Two-pack curable polyurethane resin composition

Abstract

To provide a two-pack curable polyurethane resin composition having an excellent pot life.SOLUTION: The two-pack curable polyurethane resin composition contains a main agent, a curing agent, and a hydroxide of an alkaline earth metal. The main agent contains an isocyanate group-terminated prepolymer. The curing agent contains a polyamine component.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a two-component curable polyurethane resin composition. [Background technology]

[0002] The two-component curing polyurethane resin composition is a curable composition containing a base agent and a curing agent. The base agent and the curing agent are mixed when used to form a polyurethane resin. The base agent contains, for example, an isocyanate group-terminated prepolymer, and the curing agent contains, for example, a polyamine component.

[0003] More specifically, the following two-component mixed room temperature curing paving material has been proposed as a two-component curing polyurethane resin composition. This two-component mixed room temperature curing paving material contains a base agent and a curing agent. The base agent contains a urethane prepolymer obtained by reacting polypropylene ether diol with tolylene diisocyanate. The curing agent contains dimethylthiotoluenediamine (product name Ethacure 300, manufactured by Albemarle), diisononyl phthalate as a plasticizer, calcium carbonate as a filler, and octylic acid as a catalyst (see, for example, Patent Document 1 (Level 1)). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2019-070255 A Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, two-component curing polyurethane resin compositions are required to have a longer pot life (workable time) depending on the application.

[0006] The present invention is a two-component curable polyurethane resin composition having an excellent pot life. [Means for solving the problem]

[0007] The present invention [1] comprises a two-component curing polyurethane resin composition containing a base agent containing an isocyanate-terminated prepolymer, a curing agent containing a polyamine component, and an alkaline earth metal hydroxide.

[0008] The present invention [2] comprises the two-component curing polyurethane resin composition according to the above [1], in which the ratio of the alkaline earth metal hydroxide is 10 to 1000 parts by mass per 100 parts by mass of the polyamine component.

[0009] The present invention [3] comprises the two-component curing polyurethane resin composition according to the above [1] or [2], wherein the polyamine component contains at least one selected from the group consisting of diethyltoluenediamine, halogenated diethyltoluenediamine, and dimethylthiotoluenediamine.

[0010] The present invention [4] comprises the two-component curing polyurethane resin composition according to any one of the above [1] to [3], in which the hydroxide of the alkaline earth metal contains calcium hydroxide.

[0011] The present invention [5] comprises the two-component curing polyurethane resin composition according to any one of the above [1] to [4], in which the curing agent further contains a polyol component. Effect of the Invention

[0012] In the two-component curing polyurethane resin composition of the present invention, the base agent contains an isocyanate-terminated prepolymer, and the curing agent contains a polyamine component. The two-component curing polyurethane resin composition further contains an alkaline earth metal hydroxide. Therefore, the two-component curing polyurethane resin composition has an excellent pot life. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] [1] Two-component curing polyurethane resin composition The two-component curing polyurethane resin composition is a resin composition (resin kit). The two-component curing polyurethane resin composition contains a curing agent and a base agent. The base agent and the curing agent are each prepared as an independent package. When using the two-component curing polyurethane resin composition, the base agent and the curing agent are mixed to form a polyurethane resin.

[0014] More specifically, the two-component curing polyurethane resin composition contains a base agent, a curing agent, and a hydroxide of an alkaline earth metal.

[0015] (1) Base The base material is an isocyanate group-containing component. The base material contains an isocyanate group-terminated prepolymer. The base material is preferably made of an isocyanate group-terminated prepolymer.

[0016] The isocyanate-terminated prepolymer is a reaction product between a raw material polyisocyanate and a raw material polyol.

[0017] [Raw material polyisocyanate] Examples of the raw polyisocyanate include polyisocyanate monomers and polyisocyanate derivatives. Examples of the polyisocyanate monomers include aromatic polyisocyanates, aliphatic polyisocyanates, and araliphatic polyisocyanates. Examples of the aromatic polyisocyanates include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), toluidine diisocyanate (TODI), paraphenylene diisocyanate, and naphthalene diisocyanate (NDI). Examples of the aliphatic polyisocyanates include linear aliphatic polyisocyanates and alicyclic polyisocyanates. Examples of the linear aliphatic polyisocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), and hexamethylene diisocyanate (HDI). Examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), methylene bis(cyclohexyl isocyanate) (H 12 Examples of the aromatic aliphatic polyisocyanate include xylylene diisocyanate (XDI) and tetramethyl xylylene diisocyanate (TMXDI). The polyisocyanate monomers can be used alone or in combination of two or more. Examples of the polyisocyanate derivatives include modified products obtained by modifying polyisocyanate monomers by known methods. Examples of the modified products include uretdione modified products, isocyanurate modified products, allophanate modified products, polyol modified products, biuret modified products, urea modified products, oxadiazinetrione modified products, and carbodiimide modified products. These can be used alone or in combination of two or more.

[0018] The raw material polyisocyanate can be used alone or in combination of two or more kinds. As the raw material polyisocyanate, preferably, polyisocyanate monomer is used, more preferably, diisocyanate monomer is used. As the polyisocyanate monomer, more preferably, aromatic polyisocyanate is used, further preferably, diphenylmethane diisocyanate (MDI) and tolylene diisocyanate (TDI) are used, and particularly preferably, tolylene diisocyanate (TDI) is used.

[0019] Examples of tolylene diisocyanate include 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate. These can be used alone or in combination of two or more. As tolylene diisocyanate, a preferred example is a combination of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate. In addition, as tolylene diisocyanate, a preferred example is the use of 2,4-tolylene diisocyanate alone. When these are used, particularly excellent mechanical properties can be obtained.

[0020] As the tolylene diisocyanate, a combination of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate is particularly preferred. When 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate are used in combination, the content of 2,4-tolylene diisocyanate is, for example, 40 to 95 mass%, preferably 60 to 90 mass%, based on the total amount of them. Also, the content of 2,6-tolylene diisocyanate is, for example, 5 to 60 mass%, preferably 10 to 40 mass%.

[0021] [Raw polyol] Examples of the raw material polyol include low molecular weight polyols and high molecular weight polyols.

[0022] The low-molecular-weight polyol is an organic compound having two or more hydroxyl groups in the molecule and a relatively low molecular weight. The molecular weight of the low-molecular-weight polyol is, for example, 40 or more and less than 400, and preferably 300 or less.

[0023] Examples of low molecular weight polyols include dihydric alcohols, trihydric alcohols, and tetrahydric or higher alcohols. Examples of dihydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and dipropylene glycol. Examples of trihydric alcohols include glycerin and trimethylolpropane. Examples of tetrahydric or higher alcohols include pentaerythritol and diglycerin. Examples of low molecular weight polyols include polymers obtained by addition polymerization of alkylene (C2-3) oxide with dihydric to tetrahydric alcohols so that the number average molecular weight is less than 400. These can be used alone or in combination of two or more types.

[0024] The high molecular weight polyol has two or more hydroxyl groups in the molecule and is a relatively high molecular weight organic compound. The number average molecular weight of the high molecular weight polyol is, for example, 400 or more, preferably 500 or more, and for example, 20000 or less. The number average molecular weight can be calculated by a known method from the hydroxyl group equivalent and the average number of hydroxyl groups. The number average molecular weight can be measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (hereinafter the same).

[0025] Examples of high molecular weight polyols include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer modified polyols. These can be used alone or in combination of two or more kinds.

[0026] The raw material polyols can be used alone or in combination of two or more kinds. The raw material polyol is preferably a high molecular weight polyol.

[0027] The high molecular weight polyol is preferably a polyether polyol. That is, the high molecular weight polyol preferably contains a polyether polyol, and more preferably consists of a polyether polyol.

[0028] Examples of polyether polyols include polyoxyalkylene polyols, such as polyoxyalkylene (carbon number (C) 2-3) polyols and polytetramethylene ether polyols.

[0029] Examples of polyoxyalkylene (C2-3) polyols include polyoxyethylene polyols, polyoxypropylene polyols, polyoxytriethylene polyols, and polyoxyethylene-polyoxypropylene polyols (random or block copolymers).

[0030] Examples of polytetramethylene ether polyols include ring-opening polymers (crystalline polytetramethylene ether glycol) obtained by cationic polymerization of tetrahydrofuran. Examples of polytetramethylene ether polyols include amorphous polytetramethylene ether glycol. In amorphous polytetramethylene ether glycol, tetrahydrofuran is copolymerized with alkyl-substituted tetrahydrofuran and / or dihydric alcohol. Crystallinity refers to the property of being solid at 25°C. Amorphous refers to the property of being liquid at 25°C.

[0031] The polyether polyols can be used alone or in combination of two or more kinds. As the polyether polyol, a preferable example is polyoxyalkylene (C2-3) polyol.

[0032] The average number of hydroxyl groups in the polyether polyol is, for example, 2.0 to 6.0, preferably 2.0 to 4.0, and more preferably 2.0 to 3.0.

[0033] The polyether polyol preferably contains two or more kinds of polyether polyols, and more preferably contains a polyoxyalkylene (C2-3) polyol having an average number of hydroxyl groups of 2.0 and a polyoxyalkylene (C2-3) polyol having an average number of hydroxyl groups of 3.0. The content ratio of the polyoxyalkylene (C2-3) polyol having an average number of hydroxyl groups of 2.0 and the polyoxyalkylene (C2-3) polyol having an average number of hydroxyl groups of 3.0 is appropriately set depending on the purpose and application. For example, the polyoxyalkylene (C2-3) polyol having an average number of hydroxyl groups of 2.0 is, for example, 20 to 90 mass%, preferably 40 to 80 mass%, more preferably 50 to 70 mass%, and even more preferably 55 to 65 mass%, based on the total amount of the polyoxyalkylene (C2-3) polyol having an average number of hydroxyl groups of 2.0 and the polyoxyalkylene (C2-3) polyol having an average number of hydroxyl groups of 3.0. Also, the polyoxyalkylene (C2-3) polyol having an average number of hydroxyl groups of 3.0 is, for example, 10 to 80 mass%, preferably 20 to 60 mass%, more preferably 30 to 50 mass%, and even more preferably 35 to 45 mass%.

[0034] The number average molecular weight of the polyether polyol is, for example, 400 to 15,000, preferably 500 to 13,000, more preferably 1,000 to 10,000, and still more preferably 2,000 to 5,000.

[0035] The polyether polyol preferably contains two or more kinds of polyether polyols, and more preferably contains a polyoxyalkylene (C2-3) polyol having a number average molecular weight of less than 500 and a polyoxyalkylene (C2-3) polyol having a number average molecular weight of 500 or more. The content ratio of the polyoxyalkylene (C2-3) polyol having a number average molecular weight of less than 500 and the polyoxyalkylene (C2-3) polyol having a number average molecular weight of 500 or more is appropriately set according to the purpose and application. For example, the content of the polyoxyalkylene (C2-3) polyol having a number average molecular weight of less than 500 is, for example, 1 to 30 mass%, preferably 3 to 20 mass%, more preferably 5 to 10 mass%, based on the total amount of the polyoxyalkylene (C2-3) polyol having a number average molecular weight of less than 500 and the polyoxyalkylene (C2-3) polyol having a number average molecular weight of 500 or more. The content of polyoxyalkylene (C2-3) polyol having a number average molecular weight of 500 or more is, for example, 70 to 99 mass %, preferably 80 to 97 mass %, and more preferably 90 to 95 mass %.

[0036] [Preparation of base agent] The base material (base material containing an isocyanate group-terminated prepolymer) can be obtained, for example, by reacting a raw material polyisocyanate with a raw material polyol in a predetermined ratio.

[0037] The mixing ratio of the raw polyisocyanate and the raw polyol is adjusted so that the isocyanate groups are in excess relative to the hydroxyl groups. More specifically, the equivalent ratio of the isocyanate groups in the raw polyisocyanate to the hydroxyl groups in the raw polyol (isocyanate groups / hydroxyl groups) is, for example, 1.2 to 10, preferably 1.5 to 5, and more preferably 1.8 to 2.5.

[0038] The reaction method is not particularly limited. Specific examples of the reaction method include bulk polymerization and solution polymerization. In bulk polymerization, for example, raw material polyisocyanate and raw material polyol are reacted under a nitrogen gas flow. The reaction temperature is, for example, 50 to 250°C, preferably 70 to 200°C. The reaction time is, for example, 0.5 to 24 hours, preferably 1 to 15 hours. In solution polymerization, raw material polyisocyanate and raw material polyol are reacted in the presence of a known organic solvent. The reaction temperature is, for example, 50 to 120°C, preferably 70 to 100°C. The reaction time is, for example, 0.5 to 24 hours, preferably 1 to 15 hours.

[0039] In addition, in the above reaction, a known urethanization catalyst can be added as necessary. Examples of the urethanization catalyst include amine catalysts and organometallic catalysts. The ratio of the urethanization catalyst added is appropriately set according to the purpose and application.

[0040] The reaction between the raw polyisocyanate and the raw polyol produces a reaction liquid containing an isocyanate-terminated prepolymer. The reaction liquid can be used as a base resin.

[0041] The reaction product liquid obtained by the above reaction can contain unreacted raw material polyisocyanate in addition to the isocyanate-terminated prepolymer. In other words, the base material can contain unreacted raw material polyisocyanate in addition to the isocyanate-terminated prepolymer.

[0042] The base material may not contain unreacted raw polyisocyanate. When a base material that does not contain unreacted raw polyisocyanate is required, the unreacted raw polyisocyanate is removed from the reaction product liquid. Examples of the removal method include a distillation method and an extraction method.

[0043] In addition, by selecting an equivalent ratio and reaction conditions in which no unreacted raw polyisocyanate is produced in the reaction between the raw polyisocyanate and the raw polyol, it is also possible to obtain a reaction product liquid (base material) that does not contain unreacted raw polyisocyanate.

[0044] The isocyanate group concentration of the base resin (isocyanate group content, NCO%) is, for example, 1.0 to 10.0 mass%, preferably 1.5 to 5.0 mass%, more preferably 2.0 to 4.0 mass%. The isocyanate group concentration is measured in accordance with the isocyanate group content test described in JIS K 7301 (1995).

[0045] In the two-component curing polyurethane resin composition, the base agent is prepared separately from the curing agent described below, and is mixed with the curing agent when the two-component curing polyurethane resin composition is used. The mixing ratio of the base agent and the curing agent will be described later.

[0046] (2) Hardener The curing agent is a component containing an active hydrogen group. Examples of the active hydrogen group include an amino group and a hydroxyl group. The curing agent contains a polyamine component as an essential component.

[0047] [Polyamine component] The polyamine component includes a compound containing two or more amino groups in one molecule, and more specifically, examples of the polyamine component include aromatic polyamines, araliphatic polyamines, and aliphatic polyamines.

[0048] Examples of aromatic polyamines include aromatic diamines. Examples of aromatic diamines include diethyltoluenediamine, dimethylthiotoluenediamine, 4,4'-diphenylmethanediamine, 3,3'-dichloro-4,4'-diphenylmethanediamine (MOCA), 4,4'-methylenebis(n-sec-butylaniline), 4,4'-methylenebis(2,6-diethylaniline), 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, and tetrachloro-4,4'-diaminodiphenylmethane. Examples of aromatic polyamines include diethyltoluenediamine and bis(methylthio)toluenediamine. Examples of diethyltoluenediamine include 2,4-diethyltoluenediamine and 2,6-diethyltoluenediamine. Examples of bis(methylthio)toluenediamine include bis(methylthio)-2,4-toluenediamine and bis(methylthio)-2,6-toluenediamine, which may be used alone or in combination of two or more.

[0049] Examples of the aromatic aliphatic polyamine include aromatic aliphatic diamines. Examples of the aromatic aliphatic diamine include 1,3-xylylenediamine and 1,4-xylylenediamine. These may be used alone or in combination of two or more.

[0050] Examples of the aliphatic polyamine include linear aliphatic polyamines and alicyclic polyamines.

[0051] Examples of the chain aliphatic polyamine include chain aliphatic diamine. Examples of the chain aliphatic diamine include ethylenediamine, propylenediamine, pentamethylenediamine, hexamethylenediamine, hydrazine, 1,2-diaminoethane, 1,2-diaminopropane, and 1,3-diaminopentane. These may be used alone or in combination of two or more.

[0052] Examples of alicyclic polyamines include alicyclic diamines. Examples of alicyclic diamines include 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis-(4-aminocyclohexyl)methane, diaminocyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminoethyl)cyclohexane and 1,4-bis(aminoethyl)cyclohexane. These can be used alone or in combination of two or more.

[0053] The polyamine component may also contain a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. The halogen atom may be used alone or in combination of two or more. Examples of the halogen atom include preferably chlorine and bromine, and more preferably chlorine.

[0054] More specifically, the polyamine component containing halogen atoms includes, for example, aromatic polyamines containing halogen atoms (hereinafter, halogen-containing aromatic polyamines), aromatic aliphatic polyamines containing halogen atoms (hereinafter, halogen-containing aromatic aliphatic polyamines), and the above-mentioned aliphatic polyamines containing halogen atoms (hereinafter, halogen-containing aliphatic polyamines). These are used alone or in combination of two or more kinds. The polyamine component containing halogen atoms is preferably aromatic polyamines containing halogen atoms.

[0055] Examples of halogen-containing aromatic polyamines include halogenated diethyltoluenediamine. Halogenated diethyltoluenediamine is a halogenated product of diethyltoluenediamine. Examples of diethyltoluenediamine include 2,4-diethyltoluenediamine and 2,6-diethyltoluenediamine. These can be used alone or in combination of two or more kinds.

[0056] That is, halogenated diethyltoluenediamine is a compound in which the hydrogen atom directly bonded to the benzene ring of diethyltoluenediamine is replaced with a halogen atom. Halogenated diethyltoluenediamine includes a compound in which the hydrogen at the 6th position of 2,4-diethyltoluenediamine is replaced with a halogen atom. Also, halogenated diethyltoluenediamine includes a compound in which the hydrogen at the 4th position of 2,6-diethyltoluenediamine is replaced with a halogen atom.

[0057] Examples of halogenated diethyltoluene diamines include 4-chloro-3,5-diethyltoluene-2,6-diamine, 6-chloro-3,5-diethyltoluene-2,4-diamine, 4-bromo-3,5-diethyltoluene-2,6-diamine, and 6-bromo-3,5-diethyltoluene-2,4-diamine. These can be used alone or in combination of two or more. Examples of halogenated diethyltoluene diamines include 4-chloro-3,5-diethyltoluene-2,6-diamine and 6-chloro-3,5-diethyltoluene-2,4-diamine.

[0058] The polyamine component may be used alone or in combination of two or more kinds. From the viewpoint of pot life and mechanical properties, the polyamine component is preferably an aromatic polyamine (including an aromatic polyamine containing a halogen atom), more preferably diethyltoluenediamine, halogenated diethyltoluenediamine, and dimethylthiotoluenediamine.

[0059] That is, the polyamine component preferably contains an aromatic polyamine (including an aromatic polyamine containing a halogen atom), and more preferably contains at least one selected from the group consisting of diethyltoluenediamine, halogenated diethyltoluenediamine, and dimethylthiotoluenediamine.

[0060] [Polyol component] The curing agent may contain a polyol component as an optional component. The curing agent preferably contains a polyol component. That is, the curing agent preferably contains both a polyamine component and a polyol component.

[0061] The polyol component includes, for example, the above-mentioned low molecular weight polyols and high molecular weight polyols.

[0062] Examples of the low molecular weight polyol include the low molecular weight polyols described above as the raw material polyols for the isocyanate-terminated prepolymer, more specifically, the dihydric alcohols, trihydric alcohols, and tetrahydric or higher alcohols. These may be used alone or in combination of two or more kinds.

[0063] Examples of the high molecular weight polyol include the high molecular weight polyols mentioned above as the raw material polyols for the isocyanate group-terminated prepolymer, and more specifically, polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer-modified polyols. These can be used alone or in combination of two or more kinds.

[0064] The polyol component may be used alone or in combination of two or more kinds. The polyol component preferably contains a high molecular weight polyol and does not contain a low molecular weight polyol. That is, the polyol component preferably consists of a high molecular weight polyol.

[0065] The high molecular weight polyol is preferably a polyether polyol. That is, the high molecular weight polyol preferably contains a polyether polyol, and more preferably consists of a polyether polyol.

[0066] Examples of the polyether polyol include the above-mentioned polyoxyalkylene polyols. Examples of the polyoxyalkylene polyol include the above-mentioned polyoxyalkylene (C2-3) polyols and the above-mentioned polytetramethylene ether polyols.

[0067] The polyether polyols can be used alone or in combination of two or more kinds. As the polyether polyol, a preferable example is polyoxyalkylene (C2-3) polyol.

[0068] The average number of hydroxyl groups in the polyether polyol is, for example, 2.0 to 6.0, preferably 2.0 to 4.0, more preferably 2.0 to 3.0, and still more preferably 2.0.

[0069] The number average molecular weight of the polyether polyol is, for example, 400 to 15,000, preferably 500 to 13,000, more preferably 1,000 to 10,000, still more preferably 2,000 to 5,000, and particularly preferably 2,000 to 3,000.

[0070] When the curing agent contains a polyamine component and a polyol component, the content ratio of these is appropriately set according to the purpose and use. For example, the ratio of the amino group of the polyamine component to the total amount (total moles) of the amino group of the polyamine component and the hydroxyl group of the polyol component is, for example, 50 to 99 mol%, preferably 60 to 90 mol%. Also, the ratio of the hydroxyl group of the polyol component to the total amount (total moles) of the amino group of the polyamine component and the hydroxyl group of the polyol component is, for example, 1 to 50 mol%, preferably 10 to 40 mol%.

[0071] In particular, from the viewpoint of pot life and tensile elongation, the upper limit of the ratio of the amino groups of the polyamine component to the total amount (total moles) of the amino groups of the polyamine component and the hydroxyl groups of the polyol component is more preferably 85 mol% or less, even more preferably 75 mol% or less, and especially preferably 65 mol% or less. Also, the lower limit of the ratio of the hydroxyl groups of the polyol component to the total amount (total moles) of the amino groups of the polyamine component and the hydroxyl groups of the polyol component is more preferably 15 mol% or more, even more preferably 25 mol% or more, and especially preferably 35 mol% or more. That is, from the viewpoint of pot life and tensile elongation, the ratio of the amino groups of the polyamine component to the total amount (total moles) of the amino groups of the polyamine component and the hydroxyl groups of the polyol component is more preferably 60 to 85 mol%, even more preferably 60 to 75 mol%, and especially preferably 60 to 65 mol%. Furthermore, the proportion of hydroxyl groups in the polyol component relative to the total amount (total moles) of amino groups in the polyamine component and hydroxyl groups in the polyol component is more preferably 15 to 40 mol%, further preferably 25 to 40 mol%, and particularly preferably 35 to 40 mol%.

[0072] In addition, from the viewpoint of hardness, tensile strength and tear strength, the lower limit of the ratio of the amino group of the polyamine component to the total amount (total moles) of the amino group of the polyamine component and the hydroxyl group of the polyol component is more preferably 65 mol% or more, even more preferably 75 mol% or more, and particularly preferably 85 mol% or more. In addition, the upper limit of the ratio of the hydroxyl group of the polyol component to the total amount (total moles) of the amino group of the polyamine component and the hydroxyl group of the polyol component is more preferably 35 mol% or less, even more preferably 25 mol% or less, and particularly preferably 15 mol% or less. That is, from the viewpoint of hardness, tensile strength and tear strength, the ratio of the amino group of the polyamine component to the total amount (total moles) of the amino group of the polyamine component and the hydroxyl group of the polyol component is more preferably 65 to 90 mol%, even more preferably 75 to 90 mol%, and particularly preferably 85 to 90 mol%. Furthermore, the proportion of hydroxyl groups in the polyol component relative to the total amount (total moles) of amino groups in the polyamine component and hydroxyl groups in the polyol component is more preferably 10 to 35 mol%, even more preferably 10 to 25 mol%, and particularly preferably 10 to 15 mol%.

[0073] [Preparation of hardener] The curing agent (curing agent containing a polyamine component) is prepared by a known method. For example, when the curing agent contains a polyamine component but does not contain a polyol component, the polyamine component can be used as it is as the curing agent.

[0074] In addition, when the curing agent contains a polyamine component and a polyol component, for example, the polyamine component and the polyol component can be mixed by a known method, and the mixture of the polyamine component and the polyol component can be used as the curing agent.

[0075] In the two-component curing polyurethane resin composition, the curing agent is prepared separately from the main agent and mixed with the main agent when the two-component curing polyurethane resin composition is used. The mixing ratio of the main agent and the curing agent will be described later.

[0076] (3) Hydroxides of alkaline earth metals Examples of alkaline earth metals include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). That is, examples of hydroxides of alkaline earth metals include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide. These may be used alone or in combination of two or more.

[0077] From the viewpoints of ease of handling and low cost, the hydroxide of the alkaline earth metal is preferably magnesium hydroxide or calcium hydroxide, more preferably calcium hydroxide. In other words, the hydroxide of the alkaline earth metal preferably contains magnesium hydroxide and / or calcium hydroxide, more preferably calcium hydroxide.

[0078] In the two-component curing polyurethane resin composition, the alkaline earth metal hydroxide may be prepared separately from the base agent and the curing agent, and mixed with the base agent and the curing agent when the two-component curing polyurethane resin composition is used.

[0079] In the two-component curing polyurethane resin composition, the hydroxide of an alkaline earth metal may be mixed with the base agent in advance. That is, a composition (base agent composition) containing the base agent and the hydroxide of an alkaline earth metal may be prepared in advance. Then, when the two-component curing polyurethane resin composition is used, the base agent composition and the curing agent may be mixed.

[0080] In the two-component curing polyurethane resin composition, the hydroxide of an alkaline earth metal may be mixed with the curing agent in advance. That is, a composition (curing agent composition) containing a curing agent and a hydroxide of an alkaline earth metal may be prepared in advance. Then, when the two-component curing polyurethane resin composition is used, the curing agent composition may be mixed with the main agent.

[0081] Furthermore, in the two-component curing polyurethane resin composition, the hydroxide of an alkaline earth metal may be mixed in advance with both the base agent and the curing agent. That is, a composition containing the base agent and the hydroxide of an alkaline earth metal (base agent composition) and a composition containing the curing agent and the hydroxide of an alkaline earth metal (curing agent composition) may be prepared in advance. Then, when the two-component curing polyurethane resin composition is used, the base agent composition and the curing agent composition may be mixed.

[0082] From the viewpoint of obtaining excellent workability and pot life, the hydroxide of an alkaline earth metal is preferably mixed with the curing agent in advance, that is, a composition containing the curing agent and the hydroxide of an alkaline earth metal (curing agent composition) is preferably prepared in advance.

[0083] From the viewpoint of obtaining excellent workability and pot life, when a curing agent composition is prepared, preferably, a composition containing a base agent and an alkaline earth metal hydroxide (base agent composition) is not prepared.

[0084] That is, preferably, when the two-component curing polyurethane resin composition is used, the curing agent composition and the above-mentioned base agent are mixed together.

[0085] In the two-component curing polyurethane resin composition, the content of the alkaline earth metal hydroxide is adjusted, for example, based on the mass ratio to the polyamine component in the curing agent.

[0086] More specifically, from the viewpoint of obtaining a well-balanced pot life and mechanical properties, the ratio of the alkaline earth metal hydroxide relative to 100 parts by mass of the polyamine component in the curing agent is, for example, 1 to 5,000 parts by mass, preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, still more preferably 50 to 250 parts by mass, and particularly preferably 80 to 150 parts by mass.

[0087] In particular, from the viewpoint of obtaining an excellent pot life, the lower limit of the proportion of the alkaline earth metal hydroxide relative to 100 parts by mass of the polyamine component in the curing agent is, for example, 1 part by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 50 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 100 parts by mass or more, even more preferably 200 parts by mass or more, and even more preferably 300 parts by mass or more.

[0088] Furthermore, from the viewpoint of obtaining excellent hardness, tensile strength and tear strength, the ratio of the alkaline earth metal hydroxide relative to 100 parts by mass or less of the polyamine component in the curing agent is, for example, 5,000 parts by mass or less, preferably 1,000 parts by mass or less, more preferably 500 parts by mass or less, even more preferably 250 parts by mass or less, particularly preferably 150 parts by mass or less, even more preferably 100 parts by mass or less, even more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less.

[0089] Furthermore, when the curing agent contains a polyamine component and a polyol component, the content ratio of the alkaline earth metal hydroxide can be adjusted based on the mass ratio to the total amount of the polyamine component and the polyol component.

[0090] More specifically, from the viewpoint of obtaining a well-balanced pot life and mechanical properties, the ratio of the alkaline earth metal hydroxide relative to 100 parts by mass of the total amount of the polyamine component and the polyol component is, for example, 0.5 to 5000 parts by mass, preferably 1 to 1000 parts by mass, more preferably 10 to 100 parts by mass, even more preferably 20 to 50 parts by mass, and particularly preferably 25 to 40 parts by mass.

[0091] (4) Additives The two-component curing polyurethane resin composition may further contain additives in addition to the base resin, the curing agent, and the hydroxide of an alkaline earth metal.

[0092] Examples of additives include fillers, plasticizers, catalysts, antioxidants, antioxidants, UV absorbers, heat stabilizers, light stabilizers, organic solvents, pigments, dyes, defoamers, toners, dispersants, leveling agents, thixotropic agents, antiblocking agents, release agents, lubricants, hydrolysis inhibitors, rust inhibitors, and bluing agents. These may be used alone or in combination of two or more. The amount and timing of the additives to be added are appropriately set depending on the purpose and application.

[0093] The additives preferably include a filler, a plasticizer, and a catalyst.

[0094] [Filling material] Examples of the filler include inorganic fillers (excluding hydroxides of alkaline earth metals) and organic fillers.

[0095] The inorganic filler does not contain hydroxides of alkaline earth metals. More specifically, examples of inorganic fillers include calcium carbonate, aluminum oxide, magnesium carbonate, kaolinite, halloysite, allophane, pyrophyllite, talc, sericite, illite, mica, montmorillonite, paidellite, amesite, chamosite, calcined clay, asbestos, mica, bentonite, calcium silicate, zeolite, pumice powder, slate powder, diatomaceous earth, silica sand, silica stone powder, gibbsite, boehmite, barium sulfate, calcium sulfate, metal powder, wet silica, dry silica, glass fiber, and carbon fiber. These can be used alone or in combination of two or more. Calcium carbonate is preferred.

[0096] Examples of organic fillers include wood flour, pulp powder, cotton chips, rubber powder, thermoplastic resin powder, and thermosetting resin powder. These can be used alone or in combination of two or more kinds.

[0097] The filler may be used alone or in combination of two or more kinds. As the filler, preferably, an inorganic filler is used, and more preferably, calcium carbonate is used.

[0098] The amount and timing of addition of the filler are appropriately set according to the purpose and application. For example, the filler may be prepared separately from the base agent, the curing agent, and the hydroxide of the alkaline earth metal, and mixed with the base agent and the curing agent when the two-component curing polyurethane resin composition is used. The base agent may also be mixed with the base agent and / or the curing agent in advance.

[0099] From the viewpoint of obtaining excellent workability and pot life, the filler is preferably mixed in advance with the hardener together with the hydroxide of the alkaline earth metal.

[0100] That is, preferably, a composition (curing agent composition) containing a curing agent, an alkaline earth metal hydroxide, and a filler is prepared in advance. Then, preferably, when the two-component curing polyurethane resin composition is used, the curing agent composition and the main agent are mixed.

[0101] In the two-component curing polyurethane resin composition, the content of the filler is adjusted, for example, based on the mass ratio to the hydroxide of an alkaline earth metal.

[0102] More specifically, from the viewpoint of obtaining a good balance between pot life and mechanical properties, the ratio of the alkaline earth metal hydroxide to the total amount of the alkaline earth metal hydroxide and the filler is, for example, 0.1 to 100 mass%, preferably 1 to 50 mass%, more preferably 5 to 25 mass%, and even more preferably 10 to 20 mass%. Also, the ratio of the filler to the total amount of the alkaline earth metal hydroxide and the filler is, for example, 0 to 99.9 mass%, preferably 50 to 99 mass%, more preferably 75 to 95 mass%, and even more preferably 80 to 90 mass%.

[0103] [Plasticizer] Examples of the plasticizer include phthalate ester plasticizers, adipate ester plasticizers, aliphatic dibasic acid ester plasticizers, glycol ester plasticizers, phosphate ester plasticizers, and epoxy plasticizers. These can be used alone or in combination of two or more. Examples of the plasticizer include phthalate ester plasticizers and adipate ester plasticizers. Examples of the phthalate ester plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, di-2-ethylhexyl phthalate, dinonyl phthalate, diisodecyl phthalate, ditridecyl phthalate, dibutyl pentyl phthalate, and dicyclohexyl phthalate. Examples of the adipate plasticizer include dimethyl adipate, diethyl adipate, dibutyl adipate, diheptyl adipate, diisononyl adipate, di-n-octyl adipate, diisooctyl adipate, di-2-ethylhexyl adipate, dinonyl adipate, diisononyl adipate, diisodecyl adipate, ditridecyl adipate, dibutylpentyl adipate, and dicyclohexyl adipate. These can be used alone or in combination of two or more. As the plasticizer, preferably, phthalate plasticizer is used, and more preferably, diisononyl phthalate (DINP) is used.

[0104] The amount and timing of the plasticizer to be added are appropriately set according to the purpose and application. For example, the plasticizer may be prepared separately from the base agent, the curing agent, and the hydroxide of the alkaline earth metal, and mixed with the base agent and the curing agent when the two-component curing polyurethane resin composition is used. The base agent may also be mixed with the base agent and / or the curing agent in advance.

[0105] From the viewpoint of obtaining excellent workability and pot life, the plasticizer is preferably mixed in advance with the hardener together with the hydroxide of the alkaline earth metal.

[0106] That is, preferably, a composition (curing agent composition) containing a curing agent, an alkaline earth metal hydroxide, and a plasticizer is prepared in advance. Then, preferably, when the two-component curing polyurethane resin composition is used, the curing agent composition and the main agent are mixed.

[0107] The content of the plasticizer is not particularly limited and may be appropriately determined depending on the purpose and application.

[0108] [catalyst] The catalyst is added, for example, when the curing agent contains a polyol component. That is, when the curing agent does not contain a polyol component and contains only a polyamine component, the reaction (urea reaction) between the base agent and the polyamine component proceeds even without adding a catalyst. On the other hand, when the curing agent contains a polyamine component and a polyol component, a catalyst is preferably added to promote the reaction (urethanization reaction) between the base agent and the polyol component.

[0109] The catalyst may be a known urethanization catalyst, such as an amine catalyst or an organometallic catalyst, preferably an organometallic catalyst.

[0110] Examples of the organometallic catalyst include organotin compounds, organolead compounds, organonickel compounds, organocobalt compounds, organocopper compounds, and organobismuth compounds. Examples of the organotin compounds include tin acetate, tin octoate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, and dibutyltin dichloride. Examples of the organolead compounds include lead octoate and lead naphthenate. Examples of the organonickel compounds include nickel naphthenate. Examples of the organocobalt compounds include cobalt naphthenate. Examples of the organocopper compounds include copper octoate. Examples of the organobismuth compounds include bismuth octoate and bismuth neodecanoate. These may be used alone or in combination of two or more types.

[0111] The catalyst is preferably added when the curing agent contains a polyol composition. The amount of the catalyst added is, for example, 0.1 to 1000 parts by mass, preferably 1 to 100 parts by mass, more preferably 10 to 50 parts by mass, and further preferably 15 to 30 parts by mass, relative to 100 parts by mass of the hydroxide of an alkaline earth metal. The timing of adding the catalyst is appropriately set according to the purpose and application.

[0112] Further, the additives include organic acids as promoters, but from the viewpoints of pot life and mechanical properties, the two-component curing polyurethane resin composition preferably does not contain organic acids.

[0113] [2] Method for producing two-component curing polyurethane resin composition The base agent, the curing agent, and the hydroxide of the alkaline earth metal (and further, if necessary, the additives) may be prepared individually or in advance as described above. Preferably, the curing agent and the hydroxide of the alkaline earth metal (and further, if necessary, the additives) are premixed as described above to prepare the curing agent composition.

[0114] More specifically, preferably, a liquid A (first liquid) as a base material and a liquid B (second liquid) as a curing agent composition are prepared as a two-liquid curing polyurethane resin composition.

[0115] When the two-component curing polyurethane resin composition is used, the liquids A and B are mixed. In the two-component curing polyurethane resin composition, the mixing ratio of the liquids A and B is adjusted based on, for example, the equivalent ratio between the isocyanate groups of the base material in the liquid A and the active hydrogen groups of the curing agent in the liquid B.

[0116] More specifically, from the viewpoints of pot life and mechanical properties, the equivalent ratio (isocyanate group / active hydrogen group) of the isocyanate group of the main agent in Liquid A to the active hydrogen group (total amount of amino group and hydroxyl group) of the curing agent in Liquid B is, for example, 0.8 to 1.5, preferably 0.9 to 1.2, and more preferably 0.95 to 1.2.

[0117] Moreover, industrially, the mixing ratio of liquid A and liquid B may be adjusted, for example, based on the mass of liquid A and the mass of liquid B. More specifically, from the viewpoint of pot life and mechanical properties, the ratio of liquid A to the total amount of liquid A and liquid B is, for example, 30 to 70 mass%, preferably 40 to 60 mass%. Moreover, the ratio of liquid B to the total amount of liquid A and liquid B is, for example, 30 to 70 mass%, preferably 40 to 60 mass%.

[0118] Then, liquid A and liquid B are mixed in the above ratio to obtain a resin mixture (polyurethane mixture), and the resin mixture undergoes a curing reaction to obtain a cured product (cured polyurethane product).

[0119] The conditions for curing the resin mixture are not particularly limited. For example, the curing temperature is, for example, 0 to 60° C., preferably 5 to 50° C., and more preferably 10 to 40° C. The curing time is, for example, 1 to 240 hours, and preferably 5 to 200 hours.

[0120] [3] Effects In the above two-component curing polyurethane resin composition, the base agent contains an isocyanate-terminated prepolymer, and the curing agent contains a polyamine component. The above two-component curing polyurethane resin composition further contains an alkaline earth metal hydroxide. Therefore, the above two-component curing polyurethane resin composition has an excellent pot life.

[0121] More specifically, the reaction (urea reaction) between the isocyanate-terminated prepolymer and the polyamine component is relatively fast, so that when the base agent contains the isocyanate-terminated prepolymer and the curing agent contains the polyamine component, the two-component curing polyurethane resin composition has a relatively short pot life.

[0122] In contrast, the two-component curing polyurethane resin composition further contains an alkaline earth metal hydroxide. The alkaline earth metal hydroxide inhibits the reaction (urea reaction) between the isocyanate-terminated prepolymer and the polyamine component. In other words, the alkaline earth metal hydroxide acts as a reaction retarder. As a result, the two-component curing polyurethane resin composition has an excellent pot life.

[0123] In the two-component curing polyurethane resin composition, the content of the alkaline earth metal hydroxide is preferably adjusted based on the content of the polyamine component, which provides a particularly excellent pot life.

[0124] Furthermore, in the above two-component curing polyurethane resin composition, the polyamine component preferably contains at least one selected from the group consisting of diethyltoluenediamine, halogenated diethyltoluenediamine, and dimethylthiotoluenediamine. In such a case, a particularly excellent pot life is obtained, and further, a cured product (polyurethane cured product) having excellent mechanical properties is obtained.

[0125] Furthermore, in the above two-component curing polyurethane resin composition, the alkaline earth metal hydroxide preferably contains calcium hydroxide. In such a case, a particularly excellent pot life is obtained, and further, a cured product (cured polyurethane product) having excellent mechanical properties is obtained.

[0126] Furthermore, in the above two-component curing polyurethane resin composition, the curing agent preferably contains a polyol component. That is, the curing agent preferably contains both a polyamine component and a polyol component. In such a case, a particularly excellent pot life is obtained, and further, a cured product (polyurethane cured product) having excellent mechanical properties is obtained.

[0127] More specifically, as described above, the hydroxide of an alkaline earth metal inhibits the reaction (urea reaction) between the isocyanate-terminated prepolymer and the polyamine component, that is, the hydroxide of an alkaline earth metal acts as a reaction retarder.

[0128] On the other hand, the hydroxide of an alkaline earth metal accelerates the reaction (urethane reaction) between the isocyanate-terminated prepolymer and the polyol component, that is, the hydroxide of an alkaline earth metal also acts as a reaction accelerator.

[0129] Therefore, when the curing agent contains both a polyamine component and a polyol component, the hydroxide of an alkaline earth metal suppresses the urea reaction and promotes the urea reaction, in other words, the hydroxide of an alkaline earth metal acts as a reaction regulator that adjusts the balance between the urea reaction and the urea reaction.

[0130] As a result, when the curing agent contains both a polyamine component and a polyol component and also contains an alkaline earth metal hydroxide, an excellent pot life is obtained and a cured product having particularly excellent mechanical properties is obtained.

[0131] Therefore, the above-mentioned two-component curing polyurethane resin composition and its cured product are widely used in various industrial fields. More specifically, the above-mentioned two-component curing polyurethane resin composition and its cured product are used, for example, as a waterproof material in the application of waterproof pavement in various industrial fields.

[0132] When the two-component curing polyurethane resin composition and its cured product are used as a waterproofing material, for example, the above-mentioned two-component curing polyurethane resin composition is applied to various facilities by a known application method. Examples of places where the two-component curing polyurethane resin composition is applied include floors, corridors, verandas, parking lots, and rooftops. There are no particular limitations on the application method, and known methods are used. Since such a waterproofing material is formed from the above-mentioned two-component curing polyurethane resin composition, it can be obtained with good workability and moderate pot life. EXAMPLES

[0133] Next, the present invention will be described based on synthesis examples, examples, and comparative examples, but the present invention is not limited by the following examples. Note that "parts" and "%" are based on mass unless otherwise specified. In addition, the specific numerical values ​​of the blending ratio (content ratio), physical property values, parameters, etc. used in the following description can be replaced with the upper limit value (numeric value defined as "less than or equal to" or "less than") or lower limit value (numeric value defined as "more than or equal to" or "exceeding") of the corresponding blending ratio (content ratio), physical property values, parameters, etc. described in the above "Form for carrying out the invention".

[0134] [1] Base agent (liquid A) Manufacturing Example 1 Into a 1-liter four-neck flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, the following raw material polyisocyanate and raw material polyol were placed.

[0135] <Raw material polyisocyanate> Cosmonate T-80 (product name, mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate. 2,4- / 2,6- = 80 / 20 (molar ratio), manufactured by Mitsui Chemicals) 151.3 g

[0136] <Raw polyol> Actocol D-400 (product name, polyoxypropylene glycol, high molecular weight polyol, number average molecular weight 400, average functionality 2, manufactured by Mitsui Chemicals) 68.1 g Actocol D-2000 (product name, polyoxypropylene glycol, high molecular weight polyol, number average molecular weight 2000, average functionality 2, manufactured by Mitsui Chemicals) 394.8 g Actocol T-5000 (product name, polyoxypropylene triol, high molecular weight polyol, number average molecular weight 5000, average number of functional groups 3, manufactured by Mitsui Chemicals) 305.8 g

[0137] The equivalent ratio (NCO / OH) of the isocyanate groups of the raw material polyisocyanate to the hydroxyl groups of the raw material polyol was 1.9.

[0138] Next, the raw polyisocyanate and raw polyol were reacted at 90° C. for 4 hours in a nitrogen atmosphere to obtain a reaction mixture containing an isocyanate-terminated prepolymer.

[0139] The isocyanate group content of the reaction mixture (isocyanate group-terminated prepolymer) was measured by the method described below, and when the isocyanate group content reached 3.70 mass%, the temperature of the reaction mixture was lowered to 70° C. Then, 80 g of an organic solvent (PMA, propylene glycol monomethyl ether acetate) was added to the reaction mixture.

[0140] In this manner, a base material (1) containing an isocyanate-terminated prepolymer was obtained.

[0141] The isocyanate group content of the base agent (1) was measured by the isocyanate group content test described in JIS K 7301 (1995). As a result, the isocyanate group content (NCO%) of the base agent (1) was 3.30 mass%. In addition, the viscosity of the base agent (1) at 25°C was measured using a B-8M type rotational viscometer (rotor No. 4, rotation speed 12 rpm). As a result, the viscosity of the base agent (1) was 5500 mPa s.

[0142] [2] Hardener composition (liquid B) Preparation Examples 1 to 16 According to the formulations shown in Tables 1 to 3, a polyamine component, a polyol component, an alkaline earth metal hydroxide, and additives were charged into a 1-liter four-neck flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, and stirred under a nitrogen atmosphere at 40° C. for 1 hour. As a result, curing agent compositions (1) to (16) were obtained.

[0143] [3] Two-component curing polyurethane resin composition and cured product Examples 1 to 10 and Comparative Examples 1 to 6 According to the formulations shown in Tables 4 to 6, a base resin (liquid A) and a curing agent composition (liquid B) were prepared to obtain two-liquid curing polyurethane resin compositions.

[0144] Next, the base material (liquid A) and the hardener composition (liquid B) were mixed to obtain a polyurethane mixture. The equivalent ratio (isocyanate group / active hydrogen group) of the isocyanate group of the base material in liquid A to the active hydrogen group (total amount of amino group and hydroxyl group) of the hardener in liquid B was 1.10.

[0145] Thereafter, the polyurethane mixture was degassed, poured into a predetermined mold according to the evaluation method described below, and cured for 168 hours at 23° C. and a relative humidity of 55%, to obtain a cured product.

[0146] [4] Evaluation (1) Pot life The base resin (liquid A) and the curing agent composition (liquid B) were mixed under stirring at 23°C and a relative humidity of 55% so that the total amount was 100 g. The time until the mixed viscosity reached 100,000 mPa s was then measured using a Toki Sangyo Co., Ltd. Model TV-25 B-type viscometer.

[0147] (2) Hardness A cured product having a thickness of 15 mm was produced. The hardness of the cured product was then measured using a type A durometer in accordance with JIS K6253 (2012).

[0148] (3) Tensile strength, elongation at break, and tear strength A cured product having a thickness of 2 mm was obtained. The cured product was then punched out in accordance with JIS K6251 (2010) to obtain a sample having a dumbbell shape No. 3. The tensile strength and breaking elongation of the sample were then measured at 23°C and a relative humidity of 55%.

[0149] The cured product was punched out in accordance with JIS K6252 (2007) to obtain a sample having an angle shape without a notch, and the tear strength of the sample was then measured at 23°C and a relative humidity of 55%.

[0150] The number of samples was three for each material. A universal tensile testing machine was used to measure the mechanical strength. The crosshead speed was set to 500 mm / min.

[0151] More specifically, the tensile strength at which the dumbbell-shaped No. 3 sample broke was measured using the above-mentioned device and conditions.

[0152] In addition, the elongation at break of the dumbbell-shaped No. 3 sample was measured using the above-mentioned device and conditions.

[0153] Furthermore, the maximum strength until the uncut angle-shaped sample broke was taken as the tear strength, and the tear strength was measured using the above-mentioned device and conditions.

[0154] [Table 1]

[0155] [Table 2]

[0156] [Table 3]

[0157] [Table 4]

[0158] [Table 5]

[0159] [Table 6]

[0160] Details of the abbreviations in the table are given below. D-2000: Product name Actocol D-2000, polyoxypropylene glycol, high molecular weight polyol, number average molecular weight 2000, average functionality 2, manufactured by Mitsui Chemicals DETDA 80: Product name: Primacure DETDA 80, diethyltoluenediamine, manufactured by Arcsada Japan Co., Ltd. P-25: Product name: Primacure P-25i, halogenated diethyltoluenediamine, manufactured by Arcsada Japan Co., Ltd. Ethacure 300: Trade name, dimethylthiotoluenediamine, manufactured by Albemarle Corporation DINP: Diisononyl phthalate, plasticizer, manufactured by New Japan Chemical Co., Ltd. SS#50: Calcium carbonate, filler, manufactured by Nitto Funka Kogyo Co., Ltd. Calcium hydroxide: hydroxide of alkaline earth metals, manufactured by Yabashi Kogyo Co., Ltd. Lead octylate: Nikka Octix Lead 24% (T), urethane catalyst, manufactured by Nippon Chemical Industries Co., Ltd.

Claims

1. A base material containing an isocyanate group-terminated prepolymer; A curing agent containing a polyamine component; Alkaline earth metal hydroxides A two-component curing polyurethane resin composition comprising:

2. 2. The two-component curing polyurethane resin composition according to claim 1, wherein a ratio of the hydroxide of the alkaline earth metal to 100 parts by mass of the polyamine component is 10 to 1000 parts by mass.

3. 3. The two-component curing polyurethane resin composition according to claim 1, wherein the polyamine component contains at least one selected from the group consisting of diethyltoluenediamine, halogenated diethyltoluenediamine, and dimethylthiotoluenediamine.

4. The two-component curing polyurethane resin composition according to claim 1 or 2, wherein the hydroxide of an alkaline earth metal contains calcium hydroxide.

5. The two-component curing polyurethane resin composition according to claim 1 or 2, wherein the curing agent further contains a polyol component.

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