene, methylpentene, and hexene. Examples of copolymers of olefins with other monomers include EVA (ethylene-vinyl acetate copolymer), EAA (ethylene-acrylic acid copolymer), EEA (ethylene-ethyl acrylate copolymer), and EMMA (ethylene-methyl methacrylate copolymer).

[0109] Examples of rubbers include styrene / butadiene copolymers (SBR, SBS), styrene / isoprene copolymers (SIS), acrylonitrile-butadiene copolymers (NBR), chloroprene polymers, and isobutylene / isoprene copolymers (butyl rubber).

[0110] In terms of excellent water-absorbing adhesiveness, the adhesive layer preferably contains a vinyl resin, and more preferably contains polyvinyl alcohol.

[0111] The method for forming the adhesive layer is not particularly limited, and the adhesive layer can be formed, for example, by applying an adhesive layer-forming composition onto the water-stopping material layer. After applying the adhesive layer-forming composition, drying treatment and heat treatment may be performed as necessary. The adhesive layer-forming composition may contain other components in addition to those described above. Examples of other components include solvents, ultraviolet absorbers, antioxidants, crosslinking agents, surfactants, fillers, colorants, light stabilizers, thickeners, and polymerization initiators. The thickness of the adhesive layer is, for example, 10 to 500 μm.

[0112] When the water-stopping material has the above-mentioned specific shape, the adhesive layer is preferably laminated on a surface different from the bottom surface of the water-stopping material (for example, the surface that constitutes the tip portion).

[0113] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0114] Example 1 Preparation of Composition and Fabrication of Water-Stopping Material The components listed in Table 1 were mixed in a stirring vessel to obtain the composition (parts by mass) listed in Table 1, to obtain a mixture. The mixture was placed in a mixer (product name "ARV-310," manufactured by Thinky Corporation) and subjected to reduced pressure stirring for 1 minute at a rotation speed of 900 rpm (revolutions per minute) and a pressure of 3 kPa. The mixture after reduced pressure stirring was poured into an acrylic resin container measuring 50 mm in length, 50 mm in width, and 4 mm in height, and allowed to stand at 25°C for 24 hours. The composition was then removed from the acrylic resin container, and a plate-shaped water-stopping material sample A measuring approximately 50 mm in length, 50 mm in width, and 4 mm in thickness was obtained. Separately, the mixture after reduced pressure stirring was poured into a flat glass petri dish (inner diameter 7 cm) and allowed to stand at 25°C for 24 hours. The composition was then removed from the flat glass petri dish, and a cylindrical water-stopping material sample B measuring approximately 7 cm in diameter and 4 mm in thickness was obtained.

[0115] [Measurement of physical properties] <Presence or absence of bubbles> Cross-section observation was performed using a microscope and the surface was visually observed, and the number of bubbles in each observation was measured. The cross-section of the prepared water-stopping material sample A was observed using a microscope (VHS-5000, manufactured by Keyence Corporation) with a 500 μm × 500 μm field of view at 1x objective and 500x lens magnification to confirm the presence or absence of voids. The above observation was performed on 10 cross-sections of the water-stopping material sample A. The arithmetic mean value of the number of bubbles observed in each cross-section was 1 bubble / μm. ２ If the following condition was met, it was determined to be a non-foaming type.

[0116] The results of the observation were classified and evaluated according to the following criteria: A: It was determined to be a non-foamed product. B: Air bubbles exceeding a predetermined value were observed. The results are shown in the "Presence or absence of bubbles" column in Table 1.

[0117] <Measurement of Compressive Stress Inflection Point (MPa)> Using a Strograph VE20D (manufactured by Toyo Seiki Seisakusho, Ltd.), a compression element (φ30 mm stainless steel disk surface) was placed in the center of the prepared water-stopping material sample A, and strain dispersion measurements were performed at a compression rate of 0.5 mm / min from 0 to 100% strain. A conversion curve of the stress-strain curve was obtained by logarithmically converting the vertical axis of the obtained stress-strain curve. Next, the intersection of the first approximation line obtained by the least squares method for the curve in the 30-50% strain range of the conversion curve and the second approximation line obtained by the least squares method for the curve in the 75-100% strain range of the conversion curve was determined, and the stress value (MPa) at this intersection was calculated. The strain value (%) at the intersection was also calculated and used to measure the G' ratio described below. The strain value (%) at the above intersection point for each of the waterstop material samples A in Examples 1 to 3 was 75% for Examples 1 and 2, and 64% for Example 3. The strain dispersion measurement was carried out after the prepared waterstop material sample A was placed in a test environment of 25°C for 12 hours or more. The results are shown in the "Compressive stress inflection point (MPa)" column in Table 1.

[0118] <Measurement of Viscoelastic Properties> For the prepared waterstop material sample B, strain dispersion measurements were performed using a rheometer (MCR302, manufactured by Anton Paar Inc.) under conditions of temperature: 25°C, frequency: 1 Hz, Nf = 1 N, and measurement plate: PP25, covering strains of 0.001 to 100%, and the sample was evaluated according to the following criteria. The strain dispersion measurements were performed after the prepared waterstop material sample B was placed in a test environment at 25°C for 12 hours or more. A: When there is an intersection point in the strain range of 0.001 to 100% where the values ​​of the storage modulus G' and the loss modulus G'' are the same, and the strain value at the intersection point is 50% or more, and when the storage modulus G' is greater than the loss modulus G'' throughout the entire strain range of 0.001 to 100%. B: When the sample does not fall under the category of A above. The results are shown in the "Viscoelastic Properties" column in Table 1. In Table 1, in parentheses in the "Viscoelastic properties" column, the value ">100" means that the storage modulus G' is greater than the loss modulus G'' over the entire range in the strain interval of 0.001 to 100%. In addition, other values ​​in parentheses in the "Viscoelastic properties" column in Table 1 mean the strain value (%) at which the storage modulus G' and the loss modulus G'' become equal over the strain interval of 0.001 to 100%.

[0119] <Measurement of G' Ratio> For the prepared waterstop material sample B, strain dispersion measurements were performed using a rheometer (MCR302, manufactured by Anton Paar Co., Ltd.) under conditions of temperature: 25°C, frequency: 1 Hz, Nf = 1 N, and measurement plate: PP25, covering strains of 0.001 to 100%. Next, the G' ratio (storage modulus G' / loss modulus G'') was calculated from the values ​​of storage modulus G' and loss modulus G'' at the strain value (%) at the intersection of the first approximate line and the second approximate line obtained in <Measurement of compressive stress inflection point (MPa)>. The strain dispersion measurement was performed after the prepared waterstop material sample B was placed in a test environment of 25°C for 12 hours or more. The results are shown in the "G' Ratio" column in Table 1.

[0120] <Measurement of Compressive Elastic Modulus> Using a Strograph VE20D (manufactured by Toyo Seiki Seisakusho, Ltd.), a compression element (φ30 mm stainless steel disk surface) was placed at the center of the prepared waterstop material sample A, and strain dispersion measurements were performed at a compression rate of 0.5 mm / min from 0 to 100% strain. The slope of the obtained stress-strain curve (vertical axis: stress, horizontal axis: strain) in the 20 to 30% strain range was linearly approximated using the least squares method, and this was taken as the compressive elastic modulus (unit: kPa). The strain dispersion measurements were performed after the prepared waterstop material sample A was placed in a test environment of 25°C for 12 hours or more. The results are shown in the "Compressive Elastic Modulus" column in Table 1.

[0121] [Examples 2 and 3, Comparative Examples 1 and 2] Compositions were prepared, samples were produced, and physical properties were measured in the same manner as in Example 1, except that the compositions and blending amounts were adjusted to be as shown in Table 1.

[0122] Comparative Example 3 Samples were prepared and their physical properties were measured in the same manner as in Example 1, except that aquarium putty (manufactured by Katei Kagaku Kogyo Co., Ltd., product name "Aquarium Putty") was used as the waterproofing material.

[0123] [Various Components] Each component shown in Table 1 will be explained below. [Polyol] - "Sannyx FA-195" (manufactured by Sanyo Chemical Industries, Ltd.; a trifunctional polyol containing a polyoxyalkylene structure and in which the content of oxyethylene structural units in the molecule is 70 mol% relative to all oxyalkylene structural units in the molecule) - "Excelenol 840" (manufactured by AGC Inc.; a trifunctional polyol containing a polyoxyalkylene structure and in which the content of oxyethylene structural units in the molecule is 15 mol% relative to all oxyalkylene structural units in the molecule) - "Hitohada Gel (main ingredient)" (manufactured by Exseal Co., Ltd.)

[0124] [Polyisocyanate] "Duranate TKA-100" (manufactured by Asahi Kasei Corporation) "Human Skin Gel (hardener)" (manufactured by Exseal Co., Ltd.)

[0125] [Plasticizers] "Sunflex EB-200" (manufactured by Sanyo Chemical Industries, Ltd., plasticizer having a polyoxyethylene structure) "DOTP" (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., dioctyl terephthalate)

[0126] [Catalyst] Dibutyltin dilaurate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0127] [Various particles] Delicastar H100 (starch particles, manufactured by Sanwa Starch Co., Ltd.) Sunfresh ST500MPSA (water-absorbent resin particles (polyacrylic acid-based highly absorbent particles), manufactured by Sanyo Chemical Industries, Ltd.)

[0128] [Evaluation] [Evaluation of embeddability] Evaluation samples were prepared according to the following procedure: When the layer structure in Table 1 was "with nonwoven fabric," laminate sample C was prepared, and when the layer structure was "without nonwoven fabric," waterstop material sample D was prepared, and these were used as evaluation samples for evaluating embeddability.

[0129] <Preparation of Laminate Sample C> The components listed in Table 1 were mixed in a stirring vessel to obtain the composition (parts by mass) listed in Table 1, yielding a mixture. The mixture was placed in a mixer (product name "ARV-310," manufactured by Thinky Corporation) and subjected to reduced pressure stirring for 1 minute at a rotation speed of 900 rpm (revolutions per minute) and a pressure of 3 kPa. The mixture after reduced pressure stirring was poured into a mold that had been hollowed out to a flat shape and further hollowed out to a triangular cross section along the length. After allowing to stand at 25°C for 2 hours, a nonwoven fabric (substrate, Kuraseal M) was laminated onto the mixture and allowed to stand at 25°C for at least 22 hours. The laminate was then removed from the mold to obtain Laminate Sample C, which had a waterstop layer on the substrate. A schematic diagram of Laminate Sample C is shown in Figure 2. Laminate Sample C 10 has a waterstop layer 14 made of a waterstop material on a nonwoven fabric 12 substrate. The waterstop layer 14 has a flat portion 14A including a bottom surface that contacts the nonwoven fabric 12, and protruding portions 14B that have a triangular cross-sectional shape whose width continuously decreases in the direction away from the nonwoven fabric 12 or the flat portion 14A. The flat portion 14A is approximately 100 mm long, 50 mm wide, and 1 mm thick. The protruding portions 14B have a triangular cross-sectional shape with a base of approximately 25 mm and a height of 20 mm over a length of approximately 100 mm. Note that waterstop sample D, which will be described later, is a sample in a configuration in which the nonwoven fabric 12 is not present in laminate sample C10 (in other words, a configuration in which only the waterstop layer 14 is present).

[0130] <Preparation of Waterstop Material Sample D> A waterstop sample D was obtained in the same manner as in the preparation of the laminate sample C, except that the step of attaching the nonwoven fabric was not carried out.

[0131] <Evaluation of Embeddability> As shown in Figure 3, an acrylic resin test tank (hereinafter also referred to as "test tank") 20 was prepared. The test tank had a width of 300 mm, a height of 300 mm, and a depth of 700 mm, with a wall and bottom forming a 90° angle. As shown in Figures 3 and 4, a through-hole 24 communicating with the liquid storage portion of the test tank 20 was formed in the lower region of one wall 22 of the test tank 20 (the region enclosed by a dotted line in Figure 3). The through-hole 24 was L-shaped with a gap width of 10 mm, extending along the inner bottom surface 26 and inner wall surface 28 of the test tank 20 (meaning the bottom and wall surfaces constituting the liquid storage portion), and each side of the L shape (the length of the side along the inner bottom surface 26 of the test tank 20 and the length of the side along the inner wall surface 28 of the test tank 20) ​​was 50 mm. As shown in FIG. 5 , the prepared laminate sample C or waterstop material sample D (hereinafter also referred to as the "sample") was inserted into the through-hole 24 from the liquid-containing portion side of the test water tank 20 so that the tip portion (the apex of the triangle extending in the longitudinal direction) of the protruding portion 14B of the sample faced the through-hole 24. The inserted sample was then pressed into the intersection 30 of the inner wall surface 26 and the inner bottom surface 28 of the test water tank 20 at the through-hole 24. After pressing, as shown in FIG. 6 , the intersection 30 of the inner wall surface 26 and the inner bottom surface 28 of the test water tank 20 at the through-hole 24 on the wall surface 22 was visually inspected from the outside of the test water tank 20 (the side opposite the liquid-containing portion), and embeddability was evaluated based on the presence and extent of a gap between the test water tank 20 and the sample according to the following evaluation criteria. In practical use, embeddability is preferably evaluated as B or higher.

[0132] (Evaluation criteria) A: No gap occurs between the test water tank and the sample. B: A gap of less than 1 mm occurs between the test water tank and the sample. C: A gap of 1 mm or more occurs between the test water tank and the sample.

[0133] [Workability Evaluation] Workability evaluation was carried out using the laminate sample C or the waterstop material sample D prepared in the upper part. In the layer structure in Table 1, when "nonwoven fabric is present," laminate sample C was used, and when "nonwoven fabric is absent," waterstop material sample D was used.

[0134] <Evaluation of workability> The ease of workability was judged using the following index: A: The water-stopping material did not stretch excessively and workability was good. B: The water-stopping material stretched and workability was somewhat poor.

[0135] [Evaluation of Peelability (Separability)] Peelability evaluation was carried out using laminate sample C or waterstop material sample D prepared in the upper part. In the layer structure in Table 1, laminate sample C was used when "nonwoven fabric is present," and waterstop material sample D was used when "nonwoven fabric is absent."

[0136] <Evaluation of Peelability> The ease of peeling was evaluated using the following index: A: Good peelability with no tearing. C: Poor peelability with frequent tearing.

[0137] [Evaluation of Water Absorption and Swelling Property] Evaluation samples were prepared by the following procedure: <Preparation of Waterstop Material Sample E> In the same manner as for the preparation of waterstop material sample A, waterstop material sample E having a length of about 60 mm, a width of about 60 mm and a thickness of about 2 mm was obtained.

[0138] <Evaluation of Water Absorption Swelling Property> The prepared waterstop material sample E was immersed in distilled water adjusted to 25°C, and the mass before immersion and the mass after immersion for 1 hour were measured, and the swelling ratio after immersion for 1 hour was calculated according to the following formula: Swelling ratio after immersion for 1 hour = Mass of waterstop material sample E after immersion for 1 hour / Mass of waterstop material sample E before immersion The water absorption swelling property (waterstopping ability) was evaluated from the obtained swelling ratio after immersion for 1 hour according to the following evaluation criteria. The faster the swelling ratio after immersion for 1 hour, the more quickly the waterstop material swells and the more excellent the waterstopping ability. For practical purposes, a rating of B or higher is preferable for water absorption swelling property.

[0139] (Evaluation criteria) A: Swelling ratio after immersion for 1 hour is 2.0 or more B: Swelling ratio after immersion for 1 hour is 1.1 or more and less than 2.0 C: Swelling ratio after immersion for 1 hour is less than 1.1

[0140]

[0141] The results in Table 1 clearly show that the water-stopping materials of the examples have excellent embeddability and peelability. Furthermore, a comparison between Examples 1 and 2 confirmed that when a substrate (nonwoven fabric) is attached to the water-stopping material to form a laminate, elongation during application is suppressed, further improving application properties. Furthermore, a comparison between Examples 1 and 3 confirmed that when the stress value at the intersection of the first approximate line and the second approximate line in the conversion curve is 0.40 MPa or less, the embeddability is superior.

[0142] On the other hand, the water-stopping materials of the comparative examples did not achieve the desired effect. In Comparative Example 1, the stress value at the intersection of the first and second approximate lines in the conversion curve was too large, so the gap did not fill even when pressed into the corner. On the other hand, in Comparative Example 2, the gap was filled when pressed into the corner, but when the pressure was released, the pressed state (embedded state) could not be maintained due to elastic rebound (the corner adhesion could not be maintained). In Comparative Example 3, although the embedding ability into the corner was good, the tensile elongation was small, and it easily tore when peeled off, requiring time for cleanup. Furthermore, because the water-stopping material of Comparative Example 3 does not have water-absorbing swelling properties, if gaps were left when placing the water-stopping material (putty) during construction, even small gaps could cause water intrusion.

[0143] For each example of the waterproofing material, laminate sample P1 having the specific shape shown in FIG. 7 was manufactured in accordance with the manufacturing method of laminate sample C. Laminate sample P1 had a bottom width of 15 mm, a height from the bottom to the apex of the tip of 18 mm, and an acute angle of 71° between the bottom and the inclined surface. The acute angle between the bottom and the inclined surface of laminate sample C was 58°. For laminate sample C and laminate sample P1, the samples were embedded in gaps, and water was poured into the area where the samples were present to evaluate their water flow resistance. As a result, it was confirmed that laminate sample P1 was less likely to detach from gaps and had better water flow resistance than laminate sample C.

[0144] A: First approximate straight line B: Second approximate straight line H: Intersection H1: Stress at intersection H H2: Strain at intersection H 10: Laminate sample 10A, 10B: Water-stopping material 12: Substrate (nonwoven fabric) 14: Water-stopping material layer 14A: Flat portion 14B: Protrusion 20: Test water tank 22: Wall surface 24: Through-hole 26: Inner bottom surface 28: Inner wall surface 30: Intersection portion 32: Bottom surface 34A, 34B, 34: Inclined surface 36: Orthogonal surface φ1: Acute angle X, Y, Z directions

Claims

1. A non-foaming water-sealing material, wherein when the water-sealing material is compressed to obtain a stress-strain curve with stress on the vertical axis and strain on the horizontal axis, and the vertical axis of the obtained stress-strain curve is logarithmically converted to obtain a conversion curve, a stress value H1 at an intersection H where a first approximation line obtained by the least squares method of the curve in a 30 to 50% strain range of the conversion curve intersects with a second approximation line obtained by the least squares method of the curve in a 75 to 100% strain range of the conversion curve is 1.00 MPa or less, When the storage modulus G' and loss modulus G'' of the water-stopping material are measured at a temperature of 25°C, a frequency of 1 Hz, and strains ranging from 0.001 to 100%, the strain at which the storage modulus G' and the loss modulus G'' have the same values ​​is 50% or more, or the storage modulus G' is greater than the loss modulus G'' over the entire range of strain, and the ratio of the storage modulus G' to the loss modulus G'' at the strain value H2 at the intersection point H on the conversion curve is 3.0 or less.

2. The waterproof material according to claim 1, having a compressive elastic modulus of 20 kPa or more in the strain range of 20 to 30%.

3. The water-stopping material according to claim 1 or 2, which expands upon contact with water.

4. A laminate comprising a long substrate and a water-stopping layer comprising the water-stopping material according to claim 1 or 2 disposed on the substrate.

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