WO2024058055A1 - Water-stop composition, and water-stop film - Google Patents

Water-stop composition, and water-stop film Download PDF

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Publication number
WO2024058055A1
WO2024058055A1 PCT/JP2023/032728 JP2023032728W WO2024058055A1 WO 2024058055 A1 WO2024058055 A1 WO 2024058055A1 JP 2023032728 W JP2023032728 W JP 2023032728W WO 2024058055 A1 WO2024058055 A1 WO 2024058055A1
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WIPO (PCT)
Prior art keywords
water
mass
stop
plasticizer
acid
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PCT/JP2023/032728
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French (fr)
Japanese (ja)
Inventor
晴貴 冨川
俊英 芳谷
京久 内海
廉 石川
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富士フイルム株式会社
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Publication of WO2024058055A1 publication Critical patent/WO2024058055A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/66—Sealings

Definitions

  • the present disclosure relates to a water-stop composition and a water-stop film.
  • Japanese Patent Publication No. 63-36341 discloses that a water-absorbing resin is contained in a closed-cell flexible polyurethane foam body with a closed-cell ratio of 15% or more, and that the foam is pressurized for 5 minutes using an Asker C type hardness tester. A water stop material having a hardness of 70 or less is described.
  • JP-A No. 2003-165865 discloses a water-absorbing polyurethane foam in which a mixture of a chip-like flexible polyurethane foam, a powder-like superabsorbent resin, and a binder is charged into a mold, and the mixture is heated to harden the binder.
  • a sealing material using a water-absorbing polyurethane foam manufactured by a method for manufacturing a body is described.
  • a method of covering the water inlet or water outlet with water-stopping material is being considered.
  • most of the flood damage to buildings occurs when water enters the building through gaps in objects such as windows and doors.
  • it is considered effective to cover gaps between objects such as windows and doors with waterproof materials.
  • it is required to have both workability and water-stopping ability.
  • An object of the present invention is to provide a water-stopping film using a composition for water.
  • the present disclosure includes the following aspects.
  • ⁇ 4> The water-stopping composition according to any one of ⁇ 1> to ⁇ 3>, wherein the content of the plasticizer is 5% by mass to 30% by mass based on the total amount of the waterstopping composition. thing.
  • ⁇ 5> The water stop composition according to any one of ⁇ 1> to ⁇ 4>, wherein the plasticizer contains a phthalate ester.
  • ⁇ 6> The water stop composition according to any one of ⁇ 1> to ⁇ 5>, which has a normal force of 1N or more.
  • the content of the water-absorbing crosslinked resin particles is 20% by mass or more and less than 60% by mass with respect to the total amount of the water-stopping composition.
  • Water stop composition. ⁇ 8> The water-stopping composition according to any one of ⁇ 1> to ⁇ 7>, wherein the water-absorbing cross-linked resin constituting the water-absorbing cross-linked resin particles contains a cross-linked polyacrylate.
  • a water-stop film comprising the water-stop composition according to any one of ⁇ 1> to ⁇ 8>.
  • a water-stopping composition that has excellent workability and a higher water-stopping ability than conventional ones, and a water-stopping film using the water-stopping composition.
  • a numerical range expressed using " ⁇ " means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
  • the amount of each component in the composition means the total amount of the multiple substances present in the composition. do.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step, Further, the values may be replaced with the values shown in the examples.
  • the term "step” is included not only in an independent step but also in the case where the intended purpose of the step is achieved even if the step cannot be clearly distinguished from other steps. In this disclosure, combinations of preferred aspects are more preferred aspects.
  • the water stop composition of the present disclosure includes a binder resin, a plasticizer, and water-absorbing crosslinked resin particles, and has an Asker rubber hardness of less than C50.
  • the water-stopping composition of the present disclosure has excellent workability and has higher water-stopping ability than conventional compositions.
  • the reason for this effect is presumed to be as follows.
  • the water stop composition of the present disclosure contains a plasticizer together with the binder resin, the binder resin is softened by the plasticizer.
  • the water-stopping composition of the present disclosure is considered to have higher water-stopping ability than conventional compositions, since the water-stopping composition of the present disclosure expands at a faster rate when it absorbs water.
  • the water stop composition of the present disclosure has unexpected tackiness and excellent workability because it contains a plasticizer.
  • the water stop composition of the present disclosure has an Asker rubber hardness of less than C50, has excellent flexibility, and can be arranged to follow the construction target, so it is said to have excellent workability. Conceivable.
  • both Japanese Patent Publication No. 63-36341 and Japanese Unexamined Patent Publication No. 2003-165865 describe water-stopping materials containing polyurethane foam. Since polyurethane foam has voids, it is thought that when it absorbs water, it expands first in a direction that fills the voids, and then the water-stopping material as a whole expands. Therefore, it takes a long time to stop water, and the water stopping ability is insufficient. In addition, Japanese Patent Publication No. 63-36341 and Japanese Patent Application Laid-Open No. 2003-165865 do not contain any descriptions regarding tackiness or plasticizers, so it is thought that the workability is also insufficient.
  • the water stop composition of the present disclosure includes a binder resin.
  • the number of binder resins contained in the water stopping composition may be one, or two or more.
  • binder resin is not particularly limited, and examples thereof include acrylic resin, silicone resin, polyester, polyurethane, and polyolefin.
  • the binder resin contains polyurethane.
  • Polyurethane can be obtained, for example, by reacting a diisocyanate compound and a polyol.
  • diisocyanate compound examples include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, p- or m-phenylene diisocyanate, xylylene diisocyanate, and aromatic diisocyanates such as m-tetramethylxylylene diisocyanate; cycloaliphatic diisocyanates such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexylene diisocyanate and hydrogenated tolylene diisocyanate; and Aliphatic diisocyanates such as hexamethylene diisocyanate can be mentioned.
  • polyols examples include polyoxypolyalkylene polyols, polyester polyols, polyether polyols, polycarbonate polyols, and polyacrylic polyols.
  • the water-stopping composition of the present disclosure contains a plasticizer, which will be described later, and the polyurethane is softened by the plasticizer.
  • Polyurethane softened by a plasticizer has a faster expansion rate when absorbing water than foamed polyurethane, and can stop water in a shorter time. Furthermore, since the binder resin is softened by the plasticizer, the water-absorbing crosslinked resin particles are prevented from falling off, so water can be stopped for a long time.
  • the content of polyurethane is preferably 30% by mass to 70% by mass, more preferably 40% by mass to 60% by mass, based on the total amount of the water-stopping composition.
  • the water stop composition of the present disclosure includes a plasticizer.
  • the number of plasticizers contained in the water stopping composition may be one, or two or more.
  • the water-stopping composition of the present disclosure has unexpected tackiness and excellent workability because it contains a plasticizer. In particular, it has excellent workability and adhesion to curved surfaces.
  • plasticizer is not particularly limited, and examples include polyester plasticizers, polyether ester plasticizers, polycarboxylic acid ester plasticizers, glycerin plasticizers, phosphate ester plasticizers, epoxy plasticizers, and polyacrylic acid ester plasticizers.
  • polyester plasticizers include acid components (e.g., adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and diphenyldicarboxylic acid) and diol components (e.g., propylene glycol, 1,3-butanediol). , 1,4-butanediol, 1,6-hexanediol, ethylene glycol and diethylene glycol).
  • polyester plasticizers include polyesters made of hydroxycarboxylic acids (eg, polycaprolactone). The polyester may be end-capped with a monofunctional carboxylic acid or a monofunctional alcohol. The polyester may be end-capped with an epoxy compound.
  • Commercially available products include, for example, ADEKASIZER PN-150, PN-170, P-200, and PN-350 manufactured by ADEKA Corporation.
  • the polyether ester plasticizer is preferably an organic acid ester of polyalkylene glycol.
  • the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polybutylene glycol, poly(ethylene oxide/propylene oxide) block copolymer, poly(ethylene oxide/propylene oxide) random copolymer, and polytetramethylene glycol. It will be done.
  • Aromatic units such as bisphenols may be included in the polyether chain.
  • Organic acids include, for example, monocarboxylic acids (eg, butanoic acid, isobutanoic acid, 2-ethylbutyric acid, 2-ethylhexylic acid, and decanoic acid).
  • Commercially available products include, for example, ADEKASIZER RS-1000, RS-735, and RS-700 manufactured by ADEKA Corporation.
  • polyvalent carboxylic acid ester plasticizers include aliphatic dicarboxylic acid esters, aromatic dicarboxylic acid esters, trimellitic acid esters, and citric acid esters (for example, triethyl acetyl citrate and tributyl acetyl citrate).
  • aliphatic dicarboxylic acid esters examples include adipic acid esters (e.g., diisodecyl adipate, di-n-octyl adipate, and di-n-decyl adipate), azelaic acid esters (e.g., di-2-adipate), ethylhexyl) and sebacic acid esters (eg, dibutyl sebacate and di-2-ethylhexyl sebacate).
  • adipic acid esters e.g., diisodecyl adipate, di-n-octyl adipate, and di-n-decyl adipate
  • azelaic acid esters e.g., di-2-adipate
  • ethylhexyl ethylhexyl
  • sebacic acid esters eg, dibutyl sebacate and di-2-ethy
  • aromatic dicarboxylic acid esters examples include phthalate esters (e.g., dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, diisononyl phthalate, dibenzyl phthalate, and butylbenzyl phthalate).
  • phthalate esters e.g., dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, diisononyl phthalate, dibenzyl phthalate, and butylbenzyl phthalate.
  • trimellitic acid esters examples include trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, triamyl trimellitate, trihexyl trimellitate, triheptyl trimellitate, and trimellitate.
  • Commercially available products include, for example, ADEKASIZER C-8, C-880, C-79, C810, C-9N and C-10 manufactured by ADEKA Corporation.
  • glycerin plasticizer examples include glycerin monoacetomonolaurate, glycerin diacetomonolarate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomononanate.
  • phosphate ester plasticizers examples include tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate, and tricresyl phosphate.
  • epoxy plasticizers include epoxy triglyceride made of alkyl epoxy stearate and soybean oil.
  • epoxy plasticizers include epoxy resins mainly made from bisphenol A and epichlorohydrin.
  • polyacrylic ester plasticizers examples include polymers of acrylic acid alkyl esters.
  • the polyacrylic acid ester plasticizer may have functional groups such as epoxy groups and carboxy groups.
  • Commercially available products include, for example, the Alfon series (eg, non-functional UP series) manufactured by Toagosei Co., Ltd.
  • plasticizers examples include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethyl butyrate, fatty acid amides such as stearic acid amide, and butyl oleate.
  • aliphatic carboxylic acid esters such as methyl acetyl ricinoleate and butyl acetyl ricinoleate, oxyacid esters such as pentaerythritol, sorbitol, polyacrylic esters, silicone oils and paraffins.
  • the plasticizer preferably contains a polycarboxylic acid ester plasticizer, more preferably an aromatic dicarboxylic acid ester, and even more preferably a phthalate ester.
  • the proportion of the plasticizer in the total content of the binder resin and plasticizer is preferably 20% by mass to 60% by mass, more preferably 30% by mass to 55% by mass.
  • the proportion of the plasticizer is 20% by mass or more, the binder resin is softened by the plasticizer, and the swelling of the water-absorbing crosslinked resin particles due to water absorption is less likely to be inhibited, so that water can be stopped in a shorter period of time. be able to.
  • the above ratio is 60% by mass or less, bleeding of the plasticizer is suppressed. When bleeding occurs, oil smear occurs on the surface and tackiness decreases.
  • the content of the plasticizer is preferably 5% to 30% by mass, more preferably 15% to 30% by mass, and 20% to 30% by mass, based on the total amount of the water-stopping composition. More preferably, it is expressed in mass %.
  • the content of the plasticizer is 5% by mass or more, the binder resin is softened by the plasticizer, and the swelling of the water-absorbing crosslinked resin particles due to water absorption is less likely to be inhibited, so water can be stopped in a shorter period of time. can be done.
  • the content of the plasticizer is 30% by mass or less, bleeding of the plasticizer is suppressed.
  • the water-stopping composition of the present disclosure includes water-absorbing crosslinked resin particles.
  • water-absorbing crosslinked resin particles refer to resin particles that are water-absorbent and have a crosslinked structure.
  • Water absorption means that the water absorption rate measured according to method A described in JIS K 7209:2000 (ISO62:1999) is 12% or more. Water absorption is the percentage change in mass relative to the initial mass. The water absorption rate is preferably 15% or more, more preferably 20% or more. From the viewpoint of durability, the upper limit of the water absorption rate is preferably 60% or less, more preferably 50% or less.
  • Whether or not the resin particles have a crosslinked structure can be determined by whether or not the resin particles do not dissolve when they absorb water, and whether the resin particles absorb water and become gel-like.
  • Examples of the water-absorbing crosslinked resin constituting the water-absorbing crosslinked resin particles include resins obtained by polymerizing a polysaccharide, a polymerizable monomer having an acid group, and a crosslinking agent.
  • Polysaccharide is 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 compounds.
  • Examples of the acid group in the polymerizable monomer having an acid group include a carboxy group, a sulfo group, and a phosphoric acid group.
  • the acid group is preferably a carboxy group.
  • the polymerizable monomer having an acid group may form a salt.
  • the salts formed include, for example, alkali metal salts (eg, sodium salts, potassium salts, etc.), alkaline earth metal salts (eg, calcium salts, magnesium salts, etc.), amine salts, and ammonium salts.
  • polymerizable monomers having a carboxyl group examples include (meth)acrylic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, sorbic acid, itaconic acid, and itaconic acid monoalkyl ester. , itaconic acid glycol monoether, cinnamic acid, citraconic acid, citraconic acid monoalkyl ester, and anhydrides thereof.
  • Examples of polymerizable monomers having a sulfo group include vinylsulfonic acid, allylsulfonic acid, vinyltoluenesulfonic acid, styrenesulfonic acid, 2-hydroxy-3-(meth)acryloxypropylsulfonic acid, and (meth)acrylalkylsulfone.
  • Examples include acids (eg, sulfoethyl (meth)acrylate, sulfopropyl (meth)acrylate, etc.), and (meth)acrylamidoalkylsulfonic acids (eg, 2-acrylamido-2-methylpropanesulfonic acid, etc.).
  • polymerizable monomers having a phosphoric acid group examples include (meth)acrylic acid hydroxyalkyl phosphate monoesters (for example, 2-hydroxyethyl (meth)acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, etc.) .
  • crosslinking agent for example, a polymerizable monomer having two or more polymerizable groups; a compound having a polymerizable group and a reactive group (e.g., a hydroxyl group) that can react with an acid group; and a compound that can react with an acid group.
  • a crosslinking agent for example, a polymerizable monomer having two or more polymerizable groups; a compound having a polymerizable group and a reactive group (e.g., a hydroxyl group) that can react with an acid group; and a compound that can react with an acid group.
  • examples include compounds having two or more reactive groups (for example, hydroxyl groups).
  • polymerizable monomer having two or more polymerizable groups examples include N,N'-methylenebis(meth)acrylamide, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylate.
  • Examples of compounds having a polymerizable group and a reactive group include hydroxyethyl (meth)acrylate, N-methylol (meth)acrylamide, and glycidyl (meth)acrylate.
  • Examples of compounds having two or more reactive groups include ethylene glycol, diethylene glycol, glycerin, propylene glycol, trimethylolpropane, alkanolamines (e.g., diethanolamine, etc.), and polyamines (e.g., polyethyleneimine, etc.).
  • Examples of the resin obtained by polymerizing a polysaccharide, a polymerizable monomer having an acid group, and a crosslinking agent include a crosslinked product of a starch-acrylic acid graft copolymer.
  • the water-absorbing cross-linked resin constituting the water-absorbing cross-linked resin particles is a polymer of a polysaccharide and a polymerizable monomer having an acid group (for example, a hydrolyzate of a starch-acrylonitrile graft polymer, a cellulose-acrylonitrile graft copolymer, etc.). (polymer hydrolyzate, etc.) may also be used.
  • the water-absorbing cross-linked resin constituting the water-absorbing cross-linked resin particles may be a cross-linked polysaccharide (for example, a cross-linked carboxymethyl cellulose).
  • the water-absorbing crosslinked resin constituting the water-absorbing crosslinked resin particles may be a resin obtained by polymerizing a polymerizable monomer having an acid group and the above-mentioned crosslinking agent.
  • resins include crosslinked products of acrylic acid-acrylamide copolymer, crosslinked products of polysulfonate, crosslinked products of polyacrylate/polysulfonate copolymer, and vinyl ester-unsaturated carboxylic acid copolymer.
  • Cross-linked products of saponified polymers cross-linked products of polyacrylic acid (salt), cross-linked products of acrylic acid-acrylic acid ester copolymers, cross-linked products of isobutylene-maleic anhydride copolymers, cross-linked products of polyvinylpyrrolidone, and Examples include crosslinked products of carboxylic acid-modified polyvinyl alcohol.
  • the water-absorbing crosslinked resin constituting the water-absorbing crosslinked resin particles may be a polymer of polymerizable monomers having self-crosslinking properties (for example, self-crosslinking polyacrylate, etc.).
  • the water-absorbing cross-linked resin constituting the water-absorbing cross-linked resin particles contains a cross-linked product of polyacrylic acid (salt).
  • the shape of the water-absorbing crosslinked resin particles is not particularly limited, and examples include spherical, polygonal, scaly, tabular, and irregular shapes.
  • the center particle size of the water-absorbing cross-linked resin particles is preferably 350 ⁇ m or less, more preferably 100 ⁇ m or less, and 50 ⁇ m or less, from the viewpoint of suppressing shedding of the water-absorbing cross-linked resin particles due to water absorption. is even more preferable. Further, from the viewpoint of ease of production, the center particle size of the water-absorbing crosslinked resin particles is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more.
  • the central particle size is the particle size (D50) when the volume accumulation from the small diameter side becomes 50% in the volume-based particle size distribution.
  • the central particle size can be measured using a laser diffraction/scattering particle size distribution analyzer.
  • the content of the water-absorbing crosslinked resin particles is preferably 20% by mass or more and less than 60% by mass, more preferably 40% by mass or more and less than 60% by mass, based on the total amount of the water-stopping composition. More preferably, it is 40% by mass to 58% by mass.
  • the content of the water-absorbing crosslinked resin particles is 20% by mass or more, the time required for water stopping can be further shortened.
  • the content of the water-absorbing cross-linked resin particles is 60% by mass or less, the water-absorbing cross-linked resin particles are prevented from falling off, so that water can be stopped for a long time.
  • the water-stopping composition of the present disclosure may contain components other than the binder resin, plasticizer, and absorbent crosslinked resin particles.
  • other components include absorbent polymers that do not have a crosslinked structure.
  • absorbent polymers without a crosslinked structure include (meth)acrylic polymers, vinyl polymers, and polysaccharides.
  • the content of the absorbent polymer that does not have a crosslinked structure may be 30% by mass or less based on the total amount of the waterstopping composition. It is preferably at most 20% by mass, more preferably at most 5% by mass.
  • the content of the absorbent polymer without a crosslinked structure may be 0% by mass.
  • the water stop composition of the present disclosure has an Asker rubber hardness of less than C50, preferably C40 or less, and more preferably C20 or less.
  • the lower limit of the Asker rubber hardness is not particularly limited, and is, for example, C5.
  • Asker rubber hardness may be greater than or equal to C5 and less than C50.
  • Asker rubber hardness is less than C50, workability, especially workability on curved surfaces, is excellent.
  • Asker rubber C hardness can be measured at a temperature of 25° C. using an Asker rubber hardness meter C type.
  • Normal force The water stop composition of the present disclosure preferably has a normal force of 1N or more, more preferably 5N or more, and even more preferably 15N or more.
  • the upper limit of the normal force is, for example, 50N. Normal force means the force in the normal direction that appears when the measurement plate of the rheometer is pulled up from the ground surface of the measurement sample.
  • Normal force is measured by the following method.
  • a sample for measurement is prepared and measured using a rheometer (product name "MCR302", manufactured by Anton Paar).
  • a measurement jig parallel plate PP25
  • a force of 5N is pressed against the measurement sample with a force of 5N.
  • the absolute value of the normal force when the measuring jig is pulled up at a speed of 1 cm/sec is recorded. The average value of three measurements is used.
  • the water stop composition of the present disclosure can be applied to various uses.
  • the water-stopping film of the present disclosure preferably contains the water-stopping composition described above.
  • the water stop film of the present disclosure may have only one layer, or may have two or more layers. That is, it may be a film made of a water-stopping composition, or it may be a laminated film having a layer containing a water-stopping composition.
  • the layer containing the water-stopping composition may be a layer in which the water-stopping composition is molded.
  • the thickness of the film made of the water-stopping composition is, for example, 1 mm to 10 mm.
  • the water-stop film of the present disclosure may include a water-permeable base material on the layer containing the water-stop composition.
  • the water permeable base material is not particularly limited as long as it is a base material that has water permeability.
  • water permeability means a property through which liquid water can pass.
  • the water-permeable base material preferably has pores through which water can pass.
  • the water-permeable base material has the role of holding a layer containing the water-stop composition. Further, when water passes through the water-permeable base material and enters the layer containing the water-stopping composition, the layer containing the water-stopping composition swells.
  • the water-permeable base material also has the role of bringing water into efficient contact with the layer containing the water-stopping composition.
  • the water permeable base material is preferably a layer containing fibers, and more preferably a layer containing cellulose fibers, rayon fibers, polyolefin fibers, or polyester fibers.
  • the water permeable base material is preferably a nonwoven fabric, cloth, or paper, and more preferably a nonwoven fabric.
  • the thickness of the water-permeable base material is not particularly limited, and is, for example, 15 ⁇ m to 200 ⁇ m.
  • the water-stopping composition of the present disclosure is useful as an agricultural water-retaining material and an agricultural water-retaining sheet.
  • An agricultural water retaining material that is an embodiment of the present disclosure includes a water-stopping composition that includes a binder resin, a plasticizer, and water-absorbing crosslinked resin particles, and has an Asker rubber hardness of less than C50.
  • An agricultural water-retaining sheet that is an embodiment of the present disclosure includes a water-stopping composition that includes a binder resin, a plasticizer, and water-absorbing crosslinked resin particles, and has an Asker rubber hardness of less than C50.
  • the water-stopping composition of the present disclosure has excellent workability and has higher water-stopping ability than conventional compositions. Therefore, agricultural water-retaining materials and agricultural water-retaining sheets containing the water-stopping composition of the present disclosure have excellent workability and a higher water-retaining capacity than conventional ones. Therefore, for example, by directly spraying an agricultural water retaining material onto a field, it is possible to reduce the frequency of watering agricultural crops. Furthermore, for example, by covering soil with an agricultural water retaining sheet, it is possible to reduce the frequency of watering agricultural crops.
  • Example 1 The following components were mixed in a stirring container with a capacity of 300 mL (product name "002 stirring container”, manufactured by Kinki Yoki Co., Ltd.) to obtain a mixture. 100 g of the mixture was placed in a mixer (product name "ARV-310", manufactured by Shinky Co., Ltd.), and vacuum stirring treatment was performed for 1 minute at a rotation speed of 900 rpm (revolutions per minute) and a pressure of 3 kPa. After the vacuum stirring treatment, 30 g of the mixture was poured into a flat glass petri dish (inner diameter 7 cm ⁇ ) and left at 25° C. for 24 hours.
  • sample A of the water-stopping composition in a cylindrical shape with a diameter of about 7 cm and a height of about 6 mm.
  • the mixture after being stirred under reduced pressure was poured into an acrylic resin container measuring 50 mm long, 100 mm wide, and 2 mm high, and allowed to stand at 25° C. for 24 hours. Thereafter, it was taken out from the acrylic resin container to obtain sample B of the water-stopping composition, which had a length of about 50 mm, a width of about 100 mm, and a height of about 2 mm.
  • ⁇ Binder resin Product name: “Human skin gel stock solution hardness C0”, manufactured by Exile Co., Ltd....55% by mass
  • ⁇ Water-absorbing crosslinked resin particles Product name "Sunfresh ST-500MPSA", manufactured by Sanyo Chemical Industries, Ltd., center particle size 30 ⁇ m...45% by mass
  • human skin gel stock solution hardness C0 contains 52% by mass of polyurethane and 48% by mass of diisononyl phthalate, which is a plasticizer.
  • Table 1 the corresponding contents are listed separately in a column for binder resin and a column for plasticizer.
  • Human skin gel stock solution, hardness C7 and “Human skin gel stock solution, hardness C15”, which will be described later, contain 75% by mass of polyurethane and 25% by mass of diisononyl phthalate, which is a plasticizer.
  • Example 2 to Example 8 Comparative Example 1 to Comparative Example 5> Each raw material was mixed so as to have the components and composition shown in Table 1, and samples A and B of water stop compositions were obtained in the same manner as in Example 1.
  • the measurement method and evaluation method are as follows.
  • ⁇ Asker rubber hardness> The air side of the prepared sample A was turned upward, and the Asker rubber hardness at 25° C. was measured using an Asker rubber hardness meter C type (manufactured by Asker Corporation). Note that the air surface means the surface that was in contact with the air (that is, the surface that was not in contact with the flat glass Petri dish) when Sample A was prepared.
  • ⁇ Normal Force> The prepared sample A was placed with the air side facing up and measured using a rheometer (product name "MCR302", manufactured by Anton Paar). First, a measurement jig (parallel plate PP25) was pressed against sample A with a force of 5N. Next, the absolute value of the normal force when the measuring jig was pulled up at a speed of 1 cm/sec was recorded. The average value of three measurements was adopted. If the normal force is 1N or more, there is tackiness. When the normal force is 15N or more, it can be said that the tackiness is high.
  • the time from the time when the experimental water tank was filled with water until the water stopped flowing out of the hole was measured. However, if the outflow of water did not stop after 3 hours, it was determined that the water could not be stopped.
  • the evaluation criteria are as follows. A: Water stop time is less than 15 minutes. B: Water stop time is 15 minutes or more and less than 1 hour. C: Water stop time is 1 hour or more and less than 3 hours. D: Water could not be stopped.
  • Sample B was pasted on the inside bottom and wall of the aquarium used in the above water stop time test, and the state of contact between the aquarium and sample B at the corner of the aquarium (i.e., the intersection of the bottom and the wall) was visually observed. Observed. Specifically, it was determined whether there was a gap between the aquarium and Sample B at the corner of the aquarium, and if there was a gap, the width of the gap was measured. The angle between the bottom and wall inside the tank is 90°.
  • the evaluation criteria are as follows. A: There is no gap. B: There is a gap, but the width of the gap is less than 1 mm. C: There is a gap, and the width of the gap is 1 mm or more.
  • Sample B was pasted on the inside bottom and wall of the aquarium used in the above water stop time test, and the state of contact between the aquarium and sample B at the corner of the aquarium (i.e., the intersection of the bottom and the wall) was visually observed. Observed. Specifically, it was determined whether Sample B had peeled off from the tank at the corner of the tank. The angle between the bottom and wall inside the tank is 90°.
  • the evaluation criteria are as follows. A: Not peeled off. B: Partially peeled off. C: Peeling off.
  • Examples 1 to 8 contain a binder resin, a plasticizer, and water-absorbing crosslinked resin particles, and have an Asker rubber hardness of less than C50, so they have excellent workability, and It was found that the water stopping ability was higher than that of the conventional method.
  • Comparative Example 1 a water-absorbing polymer without a cross-linked structure was included instead of the water-absorbing cross-linked resin particles, and it was found that the water stop duration was short and the durability was poor.
  • Comparative Example 2 a water-absorbing polymer without a cross-linked structure was included instead of the water-absorbing cross-linked resin particles, and it took a long time to stop water.
  • Comparative Example 4 did not contain water-absorbing crosslinked resin particles and could not stop water.

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Abstract

Provided are: a water-stop composition comprising a binder resin, a plasticizer, and water-absorbing crosslinked resin particles, and having an Asker rubber hardness of less than C50; and an application thereof.

Description

止水用組成物及び止水フィルムWater-stop composition and water-stop film
　本開示は、止水用組成物及び止水フィルムに関する。 The present disclosure relates to a water-stop composition and a water-stop film.
　浸水又は漏水の被害を軽減するために、種々の止水技術が検討されている。 In order to reduce damage caused by flooding or water leakage, various water stoppage techniques are being considered.
　例えば、特公昭６３－３６３４１号公報には、独泡率が１５％以上の独立気泡性の可撓性ポリウレタンフオーム体中に吸水性樹脂を含有させ、かつアスカーＣタイプ硬度計により加圧５分後の硬度が７０以下のものからなる止水材が記載されている。特開２００３－１６５８６５号公報には、チップ状軟質ポリウレタン発泡体と粉体状高吸水性樹脂とバインダーとの混合物を成形型に装入し、これらを加熱してバインダーを硬化させる吸水性ポリウレタン発泡体の製造方法により製造された吸水性ポリウレタン発泡体を用いたシール材が記載されている。 For example, Japanese Patent Publication No. 63-36341 discloses that a water-absorbing resin is contained in a closed-cell flexible polyurethane foam body with a closed-cell ratio of 15% or more, and that the foam is pressurized for 5 minutes using an Asker C type hardness tester. A water stop material having a hardness of 70 or less is described. JP-A No. 2003-165865 discloses a water-absorbing polyurethane foam in which a mixture of a chip-like flexible polyurethane foam, a powder-like superabsorbent resin, and a binder is charged into a mold, and the mixture is heated to harden the binder. A sealing material using a water-absorbing polyurethane foam manufactured by a method for manufacturing a body is described.
　止水技術として、水の流入口又は水の流出口を止水材で覆う方法が検討されている。例えば、建物の浸水被害の多くは、窓及び扉といった対象物の隙間を通じて建物に水が浸入することによって起こる。上記のような浸水被害を防止又は軽減するためには、窓及び扉といった対象物の隙間を止水材で覆うことが有効であると考えられる。止水材を用いる施工において、施工性と止水能との両立が求められている。 As a water-stopping technique, a method of covering the water inlet or water outlet with water-stopping material is being considered. For example, most of the flood damage to buildings occurs when water enters the building through gaps in objects such as windows and doors. In order to prevent or reduce the damage caused by flooding as described above, it is considered effective to cover gaps between objects such as windows and doors with waterproof materials. In construction using water-stopping materials, it is required to have both workability and water-stopping ability.
　本開示はこのような事情に鑑みてなされたものであり、本発明の一実施形態は、施工性に優れ、かつ、従来と比較して止水能の高い止水用組成物、及び、止水用組成物を用いた止水フィルムを提供することを目的とする。 The present disclosure has been made in view of the above circumstances, and an embodiment of the present invention provides a water-stopping composition that has excellent workability and has a higher water-stopping ability than conventional ones, and a water-stopping composition. An object of the present invention is to provide a water-stopping film using a composition for water.
　本開示は、以下の態様を含む。
＜１＞バインダー樹脂と、可塑剤と、吸水性架橋樹脂粒子と、を含み、アスカーゴム硬度がＣ５０未満である、止水用組成物。
＜２＞バインダー樹脂がポリウレタンを含む、＜１＞に記載の止水用組成物。
＜３＞バインダー樹脂及び可塑剤の合計含有量に占める可塑剤の割合が２０質量％～６０質量％である、＜１＞又は＜２＞に記載の止水用組成物。
＜４＞可塑剤の含有量が、止水用組成物の全量に対して、５質量％～３０質量％である、＜１＞～＜３＞のいずれか１つに記載の止水用組成物。
＜５＞可塑剤は、フタル酸エステルを含む、＜１＞～＜４＞のいずれか１つに記載の止水用組成物。
＜６＞ノーマルフォースが１Ｎ以上である、＜１＞～＜５＞のいずれか１つに記載の止水用組成物。
＜７＞吸水性架橋樹脂粒子の含有量が、止水用組成物の全量に対して、２０質量％以上６０質量％未満である、＜１＞～＜６＞のいずれか１つに記載の止水用組成物。
＜８＞吸水性架橋樹脂粒子を構成する吸水性架橋樹脂が、ポリアクリル酸塩の架橋物を含む、＜１＞～＜７＞のいずれか１つに記載の止水用組成物。
＜９＞＜１＞～＜８＞のいずれか１つに記載の止水用組成物を含む、止水フィルム。 The present disclosure includes the following aspects.
<1> A water-stopping composition containing a binder resin, a plasticizer, and water-absorbing crosslinked resin particles, and having an Asker rubber hardness of less than C50.
<2> The water-stopping composition according to <1>, wherein the binder resin contains polyurethane.
<3> The water-stopping composition according to <1> or <2>, wherein the proportion of the plasticizer in the total content of the binder resin and plasticizer is 20% by mass to 60% by mass.
<4> The water-stopping composition according to any one of <1> to <3>, wherein the content of the plasticizer is 5% by mass to 30% by mass based on the total amount of the waterstopping composition. thing.
<5> The water stop composition according to any one of <1> to <4>, wherein the plasticizer contains a phthalate ester.
<6> The water stop composition according to any one of <1> to <5>, which has a normal force of 1N or more.
<7> According to any one of <1> to <6>, the content of the water-absorbing crosslinked resin particles is 20% by mass or more and less than 60% by mass with respect to the total amount of the water-stopping composition. Water stop composition.
<8> The water-stopping composition according to any one of <1> to <7>, wherein the water-absorbing cross-linked resin constituting the water-absorbing cross-linked resin particles contains a cross-linked polyacrylate.
<9> A water-stop film comprising the water-stop composition according to any one of <1> to <8>.
　本開示によれば、施工性に優れ、かつ、従来と比較して止水能の高い止水用組成物、及び、止水用組成物を用いた止水フィルムが提供される。 According to the present disclosure, there are provided a water-stopping composition that has excellent workability and a higher water-stopping ability than conventional ones, and a water-stopping film using the water-stopping composition.
　以下、本開示の止水用組成物及び止水フィルムについて詳細に説明する。 Hereinafter, the water stop composition and water stop film of the present disclosure will be explained in detail.
　本開示において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
　本開示において、組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する上記複数の物質の合計量を意味する。
　本開示中に段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよく、また、実施例に示されている値に置き換えてもよい。
　本開示において、「工程」との語は、独立した工程だけでなく、他の工程と明確に区別できない場合であっても工程の所期の目的が達成されれば、本用語に含まれる。
　本開示において、好ましい態様の組み合わせは、より好ましい態様である。 In the present disclosure, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.
In the present disclosure, if there are multiple substances corresponding to each component in the composition, unless otherwise specified, the amount of each component in the composition means the total amount of the multiple substances present in the composition. do.
In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step, Further, the values may be replaced with the values shown in the examples.
In the present disclosure, the term "step" is included not only in an independent step but also in the case where the intended purpose of the step is achieved even if the step cannot be clearly distinguished from other steps.
In this disclosure, combinations of preferred aspects are more preferred aspects.
［止水用組成物］
　本開示の止水用組成物は、バインダー樹脂と、可塑剤と、吸水性架橋樹脂粒子と、を含み、アスカーゴム硬度がＣ５０未満である。 [Water stop composition]
The water stop composition of the present disclosure includes a binder resin, a plasticizer, and water-absorbing crosslinked resin particles, and has an Asker rubber hardness of less than C50.
　本開示の止水用組成物は、施工性に優れ、かつ、従来と比較して止水能が高い。かかる効果を奏する理由は、以下のように推測される。 The water-stopping composition of the present disclosure has excellent workability and has higher water-stopping ability than conventional compositions. The reason for this effect is presumed to be as follows.
　本開示の止水用組成物には、バインダー樹脂と共に可塑剤が含まれているため、バインダー樹脂が可塑剤によって軟質化される。これにより、本開示の止水用組成物は、水を吸収した際の膨張速度が速いため、従来よりも止水能が高いと考えられる。また、バインダー樹脂が可塑剤によって軟質化されることにより、吸水性架橋樹脂粒子の脱落が抑制されるため、長時間にわたり、止水させることができると考えられる。さらに、本開示の止水用組成物は、可塑剤を含むことで、予想外にタック性を有し、施工性に優れる。また、本開示の止水用組成物は、アスカーゴム硬度がＣ５０未満であり、柔軟性に優れ、止水用組成物を施工対象に追随するように配置させることができることから、施工性に優れると考えられる。 Since the water stop composition of the present disclosure contains a plasticizer together with the binder resin, the binder resin is softened by the plasticizer. As a result, the water-stopping composition of the present disclosure is considered to have higher water-stopping ability than conventional compositions, since the water-stopping composition of the present disclosure expands at a faster rate when it absorbs water. Furthermore, it is thought that by softening the binder resin with the plasticizer, the water-absorbing crosslinked resin particles are prevented from falling off, so that water can be stopped for a long time. Furthermore, the water stop composition of the present disclosure has unexpected tackiness and excellent workability because it contains a plasticizer. In addition, the water stop composition of the present disclosure has an Asker rubber hardness of less than C50, has excellent flexibility, and can be arranged to follow the construction target, so it is said to have excellent workability. Conceivable.
　これに対して、特公昭６３－３６３４１号公報及び特開２００３－１６５８６５号公報のいずれも、ポリウレタンフォームを含む止水材が記載されている。ポリウレタンフォームには空隙が存在するため、水を吸収すると、最初に空隙が埋まる方向へ膨張が進み、その後に、止水材全体としての膨張が進行するものと考えられる。そのため、止水に要する時間がかかり、止水能が不十分である。また、特公昭６３－３６３４１号公報及び特開２００３－１６５８６５号公報には、タック性に関する記載はなく、可塑剤に関する記載もないため、施工性も不十分であると考えられる。 On the other hand, both Japanese Patent Publication No. 63-36341 and Japanese Unexamined Patent Publication No. 2003-165865 describe water-stopping materials containing polyurethane foam. Since polyurethane foam has voids, it is thought that when it absorbs water, it expands first in a direction that fills the voids, and then the water-stopping material as a whole expands. Therefore, it takes a long time to stop water, and the water stopping ability is insufficient. In addition, Japanese Patent Publication No. 63-36341 and Japanese Patent Application Laid-Open No. 2003-165865 do not contain any descriptions regarding tackiness or plasticizers, so it is thought that the workability is also insufficient.
　以下、止水用組成物に含まれる各成分の詳細について説明する。 Hereinafter, details of each component contained in the water stop composition will be explained.
＜バインダー樹脂＞
　本開示の止水用組成物は、バインダー樹脂を含む。止水用組成物に含まれるバインダー樹脂は、１種のみであってもよく、２種以上であってもよい。 <Binder resin>
The water stop composition of the present disclosure includes a binder resin. The number of binder resins contained in the water stopping composition may be one, or two or more.
　バインダー樹脂の種類は特に限定されず、例えば、アクリル樹脂、シリコーン樹脂、ポリエステル、ポリウレタン及びポリオレフィンが挙げられる。 The type of binder resin is not particularly limited, and examples thereof include acrylic resin, silicone resin, polyester, polyurethane, and polyolefin.
　中でも、施工性の観点から、バインダー樹脂は、ポリウレタンを含むことが好ましい。 Among these, from the viewpoint of workability, it is preferable that the binder resin contains polyurethane.
　ポリウレタンは、例えば、ジイソシアネート化合物とポリオールとの反応によって得られる。 Polyurethane can be obtained, for example, by reacting a diisocyanate compound and a polyol.
　ジイソシアネート化合物としては、例えば、４，４’－ジフェニルメタンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、１，５－ナフタレンジイソシアネート、ｐ－又はｍ－フェニレンジイソシアネート、キシリレンジイソシアネート、及びｍ－テトラメチルキシリレンジイソシアネート等の芳香族ジイソシアネート；イソホロンジイソシアネート、４，４’－ジシクロヘキシルメタンジイソシアネート、１，４－シクロヘキシレンジイソシアネート及び水素化トリレンジイソシアネート等の脂環式ジ－イソシアネート；並びに、ヘキサメチレンジイソシアネート等の脂肪族ジイソシアネートが挙げられる。 Examples of the diisocyanate compound include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, p- or m-phenylene diisocyanate, xylylene diisocyanate, and aromatic diisocyanates such as m-tetramethylxylylene diisocyanate; cycloaliphatic diisocyanates such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexylene diisocyanate and hydrogenated tolylene diisocyanate; and Aliphatic diisocyanates such as hexamethylene diisocyanate can be mentioned.
　ポリオールとしては、例えば、ポリオキシポリアルキレンポリオール、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール、及びポリアクリルポリオールが挙げられる。 Examples of polyols include polyoxypolyalkylene polyols, polyester polyols, polyether polyols, polycarbonate polyols, and polyacrylic polyols.
　本開示の止水用組成物には、後述する可塑剤が含まれ、ポリウレタンは、可塑剤によって軟質化する。可塑剤によって軟質化したポリウレタンは、発泡ポリウレタンと比較して、水を吸収した際の膨張速度が速く、より短時間で止水することができる。また、バインダー樹脂が可塑剤によって軟質化されることにより、吸水性架橋樹脂粒子の脱落が抑制されるため、長時間にわたり、止水させることができる。 The water-stopping composition of the present disclosure contains a plasticizer, which will be described later, and the polyurethane is softened by the plasticizer. Polyurethane softened by a plasticizer has a faster expansion rate when absorbing water than foamed polyurethane, and can stop water in a shorter time. Furthermore, since the binder resin is softened by the plasticizer, the water-absorbing crosslinked resin particles are prevented from falling off, so water can be stopped for a long time.
　ポリウレタンの含有量は、止水用組成物の全量に対して、３０質量％～７０質量％であることが好ましく、４０質量％～６０質量％であることがより好ましい。 The content of polyurethane is preferably 30% by mass to 70% by mass, more preferably 40% by mass to 60% by mass, based on the total amount of the water-stopping composition.
＜可塑剤＞
　本開示の止水用組成物は、可塑剤を含む。止水用組成物に含まれる可塑剤は、１種のみであってもよく、２種以上であってもよい。 <Plasticizer>
The water stop composition of the present disclosure includes a plasticizer. The number of plasticizers contained in the water stopping composition may be one, or two or more.
　本開示の止水用組成物は、可塑剤を含むことで、予想外にタック性を有し、施工性に優れる。特に、曲面に対する施工性及び密着性に優れる。 The water-stopping composition of the present disclosure has unexpected tackiness and excellent workability because it contains a plasticizer. In particular, it has excellent workability and adhesion to curved surfaces.
　可塑剤の種類は特に限定されず、例えば、ポリエステル系可塑剤、ポリエーテルエステル系可塑剤、多価カルボン酸エステル系可塑剤、グリセリン系可塑剤、リン酸エステル系可塑剤、エポキシ系可塑剤、及びポリアクリル酸エステル系可塑剤が挙げられる。 The type of plasticizer is not particularly limited, and examples include polyester plasticizers, polyether ester plasticizers, polycarboxylic acid ester plasticizers, glycerin plasticizers, phosphate ester plasticizers, epoxy plasticizers, and polyacrylic acid ester plasticizers.
　ポリエステル系可塑剤としては、例えば、酸成分（例えば、アジピン酸、セバチン酸、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸及びジフェニルジカルボン酸）と、ジオール成分（例えば、プロピレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール、エチレングリコール及びジエチレングリコール）とを反応させてなるポリエステルが挙げられる。ポリエステル系可塑剤としては、例えば、ヒドロキシカルボン酸（例えば、ポリカプロラクトン）からなるポリエステルも挙げられる。ポリエステルは、単官能カルボン酸又は単官能アルコールで末端封鎖されていてもよい。ポリエステルは、エポキシ化合物で末端封鎖されていてもよい。市販品としては、例えば、株式会社ＡＤＥＫＡ製のアデカサイザーＰＮ－１５０、ＰＮ－１７０、Ｐ－２００及びＰＮ－３５０が挙げられる。 Examples of polyester plasticizers include acid components (e.g., adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and diphenyldicarboxylic acid) and diol components (e.g., propylene glycol, 1,3-butanediol). , 1,4-butanediol, 1,6-hexanediol, ethylene glycol and diethylene glycol). Examples of polyester plasticizers include polyesters made of hydroxycarboxylic acids (eg, polycaprolactone). The polyester may be end-capped with a monofunctional carboxylic acid or a monofunctional alcohol. The polyester may be end-capped with an epoxy compound. Commercially available products include, for example, ADEKASIZER PN-150, PN-170, P-200, and PN-350 manufactured by ADEKA Corporation.
　ポリエーテルエステル系可塑剤は、ポリアルキレングリコールの有機酸エステルであることが好ましい。ポリアルキレングリコールとしては、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール、ポリ（エチレンオキサイド・プロピレンオキサイド）ブロック共重合体、ポリ（エチレンオキサイド・プロピレンオキサイド）ランダム共重合体及びポリテトラメチレングリコールが挙げられる。ポリエーテル鎖中にビスフェノール類といった芳香族ユニットが含まれていてもよい。有機酸としては、例えば、モノカルボン酸（例えば、ブタン酸、イソブタン酸、２－エチルブチル酸、２－エチルヘキシル酸及びデカン酸）が挙げられる。市販品としては、例えば、株式会社ＡＤＥＫＡ製のアデカサイザーＲＳ－１０００、ＲＳ－７３５及びＲＳ－７００が挙げられる。 The polyether ester plasticizer is preferably an organic acid ester of polyalkylene glycol. Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polybutylene glycol, poly(ethylene oxide/propylene oxide) block copolymer, poly(ethylene oxide/propylene oxide) random copolymer, and polytetramethylene glycol. It will be done. Aromatic units such as bisphenols may be included in the polyether chain. Organic acids include, for example, monocarboxylic acids (eg, butanoic acid, isobutanoic acid, 2-ethylbutyric acid, 2-ethylhexylic acid, and decanoic acid). Commercially available products include, for example, ADEKASIZER RS-1000, RS-735, and RS-700 manufactured by ADEKA Corporation.
　多価カルボン酸エステル系可塑剤としては、例えば、脂肪族ジカルボン酸エステル、芳香族ジカルボン酸エステル、トリメリット酸エステル及びクエン酸エステル（例えば、アセチルクエン酸トリエチル及びアセチルクエン酸トリブチル）が挙げられる。 Examples of polyvalent carboxylic acid ester plasticizers include aliphatic dicarboxylic acid esters, aromatic dicarboxylic acid esters, trimellitic acid esters, and citric acid esters (for example, triethyl acetyl citrate and tributyl acetyl citrate).
　脂肪族ジカルボン酸エステルとしては、例えば、アジピン酸エステル（例えば、アジピン酸ジイソデシル、アジピン酸ジ－ｎ－オクチル－及びアジピン酸ジ－ｎ－デシル）、アゼライン酸エステル（例えば、アゼライン酸ジ－２－エチルヘキシル）及びセバシン酸エステル（例えば、セバシン酸ジブチル及びセバシン酸ジ－２－エチルヘキシル）が挙げられる。 Examples of 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-adipate), ethylhexyl) and sebacic acid esters (eg, dibutyl sebacate and di-2-ethylhexyl sebacate).
　芳香族ジカルボン酸エステルとしては、例えば、フタル酸エステル（例えば、フタル酸ジメチル、フタル酸ジエチル、フタル酸ジブチル、フタル酸ジオクチル、フタル酸ジヘプチル、フタル酸ジイソノニル、フタル酸ジベンジル、及びフタル酸ブチルベンジル）が挙げられる。 Examples of aromatic dicarboxylic acid esters include phthalate esters (e.g., dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, diisononyl phthalate, dibenzyl phthalate, and butylbenzyl phthalate). can be mentioned.
　トリメリット酸エステルとしては、例えば、トリメリット酸トリメチル、トリメリット酸トリエチル、トリメリット酸トリプロピル、トリメリット酸トリブチル、トリメリット酸トリアミル、トリメリット酸トリヘキシル、トリメリット酸トリヘプチル、トリメリット酸トリ－ｎ－オクチル、トリメリット酸トリ－２－エチルヘキシル、トリメリット酸トリノニル、トリメリット酸トリイソノニル、トリメリット酸トリス（デシル）、トリメリット酸トリス（ドデシル）、トリメリット酸トリス（テトラデシル）、トリメリット酸トリス（Ｃ８～Ｃ１２混合アルキル）、トリメリット酸トリス（Ｃ７～Ｃ９混合アルキル）及びトリメリット酸トリラウリルが挙げられる。市販品としては、例えば、株式会社ＡＤＥＫＡ製のアデカサイザーＣ－８、Ｃ－８８０、Ｃ－７９、Ｃ８１０、Ｃ－９Ｎ及びＣ－１０が挙げられる。 Examples of trimellitic acid esters include trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, triamyl trimellitate, trihexyl trimellitate, triheptyl trimellitate, and trimellitate. n-octyl, tri-2-ethylhexyl trimellitate, trinonyl trimellitate, triisononyl trimellitate, tris(decyl) trimellitate, tris(dodecyl) trimellitate, tris(tetradecyl) trimellitate, trimellitic acid Tris (C8-C12 mixed alkyl), tris (C7-C9 mixed alkyl) trimellitate and trilauryl trimellitate are mentioned. Commercially available products include, for example, ADEKASIZER C-8, C-880, C-79, C810, C-9N and C-10 manufactured by ADEKA Corporation.
　グリセリン系可塑剤としては、例えば、グリセリンモノアセトモノラウレート、グリセリンジアセトモノラウレート、グリセリンモノアセトモノステアレート、グリセリンジアセトモノオレート及びグリセリンモノアセトモノモンタネートが挙げられる。 Examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolarate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomononanate.
　リン酸エステル系可塑剤としては、例えば、リン酸トリブチル、リン酸トリ－２－エチルヘキシル、リン酸トリオクチル、リン酸トリフェニル、リン酸ジフェニル－２－エチルヘキシル及びリン酸トリクレシルが挙げられる。 Examples of phosphate ester plasticizers include tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate, and tricresyl phosphate.
　エポキシ系可塑剤としては、例えば、エポキシステアリン酸アルキルと大豆油とからなるエポキシトリグリセリドが挙げられる。エポキシ系可塑剤としては、例えば、主にビスフェノールＡとエピクロロヒドリンとを原料とするエポキシ樹脂も挙げられる。 Examples of epoxy plasticizers include epoxy triglyceride made of alkyl epoxy stearate and soybean oil. Examples of epoxy plasticizers include epoxy resins mainly made from bisphenol A and epichlorohydrin.
　ポリアクリル酸エステル系可塑剤としては、例えば、アクリル酸アルキルエステルの重合体が挙げられる。ポリアクリル酸エステル系可塑剤は、エポキシ基及びカルボキシ基といった官能基を有していてもよい。市販品としては、例えば、東亞合成株式会社製のアルフォンシリーズ（例えば、無官能のＵＰシリーズ）が挙げられる。 Examples of polyacrylic ester plasticizers include polymers of acrylic acid alkyl esters. The polyacrylic acid ester plasticizer may have functional groups such as epoxy groups and carboxy groups. Commercially available products include, for example, the Alfon series (eg, non-functional UP series) manufactured by Toagosei Co., Ltd.
　他の可塑剤としては、例えば、ネオペンチルグリコールジベンゾエート、ジエチレングリコールジベンゾエート、トリエチレングリコールジ－２－エチルブチレート等の脂肪族ポリオールの安息香酸エステル、ステアリン酸アミド等の脂肪酸アミド、オレイン酸ブチル等の脂肪族カルボン酸エステル、アセチルリシノール酸メチル、アセチルリシノール酸ブチル等のオキシ酸エステル、ペンタエリスリトール、ソルビトール、ポリアクリル酸エステル、シリコーンオイル及びパラフィン類が挙げられる。 Examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethyl butyrate, fatty acid amides such as stearic acid amide, and butyl oleate. Examples include aliphatic carboxylic acid esters such as methyl acetyl ricinoleate and butyl acetyl ricinoleate, oxyacid esters such as pentaerythritol, sorbitol, polyacrylic esters, silicone oils and paraffins.
　中でも、可塑剤は、ブリーディングを抑制する観点から、多価カルボン酸エステル系可塑剤を含むことが好ましく、芳香族ジカルボン酸エステルを含むことがより好ましく、フタル酸エステルを含むことがさらに好ましい。 Among these, from the viewpoint of suppressing bleeding, the plasticizer preferably contains a polycarboxylic acid ester plasticizer, more preferably an aromatic dicarboxylic acid ester, and even more preferably a phthalate ester.
　バインダー樹脂及び可塑剤の合計含有量に占める可塑剤の割合は、２０質量％～６０質量％であることが好ましく、３０質量％～５５質量％であることがより好ましい。可塑剤の割合が２０質量％以上であると、バインダー樹脂が可塑剤によって軟質化されることにより、吸水性架橋樹脂粒子の吸水による膨潤が阻害されにくくなるため、より短期間で、止水させることができる。上記割合が６０質量％以下であると、可塑剤のブリーディングが抑制される。ブリーディングが発生すると、表面に油にじみが発生し、タック性が低下する。 The proportion of the plasticizer in the total content of the binder resin and plasticizer is preferably 20% by mass to 60% by mass, more preferably 30% by mass to 55% by mass. When the proportion of the plasticizer is 20% by mass or more, the binder resin is softened by the plasticizer, and the swelling of the water-absorbing crosslinked resin particles due to water absorption is less likely to be inhibited, so that water can be stopped in a shorter period of time. be able to. When the above ratio is 60% by mass or less, bleeding of the plasticizer is suppressed. When bleeding occurs, oil smear occurs on the surface and tackiness decreases.
　可塑剤の含有量は、止水用組成物の全量に対して、５質量％～３０質量％であることが好ましく、１５質量％～３０質量％であることがより好ましく、２０質量％～３０質量％であることがさらに好ましい。可塑剤の含有量が５質量％以上であると、バインダー樹脂が可塑剤によって軟質化されることにより、吸水性架橋樹脂粒子の吸水による膨潤が阻害されにくくなるため、より短期間で、止水させることができる。可塑剤の含有量が３０質量％以下であると、可塑剤のブリーディングが抑制される。 The content of the plasticizer is preferably 5% to 30% by mass, more preferably 15% to 30% by mass, and 20% to 30% by mass, based on the total amount of the water-stopping composition. More preferably, it is expressed in mass %. When the content of the plasticizer is 5% by mass or more, the binder resin is softened by the plasticizer, and the swelling of the water-absorbing crosslinked resin particles due to water absorption is less likely to be inhibited, so water can be stopped in a shorter period of time. can be done. When the content of the plasticizer is 30% by mass or less, bleeding of the plasticizer is suppressed.
＜吸水性架橋樹脂粒子＞
　本開示の止水用組成物は、吸水性架橋樹脂粒子を含む。
　本開示において、吸水性架橋樹脂粒子とは、吸水性であって、架橋構造を有する樹脂粒子を意味する。 <Water-absorbing crosslinked resin particles>
The water-stopping composition of the present disclosure includes water-absorbing crosslinked resin particles.
In the present disclosure, water-absorbing crosslinked resin particles refer to resin particles that are water-absorbent and have a crosslinked structure.
　「吸水性」とは、ＪＩＳ　Ｋ　７２０９：２０００（ＩＳＯ６２：１９９９）に記載されたＡ法に準拠して測定される吸水率が１２％以上であることを意味する。吸水率は、初期質量に対する質量変化の百分率である。吸水率は、１５％以上であることが好ましく、２０％以上であることがより好ましい。吸水率の上限値は、耐久性の観点から、６０％以下であることが好ましく、５０％以下であることがより好ましい。 "Water absorption" means that the water absorption rate measured according to method A described in JIS K 7209:2000 (ISO62:1999) is 12% or more. Water absorption is the percentage change in mass relative to the initial mass. The water absorption rate is preferably 15% or more, more preferably 20% or more. From the viewpoint of durability, the upper limit of the water absorption rate is preferably 60% or less, more preferably 50% or less.
　樹脂粒子が架橋構造を有するか否かは、樹脂粒子が水を吸収した際に溶解せず、樹脂粒子が水を吸収してゲル状になるか否かによって判定することができる。 Whether or not the resin particles have a crosslinked structure can be determined by whether or not the resin particles do not dissolve when they absorb water, and whether the resin particles absorb water and become gel-like.
　吸水性架橋樹脂粒子を構成する吸水性架橋樹脂としては、例えば、多糖類と、酸基を有する重合性モノマーと、架橋剤とを重合して得られる樹脂が挙げられる。 Examples of the water-absorbing crosslinked resin constituting the water-absorbing crosslinked resin particles include resins obtained by polymerizing a polysaccharide, a polymerizable monomer having an acid group, and a crosslinking agent.
　多糖類は、単糖分子がグリコシド結合によって複数重合した物質の総称であり、例えば、アガロース、デキストラン、カラギーナン、アルギン酸、ヒアルロン酸、キチン、キトサン、デンプン、及びセルロース系化合物が挙げられる。 Polysaccharide is 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 compounds.
　酸基を有する重合性モノマーにおける酸基としては、例えば、カルボキシ基、スルホ基、及びリン酸基が挙げられる。中でも、酸基は、カルボキシ基であることが好ましい。 Examples of the acid group in the polymerizable monomer having an acid group include a carboxy group, a sulfo group, and a phosphoric acid group. Among these, the acid group is preferably a carboxy group.
　また、酸基を有する重合性モノマーは、塩を形成していてもよい。形成される塩としては、例えば、アルカリ金属塩（例えば、ナトリウム塩、カリウム塩等）、アルカリ土類金属塩（例えば、カルシウム塩、マグネシウム塩等）、アミン塩、及びアンモニウム塩が挙げられる。 Furthermore, the polymerizable monomer having an acid group may form a salt. The salts formed include, for example, alkali metal salts (eg, sodium salts, potassium salts, etc.), alkaline earth metal salts (eg, calcium salts, magnesium salts, etc.), amine salts, and ammonium salts.
　カルボキシ基を有する重合性モノマーとしては、例えば、（メタ）アクリル酸、マレイン酸、マレイン酸モノアルキルエステル、フマル酸、フマル酸モノアルキルエステル、クロトン酸、ソルビン酸、イタコン酸、イタコン酸モノアルキルエステル、イタコン酸グリコールモノエーテル、ケイ皮酸、シトラコン酸、シトラコン酸モノアルキルエステル等及びそれらの無水物が挙げられる。 Examples of polymerizable monomers having a carboxyl group include (meth)acrylic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, sorbic acid, itaconic acid, and itaconic acid monoalkyl ester. , itaconic acid glycol monoether, cinnamic acid, citraconic acid, citraconic acid monoalkyl ester, and anhydrides thereof.
　スルホ基を有する重合性モノマーとしては、例えば、ビニルスルホン酸、アリルスルホン酸、ビニルトルエンスルホン酸、スチレンスルホン酸、２－ヒドロキシ－３－（メタ）アクリロキシプロピルスルホン酸、（メタ）アクリルアルキルスルホン酸（例えば、（メタ）アクリル酸スルホエチル、（メタ）アクリル酸スルホプロピル等）、及び（メタ）アクリルアミドアルキルスルホン酸（例えば、２－アクリルアミド－２－メチルプロパンスルホン酸等）が挙げられる。 Examples of polymerizable monomers having a sulfo group include vinylsulfonic acid, allylsulfonic acid, vinyltoluenesulfonic acid, styrenesulfonic acid, 2-hydroxy-3-(meth)acryloxypropylsulfonic acid, and (meth)acrylalkylsulfone. Examples include acids (eg, sulfoethyl (meth)acrylate, sulfopropyl (meth)acrylate, etc.), and (meth)acrylamidoalkylsulfonic acids (eg, 2-acrylamido-2-methylpropanesulfonic acid, etc.).
　リン酸基を有する重合性モノマーとしては、例えば、（メタ）アクリル酸ヒドロキシアルキルリン酸モノエステル（例えば、２－ヒドロキシエチル（メタ）アクリロイルホスフェート、フェニル－２－アクリロイルロキシエチルホスフェート等）が挙げられる。 Examples of polymerizable monomers having a phosphoric acid group include (meth)acrylic acid hydroxyalkyl phosphate monoesters (for example, 2-hydroxyethyl (meth)acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, etc.) .
　架橋剤としては、例えば、２つ以上の重合性基を重合性モノマー；重合性基と、酸基と反応可能な反応性基（例えば、水酸基）とを有する化合物；及び、酸基と反応可能な反応性基（例えば、水酸基）を２つ以上有する化合物が挙げられる。 As a crosslinking agent, for example, a polymerizable monomer having two or more polymerizable groups; a compound having a polymerizable group and a reactive group (e.g., a hydroxyl group) that can react with an acid group; and a compound that can react with an acid group. Examples include compounds having two or more reactive groups (for example, hydroxyl groups).
　２つ以上の重合性基を重合性モノマーとしては、例えば、Ｎ，Ｎ’－メチレンビス（メタ）アクリルアミド、エチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、グリセリン（ジ又はトリ）アクリレート、トリメチロールプロパントリアクリレート、トリアリルアミン、トリアリルシアヌレート、トリアリルイソシアヌレート、テトラアリロキシエタン及びペンタエリスリトールトリアリルエーテルが挙げられる。 Examples of the polymerizable monomer having two or more polymerizable groups include N,N'-methylenebis(meth)acrylamide, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylate. , glycerin (di- or tri)acrylate, trimethylolpropane triacrylate, triallylamine, triallyl cyanurate, triallyl isocyanurate, tetraallyloxyethane and pentaerythritol triallyl ether.
　重合性基と反応性基とを有する化合物としては、例えば、ヒドロキシエチル（メタ）アクリレート、Ｎ－メチロール（メタ）アクリルアミド、及びグリシジル（メタ）アクリレートが挙げられる。 Examples of compounds having a polymerizable group and a reactive group include hydroxyethyl (meth)acrylate, N-methylol (meth)acrylamide, and glycidyl (meth)acrylate.
　反応性基を２つ以上有する化合物としては、例えば、エチレングリコール、ジエチレングリコール、グリセリン、プロピレングリコール、トリメチロールプロパン、アルカノールアミン（例えば、ジエタノールアミン等）、及びポリアミン（例えば、ポリエチレンイミン等）が挙げられる。 Examples of compounds having two or more reactive groups include ethylene glycol, diethylene glycol, glycerin, propylene glycol, trimethylolpropane, alkanolamines (e.g., diethanolamine, etc.), and polyamines (e.g., polyethyleneimine, etc.).
　多糖類と、酸基を有する重合性モノマーと、架橋剤とを重合して得られる樹脂としては、例えば、デンプン－アクリル酸グラフト共重合体の架橋物が挙げられる。 Examples of the resin obtained by polymerizing a polysaccharide, a polymerizable monomer having an acid group, and a crosslinking agent include a crosslinked product of a starch-acrylic acid graft copolymer.
　また、吸水性架橋樹脂粒子を構成する吸水性架橋樹脂は、多糖類と、酸基を有する重合性モノマーとの重合物（例えば、デンプン－アクリロニトリルグラフト重合体の加水分解物、セルロース－アクリロニトリルグラフト共重合体の加水分解物等）であってもよい。 In addition, the water-absorbing cross-linked resin constituting the water-absorbing cross-linked resin particles is a polymer of a polysaccharide and a polymerizable monomer having an acid group (for example, a hydrolyzate of a starch-acrylonitrile graft polymer, a cellulose-acrylonitrile graft copolymer, etc.). (polymer hydrolyzate, etc.) may also be used.
　また、吸水性架橋樹脂粒子を構成する吸水性架橋樹脂は、多糖類の架橋物（例えば、カルボキシメチルセルロースの架橋物等）であってもよい。 Further, the water-absorbing cross-linked resin constituting the water-absorbing cross-linked resin particles may be a cross-linked polysaccharide (for example, a cross-linked carboxymethyl cellulose).
　また、吸水性架橋樹脂粒子を構成する吸水性架橋樹脂は、酸基を有する重合性モノマーと上記架橋剤とを重合して得られる樹脂であってもよい。このような樹脂としては、例えば、アクリル酸－アクリルアミド共重合体の架橋物、ポリスルホン酸塩の架橋物、ポリアクリル酸塩／ポリスルホン酸塩共重合体の架橋物、ビニルエステル－不飽和カルボン酸共重合体ケン化物の架橋物、ポリアクリル酸（塩）の架橋物、アクリル酸－アクリル酸エステル共重合体の架橋物、イソブチレン－無水マレイン酸共重合体の架橋物、ポリビニルピロリドンの架橋物、及びカルボン酸変性ポリビニルアルコールの架橋物が挙げられる。 Further, the water-absorbing crosslinked resin constituting the water-absorbing crosslinked resin particles may be a resin obtained by polymerizing a polymerizable monomer having an acid group and the above-mentioned crosslinking agent. Examples of such resins include crosslinked products of acrylic acid-acrylamide copolymer, crosslinked products of polysulfonate, crosslinked products of polyacrylate/polysulfonate copolymer, and vinyl ester-unsaturated carboxylic acid copolymer. Cross-linked products of saponified polymers, cross-linked products of polyacrylic acid (salt), cross-linked products of acrylic acid-acrylic acid ester copolymers, cross-linked products of isobutylene-maleic anhydride copolymers, cross-linked products of polyvinylpyrrolidone, and Examples include crosslinked products of carboxylic acid-modified polyvinyl alcohol.
　また、吸水性架橋樹脂粒子を構成する吸水性架橋樹脂は、自己架橋性を有する重合性モノマーの重合体（例えば、自己架橋型ポリアクリル酸塩等）であってもよい。 Furthermore, the water-absorbing crosslinked resin constituting the water-absorbing crosslinked resin particles may be a polymer of polymerizable monomers having self-crosslinking properties (for example, self-crosslinking polyacrylate, etc.).
　中でも、耐久性の観点から、吸水性架橋樹脂粒子を構成する吸水性架橋樹脂は、ポリアクリル酸（塩）の架橋物を含むことが好ましい。 Among these, from the viewpoint of durability, it is preferable that the water-absorbing cross-linked resin constituting the water-absorbing cross-linked resin particles contains a cross-linked product of polyacrylic acid (salt).
　吸水性架橋樹脂粒子の形状は特に限定されず、例えば、球状、多角形状、鱗片状、平板状、不定形状等が挙げられる。 The shape of the water-absorbing crosslinked resin particles is not particularly limited, and examples include spherical, polygonal, scaly, tabular, and irregular shapes.
　吸水性架橋樹脂粒子の中心粒度は、水の吸収に伴う吸水性架橋樹脂粒子の脱落を抑制する観点から、３５０μｍ以下であることが好ましく、１００μｍ以下であることがより好ましく、５０μｍ以下であることがさらに好ましい。また、吸水性架橋樹脂粒子の中心粒度は、製造容易性の観点から、１μｍ以上であることが好ましく、１０μｍ以上であることがより好ましい。 The center particle size of the water-absorbing cross-linked resin particles is preferably 350 μm or less, more preferably 100 μm or less, and 50 μm or less, from the viewpoint of suppressing shedding of the water-absorbing cross-linked resin particles due to water absorption. is even more preferable. Further, from the viewpoint of ease of production, the center particle size of the water-absorbing crosslinked resin particles is preferably 1 μm or more, more preferably 10 μm or more.
　中心粒度は、体積基準の粒度分布において小径側からの体積累積が５０％になるときの粒径（Ｄ５０）である。中心粒度は、レーザー回折／散乱式粒度分布測定装置を用いて測定することができる。 The central particle size is the particle size (D50) when the volume accumulation from the small diameter side becomes 50% in the volume-based particle size distribution. The central particle size can be measured using a laser diffraction/scattering particle size distribution analyzer.
　吸水性架橋樹脂粒子の含有量は、止水用組成物の全量に対して、２０質量％以上６０質量％未満であることが好ましく、４０質量％以上６０質量％未満であることがより好ましく、４０質量％～５８質量％であることがさらに好ましい。吸水性架橋樹脂粒子の含有量が２０質量％以上であると、止水に要する時間をより短縮することができる。吸水性架橋樹脂粒子の含有量が６０質量％以下であると、吸水性架橋樹脂粒子の脱落が抑制されるため、長時間にわたり、止水させることができる。 The content of the water-absorbing crosslinked resin particles is preferably 20% by mass or more and less than 60% by mass, more preferably 40% by mass or more and less than 60% by mass, based on the total amount of the water-stopping composition. More preferably, it is 40% by mass to 58% by mass. When the content of the water-absorbing crosslinked resin particles is 20% by mass or more, the time required for water stopping can be further shortened. When the content of the water-absorbing cross-linked resin particles is 60% by mass or less, the water-absorbing cross-linked resin particles are prevented from falling off, so that water can be stopped for a long time.
＜他の成分＞
　本開示の止水用組成物は、バインダー樹脂、可塑剤、及び吸収性架橋樹脂粒子以外の他の成分を含んでいてもよい。他の成分としては、例えば、架橋構造を有しない吸収性ポリマーが挙げられる。架橋構造を有しない吸収性ポリマーとしては、例えば、（メタ）アクリル系重合体、ビニル系重合体、及び多糖類が挙げられる <Other ingredients>
The water-stopping composition of the present disclosure may contain components other than the binder resin, plasticizer, and absorbent crosslinked resin particles. Examples of other components include absorbent polymers that do not have a crosslinked structure. Examples of absorbent polymers without a crosslinked structure include (meth)acrylic polymers, vinyl polymers, and polysaccharides.
　止水用組成物が架橋構造を有しない吸収性ポリマーを含む場合、架橋構造を有しない吸収性ポリマーの含有量は、止水用組成物の全量に対して、３０質量％以下であることが好ましく、２０質量％以下であることがより好ましく、５質量％以下であることがさらに好ましい。架橋構造を有しない吸収性ポリマーの含有量は０質量％であってもよい。 When the water-stopping composition contains an absorbent polymer that does not have a crosslinked structure, the content of the absorbent polymer that does not have a crosslinked structure may be 30% by mass or less based on the total amount of the waterstopping composition. It is preferably at most 20% by mass, more preferably at most 5% by mass. The content of the absorbent polymer without a crosslinked structure may be 0% by mass.
＜物性＞
（アスカーゴム硬度）
　本開示の止水用組成物は、アスカーゴム硬度がＣ５０未満であり、Ｃ４０以下であることが好ましく、Ｃ２０以下であることがより好ましい。アスカーゴム硬度の下限値は特に限定されず、例えば、Ｃ５である。アスカーゴム硬度は、Ｃ５以上Ｃ５０未満であってもよい。 <Physical properties>
(Asker rubber hardness)
The water stop composition of the present disclosure has an Asker rubber hardness of less than C50, preferably C40 or less, and more preferably C20 or less. The lower limit of the Asker rubber hardness is not particularly limited, and is, for example, C5. Asker rubber hardness may be greater than or equal to C5 and less than C50.
　アスカーゴム硬度がＣ５０未満であると、施工性、特に、曲面における施工性に優れる。 When the Asker rubber hardness is less than C50, workability, especially workability on curved surfaces, is excellent.
　アスカーゴムＣ硬度は、温度２５℃において、アスカーゴム硬度計Ｃ型を用いて測定することができる。 Asker rubber C hardness can be measured at a temperature of 25° C. using an Asker rubber hardness meter C type.
（ノーマルフォース）
　本開示の止水用組成物は、ノーマルフォースが１Ｎ以上であることが好ましく、５Ｎ以上であることがより好ましく、１５Ｎ以上であることがさらに好ましい。ノーマルフォースの上限値は、例えば、５０Ｎである。
　ノーマルフォースとは、レオメータの測定プレートを測定サンプルの接地面から引き上げる時に出現する法線方向の力を意味する。 (Normal force)
The water stop composition of the present disclosure preferably has a normal force of 1N or more, more preferably 5N or more, and even more preferably 15N or more. The upper limit of the normal force is, for example, 50N.
Normal force means the force in the normal direction that appears when the measurement plate of the rheometer is pulled up from the ground surface of the measurement sample.
　ノーマルフォースが１Ｎ以上であると、タック性に優れるため、施工性に優れる。 When the normal force is 1N or more, the tack property is excellent and the workability is excellent.
　ノーマルフォースは、以下の方法で測定される。 Normal force is measured by the following method.
　測定用サンプルを準備し、レオメータ（製品名「ＭＣＲ３０２」、アントンパール社製）を用いて測定する。まず、測定治具（平行板プレートＰＰ２５）を５Ｎの力で測定サンプルに押し当てる。次に、測定治具を１ｃｍ／秒の速度で引き上げたときのノーマルフォースの絶対値を記録する。３回の測定値における平均値を採用する。 A sample for measurement is prepared and measured using a rheometer (product name "MCR302", manufactured by Anton Paar). First, a measurement jig (parallel plate PP25) is pressed against the measurement sample with a force of 5N. Next, the absolute value of the normal force when the measuring jig is pulled up at a speed of 1 cm/sec is recorded. The average value of three measurements is used.
［止水フィルム］
　本開示の止水用組成物は、さまざまな用途に適用することができる。
　本開示の止水フィルムは、上記止水用組成物を含むことが好ましい。 [Water stop film]
The water stop composition of the present disclosure can be applied to various uses.
The water-stopping film of the present disclosure preferably contains the water-stopping composition described above.
　本開示の止水フィルムは、１層のみであってもよく、２層以上であってもよい。すなわち、止水用組成物からなるフィルムであってもよく、止水用組成物を含む層を有する積層フィルムであってもよい。止水用組成物を含む層は、止水用組成物が成形された層であってもよい。 The water stop film of the present disclosure may have only one layer, or may have two or more layers. That is, it may be a film made of a water-stopping composition, or it may be a laminated film having a layer containing a water-stopping composition. The layer containing the water-stopping composition may be a layer in which the water-stopping composition is molded.
　止水用組成物からなるフィルム（積層フィルムの場合には、止水用組成物を含む層）の厚さは、例えば、１ｍｍ～１０ｍｍである。 The thickness of the film made of the water-stopping composition (in the case of a laminated film, the layer containing the water-stopping composition) is, for example, 1 mm to 10 mm.
　本開示の止水フィルムは、止水用組成物を含む層上に、透水性基材を備えていてもよい。 The water-stop film of the present disclosure may include a water-permeable base material on the layer containing the water-stop composition.
　透水性基材は、透水性を有する基材であれば特に限定されない。 The water permeable base material is not particularly limited as long as it is a base material that has water permeability.
　本開示において、「透水性」とは、液体の水が通過可能な性質を意味する。具体的には、透水性基材は、水が通過可能な孔を有することが好ましい。 In the present disclosure, "water permeability" means a property through which liquid water can pass. Specifically, the water-permeable base material preferably has pores through which water can pass.
　止水フィルムにおいて、透水性基材は、止水用組成物を含む層を保持する役割を有する。また、水が透水性基材を通過して、止水用組成物を含む層へ入りこむと、止水用組成物を含む層は膨潤する。透水性基材は、止水用組成物を含む層に対して水を効率良く接触させる役割も有する。 In the water-stop film, the water-permeable base material has the role of holding a layer containing the water-stop composition. Further, when water passes through the water-permeable base material and enters the layer containing the water-stopping composition, the layer containing the water-stopping composition swells. The water-permeable base material also has the role of bringing water into efficient contact with the layer containing the water-stopping composition.
　透水性基材は、透水性の観点から、繊維を含む層であることが好ましく、セルロース繊維、レーヨン繊維、ポリオレフィン繊維、又はポリエステル繊維を含む層であることがより好ましい。 From the viewpoint of water permeability, the water permeable base material is preferably a layer containing fibers, and more preferably a layer containing cellulose fibers, rayon fibers, polyolefin fibers, or polyester fibers.
　透水性基材は、透水性の観点から、不織布、布、又は紙であることが好ましく、不織布であることがより好ましい。 From the viewpoint of water permeability, the water permeable base material is preferably a nonwoven fabric, cloth, or paper, and more preferably a nonwoven fabric.
　透水性基材の厚さは特に限定されず、例えば、１５μｍ～２００μｍである。 The thickness of the water-permeable base material is not particularly limited, and is, for example, 15 μm to 200 μm.
　[農業用保水材、農業用保水シート］
　本開示の止水用組成物は、農業用保水材及び農業用保水シートとして有用である。 [Agricultural water retention material, agricultural water retention sheet]
The water-stopping composition of the present disclosure is useful as an agricultural water-retaining material and an agricultural water-retaining sheet.
　本開示の一実施形態である農業用保水材は、バインダー樹脂と、可塑剤と、吸水性架橋樹脂粒子と、を含み、アスカーゴム硬度がＣ５０未満である、止水用組成物を含む。 An agricultural water retaining material that is an embodiment of the present disclosure includes a water-stopping composition that includes a binder resin, a plasticizer, and water-absorbing crosslinked resin particles, and has an Asker rubber hardness of less than C50.
　本開示の一実施形態である農業用保水シートは、バインダー樹脂と、可塑剤と、吸水性架橋樹脂粒子と、を含み、アスカーゴム硬度がＣ５０未満である、止水用組成物を含む。 An agricultural water-retaining sheet that is an embodiment of the present disclosure includes a water-stopping composition that includes a binder resin, a plasticizer, and water-absorbing crosslinked resin particles, and has an Asker rubber hardness of less than C50.
　上記のとおり、本開示の止水用組成物は、施工性に優れ、かつ、従来と比較して止水能が高い。したがって、本開示の止水用組成物を含む農業用保水材及び農業用保水シートは、施工性に優れ、かつ、従来と比較して保水能が高い。
　したがって、例えば、農業用保水材を圃場に直接散布することにより、農作物への水やり頻度を低減させることが可能である。また、例えば、農業用保水シートを土壌の上に被覆することにより、農作物への水やり頻度を低減させることが可能である。 As described above, the water-stopping composition of the present disclosure has excellent workability and has higher water-stopping ability than conventional compositions. Therefore, agricultural water-retaining materials and agricultural water-retaining sheets containing the water-stopping composition of the present disclosure have excellent workability and a higher water-retaining capacity than conventional ones.
Therefore, for example, by directly spraying an agricultural water retaining material onto a field, it is possible to reduce the frequency of watering agricultural crops. Furthermore, for example, by covering soil with an agricultural water retaining sheet, it is possible to reduce the frequency of watering agricultural crops.
　以下、本開示の実施例を表すが、本開示は以下の実施例には限定されない。 Examples of the present disclosure will be described below, but the present disclosure is not limited to the following examples.
［止水用組成物の調製］
＜実施例１＞
　容量３００ｍＬの撹拌容器（製品名「００２撹拌容器」、近畿容器社製）に、下記成分を混合し、混合物を得た。混合物１００ｇをミキサー（製品名「ＡＲＶ－３１０」、シンキー社製）に入れ、回転速度９００ｒｐｍ（revolutions per minute）、圧力３ｋＰａの条件下で１分間の減圧撹拌処理を行った。
　減圧撹拌処理後の混合物を、フラットガラスシャーレ（内径７ｃｍφ）に３０ｇを流し込み、２５℃で２４時間静置した。その後、フラットガラスシャーレから取り出して、直径約７ｃｍ、高さ約６ｍｍの円柱状の止水用組成物のサンプルＡを得た。
　別途、減圧撹拌処理後の混合物を、縦５０ｍｍ、横１００ｍｍ、及び高さ２ｍｍのアクリル樹脂製容器に流し込み、２５℃で２４時間静置した。その後、アクリル樹脂製容器から取り出して、縦約５０ｍｍ、横約１００ｍｍ、高さ約２ｍｍの止水用組成物のサンプルＢを得た。
・バインダー樹脂：製品名「人肌のゲル原液　硬度Ｃ０」、エクシール社製　…５５質量％
・吸水性架橋樹脂粒子：製品名「サンフレッシュＳＴ－５００ＭＰＳＡ」、三洋化成工業社製、中心粒度３０μｍ　…４５質量％ [Preparation of water stop composition]
<Example 1>
The following components were mixed in a stirring container with a capacity of 300 mL (product name "002 stirring container", manufactured by Kinki Yoki Co., Ltd.) to obtain a mixture. 100 g of the mixture was placed in a mixer (product name "ARV-310", manufactured by Shinky Co., Ltd.), and vacuum stirring treatment was performed for 1 minute at a rotation speed of 900 rpm (revolutions per minute) and a pressure of 3 kPa.
After the vacuum stirring treatment, 30 g of the mixture was poured into a flat glass petri dish (inner diameter 7 cmφ) and left at 25° C. for 24 hours. Thereafter, it was taken out from the flat glass Petri dish to obtain sample A of the water-stopping composition in a cylindrical shape with a diameter of about 7 cm and a height of about 6 mm.
Separately, the mixture after being stirred under reduced pressure was poured into an acrylic resin container measuring 50 mm long, 100 mm wide, and 2 mm high, and allowed to stand at 25° C. for 24 hours. Thereafter, it was taken out from the acrylic resin container to obtain sample B of the water-stopping composition, which had a length of about 50 mm, a width of about 100 mm, and a height of about 2 mm.
・Binder resin: Product name: “Human skin gel stock solution hardness C0”, manufactured by Exile Co., Ltd.…55% by mass
・Water-absorbing crosslinked resin particles: Product name "Sunfresh ST-500MPSA", manufactured by Sanyo Chemical Industries, Ltd., center particle size 30 μm...45% by mass
　なお、「人肌のゲル原液　硬度Ｃ０」には、ポリウレタン５２質量％と、可塑剤であるフタル酸ジイソノニル４８質量％と、が含まれている。表１には、バインダー樹脂の欄と、可塑剤の欄と、に分けて該当する含有量を記載した。後述する「人肌のゲル原液　硬度Ｃ７」及び「人肌のゲル原液　硬度Ｃ１５」には、ポリウレタン７５質量％と、可塑剤であるフタル酸ジイソノニルが２５質量％含まれている。 Note that the "human skin gel stock solution hardness C0" contains 52% by mass of polyurethane and 48% by mass of diisononyl phthalate, which is a plasticizer. In Table 1, the corresponding contents are listed separately in a column for binder resin and a column for plasticizer. "Human skin gel stock solution, hardness C7" and "Human skin gel stock solution, hardness C15", which will be described later, contain 75% by mass of polyurethane and 25% by mass of diisononyl phthalate, which is a plasticizer.
＜実施例２～実施例８、比較例１～比較例５＞
　表１に記載の成分及び組成となるように、各原料を混合し、実施例１と同様の方法で、止水用組成物のサンプルＡ及びサンプルＢを得た。 <Example 2 to Example 8, Comparative Example 1 to Comparative Example 5>
Each raw material was mixed so as to have the components and composition shown in Table 1, and samples A and B of water stop compositions were obtained in the same manner as in Example 1.
　表１に示す各成分の詳細は以下のとおりである。 The details of each component shown in Table 1 are as follows.
（バインダー樹脂）
・ポリウレタンＡ：製品名「人肌のゲル原液　硬度Ｃ０」、エクシール社製、５２質量％分
・ポリウレタンＢ：製品名「人肌のゲル原液　硬度Ｃ７」、エクシール社製、７５質量％分
・ポリウレタンＣ：製品名「人肌のゲル原液　硬度Ｃ１５」、エクシール社製、７５質量％分
・発泡ポリウレタン：製品名「人肌のゲル原液　発泡タイプ」、エクシール社製 (binder resin)
・Polyurethane A: Product name: "Human skin gel stock solution, hardness C0", manufactured by Exile Co., Ltd., 52% by mass ・Polyurethane B: Product name: "Human skin gel stock solution, hardness C7", manufactured by Exile Co., Ltd., 75% by mass: Polyurethane C: Product name: "Human skin gel stock solution, hardness C15", manufactured by Exile Co., Ltd., 75% by mass polyurethane foam: Product name: "Human skin gel stock solution, foaming type", manufactured by Exile Co., Ltd.
（可塑剤）
・フタル酸ジイソノニル
（吸水性架橋樹脂粒子）
・ポリアクリル酸Ｎａの架橋物：製品名「サンフレッシュＳＴ－５００ＭＰＳＡ」、三洋化成工業社製、中心粒度３０μｍ
・デンプン－アクリル酸グラフト共重合体の架橋物：製品名「サンフレッシュＳＴ－１００ＭＰＳＡ」、三洋化成工業社製、中心粒度３０μｍ
（架橋構造を有しない吸水性ポリマー（表１中、「吸水性ポリマー」）
・ポリアクリル酸Ｎａ：ポリアクリル酸ナトリウム（富士フイルム和光純薬社製）
・ＣＭＣ：カルボキシメチルセルロースナトリウム（富士フイルム和光純薬社製） (Plasticizer)
・Diisononyl phthalate (water-absorbing cross-linked resin particles)
・Crosslinked product of sodium polyacrylate: Product name “Sunfresh ST-500MPSA”, manufactured by Sanyo Chemical Industries, Ltd., center particle size 30 μm
・Crosslinked product of starch-acrylic acid graft copolymer: Product name "Sunfresh ST-100MPSA", manufactured by Sanyo Chemical Industries, Ltd., center particle size 30 μm
(Water-absorbing polymer that does not have a crosslinked structure ("Water-absorbing polymer" in Table 1)
・Sodium polyacrylate: Sodium polyacrylate (manufactured by Fujifilm Wako Pure Chemical Industries)
・CMC: Sodium carboxymethyl cellulose (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
　得られたサンプルＡを用いて、アスカーゴム硬度、ノーマルフォース、吸水倍率、及び脱落量を測定した。また、得られたサンプルＢを用いて、止水能及び施工性の評価を行った。測定方法及び評価方法は以下のとおりである。 Using the obtained sample A, Asker rubber hardness, normal force, water absorption capacity, and amount of shedding were measured. In addition, the obtained sample B was used to evaluate water stopping ability and workability. The measurement method and evaluation method are as follows.
＜アスカーゴム硬度＞
　作製したサンプルＡのエアー面を上にし、アスカーゴム硬度計Ｃ型（アスカー社製）を用いて、２５℃におけるアスカーゴム硬度を測定した。なお、エアー面とは、サンプルＡを作製する際に、空気と接触していた面（すなわち、フラットガラスシャーレと接触していなかった面）を意味する。 <Asker rubber hardness>
The air side of the prepared sample A was turned upward, and the Asker rubber hardness at 25° C. was measured using an Asker rubber hardness meter C type (manufactured by Asker Corporation). Note that the air surface means the surface that was in contact with the air (that is, the surface that was not in contact with the flat glass Petri dish) when Sample A was prepared.
＜ノーマルフォース＞
　作製したサンプルＡのエアー面を上にし、レオメータ（製品名「ＭＣＲ３０２」、アントンパール社製）を用いて測定した。まず、測定治具（平行板プレートＰＰ２５）を５Ｎの力でサンプルＡに押し当てた。次に、測定治具を１ｃｍ／秒の速度で引き上げたときのノーマルフォースの絶対値を記録した。３回の測定値における平均値を採用した。ノーマルフォースが１Ｎ以上である場合、タック性がある。ノーマルフォースが１５Ｎ以上である場合、タック性が高いといえる。 <Normal Force>
The prepared sample A was placed with the air side facing up and measured using a rheometer (product name "MCR302", manufactured by Anton Paar). First, a measurement jig (parallel plate PP25) was pressed against sample A with a force of 5N. Next, the absolute value of the normal force when the measuring jig was pulled up at a speed of 1 cm/sec was recorded. The average value of three measurements was adopted. If the normal force is 1N or more, there is tackiness. When the normal force is 15N or more, it can be said that the tackiness is high.
＜吸水倍率＞
　作製したサンプルＡの質量（吸水前質量）を測定した。容量５００ｍＬの容器に脱イオン水５００ｍＬを加え、作製したサンプルＡを１時間浸漬させた。１時間後に、サンプルＡを引き上げ、紙ウエス（製品名「キムタオル（登録商標）」、日本製紙クレシア社製）に軽く押し付けて水を切った後、サンプルＡの質量（吸水後質量）を測定した。
　以下の式にしたがって、吸水倍率を算出した。
　吸水倍率（ｇ／ｇ）＝吸水後質量／吸水前質量 <Water absorption rate>
The mass (mass before water absorption) of the prepared sample A was measured. 500 mL of deionized water was added to a container with a capacity of 500 mL, and the prepared sample A was immersed for 1 hour. After 1 hour, Sample A was pulled up and lightly pressed against paper waste (product name "Kim Towel (registered trademark)", manufactured by Nippon Paper Crecia Co., Ltd.) to drain water, and the mass of Sample A (mass after water absorption) was measured. .
The water absorption capacity was calculated according to the following formula.
Water absorption capacity (g/g) = mass after water absorption / mass before water absorption
＜脱落量＞
　容量５００ｍＬの容器に脱イオン水５００ｍＬを加え、作製したサンプルＡを６時間浸漬させた。６時間後に、サンプルＡを引き上げ、脱イオン水中に脱落した吸水性架橋樹脂粒子を試験用ふるい（目開き５００μｍ、メッシュ径３２５μｍ、直径２０ｃｍ）にかけ、２５℃で１分間静置した。ふるい上に残った吸水性架橋樹脂粒子の質量を、脱落量として測定した。表１中、吸水性架橋樹脂粒子を含まない比較例については、脱落量の欄に「－」を記載した。 <Amount of falling off>
500 mL of deionized water was added to a container with a capacity of 500 mL, and the prepared sample A was immersed for 6 hours. After 6 hours, Sample A was pulled out, and the water-absorbing crosslinked resin particles that had fallen into the deionized water were passed through a test sieve (openings 500 μm, mesh diameter 325 μm, diameter 20 cm) and allowed to stand at 25° C. for 1 minute. The mass of the water-absorbing crosslinked resin particles remaining on the sieve was measured as the falling amount. In Table 1, for the comparative examples that did not contain water-absorbing crosslinked resin particles, "-" was written in the column of the amount of shedding.
＜止水能（止水時間）＞
　壁面下部に５０ｍｍの幅及び１０ｍｍの高さを有する穴を有するアクリル樹脂製の水槽を実験用水槽として準備した。水槽の幅は３００ｍｍであり、水槽の奥行は３００ｍｍであり、水槽の高さは７００ｍｍである。実験用水槽の内側の壁面にサンプルＢを、サンプルＢの横方向が水槽の穴の幅方向になる向きで貼り付け、サンプルＢのアクリル樹脂容器から剥離した面と穴とを向かい合わせた。実験用水槽に、５００ｍｍの高さまで水を入れた。実験用水槽に水を入れ終わった時点から、穴から流出する水が止まるまでの時間（すなわち、止水に要する時間）を測定した。ただし、水の流出が３時間経過後までに止まらなかった場合には、止水不可と判定した。評価基準は以下のとおりである。
　Ａ：止水時間が１５分未満である。
　Ｂ：止水時間が１５分以上１時間未満である。
　Ｃ：止水時間が１時間以上３時間未満である。
　Ｄ：止水不可であった。 <Water stop ability (water stop time)>
An aquarium made of acrylic resin having a hole with a width of 50 mm and a height of 10 mm at the lower part of the wall was prepared as an experimental aquarium. The width of the tank is 300 mm, the depth of the tank is 300 mm, and the height of the tank is 700 mm. Sample B was pasted on the inner wall of the experimental aquarium in such a way that the horizontal direction of Sample B was in the width direction of the hole in the aquarium, and the surface of Sample B that had been peeled off from the acrylic resin container faced the hole. The experimental tank was filled with water to a height of 500 mm. The time from the time when the experimental water tank was filled with water until the water stopped flowing out of the hole (that is, the time required for the water to stop flowing) was measured. However, if the outflow of water did not stop after 3 hours, it was determined that the water could not be stopped. The evaluation criteria are as follows.
A: Water stop time is less than 15 minutes.
B: Water stop time is 15 minutes or more and less than 1 hour.
C: Water stop time is 1 hour or more and less than 3 hours.
D: Water could not be stopped.
＜止水能（耐久性）＞
　上記止水時間の試験において、穴から流出する水が止まった時点から、再び穴から水が流出するまでの時間（すなわち、止水持続時間）を測定した。評価基準は以下のとおりである。止水持続時間が長いほど、耐久性に優れているといえる。
　なお、止水時間の評価結果がＤ（すなわち、止水不可）の場合には、耐久性の評価を行うことができないため、表１に「－」と記載した。
　Ａ：止水持続時間が７２時間以上である。
　Ｂ：止水持続時間が４８時間以上７２時間未満である。
　Ｃ：止水持続時間が２４時間以上４８時間未満である。
　Ｄ：止水持続時間が２４時間未満である。 <Water stop ability (durability)>
In the above-mentioned water stop time test, the time from the time when the water stopped flowing out of the hole until the water started flowing out from the hole again (that is, the water stop time duration) was measured. The evaluation criteria are as follows. It can be said that the longer the water stop duration is, the more excellent the durability is.
Note that if the water stop time evaluation result is D (that is, water cannot be stopped), durability cannot be evaluated, so it is written as "-" in Table 1.
A: Water stop duration is 72 hours or more.
B: Water stop duration is 48 hours or more and less than 72 hours.
C: Water stop duration is 24 hours or more and less than 48 hours.
D: Water stop duration is less than 24 hours.
＜施工性（曲面施工性）＞
　上記止水時間の試験で用いた水槽の内側の底面及び壁面にわたってサンプルＢを貼り付け、水槽の隅（すなわち、底面と壁面との交差部分）における、水槽とサンプルＢとの接触状態を目視で観察した。具体的には、水槽の隅において水槽とサンプルＢとの間に隙間があるか否かを判定し、隙間がある場合には隙間の幅を測定した。水槽の内側の底面と壁面とのなす角は、９０°である。評価基準は以下のとおりである。
　Ａ：隙間がない。
　Ｂ：隙間があるが、隙間の幅は１ｍｍ未満である。
　Ｃ：隙間があり、隙間の幅が１ｍｍ以上である。 <Workability (workability on curved surfaces)>
Sample B was pasted on the inside bottom and wall of the aquarium used in the above water stop time test, and the state of contact between the aquarium and sample B at the corner of the aquarium (i.e., the intersection of the bottom and the wall) was visually observed. Observed. Specifically, it was determined whether there was a gap between the aquarium and Sample B at the corner of the aquarium, and if there was a gap, the width of the gap was measured. The angle between the bottom and wall inside the tank is 90°. The evaluation criteria are as follows.
A: There is no gap.
B: There is a gap, but the width of the gap is less than 1 mm.
C: There is a gap, and the width of the gap is 1 mm or more.
＜施工性（曲面密着性）＞
　上記止水時間の試験で用いた水槽の内側の底面及び壁面にわたってサンプルＢを貼り付け、水槽の隅（すなわち、底面と壁面との交差部分）における、水槽とサンプルＢとの接触状態を目視で観察した。具体的には、水槽の隅において、サンプルＢが水槽から剥離しているか否かを判定した。水槽の内側の底面と壁面とのなす角は、９０°である。評価基準は以下のとおりである。
　Ａ：剥離していない。
　Ｂ：一部剥離している。
　Ｃ：剥がれ落ちている。 <Workability (curved surface adhesion)>
Sample B was pasted on the inside bottom and wall of the aquarium used in the above water stop time test, and the state of contact between the aquarium and sample B at the corner of the aquarium (i.e., the intersection of the bottom and the wall) was visually observed. Observed. Specifically, it was determined whether Sample B had peeled off from the tank at the corner of the tank. The angle between the bottom and wall inside the tank is 90°. The evaluation criteria are as follows.
A: Not peeled off.
B: Partially peeled off.
C: Peeling off.
　表１に示すように、実施例１～実施例８では、バインダー樹脂と、可塑剤と、吸水性架橋樹脂粒子と、を含み、アスカーゴム硬度がＣ５０未満であるため、施工性に優れ、かつ、従来と比較して止水能が高いことが分かった。 As shown in Table 1, Examples 1 to 8 contain a binder resin, a plasticizer, and water-absorbing crosslinked resin particles, and have an Asker rubber hardness of less than C50, so they have excellent workability, and It was found that the water stopping ability was higher than that of the conventional method.
　一方、比較例１では、吸水性架橋樹脂粒子の代わりに、架橋構造を有しない吸水性ポリマーが含まれており、止水持続時間が短く、耐久性に劣ることが分かった。 On the other hand, in Comparative Example 1, a water-absorbing polymer without a cross-linked structure was included instead of the water-absorbing cross-linked resin particles, and it was found that the water stop duration was short and the durability was poor.
　比較例２では、吸水性架橋樹脂粒子の代わりに、架橋構造を有しない吸水性ポリマーが含まれており、止水に要する時間が長かった。 In Comparative Example 2, a water-absorbing polymer without a cross-linked structure was included instead of the water-absorbing cross-linked resin particles, and it took a long time to stop water.
　比較例３では、アスカーゴム硬度がＣ５０以上であり、止水持続時間が短く、耐久性に劣ることが分かった。また、曲面施工性に劣ることが分かった。 It was found that in Comparative Example 3, the Asker rubber hardness was C50 or higher, the water stop duration was short, and the durability was poor. It was also found that the workability on curved surfaces was poor.
　比較例４では、吸水性架橋樹脂粒子が含まれず、止水できなかった。 Comparative Example 4 did not contain water-absorbing crosslinked resin particles and could not stop water.
　比較例５では、可塑剤が含まれず、止水できなかった。 In Comparative Example 5, no plasticizer was included and water could not be stopped.
　なお、２０２２年９月１３日に出願された日本国特許出願２０２２－１４５６４３号の開示は、その全体が参照により本明細書に取り込まれる。また、本明細書に記載された全ての文献、特許出願及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 Note that the disclosure of Japanese Patent Application No. 2022-145643 filed on September 13, 2022 is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards mentioned herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference. , incorporated herein by reference.

Claims (9)

  1. 　バインダー樹脂と、可塑剤と、吸水性架橋樹脂粒子と、を含み、
    　アスカーゴム硬度がＣ５０未満である、止水用組成物。     Contains a binder resin, a plasticizer, and water-absorbing crosslinked resin particles,
    A water-stop composition having an Asker rubber hardness of less than C50.
  2. 　前記バインダー樹脂がポリウレタンを含む、請求項１に記載の止水用組成物。 The water-stopping composition according to claim 1, wherein the binder resin contains polyurethane.
  3. 　前記バインダー樹脂及び前記可塑剤の合計含有量に占める前記可塑剤の割合が２０質量％～６０質量％である、請求項１に記載の止水用組成物。 The water-stopping composition according to claim 1, wherein the proportion of the plasticizer in the total content of the binder resin and the plasticizer is 20% by mass to 60% by mass.
  4. 　前記可塑剤の含有量が、前記止水用組成物の全量に対して、５質量％～３０質量％である、請求項１に記載の止水用組成物。 The water-stopping composition according to claim 1, wherein the content of the plasticizer is 5% by mass to 30% by mass based on the total amount of the waterstopping composition.
  5. 　前記可塑剤は、フタル酸エステルを含む、請求項１に記載の止水用組成物。 The water-stopping composition according to claim 1, wherein the plasticizer includes a phthalate ester.
  6. 　ノーマルフォースが１Ｎ以上である、請求項１に記載の止水用組成物。 The water stop composition according to claim 1, having a normal force of 1N or more.
  7. 　前記吸水性架橋樹脂粒子の含有量が、前記止水用組成物の全量に対して、２０質量％以上６０質量％未満である、請求項１に記載の止水用組成物。 The water-stopping composition according to claim 1, wherein the content of the water-absorbing crosslinked resin particles is 20% by mass or more and less than 60% by mass based on the total amount of the waterstopping composition.
  8. 　前記吸水性架橋樹脂粒子を構成する吸水性架橋樹脂が、ポリアクリル酸塩の架橋物を含む、請求項１に記載の止水用組成物。 The water-stop composition according to claim 1, wherein the water-absorbing cross-linked resin constituting the water-absorbing cross-linked resin particles contains a cross-linked polyacrylate.
  9. 　請求項１～請求項８のいずれか１項に記載の止水用組成物を含む、止水フィルム。
          A water-stop film comprising the water-stop composition according to any one of claims 1 to 8.
PCT/JP2023/032728 2022-09-13 2023-09-07 Water-stop composition, and water-stop film WO2024058055A1 (en)

Applications Claiming Priority (2)

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JP2022-145643 2022-09-13

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003165865A (en) * 2001-12-03 2003-06-10 Toyo Tire & Rubber Co Ltd Method for producing water-absorbing polyurethane foam and the polyurethane foam, and cushion material and sealing material
JP2004204093A (en) * 2002-12-26 2004-07-22 Sanyo Chem Ind Ltd Water-expanding water stop material
JP2008285580A (en) * 2007-05-17 2008-11-27 Yokohama Rubber Co Ltd:The Two-pack curing type polyurethane-based sealant composition
JP2009249498A (en) * 2008-04-07 2009-10-29 Yokohama Rubber Co Ltd:The Sealing material composition and sealing material using it
JP2011084642A (en) * 2009-10-15 2011-04-28 Yokohama Rubber Co Ltd:The Polyurethane sealing material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003165865A (en) * 2001-12-03 2003-06-10 Toyo Tire & Rubber Co Ltd Method for producing water-absorbing polyurethane foam and the polyurethane foam, and cushion material and sealing material
JP2004204093A (en) * 2002-12-26 2004-07-22 Sanyo Chem Ind Ltd Water-expanding water stop material
JP2008285580A (en) * 2007-05-17 2008-11-27 Yokohama Rubber Co Ltd:The Two-pack curing type polyurethane-based sealant composition
JP2009249498A (en) * 2008-04-07 2009-10-29 Yokohama Rubber Co Ltd:The Sealing material composition and sealing material using it
JP2011084642A (en) * 2009-10-15 2011-04-28 Yokohama Rubber Co Ltd:The Polyurethane sealing material

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