Urethane composition

Abstract

The purpose of the present invention is to provide a urethane composition which does not require use of a lead-based curing catalyst, exhibits excellent curing properties and workability, and can be advantageously used in a variety of applications, such as adhesives, coating materials, sealing materials, waterproofing materials, floor materials, wall materials and paints.　The present invention provides a urethane composition which contains: an active hydrogen-containing organic compound (A) that contains a polyol; a polyisocyanate (B); a curing catalyst (C); and an aromatic compound (D). The aromatic compound (D) has a structure represented by formula (1).

Description

[Technical Field]

[0001] The present invention relates to urethane compositions, and more particularly to curable polyurethane compositions suitably used in adhesives, coatings, sealants, waterproofing materials, flooring materials, wall materials, and paints. [Background technology]

[0002] Polyurethane resins can be cured at room temperature and possess excellent properties such as rubber elasticity, abrasion resistance, and durability, making them particularly popular in recent years as paints, flooring materials, waterproofing materials, adhesives, potting materials, wall materials, and sealants. The curing methods for these polyurethane resins are broadly classified into two types: a one-component type in which the terminal isocyanates of the polyurethane prepolymer harden with moisture in the atmosphere after application, and a two-component type in which a main component containing the polyurethane prepolymer and a hardener containing polyols are mixed at the time of application and then cured.

[0003] In two-component polyurethane compositions, lead-based catalysts have traditionally been widely used as curing catalysts. However, in recent years, the use of lead-based catalysts has become problematic from an environmental and safety perspective, and alternative curing catalysts are being investigated. For example, bismuth organic acid salts are mentioned in Patent Documents 1 and 2. However, while these have high catalytic activity, they have the problem of making it difficult to ensure sufficient pot life. Furthermore, increasing the amount of catalyst added to improve curability at low temperatures reduces the initial elongation and heat resistance. Therefore, it is necessary to set an upper limit on the amount of catalyst added, and with this upper limit, there is a problem that curing cannot be completed by the next morning during severe winters when temperatures drop below 5°C, allowing the process to proceed to the next step. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 3696452 [Patent Document 2] Patent No. 4663171 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] This invention has been made in view of these circumstances, and aims to provide a urethane composition that does not require a lead-based curing catalyst, has excellent curability and workability, and is suitable for use in various applications such as adhesives, coatings, sealants, waterproofing materials, flooring materials, wall materials, and paints. [Means for solving the problem]

[0006] The urethane composition of the present invention comprises an active hydrogen-containing organic compound (A) containing a polyol, a polyisocyanate (B), a curing catalyst (C), and an aromatic compound (D), wherein the aromatic compound (D) has a structure represented by formula (1). [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a urethane composition that does not require a lead-based curing catalyst, has excellent curability and workability, and is suitable for use in various applications such as adhesives, coatings, sealants, waterproofing materials, flooring materials, wall materials, and paints. [Modes for carrying out the invention]

[0008] The present invention will be described in detail below.

[0009] The urethane composition of the present invention contains an active hydrogen-containing organic compound (A) containing a polyol, a polyisocyanate (B), a curing catalyst (C), and an aromatic compound (D) as essential components.

[0010] <Active hydrogen-containing organic compound (A)> Active hydrogen-containing organic compound (A) is an organic compound having active hydrogen. Active hydrogen is hydrogen from a functional group capable of reacting with isocyanate to form a urethane bond or a urea bond. Examples of such functional groups include hydroxyl groups and amino groups. Examples of active hydrogen-containing organic compound (A) include organic compounds having two or more of the above functional groups in the molecule. Active hydrogen-containing organic compound (A) contains a polyol (a compound having two or more hydroxyl groups at the molecular ends). Active hydrogen-containing organic compound (A) may contain only a polyol, or it may contain both a polyol and an active hydrogen-containing organic compound other than a polyol (such as a polyamine). The polyol is not particularly limited as long as it is generally used in the manufacture of urethane compositions, but examples include polyether polyols, polyester polyols, polymer polyols, and flame-retardant polyols such as phosphorus-containing polyols and halogen-containing polyols. These polyols can be used individually or mixed as appropriate.

[0011] Examples of polyether polyols include those obtained by ring-opening addition polymerization of ethylene oxide, propylene oxide, or mixtures thereof to ethylene glycol, propylene glycol, glycerin, pentaerythritol, ethylenediamine, ethanolamine, diethanolamine, etc. as initiators, or polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.

[0012] Examples of polyester polyols include those obtained by the condensation reaction of polyhydric basic carboxylic acids such as maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid with polyhydric alcohols, as well as polymers of lactones. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, 2,4,4-trimethyl-1,3-pentanediol, cyclohexanediol, cyclohexanedimethanol, xylylene glycol, hydroquinone bis(hydroxyethyl ether), hydrogenated bisphenol A, trimethylolpropane, glycerin, 1,2,6-hexanetriol, pentaerythritol, castor oil, etc., as well as coconut oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, cottonseed oil fatty acids, tuna oil fatty acids, castor oil fatty acids, etc. Examples include those obtained by incorporating higher fatty acids into the acid component to form oil-modified polyester polyols. Furthermore, examples of lactone polymers include those obtained by ring-opening polymerization of ε-caprolactam, α-methyl-ε-caprolactam, ε-methyl-ε-caprolactam, etc.

[0013] Examples of polymer polyols include compounds obtained by polymerizing or copolymerizing polymerizable monomers containing hydroxyl groups, such as hydroxyethyl acrylate, hydroxybutyl acrylate, and trimethylolpropaneacrylic acid monoester, either alone or with monomers copolymerizable with these, such as acrylic acid, methacrylic acid, styrene, acrylonitrile, and α-methylstyrene.

[0014] Examples of the flame retardant polyol include a phosphorus-containing polyol obtained by adding an alkylene oxide to a phosphoric acid compound, a polyol or polyether polyol obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide, a polyester polyol, a halogen-containing polyol in which some or all of the hydrogen atoms of an acrylic polyol are substituted with fluorine atoms, and the like.

[0015] Examples of the polyamine include aliphatic polyamines and aromatic polyamines. Examples of the aliphatic polyamine include ethylenediamine, polyether polyamine, and the like. Examples of the aromatic polyamine include 3,3'-dichloro-4,4'-diaminodiphenylmethane, DETDA, 2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene, and mixtures thereof, a mixture such as Ethacure 100 (mass ratio of 2,4-isomer / 2,6-isomer is about 80 / 20) manufactured by Albemarle, Ethacure 420 (4,4'-methylenebis(N-sec-butylaniline)) manufactured by Albemarle, 4,4'-methylenebis(2-ethyl-6-methylaniline), and the like.

[0016] These active hydrogen-containing organic compounds can be used alone or in combination of two or more. In particular, it is preferable that the active hydrogen-containing organic compound contains both a polyol and a polyamine. In this case, the workability, curability, and mechanical properties of the composition are particularly good.

[0017] <Polyisocyanate (B)> The polyisocyanate (B) is a compound having two or more isocyanate groups in the molecule, and there is no particular limitation as long as it is a commonly used one. For example, alkylene diisocyanates such as trimethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; cycloalkylene diisocyanates such as bis(isocyanatomethyl)cyclohexane, cyclopentane diisocyanate, cyclohexane diisocyanate, and isophorone diisocyanate; aromatic diisocyanates such as tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, and diphenyl ether diisocyanate; aromatic aliphatic diisocyanates such as xylylene diisocyanate and diisocyanatediethylbenzene; triisocyanates such as triphenylmethane triisocyanate, triisocyanatobenzene, and triisocyanatotoluene; tetraisocyanates such as diphenyldimethylmethane tetraisocyanate; polymer polyisocyanates such as tolylene diisocyanate dimers and trimers; and terminal isocyanate-containing compounds obtained by reacting an excess of these polyisocyanates with low-molecular-weight active hydrogen-containing organic compounds such as ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, hydrogenated bisphenol A, hexanetriol, glycerin, pentaerythritol, castor oil, and triethanolamine, etc. can be mentioned.

[0018] The content of the polyisocyanate (B) in the urethane composition of the present invention is preferably 1 to 100 parts by mass, more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the active hydrogen-containing organic compound (A). Specifically, this content is, for example, 1, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 parts by mass, and it may also be within the range between any two of the values exemplified here.

[0019] <Curing catalyst (C)> In the present invention, tin compounds, bismuth compounds, organozinc compounds, organozirconium compounds, and organocopper compounds are preferred curing catalysts. Among these, tin compounds and bismuth compounds are preferred.

[0020] Known tin compounds can be used as the tin compound for the curing catalyst (C). Examples include divalent tin compounds such as tin octoate, tin naphthenate, tin stearate, and tin neodecanoate; tetravalent organotin compounds such as dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin diversate, dibutyltin bistriethoxysilicate, dibutyltin dioleylmalate, dibutyltin diacetate, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane, dibutyltin oxybisethoxysilicate, dibutyltin oxide, reaction products of dibutyltin oxide and phthalate esters, and reaction products of dibutyltin oxide and maleate diesters; and tetravalent organotin compounds such as dibutyltin diacetylacetonate.

[0021] As the bismuth compound for the curing catalyst (C), known organic bismuth acids can be used. For example, bismuth carboxylate, bismuth 2-ethylhexylate, bismuth neodecanoate, and bismuth resin acid salts are preferred.

[0022] Specific examples of metal catalysts that can be preferably used as the curing catalyst (C) include organozinc catalysts such as zinc 2-ethylhexylate, zinc naphthenate, and zinc neodecanoate; organozirconium catalysts such as zirconyl 2-ethylhexylate, zirconyl naphthenate, and zirconyl neodecanoate; and organocopper catalysts such as copper naphthenate.

[0023] The content of the curing catalyst (C) in the urethane composition of the present invention is preferably 0.0005 to 5 parts by mass, and more preferably 0.001 to 3 parts by mass, per 100 parts by mass of the total of the active hydrogen-containing organic compound (A) and the polyisocyanate (B). When the content of the curing catalyst (C) is within the above range, an excellent balance between curing performance and pot life is obtained. Specifically, this content is, for example, 0.0005, 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, or 5 parts by mass, and may be within the range of any two of the values ​​exemplified here.

[0024] The curing catalyst (C) can be blended with an active hydrogen-containing organic compound (A) or a polyisocyanate (B), but it is preferable to blend it with an active hydrogen-containing organic compound (A) in terms of storage stability. Furthermore, if necessary, it can be added at the construction site during the two-component mixing process as a field-added accelerator.

[0025] <Aromatic compounds (D)> The aromatic compound in this invention has a structure represented by formula (1).

[0026] [ka] (In the formula, two R 1 These are either the same or different hydrogen atoms or an alkyl group which may have branching with 1 to 8 carbon atoms, or two R atoms. 1 An alkylene group having 2 to 16 carbon atoms, which may have branches, formed by the linkage of these atoms, where n and m are the same or different, integers from 0 to 10, and two R 2 These are identical or different alkylene groups, which may have branching, and the alkylene group has 1 to 4 carbon atoms in the main carbon atom, with 4 R 3 (These are the same or different alkyl or alkenyl groups, which may have hydrogen or branching with 1 to 8 carbon atoms.)

[0027] R 1 or R 3Examples of alkyl groups that may have branching between 1 and 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, neopentyl, t-pentyl, hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, and 3,3- Dimethylbutyl group, 1,1,2-trimethylpropyl group, heptyl group, isoheptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethylpentyl group, 4,4-dimethylpentyl group Methylpentyl group, 1,1,2-trimethylbutyl group, 1,1,3-trimethylbutyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-3-methylbutyl group, 1-ethyl-1,2-dimethylpropyl group, 1-ethyl-2,2-dimethylpropyl group, 1,1-diethylpropyl group, octyl group, isooctyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl Group, 3-ethylhexyl group, 4-ethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,5-dimethylhexyl group, 5,5-dimethylhexyl group, 1,1,2-trimethylpentyl group, 1,1,3-trimethylpentyl group, 1,1,4-trimethylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl-2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1,1,2,2-tetramethylbutyl group, 1,1,2,3-tetramethylbutyl group, 1,1,3,3-tetramethylbutyl group, 2-ethyl-1,1-dimethylbutyl group, 2-ethyl-2,3-dimethylbutyl group, 2-ethyl-3,3-dimethylbutyl group, 1,1-diethylbutyl group, 1,2-diethylbutyl group, 2,2-diethylbutyl group, 1,1-diethyl-2-methylpropyl group, 1-ethyl-1,2,2-trimethylpropyl group, 1-isopropyl-1,2-dimethylpropyl group and the like can be mentioned.,

[0028] Two Rs 1 Examples of the alkylene group formed by linking two Rs to each other include those in which the terminal carbon atoms of the above alkyl groups are bonded to each other. For example, an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group and the like can be mentioned. The number of carbon atoms in the main chain of this alkylene group is preferably 5. The number of carbon atoms in this alkylene group is specifically, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, and it may also be within the range between any two of the numerical values exemplified here.,

[0029] R 2 Examples of the alkylene group of R include an ethylene group, a propylene group, an isopropylene group, a butylene group and the like. The number of carbon atoms in the main chain of this alkylene group is, for example, 1, 2, 3, 4, and it may also be within the range between any two of the numerical values exemplified here.,

[0030] R 3Examples of alkenyl groups that may have branching between 1 and 8 carbon atoms include vinyl, 1-propenyl, isopropenyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, and 1-methyl-1-butenyl groups. , 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-methyl-3-butenyl group, 3-methyl-3-butenyl group, 1-ethyl-1-propenyl group, 1-ethyl-2-propenyl group, 1,1-dimethylallyl group, 1,2-dimethyl-1-propenyl group, 1-hex Senyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4- Methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 1-vinylbutyl group, 1-ethylidenebutyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 3,3-dimethyl-1-butenyl group, 3,3-dimethyl-2-butenyl group, 1-isobutylvinyl group, 1-heptenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 5-heptenyl group, 6-heptenyl group, 2-methyl-3-hexenyl group, 2-methyl-4-hexenyl group, 2-methyl-5-hexenyl group, 3-methyl-1-hexenyl group, 3-methyl-2-hexenyl group, 3-methyl-3-hexenyl group, 3-methyl-4-hexenyl group Xenyl group, 3-methyl-5-hexenyl group, 4-methyl-1-hexenyl group, 4-methyl-2-hexenyl group, 4-methyl-3-hexenyl group, 4-methyl-4-hexenyl group, 4-methyl-5-hexenyl group, 5-methyl-1-hexenyl group, 5-methyl-2-hexenyl group, 5-methyl-3-hexenyl group, 5-methyl-4-hexenyl group, 5-methyl-5-hexenyl group, 2-ethyl-2-hexenyl group Pentenyl group, 2-vinylpentyl group, 3-ethyl-3-pentenyl group, 3-ethyl-4-pentenyl group, 1,4-dimethyl-2-pentenyl group, 2,2-dimethyl-4-pentenyl group, 2,3-dimethyl-1-pentenyl group, 2,3-dimethyl-3-pentenyl group, 3-methyl-2-methylidenepentyl group, 2-methyl-3-methylidenepentyl group, 2,3-dimethyl-3-pentenyl group, 2,4-di Methyl-1-pentenyl group, 2,4-dimethyl-2-pentenyl group, 2,4-dimethyl-4-pentenyl group, 3,3-dimethyl-4-pentenyl group, 4-methyl-3-methylenepentyl group, 3,4-dimethyl-2-pentenyl group, 3,4-dimethyl-3-pentenyl group, 4,4-dimethyl-1-pentenyl group, 2-isopropyl-3-butenyl group, 1,3,3-trimethyl-1-butenyl group, 2,3,3-trimethyl-1-butenyl group, 1-octenyl group, 2-octenyl group, 3-octenyl group, 4-octenyl group, 5-octenyl group, 6-octenyl group, 7-octenyl group, 2-methyl-3-heptenyl group, 2-methyl-4-heptenyl group, 2-methyl-5-heptenyl group, 2-methyl-6-heptenyl group, 3-methyl-1-heptenyl group, 3-methyl-2-heptenyl group, 3-methyl-3-heptenyl group, 3-methyl-4-heptenyl group, 3-methyl-5-heptenyl group, 3-methyl-6-heptenyl group, 4-methyl-1-heptenyl Tenyl group, 4-methyl-2-heptenyl group, 4-methyl-3-heptenyl group, 4-methyl-4-heptenyl group, 4-methyl-5-heptenyl group, 4-methyl-6-heptenyl group, 5-methyl-1-heptenyl group, 5-methyl-2-heptenyl group, 5-methyl-3-heptenyl group, 5-methyl-4-heptenyl group, 5-methyl-5-heptenyl group, 5-methyl-6-heptenyl group, 6-methyl-1-heptenyl group, 6-methyl-2-heptenyl group, 6-methyl-3-heptenyl group, 6-methyl-4-heptenyl group, 6-methyl-5-heptenyl group Tenyl group, 6-methyl-6-heptenyl group, 2-ethyl-1-hexenyl group, 2-ethyl-2-hexenyl group, 2-vinylhexyl group, 3-ethyl-3-hexenyl group, 3-ethyl-5-hexenyl group, 3-ethenylhexyl group, 4-ethyl-3-hexenyl group, 4-ethyl-5-hexenyl group, 2,3-dimethyl-5-hexenyl group, 2-methyl-3-methylidenehexyl group, 3,3-dimethyl-1-hexenyl group, 3,3-dimethyl-5-hexenyl group, 2,4-dimethyl-3-hexenyl group, 2-methyl-4-methylidenehexyl Syl group, 2,5-dimethyl-1-hexenyl group, 2,5-dimethyl-3-hexenyl group, 2,5-dimethyl-5-hexenyl group, 3,3-dimethyl-4-hexenyl group, 3,4-dimethyl-2-hexenyl group, 3,4-dimethyl-4-hexenyl group, 3,5-dimethyl-1-hexenyl group, 3,5-dimethyl-2-hexenyl group, 3,5-dimethyl-5-hexenyl group, 4,4-dimethyl-1-hexenyl group, 4,4-dimethyl-2-hexenyl group, 4,5-dimethyl-3-hexenyl group, 4,5-dimethyl-4-hexenyl group, 4,5-dimethyl-5-hexenyl group, 5-methylidene-2-heptanyl group, 5-methyl-3-methylenehexyl group, 5,5-dimethyl-1-hexenyl group, 5,5-dimethyl-2-hexenyl group, 5,5-dimethyl-3-hexenyl group, 2-propyl-4-pentenyl group, 2,2,4-trimethyl-3-pentenyl group, 2,3,3-trimethyl-4-pentenyl group, 2,3,4-trimethyl-4-pentenyl group, 2,4,4-trimethyl-1-pentenyl group, 3,3-dimethyl-2-methylidenepentyl group, 3,3,4-trimethyl-1-pentenyl group, 3,4,4-trimethyl Examples include ethyl-1-pentenyl group, 3,4,4-trimethyl-2-pentenyl group, 2-ethenyl-2-methylpentyl group, 2-ethyl-4-methyl-3-pentenyl group, 3-ethyl-2-methyl-1-pentenyl group, 3-ethyl-2-methyl-3-pentenyl group, 3-ethyl-3-methyl-4-pentenyl group, 3-ethyl-4-methyl-1-pentenyl group, 3-ethyl-4-methyl-2-pentenyl group, 3-ethyl-4-methyl-4-pentenyl group, 3-methyl-2-vinylpentyl group, 4-methyl-2-vinylpentyl group, and 3-isopropyl-4-pentenyl group.

[0031] R 1 and R 3 The number of carbon atoms in each atom is, for example, 1, 2, 3, 4, 5, 6, 7, or 8, and may be within the range of any two of the values ​​exemplified here.

[0032] n and m are integers between 0 and 10, and are preferably between 1 and 3 from the viewpoint of workability. Specifically, n and m are, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10, and may be within the range of any two of the numbers exemplified here.

[0033] n+m is preferably an integer between 1 and 20, and preferably between 2 and 10 from the viewpoint of physical properties and workability after curing. Specifically, n+m is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, and may be within the range of any two of the numbers exemplified here.

[0034] The aromatic compound (D) is preferably represented by the following general formula (2). [ka] (In the formula, two R 1 These are either the same or different hydrogen atoms or an alkyl group which may have branching with 1 to 8 carbon atoms, or two R atoms. 1 It is an alkylene group having 2 to 16 carbon atoms that is linked together and may have branching, and has four R 3 R is the same or different alkyl or alkenyl group which may have hydrogen or branching with 1 to 8 carbon atoms, 4 (where n represents a hydrogen or methyl group, n and m are the same or different integers between 0 and 10, and n+m represents an integer between 1 and 20.)

[0035] Specific examples of aromatic compounds (D) include 2,2-bis(4-polyoxyethyleneoxyphenyl)propane, 2,2-bis(4-polyoxypropyleneoxyphenyl)propane, ADEKA polyether BPX-11, ADEKA polyether BPX-21, 4,4′-(1-methylethylidene)bis(2-allylphenol, 2,2′-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4′-(1,3-dimethylbutylidene)diphenol, and 1,1′-bis(4-hydroxy-3-methylphenyl)cyclohexane. Aromatic compounds (D) may be a single compound or a mixture of multiple compounds.

[0036] The molar ratio of the curing catalyst (C) to the aromatic compound (D) is preferably 0.01 to 10, and more preferably 0.1 to 5. When the molar ratio is within this range, there is an excellent balance between workability and curing performance. Specifically, this molar ratio is, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and may also be within the range of any two of the values ​​exemplified here.

[0037] The curing catalyst (C) and aromatic compound (D) can also be mixed beforehand. In this case, an organic solvent or plasticizer may be added from the viewpoint of economy and workability. The organic solvent is not particularly limited as long as it is compatible with the curing catalyst and aromatic compound, but examples include aromatic compounds such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene; Aliphatic compounds such as hexane, heptane, octane, decane, tetradecane, hexadecane, and octadecane; Aliphatic monobasic acid SLs such as butyl acetate, octyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, isopropyl propionate, butyl propionate, isobutyl propionate, octyl propionate, 2-ethylhexyl propionate, cyclohexyl propionate, benzyl propionate, methyl octyl, ethyl octyl, lauryl octyl, methyl 2-ethylhexanoate, ethyl 2-ethylhexanoate, lauryl 2-ethylhexanoate, methyl oleate, ethyl oleate, butyl oleate, hexyl laurate, glycerin monooleate, etc. Mineral turpentines (mineral spirits), which are petroleum-based mixed solvents containing paraffinic, isoparaffinic, olefinic, and naphthenic hydrocarbons, such as Swazole 1000, Swazole 1500, Swazole 1800 (all manufactured by Maruzen Petrochemical Co., Ltd.), T-SOL 100, T-SOL 150 (all manufactured by JXTG Energy Corporation), Merveille 20, Merveille 30, Merveille 40 (all manufactured by Showa Shell Sekiyu K.K.); Phthalate esters such as dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, di2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, dicyclohexyl phthalate, and butylbenzyl phthalate; dimethyl adipate, diethyl adipate, dipropyl adipate, diisopropyl adipate, adipine Aliphatic dibasic acid esters such as dibutyl acid, dihexyl adipate, dioctyl adipate, di-2-ethylhexyl adipate, diisononyl adipate, diisodecyl adipate, 2-ethylhexyl azelaate, dibutyl sebacate, di-2-ethylhexyl sebacate, dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, di-2-ethylhexyl maleate, and dibutyl fumarate; Examples include dihydric alcohol esters such as diethylene glycol dibenzoate and triethylene glycol 2-ethyl butyrate; and oxyacid esters such as methyl acetylricylenolate, butyl acetylricylenolate, butyl phthalyl butyl glycolate, acetyltriethyl citrate, and acetyltributyl citrate.

[0038] In particular, organic solvents and plasticizers that are liquid at room temperature and have a boiling point of 150°C or higher, that dissolve the curing catalyst, and do not separate even when stored for a long period of time under low-temperature conditions are preferred. Mineral turpentines, phthalates, adipicates, 2-ethylhexanoic acid, neodecanoic acid, etc., are especially preferred. A boiling point of 150°C or higher is preferable in terms of handling and storage because it suppresses volatility. Furthermore, organic solvents or plasticizers that have good solubility in the curing catalyst and maintain uniformity during storage are even more preferable because they result in a uniform metal content and a stable curing time.

[0039] <Other ingredients> The urethane composition of the present invention may further contain additives commonly added to urethane compositions, such as acidic compounds, fillers, colorants, plasticizers, curing accelerators, curing retarders, anti-sagging agents, anti-aging agents, solvents, weathering agents / heat-resistant agents, and wetting / dispersing agents, for the purpose of improving economy, workability during application, and physical properties after curing.

[0040] The acidic compound has the effect of stabilizing the curing catalyst (C). The acidic compound is not particularly limited, but acidic compounds such as organic acids or inorganic acids can be used. Among these, aliphatic carboxylic acid compounds and organic sulfonic acid compounds are particularly preferred, and more preferably saturated or unsaturated linear or branched aliphatic carboxylic acids having 2 to 18 carbon atoms. Specifically, examples include saturated aliphatic carboxylic acids such as acetic acid, propionic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, and stearic acid; unsaturated aliphatic carboxylic acids such as oleic acid, linoleic acid, linolenic acid, and arachidonic acid; and saturated and unsaturated aliphatic dicarboxylic acids such as fumaric acid and maleic acid.

[0041] The molar ratio of the curing catalyst (C) to the acidic compound is preferably 0.2 to 50, and more preferably 0.5 to 20, in terms of molar ratio (acidic compound / curing catalyst). A molar ratio within this range is preferable in terms of ensuring pot life and the physical properties after curing. Specifically, this molar ratio may be, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, or within the range of any two of the values ​​exemplified here.

[0042] Examples of fillers include calcium carbonate (heavy calcium carbonate, precipitated calcium carbonate, etc.), kaolin, talc, fumed silica, precipitated silica, anhydrous silicic acid, hydrated silicic acid, clay, calcined clay, glass, bentonite, organic bentonite, shirasu balloons, glass fiber, asbestos, glass filaments, crushed quartz, diatomaceous earth, aluminum silicate, aluminum hydroxide, zinc oxide, magnesium oxide, titanium dioxide, etc. Examples of colorants include iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, etc.

[0043] Specifically, plasticizers used include phthalate esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and butyl benzyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipicate, dioctyl succinate, diisodecyl succinate, diisodecyl sebacate, and butyl oleate; glycol esters such as pentaerythritol ester; phosphate esters such as trioctyl phosphate and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate; and chlorinated paraffin.

[0044] Specifically, anti-sagging agents used include hydrogenated castor oil, anhydrous silicic acid, organic bentonite, and colloidal silica. Other additives used include vulcanization accelerators, UV absorbers, radical chain inhibitors, peroxide decomposers, and various anti-aging agents. [Examples]

[0045] The present invention will be described in detail below using examples, but this will not limit the scope of the invention.

[0046] 1. Preparation of the main ingredient <Manufacturing Example 1> 63.8 g of polypropylene glycol diol type (molecular weight 1000), 319.5 g of polypropylene glycol diol type (molecular weight 2000), and 256.5 g of polypropylene glycol triol type (molecular weight 3000) were mixed with 109.5 g of tolylene diisocyanate (equivalent ratio NCO / OH = 1.79) and reacted at 95°C to 105°C for 8 hours to obtain isocyanate-terminated TDI-based prepolymer A with an NCO content of 3.10% by mass.

[0047] <Manufacturing Example 2> 63.8 g of polypropylene glycol diol type (molecular weight 1000), 405.0 g of polypropylene glycol diol type (molecular weight 2000), and 171.0 g of polypropylene glycol triol type (molecular weight 3000) were mixed with 109.5 g of tolylene diisocyanate (equivalent ratio NCO / OH = 1.79) and reacted at 95°C to 105°C for 8 hours to obtain isocyanate-terminated TDI-based prepolymer B with an NCO content of 3.10% by mass.

[0048] <Manufacturing Example 3> 61.5 g of polypropylene glycol diol type (molecular weight 1000), 306.8 g of polypropylene glycol diol type (molecular weight 2000), 246.8 g of polypropylene glycol triol type (molecular weight 3000), and 0.015 g of bismuth octate were mixed with 134.5 g of isophorone diisocyanate (equivalent ratio NCO / OH = 1.79) and reacted at 85-95°C for 6 hours to obtain isocyanate-terminated IPDI-based prepolymer C with an NCO content of 3.10% by mass.

[0049] The details of the ingredients in the above manufacturing example are as follows: Polypropylene glycol diol type, molecular weight 1000: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Polypropylene glycol diol type, molecular weight 2000: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Polypropylene glycol triol type, molecular weight 3000: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Tolylene diisocyanate: A mixture manufactured by Tokyo Chemical Industry Co., Ltd., with a mass ratio of 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate = 80 / 20. Isophorone diisocyanate: Manufactured by Tokyo Chemical Industry Co., Ltd., isophorone diisocyanate (isomer mixture) Bismuth octylate: Manufactured by Nitto Chemical Co., Ltd., bismuth thris (2-ethylhexanoate), bismuth content 32.5%

[0050] 2. Preparation of urethane composition Two-component curable urethane compositions consisting of a main component and a curing agent were prepared with the compositions (parts by mass) shown in Tables 1 to 3.

[0051] [Table 1]

[0052] [Table 2]

[0053] [Table 3]

[0054] The details of each component in the table are as follows: Prepolymers A-C: Manufactured using manufacturing examples 1-3 Product name: "Polypropylene glycol diol type, molecular weight 700", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Product name: "Polypropylene glycol diol type, molecular weight 2000", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Product name: "EtaCure 100 Plus", manufactured by Albemar Japan Co., Ltd., contains diethylmethylbenzenediamine. Product name: 4,4′-methylenebis-(2-chloroaniline), manufactured by Tokyo Chemical Industry Co., Ltd., 4,4′-diamino-3,3′-dichlorodiphenylmethane Product name: "Super SS", manufactured by Maruo Calcium Co., Ltd., calcium carbonate. Product name "DINP", manufactured by J-Plus Co., Ltd., diisononyl phthalate. Product name: "Merveille 30", manufactured by Toa Oil Co., Ltd. Product name: Octylic acid, manufactured by KH Neochem Co., Ltd., 2-ethylhexanoic acid Product name "BI-28", manufactured by Nitto Kasei Co., Ltd., a mixture of bismastris (2-ethylhexanoate) / 2-ethylhexanoic acid = 87 / 13 (mass ratio). Product name: "K-KAT XK-651", manufactured by King Industries, made of bismastrisneodecanate. Product name: "Pukat B7", manufactured by Nippon Chemical Industrial Co., Ltd., bismuth resin acid salt. Product name: "Neostan U-28", manufactured by Nitto Kasei Co., Ltd., tin(II) octoate Product name: "Neostan U-830", manufactured by Nitto Kasei Co., Ltd., dioctyl tin dineodecanoate Product name: Nikka Octix Lead 24% (T), manufactured by Nippon Chemical Industries, Ltd., lead octoate. Product name "BA-P2", manufactured by Nippon Emulsifier Co., Ltd., PO-based bisphenol Product name: "BISPHENOL A ETHOXYLATE", manufactured by Sigma-Aldrich Co., Ltd., EO-based bisphenol. Product name: "ADEKA Polyether BPX-21", manufactured by ADEKA Corporation, PO-based bisphenol Product name: "4,4'-(1-methylethylidene)bis(2-allylphenol" Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Product name: "2,2'-Bis(4-hydroxy-3,5-dimethylphenyl)propane" Manufactured by Tokyo Chemical Industry Co., Ltd. Product name: "4,4'-(1,3-dimethylbutylidene)diphenol" Manufactured by Tokyo Chemical Industry Co., Ltd. Product name: "1,1′-Bis(4-hydroxy-3-methylphenyl)cyclohexane" Manufactured by Tokyo Chemical Industry Co., Ltd.

[0055] 3. Evaluation The following tests were performed on the obtained compositions. The results are shown in Tables 1 to 3.

[0056] As shown in the table, all examples exhibited good workability and curability, comparable to Reference Example 1, which included a lead-based curing catalyst. On the other hand, all comparative examples lacked good workability or curability in at least one of the two aspects.

[0057] 3-1. Workability Test The main component and hardener were mixed, and the viscosity was measured at 23±2℃ and 50±5%RH. The time from immediately after mixing until the viscosity reached 100 Pa·s was measured, and a pot life of 37 minutes or more, equivalent to or greater than that of a lead catalyst, was evaluated as ○, and a time of less than 37 minutes was evaluated as ×.

[0058] 3-2. Curing test The main component and hardener were mixed and cured at 3±2℃ and 50±5%RH. After 16 hours, surface hardness was measured using a durometer (Type A), and the Shore A hardness of each urethane composition was confirmed. A hardness of 36 or higher was evaluated as ○, and a hardness of less than 36 was evaluated as ×.

Claims

1. The material comprises an active hydrogen-containing organic compound (A) containing a polyol, a polyisocyanate (B), a curing catalyst (C), and an aromatic compound (D). The aromatic compound (D) has a structure represented by formula (1), The aforementioned active hydrogen-containing organic compound (A) does not have the structure represented by formula (1), The curing catalyst (C) is made of a bismuth compound, A urethane composition in which the content ratio of the curing catalyst (C) to the aromatic compound (D) is 0.1 to 5 in molar ratio (curing catalyst (C) / aromatic compound (D)). 【Chemistry 1】 (In the formula, two R １ These are either the same or different hydrogen atoms or an alkyl group that may have branching with 1 to 8 carbon atoms, or two R atoms. １ A branched alkylene group having 2 to 16 carbon atoms, formed by the linkage of these atoms, where n and m are the same or different integers from 0 to 10, and two R ２ These are identical or different alkylene groups, which may have branching, and the alkylene group has 1 to 4 carbon atoms in the main chain, and 4 R ３ (These are the same or different alkyl or alkenyl groups, which may have hydrogen or branching with 1 to 8 carbon atoms.)

2. The urethane composition according to claim 1, The bismuth compound is an organic acid bismuth salt, and the urethane composition is as described above.

3. The urethane composition according to claim 2, The bismuth organic acid salt is selected from bismastris (2-ethylhexanoate), bismastris neodecanoate, or bismuth resin acid salt in the urethane composition.

4. A urethane composition according to any one of claims 1 to 3, A urethane composition wherein aromatic compound (D) has a structure represented by formula (2). 【Chemistry 2】 (In the formula, two R １ These are either the same or different hydrogen atoms or an alkyl group that may have branching with 1 to 8 carbon atoms, or two R atoms. １ A branched alkylene group having 2 to 16 carbon atoms, formed by the linkage of these atoms, and four R ３ R is the same or different alkyl or alkenyl group which may have hydrogen or branching with 1 to 8 carbon atoms, ４ (where n represents a hydrogen or methyl group, n and m are the same or different integers from 0 to 10, and n + m represents an integer from 1 to 20.)

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