JP6021580B2 - Waterproof sheet - Google Patents

Description

  The present invention relates to a water stop sheet, and more particularly, to a water stop sheet that can quickly stop water leakage from a crack or the like generated in an aging building.

  Many of the buildings inside the station are aging and are often repaired whenever a malfunction occurs. In particular, rain leaks have a large impact on railway users, and may cause damage to equipment in the building. Therefore, it is desirable to close the location that causes the rain leak, but it is very difficult to stop the water in a wet state. Currently, as a countermeasure against water leakage, water stoppage is performed after the water leakage portion has dried. For this reason, until the water stop treatment is completed, the platform and waiting room remain wet, causing unpleasant feelings to railroad users and freezing in winter.

Patent Document 1 discloses a surfactant, gelling hydrophilic resin, gelling agent, and water as a water leakage preventing material that is inexpensive, does not require labor, and can cope with a joint surface of concrete or a wide crack. A water leakage preventing material is disclosed, which is characterized by applying or impregnating a permeable waterproofing agent containing water to a cloth or sheet.
Further, Patent Document 2 proposes a rubber band wound around a water leak location as a repair method at the water leak location of the pipe.

JP-A-11-315271 Japanese Patent No. 2729585

As shown in the above-mentioned Patent Document 1, the conventional water leakage prevention material is useful in the water leakage location after drying after water leakage stops, but when pasted in a wet state, polyacrylate, etc. There is a problem that the water-absorbent resin is peeled off due to the weight after water absorption.
Further, since the rubber band shown in Patent Document 2 is used by being wrapped around a pipe, it cannot be used when the leaking point is a flat surface, and if the shape of the leaking point such as a crack is complicated, the water stop is completely completed. It cannot be assumed. Furthermore, the rubber band shown in the same document requires a temporary fixing means for the pipe and a fastening means for the wound rubber band, and thus it takes time to stop the water leakage.
This invention makes it a subject to provide the water stop sheet | seat which can stop water easily only by sticking to a water leak location even if it is in the wet state.

The present inventors apply a water-stopping layer impregnated with a terminal isocyanate group-containing urethane prepolymer on the pressure-sensitive adhesive layer provided on the support, thereby sticking it to a leaked portion even in a wet state. It was found that the water could be easily stopped by just using it.
That is, the present invention comprises a support,
An adhesive layer covering the surface of the support;
About the whole part excluding the peripheral part of the support or a required place, a water stop layer provided on the pressure-sensitive adhesive layer,
A release film laminated and laminated on the upper side of the pressure-sensitive adhesive layer so as to enclose the water-stopping layer,
A waterproof sheet comprising:
The water-stopping layer relates to a water-stopping sheet, which is a layer formed by impregnating a fibrous base material with a terminal isocyanate group-containing urethane prepolymer.

In the present invention, preferably, the terminal isocyanate group-containing urethane prepolymer is a prepolymer obtained by reacting a polyether polyol and an organic polyisocyanate, and more preferably, the polyether polyol is a polyhydric phenol. An alkylene oxide adduct is preferred.
Moreover, in this invention, it is preferable that the said adhesive layer consists of an acrylic adhesive.
Further, in the present invention, the fibrous base material is a nonwoven fabric having a basis weight of 50 to 500 g / m ² and a thickness of 1 to 10 mm, and the water-stopping layer contains the terminal isocyanate group-containing urethane prepolymer in an amount of 0.0. It is desirable that the fibrous base material is impregnated with an impregnation amount of 05 to 2.0 g / cm ² .
More preferably, the pressure-sensitive adhesive layer is a flat layer having a rectangular shape with a side of 50 mm to 300 mm, and the water blocking layer is a flat layer having a rectangular shape with a side of 30 to 200 mm.

  The present invention also relates to a waterproof sheet product in which the waterproof sheet is sealed together with a moisture absorbent in an aluminum laminate packaging material.

The water-stop sheet of the present invention can quickly stop a water leak point simply by sticking it to a portion where water is leaking. That is, this invention does not need to wait for a water leak location to dry, and can provide the water stop sheet | seat excellent in workability | operativity and the water stop efficiency.
Moreover, the water-stop sheet product of the present invention can provide a water-stop sheet that has little deterioration in water-stop performance even after long-term storage and has excellent storage stability.

As described above, the previously proposed water leakage prevention materials and water stopping materials are applied to locations that cause water leakage such as cracks and gaps after the water leakage location has dried, thereby preventing the next possible water leakage. The purpose is to do.
Such conventional water leakage prevention materials may cause the water-absorbing resin to peel off due to the weight after water absorption at locations where water leakage is occurring right now, or lack of adhesion / stickiness to the water leakage location. It is difficult to apply due to problems such as long time required to complete the water stop due to leakage or water leakage. For this reason, it is difficult to carry out the water stop treatment until the water leakage portion is dry, and the state of being wet for a long time will continue.

Here, the present inventors examined a water-stopping material from a viewpoint different from conventional water-leakage prevention materials, such as applying to a location where water is leaking and stopping water leakage steadily. We came up with the adoption of a terminal isocyanate group-containing urethane prepolymer as a material that can react and self-adhere to the water leakage location. Also, consider locations where water leaks occur frequently and locations where water leaks are particularly problematic, and even when applied to water leaking locations from above such as rain gutters and ceilings, that is, when applied to water leaking locations from below Then, a urethane prepolymer capable of expressing a strong adhesive force that does not fall by its own weight was examined. The present inventor considers the ease of application (attachment) to a water leak location, the water stop performance, the difficulty of peeling off from the water leak location after application, etc. Each material such as a base material impregnated with a polymer was examined.
Furthermore, the present inventors considered the storage stability of the produced water-stopping sheet for a certain period or longer, considering that water leakage occurs without notice. And, a urethane-based pressure-sensitive adhesive, which has been conventionally used for many laminated sheet materials used in construction sites, etc., but the urethane prepolymer reacts with a curing accelerator contained therein and causes deterioration of storage stability. It was concluded that it would be preferable to limit the use of.
And the present inventors consider the application location of the water-stop sheet of the present invention such as rain gutter and ceiling, the adhesiveness to the water leak location from the application of the water-stop sheet until the adhesive strength of the prepolymer is expressed, In order to prevent the waterproof sheet from dropping due to its own weight from the water leakage point, the adhesion of the adhesive layer is considered to be slightly smaller than the adhesive layer. I came up with a configuration that exists.
Based on these, the present inventors made a water-stopping sheet by impregnating a water-absorbing fibrous base material with the urethane prepolymer, and placed it on a support through an adhesive layer. Completed the configuration.
Hereinafter, the water stop sheet of the present invention will be described in detail.

  The water-stop sheet of the present invention is provided on the pressure-sensitive adhesive layer with respect to the support, the pressure-sensitive adhesive layer covering the surface of the support, and the entire portion or a required portion excluding the peripheral portion of the support. A water-stop sheet, and a release film laminated and laminated on the upper side of the pressure-sensitive adhesive layer so as to enclose the water-stop layer, wherein the water-stop layer is terminated to the fibrous base material. The layer is formed by impregnating an isocyanate group-containing urethane prepolymer.

<Water stop layer>
[Terminal isocyanate group-containing urethane prepolymer]
The terminal isocyanate group-containing urethane prepolymer used in the present invention can be obtained, for example, by reacting a hydrophilic polyol such as polyether polyol or polyester polyol with an organic polyisocyanate.

<Polyether polyol>
Examples of the polyether polyol include a compound having a structure in which an alkylene oxide is added to a compound having two or more active hydrogen atoms (for example, polyhydric alcohol, polyhydric phenol, amine, etc.) and a mixture thereof.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, diglycerin, trimethylolpropane, Examples include sorbitol and pentaerythritol.
Examples of the polyhydric phenol include monocyclic polyhydric phenols such as hydroquinone, resorcin, pyrogallol, and phloroglucinol; bisphenols such as bisphenol A and bisphenol sulfone.
The compound having two or more active hydrogen atoms may be used alone or in combination of two or more compounds. When two or more compounds are mixed, three or more active hydrogen atoms are used. It is more preferable from the viewpoint of shortening the curing time that at least a part of the compound having s is contained.
Among these, a combination of a polyhydric phenol and a trihydric or higher aliphatic alcohol is preferable.

Examples of the alkylene oxide added to the compound having two or more active hydrogen atoms include alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, 1,2-, 1,3-, 1, 4- or 2,3-butylene oxide is exemplified. These alkylene oxides may be used alone (addition) or in combination of two or more (block or random addition). Among these, it is preferable to use ethylene oxide and propylene oxide in combination, and it is more preferable to use these in the form of block addition. When ethylene oxide and propylene oxide are used in combination, the proportion of ethylene oxide is preferably 50% by mass or more and more preferably 70% by mass or more based on the total mass of the added alkylene oxide.

The number of alkylene oxides added to the compound having two or more active hydrogen atoms is preferably an integer of 5 to 300, more preferably 8 to 200, based on the number of active hydrogens in the compound having active hydrogen atoms. An integer of 10 to 150 is particularly preferable. Within this range, the curability is further improved.
The hydroxyl value of the polyether polyol is not particularly limited, but is preferably 3 to 50 mgKOH / g and more preferably 5 to 30 mgKOH / g in terms of obtaining appropriate hydrophilicity.

<Polyester polyol>
Specific examples of polyester polyols include polyols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, glycerin or trimethylol propane, succinic acid, glutaric acid, adipic acid, Examples thereof include saturated or unsaturated polyvalent carboxylic acids such as maleic acid, fumaric acid and phthalic acid, condensation products with these acid anhydrides, polycaprolactone polyols, and the like. These polyester polyols can be used in combination of two or more if necessary. Of these, polyester polyols having a weight average molecular weight of 100 to 50,000 are preferably used, and those having a weight average molecular weight of 200 to 20,000 can be more preferably used.

<Organic polyisocyanate>
Examples of the organic polyisocyanate include the following aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products of these polyisocyanates.
-6-20 aromatic polyisocyanates [1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (excluding carbon in the isocyanate group, the same applies hereinafter) TDI), 4,4′- or 2,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- or p-isocyanato Phenylsulfonyl isocyanate and crude MDI];
-Aliphatic polyisocyanates having 2 to 18 carbon atoms [ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate, 2,6-diisocyanate Natomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, etc.];
C8-15 alicyclic polyisocyanate [isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) 4-cyclohexene-1,2-dicarboxylate and the like];
Araliphatic polyisocyanates having 8 to 15 carbon atoms [xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), etc.];
-Modified products of the above polyisocyanates (modified products containing carbodiimide groups, uretdione groups, uretoimine groups, urea groups, burette groups, isocyanurate groups, etc.).
Among these, aliphatic, aromatic or alicyclic polyisocyanates, particularly diisocyanates are preferable in that good water stopping performance can be obtained, and HDI, IPDI and MDI are more preferable.

<Manufacture of terminal isocyanate group-containing urethane prepolymer>
The reaction between the polyol and the organic polyisocyanate can usually be carried out by charging the polyol and the organic polyisocyanate in a reaction apparatus and stirring them, and reacting them at 60 to 160 ° C. At that time, a tin-based catalyst such as monobutyltin oxide, dibutyltin oxide, tetraoctyltin, dioctyltin oxide, dibutyltin laurate, dioctyltin laurate or the like can be used as necessary.
In the reaction between the polyol and the organic polyisocyanate, the ratio (molar ratio) of the terminal OH group of the polyol and the terminal NCO group of the organic polyisocyanate is preferably 1: 1.2 to 8, more preferably 1: 1.5 to It is preferable to make it react so that it may be set to 4.
Moreover, in the obtained terminal isocyanate group-containing urethane prepolymer, the urethane prepolymer that preferably has a content of the terminal isocyanate group of 0.5 to 10% by mass with respect to the molecular weight of the prepolymer is desirable. When the terminal isocyanate group content is within the above range, the water-swelling property of the formed water-stopping sheet (water-stopping layer) itself, and thus the water-stopping property, becomes better.

[Base material]
The fibrous base material laminated on the support described later and impregnated with the above-mentioned terminal isocyanate group-containing urethane prepolymer is not particularly limited as long as the material can be impregnated with the prepolymer, Examples include woven fabrics such as cotton fabric and soft fabric; polyester-based nonwoven fabrics, rayon-based nonwoven fabrics, cellulose-based nonwoven fabrics, vinylon-based nonwoven fabrics, and nonwoven fabrics composed of these mixed fibers; and papers such as kraft paper, crepe paper, and Japanese paper. In addition, a foam sheet obtained by foaming polyurethane, polychloroprene rubber, polyethylene or the like can also be used as a base material. Moreover, since it can affix even when the shape of a water leak location is not flat, it is preferable that a fibrous base material is a flexible raw material with the support body mentioned later.

Especially, it is preferable to use the above-mentioned various nonwoven fabrics as a fibrous base material from the viewpoint of the impregnation property of the above-mentioned terminal isocyanate group-containing urethane prepolymer, the strength of the base material itself, and the economy.
The basis weight / thickness when using a nonwoven fabric as the fibrous base material is approximately 50 to 500 g / m ² , preferably 100 to 300 g / m ² , more preferably, although it depends on the type of nonwoven fabric selected. The thickness is 150 to 250 g / m ² , and the thickness is 1 to 10 mm, preferably 2 to 5 mm.

The above fibrous base material is impregnated with the above-mentioned terminal isocyanate group-containing urethane prepolymer at an impregnation amount of about 0.05 to 2.0 g / cm ² , preferably 0.1 to 1.0 g / cm ² . A waterstop layer is formed by impregnating in an amount. When impregnation amount of terminal isocyanate group-containing urethane prepolymer is less than 0.05 g / cm ² for the fibrous base material, can not be performed waterproofing water leakage points sufficiently, also exceed 2.0 g / cm ² If it is impregnated, there is a risk that the waterproof sheet will fall from the water leakage location due to the weight of the waterproof sheet during use.

<Support>
The support used for the water-proof sheet of the present invention is not particularly limited as long as it is a material having moderate water resistance, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate. Polyester, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, styrene-butadiene or styrene-isoprene block copolymer resin, butadiene-styrene-methyl methacrylate copolymer resin, nylon, etc. Synthetic resins such as polyamide, polyurethane, polyurethane-vinyl chloride copolymer, alkoxyalkyl (meth) acrylate copolymer, polyvinyl formal, polyvinyl butyral, rayon and other cellulose derivatives, cotton, hemp, pulp (paper And made of aluminum or the like, the film-foil, woven fabric, knitted fabric, and a nonwoven fabric. In particular, resin films such as PET, polyethylene naphthalate, nylon, polypropylene, polyethylene, and vinyl chloride, aluminum foil, and paper are preferably used. In order to increase the strength, durability, and moisture resistance of the waterproof sheet, two or more of these may be used in combination as necessary. Moreover, since it can affix even when the shape of a water leak location is not flat, it is preferable that it is a flexible raw material similarly to the said fiber base material.

<Adhesive layer>
In the waterstop sheet of the present invention, the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer covering the surface of the support is not limited. For example, an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, and a rubber-based pressure-sensitive adhesive A silicone-based pressure-sensitive adhesive can be used. For example, the urethane-based pressure-sensitive adhesive is preferably used because the curing accelerator contained therein may react with the urethane prepolymer contained in the water-stopping layer to cause deterioration of the water-stopping performance after long-term storage. The pressure-sensitive adhesive layer is preferably made of an acrylic pressure-sensitive adhesive that does not have such a fear.
As an acrylic adhesive which can be used here, the polymer which polymerized 1 type, or 2 or more types of (meth) acrylic-acid alkylester in the ratio of 40 mass% or more can be mentioned, for example. The alkyl group in the above (meth) acrylic acid alkyl ester is preferably a linear or branched alkyl group having 4 to 12 carbon atoms, specifically, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate and the like can be mentioned. In addition, in this specification, (meth) acrylic acid alkyl ester means both acrylic acid alkyl ester and methacrylic acid ester.
Moreover, the commercially available tape material by which the said adhesive is apply | coated to the material quoted in the above-mentioned <support> can also be used as <support> and <adhesive layer>.

<Peeling film>
The release film used for the water-proof sheet of the present invention is not particularly limited as long as it is a moisture-proof material, but non-stretched polypropylene (CPP), stretched polypropylene (OPP), polyolefins such as polyethylene, polyethylene Films made of synthetic resins such as polyesters such as terephthalate (PET) and polybutylene terephthalate (PBT), polyurethane, polyvinyl chloride, polystyrene, paper and synthetic paper, and films made by laminating these and the above synthetic resins Or a sheet or aluminum foil, a film or sheet obtained by laminating a composite of the above materials (synthetic resin, paper, etc.) and a silicon or embossing of the surface of the single material or composite material, and further printing Alternatively, a colored one can be used.

<Waterproof sheet>
Although the manufacturing method of the water-stop sheet of the present invention is not particularly limited, for example, a pressure-sensitive adhesive is applied so as to cover the surface of the support to form a pressure-sensitive adhesive layer, and a substrate serving as the water-stopping layer is formed here. After pasting, the base isocyanate group-containing urethane prepolymer is impregnated into the water-stopping layer, and then the pressure-sensitive adhesive layer so as to cover the water-stopping layer disposed on the pressure-sensitive adhesive layer with the release film It can manufacture by coating. Alternatively, a water-stopping layer obtained by impregnating a base material with a terminal isocyanate group-containing urethane prepolymer is stuck on the pressure-sensitive adhesive layer formed on the support, and then the release film is used to form the pressure-sensitive adhesive layer. It can manufacture by coat | covering an adhesive layer so that this water stop layer distribute | arranged on may be covered.

Although the shape and size of the water-stop sheet are not particularly limited, it is preferable that the water-stop sheet is of a size that can be attached to a water leak location with one hand, that is, a size that can be placed on the palm. Moreover, in the water-stop sheet of the present invention, the water-stop layer is provided at the entire portion excluding the peripheral portion of the support or at a required location, that is, the water-stop layer is smaller than the pressure-sensitive adhesive layer. It has an area, in other words, a size slightly smaller than the pressure-sensitive adhesive layer. It is preferable that the water-stopping layer is disposed substantially at the center of the pressure-sensitive adhesive layer. The so-called water-stopping sheet of the present invention is an adhesive having no water-stopping layer disposed so as to surround the outer edge of the water-stopping layer. The agent layer is present as an adhesive part. As a result, the adhesive part can adhere to the periphery of the leaked area from when the water-stop sheet is applied until the adhesive force of the prepolymer is expressed, and thus can be easily applied to the leaked spot in a short time. It is possible to prevent water leakage from the gap between the water leakage location and the water stop sheet, and it is also possible to prevent the water stop sheet from dropping from the water leakage location due to its own weight due to the adhesiveness of the adhesive portion.

  For example, if the water-stop sheet of the present invention is a rectangular shape such as a rectangle, the pressure-sensitive adhesive layer can be a water-stop sheet that is a flat layer having a rectangular shape with a side of about 50 to 300 mm. The water blocking layer can be a flat layer having a rectangular shape with a side of about 30 to 200 mm. Specifically, the support and the pressure-sensitive adhesive layer provided thereon have a long side of about 150 mm to 300 mm, preferably about 150 mm to 200 mm, and a short side of about 50 to 150 mm, preferably about 50 to 100 mm. The waterstop layer provided on the pressure-sensitive adhesive layer has a long side of 50 to 200 mm, preferably 100 to 180 mm, and a short side of 30 to 140 mm, preferably about 50 to 100 mm. It may have a rectangular shape.

In order to prevent deterioration due to moisture absorption, the waterstop sheet of the present invention is preferably stored by being enclosed in a packaging material such as a packaging bag made of an aluminum sheet, a PET sheet or the like.
In order to further improve the storage stability, a moisture absorbent (drying agent) may be enclosed in the packaging material during storage, or dry air may be enclosed.
In addition, the waterproof sheet product formed by sealing the waterproof sheet of the present invention together with the moisture absorbent in the aluminum laminate packaging material is also an object of the present invention.

The water-stop sheet of the present invention can be used by directly sticking to a location where water leaks from the roof, ceiling, wall surface, piping or other structure of the building. It can also be used to stop water in tunnels, underground structures, or construction sites.
In particular, the water-stop sheet of the present invention can be suitably applied to cracks having a width of about 1 cm or leakage from holes having a maximum diameter of about 5 cm. Moreover, it can be applied to a crack having a length of 20 cm or more by overlapping and sticking a water-stop sheet.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

(Synthesis Example 1)
Resorcin ethylene oxide propylene oxide block adduct (based on the total mass of all added alkylene oxides, ethylene oxide content 80 mass%, hydroxyl value 11) 60 g and glycerin ethylene oxide propylene oxide block adduct (ethylene oxide content 80) 50% by mass, hydroxyl value 19) 50 g of 4,4-diphenylmethane diisocyanate was reacted to obtain a urethane prepolymer a having a terminal NCO group content of 4% by mass with respect to the molecular weight of the prepolymer.

(Synthesis Example 2)
Instead of the glycerin ethylene oxide propylene oxide block adduct, 50 g of diglycerin ethylene oxide propylene oxide block adduct (ethylene oxide content 80 mass%, hydroxyl value 28 based on the total mass of all alkylene oxides added) is used. A urethane prepolymer b having a terminal NCO group content of 4% by mass relative to the molecular weight of the prepolymer was obtained in the same manner as in Synthesis Example 1 except that

[Example 1 and Example 2]
An aluminum tape (170 × 100 mm) (adhesive layer + support) using an acrylic adhesive as the adhesive layer was used, and on the adhesive layer of the tape, as a substrate, rayon / PET = 65/35 A non-woven fabric made of mixed fibers (150 mm × 75 mm × 2 mm, basis weight 210 g / m ² ) was affixed to obtain a sheet having an adhesive portion with a width of about 10 mm on the outer edge. Next, 18 g of the urethane prepolymer obtained in Synthesis Example 1 or Synthesis Example 2 was applied to the base material part to form a water-stopping layer, and a polyethylene film was covered over the water-stopping layer, and Example 1 (urethane prepolymer a Use) or a waterproof sheet of Example 2 (use of urethane prepolymer b) was prepared.

[Test Example 1: Simple evaluation of water stop performance immediately after production and after storage in the water stop sheets of Example 1 and Example 2]
A vinyl chloride slag having an inner diameter of 55 mm and a height of 1100 mm was filled with water up to a height of 1000 mm, and a hole with a diameter of 3 mm was opened at the bottom to cause water leakage. The water-stopping sheet immediately after production, put in a packaging container, and the water-stopping sheet stored at room temperature (2 months, 4 months) were each peeled off and affixed to the water leakage part and pressure bonded. After the water-stopping construction, the one that retained the water-stopping for one month or more was regarded as acceptable (◯). The evaluation results are shown in Table 1.

[Test Example 2: Performance evaluation in a field test using the water stop sheet of Example 1]
Producing a temporary roof with a 120mm wide PVC eaves, 50mm diameter PVC eaves, and elbows, using a folded roof roof deck made of color GL steel plate with a thickness of 0.8mm as the roofing material. About 4 liters of water was allowed to flow through the concave portion (width 50 mm) and the eaves portion, and water was leaked to the attic side under each condition. Water stoppage construction was carried out with the water stop sheet of Example 1 using the urethane prepolymer a at each water leak location.
In addition, about 4 liters of water per minute is applied to the joining bolt used for the folded part of the folded plate, and water is leaked to the attic side, and a water-stop sheet is attached to the leaked portion, and water-stopping, workability and Durability was evaluated. The evaluation results are shown in Table 2.
<Waterproofness>
○: Retains water-stopping for one month or more after water-stopping construction.
<Workability>
A: The sheet can be pasted in the same shape and water stop construction can be performed.
○: A device to match the sheet with the shape of the leaking part or the sheet pressing time requires several minutes. <Durability>
◯: There is no significant change in appearance such as sheet peeling, and the flexibility of the urethane prepolymer is maintained, and the followability to the leaked portion is maintained for one month or longer.

As shown in Table 2, the water-stop sheet of the present invention has good water-stop at any location where water leaks, and the flat metal part (folded plate roof recess) should be water-stopped by simply attaching the sheet. I was able to. Further, in the case of a portion having a complicated shape of the water leakage portion or a vinyl chloride portion such as a flaw, the pressure-curing curing time after sticking the sheet was required for about 1 minute, but the water-stopping property was good.
In addition, even if the seat construction part was left for more than one month, no water leakage, deformation of the sheet appearance, or hardening of the urethane resin was observed at the construction part, indicating good water-stopping performance, durability performance, and housing follow-up performance. .

[Comparative Example 1]
In the above [Example 1 and Example 2], in place of the urethane prepolymer obtained in Synthesis Example 1 or Synthesis Example 2, polyacrylate (crosslinked polysodium acrylate gel: SAP) g was used, The water stop sheet of Comparative Example 1 was produced in the same procedure.

[Test Example 3: Evaluation of water stopping performance in water stopping sheets with different impregnating polymers in the water stopping layer]
Using the water-stop sheet of Example 1 and the water-stop sheet of Comparative Example 1 immediately after production, the water-stop performance test of each water-stop sheet was performed in the same procedure as in the above [Test Example 1].
The water-proof sheet was peeled off from the water leaking part after being stuck to the water leaking part (initial water stopping) and after 1 day (water stopping after time), and the water leaking part was retained in the water leaking part. Things were evaluated as x. The evaluation results are shown in Table 3.

  As shown in Table 3, the water-stop sheet of Example 1 using the terminal NCO group-containing urethane prepolymer as the impregnated polymer reacted with the water in the water leakage part and self-adhered to the affixed part. The water-stop sheet of Comparative Example 1 used only absorbed the water in the leaking part and did not exhibit adhesiveness, and dropped from the leaking part with the weight of the absorbed water one day later.

[Example 3]
An aluminum tape (170 × 100 mm) using a urethane-based adhesive is used as an adhesive layer, and a non-woven fabric (150 mm × X) of a mixed fiber of rayon / PET = 65/35 is used as a base material on the adhesive layer of the tape. 75 mm × 2 mm, basis weight 210 g / m ² ) was affixed to obtain a sheet having an adhesive part with a width of about 10 mm on the outer edge. Next, 18 g of the urethane prepolymer a obtained in Synthesis Example 1 was applied to the base material portion to form a water-stopping layer, and the water-stopping layer was covered with a polyethylene film to prepare a water-stopping sheet of Example 3.

[Test Example 4: Water-stop performance evaluation of water-stop sheets with different pressure-sensitive adhesive layers]
It put into the water-stop sheet packaging container of Example 1 and Example 3, and stored at normal temperature (4 months, 7 months, 12 months), these were affixed on the leaking part according to the procedure of [Test Example 1], and pressure-bonded. Evaluations were made as ○ when the water-stopping property was maintained for 1 month or more after the water-stopping construction and × when the water-stopping property could not be maintained for 1 month. The evaluation results are shown in Table 4.

  As shown in Table 4, in the pressure-sensitive adhesive layer in contact with the water-stopping layer (Example 3), a water-stopping property of 1 month or more can be maintained in use after 7 months after storage, The one using the acrylic pressure-sensitive adhesive (Example 1) kept water-stopping for one month or more even when used after 12 months from storage.

[Examples 4 to 8]
Except that the types of urethane prepolymer contained in the water-stopping layer, particularly the types of polyether polyols, were variously changed in terms of the average number of functional groups (OH number) and the addition ratio (% by mass) of ethylene oxide / propylene oxide [Examples] A water-stop sheet was produced in the same procedure and materials as in 1].
Table 5 shows the types of polyether polyols used in each example and comparative example.

[Test Example 5: Evaluation of water-stop performance in water-stop sheets with different polyether polyols of impregnated polymers]
Using the water-stopping sheets of Examples 4 to 8 immediately after production, water-stopping performance tests of the water-stopping sheets were carried out in the same procedure as in [Test Example 1].
The initial water-stopping property was evaluated as “Good” for those that were attached to the water leakage part and exhibited water-stopping properties after pressure bonding. In addition, as the water-stopping after curing, the one that added water for 5 minutes and developed water-stopping after curing, the one that added water for 10 minutes and developed water-stopping after curing, and after 10-minute curing Those that did not develop water-stopping properties were evaluated as x. The evaluation results are shown in Table 5.

As shown in Table 5, when the average functional group number of the polyether polyol was 2.5 or more (Example 6 and Example 7), the initial water stoppage was improved.
Moreover, the water-stopping property after 5 minutes was improved by making ethylene oxide 50 mass% or more (Example 4 thru | or Example 8) in the addition ratio of ethylene oxide / propylene oxide (EO / PO) of polyether polyol.

Claims (8)

A support;
An adhesive layer covering the surface of the support;
About the whole part excluding the peripheral part of the support or a required place, a water stop layer provided on the pressure-sensitive adhesive layer,
A release film laminated and laminated on the upper side of the pressure-sensitive adhesive layer so as to enclose the water-stopping layer,
A waterproof sheet comprising:
The pressure-sensitive adhesive layer is selected from the group consisting of an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and combinations thereof,
A waterproof sheet, wherein the waterproof layer is a layer formed by impregnating a fibrous base material with a terminal isocyanate group-containing urethane prepolymer. The waterstop sheet according to claim 1, wherein the terminal isocyanate group-containing urethane prepolymer is a prepolymer obtained by reacting a polyether polyol and an organic polyisocyanate. The waterstop sheet according to claim 2, wherein the polyether polyol is an alkylene oxide adduct of a polyhydric phenol. The water-stop sheet according to claim 1, wherein the pressure-sensitive adhesive layer comprises an acrylic pressure-sensitive adhesive. The waterproof sheet according to claim 1, wherein the fibrous base material is a nonwoven fabric having a basis weight of 50 to 500 g / m ² and a thickness of 1 to 10 mm. The water-stop sheet according to claim 5, wherein the water-stop layer is formed by impregnating the fibrous base material with the terminal isocyanate group-containing urethane prepolymer at an impregnation amount of 0.05 to 2.0 g / cm ² . The water-stop sheet according to claim 1, wherein the pressure-sensitive adhesive layer is a flat layer having a rectangular shape with a side of 50 mm to 300 mm, and the water-stop layer is a flat layer having a rectangular shape with a side of 30 to 200 mm. . A waterproof sheet product obtained by sealing the waterproof sheet according to any one of claims 1 to 7 together with a moisture absorbent in an aluminum laminate packaging material.