WO2020059048A1 - Set comprising main agent and curing agent, water-resistant material, and method of constructing same - Google Patents

Set comprising main agent and curing agent, water-resistant material, and method of constructing same Download PDF

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Publication number
WO2020059048A1
WO2020059048A1 PCT/JP2018/034673 JP2018034673W WO2020059048A1 WO 2020059048 A1 WO2020059048 A1 WO 2020059048A1 JP 2018034673 W JP2018034673 W JP 2018034673W WO 2020059048 A1 WO2020059048 A1 WO 2020059048A1
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Prior art keywords
less
curing agent
equivalent
agent
group
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PCT/JP2018/034673
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French (fr)
Japanese (ja)
Inventor
林　健一
国光 前畑
Original Assignee
保土谷化学工業株式会社
保土谷建材株式会社
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Application filed by 保土谷化学工業株式会社, 保土谷建材株式会社 filed Critical 保土谷化学工業株式会社
Priority to PCT/JP2018/034673 priority Critical patent/WO2020059048A1/en
Priority to JP2019165663A priority patent/JP7398228B2/en
Priority to JP2019166529A priority patent/JP7398229B2/en
Publication of WO2020059048A1 publication Critical patent/WO2020059048A1/en
Priority to JP2023170926A priority patent/JP2023171882A/en
Priority to JP2023170874A priority patent/JP2023171881A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • 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
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present invention relates to a set of a base material and a curing agent, a waterproof material, and a method for constructing the waterproof material.
  • Polyurethane waterproofing materials are used as waterproofing materials for building rooftops, verandas, corridors, etc., and are also widely used for applications such as painted flooring materials and elastic pavement of sports facilities.
  • a waterproofing material made of polyurethane for example, a waterproofing material obtained by mixing a main agent containing an isocyanate group-terminated prepolymer with a curing agent, applying the mixture, and curing the mixture is known.
  • Patent Literature 1 discloses a polyoxypropylene polyol and / or a polyoxyethylene propylene polyol as a main raw material, a main agent mainly containing an isocyanate-terminated prepolymer obtained by a reaction with tolylene diisocyanate, and a predetermined curing method.
  • a method for producing a room-temperature-curable fast-curing polyurethane coating waterproofing material which is mixed with an agent and applied and cured is disclosed.
  • JIS standards have been established for the physical properties of architectural coating waterproofing materials such as polyurethane coating waterproofing materials. In recent years, however, higher strength coating waterproofing materials have been required, and JIS standards have been revised. Has also been made. In addition, it is also required that the raw material of the waterproof material, which is expected to be applied by hand coating (including application by a machine), particularly, has an appropriate pot life in order to secure a sufficient construction time.
  • the present invention provides a set including a main agent and a curing agent, which can provide a waterproof material having excellent tensile strength, tear strength, and tensile product, and has a long pot life at the time of construction. With the goal.
  • Another object of the present invention is to provide a waterproofing material using the set and a method for constructing the waterproofing material.
  • the present invention is a set including a main agent containing an isocyanate group-terminated prepolymer and a curing agent, wherein the isocyanate group-terminated prepolymer is represented by polypropylene glycol and the following formula (1).
  • a set is provided which is a reaction product of a polyol containing a polyether glycol having a structural unit and a polyisocyanate.
  • the number average molecular weight of polypropylene glycol is preferably 4000 or less.
  • the number average molecular weight of the polyether glycol is preferably 4000 or less.
  • the polyisocyanate is preferably isophorone diisocyanate.
  • the present invention provides a waterproof material including a cured product of a mixture of a main agent and a curing agent in the above set.
  • the present invention provides a method for applying a waterproof material, comprising: a step of obtaining a mixture of a main agent and a curing agent in the above set; and a step of applying the mixture on an object to be coated.
  • curing agent which can obtain the waterproofing material excellent in the tensile strength, the tear strength, and the tensile product, and has a long pot life at the time of construction is provided. be able to. Further, according to the present invention, it is possible to provide a waterproof material using the set and a method for installing the waterproof material.
  • the number average molecular weight means a value measured using gel permeation chromatography (GPC) using polystyrene as a standard substance, and can be measured under the following conditions.
  • Apparatus TOSOH HCL-8320 (manufactured by Tosoh Corporation) Column: TSKgel G4000H + G2500H (7.5 mm ID ⁇ 30 cm) (manufactured by Tosoh Corporation) Detector: RI Eluent: THF Injection volume: 100 ⁇ L Flow rate: 1.0 mL / min Measurement temperature: 40 ° C Sample concentration: 0.3wt / vol%
  • a set according to one embodiment includes a main agent containing an isocyanate group-terminated prepolymer and a curing agent. This set is suitably used as a set for obtaining a waterproofing material made of polyurethane (a waterproofing material set).
  • the base material contains an isocyanate group-terminated prepolymer.
  • the isocyanate group-terminated prepolymer may be a reaction product of a polyol containing polypropylene glycol and a polyether glycol having a structural unit represented by the following formula (1), and a polyisocyanate.
  • the polyol contains polypropylene glycol (hereinafter, also referred to as “PPG”).
  • PPG polypropylene glycol
  • the number average molecular weight of PPG is preferably 4,000 or less, more preferably 2,000 or less, and still more preferably less than 1500, from the viewpoint of extending the pot life during construction and improving the elongation at break of the waterproof material. It is.
  • the number average molecular weight of PPG may be, for example, 400 or more, 700 or more, or 1000 or more.
  • the content of PPG in the polyol is preferably 5 to 5% based on the total amount of the polyol (chemical equivalent) from the viewpoint of extending the pot life during construction and improving the elongation at break of the waterproofing material. It is at least equivalent%, at least 10 equivalent%, at least 20 equivalent%, at least 25 equivalent%, at least 50 equivalent%, or at least 65 equivalent%.
  • the content of PPG is preferably 95 equivalent% or less, more preferably 90 equivalent% or less, further preferably 85 equivalent% or less, from the viewpoint of obtaining a coating film having excellent physical properties.
  • the polyol further contains a polyether glycol having a structural unit represented by the above formula (1).
  • the polyether glycol is composed of only the structural unit represented by the above formula (1), and has a hydroxyl group (OH group) at both ends (hereinafter also referred to as “PTMG”). It is.
  • the number average molecular weight of PTMG is preferably 4,000 or less, more preferably 3500 or less, still more preferably 3,000 or less, particularly preferably 3,000 or less, from the viewpoint of obtaining a waterproof material having further excellent tensile strength, tear strength, and tensile product. 2000 or less.
  • the number average molecular weight of PTMG may be, for example, 250 or more, 650 or more, or 850 or more.
  • PTMG can be obtained by ring-opening polymerization of tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • a commercially available product may be used as PTMG.
  • the content of PTMG is based on the total amount of the polyol (chemical equivalent) from the viewpoint of obtaining a waterproof material having more excellent tensile strength, tear strength, and tensile product. Is preferably 5 equivalent% or more, 10 equivalent% or more, 20 equivalent% or more, 25 equivalent% or more, 50 equivalent% or more, or 65 equivalent% or more.
  • the content of PTMG is preferably 95 equivalent% or less, 90 equivalent% or less, more preferably 85 equivalent% or less, 80 equivalent% or less, based on the total amount of the polyol, from the viewpoint of making the viscosity at which the handling of the main agent becomes easy. Or 75 equivalent% or less.
  • the polyether glycol is a copolymer having a structural unit represented by the above formula (1) and a structural unit represented by the following formula (2) (hereinafter referred to as “copolymer”). A ").
  • the copolymer A has a hydroxyl group at both ends.
  • Copolymer A may be a random copolymer.
  • R 1 and R 2 represents a methyl group, and the other represents a hydrogen atom. That is, R 1 may be a methyl group and R 2 may be a hydrogen atom, or R 1 may be a hydrogen atom and R 2 may be a methyl group. In each of the structural units contained in the copolymer A, the combination of R 1 and R 2 may be the same or different.
  • the content of the structural unit represented by the formula (1) is preferably 50% by mass or more, more preferably 60% by mass, based on the total amount of the structural units of the copolymer A from an economic viewpoint. %, More preferably 70% by mass or more.
  • the content of the structural unit represented by the formula (1) is preferably 97% by mass or less, more preferably 95% by mass or less, and still more preferably 93% by mass or less, from the viewpoint of lowering the freezing point of the copolymer A. is there.
  • the content of the structural unit represented by the formula (2) is preferably 2% by mass based on the total amount of the structural units of the copolymer A from the viewpoint of lowering the freezing point of the copolymer A.
  • the content is more preferably 5% by mass or more, and still more preferably 7% by mass or more.
  • the content of the structural unit represented by the formula (2) is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably, based on the total amount of the structural units of the copolymer A. 30 mass% or less.
  • the number average molecular weight of the copolymer A is preferably 3500 or less, more preferably 3000 or less, from the viewpoint of obtaining a waterproof material having further excellent tensile strength, tear strength, and tensile product. Preferably it is 2000 or less.
  • the number average molecular weight of the copolymer may be, for example, 250 or more, 650 or more, 850 or more, or 1000 or more.
  • the copolymer A can be obtained by ring-opening polymerization of tetrahydrofuran and methyltetrahydrofuran (including 2-methyltetrahydrofuran and 3-methyltetrahydrofuran).
  • a commercially available product may be used as the copolymer A.
  • the content of the copolymer A is determined based on the total amount of the polyol, from the viewpoint of obtaining a waterproof material having more excellent tensile strength, tear strength, and tensile product. Based on (chemical equivalent), it is preferably 5 equivalent% or more, 10 equivalent% or more, 20 equivalent% or more, 25 equivalent% or more, 50 equivalent% or more, or 65 equivalent% or more. From an economic viewpoint, the content of the copolymer A is 95 equivalent% or less, 90 equivalent% or less, 85 equivalent% or less, 80 equivalent% or less, or 75 equivalent% or less based on the total amount of the polyol.
  • the polyol may contain either one of PTMG or copolymer A, or may contain both.
  • the content of polyether glycol (including both PTMG and copolymer A) in the polyol is determined based on the total amount of the polyol (Chemical) from the viewpoint of obtaining a waterproof material having more excellent tensile strength, tear strength and tensile product. Eq.), Preferably at least 5 eq.%, At least 10 eq.%, At least 20 eq.%, At least 25 eq.%, At least 50 eq.%, Or at least 65 eq.%.
  • the content of the polyether glycol is preferably 90 equivalent% or less, 85 equivalent% or less, 80 equivalent% or less, or 75 equivalent% or less, based on the total amount of the polyol, from the viewpoint of extending the pot life during construction. It is.
  • the polyol may contain other polyol components in addition to polyether glycol and polypropylene glycol.
  • Other polyol components include, for example, a polyhydric alcohol having 2 to 20 carbon atoms, a polyhydric alcohol having 2 to 20 carbon atoms, or a polyhydric phenol having 6 to 26 carbon atoms to which an alkylene oxide having 2 to 4 carbon atoms is added.
  • Polyoxyalkylene polyol (excluding the above-mentioned PPG, PTMG and copolymer A), polyester polyol, polycarbonate polyol, polydiene polyol (such as polybutadiene polyol), hydrogenated product of polydiene polyol, acrylic polyol, natural oil-based It may be a polyol (such as castor oil) or a modified natural oil-based polyol.
  • the polyisocyanate is not particularly limited as long as it has two or more isocyanate groups in the molecule.
  • examples of the polyisocyanate include 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene diisocyanate, and tetramethyl Aromatic polyisocyanates such as xylene diisocyanate and naphthalene diisocyanate; aliphatic polyisocyanates such as ethylene diisocyanate, tetramethylene diisocyanate and 1,5-pentamethylene diisocyanate; isophorone diisocyanate, dicyclohexylmethane diisocyanate; norbornene methane diisocyanate; Bis (isocyanatomethyl) cycl
  • the polyisocyanate in the present invention also includes a modified polyisocyanate.
  • modified polyisocyanate include urethane group, carbodiimide group, allohanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group-containing modified products. These polyisocyanates may be used alone or in combination of two or more.
  • the polyisocyanate is preferably an alicyclic polyisocyanate, more preferably an alicyclic diisocyanate, and even more preferably isophorone diisocyanate.
  • the isocyanate group-terminated prepolymer is a reaction product of the above-mentioned polyol and polyisocyanate.
  • the isocyanate group-terminated prepolymer can be obtained by, for example, adding a polyisocyanate to a polyol at a predetermined equivalent ratio and mixing the mixture by heating.
  • the equivalent ratio of the isocyanate group (NCO group) in the polyisocyanate to the hydroxyl group (OH group) in the polyol (NCO group / OH group) is 1.4 or more, 1.5 or more, Or it may be 1.6 or more, and may be 2.2 or less, 2.0 or less, or 1.8 or less.
  • the reaction temperature of the polyol and the polyisocyanate may be 100 ° C or lower, 90 ° C or lower, or 80 ° C or lower.
  • the lower limit of the reaction temperature is not particularly limited, but is, for example, 30 ° C. or higher.
  • the content of the isocyanate group in the isocyanate group-terminated prepolymer may be 1% by mass or more, 2% by mass or more, or 3% by mass or more, and 8% by mass or less, 7% by mass or less, or 6% by mass or less. May be.
  • the main agent may further contain a plasticizer, a solvent, and the like as a viscosity adjuster in addition to the isocyanate group-terminated prepolymer for adjusting the viscosity when the main agent and a curing agent described later are mixed.
  • the main agent may further contain a catalyst and / or a retarder for efficiently reacting the isocyanate group of the polyisocyanate with the hydroxyl group of the polyol from an industrial and economic viewpoint.
  • the main agent may contain an additive from the viewpoint of improving the finish, durability, adhesion to other materials, and the like of the obtained waterproof material.
  • the viscosity of the main agent at 23 ° C. is preferably from 1000 mPa ⁇ s or more, from the viewpoint that the mixture immediately after mixing of the main agent and the curing agent can maintain the leveling at the time of application and has a viscosity enough to secure the film thickness of the coating film. It is preferably at least 3,000 mPas, more preferably at least 4,000 mPas, particularly preferably at least 5,000 mPas, and preferably at most 25,000 mPas, more preferably at most 20,000 mPas, even more preferably at most 15,000 mPas. is there.
  • the viscosity of the main agent can be measured using a rotational viscometer according to JIS ⁇ ⁇ K7301: 1995 “Testing method of tolylene diisocyanate type prepolymer for thermosetting urethane elastomer 6.2 viscosity”.
  • the curing agent may contain a hydroxyl compound such as a polyhydric alcohol, and a crosslinking agent such as a polyamine.
  • Polyamines include, for example, diethyltoluenediamine (2,4-diethyltoluenediamine, 2,6-diethyltoluenediamine), phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, MOCA Polyamine (MOCA and modified MOCA), polyalkylene ether polyol-p-aminobenzoate, polytetramethylene glycol aminobenzoate, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5- Diisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diisopropyl-2,6-diaminobenzene, 1-ethyl-3,5-diis
  • Curing agents include, in addition to crosslinking agents, plasticizers; solvents; catalysts; inorganic fillers such as calcium carbonate, talc, kaolin, zeolite, and diatomaceous earth; pigments such as chromium oxide, red iron oxide, carbon black, and titanium oxide.
  • An additive such as a wetting and dispersing agent, an anti-settling agent, a light stabilizer, an antifoaming agent, a surface conditioner, and an adhesion promoter.
  • the mixture is cured by mixing the main agent and the curing agent.
  • the obtained cured product is suitably used as a waterproof material. That is, the waterproofing material according to one embodiment includes a cured product of the mixture of the above-described main agent and curing agent.
  • the waterproof material according to the present embodiment is excellent in tensile strength, tear strength, and tensile product, and is a high-strength waterproof material.
  • this waterproofing material is evaluated by a method according to JIS A 6021: 2011 (architecture coating waterproofing material, “high-strength type”), the tensile strength is such that the following numerical values specified in the standard can be satisfied.
  • the waterproof material according to the present embodiment is also excellent in elongation at break, and is a highly stretchable waterproof material.
  • this waterproofing material is evaluated by a method according to JIS A 6021: 2011 (architecture coating waterproofing material, “high elongation type (old class 1)”), it can satisfy the following numerical values specified in the standard.
  • the elongation at break is excellent. Elongation at break (Eb): 450% or more
  • the application method includes a step of obtaining a mixture of the main agent and the curing agent in the above-described set (mixing step), and a step of applying the mixture to an object to be coated (application step).
  • the temperature (environmental temperature) at which the main agent and the curing agent are mixed may be, for example, ⁇ 5 to 40 ° C.
  • the curing agent When the curing agent contains a crosslinking agent, the curing agent has an equivalent ratio of the active hydrogen group of the crosslinking agent to the NCO group content in the main component of 0.8 or more, 0.9 or more, or 1.0 or more. As described above.
  • the curing agent may be mixed with the main component such that the equivalent ratio of the active hydrogen group of the crosslinking agent to the NCO group content in the main component is 1.5 or less, 1.3 or less, or 1.2 or less.
  • the NCO group of the isocyanate group-terminated prepolymer contained in the main agent and the curing agent It is preferable to mix them so that the equivalent ratio (NCO group / NH 2 group) to the contained amino group (NH 2 group) falls within a predetermined range.
  • the NCO group / NH 2 group is preferably at least 0.8, more preferably at least 0.9, even more preferably at least 1.0, preferably at most 1.5, more preferably at most 1.3, even more preferably Is 1.2 or less.
  • the mixture is applied to an object to be coated.
  • the object to be coated is not particularly limited, and may be a wall surface, a floor surface, or the like in a building such as a house or a building.
  • the mixture of the main agent and the curing agent according to the present embodiment is particularly suitable for application by hand coating (hand coating) because a sufficient pot life can be obtained. That is, in the mixing step, hand coating may be performed.
  • the application by hand coating includes application by a machine such as an automatic mixing device such as a static mixer and a dynamic mixer, and application using tools such as a roller, a ricin gun, an airless gun, and a brush.
  • the mixture according to the present embodiment may be applied by spraying (spray coating).
  • a sufficiently long pot life can be obtained when the waterproof material is installed. More specifically, according to the set of the main agent and the curing agent according to the present embodiment, for example, 45 minutes or more until the viscosity at 23 ° C. of the mixture of the main agent and the curing agent reaches 60,000 mPa ⁇ s, or Since it takes 55 minutes or more to reach 10,000 mPa ⁇ s, a sufficiently long pot life can be obtained.
  • the waterproofing material obtained by the above-described method is not only a use of the waterproofing material, but also a high-strength performance, a flooring material for sports facilities or the like where a high load performance is required, a covering material for a building, and a rustproofing material. Can also be used for applications.
  • an organic solvent such as xylene
  • PPG-1000 polypropylene glycol (number average molecular weight 1000, trade name "Actocol D-1000", manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.)
  • PTG-1000 polytetramethylene ether glycol (number average molecular weight 1000, trade name "PTG-1000SN", manufactured by Hodogaya Chemical Industry Co., Ltd.)
  • PTG-L1000 THF / methyl group-substituted THF random copolymer (number average molecular weight 1000, trade name "PTG-L1000", manufactured by Hodogaya Chemical Industry Co., Ltd.)
  • the main ingredients were prepared based on the compositions shown in Table 1 by the following method.
  • Polyether glycol and polypropylene glycol were charged at a predetermined equivalent ratio in a 2 liter glass kolben, and dehydration under reduced pressure was performed at 95 to 105 ° C. for 1 hour.
  • a catalyst was added under a nitrogen stream to homogenize, and then isophorone diisocyanate (trade name “VESTANAT IPDI”, manufactured by EVONIC) was gradually added until the reaction was completed. Heat with stirring at 60-80 ° C. for 2-4 hours.
  • the liquid after the reaction was cooled to room temperature, a viscosity modifier and the like were added, and the mixture was homogenized with stirring to obtain a main agent (isocyanate group-terminated prepolymer).
  • the main ingredient is an isocyanate-terminated prepolymer in which the equivalent ratio of the NCO group of the polyisocyanate to the OH group of the polypropylene glycol and polyether glycol is adjusted, and the NCO group is adjusted by adjusting the contents of the viscosity modifier, additives and catalyst. The content was adjusted to be 4% by mass.

Abstract

According to one aspect, the present invention provides a set comprising a main agent that contains an isocyanate-group-terminated prepolymer, and a curing agent, wherein the isocyanate-group-terminated prepolymer is a reaction product of polyisocyanate and a polyol containing polypropylene glycol and a polyether glycol having a structural unit represented by formula (1) below.

Description

主剤及び硬化剤のセット、防水材並びにその施工方法Set of main agent and curing agent, waterproof material and method of construction
　本発明は、主剤及び硬化剤のセット、防水材並びにその施工方法に関する。 (4) The present invention relates to a set of a base material and a curing agent, a waterproof material, and a method for constructing the waterproof material.
　ポリウレタン製の防水材（塗膜防水材）は、建物の屋上、ベランダ、廊下等の防水材として使用され、更には、塗床材、スポーツ施設の弾性舗装等の用途にも広く使用されている。ポリウレタン製の防水材としては、例えば、イソシアネート基末端プレポリマーを含む主剤を硬化剤と混合して塗工し、硬化させることによって得られる防水材が知られている。特許文献１には、ポリオキシプロピレンポリオールおよび／またはポリオキシエチレンプロピレンポリオールを主原料とするポリオールと、トリレンジイソシアネートとの反応によって得られるイソシアネート末端プレポリマーを主成分とする主剤と、所定の硬化剤とを混合して塗工、硬化せしめる常温硬化型速硬化性ポリウレタン塗膜防水材の製造方法が開示されている。 BACKGROUND ART Polyurethane waterproofing materials (coating film waterproofing materials) are used as waterproofing materials for building rooftops, verandas, corridors, etc., and are also widely used for applications such as painted flooring materials and elastic pavement of sports facilities. . As a waterproofing material made of polyurethane, for example, a waterproofing material obtained by mixing a main agent containing an isocyanate group-terminated prepolymer with a curing agent, applying the mixture, and curing the mixture is known. Patent Literature 1 discloses a polyoxypropylene polyol and / or a polyoxyethylene propylene polyol as a main raw material, a main agent mainly containing an isocyanate-terminated prepolymer obtained by a reaction with tolylene diisocyanate, and a predetermined curing method. A method for producing a room-temperature-curable fast-curing polyurethane coating waterproofing material which is mixed with an agent and applied and cured is disclosed.
特開平８－１４３８１６号公報JP-A-8-143816
　ポリウレタン塗膜防水材のような建築用塗膜防水材の物性には日本工業規格（ＪＩＳ規格）が定められているが、近年ではより強度の高い塗膜防水材が求められ、ＪＩＳ規格の改正もなされている。また、特に手塗りによる塗布（機械による塗布等を含む）が想定される防水材の原料には、十分な施工時間を確保するために適度な可使時間が得られることも求められる。 Japanese Industrial Standards (JIS standards) have been established for the physical properties of architectural coating waterproofing materials such as polyurethane coating waterproofing materials. In recent years, however, higher strength coating waterproofing materials have been required, and JIS standards have been revised. Has also been made. In addition, it is also required that the raw material of the waterproof material, which is expected to be applied by hand coating (including application by a machine), particularly, has an appropriate pot life in order to secure a sufficient construction time.
　そこで本発明は、引張強さ、引裂強さ、及び抗張積に優れた防水材を得ることができ、且つ、施工時の可使時間が長い、主剤及び硬化剤を備えるセットを提供することを目的とする。また、本発明は、当該セットを用いた防水材及びその施工方法を提供することを目的とする。 Therefore, the present invention provides a set including a main agent and a curing agent, which can provide a waterproof material having excellent tensile strength, tear strength, and tensile product, and has a long pot life at the time of construction. With the goal. Another object of the present invention is to provide a waterproofing material using the set and a method for constructing the waterproofing material.
　本発明は、第１の態様として、イソシアネート基末端プレポリマーを含有する主剤と、硬化剤とを備えるセットであって、イソシアネート基末端プレポリマーは、ポリプロピレングリコール及び下記式（１）で表される構造単位を有するポリエーテルグリコールを含有するポリオールと、ポリイソシアネートとの反応生成物である、セットを提供する。
Figure JPOXMLDOC01-appb-C000002
 As a first aspect, the present invention is a set including a main agent containing an isocyanate group-terminated prepolymer and a curing agent, wherein the isocyanate group-terminated prepolymer is represented by polypropylene glycol and the following formula (1). A set is provided which is a reaction product of a polyol containing a polyether glycol having a structural unit and a polyisocyanate.
Figure JPOXMLDOC01-appb-C000002
　第１の態様において、ポリプロピレングリコールの数平均分子量は、好ましくは４０００以下である。ポリエーテルグリコールの数平均分子量は、好ましくは４０００以下である。ポリイソシアネートは、好ましくはイソホロンジイソシアネートである。 に お い て In the first embodiment, the number average molecular weight of polypropylene glycol is preferably 4000 or less. The number average molecular weight of the polyether glycol is preferably 4000 or less. The polyisocyanate is preferably isophorone diisocyanate.
　本発明は、第２の態様として、上記のセットにおける、主剤及び硬化剤の混合物の硬化物を含む、防水材を提供する。 As a second aspect, the present invention provides a waterproof material including a cured product of a mixture of a main agent and a curing agent in the above set.
　本発明は、第３の態様として、上記のセットにおける、主剤及び硬化剤の混合物を得る工程と、混合物を被塗物上に塗布する工程と、を備える防水材の施工方法を提供する。 As a third aspect, the present invention provides a method for applying a waterproof material, comprising: a step of obtaining a mixture of a main agent and a curing agent in the above set; and a step of applying the mixture on an object to be coated.
　本発明によれば、引張強さ、引裂強さ、及び抗張積に優れた防水材を得ることができ、且つ、施工時の可使時間が長い、主剤及び硬化剤を備えるセットを提供することができる。また、本発明によれば、当該セットを用いた防水材及びその施工方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the set provided with the main agent and the hardening | curing agent which can obtain the waterproofing material excellent in the tensile strength, the tear strength, and the tensile product, and has a long pot life at the time of construction is provided. be able to. Further, according to the present invention, it is possible to provide a waterproof material using the set and a method for installing the waterproof material.
　以下、本発明の実施形態について説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments.
　本発明において、数平均分子量は（Ｍｎ）は、ポリスチレンを標準物質として、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて測定される値を意味し、以下の条件で測定することができる。
　装置：ＴＯＳＯＨ　ＨＣＬ－８３２０（東ソー（株）製）
　カラム：ＴＳＫｇｅｌ　Ｇ４０００Ｈ＋Ｇ２５００Ｈ（７．５ｍｍＩ．Ｄ×３０ｃｍ）（東ソー（株）製）
　検出器：ＲＩ
　溶離液：ＴＨＦ
　注入量：１００μＬ
　流速：１．０ｍＬ/分
　測定温度：４０℃
　サンプル濃度：０．３ｗｔ/ｖｏｌ％ In the present invention, the number average molecular weight (Mn) means a value measured using gel permeation chromatography (GPC) using polystyrene as a standard substance, and can be measured under the following conditions.
Apparatus: TOSOH HCL-8320 (manufactured by Tosoh Corporation)
Column: TSKgel G4000H + G2500H (7.5 mm ID × 30 cm) (manufactured by Tosoh Corporation)
Detector: RI
Eluent: THF
Injection volume: 100 μL
Flow rate: 1.0 mL / min Measurement temperature: 40 ° C
Sample concentration: 0.3wt / vol%
　一実施形態に係るセットは、イソシアネート基末端プレポリマーを含有する主剤と、硬化剤とを備える。このセットは、ポリウレタン製の防水材を得るためのセット（防水材用セット）として好適に用いられる。 セ ッ ト A set according to one embodiment includes a main agent containing an isocyanate group-terminated prepolymer and a curing agent. This set is suitably used as a set for obtaining a waterproofing material made of polyurethane (a waterproofing material set).
＜主剤＞
　主剤は、イソシアネート基末端プレポリマーを含有する。イソシアネート基末端プレポリマーは、ポリプロピレングリコール及び下記式（１）で表される構造単位を有するポリエーテルグリコールを含有するポリオールと、ポリイソシアネートとの反応生成物であってよい。
Figure JPOXMLDOC01-appb-C000003
 <Main agent>
The base material contains an isocyanate group-terminated prepolymer. The isocyanate group-terminated prepolymer may be a reaction product of a polyol containing polypropylene glycol and a polyether glycol having a structural unit represented by the following formula (1), and a polyisocyanate.
Figure JPOXMLDOC01-appb-C000003
　ポリオールは、ポリプロピレングリコール（以下、「ＰＰＧ」ともいう。）を含有する。ＰＰＧの数平均分子量は、施工時の可使時間をより長くする観点、及び防水材の破断時の伸び率を向上させる観点から、好ましくは４０００以下、より好ましくは２０００以下、更に好ましくは１５００未満である。ＰＰＧの数平均分子量は、例えば、４００以上、７００以上、又は１０００以上であってよい。 The polyol contains polypropylene glycol (hereinafter, also referred to as “PPG”). The number average molecular weight of PPG is preferably 4,000 or less, more preferably 2,000 or less, and still more preferably less than 1500, from the viewpoint of extending the pot life during construction and improving the elongation at break of the waterproof material. It is. The number average molecular weight of PPG may be, for example, 400 or more, 700 or more, or 1000 or more.
　ポリオール中のＰＰＧの含有量は、施工時の可使時間をより長くする観点、及び防水材の破断時の伸び率を向上させる観点から、ポリオール全量（化学当量）を基準として、好ましくは、５当量％以上、１０当量％以上、２０当量％以上、２５当量％以上、５０当量％以上、又は６５当量％以上である。ＰＰＧの含有量は、物性に優れた塗膜を得る観点から、好ましくは９５当量％以下、より好ましくは９０当量％以下、更に好ましくは８５当量％以下である。 The content of PPG in the polyol is preferably 5 to 5% based on the total amount of the polyol (chemical equivalent) from the viewpoint of extending the pot life during construction and improving the elongation at break of the waterproofing material. It is at least equivalent%, at least 10 equivalent%, at least 20 equivalent%, at least 25 equivalent%, at least 50 equivalent%, or at least 65 equivalent%. The content of PPG is preferably 95 equivalent% or less, more preferably 90 equivalent% or less, further preferably 85 equivalent% or less, from the viewpoint of obtaining a coating film having excellent physical properties.
　ポリオールは、上述した式（１）で表される構造単位を有するポリエーテルグリコールを更に含有する。ポリエーテルグリコールは、一実施形態において、上記の式（１）で表される構造単位のみからなり、両端に水酸基（ＯＨ基）を有するポリテトラメチレンエーテルグリコール（以下、「ＰＴＭＧ」ともいう。）である。 The polyol further contains a polyether glycol having a structural unit represented by the above formula (1). In one embodiment, the polyether glycol is composed of only the structural unit represented by the above formula (1), and has a hydroxyl group (OH group) at both ends (hereinafter also referred to as “PTMG”). It is.
　ＰＴＭＧの数平均分子量は、引張強さ、引裂強さ、及び抗張積に更に優れた防水材を得る観点から、好ましくは４０００以下、より好ましくは３５００以下、更に好ましくは３０００以下、特に好ましくは２０００以下である。ＰＴＭＧの数平均分子量は、例えば、２５０以上、６５０以上、又は８５０以上であってよい。 The number average molecular weight of PTMG is preferably 4,000 or less, more preferably 3500 or less, still more preferably 3,000 or less, particularly preferably 3,000 or less, from the viewpoint of obtaining a waterproof material having further excellent tensile strength, tear strength, and tensile product. 2000 or less. The number average molecular weight of PTMG may be, for example, 250 or more, 650 or more, or 850 or more.
　ＰＴＭＧは、テトラヒドロフラン（ＴＨＦ）を開環重合させて得ることができる。ＰＴＭＧとして、市販品を用いてもよい。 PTMG can be obtained by ring-opening polymerization of tetrahydrofuran (THF). A commercially available product may be used as PTMG.
　ポリオールが、ポリエーテルグリコールとしてＰＴＭＧを含有する場合、ＰＴＭＧの含有量は、引張強さ、引裂強さ、及び抗張積に更に優れた防水材を得る観点から、ポリオール全量（化学当量）を基準として、好ましくは、５当量％以上、１０当量％以上、２０当量％以上、２５当量％以上、５０当量％以上、又は６５当量％以上である。ＰＴＭＧの含有量は、主剤の取り扱いが容易となる粘度にする観点から、ポリオール全量を基準として、好ましくは、９５当量％以下、９０当量％以下、更に好ましくは８５当量％以下、８０当量％以下、又は７５当量％以下である。 When the polyol contains PTMG as a polyether glycol, the content of PTMG is based on the total amount of the polyol (chemical equivalent) from the viewpoint of obtaining a waterproof material having more excellent tensile strength, tear strength, and tensile product. Is preferably 5 equivalent% or more, 10 equivalent% or more, 20 equivalent% or more, 25 equivalent% or more, 50 equivalent% or more, or 65 equivalent% or more. The content of PTMG is preferably 95 equivalent% or less, 90 equivalent% or less, more preferably 85 equivalent% or less, 80 equivalent% or less, based on the total amount of the polyol, from the viewpoint of making the viscosity at which the handling of the main agent becomes easy. Or 75 equivalent% or less.
　ポリエーテルグリコールは、他の一実施形態において、上記の式（１）で表される構造単位と、下記式（２）で表される構造単位とを有する共重合体（以下、「共重合体Ａ」ともいう。）である。共重合体Ａは、両端に水酸基を有する。共重合体Ａは、ランダム共重合体であってよい。
Figure JPOXMLDOC01-appb-C000004
 In another embodiment, the polyether glycol is a copolymer having a structural unit represented by the above formula (1) and a structural unit represented by the following formula (2) (hereinafter referred to as “copolymer”). A "). The copolymer A has a hydroxyl group at both ends. Copolymer A may be a random copolymer.
Figure JPOXMLDOC01-appb-C000004
　式（２）において、Ｒ１及びＲ２の一方がメチル基を表し、他方が水素原子を表す。すなわち、Ｒ１がメチル基であってＲ２は水素原子であってよく、Ｒ１が水素原子であってＲ２がメチル基であってもよい。共重合体Ａに含まれる各構造単位において、Ｒ１及びＲ２の組み合わせは、互いに同一であっても異なっていてもよい。 In the formula (2), one of R 1 and R 2 represents a methyl group, and the other represents a hydrogen atom. That is, R 1 may be a methyl group and R 2 may be a hydrogen atom, or R 1 may be a hydrogen atom and R 2 may be a methyl group. In each of the structural units contained in the copolymer A, the combination of R 1 and R 2 may be the same or different.
　共重合体Ａにおいて、式（１）で表される構造単位の含有量は、経済的観点から、共重合体Ａの構造単位全量を基準として、好ましくは５０質量％以上、より好ましくは６０質量％以上、更に好ましくは７０質量％以上である。式（１）で表される構造単位の含有量は、共重合体Ａの凝固点を低下させる観点から、好ましくは９７質量％以下、より好ましくは９５質量％以下、更に好ましくは９３質量％以下である。 In the copolymer A, the content of the structural unit represented by the formula (1) is preferably 50% by mass or more, more preferably 60% by mass, based on the total amount of the structural units of the copolymer A from an economic viewpoint. %, More preferably 70% by mass or more. The content of the structural unit represented by the formula (1) is preferably 97% by mass or less, more preferably 95% by mass or less, and still more preferably 93% by mass or less, from the viewpoint of lowering the freezing point of the copolymer A. is there.
　共重合体Ａにおいて、式（２）で表される構造単位の含有量は、共重合体Ａの凝固点を低下させる観点から、共重合体Ａの構造単位全量を基準として、好ましくは２質量％以上、より好ましくは５質量％以上、更に好ましくは７質量％以上である。式（２）で表される構造単位の含有量は、経済的観点から、共重合体Ａの構造単位全量を基準として、好ましくは５０質量％以下、より好ましくは４０質量％以下、更に好ましくは３０質量％以下である。 In the copolymer A, the content of the structural unit represented by the formula (2) is preferably 2% by mass based on the total amount of the structural units of the copolymer A from the viewpoint of lowering the freezing point of the copolymer A. The content is more preferably 5% by mass or more, and still more preferably 7% by mass or more. From the economic viewpoint, the content of the structural unit represented by the formula (2) is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably, based on the total amount of the structural units of the copolymer A. 30 mass% or less.
　共重合体Ａの数平均分子量は、引張強さ、引裂強さ、及び抗張積に更に優れた防水材を得る観点から、好ましくは、３５００以下であり、より好ましくは３０００以下であり、更に好ましくは２０００以下である。共重合体の数平均分子量は、例えば、２５０以上、６５０以上、８５０以上、又は１０００以上であってよい。 The number average molecular weight of the copolymer A is preferably 3500 or less, more preferably 3000 or less, from the viewpoint of obtaining a waterproof material having further excellent tensile strength, tear strength, and tensile product. Preferably it is 2000 or less. The number average molecular weight of the copolymer may be, for example, 250 or more, 650 or more, 850 or more, or 1000 or more.
　共重合体Ａは、テトラヒドロフラン及びメチルテトラヒドロフラン（２－メチルテトラヒドロフラン及び３－メチルテトラヒドロフランを含む）を開環重合させて得ることができる。共重合体Ａとして、市販品を用いてもよい。 The copolymer A can be obtained by ring-opening polymerization of tetrahydrofuran and methyltetrahydrofuran (including 2-methyltetrahydrofuran and 3-methyltetrahydrofuran). As the copolymer A, a commercially available product may be used.
　ポリオールが、ポリエーテルグリコールとして共重合体Ａを含有する場合、共重合体Ａの含有量は、引張強さ、引裂強さ、及び抗張積に更に優れた防水材を得る観点から、ポリオール全量（化学当量）を基準として、好ましくは、５当量％以上、１０当量％以上、２０当量％以上、２５当量％以上、５０当量％以上、又は６５当量％以上である。共重合体Ａの含有量は、経済的観点から、ポリオール全量を基準として、９５当量％以下、９０当量％以下、８５当量％以下、８０当量％以下、又は７５当量％以下である。 When the polyol contains the copolymer A as a polyether glycol, the content of the copolymer A is determined based on the total amount of the polyol, from the viewpoint of obtaining a waterproof material having more excellent tensile strength, tear strength, and tensile product. Based on (chemical equivalent), it is preferably 5 equivalent% or more, 10 equivalent% or more, 20 equivalent% or more, 25 equivalent% or more, 50 equivalent% or more, or 65 equivalent% or more. From an economic viewpoint, the content of the copolymer A is 95 equivalent% or less, 90 equivalent% or less, 85 equivalent% or less, 80 equivalent% or less, or 75 equivalent% or less based on the total amount of the polyol.
　ポリオールは、ＰＴＭＧ又は共重合体Ａのいずれか一方を含有してもよく、両方を含有してもよい。 The polyol may contain either one of PTMG or copolymer A, or may contain both.
　ポリオール中のポリエーテルグリコール（ＰＴＭＧ及び共重合体Ａの両方を含む）の含有量は、引張強さ、引裂強さ、及び抗張積に更に優れた防水材を得る観点から、ポリオール全量（化学当量）を基準として、好ましくは、５当量％以上、１０当量％以上、２０当量％以上、２５当量％以上、５０当量％以上、又は６５当量％以上である。ポリエーテルグリコールの含有量は、施工時の可使時間をより長くする観点から、ポリオール全量を基準として、好ましくは、９０当量％以下、８５当量％以下、８０当量％以下、又は７５当量％以下である。 The content of polyether glycol (including both PTMG and copolymer A) in the polyol is determined based on the total amount of the polyol (Chemical) from the viewpoint of obtaining a waterproof material having more excellent tensile strength, tear strength and tensile product. Eq.), Preferably at least 5 eq.%, At least 10 eq.%, At least 20 eq.%, At least 25 eq.%, At least 50 eq.%, Or at least 65 eq.%. The content of the polyether glycol is preferably 90 equivalent% or less, 85 equivalent% or less, 80 equivalent% or less, or 75 equivalent% or less, based on the total amount of the polyol, from the viewpoint of extending the pot life during construction. It is.
　ポリオールは、ポリエーテルグリコール及びポリプロピレングリコールの他に、他のポリオール成分を含有してもよい。他のポリオール成分は、例えば、炭素数２～２０の多価アルコール、炭素数２～２０の多価アルコール若しくは炭素数６～２６の多価フェノールに炭素数２～４のアルキレンオキサイドが付加されたポリオキシアルキレンポリオール（上述のＰＰＧ、ＰＴＭＧ、及び共重合体Ａを除く）、ポリエステルポリオール、ポリカーボネートポリオール、ポリジエンポリオール（ポリブタジエンポリオール等）、ポリジエンポリオールの水添物、アクリル系ポリオール、天然油系ポリオール（ヒマシ油等）、又は天然油系ポリオールの変性物であってよい。 The polyol may contain other polyol components in addition to polyether glycol and polypropylene glycol. Other polyol components include, for example, a polyhydric alcohol having 2 to 20 carbon atoms, a polyhydric alcohol having 2 to 20 carbon atoms, or a polyhydric phenol having 6 to 26 carbon atoms to which an alkylene oxide having 2 to 4 carbon atoms is added. Polyoxyalkylene polyol (excluding the above-mentioned PPG, PTMG and copolymer A), polyester polyol, polycarbonate polyol, polydiene polyol (such as polybutadiene polyol), hydrogenated product of polydiene polyol, acrylic polyol, natural oil-based It may be a polyol (such as castor oil) or a modified natural oil-based polyol.
　ポリイソシアネートは、分子内にイソシアネート基を２以上有する化合物であれば、特に限定されない。ポリイソシアネートとしては、２，２’－ジフェニルメタンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート、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、キシレンジイソシアネート、テトラメチルキシレンジイソシアネート、ナフタレンジイソシネート等の芳香族ポリイソシアネート、エチレンジイソシアネート、テトラメチレンジイソシアネート、１，５－ペンタメチレンジイソシアネート等の脂肪族ポリイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、ノルボルネンメタンジイソシアネート、１，３－ビス（イソシアナトメチル）シクロヘキサン、１，４－ビス（イソシアナトメチル）シクロヘキサン等の脂環式イソシアネート等が挙げられる。本発明におけるポリイソシアネートはポリイソシアネートの変性物も含む。ポリイソシアネートの変性物としては、ウレタン基、カルボジイミド基、アロハネート基、ウレア基、ビューレット基、ウレトジオン基、ウレトイミン基、イソシアヌレート基又はオキサゾリドン基含有変性物が挙げられる。ポリイソシアネートは、これらを１種単独で又は２種以上を混合して用いられてよい。 The polyisocyanate is not particularly limited as long as it has two or more isocyanate groups in the molecule. Examples of the polyisocyanate include 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene diisocyanate, and tetramethyl Aromatic polyisocyanates such as xylene diisocyanate and naphthalene diisocyanate; aliphatic polyisocyanates such as ethylene diisocyanate, tetramethylene diisocyanate and 1,5-pentamethylene diisocyanate; isophorone diisocyanate, dicyclohexylmethane diisocyanate; norbornene methane diisocyanate; Bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclo Alicyclic isocyanates such as hexane and the like. The polyisocyanate in the present invention also includes a modified polyisocyanate. Examples of modified polyisocyanate include urethane group, carbodiimide group, allohanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group-containing modified products. These polyisocyanates may be used alone or in combination of two or more.
　ポリイソシアネートは、好ましくは脂環式ポリイソシアネートであり、より好ましくは脂環式ジイソシアネートであり、更に好ましくはイソホロンジイソシアネートである。 The polyisocyanate is preferably an alicyclic polyisocyanate, more preferably an alicyclic diisocyanate, and even more preferably isophorone diisocyanate.
　イソシアネート基末端プレポリマーは、上述したポリオールとポリイソシアネートとの反応生成物である。イソシアネート基末端プレポリマーは、例えば、ポリオールに所定の当量比でポリイソシアネートを加え、加熱混合することにより反応させて得ることができる。 The isocyanate group-terminated prepolymer is a reaction product of the above-mentioned polyol and polyisocyanate. The isocyanate group-terminated prepolymer can be obtained by, for example, adding a polyisocyanate to a polyol at a predetermined equivalent ratio and mixing the mixture by heating.
　ポリオール及びポリイソシアネートを混合する際、ポリオール中の水酸基（ＯＨ基）に対するポリイソシアネート中のイソシアネート基（ＮＣＯ基）の当量比（ＮＣＯ基／ＯＨ基）は、１．４以上、１．５以上、又は１．６以上であってよく、２．２以下、２．０以下、又は１．８以下であってよい。 When mixing the polyol and the polyisocyanate, the equivalent ratio of the isocyanate group (NCO group) in the polyisocyanate to the hydroxyl group (OH group) in the polyol (NCO group / OH group) is 1.4 or more, 1.5 or more, Or it may be 1.6 or more, and may be 2.2 or less, 2.0 or less, or 1.8 or less.
　ポリオール及びポリイソシアネートの反応温度は、１００℃以下、９０℃以下、又は８０℃以下であってよい。反応温度の下限は特に限定されないが、例えば３０℃以上である。 反 応 The reaction temperature of the polyol and the polyisocyanate may be 100 ° C or lower, 90 ° C or lower, or 80 ° C or lower. The lower limit of the reaction temperature is not particularly limited, but is, for example, 30 ° C. or higher.
　イソシアネート基末端プレポリマー中のイソシアネート基の含有量は、１質量％以上、２質量％以上、又は３質量％以上であってよく、８質量％以下、７質量％以下、又は６質量％以下であってよい。 The content of the isocyanate group in the isocyanate group-terminated prepolymer may be 1% by mass or more, 2% by mass or more, or 3% by mass or more, and 8% by mass or less, 7% by mass or less, or 6% by mass or less. May be.
　主剤は、主剤及び後述する硬化剤を混合した際の粘度調整等のために、イソシアネート基末端プレポリマーの他に、粘度調整剤として可塑剤、溶剤等を更に含有してもよい。主剤は、工業的及び経済的観点から、ポリイソシアネートのイソシアネート基とポリオールの水酸基とを効率的に反応させるための触媒及び／又は遅延剤を更に含有してもよい。主剤は、得られる防水材の仕上りや、耐久性、他材との密着性等を向上させる観点から、添加剤を含有してもよい。 (4) The main agent may further contain a plasticizer, a solvent, and the like as a viscosity adjuster in addition to the isocyanate group-terminated prepolymer for adjusting the viscosity when the main agent and a curing agent described later are mixed. The main agent may further contain a catalyst and / or a retarder for efficiently reacting the isocyanate group of the polyisocyanate with the hydroxyl group of the polyol from an industrial and economic viewpoint. The main agent may contain an additive from the viewpoint of improving the finish, durability, adhesion to other materials, and the like of the obtained waterproof material.
　主剤の２３℃における粘度は、主剤及び硬化剤の混合直後の混合物が施工時のレベリングを保持でき、塗膜の膜厚を確保できる程度の粘度を有する観点から、好ましくは１０００ｍＰａ・ｓ以上、より好ましくは３０００ｍＰａ・ｓ以上、更に好ましくは４０００ｍＰａ・ｓ以上、特に好ましくは５０００ｍＰａ・ｓ以上であり、また、好ましくは２５０００ｍＰａ・ｓ以下、より好ましくは２００００ｍＰａ・ｓ以下、更に好ましくは１５０００ｍＰａ・ｓ以下である。主剤の粘度は、ＪＩＳ　Ｋ　７３０１：１９９５の「熱硬化性ウレタンエラストマー用トリレンジイソシアネート型プレポリマー試験方法　６．２粘度」に準じて、回転粘度計を用いて測定することができる。 The viscosity of the main agent at 23 ° C. is preferably from 1000 mPa · s or more, from the viewpoint that the mixture immediately after mixing of the main agent and the curing agent can maintain the leveling at the time of application and has a viscosity enough to secure the film thickness of the coating film. It is preferably at least 3,000 mPas, more preferably at least 4,000 mPas, particularly preferably at least 5,000 mPas, and preferably at most 25,000 mPas, more preferably at most 20,000 mPas, even more preferably at most 15,000 mPas. is there. The viscosity of the main agent can be measured using a rotational viscometer according to JIS 試 験 K7301: 1995 “Testing method of tolylene diisocyanate type prepolymer for thermosetting urethane elastomer 6.2 viscosity”.
＜硬化剤＞
　硬化剤は、多価アルコール等のヒドロキシル化合物、ポリアミンなどの架橋剤を含有してよい。ポリアミンは、例えば、ジエチルトルエンジアミン（２，４－ジエチルトルエンジアミン、２，６－ジエチルトルエンジアミン）、フェニレンジアミン、キシリレンジアミン、２，４－トリレンジアミン、２，６－トリレンジアミン、ＭＯＣＡ系ポリアミン（ＭＯＣＡ及び変性ＭＯＣＡ）、ポリアルキレンエーテルポリオール－ｐ－アミノベンゾエート、ポリテトラメチレングリコールアミノベンゾエート、１，３，５－トリイソプロピル－２，４－ジアミノベンゼン、１－メチル－３，５－ジイソプロピル－２，４－ジアミノベンゼン、１－メチル－３，５－ジイソプロピル－２，６－ジアミノベンゼン、１－エチル－３，５－ジイソプロピル－２，４－ジアミノベンゼン、１－エチル－３，５－ジイソプロピル－２，６－ジアミノベンゼン、メチレンビス（メチルチオ）ベンゼンジアミン、Ｎ，Ｎ’－ジセカンダリーブチル－ｐ－フェニレンジアミン、４，４’－ビス（ｓｅｃ－ブチルアミン）ジフェニルメタン、３，３’，５，５’－テトラメチル－４，４’－ジアミノジフェニルメタン、３，３’，５，５’－テトラエチル－４，４’－ジアミノジフェニルメタン、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジアミノジフェニルメタン、３，３’，５，５’－テトライソプロピル－４，４’－ジアミノジフェニルメタン、３，３’－ジメチル－５，５’－ジイソプロピル－４，４’－ジアミノジフェニルメタン、３，３’－ジメチル－５，５’－ジイソブチル－４，４’－ジアミノジフェニルメタン、３，３’－ジエチル－５，５’－ジイソプロピル－４，４’－ジアミノジフェニルメタン、３，３’－ジエチル－５，５’－ジイソブチル－４，４’－ジアミノジフェニルメタン等の芳香族ポリアミン、Ｎ，Ｎ’ジ－ｓｅｃ－ブチル４，４‘－メチレンビス（シクロヘキシルアミン）、イソホロンジアミン、ノルボルネンジアミン、Ｎ，Ｎ‘－（ジシクロヘキシルメタン４，４’－ジイル）－ビスアスパラギン酸テトラエチルエステル等の脂環式ポリアミン、エチレンジアミン、トリメチレンジアミン、トリエチレンテトラミン、ジエチレントリアミン、トリアミノプロパン、２，２，４－トリメチルヘキサメチレンジアミン、２－ヒドロキシエチルエチレンジアミン、Ｎ，Ｎ‘－（２－メチルペンタン－１，５－ジイル）－ビスアスパラギン酸テトラエチルエステル、ポリオキシアルキレンアミン、ポリエーテルアミン等の脂肪族ポリアミンであってよい。これらの架橋剤は、１種を単独で又は２種以上を混合して用いられてよい。硬化剤は、架橋剤として、好ましくは芳香族ポリアミンを含有し、より好ましくはジエチルトルエンジアミンを含有する。 <Curing agent>
The curing agent may contain a hydroxyl compound such as a polyhydric alcohol, and a crosslinking agent such as a polyamine. Polyamines include, for example, diethyltoluenediamine (2,4-diethyltoluenediamine, 2,6-diethyltoluenediamine), phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, MOCA Polyamine (MOCA and modified MOCA), polyalkylene ether polyol-p-aminobenzoate, polytetramethylene glycol aminobenzoate, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5- Diisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diisopropyl-2,6-diaminobenzene, 1-ethyl-3,5-diisopropyl-2,4-diaminobenzene, 1-ethyl-3,5 -Diisopropyl-2,6-diaminobenze , Methylenebis (methylthio) benzenediamine, N, N'-disecondarybutyl-p-phenylenediamine, 4,4'-bis (sec-butylamine) diphenylmethane, 3,3 ', 5,5'-tetramethyl-4 4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3, 3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-5,5′-diisopropyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-5 5'-diisobutyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-5,5'-diisopropyl-4,4'-diaminodiphenylmethane, Aromatic polyamines such as 3,3'-diethyl-5,5'-diisobutyl-4,4'-diaminodiphenylmethane, N, N'di-sec-butyl 4,4'-methylenebis (cyclohexylamine), isophoronediamine, norbornene Alicyclic polyamines such as diamine, N, N '-(dicyclohexylmethane 4,4'-diyl) -bisaspartic acid tetraethyl ester, ethylenediamine, trimethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2 Aliphatic polyamines such as 4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, N, N '-(2-methylpentane-1,5-diyl) -bisaspartic acid tetraethyl ester, polyoxyalkyleneamine and polyetheramine so Good me. These crosslinking agents may be used alone or as a mixture of two or more. The curing agent preferably contains an aromatic polyamine as a crosslinking agent, and more preferably contains diethyltoluenediamine.
　硬化剤は、架橋剤の他に、可塑剤；溶剤；触媒；炭酸カルシウム、タルク、カオリン、ゼオライト、ケイソウ土等の無機充填材；酸化クロム、ベンガラ、酸化鉄、カーボンブラック、酸化チタン等の顔料；湿潤分散剤、沈降防止剤、光安定剤、消泡剤、表面調整剤、密着付与剤等の添加剤などを更に含有してもよい。 Curing agents include, in addition to crosslinking agents, plasticizers; solvents; catalysts; inorganic fillers such as calcium carbonate, talc, kaolin, zeolite, and diatomaceous earth; pigments such as chromium oxide, red iron oxide, carbon black, and titanium oxide. An additive such as a wetting and dispersing agent, an anti-settling agent, a light stabilizer, an antifoaming agent, a surface conditioner, and an adhesion promoter.
＜防水材＞
　以上説明したセットにおいては、主剤及び硬化剤を混合することにより、混合物が硬化する。得られた硬化物は、防水材として好適に用いられる。すなわち、一実施形態に係る防水材は、上述した主剤及び硬化剤の混合物の硬化物を含む。 <Waterproof material>
In the set described above, the mixture is cured by mixing the main agent and the curing agent. The obtained cured product is suitably used as a waterproof material. That is, the waterproofing material according to one embodiment includes a cured product of the mixture of the above-described main agent and curing agent.
　本実施形態に係る防水材は、引張強さ、引裂強さ、及び抗張積に優れており、高強度の防水材である。この防水材は、例えば、ＪＩＳ　Ａ　６０２１：２０１１（建築用塗膜防水材、「高強度形」）に準ずる方法により評価した際に、当該規格に規定する以下の数値を満足できる程度に、引張強さ、引裂強さ、及び抗張積に優れている。
　引張強さ（Ｔｂ）：１０Ｎ／ｍｍ２以上
　引裂強さ（Ｔｔ）：３０Ｎ／ｍｍ以上
　抗張積（Ｔｐ）：７００Ｎ／ｍｍ以上 The waterproof material according to the present embodiment is excellent in tensile strength, tear strength, and tensile product, and is a high-strength waterproof material. For example, when this waterproofing material is evaluated by a method according to JIS A 6021: 2011 (architecture coating waterproofing material, “high-strength type”), the tensile strength is such that the following numerical values specified in the standard can be satisfied. Excellent strength, tear strength and tensile product.
Tensile strength (Tb): 10 N / mm 2 or more Tear strength (Tt): 30 N / mm or more Tensile product (Tp): 700 N / mm or more
　本実施形態に係る防水材は、破断時の伸び率にも優れており、高伸長な防水材である。この防水材は、ＪＩＳ　Ａ　６０２１：２０１１（建築用塗膜防水材、「高伸長形（旧１類）」）に準ずる方法により評価した際に、当該規格に規定する以下の数値を満足できる程度に、破断時の伸び率に優れている。
　破断時の伸び率（Ｅｂ）：４５０％以上 The waterproof material according to the present embodiment is also excellent in elongation at break, and is a highly stretchable waterproof material. When this waterproofing material is evaluated by a method according to JIS A 6021: 2011 (architecture coating waterproofing material, “high elongation type (old class 1)”), it can satisfy the following numerical values specified in the standard. In addition, the elongation at break is excellent.
Elongation at break (Eb): 450% or more
　上述したセットを用いた、防水材の施工方法の一実施形態について説明する。一実施形態に係る施工方法は、上述したセットにおける主剤及び硬化剤の混合物を得る工程（混合工程）と、混合物を被塗物に塗布する工程（塗布工程）と、を備える。 の 一 An embodiment of a method for installing a waterproof material using the above-described set will be described. The application method according to one embodiment includes a step of obtaining a mixture of the main agent and the curing agent in the above-described set (mixing step), and a step of applying the mixture to an object to be coated (application step).
　混合工程において、主剤及び硬化剤を混合する際の温度（環境温度）は、例えば－５～４０℃であってよい。 温度 In the mixing step, the temperature (environmental temperature) at which the main agent and the curing agent are mixed may be, for example, −5 to 40 ° C.
　硬化剤が架橋剤を含有する場合、硬化剤は、主剤中のＮＣＯ基含有量に対する架橋剤の活性水素基の当量比が、０．８以上、０．９以上、又は１．０以上となるように主剤と混合されてよい。硬化剤は、主剤中のＮＣＯ基含有量に対する架橋剤の活性水素基の当量比が、１．５以下、１．３以下、又は１．２以下となるように主剤と混合されてよい。 When the curing agent contains a crosslinking agent, the curing agent has an equivalent ratio of the active hydrogen group of the crosslinking agent to the NCO group content in the main component of 0.8 or more, 0.9 or more, or 1.0 or more. As described above. The curing agent may be mixed with the main component such that the equivalent ratio of the active hydrogen group of the crosslinking agent to the NCO group content in the main component is 1.5 or less, 1.3 or less, or 1.2 or less.
　硬化剤がポリアミンを含有する場合、混合工程において主剤及び硬化剤を混合する際には、所望の可使時間を得る観点から、主剤に含まれるイソシアネート基末端プレポリマーのＮＣＯ基と、硬化剤に含まれるアミノ基（ＮＨ２基）との当量比（ＮＣＯ基／ＮＨ２基）を、所定の範囲になるように混合することが好ましい。ＮＣＯ基／ＮＨ２基は、好ましくは０．８以上、より好ましくは０．９以上、更に好ましくは１．０以上であり、好ましくは１．５以下、より好ましくは１．３以下、更に好ましくは１．２以下である。 When the curing agent contains a polyamine, when mixing the main agent and the curing agent in the mixing step, from the viewpoint of obtaining a desired pot life, the NCO group of the isocyanate group-terminated prepolymer contained in the main agent and the curing agent It is preferable to mix them so that the equivalent ratio (NCO group / NH 2 group) to the contained amino group (NH 2 group) falls within a predetermined range. The NCO group / NH 2 group is preferably at least 0.8, more preferably at least 0.9, even more preferably at least 1.0, preferably at most 1.5, more preferably at most 1.3, even more preferably Is 1.2 or less.
　塗布工程では、得られた混合物が硬化する前に、当該混合物を被塗物に塗布する。被塗物は特に限定されず、家屋又はビルディング等の建築物における壁面、床面等であってよい。本実施形態に係る主剤及び硬化剤の混合物は、十分な可使時間が得られるために、特に手塗りによる塗布（手塗り塗工）に適している。すなわち、混合工程においては、手塗り塗工がなされてよい。手塗りによる塗布には、スタティックミキサー、ダイナミックミキサー等の自動混合装置などの機械による塗布、ローラー、リシンガン、エアレスガン、刷毛等の道具を使用した塗布も含まれる。本実施形態に係る混合物は、スプレーによる塗布（スプレー塗工）がされてもよい。 (4) In the coating step, before the obtained mixture is cured, the mixture is applied to an object to be coated. The object to be coated is not particularly limited, and may be a wall surface, a floor surface, or the like in a building such as a house or a building. The mixture of the main agent and the curing agent according to the present embodiment is particularly suitable for application by hand coating (hand coating) because a sufficient pot life can be obtained. That is, in the mixing step, hand coating may be performed. The application by hand coating includes application by a machine such as an automatic mixing device such as a static mixer and a dynamic mixer, and application using tools such as a roller, a ricin gun, an airless gun, and a brush. The mixture according to the present embodiment may be applied by spraying (spray coating).
　本実施形態に係る主剤及び硬化剤のセットを用いると、防水材を施工する際に十分に長い可使時間を得ることができる。より具体的には、本実施形態に係る主剤及び硬化剤のセットによれば、例えば、主剤及び硬化剤の混合物の２３℃における粘度が６万ｍＰａ・ｓに達するまでに４５分以上、又は１０万ｍＰａ・ｓに達するまでに５５分以上を要するため、十分に長い可使時間を得ることができる。 と When the set of the main agent and the curing agent according to the present embodiment is used, a sufficiently long pot life can be obtained when the waterproof material is installed. More specifically, according to the set of the main agent and the curing agent according to the present embodiment, for example, 45 minutes or more until the viscosity at 23 ° C. of the mixture of the main agent and the curing agent reaches 60,000 mPa · s, or Since it takes 55 minutes or more to reach 10,000 mPa · s, a sufficiently long pot life can be obtained.
　上述した方法によって得られる防水材は、防水材の用途以外にも、高強度性能、高負荷性能が要求されるスポーツ施設等の床材、建築物等の被覆材、更には防錆材などの用途にも使用することができる。なお、用途によっては、作業性に応じてキシレン等の有機溶剤を混合物に加えてから施工することも可能である。 The waterproofing material obtained by the above-described method is not only a use of the waterproofing material, but also a high-strength performance, a flooring material for sports facilities or the like where a high load performance is required, a covering material for a building, and a rustproofing material. Can also be used for applications. In addition, depending on the use, it is also possible to add an organic solvent such as xylene to the mixture according to the workability before performing the work.
　以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
　以下の表において、表中の略称は以下の成分を示す。
　ＰＰＧ－１０００：ポリプロピレングリコール（数平均分子量１０００、商品名「アクトコール　Ｄ－１０００」、三井化学ＳＫＣポリウレタン（株）製）
　ＰＴＧ－１０００：ポリテトラメチレンエーテルグリコール（数平均分子量１０００、商品名「ＰＴＧ－１０００ＳＮ」、保土谷化学工業（株）製）
　ＰＴＧ－Ｌ１０００：ＴＨＦ／メチル基置換ＴＨＦランダム共重合体（数平均分子量１０００、商品名「ＰＴＧ－Ｌ１０００」、保土谷化学工業（株）製） In the following tables, abbreviations in the tables indicate the following components.
PPG-1000: polypropylene glycol (number average molecular weight 1000, trade name "Actocol D-1000", manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.)
PTG-1000: polytetramethylene ether glycol (number average molecular weight 1000, trade name "PTG-1000SN", manufactured by Hodogaya Chemical Industry Co., Ltd.)
PTG-L1000: THF / methyl group-substituted THF random copolymer (number average molecular weight 1000, trade name "PTG-L1000", manufactured by Hodogaya Chemical Industry Co., Ltd.)
＜主剤の調製＞
　実施例及び比較例においては、表１に示す組成に基づき、以下の方法により主剤を調製した。２リットルのガラスコルベンに、ポリエーテルグリコール及びポリプロピレングリコールを所定の当量比で仕込み、９５～１０５℃で１時間、減圧脱水を実施した。液温が４０℃以下になるまで冷却後、窒素気流下で触媒を加えて均一化した後、イソホロンジイソシアネート（商品名「ＶＥＳＴＡＮＡＴ　ＩＰＤＩ」、ＥＶＯＮＩＣ社製）を徐々に加え、反応が完結するまで、撹拌しながら６０～８０℃で２～４時間加熱した。反応後の液体を室温まで冷却し、粘度調整剤等を加え撹拌しながら均一化して、主剤（イソシアネート基末端プレポリマー）を得た。主剤は、ポリイソシアネートのＮＣＯ基と、ポリプロピレングリコール及びポリエーテルグリコールのＯＨ基との当量比を調整したイソシアネート末端プレポリマー、粘度調整剤、添加剤及び触媒の含有量を調整することにより、ＮＣＯ基含有量が４質量％となるように調製した。 <Preparation of main agent>
In Examples and Comparative Examples, the main ingredients were prepared based on the compositions shown in Table 1 by the following method. Polyether glycol and polypropylene glycol were charged at a predetermined equivalent ratio in a 2 liter glass kolben, and dehydration under reduced pressure was performed at 95 to 105 ° C. for 1 hour. After cooling to a liquid temperature of 40 ° C. or lower, a catalyst was added under a nitrogen stream to homogenize, and then isophorone diisocyanate (trade name “VESTANAT IPDI”, manufactured by EVONIC) was gradually added until the reaction was completed. Heat with stirring at 60-80 ° C. for 2-4 hours. The liquid after the reaction was cooled to room temperature, a viscosity modifier and the like were added, and the mixture was homogenized with stirring to obtain a main agent (isocyanate group-terminated prepolymer). The main ingredient is an isocyanate-terminated prepolymer in which the equivalent ratio of the NCO group of the polyisocyanate to the OH group of the polypropylene glycol and polyether glycol is adjusted, and the NCO group is adjusted by adjusting the contents of the viscosity modifier, additives and catalyst. The content was adjusted to be 4% by mass.
＜可使時間の評価＞
　調製した主剤と、硬化剤（ジエチルトルエンジアミン（商品名「エタキュア１００」、アルベマール・コーポレーション社製）を含む）とを、質量比が主剤：硬化剤＝１：１となるように混合した（ＮＣＯ基／ＮＨ２基＝１．１（当量比））。得られた混合物の２３℃における粘度を、ＪＩＳ　Ｋ　７３０１：１９９５の「熱硬化性ウレタンエラストマー用トリレンジイソシアネート型プレポリマー試験方法　６．２粘度」に準じて、回転粘度計（東機産業（株）ＢＨ　ＩＩ形）を用いて測定した。粘度が６万ｍＰａ・ｓ、及び１０万ｍＰａ・ｓのそれぞれに達するまでの時間を可使時間とした。測定結果を表１に示す。 <Evaluation of pot life>
The prepared base material and a curing agent (including diethyltoluenediamine (trade name “Etacur 100”, manufactured by Albemarle Corporation)) were mixed so that the mass ratio of the base material to the curing agent was 1: 1 (NCO Group / NH 2 group = 1.1 (equivalent ratio)). The viscosity of the obtained mixture at 23 ° C. was measured using a rotational viscometer (Toki Sangyo Co., Ltd.) according to JIS K 7301: 1995 “Testing method for tolylene diisocyanate type prepolymer for thermosetting urethane elastomer 6.2 viscosity”. ) BH Form II). The time required for the viscosity to reach 60,000 mPa · s and 100,000 mPa · s, respectively, was taken as the pot life. Table 1 shows the measurement results.
＜塗膜（硬化物）の物性評価（強度）＞
　可使時間の評価において優れていた実施例及び比較例については、ＪＩＳ　Ａ　６０２１：２０１１（建築用塗膜防水材、高強度形）に準じて、上述の混合物から塗膜（硬化物）を作製し、２３℃で７日経過後に、塗膜の引張強さ（Ｔｂ）、引裂強さ（Ｔｔ）、及び抗張積（Ｔｐ）を更に評価した。結果を表１に示す。 <Evaluation of physical properties (strength) of coating film (cured product)>
For Examples and Comparative Examples which were excellent in the evaluation of the pot life, according to JIS A 6021: 2011 (architecture coating waterproofing material, high-strength type), a coating film (cured product) was prepared from the above mixture. After 7 days at 23 ° C., the coating film was further evaluated for tensile strength (Tb), tear strength (Tt), and tensile product (Tp). Table 1 shows the results.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
＜塗膜（硬化物）の物性評価（破断時伸び率）＞
　実施例１～５については、上述の塗膜（硬化物）について、ＪＩＳ　Ａ　６０２１：２０１１（建築用塗膜防水材、高伸長形（旧１類））に準じて、２３℃で７日経過後に、塗膜の破断時の伸び率（Ｅｂ）を評価した。結果を表２に示す。 <Evaluation of physical properties of coating film (cured product) (elongation at break)>
In Examples 1 to 5, the coating film (cured product) described above passed 7 days at 23 ° C. in accordance with JIS A 6021: 2011 (waterproofing material for architectural coating film, high elongation type (old type 1)). Thereafter, the elongation (Eb) at break of the coating film was evaluated. Table 2 shows the results.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006

Claims (6)

  1. 　イソシアネート基末端プレポリマーを含有する主剤と、硬化剤とを備えるセットであって、
    　前記イソシアネート基末端プレポリマーは、ポリプロピレングリコール及び下記式（１）で表される構造単位を有するポリエーテルグリコールを含有するポリオールと、ポリイソシアネートとの反応生成物である、セット。
    Figure JPOXMLDOC01-appb-C000001
         A set comprising a main agent containing an isocyanate group-terminated prepolymer and a curing agent,
    The set, wherein the isocyanate group-terminated prepolymer is a reaction product of a polyol containing polypropylene glycol and a polyether glycol having a structural unit represented by the following formula (1), and a polyisocyanate.
    Figure JPOXMLDOC01-appb-C000001
  2. 　前記ポリプロピレングリコールの数平均分子量が４０００以下である、請求項１に記載のセット。 The set according to claim 1, wherein the polypropylene glycol has a number average molecular weight of 4000 or less.
  3. 　前記ポリエーテルグリコールの数平均分子量が４０００以下である、請求項１又は２に記載のセット。 The set according to claim 1, wherein the number average molecular weight of the polyether glycol is 4,000 or less.
  4. 　前記ポリイソシアネートがイソホロンジイソシアネートである、請求項１～３のいずれか一項に記載のセット。 The set according to any one of claims 1 to 3, wherein the polyisocyanate is isophorone diisocyanate.
  5. 　請求項１～４のいずれか一項に記載のセットにおける前記主剤及び前記硬化剤の混合物の硬化物を含む、防水材。 A waterproof material comprising a cured product of a mixture of the main agent and the curing agent in the set according to any one of claims 1 to 4.
  6. 　請求項１～４のいずれか一項に記載のセットにおける前記主剤及び前記硬化剤の混合物を得る工程と、
    　前記混合物を被塗物上に塗布する工程と、を備える、防水材の施工方法。     Obtaining a mixture of the main agent and the curing agent in the set according to any one of claims 1 to 4,
    A step of applying the mixture on an object to be coated.
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