WO2011122180A1 - Composition formant de la résine de polyuréthane et matériau d'étanchéité à l'eau gonflant à l'eau pour palplanche métallique - Google Patents

Composition formant de la résine de polyuréthane et matériau d'étanchéité à l'eau gonflant à l'eau pour palplanche métallique Download PDF

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Publication number
WO2011122180A1
WO2011122180A1 PCT/JP2011/054028 JP2011054028W WO2011122180A1 WO 2011122180 A1 WO2011122180 A1 WO 2011122180A1 JP 2011054028 W JP2011054028 W JP 2011054028W WO 2011122180 A1 WO2011122180 A1 WO 2011122180A1
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group
polyurethane resin
forming composition
water
organic polyisocyanate
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PCT/JP2011/054028
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English (en)
Japanese (ja)
Inventor
一郎 東久保
田中　一幸
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日本ポリウレタン工業株式会社
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Priority to JP2012508147A priority Critical patent/JP5447655B2/ja
Publication of WO2011122180A1 publication Critical patent/WO2011122180A1/fr

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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
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1021—Polyurethanes or derivatives thereof
    • 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
    • C08G2190/00—Compositions for sealing or packing joints

Definitions

  • the present invention relates to a polyurethane resin-forming composition and a water-swellable water-stopping material for steel sheet piles. More specifically, the present invention relates to a water-swellable water-swelling material for steel sheet piles having good curability, water-swelling property, water-stopping property, heat resistance and easy handling properties, and a polyurethane resin-forming composition used therefor.
  • Moisture-cure water-swelling water-stopping materials that are used in a single solution or with the addition of a catalyst are widely used as jointing materials for civil engineering and construction, caulking materials, and steel sheet piles for water-stopping purposes. It is used.
  • the water-stopping material disclosed in Patent Document 1 has a problem in that the resin deteriorates due to frictional heat generated during the driving operation of the steel sheet pile and the water-stopping property is lowered.
  • a water-swellable water-stopping material that is used by blending two liquids of a main component containing a polyisocyanate group and a curing agent containing an active hydrogen group for the purpose of improving durability.
  • the water-swellable water-stopping material disclosed in Patent Document 3 has a problem that heat resistance is insufficient.
  • an object of the present invention is to provide a water-swellable water-stopping material that is rich in heat resistance and has sufficient durability against frictional heat, and a polyurethane resin-forming composition used therefor.
  • the present invention includes the following (I) to (X).
  • (I) A polyurethane resin-forming composition for obtaining a polyurethane resin, Organic polyisocyanate composition for water-stopping material (A) having an isocyanate group content of 0.5 to 15% by mass and containing an aromatic isocyanate group-terminated prepolymer (a1) and an aliphatic organic polyisocyanate (a2) )When, An amine-based polyol (B) having a nominal average functional group number of 3 to 6, The ratio of the isocyanate groups derived from the aromatic isocyanate group-terminated prepolymer (a1) to the hydroxyl groups derived from the amine polyol (B) (number of isocyanate groups: number of hydroxyl groups) is 2: 1 to 8: 1.
  • the aromatic isocyanate group-terminated prepolymer (a1) is a reaction product of an aromatic polyisocyanate (a11) and a polyether polyol (a12),
  • the polyether polyol (a12) is a polyether polyol (a12-1) having a nominal average functional group number of 2 and an oxyethylene group content in the polyoxyalkylene chain of 50 to 100% by mass, and a nominal average functional group number of And a polyether polyol (a12-2) having an oxyethylene group content in the polyoxyalkylene chain of 50 to 100% by mass
  • the aliphatic organic polyisocyanate (a2) is an isocyanurate group-containing organic polyisocyanate (a21), an allophanate group-containing organic polyisocyanate (a22), an activity having 2 to 3 functional groups and a molecular weight of 300 or less.
  • One or more compounds selected from the group consisting of a reaction product (a23) of a hydrogen group-containing compound and an aliphatic diisocyanate And, The ratio of the isocyanate group of the aromatic isocyanate group-terminated prepolymer (a1) to the isocyanate group of the aliphatic organic polyisocyanate (a2) (number of isocyanate groups in a1: number of isocyanate groups in a2) is 8: A polyurethane resin-forming composition having a ratio of 1 to 1: 4. (II) The polyurethane resin-forming composition as described in (I) above, wherein the aliphatic organic polyisocyanate (a2) has an isocyanate group content of 5 to 50% by mass.
  • (III) The polyurethane resin-forming composition as described in (I) or (II) above, wherein the isocyanate group content in the aliphatic organic polyisocyanate (a2) is 5 to 40% by mass.
  • IV) The polyurethane resin-forming composition according to any one of (I) to (III), wherein the amine polyol (B) has a hydroxyl value of 250 to 1,200.
  • V) The polyurethane resin-forming composition according to any one of (I) to (IV), wherein the polyether polyol (a12) has a number average molecular weight of 200 to 8,000.
  • the aromatic isocyanate group-terminated prepolymer (a1) used in the present invention has one or two or more types of aromatic polyisocyanate (a11) and polyoxyalkylene chain having an oxyethylene group content of 50 to 100% by mass.
  • aromatic polyisocyanate (a11) known aromatic polyisocyanates can be used.
  • known 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (hereinafter, tolylene diisocyanate is abbreviated as TDI)
  • TDI tolylene diisocyanate
  • xylene-1,4-diisocyanate xylene-1,3- Diisocyanate
  • 4,4'-diphenylmethane diisocyanate 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate
  • polymethylene polyphenylene polyisocyanate hereinafter abbreviated as polymeric MDI
  • 2-nitro Diphenyl-4,4′-diisocyanate 2,2′-diphenylpropane-4,4′-diisocyanate
  • 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-difelmethane diisocyanate, 2,4'-difelmethane diisocyanate and mixtures thereof have a high reaction rate, And it is preferable for the reason that physical properties are good.
  • the polyether polyol (a12) is a polyether polyol having a polyoxyalkylene chain in which the ratio of oxyethylene groups in the polyoxyalkylene chain is 50 to 100% by mass.
  • this polyether polyol (a12) it is possible to obtain an isocyanate group-terminated prepolymer having excellent hydrophilicity.
  • the ratio of the polyoxyethylene group is less than 50% by mass, there is a problem in that a water-stopping material having sufficient water expandability cannot be obtained.
  • the polyether polyol (a12) is preferably represented by the general formula R [— (OR 1 ) n OH] p (where R is a polyhydric alcohol residue, (OR 1 ) n is an oxyethylene group and a carbon number of 3 to A polyoxyalkylene chain comprising 4 alkylene groups (wherein the proportion of oxyethylene groups occupies 50 to 100% by mass of the mass of the polyoxyalkylene chains), and n is a number indicating the degree of polymerization of the oxyalkylene groups.
  • R is a polyhydric alcohol residue
  • (OR 1 ) n is an oxyethylene group and a carbon number of 3 to A polyoxyalkylene chain comprising 4 alkylene groups (wherein the proportion of oxyethylene groups occupies 50 to 100% by mass of the mass of the polyoxyalkylene chains), and n is a number indicating the degree of polymerization of the oxyalkylene groups.
  • polyhydric alcohol examples include dihydric alcohols (ethylene glycol, propylene alcohol, etc.), trihydric alcohols (glycerin, trimethylolpropane, etc.), tetrahydric alcohols (erythritol, pentaerythritol, etc.), pentahydric alcohols (Arhat, xylit, etc. Etc.) and hexavalent alcohol (Sorbit, Mannich etc.).
  • the polyether polyol (a12) has a nominal average functional group number of 2 and an oxyethylene group content in the polyoxyalkylene chain of 50 to 100% by mass, and a nominal average functional group number of 3
  • a polyether resin (a12-2) having an oxyethylene group content in the polyoxyalkylene chain of 50 to 100% by mass, which makes it easy to balance the viscosity and the crosslink density. Is preferable from the viewpoint that can be obtained.
  • the nominal average functional group number refers to the number of functional groups per molecule of an initiator such as a polyhydric alcohol used when obtaining a polyether polyol (the number of active hydrogen atoms per molecule of the initiator). .
  • the proportion of the polyether polyol (a12-1) and the polyether polyol (a12-2) used is not particularly limited, but the mass ratio (a12-1: a12-2) is The ratio is preferably 2: 1 to 40: 1. If the ratio of the polyether polyol (a12-2) is less than the lower limit, the crosslink density of the water-stopping material is lowered and the strength tends to be lowered. If the ratio of the polyether polyol (a12-2) exceeds the upper limit, the viscosity of the isocyanate group-terminated prepolymer tends to be high, and workability tends to deteriorate.
  • the aromatic isocyanate group-terminated prepolymer (a1) used in the present invention comprises the polyether polyol (a12) and the aromatic polyisocyanate (a11) as active hydrogen groups derived from the polyether polyol (a12). Is obtained by reacting the aromatic polyisocyanate (a11) -derived isocyanate group (NCO group) in an excessive amount.
  • the ratio of the isocyanate group to the active hydrogen group is preferably 1.1: 1 to 3: 1.
  • a known method can be appropriately employed.
  • a mixture of the aromatic polyisocyanate (a11) and the polyether polyol (a12) can be used at 1 to 48 at 40 to 100 ° C. The method of stirring for a time is mentioned.
  • the isocyanate group (NCO group) content in the aromatic isocyanate group-terminated prepolymer (a1) is preferably 0.5 to 15% by mass, and more preferably 1.0 to 5% by mass.
  • the isocyanate group content is less than 0.5% by mass, the molecular weight becomes too large, so there is a problem that the viscosity of the isocyanate group-terminated prepolymer becomes high, and when it exceeds 15% by mass, when reacting with moisture in the air, Since the amount of carbon dioxide generated is too large, there is a problem that air bubbles increase in the water stop material obtained after curing.
  • the aliphatic organic polyisocyanate (a2) used in the present invention is an isocyanurate group-containing organic polyisocyanate (a21), an allophanate group-containing organic polyisocyanate (a22), a functional group number of 2 to 3, and a molecular weight of 300.
  • Examples of the isocyanurate group-containing organic polyisocyanate (a21) include tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), 3-methyl-1,5-pentane diisocyanate, lysine diisocyanate and other aliphatic diisocyanates; Hydrogenated tolylene diisocyanate; Hydrogenated xylene diisocyanate; Hydrogenated diphenylmethane diisocyanate; Tetramethylxylene diisocyanate; Starting from aliphatic diisocyanates such as norbornene diisocyanate, an isocyanuration catalyst is added according to a known synthesis method.
  • HDI hexamethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • 3-methyl-1,5-pentane diisocyanate lysine diisocyanate and other aliphatic diisocyanates
  • the polymerization method for example, first, a mixture of the aliphatic diisocyanate and the isocyanurate-forming catalyst is stirred at 40 to 150 ° C. for 1 to 10 hours, and then the isocyanurate-forming catalyst is deactivated. Depending on the method, a method of distilling off the unreacted aliphatic diisocyanate may be mentioned.
  • the isocyanurate-forming catalyst include organometallic compounds such as potassium acetate, quaternary ammonium salts and the like. The addition amount of such an isocyanurate-forming catalyst is preferably 0.0001 to 0.1 parts by mass with respect to 100 parts by mass of the aliphatic diisocyanate.
  • the allophanate group-containing organic polyisocyanate (a22) includes the aliphatic diisocyanate and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, cyclohexanol, 2-ethylhexanol, tridecanol.
  • an active hydrogen group-containing compound having 1 to 3 functional groups (number of active hydrogen groups) such as glycerin and a molecular weight of 300 or less as a raw material
  • an allophanatization catalyst is added and reacted according to a known synthesis method.
  • the molecular weight of the active hydrogen group-containing compound is preferably 32 to 300.
  • the allophanatization catalyst is added to a mixture in which the mass ratio of the aliphatic diisocyanate and the active hydrogen group-containing compound is 95: 5 to 60:40, and 90 to 150
  • the method include stirring at 1 ° C. for 1 to 10 hours, then deactivating the allophanatization catalyst, and removing the unreacted aliphatic diisocyanate by distillation if necessary.
  • the allophanatization catalyst include organometallic compounds such as tin octylate, and the addition amount of the allophanate catalyst is 0 with respect to 100 parts by mass of the mixture of the aliphatic diisocyanate and the active hydrogen group-containing compound. It is preferably 0.0001 to 0.1 parts by mass.
  • the reaction product (a23) of the active hydrogen group-containing compound and the aliphatic diisocyanate is the same aliphatic diisocyanate as described above, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerin, etc. have 2 to 3 functional groups and a molecular weight. It is obtained by reacting with an active hydrogen group-containing compound that is 300 or less.
  • the molecular weight of the active hydrogen group-containing compound is preferably 62 to 300.
  • the reaction method for example, first, the aliphatic diisocyanate and the active hydrogen group-containing compound are mixed at a mass ratio of 90:10 to 60:40 and stirred at 40 to 100 ° C. for 1 to 10 hours. Then, a method of distilling off the unreacted aliphatic diisocyanate as necessary is exemplified.
  • Examples of the aliphatic organic polyisocyanate (a2) include the isocyanurate group-containing organic polyisocyanate (a21), the allophanate group-containing organic polyisocyanate (a22), the number of functional groups of 2 to 3, and a molecular weight of 300.
  • the reaction product (a23) of the following active hydrogen group-containing compound and aliphatic diisocyanate these may be used alone or in combination of two or more at any ratio. At the same time, two or more of these may be synthesized and used.
  • the isocyanate group (NCO group) content in the aliphatic organic polyisocyanate (a2) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.
  • the isocyanate group content is less than 5% by mass, the molecular weight becomes too large and the blending amount with respect to the aromatic isocyanate group-terminated prepolymer (a1) increases, so that the magnification when the water-stopping material expands with water is increased.
  • the gap between the steel sheet piles may not be filled, and if it exceeds 40% by mass, the molecule of the organic polyisocyanate becomes small, so that it tends to volatilize and there is a problem that the odor is tight.
  • the ratio of the aromatic isocyanate group-terminated prepolymer (a1) to the aliphatic organic polyisocyanate (a2) is the ratio of isocyanate groups (isocyanate group of a1).
  • the number of isocyanate groups in a2) is from 8: 1 to 1: 4, and preferably from 6: 1 to 1: 1.
  • the amount of the aromatic isocyanate group-terminated prepolymer (a1) is larger than the above range, the strength, heat resistance, and consequently water-stop properties of the water-stopping material are likely to be adversely affected.
  • the amount of the aliphatic organic polyisocyanate (a2) is larger than the above range, the magnification when the water-stopping material expands with water becomes low, so that there is a possibility that the gap between the steel sheet piles cannot be filled.
  • organic polyisocyanate composition (A) used in the present invention other known stabilizers such as phosphate esters (trade name JP-508, manufactured by Johoku Chemical Industry Co., Ltd.), antifoaming agents (trade name BYK-A535, (Bikchemy Co., Ltd.) and additives such as plasticizers can be further contained.
  • phosphate esters trade name JP-508, manufactured by Johoku Chemical Industry Co., Ltd.
  • antifoaming agents trade name BYK-A535, (Bikchemy Co., Ltd.
  • additives such as plasticizers
  • amine-based polyol (B) used in the present invention a polyamine polyol obtained by adding an alkylene oxide to a compound having an amino group as an initiator can be used.
  • the compound having an amino group used for the initiator include aliphatic amines such as ammonia, ethylenediamine, hexamethylenediamine, isophoronediamine, and diethylenetriamine; aromatic amines such as tolylenediamine and diphenylaminomethane.
  • amine polyols having a highly basic aliphatic amine as an initiator are preferred in that the curing time can be shortened.
  • the number of functional groups of the amine polyol (B) is preferably 3-6. If the number of functional groups is less than 3, the strength, heat resistance, and eventually water-stopping properties of the water-stopping material are likely to be adversely affected. When the number of functional groups is larger than 6, the viscosity becomes high and handling is difficult.
  • the hydroxyl value of the amine polyol (B) is preferably 250 to 1,200.
  • the hydroxyl value is less than 250, the blending amount increases, and further, the distance between the cross-linking points increases, so that the strength, heat resistance, and consequently water-stopping property of the water-stopping material are easily adversely affected.
  • the hydroxyl value is greater than 1,200, the molecular weight is small, and therefore, it tends to volatilize and problems with odor are likely to occur.
  • the ratio between the organic polyisocyanate composition (A) and the amine-based polyol (B) is such that the isocyanate group derived from the aromatic isocyanate group-terminated prepolymer (a1) and the amine-based polyol (B). It is desirable that the ratio (number of isocyanate groups: number of hydroxyl groups) to hydroxyl groups derived from is 2: 1 to 8: 1. If there are more hydroxyl groups than the above upper limit, the urethane bond, which has a lower cohesive force than the urea bond produced when reacting with moisture in the air, will increase, and this will have an adverse effect on the strength, heat resistance, and thus water stoppage of the waterstop material. Cheap. When the number of hydroxyl groups is less than the lower limit, crosslinking by the amine-based polyol (B) is reduced, and thus the strength, heat resistance, and consequently water-stop properties of the water-stopping material are likely to be adversely affected.
  • the plasticizer (C) used in the present invention may be any known plasticizer, for example, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, di-2-ethylhexyl phthalate, phthalic acid Diisononyl, diisodecyl phthalate, butyl benzyl phthalate, diethyl adipate, dibutyl adipate, dihexyl adipate, diethylhexyl adipate, diisononyl adipate, diisodecyl adipate, bis (butyldiglycol) adipate, diethyl sebacate, sebacin Dibutyl acid, dihexyl sebacate, di-2-ethylhexyl sebacate, dimethyl maleate, diethyl maleate, dibutyl maleate, dihexyl maleate, di-2-ethylhe
  • 1-phenyl-1-xylylethane 1-phenyl-1-ethylphenylethane, and diisodecyl phthalate are preferable because a water-stopping material having good hydrolysis resistance can be obtained.
  • the proportion of the plasticizer (C) is not particularly limited, but preferably the mass of the plasticizer (C) is the above. It is good to set it as the quantity which does not exceed the total mass of an aromatic isocyanate group terminal prepolymer (a1) and the said aliphatic organic polyisocyanate (a2). If the ratio of the plasticizer (C) is too large, the magnification when the water-stopping material expands with water becomes low, and therefore there is a possibility that the gap between the steel sheet piles cannot be filled.
  • any ordinary catalyst that promotes the urethanization reaction can be used.
  • Carboxylic acid salts carboxylic acid metal salts such as potassium acetate, potassium octylate and tin octylate; and organometallic compounds such as dibutyltin laurate.
  • the polyurethane resin-forming composition of the present invention preferably contains the catalyst (D) from the viewpoint of shortening the curing time.
  • the amount used is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 2 parts by mass with respect to 100 parts by mass of the organic polyisocyanate composition (A). is there. If the amount is less than the above range, the curing time tends not to be shortened. If the amount of the catalyst (C) used is more than the above range, the curing time after blending is shortened, which may cause problems in workability. There is.
  • the water-swellable water-stopping material of the present invention can be obtained by curing the polyurethane resin-forming composition of the present invention, and is preferably used as a water-stopping material for steel sheet piles.
  • a known method can be appropriately employed. Examples thereof include a method in which the polyurethane resin-forming composition of the present invention is allowed to stand at 0 to 40 ° C. for 1 to 96 hours.
  • C-2770 HDI allophanate (manufactured by Nippon Polyurethane Industry Co., Ltd., NCO group content 19.4% by mass)
  • C-HL Adduct body of HDI (manufactured by Nippon Polyurethane Industry Co., Ltd., NCO group content 12.8% by mass)
  • MR-200 Polymeric MDI (manufactured by Nippon Polyurethane Industry Co., Ltd., NCO group content 30.7% by mass)
  • Curing agents “H1” to “H14” were obtained by using the compounds described in the raw materials of the following curing agents and mixing and stirring the components in the combinations and blending ratios shown in Table 2 until they were uniform at room temperature.
  • the curing agent was mixed with the main agent in the amounts shown in Table 3, and placed on a plastic tray having a length of 19 cm, a width of 10 cm, and a depth of 2 cm installed on a horizontal table. After pouring to a thickness of 2 mm, the cured film-like water-stopping material obtained every 4 hours by leaving at 25 ° C. is immersed in ion-exchanged water at 25 ° C. for 24 hours, and JIS No. 2 according to JIS K6251. It was punched with a dumbbell, and the tensile strength was measured at 300 mm / min using this as a test piece. The results are shown in Table 3. The time at which a tensile strength equivalent to that obtained by curing for 48 hours was taken as the curing time.
  • the ratio of the tensile strength (N) after water swelling after heating abuse to the tensile strength (N) after water swelling after room temperature curing was calculated as the heating abuse maintenance rate.
  • the results are shown in Table 3. Heat abuse maintenance rate: 80% or more is acceptable.
  • the waterstop material of the present invention obtained by adding the aliphatic organic polyisocyanate (a2) to the aromatic isocyanate group-terminated prepolymer (a1), there is a difference in the reaction rate of the isocyanate group.
  • the isocyanate group of the fast-reacting aromatic isocyanate-terminated prepolymer (a1) reacts with moisture taken in from the air to become an amino-terminated terminal, and then the slow-reacting aliphatic organic polyisocyanate (a2) isocyanate Because of the stepwise cross-linking effect that the group reacts with the amino group terminal to form a urea bond, as shown in Table 3, high post-water swelling tensile strength can be obtained even after heat abuse.
  • the water-stopping material to which the aliphatic organic polyisocyanate (a2) is not added has no difference in the reaction rate of the isocyanate group, the reaction between the isocyanate group and moisture is performed simultaneously.
  • the cross-linking effect of further reacting an amino group, which is a reaction product of water and an isocyanate group, with an unreacted isocyanate group is reduced, so that the tensile strength after water swelling after heat abuse is lowered.
  • the thing with little addition amount of the said aliphatic organic polyisocyanate (a2) similarly falls the tensile strength after water swelling.
  • the amount of the aliphatic organic polyisocyanate (a2) added is too large, the content of the isocyanate group-terminated prepolymer and the content of the oxyethylene group are relatively decreased, so that the volume swelling ratio is decreased.
  • the addition of aromatic polyisocyanate in place of the aliphatic organic polyisocyanate (a2) provides a certain degree of tensile strength after water swelling after curing at room temperature. Since the group urea bond is more likely to occur, the decrease in tensile strength after water swelling after heat abuse is significant.
  • the urethane bond is more excellent in hydrolysis resistance than the urea bond, and thus further excellent heat resistance. Properties are obtained, and there is almost no decrease in tensile strength after water swelling after heat abuse.
  • the ratio of isocyanate groups derived from the aromatic isocyanate group-terminated prepolymer (a1) to hydroxyl groups derived from the amine polyol (B) (number of isocyanate groups: number of hydroxyl groups) is more than 2: 1.
  • the ratio of the isocyanate group derived from the aromatic isocyanate group-terminated prepolymer (a1) to the hydroxyl group derived from the amine-based polyol (B) (number of isocyanate groups: number of hydroxyl groups) is less than 8: 1 Since the crosslinking effect by addition of the amine-based polyol (B) cannot be obtained, the heat abuse maintenance rate is low, and the decrease in tensile strength after water swelling after heat abuse is remarkable.
  • the present invention it is possible to provide a water-swellable water-stopping material that is rich in heat resistance and has sufficient durability against frictional heat, and a polyurethane resin-forming composition used therefor. Further, by providing a polyurethane resin-forming composition of the present invention with a catalyst, a polyurethane resin-forming composition having a suitable formability of curing in a short time while ensuring a sufficient working time is provided. Can do. Accordingly, the polyurethane resin-forming composition of the present invention and the water-swellable water-stopping material obtained thereby are preferably used as joint materials for civil engineering and building applications for the purpose of water-stopping, caulking materials, water-stopping materials for steel sheet piles, and the like. Can be used.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Sealing Material Composition (AREA)

Abstract

L'invention porte sur une composition formant de la résine de polyuréthane contenant : un prépolymère terminé par isocyanate aromatique (a1) ; un ou plusieurs composés polyisocyanates organiques aliphatiques (a2) choisis dans un groupe spécifié ; et une composition de polyisocyanate organique pour l'hydrofugation de (A) ayant une proportion en nombre et une teneur en groupes isocyanates dans un intervalle défini et un polyol d'amine (B) ayant une fonctionnalité nominale moyenne de 3-6, le rapport des groupes isocyanates aux groupes hydroxyles de celui-ci étant dans une plage spécifiée. Dans la présente invention, le prépolymère (A1) est un produit réactionnel d'un polyisocyanate aromatique (a11) et d'un polyol de polyéther (a12) et le polyol de polyéther (a12) comprend un polyéthylpoloyl (a12-1) ayant une fonctionnalité nominale moyenne de 2 et une teneur en groupes oxyéthylènes dans une plage spécifiée et un polyéthylpoloyl (a12-2) ayant une fonctionnalité nominale moyenne de 3 et une teneur en groupes oxyéthylènes dans une plage spécifiée.
PCT/JP2011/054028 2010-03-31 2011-02-23 Composition formant de la résine de polyuréthane et matériau d'étanchéité à l'eau gonflant à l'eau pour palplanche métallique WO2011122180A1 (fr)

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Cited By (1)

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CN102492288A (zh) * 2011-11-30 2012-06-13 上海东大化学有限公司 钢板桩围堰增强堵漏材料及其制备使用方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7060997B2 (ja) 2018-04-02 2022-04-27 株式会社日立ハイテク 温度制御装置、及び遺伝子検査装置
JP7264509B2 (ja) 2019-01-18 2023-04-25 日本化学塗料株式会社 硬化性水膨張止水材、止水鋼矢板、止水鋼矢板製造方法および止水工法

Citations (6)

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JPS5794056A (en) * 1980-12-02 1982-06-11 Dainippon Ink & Chem Inc Moisture-curing waterproof coating material
JPH05209165A (ja) * 1992-01-30 1993-08-20 Sunstar Eng Inc ウレタン系シーリング材
JPH06157708A (ja) * 1992-07-28 1994-06-07 Nippon Polyurethane Ind Co Ltd ポリウレタン系エラストマー用組成物
JPH08151424A (ja) * 1994-11-29 1996-06-11 Nippon Polyurethane Ind Co Ltd ポリウレタン樹脂組成物並びに該組成物を用いた接着剤、シール剤及び結束剤
JPH08169930A (ja) * 1994-10-19 1996-07-02 Nippon Polyurethane Ind Co Ltd ポリウレタン樹脂組成物並びに該組成物を用いた接着剤、シール剤及び結束剤
JP2000038567A (ja) * 1998-07-22 2000-02-08 Nippon Polyurethane Ind Co Ltd 加熱硬化型ウレタンシーリング材

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5794056A (en) * 1980-12-02 1982-06-11 Dainippon Ink & Chem Inc Moisture-curing waterproof coating material
JPH05209165A (ja) * 1992-01-30 1993-08-20 Sunstar Eng Inc ウレタン系シーリング材
JPH06157708A (ja) * 1992-07-28 1994-06-07 Nippon Polyurethane Ind Co Ltd ポリウレタン系エラストマー用組成物
JPH08169930A (ja) * 1994-10-19 1996-07-02 Nippon Polyurethane Ind Co Ltd ポリウレタン樹脂組成物並びに該組成物を用いた接着剤、シール剤及び結束剤
JPH08151424A (ja) * 1994-11-29 1996-06-11 Nippon Polyurethane Ind Co Ltd ポリウレタン樹脂組成物並びに該組成物を用いた接着剤、シール剤及び結束剤
JP2000038567A (ja) * 1998-07-22 2000-02-08 Nippon Polyurethane Ind Co Ltd 加熱硬化型ウレタンシーリング材

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102492288A (zh) * 2011-11-30 2012-06-13 上海东大化学有限公司 钢板桩围堰增强堵漏材料及其制备使用方法

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