Curable composition

Abstract

To provide a curable composition which is suitable for a large bonding surface such as a building and a civil engineering structure and has excellent adhesion even if the large bonding surface is a difficult-to-bond material (a hardly adhesive adherend) such as a polyolefin.SOLUTION: There is provided a curable composition which comprises a room temperature curable compound and an aliphatic carboxylic acid compound and / or a salt thereof, wherein the total of the blending amount of the aliphatic carboxylic acid compound and / or the salt thereof is 10 to 200 pts.mass based on 100 pts.mass (solid content) of the room temperature curable compound.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a curable composition having excellent adhesiveness to a difficult-to-bond material such as polyolefin.

Background Art

[0002] For the purpose of waterproofing, surface protection, and joining of buildings and civil engineering structures, curable compositions containing room-temperature curable resins such as polyurethane resins and modified silicone resins are widely used. Since there are various types of members in buildings and civil engineering structures, it is recommended to apply a primer to the surface of the members for the purpose of improving the adhesiveness to the members when using the curable composition. However, if there are coating unevenness or missed coating during primer application, there is a risk that sufficient adhesiveness to the members cannot be ensured, and a curable composition having excellent self-adhesiveness to the members is required. In addition, when the member is a difficult-to-bond material (a difficult-to-bond adherend) such as polyolefin, sufficient adhesiveness may not be ensured even if a primer is applied, and a primer having excellent adhesiveness to the difficult-to-bond material is required.

[0003] As an adhesive for joining various members, for example, cyanoacrylate-based adhesives are known. However, although cyanoacrylate-based adhesives cure quickly and can be applied to small-scale adhesive surfaces, they may not be applicable to medium-scale to large-scale adhesive surfaces such as buildings and civil engineering structures because they cure before the members are bonded together.

[0004] In addition, cyanoacrylate-based adhesives have a problem that sufficient adhesiveness cannot be obtained for difficult-to-bond adherends such as polyolefins such as polyethylene and polypropylene. Therefore, as a primer capable of obtaining an adhesive force by a cyanoacrylate-based adhesive for difficult-to-bond adherends such as polyolefins such as polyethylene and polypropylene, a primer composed of a composition of silicone oil, trialkylamine, and a solvent has been proposed (Patent Document 1).

[0005] Also, it has been proposed to blend a hindered amine compound having a piperidine skeleton in a predetermined amount with a difficult-to-adhere adherend without using a primer, and to adhere the blended difficult-to-adhere adherend with a cyanoacrylate adhesive (Patent Document 2).

[0006] However, in Patent Documents 1 and 2, it is limited to the case of using a cyanoacrylate adhesive as an adhesive. As described above, when a cyanoacrylate adhesive is used, it may cure before bonding members to a medium to large-sized bonding surface, so there is a problem that it may not be suitable for bonding members such as buildings and civil engineering structures. Further, in Patent Documents 1 and 2, since it is limited to the case of using a cyanoacrylate adhesive as an adhesive, there is a problem that it cannot be applied when bonding a member to a difficult-to-adhere adherend without using a cyanoacrylate adhesive.

[0007] Further, in Patent Document 1, there is room for improvement in the adhesiveness between a difficult-to-adhere adherend such as a polyolefin such as polyethylene and polypropylene and a primer.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0009] In view of the above circumstances, an object of the present invention is to provide a curable composition that can be applied to a large bonding surface such as a building or a civil engineering structure, and that has excellent adhesiveness even when the large bonding surface is a difficult-to-adhere material (difficult-to-adhere adherend) such as a polyolefin.

Means for Solving the Problems

[0010] The gist of the constitution of the curable composition of the present invention is as follows. [1] It contains a room temperature curable compound, an aliphatic carboxylic acid compound and / or a salt thereof, A curable composition characterized in that the total amount of the aliphatic carboxylic acid compound and / or a salt thereof is 10 to 200 parts by mass with respect to 100 parts by mass (solid content) of the room temperature curable compound. [2] The curable composition according to [1], wherein the room temperature curable compound is an isocyanate group-containing compound and / or a crosslinkable silyl group-containing compound. [3] The room temperature curable compound is an isocyanate group-containing compound, The curable composition according to [1] or [2], wherein the isocyanate group-containing compound is at least one compound selected from the group consisting of an organic polyisocyanate, a modified product of an organic polyisocyanate, and a reaction product of an organic polyisocyanate and / or a modified product of an organic polyisocyanate and an active hydrogen-containing compound. [4] The curable composition according to [1] or [2], wherein the aliphatic hydrocarbon group of the aliphatic carboxylic acid compound and / or a salt thereof has 6 to 24 carbon atoms. [5] Further, it contains an olefin chloride compound, The curable composition according to [1] or [2], wherein the amount of the olefin chloride compound is 1 to 50 parts by mass with respect to 100 parts by mass of the room temperature curable compound. [6] Further, it contains an additive, The curable composition according to [1] or [2], wherein the additive is at least one additive selected from the group consisting of a curing accelerator catalyst, a plasticizer, a weather stabilizer, a filler, a thixotropy-imparting agent, an adhesion improver, a storage stability improver (dehydrating agent), a coloring agent, and an organic solvent. [7] The curable composition according to [1] or [2], wherein the curable composition is a primer composition, an adhesive composition, a coating material composition, a waterproof material composition, or a sealing material composition. [8] The curable composition according to [1] or [2], characterized in that it is a primer composition, an adhesive composition, a coating material composition, a waterproofing material composition or a sealing material composition for a difficult-to-adhere material containing a polyolefin.

[0011] In the present invention, "room temperature" in the "room temperature curable compound" means normal temperature, which means 5°C to 35°C.

Advantages of the Invention

[0012] According to an aspect of the curable composition of the present invention, it contains a room temperature curable compound, an aliphatic carboxylic acid compound and / or a salt thereof, and the total blending amount of the aliphatic carboxylic acid compound and / or a salt thereof is 10 to 200 parts by mass with respect to 100 parts by mass (solid content) of the room temperature curable compound. Thus, it can be applied to large-sized bonding surfaces such as buildings and civil engineering structures, and even if the large-sized bonding surface is a difficult-to-adhere material (difficult-to-adhere adherend) such as polyolefin, a curable composition having excellent adhesiveness can be obtained.

[0013] According to an aspect of the curable composition of the present invention, since the room temperature curable compound is an isocyanate group-containing compound and / or a crosslinkable silyl group-containing compound, excellent adhesiveness can be more surely exhibited even for a difficult-to-adhere adherend such as polyolefin.

[0014] According to an aspect of the curable composition of the present invention, the room temperature curable compound is an isocyanate group-containing compound, and the isocyanate group-containing compound is at least one compound selected from the group consisting of organic polyisocyanates, modified products of organic polyisocyanates, and reaction products of organic polyisocyanates and / or modified products of organic polyisocyanates with active hydrogen-containing compounds. Thus, excellent adhesiveness can be more surely exhibited even for a difficult-to-adhere adherend such as polyolefin.

[0015] According to an aspect of the curable composition of the present invention, since the aliphatic hydrocarbon group of the aliphatic carboxylic acid compound and / or its salt has 6 to 24 carbon atoms, excellent adhesiveness can be more surely exhibited even in the case of a poorly adherent adherend such as polyolefin.

Mode for Carrying Out the Invention

[0016] Hereinafter, the curable composition of the present invention will be described in detail.

[0017] The curable composition of the present invention contains a room-temperature curable compound and an aliphatic carboxylic acid compound and / or its salt, and is characterized in that the total blending amount of the aliphatic carboxylic acid compound and / or its salt is 10 to 200 parts by mass with respect to 100 parts by mass (solid content) of the room-temperature curable compound. According to an aspect of the curable composition of the present invention, by containing a room-temperature curable compound and an aliphatic carboxylic acid compound and / or its salt, and the total blending amount of the aliphatic carboxylic acid compound and / or its salt being 10 to 200 parts by mass with respect to 100 parts by mass (solid content) of the room-temperature curable compound, it can be applied to a large adhesive surface such as a building or a civil engineering structure, and also, even if the large adhesive surface is a difficult-to-adhere material (poorly adherent adherend) such as polyolefin, a curable composition having excellent adhesiveness can be obtained.

[0018] Hereinafter, each component of the curable composition of the present invention will be described in detail.

[0019] <Room-temperature curable compound> The room-temperature curable compound is one that reacts with an active hydrogen-containing compound etc. (for example, water such as moisture) at normal temperature and cures. Further, even a curable compound that reacts with an active hydrogen-containing compound etc. and crosslinks and cures at a temperature below 5°C or above 35°C is included in the room-temperature curable compound as long as it reacts with an active hydrogen-containing compound etc. and crosslinks and cures at normal temperature (5 to 35°C).

[0020] As the room temperature curable compound, there is no particular limitation as long as it reacts with an active hydrogen-containing compound or the like at room temperature to crosslink and cure. Even for a poorly adherent adherend such as polyolefin, from the viewpoint that excellent adhesiveness can be more surely exhibited, an isocyanate group-containing compound and a crosslinkable silyl group-containing compound (hydrolyzable silyl group-containing compound) are preferable. These compounds may be used alone or in combination of two or more. Among these, an isocyanate group-containing compound is particularly preferable from the viewpoint that excellent adhesiveness can be more surely exhibited even for a poorly adherent adherend such as polyolefin.

[0021] <Isocyanate group-containing compound> The isocyanate group-containing compound is a compound having one or more isocyanate groups in the compound. The isocyanate group reacts with an active hydrogen-containing compound to form a urethane bond, a urea bond, etc. and crosslink and cure. Examples of the isocyanate group-containing compound include at least one compound selected from the group consisting of organic polyisocyanates, modified products of organic polyisocyanates, and reaction products of organic polyisocyanates and / or modified products of organic polyisocyanates with active hydrogen-containing compounds. These compounds may be used alone or in combination of two or more.

[0022] Organic polyisocyanate Organic polyisocyanates are compounds having two or more isocyanate groups in the molecule. Specifically, toluene polyisocyanates such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, diphenylmethane polyisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate, phenylene polyisocyanates such as 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4,6-trimethylphenyl-1,3-diisocyanate, and 2,4,6-triisopropylphenyl-1,3-diisocyanate, naphthalene polyisocyanates such as 1,4-naphthalene diisocyanate and 1,5-naphthalene diisocyanate, aromatic polyisocyanates such as chlorophenylene-2,4-diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate can be mentioned. Also, aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, decamethylene diisocyanate, and lysine diisocyanate, araliphatic polyisocyanates such as o-xylylene diisocyanate, m-xylylene diisocyanate, and p-xylylene diisocyanate, alicyclic polyisocyanates such as 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate can be mentioned. Furthermore, polymeric isocyanates such as polymethylene polyphenyl polyisocyanate and crude toluene diisocyanate can be mentioned. These organic polyisocyanates may be used alone or in combination of two or more kinds.

[0023] Among these organic polyisocyanates, when used in places where the curable composition is exposed to sunlight (ultraviolet rays), aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates are preferred from the viewpoint of improving the weather resistance of the curable composition. When used in places where the curable composition is not exposed to sunlight (ultraviolet rays), aromatic polyisocyanates are preferred from the viewpoints of heat resistance and economy.

[0024] Modified product of organic polyisocyanate Examples of modified products of organic polyisocyanates include modified polyisocyanates having one or more uretdione bonds, isocyanurate bonds, allophanate bonds, biuret bonds, uretonimine bonds, carbodiimide bonds, urethane bonds, or urea bonds, which are obtained by modifying the above-mentioned organic polyisocyanates. These modified products of organic polyisocyanates may be used alone or in combination of two or more.

[0025] Among these modified products of organic polyisocyanates, when used in places where the curable composition is exposed to sunlight (ultraviolet rays), modified products of aliphatic polyisocyanates, modified products of araliphatic polyisocyanates, and modified products of alicyclic polyisocyanates are preferred from the viewpoint of improving the weather resistance of the curable composition. When used in places where the curable composition is not exposed to sunlight (ultraviolet rays), modified products of aromatic polyisocyanates are preferred from the viewpoints of heat resistance and economy. Further, when the curable composition is used as a primer composition, modified polyisocyanates having an isocyanurate bond, a carbodiimide bond, or a urethane bond modified by reacting with a low molecular weight polyol such as trimethylolpropane are preferred.

[0026] Reaction product of organic polyisocyanate and / or modified product of organic polyisocyanate with an active hydrogen-containing compound Examples of the reaction product of an organic polyisocyanate and / or a modified product of an organic polyisocyanate and an active hydrogen-containing compound include isocyanate group-containing urethane resins. The isocyanate group-containing urethane resin is prepared by reacting an organic polyisocyanate and / or a modified product of an organic polyisocyanate and an active hydrogen-containing compound in a molar ratio of isocyanate group / active hydrogen of more than 1.0, preferably 1.2 or more from the viewpoint of preventing the viscosity of the isocyanate group-containing urethane resin from increasing and the workability of the curable composition from deteriorating, and 10 or less from the viewpoint of reducing the amount of carbon dioxide gas generated by the reaction of the isocyanate group with water and preventing foaming during curing, either batchwise or sequentially, so that isocyanate groups remain in the urethane resin.

[0027] The number average molecular weight of the isocyanate group-containing urethane resin is preferably 300 or more, more preferably 300 to 20,000, still more preferably 300 to 15,000, and particularly preferably 300 to 10,000. When the curable composition of the present invention is used as a primer composition, the number average molecular weight of the isocyanate group-containing urethane resin is preferably 300 or more, more preferably 300 to 10,000, still more preferably 300 to 5,000, and particularly preferably 300 to 3,000. Further, when the curable composition of the present invention is used as an adhesive composition, a coating material composition, a waterproof material composition or a sealing material composition, the number average molecular weight of the isocyanate group-containing urethane resin is preferably 1,500 or more, more preferably 1,500 to 20,000, still more preferably 1,500 to 15,000, and particularly preferably 1,500 to 10,000.

[0028] In the present invention, the number average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC). Specific measurement conditions are shown below. Equipment name: HLC-8320GPC (manufactured by Tosoh Corporation) Eluent: THF Temperature: 40 °C Detector: RI

[0029] As a method for producing an isocyanate group-containing urethane resin, a conventionally known method can be used. Specifically, an organic polyisocyanate and / or a modified product of an organic polyisocyanate and an active hydrogen-containing compound are charged into a reaction vessel made of glass, stainless steel, or the like, and if necessary, a reaction catalyst and an organic solvent are used, and the reaction is carried out while stirring at 50 to 120 °C. At this time, since the urethane resin thickens when the isocyanate group reacts with water such as moisture, it is preferable to replace the inside of the container with nitrogen gas in advance or carry out the reaction under a nitrogen gas stream.

[0030] Examples of the organic polyisocyanate include the above-mentioned organic polyisocyanates. Examples of the modified product of the organic polyisocyanate include the above-mentioned modified products of the organic polyisocyanate. In obtaining a reaction product of an organic polyisocyanate and / or a modified product of an organic polyisocyanate and an active hydrogen-containing compound, an organic polyisocyanate or a modified product of an organic polyisocyanate may be used, or an organic polyisocyanate and a modified product of an organic polyisocyanate may be used in combination.

[0031] In addition, in obtaining a reaction product of an organic polyisocyanate and / or a modified product of an organic polyisocyanate and an active hydrogen-containing compound, an organic monoisocyanate may be used together with the organic polyisocyanate and / or the modified product of the organic polyisocyanate. That is, in obtaining a reaction product of an organic polyisocyanate and / or a modified product of an organic polyisocyanate and an active hydrogen-containing compound, a mixture of an organic polyisocyanate and / or a modified product of an organic polyisocyanate and an organic monoisocyanate can be used. An organic monoisocyanate is a compound having one isocyanate group in the compound. Specifically, for example, aliphatic monoisocyanates such as n-butyl monoisocyanate, n-hexyl monoisocyanate, n-hexadecyl monoisocyanate, and n-octadecyl monoisocyanate, and aromatic monoisocyanates such as p-isopropylphenyl monoisocyanate and p-benzyloxyphenyl monoisocyanate can be mentioned.

[0032] An active hydrogen-containing compound is a compound having one or more active hydrogens (groups) in the compound. Specifically, examples include high molecular weight polyols, high molecular weight polyamines, low molecular weight polyols, low molecular weight amino alcohols, low molecular weight polyamines, and high molecular weight and low molecular weight monoalcohols. In the present invention, "high molecular weight" means "a compound having a number average molecular weight of 1,000 or more", and "low molecular weight" means "a compound having a number average molecular weight of less than 1,000".

[0033] Examples of the high molecular weight polyol include polyester polyol, polycarbonate polyol, polyoxyalkylene polyol, poly(meth)acrylic polyol, hydrocarbon polyol, animal and plant polyol, and copolyols thereof. In the present invention, "(meth)acrylic" means "acrylic and / or methacrylic".

[0034] The number average molecular weight of the high molecular weight polyol is preferably 1,000 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000. The weight average molecular weight of the high molecular weight polyol is preferably 1,500 to 50,000, more preferably 2,000 to 40,000, and particularly preferably 2,000 to 20,000.

[0035] 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 of these polycarboxylic acids, and alkyl esters such as methyl esters and ethyl esters of these polycarboxylic acids, 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, ethylene oxide or propylene oxide adducts of bisphenol A, trimethylolpropane, glycerin, and pentaerythritol. Further, examples of the polyester polyol include polyester amide polyols obtained by reacting one or more of these carboxylic acids and low molecular weight polyols with one or more low molecular weight polyamines such as butylenediamine, hexamethylenediamine, xylylenediamine, and isophoronediamine, and low molecular weight amino alcohols such as monoethanolamine and diethanolamine. Furthermore, examples of the polyester polyol include lactone-based polyester polyols obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone using low molecular weight polyols, low molecular weight polyamines, and low molecular weight amino alcohols as initiators.

[0036] Examples of the polycarbonate polyol include, for example, a polyol obtained by a dehydrochlorination reaction of low molecular weight polyols used in the synthesis of the above-described polyester polyol and phosgene, or a transesterification reaction of the above-described low molecular weight polyols with diethylene carbonate, dimethyl carbonate, diethyl carbonate, or diphenyl carbonate.

[0037] Examples of the polyoxyalkylene polyol include, in addition to the low molecular weight polyols, low molecular weight polyamines, and low molecular weight amino alcohols used in the synthesis of the above-described polyester polyol, saccharide-based low molecular weight polyhydric alcohols such as sorbitol, mannitol, sucrose, and glucose; one or more low molecular weight polyhydric phenols such as bisphenol A and bisphenol F as initiators, and one or more cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran are subjected to ring-opening addition polymerization or copolymerization to obtain polyoxyethylene polyol, polyoxypropylene polyol, polyoxybutylene polyol, polyoxytetramethylene polyol, poly-(oxyethylene)-(oxypropylene)-random or block copolymer polyol. Further, examples of the polyoxyalkylene polyol include polyester ether polyol and polycarbonate ether polyol using the above-described polyester polyol or polycarbonate polyol as an initiator. Also, examples of the polyoxyalkylene polyol include a polyol having a hydroxyl group at the molecular end obtained by reacting these various ether polyols with an organic isocyanate compound in an excess of hydroxyl group with respect to the isocyanate group. The number of alcoholic hydroxyl groups in the polyoxyalkylene polyol is preferably 2 or more, more preferably 2 to 4, and particularly preferably 2 to 3 on average per molecule.

[0038] As catalysts for synthesizing polyoxyalkylene polyols, there may be mentioned alkali metal compound catalysts such as sodium-based catalysts and potassium-based catalysts, cationic polymerization catalysts, composite metal cyanide complex catalysts such as glyme complexes and diglyme complexes of zinc hexacyanocobaltate, and phosphazene compound catalysts. Among these catalysts, alkali metal compound catalysts and composite metal cyanide complex catalysts are preferred. Further, polyoxyalkylene polyols synthesized using composite metal cyanide complex catalysts are preferred because they have a low total unsaturation degree and a low viscosity of the polyol.

[0039] Also, if necessary, as a modifier for urethane resins, polyoxyalkylene monools such as polyoxypropylene monool obtained by ring-opening addition polymerization of a cyclic ether compound such as propylene oxide using a low molecular weight monoalcohol such as methyl alcohol, ethyl alcohol, or propyl alcohol as an initiator can also be used. The number average molecular weight of the polyoxyalkylene monool is preferably from 1,000 to 10,000.

[0040] In the polyoxyalkylene polyol and polyoxyalkylene monool, the term "series" means that 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more of the portion excluding the hydroxyl group in 1 mole of the molecule is composed of polyoxyalkylene. The remaining portion may be modified with an ester, urethane, polycarbonate, polyamide, poly(meth)acrylate, polyolefin, or the like. In the present invention, "(meth)acrylate" means "acrylate and / or methacrylate".

[0041] The poly(meth)acrylic polyol is obtained by copolymerizing a hydroxyl group-containing (meth)acrylic monomer and an ethylenically unsaturated compound other than the hydroxyl group-containing (meth)acrylic monomer by a radical polymerization method such as batch polymerization or continuous polymerization in the presence or absence of a solvent. The one obtained by carrying out a continuous bulk copolymerization reaction at a high temperature of preferably 150 to 350°C, more preferably 210 to 250°C, in the absence of a solvent is preferable in that the molecular weight distribution of the reaction product is narrow and the viscosity is low. In this copolymerization reaction, 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 1.2 to 4. The glass transition point (Tg) of the poly(meth)acrylic polyol is preferably 50°C or lower, more preferably 0°C or lower, still more preferably -70 to -20°C, and particularly preferably -70 to -30°C.

[0042] The hydroxyl group-containing (meth)acrylic monomer is a (meth)acrylic monomer having at least one hydroxyl group in the molecule, and examples thereof include hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; monomethacrylates of polyhydric alcohols such as pentaerythritol tri(meth)acrylate, glycerin mono(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and polypropylene glycol mono(meth)acrylate, and hydroxyl group-retaining polyvalent (meth)acrylates. These compounds may be used alone or in combination of two or more. Among the above-mentioned hydroxyl group-containing (meth)acrylic monomers, hydroxyalkyl (meth)acrylates are preferable in that the viscosity of the poly(meth)acrylic polyol is low and the reactivity with an isocyanate group is good.

[0043] Examples of ethylenically unsaturated compounds other than the hydroxyl group-containing (meth)acrylic monomers include (meth)acrylic monomers without a hydroxyl group and ethylenically unsaturated compounds other than (meth)acrylic monomers. Examples of ethylenically unsaturated compounds other than (meth)acrylic monomers include vinyl compounds such as ethylene, propylene, isobutylene, butadiene, chloroprene, styrene, chlorostyrene, 2-methylstyrene, and divinylbenzene. Examples of (meth)acrylic monomers without a hydroxyl group include (meth)acrylic esters such as (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, tridecyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycidyl tri(meth)acrylate, and trimethylolpropane tri(meth)acrylate. These compounds may be used alone or in combination of two or more. Among the ethylenically unsaturated compounds other than the above-mentioned hydroxyl group-containing (meth)acrylic monomers, monomers of (meth)acrylic ester compounds are preferred in terms of the low viscosity of poly(meth)acrylic polyol, and methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are particularly preferred. In the present invention, "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid".

[0044] 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.

[0045] Examples of animal and plant polyols include castor oil-based polyols and silk fibroin.

[0046] Any of the above-mentioned polymer polyols may be used alone or in combination of two or more.

[0047] Examples of the low molecular weight polyol include low molecular weight aliphatic polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol; low molecular weight alicyclic polyols such as cyclohexanedimethanol and cyclohexanediol; low molecular weight aromatic polyols such as bisphenol A EO2 molar adduct, bisphenol A EO4 molar adduct, bisphenol A EO6 molar adduct, bisphenol A EO8 molar adduct, bisphenol A EO10 molar adduct, bisphenol A PO2 molar adduct, bisphenol A PO3 molar adduct, and bisphenol A PO5 molar adduct which are ethylene oxide (hereinafter sometimes referred to as "EO") adducts of bisphenol A; and low molecular weight polyols having three or more hydroxyl groups such as trimethylolethane, trimethylolpropane, hexitols, pentitols, glycerin, polyglycerin, pentaerythritol, dipentaerythritol, and tetramethylolpropane. These low molecular weight polyols may be used alone or in combination of two or more.

[0048] <Crosslinkable silyl group-containing compound> A crosslinkable silyl group-containing compound is a compound having one or more crosslinkable (hydrolyzable) silyl groups in the compound. The crosslinkable silyl group introduced into the compound undergoes a hydrolysis reaction with moisture such as moisture in the air at room temperature to form silanol groups, which then undergo a condensation reaction to crosslink and harden into a cured product. From the above, the crosslinkable silyl group-containing compound is a hydrolyzable silyl group-containing compound. Examples of the crosslinkable silyl group-containing compound include silicone resins, modified silicone resins, and silane coupling agents.

[0049] From the viewpoints of the curability of the curable composition and the physical properties after curing, it is preferable that on average, one or more crosslinkable silyl groups are contained in one molecule of the crosslinkable silyl group-containing compound, and it is particularly preferable that on average, 1 to 3 crosslinkable silyl groups are contained in one molecule. The crosslinkable silyl group is preferably represented by the following general formula from the viewpoints of easy crosslinking and easy production. [Chemical formula] (In the formula, R is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and particularly preferably a methyl group. When there are a plurality of Rs, they may be the same group or different groups. The reactive group represented by X is a hydrolyzable group selected from a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoxime group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group, and an aminooxy group. When there are a plurality of Xs, Xs may be the same group or different groups. Among these, X is preferably an alkoxy group, and particularly preferably a methoxy group or an ethoxy group. a is an integer of 0, 1, or 2, and 0 or 1 is particularly preferable.)

[0050] Silicone resin A silicone resin is a resin whose main chain is organopolysiloxane and which has crosslinkable silyl groups in its chemical structure. Specifically, there are one-component silicone resins containing organopolysiloxane having silanol groups at the terminals as the main component and low-molecular compounds containing crosslinkable silyl groups as the crosslinking component, and two-component silicone resins containing organopolysiloxane having silanol groups at the terminals as the main agent and aminooxyalkylsilane as the curing agent. Examples of the low-molecular compounds containing crosslinkable silyl groups include acyloxyalkylsilane, aminooxyalkylsilane, and alkoxyalkylsilane.

[0051] Modified silicone resin Examples of the modified silicone resins include those disclosed in JP-A-52-73998, JP-A-55-9669, JP-A-59-122541, JP-A-60-6747, JP-A-61-233043, JP-A-63-6003, JP-A-63-112642, JP-A-3-79627, JP-A-4-283259, JP-A-5-287186, JP-A-11-80571, JP-A-11-116763, and JP-A-11-130931. Specifically, examples of the modified silicone resins include those having one or more crosslinkable silyl groups in the resin and whose main chains are vinyl-based polymers, polyoxyalkylene-based polymers, (meth)acrylic-based copolymers, aliphatic hydrocarbon-based polymers such as polyisoprene, polyisobutylene, and polybutadiene, and polyester-based polymers and polysulfide polymers. Also, copolymers of the above-mentioned polymers and mixtures of the polymers are included. These modified silicone resins may be used alone or in combination of two or more.

[0052] The main chain of the modified silicone resin is preferably a polyoxyalkylene polymer, a polyoxyalkylene polymer which may be (meth)acryl-modified, or a (meth)acrylic copolymer in that the rubber physical properties such as the modulus and elongation of the cured composition are good. In the present invention, "(meth)acryl-modified" means a polymer obtained by block or pendant copolymerization of a (meth)acrylic monomer with a polyoxyalkylene polymer, a mixture of a polyoxyalkylene polymer and a (meth)acrylic copolymer, or a polymer obtained by polymerizing a (meth)acrylic monomer in a polyoxyalkylene polymer into which a crosslinkable silyl group has been introduced.

[0053] The number average molecular weight of the silicone resin and the modified silicone resin is preferably 1,000 or more, particularly preferably 6,000 to 30,000. Further, a silicone resin and a modified silicone resin having a narrow molecular weight distribution are preferable because the viscosity of the curable composition is lowered and the rubber physical properties after curing are low modulus and high elongation.

[0054] Examples of the silane coupling agent include compounds having a crosslinkable silyl group with a molecular weight of 500 or less, such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Further, examples of the silane coupling agent include one or more reactants of these silane coupling agents (for example, hydrolysis condensates of crosslinkable silyl groups, reactants with reactive functional groups other than crosslinkable silyl groups), and compounds having a number average molecular weight of 200 to 3,000.

[0055] When the curable composition of the present invention is used as an adhesive composition, a coating material composition, a waterproof material composition, or a sealing material composition, the crosslinkable silyl group-containing compound is preferably a silicone resin or a modified silicone resin. When the curable composition of the present invention is used as a primer composition, the crosslinkable silyl group-containing compound is preferably a silane coupling agent.

[0056] The content of these room-temperature curable compounds is not particularly limited, but is preferably 1% to 90% by mass based on the entire curable composition. When the curable composition of the present invention is used as a coating material composition, a waterproof material composition or a sealing material composition, it is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, and particularly preferably 20% to 70% by mass based on the entire curable composition. When the curable composition of the present invention is used as a primer composition, it is preferably 1% to 60% by mass, more preferably 3% to 50% by mass, and particularly preferably 5% to 40% by mass based on the entire curable composition.

[0057] <Aliphatic carboxylic acid compound and / or its salt> The aliphatic carboxylic acid compound is a compound having an aliphatic hydrocarbon group and one or more carboxyl groups in the compound. Examples of the aliphatic carboxylic acid compound include monocarboxylic acids and dicarboxylic acids. The salt of the aliphatic carboxylic acid compound is a salt of a compound having an aliphatic hydrocarbon group and one or more carboxyl groups in the compound. Examples of the salt of the aliphatic carboxylic acid compound include salts of monocarboxylic acids and salts of dicarboxylic acids. In the curable composition of the present invention, only one of the aliphatic carboxylic acid compound and the salt of the aliphatic carboxylic acid compound may be used, or the aliphatic carboxylic acid compound and the salt of the aliphatic carboxylic acid compound may be used in combination.

[0058] Examples of aliphatic carboxylic acid compounds that are monocarboxylic acids include saturated fatty acids and unsaturated fatty acids. Examples of saturated fatty acids that are monocarboxylic acids include acetic acid (1 carbon atom in the aliphatic hydrocarbon group), propionic acid (2 carbon atoms in the aliphatic hydrocarbon group), butyric acid (3 carbon atoms in the aliphatic hydrocarbon group), valeric acid (4 carbon atoms in the aliphatic hydrocarbon group), caproic acid (5 carbon atoms in the aliphatic hydrocarbon group), enanthic acid (6 carbon atoms in the aliphatic hydrocarbon group), caprylic acid (7 carbon atoms in the aliphatic hydrocarbon group), ethylhexanoic acid (7 carbon atoms in the aliphatic hydrocarbon group), pelargonic acid (8 carbon atoms in the aliphatic hydrocarbon group), capric acid (9 carbon atoms in the aliphatic hydrocarbon group), lauric acid (11 carbon atoms in the aliphatic hydrocarbon group), myristic acid (13 carbon atoms in the aliphatic hydrocarbon group), palmitic acid (15 carbon atoms in the aliphatic hydrocarbon group), margaric acid (16 carbon atoms in the aliphatic hydrocarbon group), stearic acid (17 carbon atoms in the aliphatic hydrocarbon group), tuberculostearic acid (18 carbon atoms in the aliphatic hydrocarbon group), arachidic acid (19 carbon atoms in the aliphatic hydrocarbon group), behenic acid (21 carbon atoms in the aliphatic hydrocarbon group), tricosylic acid (22 carbon atoms in the aliphatic hydrocarbon group), tetracosanoic acid (23 carbon atoms in the aliphatic hydrocarbon group), hexacosanoic acid (25 carbon atoms in the aliphatic hydrocarbon group), octacosanoic acid (27 carbon atoms in the aliphatic hydrocarbon group), triacontanoic acid (29 carbon atoms in the aliphatic hydrocarbon group).

[0059] Examples of unsaturated fatty acids that are monocarboxylic acids include oleic acid (17 carbon atoms in the aliphatic hydrocarbon group), linoleic acid (17 carbon atoms in the aliphatic hydrocarbon group), linolenic acid (17 carbon atoms in the aliphatic hydrocarbon group), arachidonic acid (19 carbon atoms in the aliphatic hydrocarbon group), eicosapentaenoic acid (19 carbon atoms in the aliphatic hydrocarbon group), docosahexaenoic acid (21 carbon atoms in the aliphatic hydrocarbon group).

[0060] Examples of the dicarboxylic acid include malonic acid (the number of carbon atoms in the aliphatic hydrocarbon group is 1), succinic acid (the number of carbon atoms in the aliphatic hydrocarbon group is 2), fumaric acid (the number of carbon atoms in the aliphatic hydrocarbon group is 2), maleic acid (the number of carbon atoms in the aliphatic hydrocarbon group is 2), glutaric acid (the number of carbon atoms in the aliphatic hydrocarbon group is 3), adipic acid (the number of carbon atoms in the aliphatic hydrocarbon group is 3), hexadecanedioic acid (the number of carbon atoms in the aliphatic hydrocarbon group is 14), nonadecanedioic acid (the number of carbon atoms in the aliphatic hydrocarbon group is 17), eicosanedioic acid (the number of carbon atoms in the aliphatic hydrocarbon group is 18), ethyloctadecanedioic acid (the number of carbon atoms in the aliphatic hydrocarbon group is 18), eicosadienedioic acid (the number of carbon atoms in the aliphatic hydrocarbon group is 18), vinyloctadecaenedioic acid (the number of carbon atoms in the aliphatic hydrocarbon group is 18), dimethyleicosadienedioic acid (the number of carbon atoms in the aliphatic hydrocarbon group is 20), and dimethyleicosanedioic acid (the number of carbon atoms in the aliphatic hydrocarbon group is 20).

[0061] The above-mentioned aliphatic carboxylic acid compounds may be used alone or in combination of two or more.

[0062] Examples of the salt of the aliphatic carboxylic acid compound include the sodium salt of the aliphatic carboxylic acid compound, the magnesium salt of the aliphatic carboxylic acid compound, the potassium salt of the aliphatic carboxylic acid compound, and the calcium salt of the aliphatic carboxylic acid compound. The above-mentioned salts of the aliphatic carboxylic acid compounds may be used alone or in combination of two or more.

[0063] The number of carbon atoms in the aliphatic hydrocarbon group of the aliphatic carboxylic acid compound is not particularly limited, but from the viewpoint of more surely exhibiting excellent adhesiveness even in the case of a hardly adherable adherend such as polyolefin, 6 to 24 are preferable, 8 to 22 are more preferable, 10 to 20 are further preferable, and 12 to 20 are particularly preferable.

[0064] In the curable composition of the present invention, the total amount of the aliphatic carboxylic acid compound and / or its salt is 10 parts by mass to 200 parts by mass with respect to 100 parts by mass (solid content) of the room-temperature curable compound. Since the total amount of the aliphatic carboxylic acid compound and / or its salt is in the range of 10 parts by mass to 200 parts by mass with respect to 100 parts by mass of the room-temperature curable compound, it can be applied to large bonding surfaces such as buildings and civil engineering structures. Also, even when the large bonding surface is a difficult-to-bond adherend such as polyolefin, a curable composition having excellent adhesiveness can be obtained.

[0065] The total amount of the aliphatic carboxylic acid compound and / or its salt is not particularly limited as long as it is in the range of 10 parts by mass to 200 parts by mass with respect to 100 parts by mass of the room-temperature curable compound. However, from the viewpoint of exhibiting even more excellent adhesiveness even with a difficult-to-bond adherend, the total amount of the aliphatic carboxylic acid compound and / or its salt is preferably 13 parts by mass or more, particularly preferably 15 parts by mass or more, with respect to 100 parts by mass of the room-temperature curable compound. Also, from the viewpoint of exhibiting even more excellent adhesiveness even with a difficult-to-bond adherend, the total amount of the aliphatic carboxylic acid compound and / or its salt is preferably 180 parts by mass or less, particularly preferably 160 parts by mass or less, with respect to 100 parts by mass of the room-temperature curable compound.

[0066] <Olefin chloride compound> In the curable composition of the present invention, an olefin chloride compound may be blended as needed. By blending the olefin chloride compound, the water resistance, heat resistance, and damp heat resistance of the curable composition are improved, and also, even with a difficult-to-bond adherend such as polyolefin, excellent adhesiveness can be more surely exhibited.

[0067] Examples of the olefin chloride compound include chlorinated rubber and chlorinated polyolefin.

[0068] Chlorinated rubber is a rubber having a predetermined chlorine atom content. The chlorine atom content of chlorinated rubber is not particularly limited, preferably 30% by mass to 90% by mass, more preferably 40% by mass to 85% by mass, and particularly preferably 50% by mass to 80% by mass.

[0069] As the chlorinated rubber, as long as it is obtained by chlorinating natural rubber or synthetic rubber, it is not particularly limited. For example, chlorinated natural rubber, chlorinated butadiene rubber, chlorinated butyl rubber, chlorinated isoprene rubber, butadiene / halogenated cyclic conjugated diene adduct, chlorinated butadiene styrene copolymer, brominated poly(2,3-dichloro-1,3-butadiene), α-haloacrylonitrile-co-2,3-dichloro-1,3-butadiene copolymer can be mentioned. Among these, a copolymer or rubber containing a hydrocarbon group having 4 or more carbon atoms as a raw material is preferable, and chlorinated natural rubber, chlorinated isoprene rubber, and chlorinated butadiene rubber are particularly preferable.

[0070] As a method for chlorinating natural rubber or synthetic rubber, a conventionally known method can be used. For example, a method in which natural rubber or synthetic rubber is dissolved in a chlorinated organic solvent such as carbon tetrachloride or monochlorobenzene or an organic solvent such as xylene and then chlorine gas is blown in for chlorination, a method in which natural rubber or synthetic rubber is suspended or emulsified in water and chlorine gas is blown in for chlorination, a method in which natural rubber or synthetic rubber is suspended or emulsified in water and chlorine gas is introduced while irradiating with ultraviolet rays for chlorination, and a method in which natural rubber or synthetic rubber is brought into contact with liquid chlorine for chlorination under low temperature and pressure can be mentioned. For example, polyisoprene uniformly chlorinated can be obtained by adding polyisoprene, a surfactant, and an acid such as hydrochloric acid, sulfuric acid or nitric acid to water, emulsifying, and then blowing in chlorine gas.

[0071] The weight average molecular weight of the chlorinated rubber is not particularly limited. For example, it is 1,000 or more, preferably 3,000 or more, more preferably 5,000 or more, and particularly preferably 10,000 or more. Also, the weight average molecular weight of the chlorinated rubber is, for example, 300,000 or less, preferably 200,000 or less, and particularly preferably 100,000 or less.

[0072] Examples of chlorinated rubbers include commercially available products such as CR-10, CR-20 (manufactured by Nippon Paper Industries Co., Ltd.), Pergut S-5, Pergut S-10, Pergut S-20, Pergut S-40, Pergut S-90, Pergut S-130, Pergut S-170 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Alloprene R10, R20, R40 (manufactured by ICI UK).

[0073] Examples of chlorinated polyolefins include chlorinated polyethylene, chlorinated polypropylene, and chlorinated polybutylene.

[0074] The compounding amount of the chlorinated olefin compound is not particularly limited. However, even for a difficult-to-adhere adherend such as a polyolefin, from the viewpoint of more reliably exhibiting excellent adhesiveness, 1 part by mass or more is preferable, 3 parts by mass or more is more preferable, and 5 parts by mass or more is particularly preferable with respect to 100 parts by mass (solid content) of the room-temperature curable compound. Also, the compounding amount of the chlorinated olefin compound is preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less with respect to 100 parts by mass (solid content) of the room-temperature curable compound, from the viewpoint of more reliably exhibiting excellent adhesiveness even for a difficult-to-adhere adherend such as a polyolefin.

[0075] <Additives> In the curable composition of the present invention, various additives can be blended as necessary within a range that does not impair the object of the present invention, in addition to the above-described components. The additives are used to blend into the curable composition to improve various performances such as viscosity adjustment, curing acceleration, and adhesiveness of the curable composition. Specifically, examples of the additives include a curing acceleration catalyst, a plasticizer, a weather stabilizer, a filler, a thixotropy-imparting agent, an adhesiveness improver, a storage stability improver (dehydrating agent), a colorant, and an organic solvent. These additives may be used alone or in combination of two or more.

[0076] The curing accelerator is compounded to accelerate the reaction of a room-temperature curable compound with an active hydrogen-containing compound (such as water like moisture) to cause crosslinking and curing. Further, the curing accelerator can also be used as a reaction catalyst in the production of the above-mentioned isocyanate group-containing urethane resin. When the curing accelerator is used as a reaction catalyst in the production of the isocyanate group-containing urethane resin, the reaction catalyst remaining therein may act as a curing accelerator for the curable composition.

[0077] Examples of the curing accelerator include metal-based catalysts and amine-based catalysts.

[0078] Examples of the metal-based catalysts include salts of inorganic metals and organic acids, salts of organic metals and organic acids, and metal chelate compounds. Examples of the salts of inorganic metals and organic acids include salts of various metals such as tin, bismuth, zirconium, zinc, and manganese and organic acids such as octylic acid, neodecanoic acid, stearic acid, and naphthenic acid. Specifically, for example, tin octylate, tin naphthenate, bismuth octylate, and zirconium octylate can be mentioned. Examples of the salts of organic metals and organic acids include, for example, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversatate, and the reaction product of dibutyltin oxide and phthalic acid ester. Examples of the metal chelate compounds include, for example, tin chelate compounds, zirconium chelate compounds, titanium chelate compounds, aluminum chelate compounds, bismuth chelate compounds, and iron chelate compounds. Specifically, for example, dibutyltin bis(acetylacetonate), EXCESTAR C-501 manufactured by AGC, which is a tin chelate compound, zirconium tetrakis(acetylacetonate), titanium tetrakis(acetylacetonate), aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate), bismuth tris(2-ethylhexanoate), cobalt acetylacetonate, iron acetylacetonate, copper acetylacetonate, magnesium acetylacetonate, bismuth acetylacetonate, nickel acetylacetonate, zinc acetylacetonate, and manganese acetylacetonate can be mentioned.

[0079] Examples of the amine-based catalysts include tertiary amines and salts of tertiary amines. Examples of the tertiary amines include, for example, triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,4-diazabicyclo[2,2,2]octane (DABCO). Examples of the salts of tertiary amines include salts of the above-mentioned tertiary amines and organic carboxylic acids.

[0080] These curing acceleration catalysts may be used alone or in combination of two or more kinds.

[0081] Among the above-mentioned curing acceleration catalysts, salts of inorganic metals and organic acids, salts of organic metals and organic acids, and metal chelate compounds are preferred because they are excellent in the curability of the curable composition. Salts of tin and organic acids, salts of zirconium and organic acids, salts of bismuth and organic acids, salts of organotin and organic acids, salts of organic bismuth and organic acids, tin chelate compounds, bismuth chelate compounds, and iron chelate compounds are particularly preferred.

[0082] The compounding amount of the curing acceleration catalyst is preferably 0.005 parts by mass to 5 parts by mass, and particularly preferably 0.005 parts by mass to 2 parts by mass with respect to 100 parts by mass of the room temperature curable compound.

[0083] The plasticizer is compounded to lower the viscosity of the curable composition and improve workability, and to adjust the rubber physical properties after curing of the curable composition. Specifically, for example, phthalic acid esters such as dioctyl phthalate, diisononyl phthalate, dibutyl phthalate, butyl benzyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, butyl oleate, etc. These plasticizers may be used alone or in combination of two or more kinds.

[0084] The weather resistance stabilizer is compounded to prevent oxidation, photo-degradation, and heat degradation of the curable composition and further improve weather resistance and heat resistance. Examples of the weather resistance stabilizer include hindered amine light stabilizers, hindered phenol antioxidants, and ultraviolet absorbers. These weather resistance stabilizers may be used alone or in combination of two or more kinds.

[0085] Examples of hindered amine light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl) ester of decanedioic acid, bis(1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, dimethyl succinate·1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate, Adeka Stab LA-63P and LA-68LD manufactured by ADEKA Corporation.

[0086] 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 - hydroxyphenyl)propionamide], 3,5 - bis(1,1 - dimethylethyl) - 4 - hydroxy C7 - C9 branched alkyl benzenepropionate, and 2,4 - dimethyl - 6-(1 - methylpentadecyl)phenol.

[0087] 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.

[0088] Among these weathering stabilizers, hindered amine light stabilizers and hindered phenol antioxidants are preferred in terms of having a higher effect of improving weather resistance. The compounding amount of the weathering stabilizer is preferably 0.01 to 30 parts by mass, and particularly preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the room - temperature curable compound.

[0089] The filler is blended for the purpose of increasing the amount of the curable composition and reinforcing the physical properties of the cured product. Specifically, for example, inorganic powdery fillers such as mica, kaolin, zeolite, graphite, diatomaceous earth, clay, clay, talc, slate powder, anhydrous silicic acid, quartz fine powder, aluminum powder, zinc powder, precipitated silica, etc.; calcium carbonate, magnesium carbonate, alumina, calcium oxide, magnesium oxide, etc.; inorganic fibrous fillers such as glass fiber, carbon fiber, etc.; inorganic balloon-shaped fillers such as glass balloon, shirasu balloon, silica balloon, ceramic balloon, etc.; organic powdery fillers such as wood powder, walnut shell powder, rice husk powder, pulp powder, cotton chip, rubber powder, fine powder of thermoplastic resin, fine powder of thermosetting resin, powder and hollow body of polyethylene, etc.; organic balloon-shaped fillers such as saran micro balloon, etc.; flame retardant-imparting fillers such as magnesium hydroxide, aluminum hydroxide, etc. The particle diameter of the filler is preferably 0.01 μm to 1,000 μm. These fillers may be used alone or in combination of two or more.

[0090] The thixotropy-imparting agent is blended to prevent the sag (slump) of the curable composition. Specifically, for example, inorganic thixotropy-imparting agents such as fine powder silica with an average primary particle diameter of 5 nm to 50 nm, calcium carbonate surface-treated with fatty acid, etc.; organic thixotropy-imparting agents such as urea compounds, organic bentonite, fatty acid amide, etc. These thixotropy-imparting agents may be used alone or in combination of two or more.

[0091] Examples of the fine powder silica with an average primary particle diameter of 5 nm to 50 nm include hydrophilic silica and hydrophobic silica.

[0092] The urea compound is a compound having one or more urea bonds (-NHCONH-) in the compound, and examples thereof include reaction products of organic isocyanate compounds and amine compounds.

[0093] Examples of the organic isocyanate compound include the same ones as the above-mentioned organic polyisocyanate.

[0094] Examples of the amine compound include compounds having one or more amino groups in the molecule. Examples of the amino group include a primary amino group and a secondary amino group. Examples of the monoamine having a primary amino group include butylamine, isobutylamine, hexylamine, heptylamine, 2-ethylhexylamine, octylamine, 3-methoxypropylamine, tetradecylamine, cetylamine, stearylamine, oleylamine, trimethylcyclohexylamine, benzylamine, and aniline. Examples of the diamine having a primary amino group include ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 1,7-diaminoheptane, trimethylhexamethylenediamine, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, isophoronediamine, diaminodicyclohexylmethane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, xylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane, polyoxyethylenediamine, and polyoxypropylenediamine. Examples of the triamine having a primary amino group include tri(methylamino)hexane. Examples of the monoamine having a secondary amino group include diethylamine, dipropylamine, diisopropylamine, dibutylamine, dihexylamine, di-2-ethylhexylamine, diphenylamine, dilaurylamine, distearylamine, and methyllaurylamine. Examples of the diamine having a secondary amino group include N,N'-dilaurylpropylenediamine, N,N'-distearylbutylenediamine, N-butyl-N'-laurylethylenediamine, N-butyl-N'-laurylpropylenediamine, and N-lauryl-N'-stearylbutylenediamine.Examples of the polyamine having a primary amino group and a secondary amino group include diethylenetriamine, triethylenetetramine, and methylaminopropylamine. These amine compounds may be used alone or in combination of two or more.

[0095] The fatty acid surface-treated calcium carbonate is obtained by treating the surface of heavy calcium carbonate, light calcium carbonate, or colloidal calcium carbonate with fatty acids such as fatty acids, fatty acid alkyl esters, fatty acid metal salts, and fatty acid organic salts. Examples of the fatty acid include fatty acids having 8 to 22 carbon atoms such as 2-ethylhexanoic acid (octylic acid), oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Examples of the metal salt include sodium salt, potassium salt, calcium salt, and aluminum salt, and examples of the organic salt include ammonium salt.

[0096] The adhesion improver contributes to further improving the adhesion of the curable composition. Specifically, various coupling agents such as silane-based, aluminum-based, and zirconium aluminate-based coupling agents and their partial hydrolysis condensates can be mentioned. Among these, silane-based coupling agents and their partial hydrolysis condensates are preferable in that they contribute to further improving the adhesion. These adhesion improvers may be used alone or in combination of two or more.

[0097] Examples of the silane-based coupling agent include the same ones as the above-mentioned silane coupling agent.

[0098] The storage stability improver (dehydrating agent) is blended to improve the storage stability of the curable composition. Specifically, for example, vinyltrimethoxysilane, calcium oxide, and p-toluenesulfonyl isocyanate (PTSI), which react with water present in the curable composition and function as dehydrating agents, can be mentioned. These storage stability improvers (dehydrating agents) may be used alone or in combination of two or more.

[0099] Colorants are blended to color the curable composition into a desired color and impart design properties to the composition. Specifically, examples include inorganic colorants such as titanium oxide, iron oxide, and carbon black, and organic colorants such as copper phthalocyanine. These colorants may be used alone or in combination of two or more.

[0100] Organic solvents are blended to adjust the viscosity of the curable composition and improve the extrudability and workability during casting or coating. As the organic solvent, any organic solvent that has good compatibility with the components in the curable composition and does not react with the components in the curable composition can be used without particular limitation. Specifically, for example, carbonate solvents such as dimethyl carbonate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and 2-pentanone, ester solvents such as ethyl acetate, propyl acetate, and butyl acetate, ether solvents such as diethyl ether and dipropyl ether, aliphatic hydrocarbon solvents such as n-hexane and n-heptane, alicyclic hydrocarbon solvents such as cyclohexane, aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene, and petroleum fraction solvents such as mineral spirit, industrial gasoline, ligroin, and kerosene can be mentioned. These organic solvents may be used alone or in combination of two or more. The blending amount of the organic solvent is not particularly limited, and it can be blended in an amount of 0 to 99% by mass based on the total curable composition. When the curable composition of the present invention is used as a primer composition, 10 to 99% by mass is preferable, more preferably 30 to 95% by mass, and particularly preferably 50 to 90% by mass based on the total curable composition. Further, when the curable composition of the present invention is used as an adhesive composition, a coating material composition, a waterproof material composition, or a sealing material composition, 0 to 90% by mass is preferable, 0 to 80% by mass is preferable, and particularly 0 to 70% by mass is preferable based on the total curable composition.

[0101] Since the curable composition of the present invention reacts with water such as moisture and crosslinks and cures, it can be used as a one-component curable composition. Further, since it reacts with polyol, polyamine, and polythiol and crosslinks and cures, it can be used as a two-component curable composition.

[0102] The manufacturing method of the curable composition of the present invention is not particularly limited and can be carried out by known methods. Specifically, a room temperature curable compound, an aliphatic carboxylic acid compound and / or its salt, and, if necessary, an olefin chloride compound and an additive are charged into a mixing (kneading) container equipped with a stirring device made of glass, stainless steel, iron, etc., water such as moisture is blocked, and stirring and mixing are carried out under a dry nitrogen stream for production.

[0103] The members (adherends) that can be used in the curable composition of the present invention are not particularly limited, but specifically, wood materials such as solid wood, plywood, and laminated wood, metal materials such as iron, copper, stainless steel, galvanized steel sheet, galvanized iron, aluminum, and titanium, synthetic resin materials such as polyvinyl chloride resin, polyamide resin, (meth)acrylic resin, phenolic resin, epoxy resin, polyester resin, polycarbonate resin, ABS (Acrylonitrile-Butadiene-Styrene-copolymer), FRP (Fiber Reinforced Plastic), rubber materials such as natural rubber, and inorganic materials such as tiles, glass, bricks, tiles, mortar, concrete, slate, ALC (Autoclaved Lightweight Concrete), siding, porcelain, marble, and granite are mentioned.

[0104] The curable composition of the present invention particularly exhibits excellent adhesiveness to difficult-to-bond materials (difficult-to-bond adherends). The difficult-to-bond materials (difficult-to-bond adherends) are not particularly limited, but for example, rubber materials and polyolefin-based resins are mentioned. The rubber materials are not particularly limited, but for example, chloroprene rubber, nitrile rubber, ethylene propylene rubber, ethylene propylene diene rubber (EPDM), butyl rubber, chlorosulfonated polyethylene rubber, urethane rubber, and fluororubber are mentioned. Also, the polyolefin-based resins are not particularly limited, but for example, polyethylene, polypropylene, and polybutene are mentioned.

Examples

[0105] Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not construed as being limited thereto.

[0106] [Synthesis Example 1] (Isocyanate Group-Containing Urethane Resin Solution) While flowing nitrogen gas through a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, and heating / cooling device, 253.0 g of ethyl acetate, 69.0 g of an isocyanurate form of isophorone diisocyanate (VESTANAT T1890E, solid content 70% by mass, butyl acetate 30% by mass, NCO content 12% by mass, manufactured by Evonik Japan Co., Ltd.) were charged. While stirring, 31.0 g of a polyacrylic polyol (ARUFON UH-2041, manufactured by Toagosei Co., Ltd., hydroxyl value 120 mgKOH / g-resin, glass transition temperature -50°C, number average molecular weight 1,320, weight average molecular weight 2,260, and the number of hydroxyl groups calculated from the hydroxyl value and number average molecular weight was 2.8 on average per molecule), and 2.0 g of dibutyltin dilaurate diluted 10-fold with ethyl acetate as a reaction catalyst were charged. After heating to 70 - 80°C and reacting for 1 hour, it was cooled to room temperature to obtain an isocyanate group-containing urethane resin solution. In addition, the solid content (resin content) obtained by weighing 1.5 g of the isocyanate group-containing urethane resin solution obtained as described above onto an aluminum dish with an inner diameter of 6 cm and placing it in an oven at 50°C for 1 hour and then measuring was 28.0% by mass.

[0107] [Example 1] While flowing nitrogen gas through a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, and heating / cooling device, 100.0 g of the isocyanate group-containing urethane resin solution obtained in Synthesis Example 1 was charged. While stirring, 5.8 g of chlorinated rubber (Pergut S20, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was charged. After heating to 50°C and stirring for 60 minutes, it was cooled to room temperature, 11.7 g of calcium stearate (manufactured by Fujifilm Wako Pure Chemical Corporation) was charged, and further stirred for 30 minutes to obtain a curable composition.

[0108] [Example 2] In Example 1, the same operation as in Example 1 was performed except that 23.4 g of calcium stearate was charged to obtain a curable composition.

[0109] [Example 3] In Example 1, a curable composition was obtained in the same manner as in Example 1, except that 11.7 g of calcium 2-ethylhexanoate (manufactured by Fuji Film Wako Pure Chemical Corporation) was charged.

[0110] [Comparative Example 1] In Example 1, a curable composition was obtained in the same manner as in Example 1, except that calcium stearate was not blended.

[0111] [Example 4] While flowing nitrogen gas into a stirrer and a mixing vessel equipped with a nitrogen seal tube, 100.0 g of a one-component urethane-based primer composition (OP-2019, isocyanate group-containing urethane resin 20 to 30% by mass, ethyl acetate 65 to 75% by mass, butyl acetate 1 to 10% by mass, toluene 0.1 to 0.3% by mass, manufactured by Autochem Industries, Ltd.) and 25.0 g of calcium stearate were charged and stirred for 30 minutes to obtain a curable composition. In addition, the solid content (resin content) determined by measuring after weighing 1.5 g of OP-2019 on an aluminum dish with an inner diameter of 6 cm and placing it in an oven at 50 °C for 1 hour was 26.0% by mass.

[0112] [Example 5] In Example 4, a curable composition was obtained in the same manner as in Example 4, except that 5.0 g of calcium stearate was charged.

[0113] [Example 6] In Example 4, a curable composition was obtained in the same manner as in Example 4, except that 10.0 g of calcium stearate was charged.

[0114] [Example 7] In Example 4, a curable composition was obtained in the same manner as in Example 4, except that 20.0 g of calcium stearate was charged.

[0115] [Example 8] In Example 4, a curable composition was obtained by performing the same operations as in Example 4 except that 40.0 g of calcium stearate was charged.

[0116] [Comparative Example 2] A one-component urethane-based primer composition (OP-2019) was used as the curable composition.

[0117] [Preparation Example 1] While flowing nitrogen gas into a mixing container equipped with a stirrer and a nitrogen seal tube, 100.0 g of a polyoxypropylene-based resin containing a trimethoxysilyl group (number average molecular weight 23,000), 130.0 g of dioctyl phthalate, 350.0 g of heavy calcium carbonate previously dried in a dryer at 90 to 100 °C, and 210.0 g of surface-treated calcium carbonate (Calfine 500, manufactured by Maruo Calcium Co., Ltd.) were charged, and the mixture was stirred and mixed until the contents became uniform. Next, 1.5 g of a hindered phenol-based antioxidant (Irganox 1010, manufactured by BASF Japan Ltd.) and 6.2 g of vinyltrimethoxysilane (Silace S210, manufactured by JNC Corporation) were charged, and the mixture was stirred and mixed at 20 to 30 °C. Then, 0.3 g of dibutyltin dilaurate and 4.4 g of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Silace S320, manufactured by JNC Corporation) were added, and the mixture was further mixed for 30 minutes. After that, degassing was performed under reduced pressure at 30 to 100 hPa, and the container was filled and sealed to obtain a one-component moisture-curing modified silicone-based sealing material composition.

[0118] The following performance evaluations were performed using the curable compositions of Examples 1 to 2 and Comparative Example 1. The compositions and performance evaluations of the curable compositions are shown in Table 1.

[0119] [Tensile Adhesion Test] A tensile adhesion test was conducted in accordance with 5.20 Tensile Adhesion Test of the test method for building sealants of JIS A 1439:2016, and the 50% tensile stress (M 50 ) and maximum tensile stress (T max ) of the sealant and the elongation at maximum load (E max) was determined. As the adherend, a 50 mm × 50 mm × 5 mm polyethylene plate was used. The curable compositions of Examples 1 to 2 and Comparative Example 1 were applied to the adherend surface at a coating amount of 80 g / m 2 and then allowed to stand at room temperature for 30 minutes and dried and cured. As the sealing material, a one-component moisture-curing urethane-based sealing material (Auton Exceed, manufactured by Autochem Industries, Ltd.) was used. The sealing material was cured by curing at 50°C and 80% RH for 3 days.

[0120]

Table 1

[0121] Using the curable compositions of Example 2 and Comparative Example 1, the following performance evaluations were conducted. The performance evaluations are shown in Table 2.

[0122] [Tensile Adhesion Test] In accordance with 5.20 Tensile Adhesion Test of the test method for building sealing materials of JIS A 1439:2016, a tensile adhesion test was conducted to obtain the 50% tensile stress (M 50 ), maximum tensile stress (T max ), and elongation at maximum load (E max ) of the sealing material. As the adherend, a 50 mm × 50 mm × 5 mm polypropylene plate was used. The curable compositions obtained in Example 2 and Comparative Example 1 were applied to the adherend surface at a coating amount of 80 g / m 2 and then allowed to stand at room temperature for 30 minutes and dried and cured. As the sealing material, a one-component moisture-curing urethane-based sealing material (Auton Exceed, manufactured by Autochem Industries, Ltd.) was used. The sealing material was cured by curing at 50°C and 80% RH for 3 days.

[0123]

Table 2

[0124] Using the curable compositions of Example 2 and Comparative Example 1, the following performance evaluations were conducted. The performance evaluations of the curable compositions are shown in Table 3.

[0125] [Tensile Adhesion Test] In accordance with the tensile adhesion test in 5.20 of the test method for building sealants specified in JIS A 1439:2016, the tensile adhesion test was conducted to determine the 50% tensile stress (M 50 ), maximum tensile stress (T max ), and elongation rate at maximum load (E max ) of the sealant. As the adherend, a polyethylene plate with dimensions of 50 mm × 50 mm × 5 mm was used. The curable compositions obtained in Example 2 and Comparative Example 1 were applied to the adherend surface at a coating amount of 80 g / m 2 , left to stand at room temperature for 30 minutes, and then dried and cured. As the sealant, the one-component moisture-curing modified silicone-based sealant obtained in Preparation Example 1 was used. The sealant was cured by curing at 35°C and 70% RH for 3 days.

[0126]

Table 3

[0127] The following performance evaluations were carried out using the curable compositions of Example 3 and Comparative Example 1. The compositions and performance evaluations of the curable compositions are shown in Table 4.

[0128] [X-Cut Adhesion Test] The curable compositions obtained in Example 3 and Comparative Example 1 were applied to the adherend surfaces of each adherend (acrylic plate, polyamide resin (nylon 6,6) plate, chloroprene plate, ethylene propylene rubber (EPDM) plate), which are flat plates with dimensions of 50 mm in length and 50 mm in width, at a coating amount of 80 g / m 2 , left to stand at room temperature for 30 minutes, and then dried and cured. A cutter was used to make an X-shaped cut (intersection angle of 30 degrees) through the obtained cured coating film. A cutter blade was inserted into the intersection part to create a trigger for peeling the cured coating film, and the cured coating film was pulled as it was to evaluate the adhesion according to the following criteria. Evaluation Criteria ○: A trigger can be created, but when attempting to peel, the adhesion is so strong that the cured coating film breaks. △: The adhesion is strong, but it can be peeled off slowly when pulled. ×: The adhesion is weak and it peels off easily.

[0129]

Table 4

[0130] The following performance evaluations were conducted using the curable compositions of Example 4 and Comparative Example 2. Table 5 shows the compositions and performance evaluations of the curable compositions.

[0131] [Simple Adhesion Test] On the adherend surfaces of each adherend (polycarbonate plate, polypropylene plate, acrylic plate, polyamide resin (nylon 6,6) plate, chloroprene plate, unsaturated polyester plate), which are flat plates with a length of 50 mm and a width of 50 mm, the curable compositions obtained in Example 4 and Comparative Example 2 were applied at a coating amount of 80 g / m 2 . After application, the samples were allowed to stand at room temperature for 30 minutes and then dried and cured. Next, a fluororesin tape was attached to a 50 mm (length) × 10 mm (width) area at the end of the coated surface of each adherend. Then, a one-component moisture-curing urethane-based sealing material (Auton Sealer 101NS, manufactured by Auton Chemical Industry Co., Ltd.) was placed in a bead shape (linear shape) with an approximate width of 20 mm, a height of 10 mm, and a length of 50 mm from the surface of the fluororesin tape to the surface of the cured product, and cured by curing at 50 °C and 80% RH for 3 days. One end of the bead-shaped cured product (the fluororesin tape side) was pinched by hand and folded back 180° in the length direction and pulled, and the adhesiveness was evaluated according to the following criteria.

[0132] Note that the content in parentheses in Table 5 indicates the failure situation (visual inspection) caused by tension. CF represents cohesive failure of the sealing material, and PF represents interfacial peeling between the curable composition and the adherend. Cohesive failure of the sealing material is a phenomenon in which the sealing material finally fails when the pulling force is increased because the adhesiveness between both the sealing material and the curable composition and the curable composition and the adherend is good. In addition, interfacial peeling between the curable composition and the adherend occurs when the adhesive strength between the curable composition and the adherend is weaker than the fracture strength of the sealing material and the adhesive strength between the sealing material and the curable composition. Evaluation Criteria ○: Does not peel off even when strongly pulled, resulting in cohesive failure of the sealing material ×: Peels off easily when pulled, resulting in interfacial peeling

[0133] [Compressive Shear Adhesion Strength Test] From the lower end of adherend A with a length of 75 mm, a width of 25 mm, and a thickness of 5 mm, in a range of 25 mm in length × 25 mm in width (one side), the curable compositions obtained in Example 4 and Comparative Example 2 were each applied at a coating amount of about 25 - 40 g / m 2 . Then, the coated surface of adherend A and a range of 25 mm in length × 25 mm in width from the upper end of adherend B with a length of 75 mm, a width of 25 mm, and a thickness of 5 mm were bonded and fixed to prepare a test piece. The shape of the test piece conformed to the preparation of the test piece in 6.3 of JIS K 6852 (1994): Test Method for Compressive Shear Adhesion Strength of Adhesives. The test piece was cured by curing at 23°C and 50% RH for 7 days. The test pieces (combinations of adherend A - adherend B) were polypropylene plate - polypropylene plate and EPDM plate - EPDM plate.

[0134] [Table 5]

[0135] The following performance evaluations were carried out using the curable compositions of Examples 5 - 8 and Comparative Example 2. The compositions and performance evaluations of the curable compositions are shown in Table 6.

[0136] [Tensile Adhesion Test] According to 5.20 Tensile Adhesion Test in JIS A 1439:2016 Test Methods for Building Sealants, a tensile adhesion test was carried out to determine the 50% tensile stress (M 50 ), maximum tensile stress (T max ) and elongation at maximum load (E max ) of the sealant. As the adherend, a polyethylene plate of 50 mm × 50 mm × 5 mm was used. After applying the curable compositions obtained in Examples 5 - 8 and Comparative Example 2 to the adherend surface at a coating amount of 80 g / m 2 , it was left standing at room temperature for 30 minutes and then dried and cured. As the sealant, a one - component moisture - curing urethane - based sealant (Auton Sealer 101NS, manufactured by Auton Chemical Industry Co., Ltd.) was used. The sealant was cured by curing at 50°C and 80% RH for 3 days.

[0137]

Table 6

[0138] From the results in Table 1, compared with the curable composition of Comparative Example 1, the curable compositions of Examples 1 to 2 had higher 50% tensile stress, maximum tensile stress, and elongation rate at maximum load in the tensile adhesion test using a one-component moisture-curing urethane-based sealing material, and were found to have excellent adhesion to a polyethylene plate, which is a difficult-to-bond material.

[0139] From the results in Table 2, compared with the curable composition of Comparative Example 1, the curable composition of Example 2 had higher 50% tensile stress, maximum tensile stress, and elongation rate at maximum load in the tensile adhesion test using a one-component moisture-curing urethane-based sealing material, and was found to have excellent adhesion to a polypropylene plate, which is a difficult-to-bond material.

[0140] From the results in Table 3, compared with the curable composition of Comparative Example 1, the curable composition of Example 2 had higher 50% tensile stress, maximum tensile stress, and elongation rate at maximum load in the tensile adhesion test using a one-component moisture-curing modified silicone-based sealing material, and was found to have excellent adhesion to a polyethylene plate, which is a difficult-to-bond material.

[0141] From the results in Table 4, it was found that the curable composition of Example 3 was excellent in adhesion to all adherends including EPDM, which is a difficult-to-bond material, in the X-cut adhesion test.

[0142] From the results in Table 5, in the simple adhesion test, it was found that all the failure conditions of the specimens were cohesive failures of the sealing material, and the curable composition of Example 4 was excellent in adhesion to all adherends including polypropylene, which is a difficult-to-bond material. Also, from the results in Table 5, compared with the curable composition of Comparative Example 2, the curable composition of Example 4 had high strength in the compression shear adhesion strength test and was found to be excellent in adhesion to a polypropylene plate and an EPDM plate, which are difficult-to-bond materials.

[0143] From the results in Table 6, the curable compositions of Examples 5 to 8 were found to have higher 50% tensile stress, maximum tensile stress, and elongation rate at maximum load in the tensile adhesion test using a one-component moisture-curing urethane-based sealing material, and to be excellent in adhesion to a polyethylene plate, which is a difficult-to-adhere material, as compared with the curable composition of Comparative Example 2.

Industrial Applicability

[0144] The curable composition of the present invention can be suitably used for construction and civil engineering applications. Further, the curable composition of the present invention can be suitably used as a primer composition, an adhesive composition, a coating material composition, a waterproof material composition, or a sealing material composition. In particular, it can be suitably used as a primer composition, an adhesive composition, a coating material composition, a waterproof material composition, or a sealing material composition for difficult-to-adhere materials containing polyolefins such as polyethylene, polypropylene, and EPDM.

Claims

1. A curable composition containing a room-temperature curable compound and an aliphatic carboxylic acid compound and / or a salt thereof, wherein the total amount of the aliphatic carboxylic acid compound and / or the salt thereof is 10 to 200 parts by mass with respect to 100 parts by mass (solid content) of the room-temperature curable compound.

2. The curable composition according to claim 1, wherein the room-temperature curable compound is an isocyanate group-containing compound and / or a crosslinkable silyl group-containing compound.

3. The room-temperature curable compound is an isocyanate group-containing compound, and the isocyanate group-containing compound is at least one compound selected from the group consisting of an organic polyisocyanate, a modified product of an organic polyisocyanate, and a reaction product of an organic polyisocyanate and / or a modified product of an organic polyisocyanate and an active hydrogen-containing compound. The curable composition according to claim 1 or 2.

4. The curable composition according to claim 1 or 2, wherein the aliphatic hydrocarbon group of the aliphatic carboxylic acid compound and / or the salt thereof has 6 to 24 carbon atoms.

5. Furthermore, it contains an olefin chloride compound, and the amount of the olefin chloride compound is 1 to 50 parts by mass with respect to 100 parts by mass of the room-temperature curable compound. The curable composition according to claim 1 or 2.

6. Furthermore, it contains an additive, and the additive is at least one additive selected from the group consisting of a curing accelerator catalyst, a plasticizer, a weather resistance stabilizer, a filler, a thixotropy-imparting agent, an adhesion improver, a storage stability improver (dehydrating agent), a colorant, and an organic solvent. The curable composition according to claim 1 or 2.

7. The curable composition according to claim 1 or 2, wherein the curable composition is a primer composition, an adhesive composition, a coating material composition, a waterproof material composition, or a sealing material composition.

8. The curable composition according to claim 1 or 2, wherein the curable composition is a primer composition, an adhesive composition, a coating material composition, a waterproof material composition, or a sealing material composition for a difficult-to-adhere material containing polyolefin.

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