JP5039328B2 - One-part moisture-curable polyurethane composition - Google Patents

Description

  The present invention relates to a moisture curable polyurethane composition, and more particularly to a moisture curable polyurethane composition suitably used for adhesives, coating materials, sealing materials, waterproofing materials, flooring materials, wall materials, paints and the like.

  Polyurethane resin can be cured at room temperature and at room temperature, and has excellent properties such as rubber elasticity, abrasion resistance, and durability, so it can be used for paints, flooring, waterproofing materials, adhesives, potting materials, wall materials, and sealing. In recent years, it has been particularly used as a material. The curing method for these polyurethane resins consists of a one-component type in which the terminal isocyanate of the polyurethane prepolymer is cured with moisture in the atmosphere after construction, a main agent containing the polyurethane prepolymer and a curing agent containing polyols. It is roughly classified into a two-pack type that is mixed and cured.

  The two-pack type is easy to adjust the curing rate, but it is necessary to mix each component during construction and handling is complicated. On the other hand, the one-pack type has a simple construction method but has problems such as slow curing, poor storage stability, and foaming. Also, the sealing material using aromatic diisocyanate is low in flexibility due to the excellent high cohesion force derived from the benzene ring, and has a high modulus at the time of extension, so it does not follow the expansion and contraction of the joint, Have the problem of destroying.

  In order to solve these problems, a one-component polyurethane composition containing a latent curing agent has been proposed. For example, Patent Document 1 discloses a polyurethane composition containing polyaldimine as a latent curing agent. However, these compositions have a problem in curability such that the curability is remarkably lowered during construction in a low temperature and low humidity environment such as in winter. There is also a method of adding an organic acid to the composition in advance for the purpose of improving curability, but in this case, the long-term storage property of the composition deteriorates in proportion to the amount added, which is not practical. Further, Patent Documents 2 and 3 each disclose a method in which an isocyanate or an acid is mixed with an isocyanate composition immediately before construction. However, this method has a problem in workability during construction.

  In order to solve the above problem, the present inventors have at least one selected from the group consisting of a polyisocyanate compound and / or a urethane prepolymer, a polyaldimine, a hydrolyzable ester compound and p-toluenesulfonyl isocyanate. And a moisture-curable polyurethane composition containing the same (Patent Document 4). The moisture-curable polyurethane composition described in Patent Document 4 has improved curability in a low-temperature environment as compared with the conventional one, but there is a demand for faster curing in the extremely cold region, and the construction period is also in other regions. For convenience, there has been a case where further improvement in the curing rate is desired in order to speed up the construction.

On the other hand, 1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter also referred to as DBU) and DBU phenol salt are used as curing catalysts for two-component heat-curable polyurethane adhesives. (For example, see Patent Documents 5 and 6). DBU has a high reactivity, and as a curing catalyst, if it is used in a one-pack type, the stability is deteriorated. Therefore, it has been conventionally necessary to use a two-pack type. Moreover, as described in Patent Document 7, in the case of the one-pack type, it has been used as a foaming catalyst for producing polyurethane foam.
JP-A-4-279620 JP 7-216044 A Japanese Patent Laid-Open No. 7-25976 JP 2006-36807 A JP 2005-89527 A JP 2006-37028 A Japanese Patent Laid-Open No. 2006-8779

  The present invention has no cured foam, can be cured at extremely low temperatures, is excellent in stability, curability, workability, storage stability, adhesive, coating material, sealing material, waterproof material, flooring, It aims at providing the moisture hardening type polyurethane composition used suitably for various uses, such as a wall material and a coating material.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, the present invention has a polyisocyanate compound and / or a urethane prepolymer as a main component, an N-hydroxyalkyl-oxazolidine compound and / or polyaldimine, and p-toluene. In addition, a predetermined amount of DBU is added to a polyurethane composition containing at least one selected from the group consisting of a sulfonyl isocyanate and a hydrolyzable ester compound, whereby DBU is a latent curing agent. Strongly acting on hydroxyalkyl-oxazolidine and polyaldimine, can be cured at extremely low temperatures, and has excellent stability and can be used in a one-part type despite the incorporation of DBU that has been used in two-part type. It has been found that a moisture-curable polyurethane composition can be obtained.

That is, the one-component moisture-curable polyurethane composition of the present invention comprises (A) a polyisocyanate compound and / or a urethane prepolymer, (B) an N-hydroxyalkyl-oxazolidine compound and / or a polyaldimine, and (C) p. -Selected from the group consisting of at least one selected from the group consisting of toluenesulfonyl isocyanate and hydrolysable ester compounds, and (D) 1,8-diazabicyclo (5,4,0) undecene-7 and salts thereof containing at least one, for the component (a) 100 parts by mass of, characterized by blending less than the component (D) 0.0 25 parts by 1 part by mass or more.

  The salt of 1,8-diazabicyclo (5,4,0) undecene-7 is a phenol salt of 1,8-diazabicyclo (5,4,0) undecene-7 and / or 1,8-diazabicyclo (5,4 , 0) Undecen-7 octylate is preferred.

  According to the present invention, there is no foaming of a cured product, it can be cured at an extremely low temperature, and it has excellent stability, curability, workability, and storage stability, and is an adhesive, coating material, sealing material, waterproof material, floor It is possible to provide a moisture-curable polyurethane composition that is suitably used for various applications such as materials, wall materials, and paints. The moisture-curable polyurethane composition of the present invention is cured by moisture at room temperature and can be used in a one-pack type, and is extremely excellent in workability.

  Embodiments of the present invention will be described below, but these embodiments are exemplarily shown, and it goes without saying that various modifications can be made without departing from the technical idea of the present invention.

  The moisture-curable polyurethane composition of the present invention comprises (A) a polyisocyanate compound and / or urethane prepolymer, (B) an N-hydroxyalkyl-oxazolidine compound and / or polyaldimine, and (C) p-toluenesulfonyl isocyanate. And at least one selected from the group consisting of hydrolyzable ester compounds, and (D) at least one selected from the group consisting of 1,8-diazabicyclo (5,4,0) undecene-7 and salts thereof , As an essential component.

  The polyisocyanate compound of the component (A) is a compound having 2 or more isocyanate groups in one molecule, and is generally a compound containing 2 to 5 isocyanate groups in one molecule, an alkylene group, More preferably, two or more isocyanates are bonded to a cycloalkylene group, a phenylene group or the like.

  Examples of the polyisocyanate compound include 1) tolylene diisocyanate (including various mixtures of isomers), diphenylmethane diisocyanate (including various mixtures of isomers), 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 1,4-phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, 1,4-cyclohexyl diisocyanate , 1-methyl-2,4-diisocyanato-cyclohexane, 2,4,4-trimethyl-1,6-diisocyanato-hexane and other diisocyanates 2) Triisocyanates such as 4 · 4 ′ · 4 ″ -triphenylmethane triisocyanate, tris (4-phenylisocyanato) thiophosphate, 3) Urethane-modified products, isocyanurate-modified products of the isocyanates, carbodiimides And polyfunctional isocyanates such as crude modified tolylene isocyanate, polymethylene / polyphenyl isocyanate, and the like.

  As the urethane prepolymer of the component (A), a known polyurethane prepolymer having a plurality of isocyanate groups can be widely used. Two or more organic polyisocyanate compounds and two or more in one molecule such as a polyol and a polyamine can be used. It can be obtained by reacting a known compound having active hydrogen with a known method. Free isocyanate groups remain in the polyurethane prepolymer.

  As a known compound having two or more active hydrogens in one molecule, specifically, two or more hydroxyl groups, one or more amino groups, two or more mercapto groups, or a hydroxyl group There are compounds having an amino group, or compounds having a hydroxyl group and a mercapto group, such as water, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose and other polyhydric alcohols, aniline, and tolylene. Examples include amines, aromatic amines such as p, p′-diamino-diphenylmethane, aliphatic amines such as ethylenediamine, ethanolamine, and diethanolamine, or alkanolamines. Further, polyether polyols obtained by addition polymerization of propylene oxide or propylene oxide and ethylene oxide to these compounds or a mixture of these compounds, and polyether polyamines obtained by converting hydroxyl groups of the polyether polyols to amino groups Kind.

  Further, as known compounds having two or more active hydrogens, for example, polytetramethylene ether polyols, polycarbonate polyols, polycaprolactone polyols, polyester polyols such as polyethylene adipate, polybutadiene polyols, castor oil and the like. Of higher fatty acid esters, polyether polyols, polyester polyols, polymer polyols obtained by grafting vinyl monomers, and known ethylenically unsaturated monomers having one or more active hydrogens in one molecule. And ethers having a mercapto group.

  The method for producing the urethane prepolymer may be a known method, and is not particularly limited. For example, the urethane prepolymer can be produced by reacting a polyisocyanate compound and a compound having active hydrogen at 100 ° C. for several hours. The isocyanate group content is preferably 0.5 to 20% by mass.

  The component (B) is at least one selected from the group consisting of an N-hydroxyalkyl-oxazolidine compound (B1) and a polyaldimine (B2), and the oxazolidine compound (B1) and the polyaldimine (B2) are You may use together and you may use only any one.

  The N-hydroxyalkyl-oxazolidine compound (B1) is a compound having a hydroxyl group at the terminal of the alkyl group substituted on the nitrogen atom of the oxazolidine ring, and is obtained by a known condensation reaction between a dihydroxyalkylamine and a ketone or aldehyde. can get. The N-hydroxyalkyl-oxazolidine compound (B1) is preferably an oxazolidine compound represented by the following general formula (1).

In said formula (1), R < ¹ > is a C2-C5 alkylene group, and an ethylene group or an isoprene group is preferable.
In the formula (1), R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and examples thereof include a hydrogen atom, a methyl group, an ethyl group, a propyl group, and an isopropyl group, and the hydrogen atom or the methyl group is preferable.
In the formula (1), R ³ and R ⁴ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ³ and R ⁴ may be the same or different. The hydrocarbon group in R ³ and R ⁴ may be any of a saturated or unsaturated chain hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, and an aromatic hydrocarbon group. 7 aliphatic hydrocarbon groups and aromatic hydrocarbon groups having 6 to 10 carbon atoms are preferred, alkyl groups having 1 to 7 carbon atoms such as methyl, ethyl, isopropyl and isopentyl groups, phenyl groups and toluyl groups. , A benzyl group and the like are more preferable. One of R ³ and R ^{4 in} the formula (1) is preferably a hydrogen atom, and the other is preferably a hydrocarbon group having 1 to 20 carbon atoms.

  Specific examples of the N-hydroxyalkyl-oxazolidine compound (B1) include 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, 2-phenyl-3- (2-hydroxyethyl) oxazolidine, 2- ( 1-methylbutyl) -3- (2-hydroxyethyl) oxazolidine, 2-isopropyl-3- (2-hydroxypropyl) -5-methyloxazolidine and the like are preferable.

  The blending ratio of the N-hydroxyalkyl-oxazolidine compound (B1) is not particularly limited, but the hydroxyl group formed by hydrolysis and ring opening of the oxazolidine compound, the polyisocyanate compound and / or the urethane prepolymer (A). The equivalent ratio (NCO / OH) with the isocyanate group contained is preferably 2 to 10, more preferably 2 to 5.

  As the polyaldimine (B2) of the component (B), conventionally known polyaldimines that generate amines by hydrolysis can be widely used, but polyaldimines derived from aromatic aldehydes are preferred, and the following general formula ( The polyaldimine represented by 2) is more preferred. These polyaldimines may be used alone or in combination of two or more.

In the formula (2), R ⁵ is an aryl group having 6 to 15 carbon atoms, and examples thereof include a phenyl group and a substituted phenyl group substituted with one or more substituents. As a substituent, a C1-C9 alkyl group, a C1-C9 alkoxy group, etc. are preferable. The number of substituents of the aryl group is preferably 1 to 3. Specific examples of R ⁵ include a phenyl group, a methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a dimethylphenyl group, a methoxyphenyl group, an ethoxyphenyl group, and a propoxyphenyl group. Can be mentioned. R ⁵ may be the same or different in one molecule.

In the formula (2), R ⁶ is a divalent or trivalent hydrocarbon group having 2 to 15 carbon atoms, a divalent or trivalent polyoxyalkylene group having a molecular weight of 70 to 6,000, and an amino residue of isophoronediamine. Or an amino residue of an amine represented by the following general formula (3). In formulas (2) and (3), n represents 2 or 3.

However, in formula (3), R ⁷ is a hydrocarbon group having 6 to 13 carbon atoms and comprising a divalent or trivalent bicyclo ring or a tricyclo ring, and the carbon number of the bicyclo ring or tricyclo ring. Is preferably 5-12. Furthermore, the cyclo ring may have a substituent. As the substituent, an alkyl group such as a methyl group, an ethyl group, or a propyl group is preferable.

  The manufacturing method of the said polyaldimine (B2) is not specifically limited, It can manufacture simply by well-known methods, such as making a polyamine and an aldehyde react. For example, polyamine and aldehyde are heated in an acid catalyst in a solvent such as toluene, xylene, methylcyclohexane or butyl acetate to perform azeotropic dehydration, and the distillation of water stops in the water droplet separator. The polyaldimine is obtained by continuing the reaction until. The mixing ratio of polyamine and aldehyde is suitably 1 to 2 equivalents of aldehyde with respect to 1 equivalent of amine. The reaction is usually complete in a few hours. After completion of the reaction, polyaldimine can be obtained by distilling off the aldehyde, the solvent and the like by reducing the reaction mixture under reduced pressure.

Examples of the polyamine include (a) aliphatic diamines such as ethylenediamine, 1,3-diaminopropane, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, and 4,4′-diamino. Dicyclohexylmethane, isophoronediamine, bisaminomethylcyclohexane, 2,5- or 2,6-diaminomethylbicyclo [2.2.1] heptane, diaminocyclohexane, 3 (4), 8 (9) -bis (aminomethyl) -Alicyclic diamines such as tricyclo [5.2.1.0 ^2.6 ] decane, diaminodiphenylmethane, diaminodiphenyl ether, xylylenediamine, phenylenediamine, 3,5-diethyltoluene-2,4- or 2,6-diamine Aromatic diamine etc. Diamines such as polyoxyalkylene diamines obtained by converting the hydroxyl groups of polyoxyalkylene glycols obtained by addition polymerization of propylene oxide and / or ethylene oxide to water, ethylene glycol, propylene glycol and the like, and ( b) Addition polymerization of propylene oxide and / or ethylene oxide to triamine such as 1,3,5-tris (aminomethyl) benzene, 1,3,5-tris (aminomethyl) cyclohexane, glycerin, trimethylolpropane, etc. Triamines such as polyoxyalkylene triamine obtained by converting the hydroxyl group of the obtained polyoxyalkylene triols to amino groups are exemplified, and a low melting point polyamine having a melting point of 50 ° C. or lower is particularly preferable.

  Examples of the aldehyde include benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, 4-ethylbenzaldehyde, 4-propylbenzaldehyde, 4-butylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,4, 5-Trimethylbenzaldehyde, p-anisaldehyde, p-ethoxybenzaldehyde and the like can be mentioned.

  The blending ratio of the polyaldimine (B2) is not particularly limited, but the number of amino groups of the polyamine generated by hydrolysis of the polyaldimine (B2) and the isocyanate group contained in the polyisocyanate compound and / or the urethane prepolymer (A) It is desirable that the ratio to the number of be 0.5 to 6.0, more preferably 0.7 to 3.0.

  The component (C) of the present invention is a compound that promotes hydrolysis of the oxazolidine compound (B1) and the polyaldimine (B2), and examples thereof include p-toluenesulfonyl isocyanate (PTSI) and hydrolyzable swell compounds. These compounds can be used alone or in combination of two or more. When two or more types are used in combination, the combination is not particularly limited, and for example, a hydrolyzable ester compound and p-toluenesulfonyl isocyanate may be used in combination.

  The hydrolyzable ester compound is hydrolyzed with water to produce a free acid, and promotes hydrolysis of an oxazolidine compound or polyaldimine. For example, esters such as methyl formate, methyl orthoformate, ethyl orthoformate Orthoformate such as cyclohexanone and acetal such as cyclohexanone dimethyl acetal are preferred in terms of storage stability. Although p-toluenesulfonyl isocyanate can be obtained by using phosgene or a known isocyanate synthesis method by Hofmann decomposition, commercially available products such as Additive TI manufactured by Sumitomo Bayer Urethane Co., Ltd. can be used. Moreover, derivatives of p-toluenesulfonyl isocyanate may be used, and these derivatives are also included in the present invention.

  The blending ratio of the component (C) is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 6 parts by mass with respect to 100 parts by mass of the component (A).

  Component (D) of the present invention is one or more selected from the group consisting of 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) and DBU salt, Examples thereof include octylate, phenol salt, oleate, p-toluenesulfonate, formate, orthophthalate and the like, and phenol salt and octylate are more preferable.

  In this invention, a component (D) is 0.01 mass part or more and less than 1 mass part with respect to 100 mass parts of components (A), Preferably it is 0.025 mass part or more and 0.75 mass part or less. When the amount was less than 0.01 part by mass, the low-temperature curability was not sufficient, and when 1 part by mass or more was blended, the stability was poor and foaming was observed.

  In addition to the above-described components, the moisture-curable polyurethane composition of the present invention includes, if necessary, colorants such as fillers, plasticizers, pigments and dyes, antistatic agents, flame retardants, adhesion-imparting agents, thixotropy. You may mix | blend an imparting agent, a silane coupling agent, a dispersing agent, antioxidant, a stabilizer, a curing catalyst, a solvent, etc.

  Examples of the filler include organic or inorganic materials of various shapes, such as calcium carbonate, magnesium carbonate, and zinc carbonate; carbon black; clay; talc; fumed silica, calcined silica, precipitated silica, ground silica, and fused silica; Kaolin; diatomaceous earth; zeolite; titanium oxide, quicklime, iron oxide, zinc oxide, barium oxide, magnesium oxide; aluminum sulfate; vinyl chloride paste resin; glass balloon, shirasu balloon, saran balloon, phenol balloon, vinylidene chloride resin balloon, etc. Inorganic balloons, organic balloons, and the like; or these fatty acid and fatty acid ester-treated products can be used, and these can be used alone or in combination.

  Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP), dilauryl phthalate (DLP), butyl benzyl phthalate (BBP), dioctyl adipate, diisononyl phthalate, diisodecyl adipate, diisodecyl phthalate, trioctyl phosphate, Tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, propylene glycol adipate polyester, butylene glycol adipate polyester, alkyl epoxy stearate, epoxidized soybean oil, and the like can be used alone or in combination it can.

  Examples of the thixotropy imparting agent include fumed silica, colloidal silica, fatty acid amide wax, aluminum stearate, surface-treated bentonite, polyethylene short fiber, phenol resin short fiber, Aerosil (manufactured by Nippon Aerosil Co., Ltd.), Disparon (manufactured by Enomoto Kasei Co., Ltd.) And the like, and it is preferable to use hydrophobic fine powder silica.

  Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, and octane, alicyclic hydrocarbons such as methylcyclohexane, petroleum-based solvents ranging from gasoline to kerosene fractions, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB), esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methylcyclohexanone, tetrahydrofuran, cellosolve acetate Ether-containing esters such as butyl cellosolve acetate, nitrogen-containing solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone Aromatic solvents are preferred

  Examples of the antistatic agent generally include ionic compounds such as quaternary ammonium salts and amines, and hydrophilic compounds such as polyethylene glycol and ethylene oxide derivatives. Examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins and the like. Examples of the flame retardant include chloroalkyl phosphate, dimethyl methyl phosphonate, bromine, phosphorus compound, ammonium polyphosphate, diethyl bishydroxyethyl amino phosphate and the like. Examples of the colorant include organic pigments such as azo pigments and copper phthalocyanine pigments, pigments such as various inorganic pigments, carbon black, titanium white, chromium oxide, and bengara. Examples of the stabilizer include hindered phenol compounds and triazole compounds.

  The method for producing the moisture-curable polyurethane composition of the present invention is not particularly limited, but preferably, each component is added with other additives as necessary and sufficiently kneaded under reduced pressure or in an inert atmosphere to be uniform. It is good to make it a composition by dispersing. The moisture-curable polyurethane composition of the present invention can be used as a one-component type, and is excellent in workability because it is not necessary to mix each component during construction.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

(Synthesis Example 1)
880 parts by mass of 2,4-tolylene diisocyanate, 2608 parts by mass of polyoxypropylene glycol (molecular weight 2000), and 1920 parts by mass of polyoxypropylene triol (molecular weight 3000) are reacted at 100 ° C. for 10 hours to form isocyanate groups. A terminal polyurethane prepolymer was obtained. The terminal NCO group was 2.92% by mass.

Example 1
A moisture-curable polyurethane composition having the composition shown in Table 1 was prepared as follows. The NCO group / oxazolidine-derived OH group in the urethane prepolymer was set to 2.2.
Into a 3 liter planetary mixer, DINP, surface-treated calcium carbonate, and heavy calcium carbonate were put, kneaded for 15 minutes at room temperature, and then dehydrated in vacuum for 1 hour while kneading at 100 ° C. . Next, component (A) urethane prepolymer, oxazolidine as component (B), PSTI as component (C), and DBU octylate as component (D) are added, kneaded at room temperature for 15 minutes, and moisture cured. A type polyurethane composition was obtained.

The amount of each compounding substance in Table 1 is shown in parts by mass, and * 1 to * 11 are as follows.
* 1) Urethane prepolymer: urethane prepolymer obtained in Synthesis Example 1 * 2) Oxazolidine 1: 2-isopropyl-3- (2-hydroxyethyl) oxazolidine * 3) Oxazolidine 2: 2-phenyl-3- (2- Hydroxyethyl) oxazolidine * 4) Polyaldimine: dialdimine (amine value 337 mgKOH / g), manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name ALD-1
* 5) DBU octylate: San Apro Co., Ltd., trade name U-CAT SA 102
* 6) DBU phenol salt: San Apro Co., Ltd., trade name U-CAT SA 1
* 7) Surface treated calcium carbonate: Maruo Calcium Co., Ltd., trade name Calfine 200

(Examples 2 to 8)
A moisture-curable polyurethane composition was prepared in the same manner as in Example 1 except that the composition shown in Table 1 was changed. In Example 7, NCO group in urethane prepolymer / OH group derived from oxazolidine = 2.2, and in Example 8, NCO group in urethane prepolymer / NH ₂ group derived from polyaldimine = 2.2. It was.

(Comparative Examples 1-8)
As shown in Table 2 below, a moisture-curable polyurethane composition was prepared in the same manner as in Example 1 except that the compounding substances were changed.

The amount of each compounding substance in Table 2 is shown in parts by mass, * 1, 2, 5 and 7 are the same as in Table 1, and * 8 to * 12 are as follows.
* 8) Tin-based catalyst: dibutyltin dilaurate, manufactured by Nitto Kasei Co., Ltd., trade name Neostan U-100
* 9) Bismuth catalyst: manufactured by Nitto Kasei Co., Ltd., trade name Neostan U-600
* 10) 2-ethylhexanoic acid: manufactured by Taoka Chemical Co., Ltd. * 11) acidic phosphate ester: butyl acid phosphate, manufactured by Daihachi Chemical Industry Co., Ltd. * 12) Amine-based moisture curing catalyst: morpholine, sunapro ( Product name U-CAT 660M

The following measurement was performed on the obtained composition. The results are shown in Tables 3 and 4.
1) Low-temperature curability The obtained composition was filled in a container having a diameter of 50 mm and a depth of 10 mm, and was allowed to stand at −10 ° C. and 5% RH for 7 days, and then the cured state of the composition was evaluated. The evaluation criteria are as follows.
(Circle): The composition hardened | cured and even if it pressed the composition with the finger | toe, the molded object did not adhere to the finger | toe.
X: The composition was not cured.

2) Film formation time The obtained composition was filled in a container having a diameter of 50 mm and a depth of 5 mm and left at 23 ° C. and 50% RH, and the time until a thin film was formed on the surface was measured. The composition was allowed to stand at 50 ° C. for 7 days, and the film formation time was measured in the same manner. In the table, the case where film formation was observed when allowed to stand at 50 ° C. was indicated by x.

3) Viscosity The initial viscosity of the composition obtained and the viscosity after standing at 50 ° C. for 7 days were measured using a B-type viscometer (measurement temperature 25 ° C.). The ratio between the viscosity after 7 days at 50 ° C. and the initial viscosity (viscosity after 7 days at 50 ° C./initial viscosity) was shown as the thickening rate. In the table, the gelation of the composition after standing at 50 ° C. for 7 days is indicated by x.

4) Foaming property The obtained composition was allowed to stand at 50 ° C. for 7 days, and then the presence or absence of foaming of the cured product was visually observed. The evaluation criteria are as follows.
○: No foaming, Δ: No problem in appearance, some foaming, ×: foaming.

5) Physical property test of cured product The obtained composition was molded into a container having a diameter of 50 mm and a depth of 20 mm, and allowed to stand at 23 ° C. and 50% RH for 1 week, and then the hardness of the cured product was measured with a hardness meter ASKER C. .
Furthermore, JIS A 1439 5.3. In accordance with the tensile property test, a tensile test was performed to measure the modulus, elongation at break and elongation at 50% elongation.

As shown in Tables 3 and 4, the moisture-curable polyurethane composition of the present invention can be cured even at an extremely low temperature of −10 ° C., has excellent stability, and does not foam during curing.

Claims (2)

(A) a polyisocyanate compound and / or a urethane prepolymer;
(B) an N-hydroxyalkyl-oxazolidine compound and / or a polyaldimine;
(C) at least one selected from the group consisting of p-toluenesulfonyl isocyanate and a hydrolyzable ester compound;
(D) at least one selected from the group consisting of 1,8-diazabicyclo (5,4,0) undecene-7 and salts thereof;
Contains, relative to the component (A) 100 parts by mass of the component (D) 0.0 single-liquid characterized by blending less than 1 part by mass 25 parts by mass or more moisture-curable polyurethane composition. The salt of 1,8-diazabicyclo (5,4,0) undecene-7 is a phenol salt of 1,8-diazabicyclo (5,4,0) undecene-7 and / or 1,8-diazabicyclo (5,4 , 0) The octylate of undecene-7, the one-part moisture-curable polyurethane composition according to claim 1.