Two-component curable composition

Abstract

To provide a two-part curable composition that shows excellent foaming inhibitory effect even when used in a high-temperature high-humidity atmosphere or for an adherend with a high moisture content.SOLUTION: A two-part curable composition contains a basis containing a polyol (A), a curing agent containing an isocyanate group-containing compound (B), which is an organic isocyanate compound and / or an isocyanate group-containing urethane prepolymer, and a fatty acid ester (C).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a two-component curable composition containing an organic isocyanate compound and / or an isocyanate group-containing urethane prepolymer.

Background Art

[0002] In polyurethane-based curable compositions having a urethane prepolymer having an isocyanate group at the terminal as a main component of the cured product, there are a one-component curable composition that cures by reacting with moisture in the air, and a two-component curable composition that cures by reacting a main agent containing a urethane prepolymer with a curing agent containing a component that reacts with an isocyanate group such as a polyol at the time of use.

[0003] In the case of a one-component curable composition, curing may be extremely slow in an environment in winter (low temperature and low humidity), and since it cures from the surface by reacting with moisture in the air, when the coating film has a thickness, curing inside the coating film becomes slow. When trying to solve the above problems of the one-component curable composition, there is a problem that the coating film is likely to foam. From the above, in applications such as fillers, sealing materials, and adhesives, two-component curable compositions are used as polyurethane-based curable compositions.

[0004] However, in conventional two-component polyurethane-based curable compositions, when the moisture content of the base is high or in an atmosphere of high temperature and high humidity, the isocyanate group and water may react to cause foaming. When repairing cracks occurring on the road surface, if foaming due to moisture in the base occurs, there is a risk of deterioration of the appearance and tripping and falling due to swelling of the repaired portion. In order to suppress foaming, there have been problems such as having to use a highly harmful metal-based catalyst such as a lead-based catalyst to selectively promote the reaction between isocyanate and polyol.

[0005] To solve these problems, methods have been proposed such as a method of containing a compound that generates an amine or a hydroxyl group by reaction with water in the main agent (Patent Document 1), a method of containing a calcium salt of a fatty acid in the main agent (Patent Document 2), a method of containing surface-treated calcium carbonate treated with a specific surface treatment agent (Patent Document 3), etc. However, all of these methods have insufficient effects and have problems of affecting the physical properties of the cured product.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0007] In view of the above problems, an object of the present invention is to provide a two-component curable composition that can obtain an excellent foam suppression effect even when used in an atmosphere of high temperature and high humidity or on a substrate with a high water content.

Means for Solving the Problems

[0008] As a result of intensive studies, the present inventors have found that the following curable composition is effective. That is, the gist of the configuration of the present invention is as follows. [1] A two-component curable composition comprising a main agent containing a polyol (A), a curing agent containing an organic isocyanate compound and / or an isocyanate group-containing compound (B) that is an isocyanate group-containing urethane prepolymer, and a fatty acid ester (C). [2] The two-component curable composition according to [1], wherein the polyol (A) contains a castor oil-based polyol. [3] The two-component curable composition according to [1], wherein the polyol (A) contains a polyoxyalkylene polyol. [4] The two-component curable composition according to any one of [1] to [3], wherein the fatty acid of the fatty acid ester (C) has 3 to 25 carbon atoms. [5] The two-component curable composition according to any one of [1] to [4], wherein the fatty acid ester (C) is a fatty acid methyl ester. [6] The two-component curable composition according to any one of [1] to [5], which contains 20 to 200 parts by mass of the fatty acid ester (C) with respect to 100 parts by mass of the polyol (A). [7] The two-component curable composition according to any one of [1] to [5], which contains 40 to 200 parts by mass of the fatty acid ester (C) with respect to 100 parts by mass of the polyol (A). [8] The two-component curable composition according to any one of [1] to [7], wherein the isocyanate group-containing compound (B) is an isocyanate group-containing urethane prepolymer. [9] The two-component curable composition according to any one of [1] to [8], which is for road surface repair.

[10] A two-component road surface repair agent containing the two-component curable composition according to any one of [1] to [9].

Advantages of the Invention

[0009] According to the two-component curable composition of the present invention, by including a main agent containing a polyol (A), a curing agent containing an organic isocyanate compound and / or an isocyanate group-containing compound (B) which is an isocyanate group-containing urethane prepolymer, and a fatty acid ester (C), an excellent foam suppression effect can be obtained even when used for an adherend in a high-temperature and high-humidity atmosphere or with a high moisture content. Further, according to the two-component curable composition of the present invention, by including a main agent containing a polyol (A), a curing agent containing an organic isocyanate compound and / or an isocyanate group-containing compound (B) which is an isocyanate group-containing urethane prepolymer, and a fatty acid ester (C), a finger-touch drying time equivalent to the conventional one and excellent followability with respect to the movement of a member at the site to which the two-component curable composition is applied can be obtained.

[0010] According to the two-component curable composition of the present invention, since the polyol (A) contains a castor oil-based polyol and / or a polyoxyalkylene-based polyol, it can more surely contribute to an excellent foam suppression effect.

[0011] According to the two-component curable composition of the present invention, when the fatty acid of the fatty acid ester (C) has 3 to 25 carbon atoms, an excellent foam suppression effect can be more surely obtained.

[0012] According to the two-component curable composition of the present invention, since the fatty acid ester (C) is a fatty acid methyl ester, the foam suppression effect is further improved.

[0013] According to the two-component curable composition of the present invention, by containing 20 to 200 parts by mass of the fatty acid ester (C) with respect to 100 parts by mass of the polyol (A), an excellent foam suppression effect can be more surely obtained.

[0014] According to the two-component curable composition of the present invention, by containing 40 to 200 parts by mass of the fatty acid ester (C) with respect to 100 parts by mass of the polyol (A), the foam suppression effect is further improved.

[0015] According to the two-component curable composition of the present invention, since the isocyanate group-containing compound (B) is an isocyanate group-containing urethane prepolymer, while obtaining excellent curability, the foaming suppression effect is further improved.

Embodiments for Carrying Out the Invention

[0016] The details of the two-component curable composition of the present invention will be described below. The two-component curable composition of the present invention includes a main agent containing a polyol (A), a curing agent containing an organic isocyanate compound and / or an isocyanate group-containing compound (B) which is an isocyanate group-containing urethane prepolymer, and a fatty acid ester (C). In the curable composition of the present invention, a polyol (A) is included as the main component of the main agent, and an organic isocyanate compound and / or an isocyanate group-containing urethane prepolymer is included as the main component of the isocyanate group-containing compound (B).

[0017] According to the two-component curable composition of the present invention, by including a main agent containing a polyol (A), a curing agent containing an organic isocyanate compound and / or an isocyanate group-containing compound (B) which is an isocyanate group-containing urethane prepolymer, and a fatty acid ester (C), even when used for a substrate in a high-temperature and high-humidity atmosphere or a substrate with a high moisture content, an excellent foaming suppression effect can be obtained, and also, a finger-touch drying time equivalent to the conventional one and excellent followability with respect to the movement of the member at the site where the two-component curable composition is applied can be obtained.

[0018] The details of each component of the curable composition of the present invention will be described below.

[0019] <Polyol (A)> Examples of the polyol (A) include polymer polyols, low molecular weight polyols, and low molecular weight amino alcohols. These polyols can be used alone or in combination of two or more. In this specification, "polymer" means a number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) of 1,000 or more, and "low molecular weight" means a number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) of less than 1,000.

[0020] Examples of the polyol (A) include polyester polyols, polycarbonate polyols, polyoxyalkylene-based polyols, hydrocarbon-based polyols, poly(meth)acrylic-based polyols, animal and plant-based polyols, copolyols thereof, or mixtures of two or more thereof. The number average molecular weight in terms of polystyrene of the polyol (A) by gel permeation chromatography is preferably from 1,000 to 100,000, more preferably from 1,000 to 30,000, and particularly preferably from 1,000 to 20,000. When the number average molecular weight is less than 1,000, the rubber elastic physical properties such as the elongation after curing of the obtained two-component curable composition tend to decrease. When the number average molecular weight exceeds 100,000, the viscosity of the obtained two-component curable composition tends to increase, and the workability during construction tends to decrease. In this specification, "(meth)acrylic" means "acrylic and / or methacrylic".

[0021] The molecular weight distribution of the polyol (A) [the ratio of the mass average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography = Mw / Mn] is not particularly limited, but from the viewpoint of being able to reduce the viscosity of the obtained two-component curable composition and having good rubber elastic physical properties after curing of the obtained two-component curable composition, it is preferably 1.6 or less, and particularly preferably from 1.0 to 1.3.

[0022] <Polyester polyol> Examples of the polyester polyol include those obtained by reacting one or more carboxylic acids including polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, anhydrides thereof, or alkyl esters such as methyl ester and ethyl ester, with one or more low molecular weight polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, an ethylene oxide or propylene oxide adduct of bisphenol A, trimethylolpropane, glycerin, or pentaerythritol. Further, examples of the polyester amide polyol include those obtained by reacting one or more of the above carboxylic acids and low molecular weight polyols with one or more low molecular weight polyamines such as butylenediamine, hexamethylenediamine, xylylenediamine, isophoronediamine, or low molecular weight amino alcohols such as monoethanolamine and diethanolamine. Also, examples of the lactone-based polyester polyol include those obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-butyrolactone using low molecular weight polyols, low molecular weight polyamines, or low molecular weight amino alcohols as initiators.

[0023] <Polycarbonate polyol> Examples of the polycarbonate polyol include polyols obtained by a dehydrochlorination reaction of phosgene with the low molecular weight polyols used in the synthesis of the above polyester polyol, and polyols obtained by a transesterification reaction of the low molecular weight polyols with diethylene carbonate, dimethyl carbonate, diethyl carbonate, or diphenyl carbonate.

[0024] <Polyoxyalkylene polyol> Examples of the polyoxyalkylene polyol include polyoxyalkylene triol and polyoxyalkylene diol. In this specification, the "series" of the polyoxyalkylene polyol means that 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more of the portion excluding the hydroxyl group in the molecule is composed of polyoxyalkylene, and the remaining portion may be modified with an ester, urethane, polycarbonate, polyamide, poly(meth)acrylate, polyolefin, etc. As the polyoxyalkylene polyol, those in which 95% by mass or more of the molecule excluding the hydroxyl group is composed of polyoxyalkylene are particularly preferred.

[0025] Examples of the polyoxyalkylene polyol include, in addition to the low molecular weight polyols, low molecular weight polyamines, low molecular weight amino alcohols, and polycarboxylic acids used in the synthesis of the polyester polyol, saccharide-based low molecular weight polyalcohols such as sorbitol, mannitol, sucrose, and glucose; one or more of low molecular weight polyhydric phenols such as bisphenol A and bisphenol F as initiators, and one or more of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, and cyclic ether compounds such as tetrahydrofuran are subjected to ring-opening addition polymerization or copolymerization (hereinafter, "polymerization or copolymerization" may be referred to as "(co)polymerization"). Examples thereof include polyoxyethylene polyol, polyoxypropylene polyol, polyoxybutylene polyol, polyoxytetramethylene polyol, poly-(oxyethylene)-(oxypropylene)-random or block copolymer polyol, etc.

[0026] Examples of the polyoxyalkylene polyol include polyester ether polyols and polycarbonate ether polyols initiated with the above polyester polyol or polycarbonate polyol. Further examples include polyoxyalkylene polyols having a hydroxyl group at the molecular end, which are obtained by reacting the above various polyols with an organic isocyanate in an excess of hydroxyl groups relative to the isocyanate groups.

[0027] As the polyoxyalkylene triol, polyoxypropylene triol, polyoxyethylene triol, and polyoxyethylene propylene triol are preferable, and polyoxypropylene triol and polyoxyethylene propylene triol are more preferable. As the polyoxyalkylene diol, polyoxypropylene diol, polyoxyethylene diol, and polyoxyethylene propylene diol are preferable, and polyoxypropylene diol and polyoxyethylene propylene diol are more preferable.

[0028] The number of alcoholic hydroxyl groups in the polyoxyalkylene polyol is not particularly limited, but is preferably 2 or more on average per molecule, more preferably 2 to 4, and particularly preferably 2 to 3.

[0029] Examples of the catalyst used in the preparation of the polyoxyalkylene polyol include cesium alkoxides such as cesium hydride, cesium methoxide, and cesium ethoxide, cesium-based compounds such as cesium hydroxide, diethyl zinc, iron chloride, metal porphyrin, phosphazenium compounds, and double metal cyanide complexes (for example, glyme complexes and diglyme complexes of zinc hexacyanocobaltate).

[0030] The total unsaturation of the polyoxyalkylene polyol is not particularly limited, but is preferably 0.1 meq / g or less, more preferably 0.07 meq / g or less, and particularly preferably 0.04 meq / g or less.

[0031] <Hydrocarbon-based polyol> Examples of hydrocarbon polyols include polyolefin polyols such as polybutadiene polyol and polyisoprene polyol; polyalkylene polyols such as hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol; and halogenated polyalkylene polyols such as chlorinated polypropylene polyol and chlorinated polyethylene polyol.

[0032] <Poly(meth)acrylic polyol> As the poly(meth)acrylic polyol, an ethylenically unsaturated compound containing at least a hydroxyl group-containing (meth)acrylic monomer is polymerized by a known radical polymerization method such as batch polymerization or continuous polymerization in the presence or absence of a polymerization initiator, preferably at 150 to 350 °C, more preferably at 210 to 250 °C by high-temperature continuous polymerization reaction. The resulting product is suitable because the molecular weight distribution of the reaction product is narrow and the viscosity is low.

[0033] The poly(meth)acrylic polyol may be obtained by polymerizing a hydroxyl group-containing (meth)acrylic monomer alone, or may be obtained by copolymerizing two or more kinds of hydroxyl group-containing (meth)acrylic monomers, or may be obtained by copolymerizing one or more kinds of hydroxyl group-containing (meth)acrylic monomers and an ethylenically unsaturated compound other than the hydroxyl group-containing (meth)acrylic monomer. Among these, since it is easy to adjust the hydroxyl group content of the poly(meth)acrylic polyol and it is easy to select the physical properties after curing of the two-component curable composition, one or more kinds of hydroxyl group-containing (meth)acrylic monomers and one or more kinds of these other ethylenically unsaturated compounds are copolymerized. What is obtained is preferred. At the time of the copolymerization, it is preferable to use the hydroxyl group-containing (meth)acrylic monomer so that the average number of hydroxyl group functions per molecule of the poly(meth)acrylic polyol is 1.0 to 10.0, and it is particularly preferable to use it so that it is 1.2 to 3.0. When the average number of hydroxyl group functions per molecule of the poly(meth)acrylic polyol exceeds 10.0, the physical properties after curing tend to become hard and the rubber-like elasticity decreases. Among these, a poly(meth)acrylic polyol having a number average molecular weight in terms of polystyrene of 1,000 to 30,000 by gel permeation chromatography is preferable, and a poly(meth)acrylic polyol having a number average molecular weight of 2,000 to 15,000 is particularly preferable. Further, the glass transition temperature (Tg) of the poly(meth)acrylic polyol is preferably 0°C or lower, more preferably -70°C to -20°C, and particularly preferably -70°C to -30°C. Further, the viscosity of the poly(meth)acrylic polyol at 25°C is preferably 100,000 mPa·s or less, and particularly preferably 50,000 mPa·s or less. When the number average molecular weight exceeds 30,000, the Tg exceeds 0°C, and the viscosity at 25°C exceeds 100,000 mPa·s, the workability during construction of the resulting two-component curable composition tends to decrease.

[0034] As the hydroxyl group-containing (meth)acrylic monomer, an alcoholic hydroxyl group-containing (meth)acrylic monomer is preferable in view of its good reactivity with the isocyanate group of the isocyanate group-containing compound (B). Specifically, for example, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate; monomethacrylates of polyhydric alcohols or polyacrylates with residual hydroxyl groups such as pentaerythritol tri(meth)acrylate, glycerin mono(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. can be mentioned.

[0035] Examples of other ethylenically unsaturated compounds include ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, (meth)acrylic acid, vinyl acetate, styrene, 2-methylstyrene, divinylbenzene, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, behenyl (meth)acrylate, benzyl (meth)acrylate, glycidyl (meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, polyurethane di(meth)acrylate, acrylic acid dimer, polyester poly(meth)acrylate, 1,6-hexanediol di(meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)acrylate, tridecyl (meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and the like. Among these, as the ethylenically unsaturated compound, from the viewpoint of the properties after curing of the two-component curable composition, monomers of (meth)acrylate-based compounds, (meth)acrylic-based compounds such as acrylamide, methacrylamide, acrylonitrile, etc. are preferable, and methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate are particularly preferable.

[0036] These can be used alone or in combination of two or more. Further, one or more (meth)acrylic monomers having 9 or less carbon atoms and one or more (meth)acrylic monomers having 10 or more carbon atoms may be used in combination.

[0037] <Plant and animal-based polyol> Examples of the plant and animal-based polyol include castor oil-based polyol. The castor oil-based polyol is a polymer derived from castor oil. Examples of the castor oil-based polyol include alkylene oxide adducts of castor oil, epoxidized products of castor oil, halogenated products of castor oil, transesterification products of castor oil and polyhydric alcohols, etc. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, trimethylolethane, glycerin, diglycerin, pentaerythritol, dipentaerythritol, polyester polyol, polycaprolactone polyol, polytetramethylene glycol, polybutadiene polyol, polycarbonate polyol, (meth)acrylic polyol, etc.

[0038] The acid value of the castor oil-based polyol is not particularly limited, but is preferably 10 mgKOH / g or less from the viewpoint of obtaining excellent film-forming properties.

[0039] Among the above polyols (A), polymer polyols are preferred in terms of good rubber physical properties and adhesiveness of the obtained two-component curable composition. Among them, castor oil-based polyols and polyoxyalkylene-based polyols are particularly preferred because they can more surely contribute to an excellent foam suppression effect.

[0040] <Isocyanate group-containing compound (B)> In the present invention, as the isocyanate group-containing compound (B), an organic isocyanate compound (b1) and / or an isocyanate group-containing urethane prepolymer (b2) is used.

[0041] <Organic isocyanate compound (b1)> Examples of the organic isocyanate compound include an organic polyisocyanate and an organic monoisocyanate that may be used as necessary for modifying the isocyanate group-containing urethane prepolymer. Examples of the organic polyisocyanate include an aromatic polyisocyanate in which an isocyanate group is bonded to an aromatic hydrocarbon, an aromatic aliphatic polyisocyanate having an aromatic ring and an isocyanate group bonded to an aliphatic hydrocarbon group, and an aliphatic polyisocyanate composed only of aliphatic hydrocarbon groups.

[0042] <Aromatic polyisocyanate> Examples of the aromatic polyisocyanate include diphenylmethane diisocyanates (MDIs) such as 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate; toluene diisocyanates (TDIs) such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate; phenylenediisocyanate, diphenyldiisocyanate, naphthalenediisocyanate, diphenyl ether diisocyanate, and the like.

[0043] <Aromatic aliphatic polyisocyanate> Examples of the aromatic aliphatic polyisocyanate include xylylene diisocyanate and the like.

[0044] <Aliphatic polyisocyanate> Examples of aliphatic polyisocyanates include aliphatic polyisocyanates such as hexamethylene diisocyanate, pentamethylene diisocyanate, propylene diisocyanate, and butylene diisocyanate; alicyclic polyisocyanates such as cyclohexane diisocyanate, methylene bis(cyclohexyl isocyanate), and isophorone diisocyanate.

[0045] In addition, carbodiimide-modified products, biuret-modified products, allophanate-modified products, dimers, trimers, or polymethylene polyphenyl polyisocyanates (crude MDI, polymeric MDI) of the above-mentioned various polyisocyanates are also included. These compounds can be used alone or in combination of two or more. Among these, in terms of excellent rubber elasticity after curing of the two-component curable composition, among aromatic polyisocyanates, MDIs are preferred, among aromatic aliphatic polyisocyanates, xylylene diisocyanate is preferred, and among aliphatic polyisocyanates, hexamethylene diisocyanate and isophorone diisocyanate are preferred.

[0046] <Organic Monoisocyanate> As the organic monoisocyanate, it only needs to contain one isocyanate group in the molecule. As the organic group other than the isocyanate group, a hydrophobic organic group that does not contain a functional group having curability against moisture (such as water) is preferred. Specific examples of the organic monoisocyanate include aliphatic monoisocyanates such as n-butyl monoisocyanate, n-hexyl monoisocyanate, n-tetradecyl monoisocyanate, n-hexadecyl monoisocyanate, and octadecyl monoisocyanate; aromatic monoisocyanates such as chlorophenyl monoisocyanate, 3,5-dichlorophenyl monoisocyanate, p-fluorophenyl monoisocyanate, and p-isopropylphenyl monoisocyanate. Among these, aliphatic monoisocyanates are preferred, and octadecyl monoisocyanate is particularly preferred.

[0047] <Isocyanate group-containing urethane prepolymer (b2)> The isocyanate group-containing urethane prepolymer is obtained by reacting an organic isocyanate compound and an active hydrogen-containing compound under conditions where the isocyanate groups are in excess relative to the active hydrogen (groups). Specifically, the active hydrogen-containing compound and the organic isocyanate compound are reacted simultaneously or sequentially in a range where the molar ratio of the isocyanate groups / active hydrogen (groups) in the raw materials is 1.2 to 10 / 1.0, preferably 1.5 to 5.0 / 1.0, so that isocyanate groups remain in the urethane prepolymer skeleton. When the molar ratio is less than 1.2 / 1.0, the number of crosslinking points of the resulting isocyanate group-containing urethane prepolymer becomes too small, and the elongation and tensile strength after curing of the two-component curable composition tend to decrease, and also the rubber physical properties and adhesiveness tend to decrease. On the other hand, when the above molar ratio exceeds 10 / 1.0, when the isocyanate group-containing urethane prepolymer reacts with moisture, the amount of carbon dioxide gas generated increases, and foaming tends to occur.

[0048] Also, the isocyanate group content of the isocyanate group-containing urethane prepolymer is not particularly limited, but from the point that appropriate fluidity is imparted to the two-component curable composition and the coating workability of the two-component curable composition is further improved, 0.3 mass% or more and 15.0 mass% or less is preferable, and 3.5 mass% or more and 7.0 mass% or less is particularly preferable. Also, when the isocyanate group content is less than 0.3 mass%, since the number of crosslinking points of the isocyanate group-containing urethane prepolymer is small, sufficient adhesiveness tends not to be obtained. On the other hand, when the isocyanate group content exceeds 15.0 mass%, the number of crosslinking points of the isocyanate group-containing urethane prepolymer increases and the rubber elasticity tends to decrease, and due to the generation of carbon dioxide gas by the reaction of the isocyanate group-containing urethane prepolymer with moisture, an excellent foam suppression effect tends not to be obtained more reliably.

[0049] As a method for producing an isocyanate group-containing urethane prepolymer, a method may be mentioned in which an active hydrogen-containing compound and an organic isocyanate compound are charged into a reaction vessel made of glass, stainless steel, or the like, and reacted at 50 to 120 °C in the presence or absence of a reaction catalyst. At this time, since the isocyanate group reacts with moisture and the resulting isocyanate group-containing urethane prepolymer thickens, it is preferable to carry out the reaction in a state where moisture is blocked, such as nitrogen gas substitution or under a nitrogen gas stream.

[0050] <organic isocyanate compound> Examples of the organic isocyanate compound include the above-mentioned organic isocyanate compound (b1).

[0051] <active hydrogen-containing compound> Examples of the active hydrogen-containing compound include the above polyol (A), and in addition to the above polyol (A), high molecular polyamines and the like can be mentioned. Further, examples of the chain extender used as necessary include low molecular amino alcohols, low molecular polyamines, high molecular monools and low molecular monools used as necessary for modifying the isocyanate group-containing urethane prepolymer.

[0052] <high molecular polyamine> Examples of the high molecular polyamine include polyamines in which an amino group is bonded to a branched carbon at the molecular end, based on polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetramethylene glycol (PTMG). Examples of commercially available high molecular polyamines include "Jeffamine" manufactured by Huntsman Corporation.

[0053] <low molecular amino alcohol> Examples of the low molecular amino monoalcohol include ethanolamine, heptanolamine, propanolamine, methanolamine, diethanolamine, dimethylethanolamine, N-methylethanolamine, and the like.

[0054] <low molecular polyamine> Examples of the low molecular weight polyamine include butylenediamine, hexamethylenediamine, xylylenediamine, isophoronediamine, and the like.

[0055] <Monoalcohol> Examples of the low molecular weight monoalcohol used for modifying the isocyanate group-containing urethane prepolymer include low molecular weight monoalcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol. Examples of the high molecular weight monoalcohol include polyoxyalkylene monoalcohols such as polyoxypropylene monoalcohol obtained by ring-opening addition polymerization of a cyclic ether compound such as propylene oxide using the low molecular weight monoalcohol as an initiator.

[0056] As the isocyanate group-containing compound (B), an isocyanate group-containing urethane prepolymer (b2) is preferable from the viewpoint of obtaining excellent curability and further improving the foam suppression effect. Further, from the viewpoint of the rubber physical properties of the cured product, the active hydrogen-containing compound used for synthesizing the isocyanate group-containing urethane prepolymer (b2) is preferably the above polyol (A), more preferably a polyalkylene polyol, and particularly preferably a polyoxypropylene polyol.

[0057] The blending amount of the isocyanate group-containing compound (B) is not particularly limited. However, the lower limit value of the blending amount of the isocyanate group-containing compound (B) is preferably 30 parts by mass, more preferably 50 parts by mass, and particularly preferably 100 parts by mass with respect to 100 parts by mass of the polyol (A) from the viewpoint of imparting excellent curability to the two-component curable composition. On the other hand, the upper limit value of the blending amount of the isocyanate group-containing compound (B) is preferably 350 parts by mass, more preferably 300 parts by mass, and particularly preferably 250 parts by mass with respect to 100 parts by mass of the polyol (A) from the viewpoint of reliably suppressing foaming due to moisture.

[0058] <Fatty acid ester (C)> In the two-component curable composition of the present invention, by blending the fatty acid ester (C), even when used for an adherend in a high-temperature and high-humidity atmosphere or with a high moisture content, an excellent foam suppression effect can be imparted to the cured product of the two-component curable composition.

[0059] The fatty acid ester (C) is not particularly limited as long as it is an ester of a fatty acid and an alcohol. However, as the fatty acid, a fatty acid having 3 to 25 carbon atoms is preferable from the viewpoint that an excellent foam suppression effect is easily obtained, a fatty acid having 5 to 22 carbon atoms is more preferable from the viewpoint that an excellent foam suppression effect is more reliably obtained, and a fatty acid having 12 to 18 carbon atoms is particularly preferable. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid. Also, from the viewpoint of compatibility, a fatty acid ester that is liquid at normal temperature is preferable. Further, as the alcohol, a linear aliphatic monoalcohol having 1 to 4 carbon atoms is preferable from the viewpoint that an excellent foam suppression effect is easily obtained, a linear aliphatic monoalcohol having 1 to 2 carbon atoms is more preferable, and methanol is particularly preferable.

[0060] As the fatty acid ester, for example, methyl propionate, ethyl propionate, methyl decanoate, ethyl decanoate, methyl 10-undecenoate, ethyl 10-undecenoate, methyl laurate, ethyl laurate, methyl palmitate, ethyl palmitate, methyl stearate, ethyl stearate, methyl oleate, ethyl oleate, methyl naphthenate, ethyl naphthenate, methyl neodecanoate, ethyl neodecanoate, etc. are preferable. Also, methyl fatty acid ester is particularly preferable in terms of further improving the foam suppression effect.

[0061] The blending amount of the fatty acid ester is not particularly limited. However, from the viewpoint that the cured product of the two-component curable composition can more surely obtain an excellent foam suppression effect, the lower limit value of the blending amount of the fatty acid ester is preferably 20 parts by mass, more preferably 30 parts by mass, and particularly preferably 40 parts by mass with respect to 100 parts by mass of the polyol (A). On the other hand, from the viewpoint of maintaining the physical properties of the cured product, the upper limit value of the blending amount of the fatty acid ester is preferably 300 parts by mass, more preferably 250 parts by mass, and particularly preferably 200 parts by mass with respect to 100 parts by mass of the polyol (A).

[0062] In the two-component curable composition of the present invention, various additives can be contained as other components in addition to the polyol (A), the isocyanate group-containing compound (B), and the fatty acid ester (C) as necessary. The additives are used to improve various performances such as viscosity adjustment, curing acceleration, and adhesiveness of the two-component curable composition when blended therein. Examples of the various additives include a curing acceleration catalyst, a weather resistance stabilizer, a storage stability improver, a coloring agent, a thixotropy imparting agent, a filler, an adhesiveness imparting agent, and the like. These can all be used alone or in combination of two or more kinds.

[0063] <Curing acceleration catalyst> The curing accelerator is used to promote the reaction between the main agent containing polyol (A) and the curing agent containing an isocyanate group-containing compound (B), and to promote the curing of the two-component curable composition. Examples of the curing accelerator include organometallic compounds and amines. Examples of the organometallic compounds include divalent organotin compounds such as tin octylate and tin naphthenate; tetravalent organotin compounds such as dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversatate, dibutyltin oxide, dibutyltin bis(triethoxysilicate), and the reaction product of dibutyltin oxide and phthalic acid ester; chelate compounds of various metals such as dibutyltin bis(acetylacetonate), tin-based chelate compounds (e.g., EXCESTARC-501 manufactured by Asahi Glass Co., Ltd.), zirconium tetrakis(acetylacetonate), titanium tetrakis(acetylacetonate), aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate), cobalt acetylacetonate, iron acetylacetonate, copper acetylacetonate, magnesium acetylacetonate, bismuth acetylacetonate, nickel acetylacetonate, zinc acetylacetonate, and manganese acetylacetonate; titanates such as tetra-n-butyl titanate and tetrapropyl titanate; metal organic acid salts of various metals other than tin such as manganese, iron, cobalt, copper, zinc, zirconium, lead, and bismuth, and various organic acids such as octylic acid, stearic acid, and naphthenic acid. Examples of the amines include tertiary amines such as triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,4-diazabicyclo[2,2,2]octane (DABCO), N-methylmorpholine, and N-ethylmorpholine, or salts of these amines and carboxylic acids. These can be used alone or in admixture of two or more.Among these, organometallic compounds are preferred because they are liquids with high reaction rates and relatively low toxicity and volatility. Organotin compounds and metal chelate compounds are more preferred, and dioctyltin dineodecanoate is particularly preferred.

[0064] From the viewpoints of the curing rate, physical properties of the cured product, etc., the compounding amount of the curing accelerator is preferably 0.001 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.02 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the polyol (A).

[0065] <Weather resistance stabilizer> The weather resistance stabilizer is used to prevent oxidation, photo-degradation, and thermal degradation of the cured product of the two-component curable composition, and to further improve not only the weather resistance but also the heat resistance. Specific examples of the weather resistance stabilizer include, for example, hindered amine light stabilizers, hindered phenol antioxidants, ultraviolet absorbers, etc. Examples of the hindered amine light stabilizer include bis(1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, etc. Also, low molecular weight hindered amine light stabilizers with a molecular weight of less than 1000 such as LA-52, LA-57, LA-62, LA-67, LA-77, LA-82, LA-87 of the Adeka Stab series manufactured by Asahi Denka Kogyo Co., Ltd., and high molecular weight hindered amine light stabilizers with a molecular weight of 1000 or more such as LA-63P, LA-68LD of Asahi Denka Kogyo Co., Ltd., and 119FL, 2020FDL, 944FD, 944LD of the Chimassorb series of the trade name manufactured by Ciba Specialty Chemicals are also included.

[0066] Examples of the hindered phenol antioxidants include pentaerythritol - tetrakis[3-(3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionate], octadecyl - 3-(3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionate, N,N′ - hexane - 1,6 - diylbis[3-(3,5 - di - tert - butyl - 4 - hydroxyphenylpropionamide], 3,5 - bis(1,1 - dimethylethyl)-4 - hydroxy C7 - C9 branched alkyl benzenepropionate, 2,4 - dimethyl - 6-(1 - methylpentadecyl)phenol, and the like.

[0067] Examples of the ultraviolet absorbers include benzotriazole - type ultraviolet absorbers such as 2-(3,5 - di - tert - butyl - 2 - hydroxyphenyl)-5 - chlorobenzotriazole, triazine - type ultraviolet absorbers such as 2-(4,6 - diphenyl - 1,3,5 - triazin - 2 - yl)-5 - [(hexyl)oxy]-phenol, benzophenone - type ultraviolet absorbers such as octabenzone, and benzoate - type ultraviolet absorbers such as 2,4 - di - tert - butylphenyl - 3,5 - di - tert - butyl - 4 - hydroxybenzoate.

[0068] The weather resistance stabilizers can be used alone or in combination of two or more. Among these, the hindered amine light stabilizers alone, the hindered phenol antioxidants alone, and the combination of the hindered amine light stabilizers and the hindered phenol antioxidants, that is, the hindered amine light stabilizers and / or the hindered phenol antioxidants are preferred because they are excellent in improving weather resistance and heat resistance.

[0069] The compounding amount of the weather resistance stabilizer is preferably 0.1 part by mass or more and 20 parts by mass or less, and particularly preferably 0.5 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polyol (A).

[0070] <Storage Stability Improver> Examples of the storage stability improver include compounds that react with moisture present in the curing agent of the two-component curable composition, such as low-molecular crosslinkable silyl group-containing compounds like vinyltrimethoxysilane, calcium oxide, magnesium oxide, p-toluenesulfonyl isocyanate, and the like. Among these, calcium oxide is preferred in terms of reliably improving the storage stability of the two-component curable composition.

[0071] The blending amount of the storage stability improver is preferably 0.001 part by mass or more and 5 parts by mass or less, and particularly preferably 0.01 part by mass or more and 1 part by mass or less, based on 100 parts by mass of the polyol (A).

[0072] <Colorant> The colorant can be appropriately selected according to the desired color to be imparted to the two-component curable composition. Examples of the colorant include inorganic colorants such as titanium oxide, iron oxide, carbon black, and organic colorants such as copper phthalocyanine. The blending amount of the colorant is preferably more than 0 part by mass and 50 parts by mass or less, more preferably 0.01 part by mass or more and 10 parts by mass or less, and particularly preferably 0.1 part by mass or more and 25 parts by mass or less, based on 100 parts by mass of the polyol (A).

[0073] <Thixotropy-imparting agent> The thixotropy imparting agent contributes to imparting thixotropy to the two-component curable composition of the present invention and preventing the occurrence of sag (slump) when the two-component curable composition is applied. Examples of the thixotropy imparting agent include inorganic thixotropy imparting agents such as calcium carbonate surface-treated with an organic acid compound (organic acid compound surface-treated calcium carbonate), hydrophilic colloidal silica, and hydrophobic colloidal silica; and organic thixotropy imparting agents such as fatty acid amides and organic bentonite. Among these, calcium carbonate surface-treated with an organic acid compound is preferred in terms of further improving the discharge workability of the resulting two-component curable composition. Calcium carbonate surface-treated with an organic acid compound is obtained by treating (for example, coating) the surface of fine powder calcium carbonate such as synthetic calcium carbonate with an organic acid compound such as a fatty acid like stearic acid or its alkyl ester, a fatty acid metal salt like calcium stearate, or a resin acid. Examples of commercially available products include CC, DD, CCR, U of the Blanc Fixe series manufactured by Shiraishi Kogyo Co., Ltd., and 100, 200, 200M of the Calcfine series manufactured by Maruo Calcium Co., Ltd.

[0074] The blending amount of the thixotropy imparting agent is not particularly limited. For example, it is preferably 5 to 50 parts by mass, and particularly preferably 10 to 40 parts by mass, per 100 parts by mass of the polyol (A).

[0075] <Filler> The filler contributes to imparting strength to the cured product of the two-component curable composition of the present invention. Examples of the filler include mica, kaolin, zeolite, graphite, diatomaceous earth, clay, clay, talc, slate powder, anhydrous silicic acid, fine quartz powder, aluminum powder, zinc powder, synthetic silica such as precipitated silica, calcium carbonate whose surface is not treated (coated, etc.) with a compound such as an organic acid-based compound (sometimes simply referred to as "calcium carbonate"), magnesium carbonate, inorganic powdery fillers such as alumina; fibrous fillers such as glass fiber and carbon fiber; wood powder, walnut flour, rice husk powder, pulp powder, cotton chip, rubber powder, polyamide resin, polyester resin, polyurethane resin, silicone resin, vinyl chloride resin, vinyl acetate resin, polyolefin resins such as polyethylene and polypropylene, (meth)acrylic resin, epoxy resin, phenolic resin, urea resin, melamine resin, etc. organic fillers such as powders of thermoplastic resins or thermosetting resins, flame-retardant-imparting fillers such as magnesium hydroxide and aluminum hydroxide, and the like. Among these, calcium carbonate is preferable in terms of easy availability and reliable strength imparting. As the particle diameter of the filler, for example, 0.01 μm or more and 1,000 μm or less is preferable.

[0076] The blending amount of the filler is not particularly limited, but for example, 5 parts by mass or more and 40 parts by mass or less, and particularly preferably 10 parts by mass or more and 30 parts by mass or less, are preferable with respect to 100 parts by mass of the polyol (A).

[0077] <Adhesion-imparting agent> Examples of the adhesion promoter include coupling agents, epoxy resins, alkyl titanates, organic polyisocyanates, etc. Examples of the coupling agent include various coupling agents such as silane-based, aluminum-based, and zircoaluminate-based coupling agents and / or their partial hydrolysis condensates. Among these, silane coupling agents and / or their partial hydrolysis condensates are preferable in terms of excellent adhesiveness. Examples of the silane-based coupling agent include alkoxysilanes having functional groups such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and isopropenoxysilanes. Further, examples of the silane-based coupling agent include low molecular weight compounds having a molecular weight of 500 or less, preferably 400 or less, and / or compounds having a molecular weight of 200 to 3,000 which are partial hydrolysis condensates of one or more silane-based coupling agents.

[0078] The blending amount of the adhesion promoter is not particularly limited. For example, with respect to 100 parts by mass of the polyol (A), 0.05 part by mass or more and 1.00 part by mass or less is preferable, and 0.10 part by mass or more and 0.50 part by mass or less is particularly preferable.

[0079] The two-component curable composition of the present invention can be used, for example, for repairing road surfaces such as roads in addition to applications such as fillers, sealants, and adhesives. That is, it can be made into a two-component road surface repair agent containing the two-component curable composition. As a construction method when using the two-component curable composition of the present invention for road surface repair, for example, it can be repaired by filling the damaged part of the road surface with the two-component curable composition of the present invention.

Examples

[0080] Next, the two-component curable composition of the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

[0081] (Preparation of Liquid A containing the main component) <Liquid A-1> While flowing nitrogen gas into a kneading and reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, and heating / cooling device, 500 g of castor oil-based polyol (URICF-60 manufactured by Ito Oil Co., Ltd., number of hydroxyl groups per molecule: 3, hydroxyl value: 215 mgKOH / g), 160 g of dimethyl carbonate, and 2.2 g of dioctyltin dineodecanoate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-830) were charged, stirred and mixed at room temperature to prepare Liquid A-1.

[0082] <Liquid A-2> Liquid A-2 was prepared in the same manner as Liquid A-1 except that 140 g of dimethyl carbonate was used. <Liquid A-3> Liquid A-3 was prepared in the same manner as Liquid A-1 except that 800 g of calcium oxide was further used. <Liquid A-4> Liquid A-4 was prepared in the same manner as Liquid A-3 except that 400 g of methyl oleate was further used as the fatty acid ester. <Liquid A-5> Liquid A-5 was prepared in the same manner as Liquid A-1 except that 680 g of polyoxypropylene triol (manufactured by AGC Inc., trade name: Excenol 1030, number average molecular weight 1000) was used instead of the castor oil-based polyol and 180 g of dimethyl carbonate was used. <A-6 liquid> A-6 liquid was prepared in the same manner as A-1 liquid, except that 83 g of dimethyl carbonate and 1.1 g of dioctyltin dineodecanoate were used. <A-7 liquid> A-7 liquid was prepared in the same manner as A-1 liquid, except that 400 g of methyl propionate was used.

[0083] (Preparation of Liquid B, a component containing a curing agent) <B-1 liquid> While flowing nitrogen gas through a kneading and reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, and heating / cooling device, 266.0 g of polyoxypropylene triol (manufactured by AGC Inc., trade name: Excenol 4030, number average molecular weight 4000), 417.5 g of polyoxypropylene diol (manufactured by AGC Inc., trade name: Excenol 3021, number average molecular weight 3300), 20.0 g of a hindered phenol antioxidant (manufactured by BASF Japan Ltd., IRGANOX 1010, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), and 0.05 g of 2-ethylhexyl acid phosphate (trade name: JP-508, manufactured by Johoku Chemical Industry Co., Ltd.) were charged and stirred and mixed. Next, 304.0 g of diphenylmethane diisocyanate and 0.1 g of zirconium octylate as a curing acceleration catalyst were charged while stirring, and then heated and reacted at 70 to 75 °C for 1 hour. Thereafter, it was cooled to room temperature, and 64.0 g of diisononyl phthalate (DINP), 400.0 g of methyl oleate as a fatty acid ester, and 1.0 g of p-toluenesulfonyl isocyanate were charged, and further stirred and mixed for 30 minutes until uniform to prepare B-1 liquid.

[0084] <B-2 liquid> B-2 liquid was adjusted in the same manner as B-1 liquid, except that DINP was not used. <B-3 liquid> B-3 liquid was prepared in the same manner as B-2 liquid, except that 175.0 g of methyl oleate was used. <B-4 liquid> B-4 solution was prepared in the same manner as B-1 solution, except that 800.0 g of methyl oleate was used. <B-5 solution> B-5 solution was prepared in the same manner as B-1 solution, except that methyl oleate was not used. <B-6 solution> B-6 solution was prepared in the same manner as B-1 solution, except that 435.0 g of methyl oleate was used.

[0085] <B-7 solution> B-7 solution was prepared in the same manner as B-1 solution, except that neither methyl oleate nor DINP was used. <B-8 solution> B-8 solution was prepared in the same manner as B-2 solution, except that ethyl oleate was used instead of methyl oleate as the fatty acid ester. <B-9 solution> B-9 solution was prepared in the same manner as B-2 solution, except that methyl 10-undecenoate was used instead of methyl oleate as the fatty acid ester. <B-10 solution> B-10 solution was prepared in the same manner as B-2 solution, except that methyl palmitate was used instead of methyl oleate as the fatty acid ester. <B-11 solution> B-11 solution was prepared in the same manner as B-2 solution, except that methyl decanoate was used instead of methyl oleate as the fatty acid ester.

[0086] <B-12 solution> While flowing nitrogen gas through a kneading and reaction vessel equipped with a stirrer, a thermometer, a nitrogen seal tube, and a heating / cooling device, 268.0 g of polymeric MDI (manufactured by Tosoh Corporation, trade name: Millionate MR-200, NCO content 30.5 - 32.0 mass%) and 207.0 g of methyl oleate as the fatty acid ester were charged, and stirred and mixed for 30 minutes until uniform to prepare B-12 solution. <B-13 solution> B-13 solution was prepared in the same manner as B-12 solution, except that 186.0 g of m-xylylene diisocyanate (manufactured by Mitsui Chemicals, Inc., trade name: Takenate 500) was used instead of polymeric MDI. <B-14 liquid> The B-14 liquid was prepared in the same manner as the B-12 liquid except that methyl oleate was not used. <B-15 liquid> The B-15 liquid was prepared in the same manner as the B-13 liquid except that methyl oleate was not used.

[0087] The test methods for the evaluation items are described below. (1) Swelling test The liquid A containing the main agent, the liquid B containing the curing agent, and purified water that had been left standing in an atmosphere of 23°C for 24 hours were used as samples. In an atmosphere of 23°C and 50% relative humidity, the liquid A and the liquid B at the ratios shown in Tables 1 to 3 below, and 0.3% by mass of purified water with respect to the total mass of the liquid A and the liquid B were mixed, and immediately filled into a glass container with a diameter of 32 mm and a thickness of 65 mm so that the surface of the composition was at the same height as the marked line (30 mm from the bottom) on the side of the container. After standing for 2 hours for curing, the height (unit: mm) from the marked line on the surface of the cured product was measured. Those with a height of less than 9.0 mm and complete curing were judged as qualified.

[0088] (2) Touch-dry time The liquid A containing the main agent and the liquid B containing the curing agent that had been left standing in an atmosphere of 23°C for 24 hours were used as samples. In an atmosphere of 23°C and 55% relative humidity, the liquid A and the liquid B were mixed at the ratios shown in Tables 1 to 3 below, and immediately a test piece with a thickness of about 3 mm was made flat with a spatula or the like on a glass plate so that no bubbles were formed and left standing. With a fingertip cleaned with ethyl alcohol, the surface of the test piece was lightly touched at three places, and the time required until the sample on the surface of the test piece no longer adhered to the fingertip from the start of mixing was measured.

[0089] (3) Rubber physical properties (tensile stress at break, elongation at break, and tensile stress at 50% elongation) A liquid containing the main agent and B liquid containing the curing agent that had been left standing for 24 hours in an atmosphere of 23°C were used as samples. The A liquid and the B liquid were mixed at the ratios shown in Tables 1 to 3 below in an atmosphere of 23°C and a relative humidity of 55%, and immediately poured into a mold that had been subjected to a mold release treatment, taking care not to entrap air bubbles so as to achieve a thickness of approximately 2.5 mm, and left standing for 7 days. After standing for 7 days, the mold was removed to produce a test piece of the cured sheet. Using the produced test piece, a test was conducted in accordance with JIS K 6251:2004 in the shape of dumbbell No. 3, and the tensile stress at break (Tb), elongation at break (Eb), and tensile stress at 50% elongation (M50) were measured.

[0090] The blending ratios of the respective components and the evaluation results in the examples and comparative examples are shown in Tables 1 to 3 below. In addition, the blending amounts in Tables 1 to 3 below mean parts by mass unless otherwise specified, and a blank means no blending.

[0091]

Table 1

[0092]

Table 2

[0093]

Table 3

[0094] As shown in Tables 1 to 3 above, in Examples 1 to 14 containing a main agent containing polyol (A), a curing agent containing an organic isocyanate compound and / or an isocyanate group-containing compound (B) which is an isocyanate group-containing urethane prepolymer, and a fatty acid ester (C), under an atmosphere of 23°C and 50% relative humidity, the result of the swelling test was 8.5 mm or less in height, and the swelling was suppressed by an excellent anti-foaming effect. Therefore, it was found that in Examples 1 to 14, an excellent anti-foaming effect can be obtained for an object to be adhered under a high-temperature and high-humidity atmosphere or an object to be adhered with a high moisture content. Also, in Examples 1 to 14, a finger-touch drying time generally equivalent to that of the conventional art was obtained. Further, in Examples 1 to 14, the rubber physical properties were also superior to those of the conventional art, and it was found that excellent followability can be obtained with respect to the movement of members at the site where the two-component curable composition of the present invention was applied.

[0095] In particular, Examples 2 and 4 containing 40 parts by mass or more of fatty acid ester (C) with respect to 100 parts by mass of polyol (A) had further reduced swelling compared to Example 3 containing less than 40 parts by mass of fatty acid ester (C) with respect to 100 parts by mass of polyol (A). Also, from the comparison between Example 2 and Example 8, the swelling was further reduced for fatty acid methyl ester than for fatty acid ethyl ester.

[0096] Further, from the comparison between Example 2 and Examples 13 and 14, the swelling was more reduced when an isocyanate group-containing urethane prepolymer was blended rather than an organic isocyanate compound as the isocyanate group-containing compound (B).

[0097] On the other hand, in Comparative Examples 1 to 5 where no fatty acid ester was blended, the height of the swelling test was 9.0 mm or more in all cases, and an excellent anti-foaming effect could not be obtained.

Industrial Applicability

[0098] The two-component curable composition of the present invention can provide an excellent foam suppression effect even when used in an atmosphere of high temperature and high humidity or on a substrate with a high moisture content, so it can be used in a wide range of fields. For example, it has high utility value in fields where it is necessary to cope with environmental changes such as temperature and humidity, such as road surface repair, etc.

Claims

1. A two-component curable composition comprising a main agent containing a polyol (A), a curing agent containing an organic isocyanate compound and / or an isocyanate group-containing urethane prepolymer as the isocyanate group-containing compound (B), and a fatty acid ester (C), wherein the polyol (A) contains a castor oil-based polyol, the fatty acid ester (C) is an ester of a saturated fatty acid having 3 to 25 carbon atoms or an unsaturated fatty acid having 5 to 25 carbon atoms and a linear aliphatic monoalcohol having 1 to 4 carbon atoms.

2. The two-component curable composition according to Claim 1, wherein the fatty acid ester (C) is a fatty acid methyl ester.

3. The two-component curable composition according to Claim 1 or 2, containing 20 to 200 parts by mass of the fatty acid ester (C) with respect to 100 parts by mass of the polyol (A).

4. The two-component curable composition according to any one of Claims 1 to 3, containing 40 to 200 parts by mass of the fatty acid ester (C) with respect to 100 parts by mass of the polyol (A).

5. The two-component curable composition according to any one of Claims 1 to 4, wherein the isocyanate group-containing compound (B) is an isocyanate group-containing urethane prepolymer.

6. The two-component curable composition according to any one of Claims 1 to 5, which is for road surface repair.

7. A two-component road surface repair agent containing the two-component curable composition according to any one of Claims 1 to 6.

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