JP7335589B2 - One-component moisture-curing adhesive composition for flooring - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable composition excellent in adhesiveness, water resistance and stringiness.

Curable compositions containing isocyanate group-containing resins and crosslinkable silyl group-containing resins as curing components are widely used as sealing materials, adhesives, and waterproof materials for construction and civil engineering because of their excellent workability and adhesiveness. It is In particular, a polyurethane-based curable composition containing an isocyanate group-containing resin as a curing component is easily cured by reacting with water such as moisture in the air, and has adhesiveness and water resistance to building members such as concrete, wood, and resins. Due to its good properties, its usage and application range are increasing.

When a polyurethane-based curable composition is used as an adhesive for resin members (eg, vinyl chloride sheets, vinyl chloride tiles, etc.), the adhesive is required to have strong adhesion to the resin members. In order to improve the adhesiveness, the applicant has proposed a method of improving the adhesiveness by using a curable composition in which an isocyanurate compound is blended with an isocyanate group-containing urethane prepolymer (for example, Patent Document 1 ).

Performances other than adhesiveness required for adhesives include water resistance and stringiness. However, no curable composition has yet been proposed that simultaneously improves water resistance and stringiness while having excellent adhesiveness.

JP-A-2003-138239

The present invention provides a curable composition that is excellent in adhesion to resin members such as vinyl chloride resin, water resistance, and stringiness.

As a result of intensive studies by the present inventors in order to solve the above problems, a curable composition containing an isocyanate group-containing urethane prepolymer having no isocyanurate ring and an isocyanate group-containing urethane prepolymer having an isocyanurate ring is a chlorinated The inventors have found that the adhesiveness to resin members such as vinyl resins, water resistance, and stringiness are excellent, and have completed the present invention.

That is, the present invention solves the above problems by providing a curable composition shown in (1) to (12) below.
(1) A curable composition comprising an isocyanate group-containing urethane prepolymer having no isocyanurate ring and an isocyanate group-containing urethane prepolymer having an isocyanurate ring.
(2) The curable composition according to (1), wherein the isocyanate group-containing urethane prepolymer having an isocyanurate ring is a reaction product of an isocyanurate-modified polyisocyanate and an active hydrogen-containing compound.
(3) The curable composition according to (1) or (2), wherein the isocyanate group-containing urethane prepolymer having an isocyanurate ring has a number average molecular weight of 600 to 6,000.
(4) The curable composition according to any one of (1) to (3), wherein the isocyanate group-containing urethane prepolymer having an isocyanurate ring has an isocyanate group content of 2 to 30% by mass. thing.
(5) The curable composition according to (2), wherein the isocyanurate-modified polyisocyanate is a modified polyisocyanate of an organic polyisocyanate containing an aliphatic polyisocyanate and/or an alicyclic polyisocyanate.
(6) The curable composition according to (2) or (5), wherein the isocyanurate-modified polyisocyanate is a modified polyisocyanate of an organic polyisocyanate containing hexamethylene diisocyanate and/or isophorone diisocyanate.
(7) The curable composition according to (2), wherein the active hydrogen-containing compound is an active hydrogen-containing compound containing a polyol having a number average molecular weight of 50-900.
(8) The content of the isocyanate group-containing urethane prepolymer having an isocyanurate ring is such that the isocyanate group-containing urethane prepolymer having the isocyanurate ring is contained per 1 mol of the isocyanate group of the isocyanate group-containing urethane prepolymer having no isocyanurate ring. The curable composition according to any one of (1) to (7), wherein the number of moles of isocyanate groups in the urethane prepolymer is 0.5 to 5.
(9) Furthermore, one selected from a curing accelerator catalyst, a plasticizer, a weather stabilizer, a filler, a thixotropic agent, an adhesion agent, a storage stability improver (dehydrating agent), a colorant, and an organic solvent. The curable composition according to any one of (1) to (8), which contains the above additives.
(10) The curable composition according to any one of (1) to (9), which is a curable composition for construction or civil engineering.
(11) The curable composition according to any one of (1) to (10), which is an adhesive composition.
(12) The curable composition according to any one of (1) to (11), which is an adhesive composition for vinyl chloride resin.

The curable composition of the present invention is excellent in adhesion to resin members such as vinyl chloride resin, water resistance and stringiness.

The curable composition of the present invention will be explained. The curable composition of the present invention is characterized by containing an isocyanate group-containing urethane prepolymer having no isocyanurate ring and an isocyanate group-containing urethane prepolymer having an isocyanurate ring. Each component will be described in detail below.

The isocyanate group-containing urethane prepolymer having no isocyanurate ring is a urethane resin having at least one isocyanate group in one molecule and having no isocyanurate ring. The isocyanate groups of the isocyanate group-containing urethane prepolymer having no isocyanurate ring react with the active hydrogen-containing compound to form urethane bonds, urea bonds, etc., and are crosslinked and cured. In addition, the isocyanate group-containing urethane prepolymer having no isocyanurate ring functions as a curing component in the curable composition of the present invention and imparts good adhesiveness to adherends to the cured composition.

An isocyanate group-containing urethane prepolymer having no isocyanurate ring can be produced by reacting an organic isocyanate compound and an active hydrogen-containing compound all at once or sequentially so that isocyanate groups remain in the urethane prepolymer. The molar ratio of the isocyanate group of the organic isocyanate compound to the active hydrogen (group) of the active hydrogen-containing compound (isocyanate group/active hydrogen) is the number of moles of the isocyanate group of the organic isocyanate compound to the active hydrogen (group) of the active hydrogen-containing compound. Although it is not particularly limited as long as it is larger than the number of moles, it is preferably 1.2 to 10, more preferably 1.2 to 5.

The isocyanate group-containing urethane prepolymer having no isocyanurate ring preferably has an isocyanate group content of 0.3 to 10% by mass, more preferably 0.5 to 5% by mass.

The number average molecular weight of the isocyanate group-containing urethane prepolymer having no isocyanurate ring is preferably 1,500 or more, more preferably 1,500 to 20,000, even more preferably 1,500 to 15,000. ~10,000 is particularly preferred. In addition, the number average molecular weight in this specification is a numerical value converted into polystyrene measured by gel permeation chromatography (GPC). When the number average molecular weight is small and cannot be measured by gel permeation chromatography, the number average molecular weight herein is a value measured by gas chromatography-mass spectrometry (GC-MS) or liquid chromatography-mass spectrometry (LC-MS). be.

As a method for producing an isocyanate group-containing urethane prepolymer having no isocyanurate ring, a conventionally known method can be used. Specifically, for example, an organic isocyanate compound and an active hydrogen-containing compound are charged in a reaction vessel made of glass or stainless steel, and if necessary, a reaction catalyst or an organic solvent is used, and the reaction is performed while stirring at 50 to 120 ° C. There is a method to make At this time, if the isocyanate group reacts with water such as moisture, the urethane prepolymer will thicken, so it is preferable to replace the inside of the container with nitrogen gas in advance or perform the reaction under a nitrogen gas stream.

Specific examples of reaction catalysts include metal-based catalysts and amine-based catalysts.

Examples of metal-based catalysts include salts of metals and organic acids, salts of organic metals and organic acids, and metal chelate compounds. Salts of metals and organic acids include salts of various metals such as tin, zirconium, zinc and manganese with organic acids such as octylic acid, neodecanoic acid, stearic acid and naphthenic acid. Specific examples include tin octylate, tin naphthenate, zirconium octylate, and the like. Salts of organic metals and organic acids include dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversatate, and reaction of dibutyltin oxide with phthalates. things, etc. Examples of metal chelate compounds include dibutyltin bis (acetylacetonate), tin-based chelate compound EXCESTAR C-501 manufactured by AGC Corporation, zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), aluminum tris (acetylacetonate), and aluminum tris (acetylacetonate). acetonate), aluminum tris (ethylacetoacetate), acetylacetonate cobalt, acetylacetonate iron, acetylacetonate copper, acetylacetonate magnesium, acetylacetonate nickel, acetylacetonate zinc, acetylacetonate manganese, and the like.

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

When a reaction catalyst is used in the production of an isocyanate group-containing urethane prepolymer having no isocyanurate ring, the reaction catalyst remaining in the urethane prepolymer may act as a catalyst for accelerating the curing of the curable composition.

Specific examples of organic solvents include carbonate solvents such as dimethyl carbonate, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and butyl acetate, aliphatic solvents such as n-hexane, Examples include alicyclic solvents such as cyclohexane, aromatic solvents such as toluene and xylene, and organic solvents such as petroleum fraction solvents such as mineral spirits and industrial gasoline.

Specific examples of organic isocyanate compounds include organic polyisocyanates. An organic polyisocyanate is a compound having two or more isocyanate groups in one molecule. Specifically, for example, toluene polyisocyanates such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate and the like. diphenylmethane polyisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4,6-trimethylphenyl-1,3-diisocyanate, 2,4,6-triisopropylphenyl -phenylene polyisocyanates such as 1,3-diisocyanate, naphthalene polyisocyanates such as 1,4-naphthalene diisocyanate and 1,5-naphthalene diisocyanate, chlorophenylene-2,4-diisocyanate, 4,4'-diphenyl ether diisocyanate, 3, Aromatic polyisocyanates such as 3'-dimethyldiphenylmethane-4,4'-diisocyanate and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate are included. In addition, 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl- Aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, decamethylene diisocyanate and lysine diisocyanate, araliphatic polyisocyanates such as o-xylylene diisocyanate, m-xylylene diisocyanate and p-xylylene diisocyanate, 1,4- Alicyclic polyisocyanates such as 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 are included. Furthermore, modified isocyanates obtained by modifying these organic polyisocyanates and having at least one uretdione bond, allophanate bond, buret bond, uretonimine bond, carbodiimide bond, urethane bond or urea bond are included. All of these can be used singly or in combination of two or more.

Among these, aromatic polyisocyanates, araliphatic polyisocyanates, and modified isocyanates obtained by modifying these organic polyisocyanates are preferred because the curable compositions are excellent in adhesiveness, curability, and mechanical properties.

Organic monoisocyanates can also be used together with organic polyisocyanates. That is, a mixture of the aforementioned organic polyisocyanate and organic monoisocyanate can be used as the organic isocyanate compound. Organic monoisocyanate is a compound having one isocyanate group in one molecule, and specific examples include n-butyl monoisocyanate, n-hexyl monoisocyanate, n-hexadecyl monoisocyanate, n-octadecyl monoisocyanate isocyanate, p-isopropylphenyl monoisocyanate, p-benzyloxyphenyl monoisocyanate and the like.

An active hydrogen-containing compound is a compound having one or more active hydrogens (groups). Specific examples include polymer polyols, polymer monools, and low-molecular-weight polyols. These can be used singly or in combination of two or more. In this specification, "high molecular weight" means a number average molecular weight of 1,000 or more, and "low molecular weight" means a number average molecular weight of less than 1,000.

Specific examples of polymer polyols include polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, hydrocarbon polyols, poly(meth)acrylate polyols, and animal and plant polyols. Among them, polyoxyalkylene-based polyols and poly(meth)acrylate-based polyols are preferred. As used herein, "(meth)acrylate" means "acrylate and/or methacrylate."

The number average molecular weight of the polymer polyol is preferably 1,000 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000.

Examples of polyoxyalkylene-based polyols include polyoxyalkylene-based triols and polyoxyalkylene-based diols.

In this specification, the "system" of the polyoxyalkylene-based polyol means that 50% by mass or more, further 80% by mass or more, particularly 90% by mass or more of the portion excluding hydroxyl groups in the molecule is composed of polyoxyalkylene. If so, it means that the remainder may be modified with esters, urethanes, polycarbonates, polyamides, poly(meth)acrylates, polyolefins, and the like. It is particularly preferred that 95 mass % or more of the molecule excluding hydroxyl groups is composed of polyoxyalkylene.

Polyoxyalkylene-based triols and polyoxyalkylene-based diols can be produced, for example, by ring-opening addition polymerization of alkylene oxide as an initiator using a polymerization catalyst. The total degree of unsaturation of the polyoxyalkylene triol and polyoxyalkylene diol 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.

Examples of the polymerization catalyst include alkali metal compound catalysts such as sodium-based catalysts and potassium-based catalysts, cationic polymerization catalysts, double metal cyanide complex catalysts such as zinc hexacyanocobaltate glyme complexes and diglyme complexes, and phosphazene compound catalysts. . Among these, alkali metal compound catalysts and double metal cyanide complex catalysts are preferred.

As the initiator, a compound having 2 to 3 active hydrogens (groups) (hydroxyl groups and amino groups capable of reacting with alkylene oxide) in one molecule is used. In addition to these, a small amount of a compound having 4 active hydrogens (groups) in one molecule can also be used.

A compound having 3 active hydrogens (groups) in one molecule is mainly used as an initiator for producing a polyoxyalkylene triol. Specific examples of compounds having 3 active hydrogen atoms in one molecule include trihydric alcohols such as glycerin and trimethylolpropane.

A compound having 2 active hydrogens (groups) in one molecule is mainly used as an initiator for producing a polyoxyalkylene diol. Specific examples of compounds having two active hydrogen atoms in one molecule include ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, bisphenol A, bisphenol F, and the like. hydric alcohols.

Specific examples of alkylene oxides include ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane and the like. Among these, propylene oxide, ethylene oxide, and a combination of propylene oxide and ethylene oxide are preferred, and propylene oxide and a combination of propylene oxide and ethylene oxide are particularly preferred.

As the polyoxyalkylene triol, polyoxypropylene triol, polyoxyethylene triol, and polyoxyethylene propylene triol are preferable, and polyoxypropylene triol and polyoxyethylene propylene triol are more preferable. The number average molecular weight of the polyoxyalkylene triol is preferably 1,000 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000.

As used herein, "oxyethylene propylene" includes an oxyethylene group (--CH ₂ CH ₂ O--) and an oxypropylene group (--CH(CH ₃ )CH ₂ O--) in its molecule.

As the polyoxyalkylene diol, polyoxypropylene diol, polyoxyethylene diol and polyoxyethylene propylene diol are preferable, and polyoxypropylene diol and polyoxyethylene propylene diol are more preferable. The number average molecular weight of the polyoxyalkylene diol is preferably 1,000 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000.

Examples of polyester polyols include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, trimellit One or more carboxylic acids including polycarboxylic acids such as acids, their anhydrides or alkyl esters such as methyl esters and ethyl esters, 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, Low-molecular-weight polyols such as 8-octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adducts of bisphenol A, trimethylolpropane, glycerin or pentaerythritol polyester polyols obtained by reaction with one or more of the class. In addition to these carboxylic acids and low-molecular-weight polyols, one of low-molecular-weight polyamines such as butylenediamine, hexamethylenediamine, xylylenediamine and isophoronediamine, and low-molecular-weight aminoalcohols such as monoethanolamine and diethanolamine. Also included are polyesteramide polyols obtained by reacting the above.

Polycarbonate polyols include, for example, the dehydrochlorination reaction of the low-molecular-weight polyols used in the synthesis of the polyester polyols described above and phosgene, or the esters of the low-molecular-weight polyols described above with diethylene carbonate, dimethyl carbonate, diethyl carbonate, and diphenyl carbonate. Examples include those obtained by exchange reactions.

As the poly(meth)acrylate-based polyol, for example, a (meth)acrylate monomer containing a hydroxyl group such as hydroxyethyl (meth)acrylate and another (meth)acrylic acid alkyl ester monomer are combined, if necessary. and copolymerized using a radical polymerization initiator.

Hydrocarbon-based polyols include, for example, polyolefin polyols such as polybutadiene polyol and polyisoprene polyol; polyalkylene polyols such as hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol; halogenated polyols such as chlorinated polypropylene polyol and chlorinated polyethylene polyol; Alkylene polyol etc. are mentioned.

Animal and plant polyols include, for example, castor oil polyols and silk fibroin.

Any of the above polymer polyols can be used alone or in combination of two or more.

Polymeric monools include polyoxyalkylene monools.

The number average molecular weight of the polymeric monool is preferably 1,000 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000.

In the present specification, the "system" of the polyoxyalkylene-based monool means that 50% by mass or more, further 80% by mass or more, particularly 90% by mass or more of the portion excluding hydroxyl groups in the molecule is composed of polyoxyalkylene. If so, it means that the remainder may be modified with esters, urethanes, polycarbonates, polyamides, poly(meth)acrylates, polyolefins, and the like. It is particularly preferred that 95 mass % or more of the molecule excluding hydroxyl groups is composed of polyoxyalkylene.

A polyoxyalkylene monool is obtained, for example, by subjecting an initiator to ring-opening addition polymerization of an alkylene oxide in the presence of a polymerization catalyst. The total degree of unsaturation of the polyoxyalkylene monool 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.

Examples of the polymerization catalyst include alkali metal compound catalysts such as sodium-based catalysts and potassium-based catalysts, cationic polymerization catalysts, double metal cyanide complex catalysts such as zinc hexacyanocobaltate glyme complexes and diglyme complexes, and phosphazene compound catalysts. . Among these, alkali metal compound catalysts and double metal cyanide complex catalysts are preferred.

A compound having one active hydrogen (group) per molecule is mainly used as an initiator for producing a polyoxyalkylene monool. Specific examples of compounds having one active hydrogen (group) per molecule include, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, and the like. monohydric phenols such as phenol and nonylphenol; and secondary amines such as dimethylamine and diethylamine.

Specific examples of alkylene oxides include ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane and the like. Among these, propylene oxide, ethylene oxide, and a combination of propylene oxide and ethylene oxide are preferred, and propylene oxide and a combination of propylene oxide and ethylene oxide are particularly preferred.

As the polyoxyalkylene monool, polyoxypropylene monool, polyoxyethylene monool and polyoxyethylene propylene monool are preferable, and polyoxypropylene monool and polyoxyethylene propylene monool are more preferable.

Examples of low-molecular-weight polyols include 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-cyclo Hexanedimethanol, trimethylolpropane, glycerin, pentaerythritol, bisphenol skeleton-containing polyether polyols, polyester polyols, polycarbonate polyols, polyoxyalkylene polyols, hydrocarbon polyols, animal and plant polyols, copolyols thereof, and the like. . Any of these low-molecular-weight polyols can be used alone or in combination of two or more. Among these, 1,4-butanediol, neopentyl glycol, and bisphenol skeleton-containing polyether polyol are preferred because the curable composition has excellent adhesiveness and mechanical properties.

The number average molecular weight of the low-molecular-weight polyol is not particularly limited as long as it is less than 1,000, preferably 50-900, particularly preferably 50-600.

An isocyanate group-containing urethane prepolymer having an isocyanurate ring is a urethane resin having one or more isocyanate groups and one or more isocyanurate rings in one molecule. An isocyanate group-containing urethane prepolymer having an isocyanurate ring reacts with an active hydrogen-containing compound to form a urethane bond, a urea bond, etc. in the same manner as an isocyanate group-containing urethane prepolymer having no isocyanurate ring, and is crosslinked and cured. In addition, the isocyanate group-containing urethane prepolymer having an isocyanurate ring improves adhesiveness and imparts excellent water resistance and good stringiness when adhering members to be adhered.

An isocyanate group-containing urethane prepolymer having an isocyanurate ring is produced by reacting an organic isocyanate compound containing an isocyanurate-modified polyisocyanate with an active hydrogen-containing compound all at once or sequentially so that the isocyanate group remains in the urethane prepolymer. can be manufactured. The molar ratio of the isocyanate group of the organic isocyanate compound to the active hydrogen (group) of the active hydrogen-containing compound (isocyanate group/active hydrogen) is the number of moles of the isocyanate group of the organic isocyanate compound to the active hydrogen (group) of the active hydrogen-containing compound. There is no particular limitation as long as it is greater than the number of moles, but 2 to 15 is preferred, and 2 to 10 is more preferred.

The isocyanate group content of the isocyanate group-containing urethane prepolymer having an isocyanurate ring is preferably 2 to 30% by mass, particularly preferably 5 to 25% by mass.

The number average molecular weight of the isocyanate group-containing urethane prepolymer having an isocyanurate ring is preferably 600 to 6,000, more preferably 800 to 4,000, and particularly preferably 1,000 to 2,000.

As a method for producing an isocyanate group-containing urethane prepolymer having an isocyanurate ring, a conventionally known method can be used. Specifically, for example, an isocyanurate-modified polyisocyanate and an active hydrogen-containing compound are charged into a reaction vessel made of glass or stainless steel, and if necessary, a reaction catalyst or an organic solvent is used, and the mixture is stirred at 50 to 120°C. A method of reacting while At this time, if the isocyanate group reacts with water such as moisture, the urethane prepolymer will thicken, so it is preferable to replace the inside of the container with nitrogen gas in advance or perform the reaction under a nitrogen gas stream.

Examples of the reaction catalyst include reaction catalysts similar to the reaction catalysts that can be used in the production of the isocyanate group-containing urethane prepolymer having no isocyanurate ring. Moreover, examples of the organic solvent include the same organic solvents as those usable for the production of the isocyanate group-containing urethane prepolymer having no isocyanurate ring.

When a reaction catalyst is used in the production of an isocyanate group-containing urethane prepolymer having an isocyanurate ring, the reaction catalyst remaining in the urethane prepolymer may act as a curing acceleration catalyst for the curable composition.

The isocyanurate-modified polyisocyanate will be explained. An isocyanurate-modified polyisocyanate is a compound having two or more isocyanate groups and one or more isocyanurate rings in one molecule.

The isocyanurate-modified polyisocyanate can be obtained by subjecting an organic polyisocyanate to an isocyanurate reaction using an isocyanurate catalyst. As a method for producing the isocyanurate-modified polyisocyanate, a conventionally known method can be used. Specifically, for example, an organic polyisocyanate and an isocyanurate-forming catalyst are charged in a reaction vessel made of glass or stainless steel, and if necessary, an organic solvent is used, and the isocyanurate-forming reaction is performed while stirring at 30 to 90°C. There is a method to make Acidic compounds such as sulfuric acid and phosphoric acid can be used to terminate the isocyanurate reaction. Further, after completion of the isocyanurate-forming reaction treatment, unreacted organic polyisocyanate monomers can be removed by a method such as thin film distillation.

Examples of the organic polyisocyanate for producing the isocyanurate-modified polyisocyanate include the same organic polyisocyanates that can be used for producing the aforementioned isocyanurate ring-free isocyanate group-containing urethane prepolymer. Any of these organic polyisocyanates can be used alone or in combination of two or more. Among these, organic polyisocyanates containing aliphatic polyisocyanates and/or alicyclic polyisocyanates are preferred, and hexamethylene diisocyanate and/or isophorone diisocyanate are particularly preferred.

Examples of the organic isocyanate compound other than the isocyanurate-modified polyisocyanate include those similar to the organic polyisocyanate and organic monoisocyanate that can be used in producing the isocyanate group-containing urethane prepolymer having no isocyanurate ring. .

Examples of the active hydrogen-containing compound used in producing the isocyanate group-containing urethane prepolymer having an isocyanurate ring include low-molecular-weight polyols and mixtures of low-molecular-weight polyols and low-molecular-weight monools.

Examples of low-molecular-weight polyols include 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-cyclo Hexanedimethanol, trimethylolpropane, glycerin, pentaerythritol, bisphenol skeleton-containing polyether polyols, polyester polyols, polycarbonate polyols, polyoxyalkylene polyols, hydrocarbon polyols, animal and plant polyols, copolyols thereof, and the like. . Any of these low-molecular-weight polyols can be used alone or in combination of two or more. Among these, neopentyl glycol, glycerin, and 3-methyl-1,5-pentanediol are preferable because the isocyanate group-containing urethane prepolymer having an isocyanurate ring is easily dissolved in an organic solvent.

The number average molecular weight of the low-molecular-weight polyol is not particularly limited as long as it is less than 1,000, but is preferably 50-900, particularly preferably 50-600.

Examples of low-molecular-weight monools include linear or branched aliphatic monools having 1 to 18 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, and decanol. be done. Any of these low-molecular-weight monools can be used alone or in combination of two or more.

The amount of the isocyanate group-containing urethane prepolymer having an isocyanurate ring to be blended is the isocyanate group of the isocyanate group-containing urethane prepolymer having an isocyanurate ring per 1 mol of the isocyanate group of the isocyanate group-containing urethane prepolymer having no isocyanurate ring. is preferably from 0.5 to 5, more preferably from 1 to 3.

The curable composition of the present invention may optionally contain various additives in addition to the components described above, as long as the objects of the present invention are not impaired. Additives are used to improve various properties of the curable composition, such as viscosity adjustment, curing acceleration, and adhesiveness, by blending with the curable composition. Specific examples include curing accelerator catalysts, plasticizers, weather stabilizers, fillers, thixotropic agents, adhesion improvers, storage stability improvers (dehydrating agents), colorants, organic solvents, and the like. can be done. All of these can be used singly or in combination of two or more.

The curing acceleration catalyst is used to promote cross-linking and curing of the isocyanate group-containing urethane prepolymer having no isocyanurate ring and the isocyanate group-containing urethane prepolymer having an isocyanurate ring by reacting with water such as moisture. use. In addition, the curing accelerator catalyst is a curing agent (for example, a compound having a hydroxyl group, an amino group, or a thiol group) when the curable composition of the present invention is used as a two-part reaction curable composition, and an isocyanate of the urethane prepolymer. Used to promote reaction with groups.

Specific examples of curing acceleration catalysts include catalysts similar to the reaction catalysts that can be used in the production of the isocyanate group-containing urethane prepolymer having no isocyanurate ring.

All curing acceleration catalysts can be used alone or in combination of two or more.

The amount of the curing accelerator catalyst is 0.005 to 5 parts by mass with respect to 100 parts by mass of the total amount of the isocyanate group-containing urethane prepolymer having no isocyanurate ring and the isocyanate group-containing urethane prepolymer having an isocyanurate ring. 0.005 to 2 parts by mass is particularly preferred.

The plasticizer is used for the purpose of lowering the viscosity of the curable composition to improve workability and adjusting the physical properties of the rubber after curing of the curable composition. Specifically, for example, phthalates such as dioctyl phthalate, diisononyl phthalate, dibutyl phthalate, and butyl benzyl phthalate; aliphatic carboxylic acids such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, and butyl oleate; Low molecular weight plasticizers such as acid esters; urethanization, etherification or Esterified high molecular weight plasticizer with a number average molecular weight of 1,000 or more; high molecular weight plasticizer with a number average molecular weight of 1,000 or more that does not react with isocyanate groups such as polystyrenes such as poly-α-methylstyrene and polystyrene is mentioned. All of these can be used singly or in combination of two or more.

The amount of the plasticizer to be blended is preferably 1 to 200 parts by mass, preferably 2 to 50 parts by mass, with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer having no isocyanurate ring and the isocyanate group-containing urethane prepolymer having an isocyanurate ring. Part is more preferred.

The weather stabilizer is used for the purpose of preventing oxidation, light deterioration and heat deterioration of the curable composition and further improving weather resistance and heat resistance. Weather stabilizers include hindered amine light stabilizers, hindered phenol antioxidants, and ultraviolet absorbers. All of these can be used singly or in combination of two or more.

Examples of hindered amine light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-1(octyloxy)decanedioate, -4-piperidyl) ester, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalo ate, 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 and other low molecular weight compounds having a molecular weight of less than 1,000; 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 -In addition to triazine condensates, high-molecular-weight compounds having a molecular weight of 1,000 or more, such as Adekastab LA-63P and LA-68LD manufactured by ADEKA Corporation, can be mentioned.

Hindered phenol antioxidants include, for example, 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)propioamide], benzenepropanoic acid 3,5 -bis(1,1-dimethylethyl)-4-hydroxy C7-C9 side chain alkyl esters, 2,4-dimethyl-6-(1-methylpentadecyl)phenol.

UV absorbers include, for example, benzotriazole-based UV absorbers such as 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole; 2-(4,6-diphenyl- Triazine UV absorbers such as 1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol; benzophenone UV absorbers such as octabenzone; 2,4-di-tert-butylphenyl -3,5-di-tert-butyl-4-hydroxybenzoate and other benzoate-based UV absorbers.

Among these, hindered amine-based light stabilizers and hindered phenol-based antioxidants are preferred because they are highly effective in improving weather resistance. The blending amount of the weather stabilizer is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the isocyanate group-containing urethane prepolymer having no isocyanurate ring and the isocyanate group-containing urethane prepolymer having an isocyanurate ring. Preferably, 0.1 to 5 parts by mass is more preferable.

The filler is used for the purpose of extending the curable composition and reinforcing the physical properties of the cured product of the curable composition. Fillers include inorganic fillers and organic fillers. Inorganic fillers include heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, mica, kaolin, zeolite, graphite, diatomaceous earth, clay, clay, talc, anhydrous silicic acid, quartz, aluminum powder, zinc powder, hydroxide Inorganic powdery fillers such as calcium, magnesium carbonate and alumina; and inorganic fibrous fillers such as glass fibers and carbon fibers. Organic fillers include organic powdery fillers such as wood flour, walnut flour, rice hull flour, pulp flour, rubber powder, and thermoplastic or thermosetting resin powder. Further, examples of fillers include flame-retardant-imparting fillers such as magnesium hydroxide and aluminum hydroxide. All of these can be used singly or in combination of two or more.

The amount of the filler compounded is preferably 1 to 500 parts by mass with respect to the total amount of 100 parts by mass of the isocyanate group-containing urethane prepolymer having no isocyanurate ring and the isocyanate group-containing urethane prepolymer having an isocyanurate ring. More preferably up to 300 parts by mass, particularly preferably 10 to 200 parts by mass.

The thixotropy imparting agent imparts thixotropic properties to the curable composition, for the purpose of maintaining the shape of the application when the curable composition is applied by bead coating, combed trowel, etc., and for applying the curable composition on a vertical surface or It is used for the purpose of preventing sagging and slump when used on an inclined surface. Examples of thixotropic agents include inorganic thixotropic agents and organic thixotropic agents. Examples of inorganic thixotropic agents include surface-treated calcium carbonate and fine powder silica. Examples of organic thixotropic agents include urea compounds, organic bentonites, and fatty acid amides. All of these can be used singly or in combination of two or more.

Surface-treated calcium carbonate is obtained by treating the surface of heavy calcium carbonate, light calcium carbonate, or colloidal calcium carbonate with a fatty acid such as fatty acid, fatty acid alkyl ester, fatty acid metal salt, or fatty acid organic salt. Examples of fatty acids include fatty acids having 10 to 25 carbonic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid. Examples of metal salts include sodium salts, potassium salts, calcium salts and aluminum salts, and examples of organic salts include ammonium salts.

Examples of finely divided silica include hydrophilic silica and hydrophobic silica. All of these can be used singly or in combination of two or more.

Examples of hydrophilic silica include natural silica obtained by finely pulverizing quartz, silica sand, etc., and synthetic silica such as dry silica and wet silica. Dry silica is obtained by burning a silane-based gas such as silicon tetrachloride in an oxyhydrogen flame, and is sometimes called fumed silica. Wet-process silica includes precipitation silica, which is obtained by neutralizing sodium silicate with a mineral acid to precipitate silica in a solution, and is sometimes called white carbon.

Examples of hydrophobic silica include those made hydrophobic by subjecting hydrophilic silica to surface treatment using an organosilicon compound having reactivity with hydrophilic silica.

The amount of the thixotropy-imparting agent is preferably 10 to 50 parts by mass with respect to 100 parts by mass of the total amount of the isocyanate group-containing urethane prepolymer having no isocyanurate ring and the isocyanate group-containing urethane prepolymer having an isocyanurate ring. .

The adhesion improver is used for the purpose of improving the adhesion of the curable composition. Specifically, for example, various coupling agents such as silane-based, aluminum-based, and zirco-aluminate-based coupling agents and partial hydrolysis condensates thereof can be used. Among these, the silane coupling agent and its partial hydrolysis condensate are preferable because of their excellent adhesiveness.

Silane-based coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane and other vinylsilane coupling agents, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, epoxysilane coupling agents such as 3-glycidoxypropyltriethoxysilane, styrylsilane coupling agents such as p-styryltrimethoxysilane ring agents, methacrylic coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxy Acrylsilane coupling agents such as propyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl) Aminosilane coupling agents such as 2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, ureidosilane coupling agents such as 3-ureidopropyltrialkoxysilane, isocyanate silane coupling agents such as 3-isocyanatopropyltriethoxysilane ring agents, isocyanurate silane coupling agents such as tris-(trimethoxysilylpropyl) isocyanurate, and mercaptosilane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. Examples of the silane coupling agent include partial hydrolysis condensates of silane coupling agents obtained by partially hydrolyzing and condensing the alkoxy groups of these silane coupling agents. All of these can be used singly or in combination of two or more. Among these, epoxysilane coupling agents, aminosilane coupling agents and mercaptosilane coupling agents are preferred.

The amount of the adhesion improver is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the isocyanate group-containing urethane prepolymer having no isocyanurate ring and the isocyanate group-containing urethane prepolymer having an isocyanurate ring. Preferably, 0.5 to 5 parts by mass is particularly preferred.

A storage stability improver (dehydrating agent) is used for the purpose of improving the storage stability of the curable composition. Specific examples include vinyltrimethoxysilane, calcium oxide, and p-toluenesulfonyl isocyanate, which react with water present in the curable composition to act as a dehydrating agent. All of these can be used singly or in combination of two or more.

The coloring agent is used for the purpose of coloring the curable composition in a desired color and imparting design properties to the cured product. Specific examples include inorganic pigments such as carbon black, titanium oxide and iron oxide, and organic pigments such as copper phthalocyanine. All of these can be used singly or in combination of two or more.

The organic solvent is used for the purpose of improving workability during application of the curable composition by lowering the viscosity of the curable composition. Any organic solvent can be used without particular limitation as long as it has good compatibility with other components in the curable composition and does not react with other components. Specifically, for example, the same organic solvents that can be used in producing an isocyanate group-containing urethane prepolymer having no isocyanurate ring can be used. Any of these organic solvents can be used alone or in combination of two or more.

Since the curable composition of the present invention cures by reacting with water such as moisture, it can be used as a one-component moisture-curable composition. Moreover, it can also be used as a two-component reaction curable composition containing the curable composition of the present invention as a main component and an active hydrogen-containing compound such as polyamine, polyol, or polythiol as a curing agent. The curable composition of the present invention is excellent in workability because there is no need to mix the main agent and the curing agent, and there is no curing failure due to mixing errors or insufficient mixing. preferable.

The method for producing the curable composition of the present invention is not particularly limited, but specific examples include, for example, an isocyanate group-containing urethane prepolymer having no isocyanurate ring, an isocyanate group-containing urethane prepolymer having an isocyanurate ring, and If necessary, the additive is charged into a mixing vessel made of glass, stainless steel, etc., equipped with a stirring device that can shut out water such as moisture, and is stirred under a stream of dry air or dry nitrogen until it becomes uniform. can be done. Moreover, a batch method or a continuous method can be used as a method for producing the curable composition.

Since the curable composition of the present invention is thickened and cured by water such as moisture, it is preferably stored in a sealed container that can block water such as moisture. The container is not particularly limited as long as it can block water such as humidity. Specific examples include metal or resin cans, aluminum or resin bags, paper or resin cartridges, and the like.

An example of the method of using the curable composition of the present invention as an adhesive composition will be described. The substrate to which the curable composition of the present invention is applied is, for example, a building substrate, and specifically, it is preferably applied to a building substrate formed of, for example, mortar, concrete, fiber-reinforced cement board, or plywood. can do. The floor material to be adhered to the base is made of resin, for example, and has a tile shape, a sheet shape, a long sheet shape, or the like. Materials for floor materials include vinyl chloride resin, polyolefin resin such as polypropylene and polystyrene, polyurethane resin, synthetic rubber such as styrene-butadiene rubber, polycarbonate resin, polyphenylene oxide, polyester resin such as polybutylene terephthalate, melamine resin, Examples include natural rubber, ABS resin, and the like. Among these, it is particularly suitable for vinyl chloride resin.

The bonding method using the curable composition of the present invention includes, for example, a method of applying the curable composition of the present invention to a substrate, then laying a flooring material thereon, and applying pressure to the flooring material. A method in which the curable composition of the present invention is applied, and then the curable composition-coated side of the flooring material is placed on the substrate with the curable composition-coated side facing the substrate, and pressed to adhere. A method of applying the curable composition of the present invention, then joining the coated surfaces of the curable composition of the present invention and pressing them to adhere them may be mentioned. Examples of the method of applying the curable composition of the present invention include a method of applying using trowels such as combed trowels, spatulas, brushes, roll coaters, etc., and a method of applying in the form of beads or dots using a nozzle. A known method such as a method of applying to a surface or a method of spray coating can be used.

Examples and the like of the present invention are shown below, but the present invention should not be construed as being limited to the examples and the like.

[Synthesis Example 1] Isocyanate group-containing urethane prepolymer having no isocyanurate ring Into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen seal tube, and a heating/cooling device, 290.0 g of ethyl acetate, polyoxy Propylene triol (T-4000, hydroxyl value 42.0, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) 391.2 g, polyester diol (Teslac 2455, hydroxyl value 57.6, manufactured by Hitachi Chemical Co., Ltd.) 57.1 g, bisphenol 107.1 g of the propylene oxide adduct of A (BAP-3G, hydroxyl value 276.0, manufactured by Nippon Nyukazai Co., Ltd.) was charged, and 4,4'-diphenylmethane diisocyanate (MDI-100, Wanhua Chemical Japan Co., Ltd.) was stirred while stirring. ), 77.2 g of a mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate (MDI-50, manufactured by Wanhua Chemical Japan Co., Ltd.), and 0.2 g of zirconium octylate. , and reacted at 75-80° C. for 2 hours. When the isocyanate group content was below the theoretical value, the reaction was terminated to synthesize an isocyanate group-containing urethane prepolymer having no isocyanurate rings. The resulting isocyanate group-containing urethane prepolymer having no isocyanurate ring had a number average molecular weight of 2,800 and an isocyanate group content of 1.35% by mass.

[Synthesis Example 2] Urethane Prepolymer Containing Isocyanate Groups Having Isocyanurate Rings Into a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, and heating/cooling device, 300.0 g of ethyl acetate and neopentyl glycol are poured into a reaction vessel equipped with a heating/cooling device while flowing nitrogen gas. 35.5 g of was charged, and while stirring, 664.4 g of isocyanurate of hexamethylene diisocyanate (HDT, NCO content 21.55%, manufactured by Vencorex) and 0.02 g of dibutyltin dilaurate were charged, heated to 75 The reaction was allowed to proceed at ~80°C for 2 hours. When the isocyanate group content became below the theoretical value, the reaction was terminated to synthesize an isocyanate group-containing urethane prepolymer having isocyanurate rings. The obtained isocyanate group-containing urethane prepolymer having an isocyanurate ring had a number average molecular weight of 1,440 and an isocyanate group content of 11.40% by mass.

[Example 1]
100.0 g of the isocyanate group-containing urethane prepolymer having no isocyanurate ring of Synthesis Example 1 and the isocyanurate ring of Synthesis Example 2 are added to a mixing vessel equipped with a stirrer, a heating and cooling device, and a nitrogen seal tube, while flowing nitrogen gas. 20.0 g of an isocyanate group-containing urethane prepolymer and 38.4 g of ethyl acetate were charged, and dried in advance with stirring in a dryer at 100 to 110 ° C. to a water content of 0.05% by mass or less. 103.3 g of calcium (HTO-6, manufactured by Hitachi Saiseki Co., Ltd.) and 26.2 g of fatty acid surface-treated calcium carbonate (CCR-S, manufactured by Shiraishi Calcium Co., Ltd.) were charged and mixed until the contents were uniform. Furthermore, 1.7 g of silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), 1.3 g of finely powdered silica (QS-102, manufactured by Tokuyama Co., Ltd.), and 2.6 g of paratoluenesulfonyl isocyanate. , charged, and mixed until the content was uniform to obtain a curable composition. The amount of the isocyanate group-containing urethane prepolymer having an isocyanurate ring in the curable composition thus obtained is 1 mol of the isocyanate group of the isocyanate group-containing urethane prepolymer having no isocyanurate ring. The number of moles of isocyanate groups in the isocyanate group-containing urethane prepolymer having nurate rings was 1.69 mol.

[Comparative Example 1]
A curable composition was obtained in the same manner as in Example 1 except that the isocyanate group-containing urethane prepolymer having an isocyanurate ring of Synthesis Example 2 was not blended.

[Comparative Example 2]
In Example 1, instead of the isocyanate group-containing urethane prepolymer having an isocyanurate ring in Synthesis Example 2, 6.3 g of an isocyanurate form of hexamethylene diisocyanate (HDT, NCO content: 21.55%, manufactured by Vencorex). A curable composition was obtained by performing the same operation except for blending.

<Evaluation of curable composition>
Using the curable compositions of Example 1 and Comparative Examples 1 and 2, the following performance evaluation tests were conducted. Table 1 shows the composition of the curable composition and the results of the performance evaluation test.
[Tensile bond strength]
A tensile bond strength test was conducted according to JIS A 5536:2015 "Adhesives for floor finishing materials", 6.3.2 Tensile bond strength (test for polymer-based floor coverings). The base material is 70mm long x 70mm wide x 20mm thick mortar, and the floor material is vinyl chloride resin tiles (Royal Stone, manufactured by Toli Co., Ltd.) 40mm long x 40mm wide x 3mm thick, and the open time is 20 minutes. did. Normal curing conditions were 23° C. and 50% RH for 48 hours, and water immersion curing conditions were 23° C. and 50% RH for 48 hours, and then immersed in 23° C. water for 168 hours.
[Peel adhesion strength]
In accordance with JIS A 5536:2015 "Adhesives for floor finishing materials", 6.3.3 Peel adhesion strength (test for polymer-based flooring materials), a 90-degree peel adhesion strength test was conducted. The base material is 150 mm long x 70 mm wide x 10 mm thick mortar, and the floor material is a vinyl chloride resin sheet (Takitron MT sheet, manufactured by Takiron C.I. Co., Ltd.) measuring 20 mm long x 25 mm wide x 3 mm thick, and the open time is 20. minute. Normal curing conditions were 23° C. and 50% RH for 48 hours, and water immersion curing conditions were 23° C. and 50% RH for 48 hours, and then immersed in 23° C. water for 168 hours.
[Pastable time]
JIS A 5536: 2015 "Adhesive for floor finishing materials" 6.3.3 Peel adhesion strength test (test for polymer-based flooring materials) In the peel adhesion strength test, the base material is 150 mm long x 70 mm wide. × 10 mm thick mortar, the floor material is a vinyl chloride resin sheet (Takistron MT sheet, manufactured by Takiron C.I. Co., Ltd.) with a length of 20 mm × width of 25 mm × thickness of 3 mm, and after applying a curable composition (adhesive) A 90 degree peel strength test was conducted with an open time of 30 minutes or 60 minutes. The curing conditions were 23° C. and 50% RH for 48 hours.
[Stringiness]
JIS A 5536: 2015 "Adhesives for floor finishing materials" 6.3.3 Peel adhesion strength (test for polymer floor coverings) 90 degree peel adhesion strength test Using the same test specimen , The base material and the floor material were adhered with an open time of 30 minutes or 60 minutes after application of the curable composition (adhesive). After reciprocating a 5-kg roller from above the floor material twice, the stringiness of the curable composition was visually observed while turning up one end of the floor material at 90 degrees, and evaluated as follows.
Visual evaluation ○: Stringiness is clearly observed in the curable composition △: Stringiness is slightly observed in the curable composition ×: No stringiness is observed in the curable composition

From the results in Table 1, the curable composition of the present invention (Example 1) was compared with the curable compositions of Comparative Examples 1 and 2 in terms of tensile adhesive strength and 90 degree peel strength under normal conditions and after immersion in water. The adhesion strength was high, and the adhesion and water resistance were excellent. In addition, the curable composition of the present invention, compared with the curable compositions of Comparative Examples 1 and 2, has a high 90 degree peel adhesive strength after an open time of 30 minutes or 60 minutes, and a stickable time It was found to be excellent in workability because it can be taken for a long time. Furthermore, the curable composition of the present invention was excellent in stringiness after application.

As described above, the curable composition of the present invention is excellent in adhesiveness, water resistance, workability and stringiness, and therefore can be suitably used for construction and civil engineering. Moreover, the curable composition of the present invention can be used as an adhesive composition, a sealant composition, and a waterproof material composition. The curable composition of the present invention is particularly suitable for use as an adhesive for vinyl chloride resins.

Claims (9)

Containing an isocyanate group-containing urethane prepolymer having no isocyanurate ring and an isocyanate group-containing urethane prepolymer having an isocyanurate ring,
The isocyanate group-containing urethane prepolymer having no isocyanurate ring comprises an organic isocyanate compound (excluding isocyanurate-modified polyisocyanate), a high molecular weight polyol having a number average molecular weight of 1,000 to 30,000, and a number average molecular weight of 1. a reactant of one or more active hydrogen-containing compounds selected from polymeric monools having a molecular weight of 50 to 30,000 and low molecular weight polyols having a number average molecular weight of 50 to 900;
The isocyanate group-containing urethane prepolymer having an isocyanurate ring is a reaction product of an organic isocyanate compound containing an isocyanurate-modified polyisocyanate and an active hydrogen-containing compound containing a low molecular weight polyol having a number average molecular weight of 50 to 900,
The amount of the isocyanate group-containing urethane prepolymer having an isocyanurate ring to be blended is the isocyanate group-containing urethane prepolymer having the isocyanurate ring per 1 mol of the isocyanate group of the isocyanate group-containing urethane prepolymer having no isocyanurate ring. A one-component moisture- curable adhesive composition for flooring, characterized in that the number of moles of isocyanate groups in is 0.5 to 5 . 2. The one-component moisture- curable adhesive composition according to claim 1 , wherein the isocyanate group-containing urethane prepolymer having an isocyanurate ring has a number average molecular weight of 600 to 6,000. 3. The one-component moisture- curable adhesive composition according to claim 1, wherein the isocyanate group-containing urethane prepolymer having an isocyanurate ring has an isocyanate group content of 2 to 30% by mass. 4. The one according to any one of claims 1 to 3, wherein the isocyanurate-modified polyisocyanate is a modified polyisocyanate of an organic polyisocyanate containing an aliphatic polyisocyanate and/or an alicyclic polyisocyanate. A liquid moisture- curable adhesive composition. 5. The one-component moisture- curing according to any one of claims 1 to 4, wherein the isocyanurate-modified polyisocyanate is a modified polyisocyanate of an organic polyisocyanate containing hexamethylene diisocyanate and/or isophorone diisocyanate. adhesive composition. Furthermore, one or more additions selected from curing acceleration catalysts, plasticizers, weather stabilizers, fillers, thixotropic agents, adhesion agents, storage stability improvers (dehydrating agents), colorants and organic solvents 6. The one-pack type moisture- curable adhesive composition according to any one of claims 1 to 5 , characterized by containing an agent. The one-component moisture -curable adhesive composition according to any one of claims 1 to 6 , wherein the one-component moisture- curable adhesive composition is a one-component moisture-curable adhesive composition for construction or civil engineering. A liquid moisture- curable adhesive composition. The one-component moisture- curable adhesive composition according to any one of claims 1 to 7 , wherein the one-component moisture-curable adhesive composition is a one-component moisture-curable adhesive composition for vinyl chloride resin. Mold moisture curable adhesive composition. A bonding method comprising applying the one-component moisture-curable adhesive composition according to any one of claims 1 to 8 to a substrate, laying a flooring material thereon, and applying pressure to bond the substrate and the flooring material together.