JPH04279620A - Wet-curable polyurethane composition containing polyaldimine, water-repellent material, floor material, wall material and coating material respectively containing the composition - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a specific polyaldimine and a polyisocyanate, etc., having excellent curability and storage stability, and useful as a water-repellent material, etc. CONSTITUTION:The objective composition contains a polyaldimine of the formula (X is 6-15C aryl; Y is 2-15C divalent or trivalent hydrocarbon, divalent or trivalent polyoxyalkylene having a mol.wt. of 70-6000; (n) is 2, 3) and produced by reacting a polyamine such as ethylene diamine with an aldehyde such as benzaldehyde, and a polyisocyanate such as tolylene diisocyanate and/or a polyurethane prepolymer having plural isocyanate groups. The ratio of the number of the amino groups of the polyamine produced by the hydrolysis of the polyaldimine to the number of the isocyanate groups contained in the polyisocyanate and/or the polyurethane prepolymer having the isocyanate groups is preferably 0.7-1.5 in the mixture.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a moisture-curable polyurethane composition containing a polyaldimine that is hydrolyzed to produce a polyamine, and a waterproof material containing the composition.
Regarding flooring materials, sealing materials, wall materials, and paints.

0002

[Prior Art] Polyurethane resins have been particularly used in recent years as paints, flooring materials, waterproofing materials, adhesives, wall materials, and sealing materials because of their excellent properties such as rubber elasticity, abrasion resistance, and durability. ing.

These polyurethane resins are of the one-component type, which is cured by reacting the terminal isocyanate group of the polyurethane prepolymer with atmospheric moisture after being applied to the object, and the other is the one-component type, which is cured by reacting the terminal isocyanate group of the polyurethane prepolymer with moisture in the atmosphere, and the polyurethane resin contains a base resin containing a polyurethane prepolymer and a polyol. It is broadly divided into two-component type, in which a curing agent is mixed with the curing agent and hardened at the time of construction.

[0004]One-component polyurethane can be used by anyone because of its simple construction method, and has recently attracted particular attention.

[0005] This one-component polyurethane is called a moisture-curable polyurethane, and the following compositions are known. (1) Due to the reaction between polyisocyanate and moisture (moisture), that is, the decarboxylation of the reaction product between isocyanate and water, a part of the polyisocyanate becomes an amine, and the generated amine reacts with the remaining polyisocyanate and hardens. Moisture-curable polyurethane composition that utilizes the reaction of (2) Moisture-curable composition comprising polyaldimine or polyketimine and polyisocyanate (British Patent No. 10
64841, German Patent No. 3607996A) (3) Moisture-curable polyurethane compositions consisting of polyenamines and polyisocyanates (UK Patent No. 1575666, German Patent No. 2125247). However, although the composition (1) has relatively good storage stability in a closed container, it has the disadvantage of extremely poor curing properties and foaming during application. An amine catalyst or a tin catalyst can be used to improve curing properties, but in this case storage stability deteriorates and foaming becomes intense, making them unsuitable for practical use.

In the composition (2), since the polyaldimine or polyketimine reacts with the polyisocyanate during storage, when it is used as a moisture-curable polyurethane composition, it is necessary to impart steric hindrance to the polyaldimine or polyketimine. , it is necessary to block the isocyanate groups to prevent the above reaction.

[0007] The sterically hindered polyaldimines disclosed in British Patent No. 1064841 or German Patent No. 3607996A are all made from aliphatic aldehydes, and have slow curing properties or poor storage stability. Therefore, it is not suitable for practical use. In particular, the polyaldimine disclosed in German patent 3607996A is
It uses aromatic amine as a raw material and has excellent physical properties such as mechanical strength, but it has the drawbacks of slow curing and lack of storage stability at high temperatures.

[0008] Also in the composition (3), since polyenamine reacts with polyisocyanate, when an aromatic isocyanate is used as the polyisocyanate, it is necessary to block the isocyanate groups as in the case of polyketimine. Therefore, like polyketimine, this composition is not suitable for practical use. On the other hand, it is known that polyisocyanates with relatively low reactivity, such as aliphatic polyisocyanates or alicyclic polyisocyanates, can be used in sealing materials, etc.
This material has the characteristics of non-foaming and fast curing. However, polyenamines, albeit very gradually,
Because it reacts with aliphatic polyisocyanates or alicyclic polyisocyanates, it has poor storage stability for long periods of time or at temperatures slightly higher than room temperature, even in a closed container. In addition, the initial physical properties are not maintained or the viscosity increases significantly, resulting in a significant deterioration in workability. Therefore, none of the conventional known techniques were satisfactory. In other words, it has good storage stability in a closed container, excellent initial mechanical strength, high retention of initial properties during high-temperature storage, no gelation, etc., and good viscosity stability. Fast curing due to atmospheric moisture and no foaming are extremely important properties for this type of polyurethane, and its quality determines its commercial value in the market. In addition, it has a moisture-curing polyurethane composition that has high storage stability in a sealed container, in other words, can be stored for a long period of time with a constant viscosity, hardens quickly under humidity, does not foam, and has excellent mechanical strength. Something is strongly desired.

[0009]

[Problems to be Solved by the Invention] The present invention has been made to solve the above problems, and its purpose is to provide a moisture-curing product that has excellent storage stability, good curing properties, and can be used for various purposes. An object of the present invention is to provide a polyurethane composition and waterproofing materials, flooring materials, sealing materials, wall materials, and paints containing the composition.

0010

[Means for Solving the Problems] As a result of intensive research into the above-mentioned problems, the present inventors have developed a method in which polyaldimine derived from aromatic aldehydes is used and hydrolyzed by moisture in the air. This idea led to the completion of the present invention. In the present invention, by using a polyaldimine having an aromatic ring, the curability and mechanical strength of the moisture-curable polyurethane composition were improved, and the storage stability was improved. This has made it possible to develop it into a variety of applications. That is, the present invention provides (1
) The following general formula (I)

[0011]

[Chemical formula 3] (However, X represents an aryl group having 6 to 15 carbon atoms. Y represents a divalent or trivalent hydrocarbon group having 2 to 15 carbon atoms,
Or it represents a divalent or trivalent polyoxyalkylene group with a molecular weight of 70 to 6,000. n represents 2 or 3. ) and a polyurethane prepolymer containing a polyisocyanate and/or a plurality of isocyanate groups, (2) Y is a diamine or triamine amino acid having a melting point of 50° C. or less. (3) Y is a residue of the following general formula (II)

0012

embedded image (where Z represents a hydrocarbon group having 6 to 13 carbon atoms and consisting of a divalent or trivalent cyclo, bicyclo, or tricyclo ring; n represents 2 or 3) (4) Y is isophorone diamine, 1,3-bis(aminomethyl)cyclohexane, 2
,5- or 2,6-bis(aminomethyl)bicyclo[2
,2,1] is an amino residue of heptane.

Furthermore, the present invention provides (5) the above (1) to (4).
A moisture-curable polyurethane waterproofing material comprising a moisture-curable polyurethane composition and a filler, (6) the above (1)
- (4) A moisture-curable polyurethane flooring material containing the moisture-curable polyurethane composition and a filler, (7) The moisture-curable polyurethane composition of (1) to (4) above and a thixotropic agent. (8) A moisture-curable polyurethane wall material containing the moisture-curable polyurethane composition of (1) to (4) above and a thixotropic agent, ( 9) Above (1) to (4)
A moisture-curable polyurethane paint comprising a moisture-curable polyurethane composition.

The present invention will be explained in detail below.

In the present invention, the moisture-curable polyurethane composition contains a polyaldimine and a polyisocyanate and/or a polyurethane prepolymer having a plurality of isocyanate groups.

The polyaldimine used in the present invention has the following general formula (I).

[0017]

[C5] This is a compound represented by

Here, X represents an aryl group having 6 to 15 carbon atoms. The aryl group represented by X includes phenyl group and 1
There are substituted phenyl groups substituted with the above substituents. Substituents include alkyl groups having 1 to 9 carbon atoms, and 1 to 9 carbon atoms.
An alkoxy group such as No. 9 is preferable.

The number of substituents on the above aryl group is 1 to 3.
Preferably.

Specific examples of the aryl group represented by X include phenyl group, methylphenyl group, ethylphenyl group,
Preferred are propylphenyl group, butylphenyl group, dimethylphenyl group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, and the like.

Further, X may be different within one molecule or may be the same.

Y has 2 to 15 carbon atoms and is divalent or trivalent
It represents a valent hydrocarbon group, or a divalent or trivalent polyoxyalkylene group with a molecular weight of 70 to 6,000. In addition, n
indicates 2 or 3. Preferred hydrocarbon groups include divalent or trivalent alkyl groups, cycloalkyl groups, and aryl groups.

The alkyl group has a linear carbon number of 4 to
8. Those having a branched carbon number of 4 to 10 are preferable. As the cycloalkyl group, those having 1 to 3 cyclo rings can be used, and one cyclo ring preferably has 5 to 12 carbon atoms. Furthermore, the cyclo ring may have a substituent. As the substituent, an alkyl group such as methyl, ethyl, propyl, etc. are preferable. Aryl groups include phenyl and substituted phenyl groups. The number of substituents is 1 to 3. Examples of the substituent include an alkyl group having 1 to 9 carbon atoms.

As the divalent polyoxyalkylene group,
There are groups derived from polyoxyalkylene glycols obtained by addition polymerization of propylene oxide and/or ethylene oxide to water, ethylene glycol, propylene glycol, etc.

As the trivalent polyoxyalkylene group,
There are groups derived from polyoxyalkylene triols obtained by addition polymerization of propylene oxide and/or ethylene oxide to glycerin, trimethylolpropane, etc.

These divalent or trivalent polyoxyalkylene groups preferably have a molecular weight of 70 to 6,000. If the molecular weight is less than 70, it is unsuitable for practical use. If the molecular weight exceeds 6000, the physical properties of the composition after curing will be poor.

The polyaldimine represented by the above general formula (I) can be easily produced by a method such as reacting a polyamine with an aldehyde.

Examples of polyamines include 1) aliphatic diamines such as ethylenediamine, 1,3-diaminopropane, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, and 4,4'-diaminodicyclohexyl; Methane, isophoronediamine, bisaminomethylcyclohexane, 2,5- or 2,6-diaminomethylbicyclo[2,2,1]heptane, diaminocyclohexane,
Alicyclic diamines such as 3(4),8(9)-bis(aminomethyl)-tricyclo[5.2.1.02.6]decane, diaminodiphenylmethane, diaminodiphenyl ether, xylylene diamine, phenylene diamine, 3
, 5-diethyltoluene-2,4- or 2,6-diamine, etc., polyoxyalkylene glycols obtained by addition polymerization of propylene oxide and/or ethylene oxide to aromatic diamines such as water, ethylene glycol, propylene glycol, etc. Diamines such as polyoxyalkylene diamines obtained by converting the hydroxyl groups of There are triamines such as polyoxyalkylene triamine obtained by converting the hydroxyl groups of polyoxyalkylene triols obtained by addition polymerization of propylene oxide and/or ethylene oxide to glycerin, trimethylolpropane, etc. into amino groups.

Among these, low melting point polyamines having a melting point of 50° C. or less are particularly preferred. Polyaldimines made from polyamines with high melting points are solid and may be inconvenient to handle.

Examples of the low melting point polyamine include ethylenediamine, 1,3-diaminopropane, tetramethylenediamine, hexamethylenediamine, isophoronediamine, bisaminomethylcyclohexane, 2,5- or 2,6-
Diaminomethylbicyclo[2,2,1]heptane, xylylene diamine, diaminocyclohexane, 3,5-diethyltoluene-2,4- or 2,6-diamine, 1,
3,5-tris(aminomethyl)cyclohexane, 3(
4),8(9)-bis(aminomethyl)-tricyclo[
5.2.1.02.6] Decane, polyoxyalkylene triamine, etc. are preferred.

Further, examples of the aldehyde to be reacted with the polyamine include benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde,
Preferred are 4-ethylbenzaldehyde, 4-propylbenzaldehyde, 4-butylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde, p-anisaldehyde, p-ethoxybenzaldehyde, and the like.

[0032] As a method for producing polyaldimine, the following method is preferable. For example, the above polyamine and the above aldehyde are mixed in a solvent such as toluene or xylene,
Azeotropic dehydration reaction is carried out by heating under an acid catalyst. Polyaldimine is obtained by continuing the reaction in the water droplet separator until the distillation of water stops. The mixing ratio of the above polyamine and the above aldehyde is amine 1
1 to 2 equivalents of aldehyde per equivalent are suitable. The reaction usually completes within a few hours. After the reaction is completed, the aldehyde, solvent, etc. can be distilled off by reducing the pressure of the reaction mixture, etc., to obtain polyaldimine.

In the present invention, a moisture-curable polyurethane composition is prepared by mixing the above polyaldimine with a polyisocyanate and/or a polyurethane prepolymer having a plurality of isocyanate groups.

Polyisocyanate is a compound having two or more isocyanate groups in one molecule, generally one
Compounds containing 2 to 5 isocyanate groups in the molecule are preferred.

As such compounds, those having two or more isocyanates bonded to an alkylene group, cycloalkylene group, phenylene group, etc. are preferred. Examples of these compounds 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-diisocyanate
Diisocyanates such as cyclohexane, 2,4,4-trimethyl-1,6-diisocyanato-hexane, 2)4
・Triisocyanates such as 4', 4''-triphenylmethane triisocyanate and tris(4-phenylisocyanato)thiophosphate, 3) Urethane-modified products, isocyanurate-modified products, carbodiimidized products of the above-mentioned isocyanates, Polyfunctional isocyanates such as biuret-modified products, crude tolylene isocyanate, and polymethylene/polyphenylisocyanate.

The polyurethane prepolymer having a plurality of isocyanate groups used in the present invention contains the various organic polyisocyanate compounds mentioned above, known polyols, known polyamines, etc. having two or more active hydrogens in one molecule. It is obtained by reacting a known compound with a known method, and free isocyanate groups remain in the polyurethane prepolymer.

Known compounds having two or more active hydrogens in one molecule include two or more hydroxyl groups, one or more amino groups, two or more mercapto groups,
Alternatively, it is a compound having a hydroxyl group and an amino group, or a compound having a hydroxyl group and a mercapto group. For example, water, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, or aniline, tolylene diamine, p, p
These are aromatic amines such as '-diamino-diphenylmethane, aliphatic amines such as ethylenediamine, ethanolamine, diethanolamine, or alkanolamines.

Furthermore, polyether polyols obtained by addition polymerizing propylene oxide or propylene oxide and ethylene oxide to these compounds or mixtures of these compounds, and polyether polyols obtained by converting the hydroxyl groups of the polyether polyols to amino groups. They are polyether polyamines.

Furthermore, polytetramethylene ether polyols, polycarbonate polyols, polycaprolactone polyols, polyester polyols such as polyethylene adipate, polybutane polyols, esters of higher fatty acids such as castor oil, and polyethers. Polymer polyols obtained by grafting vinyl monomers onto polyols or polyester polyols, compounds obtained by copolymerizing known ethylenically unsaturated monomers having one or more active hydrogen per molecule, and having mercapto groups. They are ethers.

The reaction is carried out, for example, by reacting polyisocyanate with a known compound having active hydrogen at 100° C. for several hours. Its isocyanate group content is 0.5-
20. Weight percent is preferred.

The moisture-curable polyurethane composition of the present invention comprises the above-mentioned polyaldimine, the above-mentioned polyisocyanate and/or
Alternatively, it can be produced by mixing it with the above polyurethane prepolymer having an isocyanate group.

The mixing ratio is such that the ratio of the number of amino groups of the polyamine produced by hydrolysis of polyaldimine to the number of isocyanate groups contained in the polyisocyanate and/or polyurethane prepolymer having isocyanate groups is 0.
．． It is desirable to set it to 5 to 2.0, preferably 0.7 to 1.5.

The moisture-curable polyurethane composition of the present invention produced as described above can be used as it is for various purposes, such as sealing materials, waterproofing materials,
Useful as flooring materials, wall materials, paints, and adhesives.

Furthermore, the moisture-curable polyurethane composition of the present invention may contain the following fillers, thixotropic agents, plasticizers, solvents, and adhesion promoters in order to adjust the viscosity, resin physical properties, and resistance depending on the application. It is also possible to use a mixture of agents, colorants, stabilizers, catalysts for accelerating curing, and the like.

For example, when manufacturing waterproof materials and flooring materials, it is preferable to further add a filler to the moisture-curable polyurethane composition consisting of the dialdimine and the polyisocyanate and/or polyurethane prepolymer having isocyanate groups. .

Examples of fillers include calcium carbonate, talc, kaolin, aluminum sulfate, zeolite, diatomaceous earth, vinyl chloride paste resin, glass balloons, vinylidene chloride resin balloons, etc.
It is used in a range of 20 to 60% by weight, preferably 20 to 60% by weight.

For example, in the production of sealants and wall materials, a thixotropic agent may be added to a moisture-curable polyurethane composition comprising the dialdimine and the polyisocyanate and/or isocyanate group-containing polyurethane prepolymer. It is preferable to add

Examples of thixotropic agents used in the present invention include colloidal silica, fatty acid amide wax, aluminum stearate, surface-treated bentonite, short polyethylene fibers, short phenolic resin fibers, etc. -15% by weight, preferably 0.5-10% by weight.

Further, examples of the plasticizer used in the present invention include dioctyl phthalate, dibutyl phthalate, dilauryl phthalate, butylbenzyl phthalate,
These include dioctyl adipate, diisodecyl adipate, diisodecyl phthalate, trioctyl phosphate, etc., and can be blended in the composition in an amount of up to 50% by weight, preferably in the range of 0 to 40% by weight.

Examples of the solvent used in the present invention include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, and octane, petroleum solvents ranging from gasoline to kerosene fractions, Esters such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone,
Examples include ketones such as methyl isobutyl ketone, and ether esters such as cellosolve acetate and butyl cellosolve acetate, which can be used in the composition in an amount of up to 50% by weight, preferably in the range of 0 to 40% by weight.

[0051] As the adhesion promoter, known silane coupling agents and the like are preferred. It can be used in the composition up to 5% by weight, preferably in the range of 0.05-2% by weight.

[0052] As the coloring agent, carbon black, titanium white, chromium oxide, red iron oxide, etc. can be used. The blending amount is preferably 0.1 to 5% by weight.

[0053] As the stabilizer, hindered phenol compounds, triazole compounds, etc. can be used. The blending amount is approximately 0.1 to 2% by weight.

Furthermore, in the present invention, a curing accelerating catalyst can also be blended. Preferred examples of the curing accelerating catalyst include carboxylic acids, sulfonic acids, phosphoric acids, and phosphoric esters. The blending amount is preferably about 0.05 to 5% by weight.

[0055] There are no particular restrictions on the method of blending these.
Necessary additives, such as fillers, plasticizers, thixotropic agents, and other auxiliary agents, may be mixed by simple mixing or by other known methods, such as stirring and mixing using a mixer such as a planetary mixer or a dissolver. After that, polyisocyanate and/or
Alternatively, a polyurethane prepolymer having isocyanate groups and dialdimine may be added and thoroughly mixed. When the water content of various additives is high, it is necessary to dehydrate them in advance or add a dehydrating agent such as zeolite. The resulting moisture-curable polyurethane composition can be used immediately or can be stored in a closed can under a nitrogen stream. In this case, the storage stability is extremely good when kept in a closed container and isolated from moisture in the air, and even when stored at temperatures higher than room temperature, the retention of physical properties is high and the viscosity stability is also good. be. Moreover, once opened, it cures immediately upon exposure to moisture in the air, and unlike conventional moisture-curing polyurethanes, it is non-foaming and can provide various polyurethane products with excellent mechanical properties.

The moisture-curable polyurethane composition according to the present invention has excellent not only curability but also long-term storage stability. Sealing materials, wall materials, waterproofing materials, flooring materials, and paints made by mixing this composition with fillers, thixotropic agents, and others according to the purpose also have excellent storage stability and workability. Moreover, when applied, it can be rapidly cured by the moisture in the air. Furthermore, the cured product has high modulus and excellent mechanical strength.

[0057]

[Examples] The present invention will be explained in more detail with reference to Examples below. In the examples, parts indicate parts by weight.

Synthesis Example 1 of Dialdimine (ALD-1) 88 parts (2.0 equivalents) of tetramethylene diamine, 0.1 part of formic acid and 500 parts of toluene was added and mixed at room temperature under a nitrogen stream. After about 10 minutes, 300 parts (2.5 equivalents) of p-tolualdehyde was added dropwise from the dropping funnel over about 30 minutes. When the temperature was then raised, reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, increase the external temperature to 1
The temperature was set at 50°C. Subsequently, the pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted p-tolualdehyde were distilled off. The reaction product (ALD-1) obtained after distillation was 290
It was a department. Furthermore, as a result of measuring the infrared absorption spectrum of the obtained reaction product, a characteristic absorption spectrum of -N=CH- was observed at 1640 cm-1. Dialdimine ALD-1 had an amine value of 381 mgKOH/g and was a yellow liquid at room temperature.

Synthesis Example 2 of Dialdimine (ALD-2) 116 parts (2.0 equivalents) of tetramethylene diamine, 0.1 part of formic acid and 500 parts of toluene was added and mixed at room temperature under a nitrogen stream. After about 10 minutes, 265 parts (2.5 equivalents) of benzaldehyde was added dropwise from the dropping funnel over about 30 minutes. When the temperature was further increased, reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, increase the external temperature to 1
The temperature was set at 50°C. Subsequently, the pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted tolualdehyde were distilled off. The amount of reaction product (ALD-2) obtained after distillation was 290 parts. Furthermore, as a result of measuring the infrared absorption spectrum of the obtained reaction product, a characteristic absorption spectrum of -N=CH- was observed at 1640 cm-1. Dialdimine ALD-2 had an amine value of 381 mgKOH/g and was a yellow liquid at room temperature.

Synthesis Example 3 of Dialdimine (ALD-3) Approximately 60% of the 2,5-isomer and 2,6-isomer 4 were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a water separator.
0% mixture of diaminomethylbicyclo[2,2,
1] 154 parts (2.0 equivalents) of heptane, 0.1 part of formic acid, and 500 parts of toluene were added and mixed at room temperature under a nitrogen stream. After about 10 minutes, add benzaldehyde 2 from the dropping funnel.
65 parts (2.5 equivalents) were added dropwise over about 30 minutes. When the temperature was further increased, reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, the external temperature was set to 150°C. Subsequently, the pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted tolualdehyde were distilled off. The amount of reaction product (ALD-3) obtained after distillation was 328 parts. In addition, as a result of measuring the infrared absorption spectrum of the obtained reaction product, it was found that 1640
A characteristic absorption spectrum of -N=CH- was observed at cm-1. Dialdimine ALD-3 has an amine value of 337 mgKOH/
g, and was a pale yellow liquid at room temperature.

Synthesis Example 4 of Dialdimine (ALD-4) About 60% of the 2,5-isomer and the 2,6-isomer 4 were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a water separator.
0% mixture of diaminomethylbicyclo[2,2,
1] 154 parts (2.0 equivalents) of heptane, 0.1 part of formic acid, and 500 parts of toluene were added and mixed at room temperature under a nitrogen stream. After about 10 minutes, 300 parts (2.5 equivalents) of p-tolualdehyde was added dropwise from the dropping funnel over about 30 minutes. The temperature was further increased, and reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, the external temperature was set to 150°C. Subsequently, the pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted p-tolualdehyde were distilled off. The amount of reaction product (ALD-4) obtained after distillation was 354 parts. In addition, as a result of measuring the infrared absorption spectrum of the obtained reaction product, it was found that 1
A characteristic absorption spectrum of -N=CH- was observed at 640 cm-1. Dialdimine ALD-4 has an amine value of 310 mgKOH/
g, and was a pale yellow liquid at room temperature.

Synthesis Example 5 of Dialdimine (ALD-5) Approximately 60% of the 2,5-isomer and 2,6-isomer 4 were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a water separator.
0% mixture of diaminomethylbicyclo[2,2,
1] 154 parts (2.0 equivalents) of heptane, 0.1 part of formic acid, and 500 parts of toluene were added and mixed at room temperature under a nitrogen stream. After about 10 minutes, 335 parts (2.5 equivalents) of 4-ethylbenzaldehyde was added dropwise from the dropping funnel over about 30 minutes. The temperature was further increased, and reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, the external temperature was set to 150°C. Subsequently, the pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted 4-ethylbenzaldehyde were distilled off. The reaction product (ALD-5) obtained after distillation was 382 parts. Furthermore, as a result of measuring the infrared absorption spectrum of the obtained reaction product, a characteristic absorption spectrum of -N=CH- was observed at 1640 cm-1. Dialdimine ALD-5 had an amine value of 285 mgKOH/g and was a pale yellow liquid at room temperature.

Synthesis Example 6 of Dialdimine (ALD-6) Approximately 60% of the 2,5-isomer and 2,6-isomer 4 were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a water separator.
0% mixture of diaminomethylbicyclo[2,2,
1] 154 parts (2.0 equivalents) of heptane, 0.1 part of formic acid, and 500 parts of toluene were added and mixed at room temperature under a nitrogen stream. After about 10 minutes, 340 parts (2.5 equivalents) of p-anisaldehyde was added dropwise from the dropping funnel over about 30 minutes. The temperature was further increased, and reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, the external temperature was set to 150°C. Subsequently, the pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted p-anisaldehyde were distilled off. The amount of reaction product (ALD-6) obtained after distillation was 383 parts. In addition, as a result of measuring the infrared absorption spectrum of the obtained reaction product, it was found that 1
A characteristic absorption spectrum of -N=CH- was observed at 640 cm-1. Dialdimine ALD-6 has an amine value of 286 mg
KOH/g, and was a pale yellow liquid at room temperature.

Synthesis Example 7 of Dialdimine (ALD-7) 170 parts (2.0 equivalents) of isophorone diamine was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a water separator.
, 0.1 part of formic acid, and 500 parts of toluene were added and mixed at room temperature under a nitrogen stream. After about 10 minutes, 265 parts (2.5 equivalents) of benzaldehyde was added dropwise from the dropping funnel over about 30 minutes. The temperature was further increased, and reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, the external temperature was set to 150°C. Subsequently, the pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted benzaldehyde were distilled off. The amount of reaction product (ALD-7) obtained after distillation was 343 parts. Furthermore, as a result of measuring the infrared absorption spectrum of the obtained reaction product, a characteristic absorption spectrum of -N=CH- was observed at 1640 cm-1. Dialdimine ALD-7 had an amine value of 320 mgKOH/g and was a pale yellow liquid at room temperature.

Synthesis Example 8 of Dialdimine (ALD-8) 170 parts (2.0 equivalents) of isophorone diamine was placed in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and water separator.
, 0.1 part of formic acid, and 500 parts of toluene were added and mixed at room temperature under a nitrogen stream. After about 10 minutes, remove m from the dropping funnel.
- 300 parts (2.5 equivalents) of tolualdehyde was added dropwise over about 30 minutes. The temperature was further increased, and reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, increase the outside temperature to 150℃
It was set to Subsequently, the pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted m-tolualdehyde were distilled off. The amount of reaction product (ALD-8) obtained after distillation was 372 parts. Furthermore, as a result of measuring the infrared absorption spectrum of the obtained reaction product, a characteristic absorption spectrum of -N=CH- was observed at 1640 cm-1. Dialdimine ALD-8 had an amine value of 297 mgKOH/g and was a pale yellow liquid at room temperature.

Synthesis Example 9 of Dialdimine (ALD-9) 142 parts of bisaminomethylcyclohexane (
2.0 equivalents), 0.1 part of formic acid, and 500 parts of toluene were added and mixed at room temperature under a nitrogen stream. After about 10 minutes, 335 parts of 4-ethylbenzaldehyde (2.
5 equivalents) was added dropwise over about 30 minutes. The temperature further increases to about 90
Reflux started at ℃, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, the external temperature was set to 150°C. Subsequently, the pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted 4-ethylbenzaldehyde were distilled off. The amount of reaction product (ALD-9) obtained after distillation was 371 parts. In addition, as a result of measuring the infrared absorption spectrum of the obtained reaction product, it was found that 1640 cm
A characteristic absorption spectrum of -N=CH- was observed in -1. Dialdimine ALD-9 has an amine value of 297 mgKOH/g
It was a pale yellow liquid at room temperature.

Dialdimine (ALD-10) Synthesis Example 10
210 parts (2.0 equivalents) of 4,4'-diaminodicyclohexylmethane, 0.1 part of formic acid, and 500 parts of toluene were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a water separator, and the mixture was heated with a nitrogen stream. and mixed at room temperature. Approximately 1
After 0 minutes, 300 parts of p-tolualdehyde (
2.5 equivalents) was added dropwise over about 30 minutes. The temperature was further increased, and reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, the external temperature was set to 150°C. Subsequently, the pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted p-
Tolualdehyde was distilled off. The reaction product obtained after distillation (A
LD-10) was 410 parts. In addition, as a result of measuring the infrared absorption spectrum of the obtained reaction product, it was found that 1640 cm-
1, a characteristic absorption spectrum of -N=CH- was observed. Dialdimine ALD-10 has an amine value of 268 mgKOH/g
It was a pale yellow solid at room temperature.

Dialdimine (ALD-11) Synthesis Example 11
In a reaction vessel equipped with a stirrer, thermometer, addition funnel, and water separator, 3,5-diethyltoluene-2, which is a mixture of about 80% 2,4-isomer and about 20% 2,6-isomer, was added.
, 178 parts (2.0 equivalents) of 4- and 2,6-diamine,
0.1 part of formic acid and 500 parts of toluene were added and mixed at room temperature under a nitrogen stream. After about 10 minutes, 265 parts (2.5 equivalents) of benzaldehyde was added dropwise from the dropping funnel over about 30 minutes. The temperature was further increased, and reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, the external temperature was set to 150°C. Next, reduce the pressure to 1 mmHg with a vacuum pump,
Toluene and unreacted benzaldehyde were distilled off. The amount of reaction product (ALD-11) obtained after distillation was 351 parts. Furthermore, as a result of measuring the infrared absorption spectrum of the obtained reaction product, a characteristic absorption spectrum of -N=CH- was observed at 1640 cm-1. Dialdimine ALD-11 had an amine value of 315 mgKOH/g and was a pale yellow liquid at room temperature.

Dialdimine (ALD-12) Synthesis Example 12
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a water separator, 114 parts (2.0 equivalents) of 1,3,5-tris(aminomethyl)cyclohexane, 0.1 part of formic acid, and 500 parts of toluene were added. and mixed at room temperature under a nitrogen stream. After about 10 minutes, add benzaldehyde 26 from the dropping funnel.
5 parts (2.5 equivalents) were added dropwise over about 30 minutes. The temperature was further increased, and reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, the external temperature was set to 150°C. continue,
The pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted benzaldehyde were distilled off. The amount of reaction product (ALD-12) obtained after distillation was 299 parts. In addition, as a result of measuring the infrared absorption spectrum of the obtained reaction product, it was found that 1640c
A characteristic absorption spectrum of -N=CH- was observed at m-1. Dialdimine ALD-12 has an amine value of 386 mgKOH
/g, and was a pale yellow liquid at room temperature.

Dialdimine (ALD-13) Synthesis Example 13
Polyoxyethylene diamine (Texac
o Manufactured by Chemical Company, Trademark:
JEFFAMINE EDR-148, molecular weight 148
), 0.1 part of formic acid, and 500 parts of toluene were added and mixed at room temperature under a nitrogen stream. Approximately 1
After 0 minutes, 405 parts (2.5 equivalents) of p-isobutylbenzaldehyde was added dropwise from the dropping funnel over about 30 minutes. The temperature was further increased, and reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, the external temperature was set to 150°C. Subsequently, the pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted p-isobutylbenzaldehyde were distilled off. The amount of reaction product (ALD-13) obtained after distillation was 435 parts. Furthermore, as a result of measuring the infrared absorption spectrum of the obtained reaction product, a characteristic absorption spectrum of -N=CH- was observed at 1640 cm-1. Dialdimine ALD-13 has an amine value of 2
It had a concentration of 57 mgKOH/g and was a pale yellow liquid at room temperature.

Dialdimine (ALD-14) Synthesis Example 14
A reaction vessel equipped with a stirrer, thermometer, addition funnel, and water separator was charged with polyoxypropylene diamine (Tex
co Chemical Company, trademark: JEFFAMINE D-230, molecular weight 230)
230 parts (2.0 equivalents), formic acid 0.1 part and toluene 5
00 parts and mixed at room temperature under a nitrogen stream. about 10
After 340 parts of p-anisaldehyde (
2.5 equivalents) was added dropwise over about 30 minutes. The temperature was further increased, and reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, the external temperature was set to 150°C. Subsequently, the pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted p-
Anisaldehyde was distilled off. The reaction product obtained after distillation (
ALD-14) was 464 parts. In addition, as a result of measuring the infrared absorption spectrum of the obtained reaction product, it was found that 1640 cm
A characteristic absorption spectrum of -N=CH- was observed in -1. Dialdimine ALD-14 has an amine value of 241 mgKOH/
g, and was a pale yellow liquid at room temperature.

Trialdimine (ALD-15) Synthesis Example 1
5 Add polyoxypropylene triamine (Tex
Manufactured by aco Chemical Company, trademark: JEFFAMINE T-403, molecular weight 440
), 0.1 part of formic acid, and 500 parts of toluene were added and mixed at room temperature under a nitrogen stream. Approximately 1
After 0 minutes, 370 parts (2.5 equivalents) of p-isopropylbenzaldehyde was added dropwise from the dropping funnel over about 30 minutes. The temperature was further increased, and reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 36 parts. Next, the external temperature was set to 150°C. Subsequently, the pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted p-isopropylbenzaldehyde were distilled off. The reaction product (ALD-15) obtained after distillation was 552
It was a department. Furthermore, as a result of measuring the infrared absorption spectrum of the obtained reaction product, a characteristic absorption spectrum of -N=CH- was observed at 1640 cm-1. dialdimine ALD-15
had an amine value of 304 mgKOH/g and was a pale yellow liquid at room temperature.

Trialdimine (ALD-16) Synthesis Example 1
6 Add polyoxypropylene triamine (Tex
Manufactured by aco Chemical Company, trademark: JEFFAMINE T-5000, molecular weight 50
00), 0.5 part of formic acid, and 2000 parts of toluene were added and mixed at room temperature under a nitrogen stream. After about 10 minutes, add 15% of benzaldehyde from the dropping funnel.
9 parts (1.5 equivalents) were added dropwise over about 30 minutes. The temperature was further increased, and reflux started at about 90°C, and separation and distillation of water was observed in the water separator. Subsequently, the reaction was continued for about 6 hours under reflux until water distillation stopped. The amount of water distilled off was 21 parts. Next, the external temperature was set to 150°C. continue,
The pressure was reduced to 1 mmHg using a vacuum pump, and toluene and unreacted benzaldehyde were distilled off. The amount of reaction product (ALD-16) obtained after distillation was 2103 parts. In addition, as a result of measuring the infrared absorption spectrum of the obtained reaction product, it was found that 164
A characteristic absorption spectrum of -N=CH- was observed at 0 cm-1. Trialdimine ALD-16 has an amine value of 32 mgK
OH/g, and was a pale yellow liquid at room temperature.

Example 1 54 parts of ALD-2 and biuret-modified hexamethylene polyisocyanate (manufactured by Mitsui Toatsu Chemical Co., Ltd., trademark:
100 parts of Olester NP-1000 (NCO content: 17% by weight) were mixed, sealed tightly and stored at 50°C for 30 days, but almost no change in properties was observed.

After storage, it was applied to a thickness of 0.5 mm on a glass plate and left in an atmosphere of 50% relative humidity and 25° C., and the surface was cured in 1.5 hours. Orester NP
When only -1000 was treated in the same way, the surface did not harden even after 24 hours. Example 2 20 parts of ALD-3, 70 parts of dioctyl phthalate, polyoxypropylene glycol (PPG)/tolylene diisocyanate (TDI) based prepolymer (manufactured by Mitsui Toatsu Chemical Co., Ltd., trademark: Hypren P-305, containing NCO) amount, 2.8% by weight) were mixed, sealed, and 50 parts
Although it was stored at ℃ for 30 days, almost no change was observed in the properties.

After storage, it was coated on a glass plate to a thickness of 0.5 mm and left in an atmosphere of 50% relative humidity and 25° C., and the surface hardened in 1.5 hours. Hyprene P-
When only No. 305 was treated in the same manner, the surface did not harden even after 10 hours. Example 3 89 parts of ALD-11, trimethylolpropane adduct of TDI (manufactured by Mitsui Toatsu Chemical Co., Ltd., trademark: OLESTAR P45-75S, NCO content 11.6% by weight) 2
00 parts were mixed, sealed tightly and stored at 50°C for 30 days, but almost no change in properties was observed.

After storage, it was applied to a thickness of 0.5 mm on a glass plate and left in an atmosphere of 50% relative humidity and 25° C., and the surface was cured in 3 hours. Orester P45-
When only 75S was treated in the same manner, the surface did not harden even after 10 hours. Example 4 220 parts of ALD-16, trimethylolpropane adduct of TDI (manufactured by Mitsui Toatsu Chemical Co., Ltd., trademark: OLESTAR P45-75S, NCO content 11.6% by weight)
50 parts were mixed, sealed tightly and stored at 50°C for 30 days, but no change was observed.

After storage, it was applied to a thickness of 0.5 mm on a glass plate and left in an atmosphere of 50% relative humidity and 25° C., and the surface was cured in 3 hours. Orester P45-
When only 75S was treated in the same manner, the surface did not harden even after 10 hours. (Examples and Comparative Examples of Moisture-curable Polyurethane Waterproofing Materials) In Examples 5 to 10, moisture-curable polyurethane waterproofing materials were produced and evaluated.

Curing property: JIS-A5758 (1986)
The time required to become tack-free was measured according to Section 6-10.

Storage stability was determined by measuring the change in viscosity using a B-type rotational viscometer after the moisture-curing polyurethane waterproofing material was stored in a hermetically sealed manner for a certain period of time.

[0081] The mechanical properties of the waterproofing material cured after construction are as per JIS
- Measured by K6301. That is, after construction, the sample was left at 23°C and 50% relative humidity for 7 days, and the sample was further heated at 50°C.
The 100% elongation modulus, tensile strength, and elongation were measured when the sample was left for 7 days. The formulation and evaluation are shown in Table 1. For comparison, the formulations and evaluations of Comparative Examples 1 and 2 are also shown in the same table. Example 5 The following raw materials were used in the example.

Dialdimine: ALD synthesized in Synthesis Example 1
-1 Polyurethane prepolymer terminated with isocyanate groups: 598 parts of 2,4-tolylene diisocyanate and polyoxypropylene glycol (molecular weight 2000)
2600 parts and 1802 parts of polyoxypropylene triol (molecular weight 3000) were reacted at 100° C. for 10 hours. The terminal NCO group is 1.89% by weight, the viscosity is 41,
000 cps/25°C.

[0083] In a 3 liter planetary mixer, 200 parts of dioctyl phthalate, 600 parts of calcium carbonate,
50 parts of titanium oxide and 10 parts of a weathering stabilizer (manufactured by Ciba Geigy, Irganox 1010) were added and kneaded for 15 minutes at room temperature, followed by dehydration in a vacuum for 1 hour while kneading at 100°C. Next, 700 parts of prepolymer and 42 parts of dialdimine (ALD-1) were added and kneaded for 15 minutes at room temperature. Furthermore, 10 parts of an anti-settling agent (hydrophobic silica #R-972 manufactured by Nippon Aerosil Co., Ltd.) and 150 parts of toluene were added and kneaded in a vacuum at room temperature for 10 minutes to obtain a moisture-curable polyurethane waterproofing material of the present invention.

[0084] As shown in Table 1, this waterproof material had a short tack-free time and excellent curing properties. Further, the viscosity after sealed storage at 50° C. for 14 days was maintained at a good level for practical use, and the cured product after moisture curing had no foaming and had excellent physical properties. Example 6 In Example 5, dialdimine (
The treatment was carried out in exactly the same manner as in Example 5, except that 48 parts of ALD-3) was used.

As shown in Table 1, the tack-free time was short and the curing properties were excellent. Further, the viscosity after sealed storage at 50° C. for 14 days was good for practical use, and the cured product after moisture curing had no foaming and had excellent physical properties. Example 7 In Example 5, dialdimine (
The treatment was carried out in exactly the same manner as in Example 5, except that 52 parts of ALD-4) was used.

As shown in Table 1, the tack-free time was short and the curing properties were excellent. Further, the viscosity after sealed storage at 50° C. for 14 days was good for practical use, and the cured product after moisture curing had no foaming and had excellent physical properties. Example 8 In Example 5, dialdimine (
The treatment was carried out in exactly the same manner as in Example 5, except that 56 parts of ALD-5) was used.

As shown in Table 1, the results showed that the tack free time was short and the curing properties were excellent. Further, the viscosity after sealed storage at 50° C. for 14 days was good for practical use, and the cured product after moisture curing had no foaming and had excellent physical properties. Example 9 In Example 5, dialdimine (
The treatment was carried out in exactly the same manner as in Example 5, except that 50 parts of ALD-7) was used.

As shown in Table 1, the results showed that the tack-free time was short and the curing properties were excellent. Further, the viscosity after sealed storage at 50° C. for 14 days was good for practical use, and the cured product after moisture curing had no foaming and had excellent physical properties. Example 10 In Example 5, the same procedure as in Example 5 was carried out except that 67 parts of dialdimine (ALD-14) synthesized in Synthesis Example 14 was used.

As shown in Table 1, the tack-free time was short and the curing properties were excellent. Further, the viscosity after sealed storage at 50° C. for 14 days was good for practical use, and the cured product after moisture curing had no foaming and had excellent physical properties.

[0090] Furthermore, the compositions produced in Examples 5 to 10 were as follows:
Even after storage, it maintained its performance as a moisture-curing polyurethane flooring material. Comparative Example 1 In Synthesis Example 1, aromatic polyamine MD was used as the amine.
A-150 (polymeric methylene dianiline manufactured by Mitsui Toatsu Chemical Co., Ltd.) was treated in the same manner as in Synthesis Example 1 except that trimethylacetaldehyde was used as the aldehyde to obtain polyaldimine (ALD-17: amine value 299 mg).
KOH/g) was obtained.

Next, in Example 5, the same procedure as in Example 5 was carried out except that 54 parts of the above polyaldimine (ALD-17) was used.

As shown in Table 1, the tack free time was long and the curing properties were poor. Comparative Example 2 The same procedure as in Example 5 was carried out except that dialdimine was not used.

As shown in Table 1, the tack free time was extremely long and the curing properties were extremely poor. Moreover, the cured product after moisture curing was foamed and had poor mechanical properties, impairing its commercial value as a waterproof material.

[0094]

[Table 1] (Examples and Comparative Examples of Moisture Curing Polyurethane Sealing Materials) In Examples 11 to 16, moisture curing polyurethane sealing materials were produced and evaluated.

Curability is JIS-A5758 (1986)
The time required to become tack-free was measured according to Section 6-10.

Storage stability was determined according to JIS-K28 after the moisture-curing polyurethane sealant was stored in a sealed manner for a certain period of time.
08 (1961), the 1-second and 5-second values of penetration [1
0-1 mm] was measured.

The mechanical properties of the sealant cured after application were measured according to JIS-K6301. That is, after construction 23
C. and 50% relative humidity for 7 days, and the sample was further left at 50.degree. C. for 7 days, after which the 100% elongation modulus, tensile strength, and elongation were measured.

The formulation and evaluation are shown in Table 2. For comparison, the formulations and evaluations of Comparative Examples 3 and 4 are also shown in the same table. Example 11 The following raw materials were used in the example.

Dialdimine: ALD-3 isocyanate group-terminated polyurethane prepolymer synthesized in Synthesis Example 3: Prepolymer used in Example 5.

[0100] In a 3 liter planetary mixer, 390 parts of dioctyl phthalate, 450 parts of calcium carbonate,
50 parts of titanium oxide and 10 parts of a weathering stabilizer (manufactured by Ciba Geigy, Irganox 1010) were added and kneaded for 15 minutes at room temperature, followed by dehydration in a vacuum for 1 hour while kneading at 100°C. Next, 800 parts of prepolymer and 54 parts of dialdimine (ALD-3) were added, and 15 parts of
Kneaded in minutes. Additionally, 100 parts of a thixotropic agent (hydrophobic silica #R-972 manufactured by Nippon Aerosil Co., Ltd.) and 1 part of toluene were added.
70 parts were added and kneaded in vacuum at room temperature for 10 minutes to obtain a moisture-curable polyurethane sealing material of the present invention.

[0101] As shown in Table 2, this sealant had a shorter tack-free time and better curing properties than a sealant not containing aldimine. In addition, the viscosity after sealed storage at 50° C. for 14 days was good for practical use, and the cured product after application had no foaming and had excellent physical properties. Example 12 In Example 11, the same procedure as in Example 11 was carried out except that 64 parts of dialdimine (ALD-6) synthesized in Synthesis Example 6 was used.

[0102] As shown in Table 2, the tack free time was short and the curing properties were excellent. Further, the workability after sealed storage at 50° C. for 14 days was good, and the cured product after application had no foaming and had excellent physical properties. Example 13 In Example 11, the same procedure as in Example 11 was carried out except that 62 parts of dialdimine (ALD-8) synthesized in Synthesis Example 8 was used.

As shown in Table 2, the tack-free time was short and the curing properties were excellent. Further, the workability after sealed storage at 50° C. for 14 days was good, and the cured product after application had no foaming and had excellent physical properties. Example 14 In Example 11, the same procedure as in Example 11 was carried out except that 62 parts of dialdimine (ALD-9) synthesized in Synthesis Example 9 was used.

As shown in Table 2, the results showed that the tack-free time was short and the curing properties were excellent. Further, the workability after sealed storage at 50° C. for 14 days was good, and the cured product after application had no foaming and had excellent physical properties. Example 15 Example 11 except that 68 parts of dialdimine (ALD-10) synthesized in Synthesis Example 10 was used in Example 11.
was treated in exactly the same way.

As shown in Table 2, the tack-free time was short and the curing properties were excellent. Further, the workability after sealed storage at 50° C. for 14 days was good, and the cured product after application had no foaming and had excellent physical properties. Example 16 Example 11 except that 71 parts of dialdimine (ALD-13) synthesized in Synthesis Example 13 was used in Example 11.
was treated in exactly the same way.

As shown in Table 2, the tack-free time was short and the curing properties were excellent. Further, the workability after sealed storage at 50° C. for 14 days was good, and the cured product after application had no foaming and had excellent physical properties.

Furthermore, the compositions produced in Examples 11 to 16 retained their performance as moisture-curable polyurethane wall materials. Comparative Example 3 Dialdimine (ALD-18: amine value: 441 mgKOH/g) was obtained in the same manner as in Synthesis Example 1, except that hexamethylene diamine was used as the amine and trimethylacetaldehyde was used as the aldehyde.

Next, in Example 11, the same procedure as in Example 11 was carried out except that 42 parts of the above dialdimine (ALD-18) was used.

As shown in Table 2, the storage stability was very poor. Comparative Example 4 The same procedure as in Example 11 was carried out except that dialdimine was not used.

As shown in Table 2, the tack-free time was extremely long and the curing properties were extremely poor. Furthermore, the cured product after moisture curing was inferior in mechanical properties due to foaming.

In this example, a waterproofing material and a sealing material were produced, but since they have the same composition and can be used as flooring and walling materials as they are, and are cured in the same way, The description as an example will be omitted.

[0112]

[Table 2] (Examples and comparative examples of moisture-curable polyurethane paints) In Examples 17 and 18, moisture-curable polyurethane paints were produced and evaluated.

[0113] Curability is JIS-A5758 (1986)
The time required to become tack-free was measured according to Section 6-10.

Storage stability was determined by measuring the change in viscosity using a B-type rotational viscometer after storing the moisture-curing polyurethane paint in a sealed manner for a certain period of time.

[0115] The mechanical properties of the paint cured after application are JIS-
Measured using K6301. That is, after coating, the sample was left at 23° C. and 50% relative humidity for 7 days, and the sample was further left at 50° C. for 7 days, and the 100% elongation modulus, tensile strength, and elongation were measured.

[0116] The formulation and evaluation are shown in Table 3. For comparison, the formulation and evaluation of Comparative Example 5 are also shown in the same table.

[0117]

[Table 3] Example 17 The following raw materials were used in the example. Trialdimine: ALD-12 synthesized in Synthesis Example 12 Isocyanate group-terminated polyurethane prepolymer: Adduct of toluene diisocyanate and polyoxytetramethylene glycol (manufactured by Mitsui Toatsu Chemical Co., Ltd., Hypren L167, NCO% content 6.4%) In a 3-liter flask, 1000 parts of prepolymer, 201 parts of trialdimine (ALD-12), 600 parts of xylene, thixotropic agent (hydrophobic silica #R- manufactured by Nippon Aerosil Co., Ltd.)
972) and stirred at room temperature for 1 hour to obtain a moisture-curable polyurethane paint of the present invention.

[0118] As shown in Table 3, this paint had a short tack-free time and excellent curing properties. Also, 1 at 50℃
The viscosity after 4 days of sealed storage was good for practical use, and the cured product after moisture curing had no foaming and had excellent physical properties. Example 18 In Example 17, the same procedure as in Example 17 was carried out except that 256 parts of trialdimine (ALD-15) synthesized in Synthesis Example 15 was used.

[0119] As shown in Table 3, the tack-free time was short and the curing properties were excellent. Further, the workability after sealed storage at 50° C. for 14 days was good, and the cured product after moisture curing had no foaming and had excellent physical properties. Comparative Example 5 In Synthesis Example 1, 1,3,5-tris(
Aminomethyl) cyclohexane was treated in the same manner as in Synthesis Example 1 except that trimethylacetaldehyde was used as the aldehyde to obtain trialdimine (ALD-19: amine value 447 mgKOH/g).

Next, in Example 17, the same procedure as in Example 17 was carried out except that 174 parts of the above trialdimine (ALD-19) was used.

[0121] As shown in Table 3, the storage stability was very poor.

Claims (9)

[Claims] Claim 1: The following general formula (I) [Formula 1] (wherein, X represents an aryl group having 6 to 15 carbon atoms; Y represents a divalent or trivalent hydrocarbon group having 2 to 15 carbon atoms;
Or it represents a divalent or trivalent polyoxyalkylene group with a molecular weight of 70 to 6,000. n represents 2 or 3. ) and a polyurethane prepolymer having a polyisocyanate and/or a plurality of isocyanate groups. 2. The moisture-curable polyurethane composition according to claim 1, wherein Y is an amino residue of a diamine or triamine having a melting point of 50° C. or less. 3. Y is represented by the following general formula (II) (wherein Z is a hydrocarbon group having 6 to 13 carbon atoms and consisting of a divalent or trivalent cyclo ring, bicyclo ring, or tricyclo ring) The moisture-curable polyurethane composition according to claim 1, which is an amino residue of an amine represented by the following formula (n represents 2 or 3). 4. Y is isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, 2,5- or 2,
The moisture-curable polyurethane composition according to claim 1, which is an amino residue of 6-bis(aminomethyl)bicyclo[2,2,1]heptane. 5. A moisture-curable polyurethane waterproofing material comprising the moisture-curable polyurethane composition according to any one of claims 1 to 4 and a filler. 6. A moisture-curable polyurethane flooring comprising the moisture-curable polyurethane composition according to any one of claims 1 to 4 and a filler. 7. A moisture-curable polyurethane sealing material comprising the moisture-curable polyurethane composition according to any one of claims 1 to 4 and a thixotropic agent. 8. A moisture-curable polyurethane wall material comprising the moisture-curable polyurethane composition according to any one of claims 1 to 4 and a thixotropic agent. 9. A moisture-curable polyurethane paint comprising the moisture-curable polyurethane composition according to any one of claims 1 to 4.