Moisture-curing composition

Abstract

The present invention aims to provide a moisture-curing composition that can yield a cured product with excellent properties, including flame retardancy and adhesive properties. [Solution] A moisture-curing composition comprising a urethane prepolymer U having isocyanate groups at its molecular ends, a latent curing agent L that generates an amine by hydrolysis, and a flame retardant F, wherein the flame retardant F comprises two or more different compounds. The flame retardant F comprises a compound M having a structure in which an amine having a triazine ring and a cyclic ketone are hydrogen-bonded, and a phosphate ester compound C having a viscosity of 1 mPa·s to 500 mPa·s at 25°C. The phosphate ester compound C mainly consists of tris(2-chloro-1-methylethyl) phosphate, trixylenyl phosphate, or trioctyl phosphate. The compound M mainly consists of melamine cyanurate.

Description

[Technical Field]

[0001] The present invention relates to a moisture-curing composition having flame-retardant properties. More specifically, the present invention relates to a moisture-curing composition that can be used in industrial applications including adhesives, sealants, and coatings, and that can provide cured products with excellent properties, including flame-retardant and adhesive properties. [Background technology]

[0002] Moisture-curing compositions play a crucial role in many industrial applications, such as adhesives, sealants, or coatings. Their curing is achieved through crosslinking reactions that proceed under the influence of water, primarily via free or latent reactive groups such as isocyanate or silane groups. These reactive groups react with each other, or with themselves, primarily through contact with moisture from the air, resulting in a polymer network formed by covalent bonding of the components present in the composition.

[0003] A very wide range of products with individual properties that are versatile depending on the application field can be formulated in the field of moisture-curing compositions. Playing an important role here are mixtures such as fillers, plasticizers, additives, and adhesion promoters, which significantly influence the properties of the formulation, such as adhesion, mechanical properties, and processability. Therefore, moisture-curing compositions that have flame retardant properties and high thermal stability and can be used in places where flame retardancy is desired or even required, such as buildings, transportation systems, electrical products, storage facilities for highly flammable materials, or piping systems, are also known.

[0004] Silicone possesses good thermal stability and is therefore technically suitable for flame-retardant applications; in particular, silicone-based adhesives and sealant compositions are commonly used. On the other hand, silicone generally exhibits relatively poor adhesion to many substrates, cannot be painted over, and tends to form permanent stains due to the migration of plasticizers to porous substrates.

[0005] Moisture-curing compositions primarily composed of polyurethane or silane-modified polymers are less thermally stable than silicones in themselves, but they do not exhibit the aforementioned drawbacks. Furthermore, as mentioned above, these can be compounded in a variety of ways to improve their flame-retardant properties, resulting in good flame-retardant properties similar to those of silicones.

[0006] Therefore, flame retardants are typically used as compounding agents to delay or even completely prevent combustion fires. Known flame retardants include, for example, organic flame retardants such as halogen-containing flame retardants, but phosphorus-containing substances that form an intomescent intermediate layer under the action of flames are increasing in order to reduce toxicity and environmental problems.

[0007] Patent Document 1 discloses a moisture-curing composition containing a flame retardant. The moisture-curing composition described in Patent Document 1, in addition to a urethane prepolymer, contains surface-coated precipitated aluminum trihydrate as a flame retardant, aiming to provide a cured product that is not only excellent in flame retardancy but also in various mechanical properties such as tensile strength. However, research by the present inventors has revealed that there is room for further improvement in the moisture-curing composition described in Patent Document 1 in terms of improving the flame retardancy of the cured product, adhesion to various substrates, and other properties.

[0008] Patent documents 2-4 disclose moisture-curing compositions intended to provide cured products with excellent heat resistance. However, it has been found that the moisture-curing compositions described in these patent documents have room for further improvement in terms of the flame retardancy, adhesion to various substrates, and other properties of the cured products. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Patent No. 6963002 [Patent Document 2] Japanese Patent Publication No. 2011-68806 [Patent Document 3] Japanese Patent Publication No. 2023-51091 [Patent Document 4] Patent No. 4328222 [Overview of the project] [Means for solving the problem]

[0010] The present invention aims to provide a moisture-curing composition that can yield a cured product with excellent properties, including flame retardancy and adhesive properties.

[0011] To achieve the above objective, the present invention has the following configuration in one embodiment. [1] A moisture-curing composition according to a preferred embodiment of the present invention is: A urethane prepolymer U having isocyanate groups at the molecular ends, A latent curing agent L that generates an amine by hydrolysis, A moisture-curing composition comprising a flame retardant F, The flame retardant F is a moisture-curing composition comprising two or more different compounds. [2] The aforementioned flame retardant F comprises a compound M having a structure in which a triazine ring-containing amine and a cyclic ketone are hydrogen-bonded, and a phosphate ester compound C having a viscosity of 1 mPa·s to 500 mPa·s at 25°C, according to [1], in a moisture-curing composition. [3] The moisture-curing composition according to [2], wherein the phosphate ester compound C has a halogen-substituted hydrocarbon group, an aromatic hydrocarbon group, or a branched aliphatic hydrocarbon group. [4] The moisture-curing composition according to [2] or [3], wherein the phosphate ester compound C is mainly composed of tris(2-chloro-1-methylethyl) phosphate, trixylenyl phosphate, or trioctyl phosphate. [5] The moisture-curing composition according to any one of [2] to [4], wherein the compound M contains melamine cyanurate as a main component. [6] The compound M is present in an amount of 10 to 100 parts by weight based on 100 parts by weight of the urethane prepolymer U, The moisture-curing composition according to any one of [2] to [5], wherein the compound C is present in an amount of 10 to 100 parts by weight based on 100 parts by weight of the urethane prepolymer U. [7] Preparing a moisture-curing composition according to any one of [1] to [6], Curing the moisture-curing composition to obtain a cured product, and comprising: A method for producing a cured product.

Advantages of the Invention

[0012] The moisture-curing composition of the present invention can provide a cured product excellent in properties including flame retardant properties and adhesion properties.

[0013] The present invention will be described in detail below.

[0014] [Moisture-curing composition] The moisture-curing composition according to an embodiment of the present invention includes a urethane prepolymer U, a latent curing agent L, and a flame retardant F. The flame retardant F includes two or more different compounds. Preferably, the flame retardant F includes a compound M having a structure in which an amine having a triazine ring and a cyclic ketone are hydrogen-bonded, and a phosphoric acid ester compound C having a viscosity of 1 mPa·s to 500 mPa·s at 25°C.

[0015] In this specification, when a specific component is a "main component", it means that the specific component is present in a content of 50 parts by weight or more based on 100 parts by weight of the component containing the specific component. In other preferred embodiments, the specific component may be 70 parts by weight or more, 80 parts by weight or more, or 90 parts by weight or more based on 100 parts by weight of the component containing the specific component.

[0016] In this specification, “molecular weight” is understood to mean the molar mass (grams per mole) of a molecule or part of a molecule, also called a “radical.” “Average molecular weight” means the number-average Mn of an oligomer or polymer mixture of molecules or radicals, which is typically determined by gel permeation chromatography (GPC) against polystyrene as a standard.

[0017] In this specification, “storage stability” or “storage possible” means that a substance or composition can be stored in a suitable container at room temperature for a long period of time, typically at least 3 months to a maximum of 6 months or more, without any change in its use or properties, particularly viscosity and crosslinking rate, to a certain extent in relation to its use, as a result of storage.

[0018] In this specification, room temperature refers to a temperature of approximately 23°C.

[0019] The viscosities described herein were measured using a Type B viscometer (manufactured by Toki Sangyo Co., Ltd.) under conditions of 25°C, in accordance with the method described in JIS K 7117-2:1991.

[0020] The moisture-curing composition of the present invention contains urethane prepolymer U in an amount preferably 5% to 80% by weight, more preferably 10% to 50% by weight, and even more preferably 15% to 30% by weight, based on 100% by weight of the composition.

[0021] In this specification, the term "polyurethane polymer" encompasses all polymers produced by the so-called diisocyanate polyaddition method, including polymers that are substantially or completely free of urethane groups. Examples of polyurethane polymers include polyether polyurethanes, polyester polyurethanes, polyether polyureas, polyureas, polyester polyureas, polyisocyanurates, and polycarbodiimides.

[0022] The urethane prepolymer U preferably has free isocyanate groups or latent isocyanate groups at its molecular ends. The urethane prepolymer U may be a polymer obtained by the reaction of, for example, at least one polyol with at least one polyisocyanate (preferably diisocyanate). This reaction can be carried out by reacting the polyol and polyisocyanate in a conventional manner, for example, at a temperature of 50°C to 100°C, with an optional catalyst. The polyisocyanate is added in an excess amount of isocyanate groups relative to the hydroxyl groups of the polyol.

[0023] The excess polyisocyanate is selected such that free isocyanate groups remain in the polyurethane polymer obtained after all the hydroxyl groups of the polyol have reacted, at a concentration of 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, and particularly preferably 0.3 to 2.5 parts by weight, per 100 parts by weight of the urethane prepolymer U.

[0024] Urethane prepolymer U can be optionally manufactured in combination with a plasticizer. The plasticizer used does not contain isocyanate-reactive groups.

[0025] A polyurethane polymer having free isocyanate groups in the listed proportions, obtained from the reaction of a diisocyanate with a high molecular weight diol, is preferred, with an NCO:OH ratio of 1.3:1 to 4:1, particularly 1.5:1 to 3:1, and especially preferably 1.7:1 to 2.5:1.

[0026] Suitable polyols for the production of polyurethane polymer U include polyether polyols, styrene-acrylonitrile grafted polyether polyols, polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols, polyhydroxyl functional oils or fats, or polyhydrocarbon polyols, and mixtures thereof.

[0027] Preferred polyether polyols, also known as polyoxyalkylene polyols or oligoetherols, are particularly suitable starting molecules having two or more active hydrogen atoms, such as water, ammonia, or compounds having multiple OH or NH groups (e.g., 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, isomers dipropylene glycol and tripropylene glycol, isomers butanediol, pentanediol, hexanediol). Polymer products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, oxetane, tetrahydrofuran, or mixtures thereof, which can be polymerized using (such as heptanediol, octanediol, nonanediol, decanediol, undecanediol, 1,3- and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, aniline, and mixtures of the listed compounds). For example, both low-unsaturation polyoxyalkylene polyols produced using so-called bimetallic cyanide complex catalysts (measured by ASTM D-2849-69 and reported as milliequivalents of unsaturation per gram of polyol (mEq / g)) (DMC catalysts) and relatively high-unsaturation polyoxyalkylene polyols produced using anionic catalysts such as NaOH, KOH, CsOH, or alkali metal alkoxides can be used.

[0028] Particularly preferred are polyoxyethylene polyols and polyoxypropylene polyols, especially polyoxyethylene diols, polyoxypropylene diols, polyoxyethylene triols, and polyoxypropylene triols.

[0029] Particularly preferred are polyoxyalkylenediols or polyoxyalkylentriols having a degree of unsaturation of less than 0.02 mEq / g and a molecular weight in the range of 1,000 to 30,000 g / mol, as well as polyoxyethylenediols, polyoxyethylenetriols, polyoxypropylenediols, and polyoxypropylenetriols having a molecular weight of 400 to 20,000 g / mol.

[0030] Equally preferred are so-called ethylene oxide-terminated ("EO-end-capped") polyoxypropylene polyols. The latter are special polyoxypropylene polyoxyethylene polyols obtained, for example, when a pure polyoxypropylene polyol, particularly polyoxypropylene diols and triols, is further alkoxylated with ethylene oxide after the completion of the polypropoxylation reaction, resulting in the presence of primary hydroxyl groups. Preferred in this case are polyoxypropylene polyoxyethylenediols and polyoxypropylene polyoxyethylenetriols.

[0031] Suitable polyester polyols are particularly polyesters having at least two hydroxyl groups, which can be produced by known methods, especially polycondensation of hydroxycarboxylic acids, or polycondensation of aliphatic and / or aromatic polycarboxylic acids with dihydric or polyhydric alcohols.

[0032] Particularly preferred are polyester polyols produced from dihydric to trihydric alcohols such as 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerol, and 1,1,1-trimethylolpropane; or mixtures of the aforementioned alcohols with organic dicarboxylic acids or their anhydrides or esters (e.g., succinic acid, glutaric acid, adipic acid, trimethyladipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, dimeric fatty acids, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid, trimellitic acid, trimellitic anhydride, etc.); or mixtures of the aforementioned acids with polyester polyols formed from lactones (e.g., ε-caprolactone, etc.).

[0033] Particularly preferred are polyester diols, especially those produced from dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dimeric fatty acids, phthalic acid, isophthalic acid, and terephthalic acid, or lactones such as ε-caprolactone, and dihydric alcohols such as ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, dimeric fatty acid diol, and 1,4-cyclohexanedimethanol.

[0034] Suitable polycarbonate polyols are those obtained by the reaction of the aforementioned alcohols used to construct polyester polyols, particularly using dialkyl carbonates (such as dimethyl carbonate), diaryl carbonates (such as diphenyl carbonate), or phosgene. Polycarbonate diols, especially amorphous polycarbonate diols, are particularly preferred.

[0035] A more suitable polyol is a poly(meth)acrylate polyol.

[0036] For example, polyhydroxy functional oils such as natural oils and fats (especially castor oil) or so-called oleochemical polyols obtained by chemical modification of natural oils and fats, such as epoxy polyesters or epoxy polyethers obtained by epoxidation of unsaturated oils and subsequent ring-opening with carboxylic acids or alcohols, or polyols obtained by hydroformylation and hydrogenation of unsaturated oils are also suitable. Polyols obtained from natural oils and fats by decomposition processes such as alcohol decomposition or ozonolysis, and subsequent chemical bonding (e.g., transesterification or dimerization) of the decomposition products or derivatives obtained thereby are also suitable. Suitable decomposition products of natural oils and fats are particularly fatty acids and aliphatic alcohols and fatty acid esters, especially methyl esters (FAMEs) that can be derived to hydroxy fatty acid esters by hydroformylation and hydrogenation, for example.

[0037] Furthermore, equally suitable are polyhydrocarbon polyols, also known as oligohydrocarbons, such as polyhydroxy-functional ethylene-propylene, ethylene-butylene, or ethylene-propylene-diene copolymers (e.g., those manufactured by Kraton Polymers, USA), or polyhydroxy-functional copolymers of a diene such as 1,3-butadiene or a diene mixture with a vinyl monomer such as styrene, acrylonitrile, or isobutylene, or polyhydroxy-functional polybutadiene polyols, such as those synthesized by oxidation of polybutadiene or copolymerization of 1,3-butadiene with allyl alcohol, which can be hydrogenated.

[0038] For example, polyhydroxy-functionalized acrylonitrile / butadiene copolymers, such as those that can be produced from epoxides or amino alcohols, and carboxyl-terminated acrylonitrile / butadiene copolymers commercially available from Emerald Performance Materials, LLC, USA under the name Hypro®CTBN are also suitable.

[0039] The polyol preferably has a molecular weight of 250 to 30,000 g / mol, and particularly preferably 1,000 to 20,000 g / mol, and an average OH functional value in the range of 1.6 to 3.

[0040] The polyol is preferably a polyether polyol, and more preferably a polyoxyethylene polyol, polyoxypropylene polyol, and polyoxypropylene polyoxyethylene polyol. The polyol is even more preferably a polyoxyethylene diol, polyoxypropylene diol, polyoxyethylene triol, polyoxypropylene triol, polyoxypropylene polyoxyethylene diol, or polyoxypropylene polyoxyethylene triol.

[0041] In addition to the polyols mentioned above, those that can be used in combination in the production of polyurethane polymers containing terminal isocyanate groups include small amounts of low molecular weight dihydric or polyhydric alcohols, such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, isomers dipropylene glycol and tripropylene glycol, isomers butanediol, pentanediol, hexanediol, heptanediol, octanediol, and nonanediol. These include hydroxyl, decanediol, undecanediol, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric aliphatic alcohols, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols (such as xylitol, sorbitol, or mannitol), sugars (such as sucrose), other larger polyhydric alcohols, low molecular weight alkoxylate products of the aforementioned dihydric and polyhydric alcohols, and mixtures of the aforementioned alcohols.

[0042] Examples of polyisocyanates that can be used for the production of polyurethane polymers include commercially available polyisocyanates, particularly diisocyanates.

[0043] Examples of suitable diisocyanates include 1,6-hexamethylene diisocyanate (HDI), 2-methylpentamethylene 1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,12-dodecamethylene diisocyanate, lysine and lysine ester diisocyanates, cyclohexane 1,3-diisocyanate, and cyclohexane 1,4-di Isocyanates, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (=isophorone diisocyanate or IPDI), perhydro-2,4'-diphenylmethane diisocyanate and perhydro-4,4'-diphenylmethane diisocyanate, 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1,3- and 1,4-bis(isocyanatomethyl) cyclohexane Crohexane, m- and p-xylylene diisocyanates (m- and p-XDI), m- and p-tetramethyl-1,3-xylylene diisocyanate, m- and p-tetramethyl-1,4-xylylene diisocyanate, bis(1-isocyanato-1-methylethyl)naphthalene, 2,4- and 2,6-tolylene diisocyanate (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate Examples include (MDI), 1,3- and 1,4-phenylenediisocyanates, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene 1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatobiphenyl (TODI), oligomers and polymers of the isocyanates, and any desired mixtures of the aforementioned isocyanates, among which MDI and TDI are particularly preferred.

[0044] In order to improve storage stability by preventing the isocyanate group from reacting too quickly, the urethane prepolymer U may have its isocyanate groups blocked to form latent isocyanate groups.

[0045] Blocking isocyanate groups to generate blocked or potential isocyanate groups via a suitable blocking agent capable of thermally reversible reactions with isocyanate groups is a common technique in the art, and such blocking can be easily performed by those skilled in the art. For example, blocking agents / blocking groups described in Douglas A. Wick's reviews Progress in Organic Coatings 36 (1999), 148-172 and Progress in Organic Coatings 41 (2001), 1-83 can be used.

[0046] [Latent hardener L] The moisture-curing composition of the present invention contains a latent curing agent L.

[0047] The latent curing agent preferably contains at least one group selected from aldimino groups, ketimino groups, enamino groups and oxazolidino groups, and at least one further group selected from hydroxyl groups, primary and secondary amino groups, aldimino groups, ketimino groups, enamino groups and oxazolidino groups.

[0048] Potential curing agents containing hydroxyl groups or primary or secondary amino groups are particularly suitable for two-component or multi-component compositions. When used in one-component compositions, they react with isocyanates to form reaction products having aldimino, ketimino, enamino, or oxazolidino groups. Here, it is possible to reduce the content of monomeric diisocyanates in polymers containing isocyanate groups, which is advantageous for toxicological reasons.

[0049] The latent curing agent more preferably contains two or three reactive groups selected from aldimino groups and oxazolidino groups. Such a latent curing agent is particularly suitable for one-component compositions.

[0050] Di- or trialdimine or bisoxazolidine are preferred.

[0051] A suitable bisoxazolidine is, in particular, formula [ka] (wherein D is a divalent hydrocarbyl group having 6 to 15 carbon atoms, particularly 1,6-hexamethylene or (1,5,5-trimethylcyclohexane-1-yl)methane-1,3 or 4(2)-methyl-1,3-phenylene, and E is an organic group having 3 to 30 carbon atoms, particularly 2-propyl, or 3-heptyl, or phenyl, or alkyl-substituted phenyl, particularly 4-decylphenyl, 4-undecylphenyl, 4-dodecylphenyl, 4-tridecylphenyl, or 4-tetradecylphenyl, where 4-alkyl groups are mainly in branched form. It is a compound of [the compound].

[0052] The latent curing agent is preferably of the formula [ka] (In the formula, y is 2 or 3, A is an organic group having 2 to 23 carbon atoms, and B is an organic group having 6 to 30 carbon atoms.) It is algimine.

[0053] A is preferably an alkylene group that may optionally have a cyclic component, or a divalent or trivalent polyoxyalkylene group having 5 to 15 carbon atoms, particularly 1,6-hexylene, (1,5,5-trimethylcyclohexane-1-yl)methane-1,3 or α,ω-polyoxypropylene having an average molecular weight Mn in the range of 170 to 300 g / mol, or tris(ω-polyoxypropylene) derived from trimethylolpropane having an average molecular weight Mn in the range of 330 to 500 g / mol.

[0054] B is preferably an organic group having 7 to 22 carbon atoms, particularly 2,2-dimethyl-3-acetoxypropylidene, 2,2-dimethyl-3-lauroyloxypropylidene, 2,2-dimethyl-3-(N-morpholino)propylidene, benzylidene, or alkyl-substituted benzylidene, particularly 4-decylbenzylidene, 4-undecylbenzylidene, 4-dodecylbenzylidene, 4-tridecylbenzylidene, or 4-tetradecylbenzylidene, where the 4-alkyl group is mainly branched.

[0055] More preferably, B is a group having at least 15 carbon atoms, particularly 2,2-dimethyl-3-lauroyloxypropylenene or alkyl-substituted benzylidene. Such aldimines are odorless.

[0056] formula [ka] The aldimine, in particular, removes water from the condensation while following the formula A-(NH2) y It is obtained by reacting the amine with the aldehyde of formula O=B.

[0057] Preferred amine A-(NH2) y These include aliphatic or alicyclic primary diamines or triamines, particularly hexamethylene-1,6-diamine, isophorone diamine, α,ω-polyoxypropylenediamines having an average molecular weight Mn in the range of 200 to 350 g / mol, particularly Jeffamine® D-230 (from Huntsman Corp.), or tris(ω-polyoxypropyleneamine) derived from trimethylolpropane, particularly Jeffamine® T-403 (from Huntsman Corp.).

[0058] Preferred aldehyde O=B are aldol esters of carboxylic acids, particularly 2,2-dimethyl-3-acetoxypropanal, 2,2-dimethyl-3-lauroxyloxypropanal, 2,2-dimethyl-3-(N-morpholino)propanal, benzaldehyde or alkyl-substituted benzaldehydes, particularly 4-decylbenzaldehyde, 4-undecylbenzaldehyde, 4-dodecylbenzaldehyde, 4-tridecylbenzaldehyde or 4-tetradecylbenzaldehyde, which are mainly branched by 4-alkyl groups, and mixtures of these alkyl-substituted benzaldehydes.

[0059] When exposed to moisture, the latent curing agent releases amino groups and, optionally, hydroxyl groups, which react with isocyanates to function as crosslinking agents. This results in the release of aldehydes or ketones.

[0060] If B is a preferred aldehyde of formula O=B, particularly a long-chain group having 15 or more carbon atoms, it does not cause odor problems, remains in the composition after curing, has excellent compatibility, and functions as a plasticizer.

[0061] Compared to the direct reaction between water and isocyanate, crosslinking with a latent curing agent has the advantage of not releasing CO2 and significantly reduces the tendency for blister formation during the curing process.

[0062] The moisture-curing composition of the present invention preferably contains an amount of latent curing agent such that the ratio of the number of reactive groups that can be released from the latent curing agent L to the number of isocyanate groups is in the range of 0.1 to 1.5, preferably 0.2 to 1.1, and particularly 0.3 to 1.0.

[0063] [Content of latent hardener L] The latent curing agent L is preferably present in an amount of 1 to 40 parts by weight per 100 parts by weight of urethane prepolymer U. More preferably, the latent curing agent L is present in an amount of 2 to 30 parts by weight, even more preferably 3 to 25 parts by weight, particularly preferably 4 to 20 parts by weight, and most preferably 5 to 15 parts by weight per 100 parts by weight of urethane prepolymer U.

[0064] [Flame retardant F] The moisture-curing composition of the present invention contains a flame retardant F. Preferably, the flame retardant F contains a compound M having a structure in which a triazine ring-containing amine and a cyclic ketone are hydrogen-bonded, and a phosphate ester compound C having a viscosity of 1 mPa·s to 500 mPa·s at 25°C.

[0065] [Content of flame retardant F] The flame retardant F is preferably present in an amount of 30 to 200 parts by weight per 100 parts by weight of urethane prepolymer U. More preferably, the flame retardant F is present in an amount of 60 to 170 parts by weight, even more preferably 70 to 160 parts by weight, particularly preferably 80 to 150 parts by weight, particularly more preferably 90 to 140 parts by weight, and most preferably 100 to 130 parts by weight per 100 parts by weight of urethane prepolymer U. The amount of flame retardant F as described above is the total weight of components having higher flame retardancy compared to general hydrocarbon compounds, including compound M and compound C.

[0066] [Ratio of compound M to compound C] The weight ratio of compound M to compound C (compound M:compound C) is preferably 1:10 to 10:1, more preferably 1:5 to 5:1, even more preferably 1:3 to 3:1, particularly preferably 1:2 to 2:1, and most preferably 1:1.5 to 1.5:1.

[0067] [Compound M] Compound M has a structure in which a triazine ring-containing amine and a cyclic ketone are hydrogen-bonded. It is preferable that compound M does not contain halogen elements.

[0068] The triazine ring of the above amine is any one of 1,2,3-triazine, 1,2,4-triazine, or 1,3,5-triazine. The above amine is preferably a compound having a 1,3,5-triazine ring and at least one amino group bonded to a carbon atom of the 1,3,5-triazine ring.

[0069] The cyclic ketone is preferably a compound having a 1,3,5-triazine ring and at least one oxygen double-bonded to a carbon atom of the 1,3,5-triazine ring. The oxygen double-bonded to a carbon atom of the 1,3,5-triazine ring can change to a hydroxyl group by tautomerism. The cyclic ketone may be isocyanuric acid, or an isocyanuric acid derivative in which a hydrogen group bonded to a nitrogen atom of the 1,3,5-triazine ring is substituted with another organic group as long as it can form a hydrogen bond with the above amine.

[0070] Isocyanuric acid and isocyanuric acid derivatives are preferably represented by the following formula (1). [Chemical formula] [In the formula, R 1 , R 2 , R 3 are each independently a hydrogen atom or an arbitrary organic group. R 1 , R 2 , R 3 are preferably such that at least one of them is a hydrogen atom. R 1 , R 2 , R 3 are more preferably such that two of them are hydrogen atoms and the remaining one is an arbitrary organic group, and even more preferably all three are hydrogen. The organic group is preferably one that does not interfere with the above hydrogen bond, and may be, for example, an organic group having 1 to 5 elements.]

[0071] [Content of compound M] Compound M is preferably present in an amount of 30 to 100 parts by weight per 100 parts by weight of urethane prepolymer U. More preferably, compound M is present in an amount of 35 to 90 parts by weight, even more preferably 40 to 80 parts by weight, particularly preferably 45 to 70 parts by weight, and most preferably 50 to 60 parts by weight per 100 parts by weight of urethane prepolymer U.

[0072] [Phosphate ester compound C] The phosphate ester compound C is a compound having a viscosity of 1 mPa·s to 500 mPa·s at 25°C. Preferably, the phosphate ester compound C has a viscosity of 2 mPa·s to 400 mPa·s at 25°C, more preferably 2 mPa·s to 350 mPa·s at 25°C, even more preferably 3 mPa·s to 300 mPa·s at 25°C, particularly preferably 5 mPa·s to 250 mPa·s at 25°C, and most preferably 10 mPa·s to 200 mPa·s at 25°C. By having the phosphate ester compound C within the above preferred range of viscosity, the cured product obtained from the moisture-curable composition of the present invention will have superior adhesive properties and physical properties.

[0073] [Halogen-containing phosphate ester compound C-1] The phosphate ester compound C may also be a halogen-containing phosphate ester compound C-1. The halogen-containing phosphate ester compound C-1 is preferably a product of an esterification reaction between a halogen-containing alcohol and phosphoric acid, and more preferably has a halogenated alkyl group. A halogenated alkyl group is a group in which one or more hydrogen atoms of an alkyl group are substituted with halogen atoms.

[0074] The halogenated alkyl group in halogen-containing phosphate ester compound C-1 is preferably a halogenated alkyl group having 1 to 10 carbon atoms. The number of carbon atoms is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Halogen-containing phosphate ester compound C-1 preferably contains at least one of a bromine atom or a chlorine atom, and more preferably a chlorine atom. The halogens in compound C-1 are preferably 3 or less per molecule, more preferably 2 or less, and preferably 1. In other words, compound C is preferably a phosphate ester having one chlorine atom.

[0075] [Specific examples of halogen-containing phosphate ester compounds C-1] Halogen-containing phosphate ester compound C-1 is, for example, tris(bromocresyl)phosphate, tris(4-bromo-3-methylphenyl)phosphate, tris(dibromophenyl)phosphate, tris(2,4,6-tribromophenyl)phosphate, tris(tribromophenyl)phosphate, tris(tribromoneopentyl)phosphate, tris(2-bromooctyl)phosphate, tris(2-bromoisopropyl)phosphate, tris(2-bromopropyl)phosphate, tris(bromopropyl P,P'-[2,2-bis(bromomethyl)propane-1,3-diyl]-P,P'-bis(2-bromo-3-chloropropyl)-P,P'-bis(2-bromo-3-chloropropyl)-P,P-bis(2,3-dichloropropyl)bis(phosphate), tri(2-bromoethyl)phosphate Tris(2-chloro-1-methylethyl) phosphate, Tris(2-chloro-1-(chloromethyl)ethyl) phosphate, Tetrakis(2-chloroethyl)dichloroisopentyl diphosphate, 2,2'-[[2,2-bis(chloromethyl)propane-1,3-diyl]bis(oxy)]bis[5,5-dimethyl-1,3,2-dioxaphospholinane]2,2'-dioxide, Tris[2-bromo-1-(chloromethyl)ethyl] phosphate, Bromoethylbromopentyl Chloroethyl phosphate, bis(1,3-dichloro-2-propyl)3-chloro-2,2-dibromomethyl-1-propyl phosphate, tris(2-bromo-3-chloropropyl) phosphate, bis(bromopropyl)chloroethyl phosphate, 1,2-dibromo-2,2-dichloroethyldimethyl phosphate, 2-bromo-1-(chloromethyl)ethyl 3-bromo-2,2-dimethylpropyl 2-chloro-1-(chloromethyl)ethyl phosphate, tris(1-bromo-3-chloropropyl) phosphate, 2,It may be 4-dibromophenyldiphenyl phosphate or o-chlorophenyldiphenyl phosphate. Among these, tris(2-chloro-1-methylethyl) phosphate is particularly preferred.

[0076] [Phosphate ester compound C-2 containing an aromatic hydrocarbon group] The phosphate ester compound C may also be a phosphate ester compound C-2 having an aromatic hydrocarbon group. Preferably, the phosphate ester compound C-2 is a phosphate triester obtained by an esterification reaction between an alcohol containing at least one aromatic ring and phosphoric acid, and more preferably, a phosphate triester obtained by an esterification reaction between an alcohol containing at least one aromatic ring and phosphoric acid.

[0077] [Specific examples of phosphate ester compounds C-2 having aromatic hydrocarbon groups] The phosphate ester compound C-2 may be, for example, triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresylphenyl phosphate (CDP), or 2-ethylhexyldiphenyl phosphate. Among these, tricresyl phosphate or trixylenyl phosphate is preferred, and trixylenyl phosphate is particularly preferred.

[0078] [Phosphate ester compound C-3 having branched aliphatic hydrocarbon groups] The phosphate ester compound C may be a phosphate ester compound C-3 having a branched aliphatic hydrocarbon group. Preferably, the phosphate ester compound C-3 is a phosphate triester obtained by the esterification reaction of an aliphatic alcohol having a branched aliphatic hydrocarbon group with phosphoric acid. The branched aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having a main chain of 2 to 20 carbon atoms and at least one side chain of 1 to 3 carbon atoms bonded to the side chain, and more preferably an aliphatic hydrocarbon group having a main chain of 5 to 10 carbon atoms and one side chain of 1 to 2 carbon atoms bonded to the side chain.

[0079] [Specific examples of phosphate ester compounds C-3 having branched aliphatic hydrocarbon groups] The phosphate ester compound C-3 may be triisopropyl phosphate, tributoxyethyl phosphate, or trioctyl phosphate. The above phosphate triester is particularly preferably trioctyl phosphate.

[0080] [Content of phosphate ester compound C] The phosphate ester compound C is preferably present in an amount of 25 to 100 parts by weight per 100 parts by weight of urethane prepolymer U. More preferably, compound C is present in an amount of 30 to 90 parts by weight, even more preferably 35 to 80 parts by weight, particularly preferably 40 to 70 parts by weight, and most preferably 45 to 60 parts by weight per 100 parts by weight of urethane prepolymer U. The amount of phosphate ester compound C referred to here is the total weight of all phosphate ester compounds, including phosphate ester compound C-1, phosphate ester compound C-2, and phosphate ester compound C-3.

[0081] [Adhesion promoters and / or crosslinking agents] The moisture-curing composition of the present invention may optionally further contain an adhesion promoter and / or a crosslinking agent. The adhesion promoter and / or crosslinking agent may be, for example, aminosilanes (especially 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-N'-[3-(trimethoxysilyl)propyl]ethylenediamine or analogs thereof having ethoxy instead of a methoxy group, and N-phenyl-, N-cyclohex Sil- or N-alkylaminosilanes, etc., mercaptosilanes, epoxysilanes, (meth)acrylosilanes, anhydridosilanes, carbamatesilanes, alkylsilanes or iminosilanes, oligomeric forms of these silanes, adducts formed from epoxysilanes or (meth)acrylosilanes or anhydridosilanes and primary aminosilanes, amino-functional alkylsilsesquioxanes (especially amino-functional methylsilsesquioxanes or amino-functional propylsilsesquioxanes). Particularly preferred are 3-amino-propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane or 3-ureidopropyltrimethoxysilane, or oligomeric forms of these silanes.

[0082] [Content of adhesion promoter and / or crosslinking agent] The adhesion promoter and / or crosslinking agent preferably constitutes 0.001 to 15% by weight of 100% by weight of the moisture-curing composition. The content of the adhesion promoter and / or crosslinking agent is preferably 0.005 to 10% by weight, more preferably 0.01 to 5% by weight, even more preferably 0.05 to 3% by weight, and even more preferably 0.1 to 1.0% by weight, based on 100% by weight of the moisture-curing composition.

[0083] [Desiccant] The moisture-curing composition of the present invention may optionally further contain a desiccant. The desiccant may be, for example, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, or organoalkoxysilane having a functional group at the α-position of a silane group (particularly N-(methyldimethoxysilylmethyl)-O-methylcarbamate, (methacryloxymethyl)silane, methoxymethylsilane), orthoformate ester, calcium oxide, or molecular sieve, particularly vinyltrimethoxysilane or vinyltriethoxysilane.

[0084] [Desiccant content] The desiccant is preferably present in an amount of 0.005 to 15% by weight relative to 100% by weight of the moisture-curable composition. More preferably, the desiccant is present in an amount of 0.01 to 10% by weight, even more preferably in an amount of 0.03 to 5% by weight, particularly preferably in an amount of 0.05 to 3% by weight, and most preferably in an amount of 0.1 to 1.0% by weight relative to 100% by weight of the moisture-curable composition.

[0085] [Plasticizer] The moisture-curing composition of the present invention may optionally further contain a plasticizer. The plasticizer may be, for example, a carboxylic acid ester such as phthalate (preferably dioctyl phthalate, bis(2-ethylhexyl) phthalate, bis(3-propylheptyl) phthalate, diisononyl phthalate, or diisodecyl phthalate), a diester of orthocyclohexanedicarboxylic acid (preferably diisononyl-1,2-cyclohexanedicarboxylate), an adipate (preferably dioctyl adipate, bis(2-ethylhexyl) adipate), an azelate (preferably bis(2-ethylhexyl) azelate), a sebacate (preferably bis(2-ethylhexyl) sebacate, or diisononyl sebacate), a polyol (preferably polyoxyalkylene polyol or polyester polyol), a glycol ether, a glycol ester, an organophosphate ester, a sulfonic acid ester, a sulfonamide, a polybutene, or a fatty acid methyl or ethyl ester derived from natural oils and fats, also known as "biodiesel."

[0086] [Plasticizer content] The plasticizer is preferably present in an amount of 0 to 40% by weight relative to 100% by weight of the moisture-curable composition. The plasticizer content is more preferably 0.1 to 30% by weight, even more preferably 0.3 to 25% by weight, particularly preferably 0.5 to 20% by weight, and most preferably 1 to 10% by weight, relative to 100% by weight of the moisture-curable composition.

[0087] [Filler] The moisture-curing composition of the present invention may optionally further contain a filler. The filler may be an inorganic filler or an organic filler. The inorganic or organic filler may be, for example, natural, crushed, or precipitated calcium carbonate coated with fatty acids (especially stearic acid), barite, talc, quartz powder, quartz sand, dolomite, wollastonite, kaolin, calcined kaolin, mica (potassium aluminum silicate), molecular sieves, aluminum oxide, aluminum hydroxide, magnesium hydroxide, silica such as fine silica produced by thermal decomposition, industrially produced carbon black, graphite, metal powder (aluminum, copper, iron, silver, or steel, etc.), PVC powder, or hollow spheres.

[0088] [Filler content] The filler is preferably present in an amount of 1.0 to 60% by weight relative to 100% by weight of the moisture-curing composition. More preferably, the filler is present in an amount of 2.0 to 55% by weight, even more preferably 3.0 to 50% by weight, particularly preferably 4.0 to 45% by weight, and most preferably 5.0 to 40% by weight relative to 100% by weight of the moisture-curing composition.

[0089] [catalyst] The moisture-curing composition of the present invention may contain at least one catalyst for crosslinking isocyanate groups. Suitable catalysts include metal compounds and / or basic nitrogen or phosphorus compounds.

[0090] [Catalyst content] The catalyst is preferably present in an amount of 0.005 to 5% by weight relative to 100% by weight of the moisture-curable composition. More preferably, the catalyst may be present in an amount of 0.01 to 1% by weight relative to 100% by weight of the moisture-curable composition.

[0091] Suitable metal compounds are, in particular, compounds of tin, titanium, zirconium, aluminum, or zinc (especially diorganosin(IV) compounds such as dibutyltin(IV) diacetate, dibutyltin(IV) dilaurate, dibutyltin(IV) dynedecanoate, or dibutyltin(IV) bis(acetylacetonate) and dioctyltin(IV) dilaurate), as well as complexes of titanium(IV), zirconium(IV), aluminum(III), or zinc(II) having alkoxy, carboxylate, 1,3-diketonate, 1,3-ketoesterate, or 1,3-ketoamide ligands.

[0092] Preferred organotinates are particularly titanium(IV) complexes.

[0093] Particularly suitable are the commercially available products Tyzor® AA, GBA, GBO, AA-75, AA-65, AA-105, DC, BEAT, BTP, TE, TnBT, KTM, TOT, TPT or IBAY (all from Dorf Ketal); Tytan PBT, TET, X85, TAA, ET, S2, S4 or S6 (all from Borica Company Ltd.); and Ken-React® KR® TTS, 7, 9QS, 12, 26S, 33DS, 38S, 39DS, 44, 134S, 138S, 133DS, 158FS or LICA® 44 (all from Kenrich Petrochemicals).

[0094] Suitable basic nitrogen or phosphorus compounds include imidazole, pyridine, phosphazene base, or preferably amine, hexahydrotriazine, biguanide, guanidine, or amidine.

[0095] Preferred amines are particularly alkyl, cycloalkyl, or aralkylamines; for example, amide-containing polyamines, so-called polyamidoamines, such as those commercially available under the trademark names Versamid® (Cognis), Aradur® (Huntsman), Euretek® (Huntsman), or Beckopox® (Cytec); or aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-N'-[3-(trimethoxysilyl)propyl]ethylenediamine, or analogs thereof having an ethoxy group instead of a methoxy group on silicon.

[0096] Preferred hexahydrotriazines are, in particular, 1,3,5-hexahydrotriazine or 1,3,5-tris(3-(dimethylamino)propyl)hexahydrotriazine.

[0097] Preferred biguanides are particularly biguanides, 1-butyl biguanides, 1,1-dimethyl biguanides, 1-butyl biguanides, 1-phenyl biguanides, or 1-(o-tolyl) biguanides (OTBG).

[0098] Suitable guanidines include, in particular, 1-butylguanidine, 1,1-dimethylguanidine, 1,3-dimethylguanidine, 1,1,3,3-tetramethylguanidine (TMG), 2-(3-(trimethoxysilyl)propyl)-1,1,3,3-tetramethylguanidine, 2-(3-(methyldimethoxysilyl)propyl)-1,1,3,3-tetramethylguanidine, and 2-(3-(triethoxysilyl)propyl)-1,1,3,3-tetramethylguanidine. These are anidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-cyclohexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-phenylguanidine, 1-(o-tolyl)guanidine (OTG), 1,3-diphenylguanidine, 1,3-di(o-tolyl)guanidine, or 2-guanidinobenzimidazole.

[0099] Preferred amidines include, in particular, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene, 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N'-di-n-hexylacetami These are din (DHA), 2-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 2,5,5-trimethyl-1,4,5,6-tetrahydropyrimidine, N-(3-trimethoxysilylpropyl)-4,5-dihydroimidazole, or N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0100] Furthermore, the composition may contain an acid, particularly a carboxylic acid, as a co-catalyst. Formic acid, lauric acid, stearic acid, isostearic acid, oleic acid, 2-ethyl-2,5-dimethylcaproic acid, 2-ethylhexanoic acid, neodecanoic acid, aromatic carboxylic acids (such as salicylic acid), and aliphatic carboxylic acids such as fatty acid mixtures obtained from the saponification of natural oils or di- and polycarboxylic acids (particularly poly(meth)acrylic acid).

[0101] The moisture-curing compositions of the present invention are preferably manufactured and stored in a state free of moisture. When moisture is removed, the moisture-curing compositions of the present invention typically have storage stability, particularly in suitable packaging or assemblies such as bottles, canisters, pouches, buckets, tanks, or cartridges.

[0102] The moisture-curing composition of the present invention may be a one-component composition, or, if necessary, a multi-component composition of two or more components. In this specification, "one-component" refers to a composition in which all components are stored in a mixture in the same container and are curable with moisture. In this specification, "two-component" refers to a composition in which the components are present in two different components stored in separate containers. The two components are mixed with each other only immediately before or during application of the composition, and the mixed composition optionally cures under the action of moisture.

[0103] The moisture-curing composition of the present invention is preferably applied and cured at room temperature, specifically within a temperature range of 0°C to 45°C, more preferably 5°C to 35°C.

[0104] The water required to cure the moisture-curing composition of the present invention may be derived from air (atmospheric humidity). The moisture-curing composition of the present invention may be brought into contact with a water-containing component, for example, by painting (e.g., together with a lubricant) or spraying. Water or a water-containing component may be added to the composition at the time of application, for example, in the form of a liquid or paste. A paste is particularly suitable when the composition itself is in the form of a paste.

[0105] The moisture-curing composition of the present invention, when cured by atmospheric humidity, cures from the outside inward, initially forming a skin on the surface of the composition. The so-called skin time is a measure of the curing rate of the composition. The curing rate is typically determined by various factors, such as water availability and temperature.

[0106] The moisture-curing composition of the present invention is preferably used in industrial applications such as adhesives, sealants, or coatings.

[0107] When used as an adhesive or sealant, the moisture-curing composition of the present invention preferably has a paste-like consistency with pseudoplastic properties. This type of paste-like sealant or adhesive is applied to a substrate from a standard cartridge, which is manually operated, particularly using compressed air or batteries, or optionally via a dispensing robot, from a tank or pail using a liquid pump or extruder.

[0108] When used as a coating, the moisture-curing composition of the present invention is preferably liquid at room temperature and has a liquid consistency that exhibits self-leveling properties. It is preferable that it has slight thixotropy so that the coating can be applied to vertical or inclined surfaces without immediately running off. The moisture-curing composition of the present invention is applied, for example, using a roller or brush.

[0109] The moisture-curing composition of the present invention is applied to at least one substrate.

[0110] The base material is, for example, - Glass, glass ceramics, concrete, mortar, brick, tile, gypsum, and natural stone (limestone, granite, or marble, etc.); - Metals and alloys such as aluminum, iron, steel, or non-ferrous metals, as well as metals or alloys with surface finishes such as galvanized or chromium-plated metals; - Leather, textiles, paper, wood, wood-based materials, and resin-textile composites and other polymer composites bonded with resins such as phenolic resin, melamine resin, or epoxy resin; - Plastics such as polyvinyl chloride (rigid and flexible PVC), acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate (PC), polyamide (PA), polyester, poly(methyl methacrylate) (PMMA), epoxy resin, polyurethane (PUR), polyoxymethylene (POM), polyolefin (PO), polyethylene (PE) or polypropylene (PP), ethylene / propylene copolymer (EPM) and ethylene / propylene / diene copolymer (EPDM), as well as fiber-reinforced plastics such as carbon fiber reinforced plastic (CFP), glass fiber reinforced plastic (GFP) and sheet molded compound (SMC); - A coated substrate such as powder-coated metal or alloy; - Paints or varnishes, especially automotive topcoats, may be used.

[0111] The substrate to which the moisture-curing composition of the present invention is applied may be pre-treated by chemical or physical methods, if necessary. [Examples]

[0112] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0113] [Manufacturing of polyurethane polymer U] 500 g of polyoxypropylene diol (Acclaim® 4200N, Covestro; OH value 28.1 mg KOH / g), 2000 g of polyoxypropylene polyoxyethylene triol (Caradol® MD34-02, Shell; OH value 35.0 mg KOH / g), and 245 g of tolylene diisocyanate (TDI; Desmodur® T80P, Covestro) were reacted at 80°C to obtain an NCO-terminated urethane prepolymer with a free isocyanate group content of 1.88% by weight (determined by titration). The urethane prepolymer was cooled to room temperature and stored after removing moisture.

[0114] Manufacturing of moisture-curing compositions The urethane prepolymer was initially placed in a vacuum mixer with a plasticizer and aldimin-1 under nitrogen, followed by the addition of a filler and mixing. A catalyst was added to the mixture, and the mixture was heated under vacuum at 1000-1200 rpm for 20 minutes to obtain a uniform paste. This paste was then filled into an airtight cartridge. The airtight cartridge was used to produce test specimens. The compositions for each example and comparative example are shown in Table 1.

[0115] [Table 1]

[0116] The details of the compositions and reference examples listed in Table 1 are as follows. Melamine cyanurate: Product name MC-4500 (Nissan Chemical Corporation) Tris(2-chloro-1-methylethyl)phosphate: A compound having a viscosity of 70 mPa·s at 25°C and the following structure. [ka] Trixylenyl phosphate: A compound having a viscosity of 172 mPa·s at 25°C and the following structure. [ka] Trioctyl phosphate: A compound having a viscosity of 14 mPa·s at 25°C and the following structure. [ka] Aluminum hydroxide: (Product name "CL-303", powder form, Sumitomo Chemical Co., Ltd.) Organophosphate-based flame retardant: (Product name "Exolit OP 1312", powder form, manufactured by Clariant) Phosphoric acid and ester mixture: (Product name "ADEKA Stab FP-900L", liquid with viscosity >10,000 mPa·s at 25°C, manufactured by ADEKA Corporation) Flame retardant: (Product name "ADEKA Stab FP-2500S", a mixture of phosphate compounds, diphosphate and piperazine compounds, and zinc oxide, in powder form, manufactured by ADEKA Corporation) Latent curing agent: A compound having the following structure [ka] Comparative Example 1: Our Conventional Product Example 1: An example belonging to a preferred embodiment of the present invention Example 2: An example belonging to a preferred embodiment of the present invention Example 3: An example belonging to a preferred embodiment of the present invention Comparative Example 2: Comparative Example without Compound M Comparative Example 3: Comparative Example without Phosphate Ester Compound C Comparative Example 4: Comparative example containing aluminum hydroxide instead of compound M Comparative Example 5: A comparative example containing "Exolit OP 1312," a flame retardant based on an organic phosphate, instead of phosphate ester compound C. Comparative Example 6: Comparative example containing "Adekastab FP-900L" instead of phosphate ester compound C Comparative Example 7: Comparative example containing "Adekastab FP-2500S" instead of phosphate ester compound C

[0117] The properties of the moisture-curing compositions obtained in the examples and comparative examples were evaluated. The results are shown in Table 2.

[0118] [Extruded] Extrusion force was measured. After allowing each sample composition to stand at 23°C and 50% humidity for at least 12 hours, the composition was extruded from a 3 mm diameter die at a speed of 60 mm / min using a ZwickRöell Universal test machine (Z010). The force (N) applied at this time was measured and the extrusion properties were evaluated according to the following criteria. Good: The extrusion force is less than 1000N, and it can be easily extruded using a handgun. Bad: The pushing force is over 1000N, making it difficult to push out using a handgun.

[0119] [Cut-off string] The compositions obtained in each example and comparative example were filled into a 10 mm thick mold, and the surface was smoothed. A Teflon® cylinder (20 mm in diameter) was then inserted 5 mm into the mold and held for 1 second. The cylinder was lifted at a speed of 25 cm / 4 seconds, and the length of the thread break (mm) at this time was measured. The following criteria were used for evaluation. Good: Thread breakage is less than 100mm. Poor: Thread breakage of 100mm or more.

[0120] [Skin Time] Skin time (HBZ) was determined by applying several grams of each moisture-curing composition of the examples and comparative examples to corrugated cardboard in a film thickness of approximately 2 mm, and measuring the time (in minutes) until no residue remained on the pipette when the surface of the composition was gently tapped using an LDPE pipette under standard climate conditions.

[0121] [Non-foaming test] The moisture-curing compositions of each example and comparative example were filled into molds approximately 20 mm wide, 15 mm deep, and 100 mm long, made from 18 mm square beech wood. After smoothing the surface, the molds were cured at 35°C and 80% humidity for 7 days before the cured products were removed. Each cured product was evaluated according to the following criteria by checking for surface blistering and for internal air bubbles by cutting the cured product. Good: There were very few surface blisters and internal air bubbles, making it suitable for use as a sealant. Poor: There were many surface blisters and internal air bubbles, making it unsuitable for use as a sealant.

[0122] [Shore A hardness (room temperature)] Shore A hardness (room temperature) was measured according to ISO 48-4:2018 using disc-shaped test specimens (42 mm in diameter, 6 mm thick) obtained by curing the moisture-curing compositions of each example and comparative example at 23°C and 50% relative humidity for 28 days.

[0123] [Shore A hardness (90°C)] Shore A hardness (90°C) was measured according to ISO 48-4:2018 using disc-shaped test specimens (42 mm in diameter, 6 mm thick) obtained by curing the moisture-curing compositions of each example and comparative example at 23°C and 50% relative humidity for 28 days, followed by curing at 90°C for another 28 days. Shore A hardness was evaluated according to the following criteria. Good: The decrease from the room temperature value was less than 15%. Normal: A decrease of 15% or more but less than 50% from the value at room temperature. Poor: A decrease of 50% or more from the value at room temperature.

[0124] [Dumbbell breaking strength, dumbbell elongation at breaking, and modulus of elasticity] A 2 mm thick dumbbell-shaped test piece A was cut from the cured product obtained by curing the moisture-curing compositions of each example and comparative example. Furthermore, a similar cured product was cured at 70°C for 28 days and then cut in the same manner to obtain test piece B. Furthermore, a similar cured product was heated at 90°C for 14 days and then cut in the same manner to obtain test piece C. Tensile tests were performed on these test pieces in accordance with JIS K6251:2017, and the dumbbell breaking strength, dumbbell elongation at breaking, and modulus of elasticity (tensile modulus) were measured and evaluated according to the following criteria under the conditions of a temperature of 23°C and a crosshead speed (tensile speed) of 200 mm / min. Good: Products in which the physical properties deteriorated by less than 15% after heating. Normal: Products in which the decrease in physical properties after heating was 15% or more but less than 50%. Poor: Products where the physical properties deteriorated by 50% or more after heating.

[0125] [Adhesion Test] The moisture-curing compositions obtained in each example and comparative example were applied to the substrates described in (1) to (10) below to obtain the respective cured products. After curing each cured product, the cured product was pulled from the edge, and the attached portion was peeled off by making cuts with a cutter to perform an adhesion test to the substrate. (1) Concrete (Product name: Mortar board (ISO), manufactured by TP Giken Co., Ltd.) (2) Concrete treated with primer (product name: SikaPrimer-3N, manufactured by Sika) (product name: Mortar board (ISO), manufactured by TP Giken Co., Ltd.) (3) Aluminum anodized coating (Product name: Aluminum plate (A5052P), manufactured by TP Giken Co., Ltd.) (4) Aluminum anodized film treated with primer (product name: SikaAktivator-205, manufactured by Sika) (product name: Aluminum plate (A5052P), manufactured by TP Giken Co., Ltd.) (5) Pre-treated SUS304 (Product name: JIS G 4305, manufactured by Testpiece Co., Ltd.) (6) SUS304 treated with an activator (product name: SikaAktivator-205, manufactured by Sika) (product name: JIS, G, 4305, manufactured by Testpiece Co., Ltd.) (7) Pre-treated galvalume steel sheet (product name: Galvalume Steel Sheet (registered trademark), manufactured by TP Giken Co., Ltd.) (8) Galvalume steel sheet treated with an activator (product name: SikaAktivator-205, manufactured by Sika) (product name: Galvalume Steel Sheet (registered trademark), manufactured by TP Giken Co., Ltd.) (9) Pre-treated polyvinyl chloride resin sheet (product name: rigid PVC (gray), manufactured by Testpiece Co., Ltd.) (10) Polyvinyl chloride resin sheet treated with primer (product name: SikaPrimer-215, manufactured by Sika) (product name: Rigid PVC (Gray), manufactured by Testpiece Co., Ltd.)

[0126] [Criteria for evaluating adhesiveness] Each sample was cured for 14 days under Condition 1 (23°C, 50% relative humidity), then cured for 7 days under Condition 2 (immersion in water), and then cured for 3 days under Condition 3 (80°C) before undergoing an adhesion test. Samples with a cured material adhering to the substrate of 75% or more after curing were evaluated as "good." Samples with a cured material adhering to the substrate of less than 75% were evaluated as "poor."

[0127] [Evaluation criteria for fire resistance] The changes in each sample when heated in a muffle furnace were observed and evaluated according to the following criteria. Good: Even when heated to 1000°C, it did not develop significant cracks or damage and maintained its shape as a sealant. Normal: Even when heated to 700°C, the sample did not develop significant cracks or damage and maintained its shape as a sealant. At higher temperatures, cracks and damage occurred in the sample. Poor: The sample melted at temperatures below 700°C, indicating insufficient flame retardancy.

Claims

1. A urethane prepolymer U having isocyanate groups at the molecular ends, A latent curing agent L that generates amines by hydrolysis, A moisture-curing composition comprising a flame retardant F, The flame retardant F comprises two or more different compounds, The flame retardant F comprises a compound M having a structure in which a triazine ring-containing amine and a cyclic ketone are hydrogen-bonded, and a phosphate ester compound C having a viscosity of 1 mPa·s to 500 mPa·s at 25°C. The compound M is present in an amount of 10 to 100 parts by weight relative to 100 parts by weight of the urethane prepolymer U. A moisture-curing composition in which compound C is present in an amount of 10 to 100 parts by weight per 100 parts by weight of the urethane prepolymer U.

2. A step of preparing the moisture-curing composition described in claim 1, The process includes the step of curing the moisture-curing composition to obtain a cured product. Method for producing hardened products.

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