JPH1160669A - One-package moisture-curing urethane composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition which exhibits excellent long-term storability at high temperatures by including an isocyanate-containing polyurethane prepolymer obtained by reacting a polyisocyanate compound with a polyoxyalkylene polyol having a specified hydroxyl value and a specified total unsaturation value and a latent curing agent. SOLUTION: This composition comprises a polyurethane prepolymer having an isocyanate content of 0.3-7.0 wt.% and obtained by reacting a polyisocyanate compound with a polyoxyalkylene polyol having a hydroxyl value OHV (mgKOH/g) of 5-60 and satisfying the formula: USV<= 1.2/OHV (wherein USV is the total unsaturation value (meq/g) and a latent curing agent which forms an amine upon hydrolysis. The polyocyalkylene polyol is obtained by polymerizing an alkylene oxide in the presence of a phosphazenium represented by formula I or II. In the formulae I, II, (a) to (g) are each 0.3; R is a 1-10C hydrocarbon group or the like; Z<x-> is an x-valent anion of an active hydrogen compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane resin composition used as a sealing material, a waterproof material, a wall material, a floor material, a paint, or an adhesive, and in particular, a one-part moisture-curable urethane composition having excellent long-term storage properties. About things.

[0002]

2. Description of the Related Art Polyurethane resins have excellent properties such as rubber elasticity, abrasion resistance, cold resistance, and durability.
In recent years, it has been particularly used as a sealing material, a waterproof material, a wall material, a floor material, a paint, and an adhesive. The production method of these polyurethane resins is that a one-pack type in which the terminal NCO group of the polyurethane prepolymer is cured by atmospheric moisture after the construction, and a curing agent containing the main component containing the polyurethane prepolymer and a polyol are applied. It is roughly classified into a two-pack type that mixes and cures when mixed.

[0003] The two-pack type is easy to control the curing speed, but it is necessary to measure each component at the time of construction and to stir and mix. Accordingly, there may be a case where the physical properties of the cured product are deteriorated or the curing is poor due to an error in the operation of the measurement and the stirring and mixing.

[0004] On the other hand, the one-pack type is easy to apply, but has disadvantages such as slow curing and foaming. As a method for remedying this drawback, a one-part moisture-curable composition containing a latent curing agent that produces an amine by hydrolysis has been devised.

[0005]

However, since these compositions tend to increase in viscosity during storage, when they are used after being stored for a long period of time, the compositions become highly viscous and discharge from the container is difficult. In some cases, it becomes difficult, the workability is reduced, or the work is not possible. In particular, as the temperature during storage is higher, the increase in viscosity becomes more remarkable. Therefore, when storing for a long period of time, it is necessary to store in a low-temperature warehouse or the like, which is also a factor of economical deterioration.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to improve the above problems, and as a result, the polyisocyanate compound and the hydroxyl value OHV (mgKOH / g) were 5 to 5.
60, and the total degree of unsaturation USV (meq / g) is represented by the following formula (1):

[0007]

Embedded image A one-pack moisture-curable urethane composition using a polyurethane prepolymer obtained by reacting with a polyoxyalkylene polyol satisfying USV ≦ 1.2 / OHV (1) is stored for a long time at a high temperature. It was found that even in the case where the composition was used, the viscosity of the composition did not increase and the composition was maintained at a low viscosity, so that the application was easy, and the cured material properties after the application were excellent.

Further, the present inventors have used a polyurethane prepolymer obtained by using a polyoxyalkylene polyol produced by polymerizing an alkylene oxide compound in the presence of a phosphazenium compound as the polyoxyalkylene polyol. Even with a one-part moisture-curable urethane composition, as described above, even when stored at a high temperature for a long period of time, the viscosity of the composition does not increase and the construction is easy to maintain because it has a low viscosity, and the cured product after construction They have found that they have excellent physical properties, and have completed the present invention. That is, the present invention provides the following (1) to (4). (1) (a) A polyisocyanate compound having a hydroxyl value OHV (mg KOH / g) of 5 to 60 and a total unsaturation USV (meq / g) of the following formula (1)

[0009]

Embedded image A polyurethane prepolymer having an isocyanate group obtained by a reaction with a polyoxyalkylene polyol satisfying USV ≦ 1.2 / OHV (1), and (b) a latent curing in which an amine is formed by hydrolysis. , A one-part moisture-curable urethane composition comprising: (2) (a) A polyisocyanate compound and the following general formula (2) [Chemical formula 10] or general formula (3) [Chemical formula 11]

[0010]

Embedded image

[0011]

Embedded image (However, a, b and c in the general formula (2) or d, e, f and g in the general formula (3) are each 0 or 3
The following positive integers are not all 0 at the same time. R
Is a same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. x represents the number of phosphazenium cations, and Z ^x- represents the x-valent anion of the active hydrogen compound. A) a polyurethane prepolymer having an isocyanate group obtained by reaction with a polyoxyalkylene polyol produced by polymerizing an alkylene oxide compound in the presence of a phosphazenium compound represented by One-part moisture-curable urethane composition comprising: a latent curing agent; (3) (a) A polyisocyanate compound and the following general formula (2) [Chemical formula 12] or the general formula (3) [Chemical formula 13]

[0012]

Embedded image

[0013]

Embedded image (However, a, b and c in the general formula (2) or d, e, f and g in the general formula (3) are each 0 or 3
The following positive integers are not all 0 at the same time. R
Is a same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. x represents the number of phosphazenium cations, and Z ^x- represents the x-valent anion of the active hydrogen compound. ) Is a polyoxyalkylene polyol produced by polymerizing an alkylene oxide compound in the presence of a phosphazenium compound represented by the formula (I), wherein the hydroxyl value OHV (mgK
OH / g) is 5 to 60, and the total degree of unsaturation is USV
(Meq / g) is represented by the following formula (1)

[0014]

Embedded image A polyurethane prepolymer having an isocyanate group obtained by reaction with a polyoxyalkylene polyol satisfying USV ≦ 1.2 / OHV (1), and (b) a latent curing in which an amine is formed by hydrolysis. , A one-part moisture-curable urethane composition comprising: (4) The latent curing agent which produces an amine by hydrolysis is represented by the following general formula (4):

[0015]

Embedded image Y-(— N ＝ CH—X) n (4) (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 a divalent or trivalent polyoxyalkylene group having a molecular weight of 70 to 6000. n represents 2 or 3. The one-part moisture-curable urethane composition according to any one of (1) to (3), which is a polyaldimine represented by the following formula (1).

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The polyurethane prepolymer having an isocyanate group used in the present invention is a polyisocyanate compound having a hydroxyl value OHV (mgKOH / g) of 5 to 5.
60, and the total degree of unsaturation USV (meq / g) is represented by the following formula (1):

Embedded image A polyoxyalkylene polyol satisfying USV ≦ 1.2 / OHV (1) is reacted by a known method so that free isocyanate groups remain. As the production method, it is produced by reacting a polyisocyanate compound with the above polyoxyalkylene polyol at 100 ° C. for several hours. The isocyanate group content is preferably from 0.3 to 7.0% by weight, and a particularly preferred range is from 0.5 to 5.0% by weight.

Here, the total degree of unsaturation (C = C) in the polyoxyalkylene polyol refers to an unsaturated group at a molecular terminal generated mainly by a side reaction of propylene oxide when a polyoxyalkylene polyol is synthesized. It is an index of the amount of monools. Since the monol has a low molecular weight as compared with the polyoxyalkylene polyol produced by the main reaction, the molecular weight distribution of the polyoxyalkylene polyol is significantly widened and the average number of functional groups is reduced. Therefore, when a polyoxyalkylene polyol having a high monol content is used, various physical properties such as an increase in hysteresis, a decrease in hardness and a decrease in elongation are caused. Therefore, monool (C = C)
Is preferably completely absent, if possible, but should be as small as possible.

Examples of the polyisocyanate used here 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, tetramethyl xylylene diisocyanate, naphthylene diisocyanate, dicyclohexyl methane 4.4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated xylene diisocyanate, 1.4 -Cyclohexyl diisocyanate, 1
-Methyl-2,4-diisocyanato-cyclohexane,
Diisocyanates such as 2,4,4-trimethyl-1,6-diisocyanato-hexane;

2) Triisocyanates such as 4,4'-4 "-triphenylmethane triisocyanate and tris (4-phenylisocyanato) thiophosphate; 3) Modified urethane-modified isocyanates and isocyanurates of the above-mentioned isocyanates Products, modified carbodiimidized products, modified buretized products, crude tolylene diisocyanate, polymethylene / polyphenyl isocyanate, etc., and polyhydric isocyanates.
V (mgKOH / g) is 5 to 60, and the total degree of unsaturation USV (meq / g) is represented by the following formula (1):

[0020]

Embedded image A polyoxyalkylene polyol satisfying USV ≦ 1.2 / OHV (1) is, for example, Zn ₃ [Co (CN) ₆ ] ₂ as described in JP-B-44-551. Metal cyanide complexes such as
It is obtained by adding an alkylene oxide to an active hydrogen compound using cesium hydroxide or a phosphazenium compound as described in JP-A-7-278289 as a catalyst.

In particular, when a phosphazenium compound is used as a catalyst, a metal component which adversely affects the reaction during the production of the polyurethane prepolymer or the physical properties of the cured product of the polyurethane composition, etc., is contained in the produced polyoxyalkylene polyol. Is more preferable since it does not remain in
It is not preferable to use a commonly used catalyst such as KOH because the total unsaturation is increased.

The polyoxyalkylene polyol obtained by using a phosphazenium compound as a catalyst in the present invention refers to an alkylene oxide compound in the presence of a phosphazenium compound represented by the general formula (2) or (3). Is a polyoxyalkylene polyol produced by polymerizing

The phosphazenium compound in the present invention is represented by the following general formula (2) [formula 18] or the general formula (3)
A salt of a phosphazenium cation having the structure represented by the following formula [Chemical Formula 19] and an active hydrogen compound anion, wherein the phosphazenium cation has an ultimate structural formula whose charge is localized on a central phosphorus atom. As a representative, countless other extreme structural formulas are drawn, and the charges are actually nonpolarized as a whole.

[0024]

Embedded image

[0025]

Embedded image (However, a, b and c in the general formula (2) or d, e, f and g in the general formula (3) are each 0 or 3
The following positive integers are not all 0 at the same time. R
Is a same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. x represents the number of phosphazenium cations, and Zx- represents an x-valent anion of the active hydrogen compound. )

A, b and c in the phosphazenium compound represented by the general formula (2) are each a positive integer of 0 or 3 or less, preferably 0 or 2 or less. More preferably, regardless of the order of a, b and c, (2, 1, 1), (1, 1, 1), (0, 1, 1)
Or a number in the combination of (0, 0, 1). D in the phosphazenium compound represented by the general formula (3),
e, f and g are each a positive integer of 0 or 3 or less, and preferably a positive integer of 0 or 2 or less. More preferably, regardless of the order of d, e, f and g,
(2, 1, 1, 1), (1, 1, 1, 1), (0, 1,
1, 1), (0, 0, 1, 1) or (0, 0, 0, 1)
Is the number in the combination. More preferably,
(1,1,1,1), (0,1,1,1), (0,0,
1, 1) or (0, 0, 0, 1).

R in the phosphazenium compound represented by the general formula (2) or (3) is the same or different and is an aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms. Typically, this R is, for example, methyl, ethyl, normal-propyl, isopropyl, allyl, normal-butyl, sec-butyl, tert-butyl,
-Butenyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, isopentyl, tert
-Pentyl, 3-methyl-2-butyl, neopentyl,
Normal-hexyl, 4-methyl-2-pentyl, cyclopentyl, cyclohexyl, 1-heptyl, 3-heptyl, 1-octyl, 2-octyl, 2-ethyl-1-
Aliphatic or aromatic such as hexyl, 1,1-dimethyl-3,3-dimethylbutyl (commonly called tert-octyl), nonyl, decyl, phenyl, 4-toluyl, benzyl, 1-phenylethyl or 2-phenylethyl Selected from the hydrocarbon groups of Of these, methyl, ethyl, normal-propyl, isopropyl, tert-butyl,
tert-pentyl or 1,1-dimethyl-3,3
-An aliphatic hydrocarbon group having 1 to 10 carbon atoms such as dimethylbutyl is preferable, and a methyl group or an ethyl group is more preferable.

Further, when two Rs on the same nitrogen atom in the phosphazenium compound represented by the general formula (2) or (3) are bonded to each other to form a ring structure, The divalent group (RR) is a divalent hydrocarbon group having a main chain having 4 to 6 carbon atoms (the ring is a 5- to 7-membered ring containing a nitrogen atom), for example, tetramethylene , Pentamethylene or hexamethylene, and the main chain thereof is substituted with an alkyl group such as methyl or ethyl. Preferably, it is tetramethylene or pentamethylene. Such a ring structure may be used for all possible nitrogen atoms in the phosphazenium cation, or a part thereof may be used. X in the phosphazenium compound represented by the general formula (2) or (3)
Is not uniform depending on the type of active hydrogen compound, but usually 1
To 8, preferably 1.

The phosphazenium compound represented by the general formula (2) or (3) is, for example, a salt and an activity of the phosphazenium cation and the inorganic anion in the general formula (2) or (3). A method of reacting a salt of a hydrogen compound with an alkali metal or alkaline earth metal, or a salt of a phosphazenium cation in the general formula (2) or (3) with an anion of another active hydrogen compound and active hydrogen It can be obtained by a method of reacting a compound. The phosphazenium compound represented by the general formula (2) is, for example, a compound represented by the following general formula (5)

[0030]

Embedded image (In the formula, a, b and c are each a positive integer of 0 or 3 or less, but not all 0 at the same time. R is the same or different and is a hydrocarbon group having 1 to 10 carbon atoms.) In some cases, two Rs on the same nitrogen atom may be bonded to each other to form a ring structure.) And an active hydrogen compound. In addition, general formula (2) or general formula (3)
Any method may be used as long as the method obtains the phosphazenium compound represented by

The active hydrogen compound in the present invention is a compound having an active hydrogen atom on an oxygen atom, for example, water, for example, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, lauric acid, stearic acid, oleic acid. Acid, phenylacetic acid, dihydrocinnamic acid, cyclohexanecarboxylic acid,
A carboxylic acid having 1 to 20 carbon atoms such as benzoic acid, paramethylbenzoic acid or 2-carboxynaphthalene, for example, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, itaconic acid, butanetetracarboxylic acid 2 to 20 carbon atoms such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid or pyromellitic acid
Polycarboxylic acids having 2 to 6 carboxyl groups, for example, N, N-diethylcarbamic acid,
N-carboxypyrrolidone, N-carboxyaniline,
Carbamic acids such as N, N'-dicarboxy-2,4-toluenediamine; for example, methanol, ethanol, normal-propanol, isopropanol, normal-butyl alcohol, sec-butyl alcohol;
tert-butyl alcohol, isopentyl alcohol, tert-pentyl alcohol, normal-octyl alcohol, lauryl alcohol, cetyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol, crotyl alcohol, methylvinylcarbinol, benzyl alcohol, 1-phenyl Alcohols having 1 to 20 carbon atoms such as ethyl alcohol, triphenylcarbinol or cinnamyl alcohol; for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol,
1,3-propanediol, 1,3-butanediol,
1,4-butanediol, 1,6-hexanediol,
C2-C2 such as 1,4-cyclohexanediol, trimethylolpropane, glycerin, diglycerin, pentaerythritol or dipentaerythritol
Polyhydric alcohols having 0 to 2 hydroxyl groups, such as sugars such as glucose, sorbitol, dextrose, fructose or sucrose or derivatives thereof, such as phenol, 2-naphthol, 2,6-dihydroxy Aromatic compounds having 1 to 3 hydroxyl groups having 6 to 20 carbon atoms, such as naphthalene or bisphenol A, such as polyethylene oxide, polypropylene oxide or copolymers thereof, having 2 to 8 terminals. And polyalkylene oxides having 1 to 8 hydroxyl groups at their terminals.

Furthermore, the active hydrogen compound in the present invention is a compound having an active hydrogen atom on a nitrogen atom, such as methylamine, ethylamine, normal-propylamine, isopropylamine, normal-butylamine, isobutylamine, sec. -Butylamine, t
tert-butylamine, cyclohexylamine, benzylamine, β-phenylethylamine, aniline, o-
Aliphatic or aromatic primary amines having 1 to 20 carbon atoms such as toluidine, m-toluidine or p-toluidine, such as dimethylamine, methylethylamine, diethylamine, di-normal-propylamine,
Aliphatic or aromatic secondary amines having 2 to 20 carbon atoms such as ethyl-normal-butylamine, methyl-sec-butylamine, dipentylamine, dicyclohexylamine, N-methylaniline or diphenylamine, for example, ethylenediamine, di ( 2-aminoethyl) amine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, tri (2-aminoethyl) amine, N, N'-dimethylethylenediamine, N, N'-
2 to 3 carbon atoms having 2 to 20 carbon atoms such as diethylethylenediamine or di (2-methylaminoethyl) amine;
Polyamines having a primary or secondary amino group, such as pyrrolidine, piperidine, morpholine or 1,2,3,4-tetrahydroquinoline.
To 20 saturated cyclic secondary amines having 4 to 20 carbon atoms such as 3-pyrroline, pyrrole, indole, carbazole, imidazole, pyrazole or purine.
Unsaturated cyclic secondary amines such as piperazine, pyrazine, 1,4,7-triazacyclononane and the like. Trivalent amines such as acetamido, propionamido, N-methylpropionamido,
Unsubstituted or N-methyl having 2 to 20 carbon atoms such as N-methylbenzoic acid amide or N-ethylstearic acid amide
Monosubstituted acid amides such as 2-pyrrolidone, ε
And 5- to 7-membered cyclic amides such as caprolactam, for example, imides of dicarboxylic acids having 4 to 10 carbon atoms such as succinimide, maleic imide or phthalimide.

Of these active hydrogen compounds, preferred is water, for example, methanol, ethanol, normal-propanol, isopropanol, normal-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol.
Butyl alcohol, isopentyl alcohol, tert
-Pentyl alcohol, normal-octyl alcohol, lauryl alcohol, cetyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol,
Alcohols having 1 to 20 carbon atoms such as crotyl alcohol, methyl vinyl carbinol, benzyl alcohol, 1-phenylethyl alcohol, triphenyl carbinol or cinnamyl alcohol; for example, ethylene glycol, propylene glycol, diethylene glycol, Propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, trimethylolpropane, glycerin, diglycerin, pentaerythritol or Polyhydric alcohols having 2 to 8 carbon atoms and having 2 to 8 hydroxyl groups, such as dipentaerythritol, such as glucose, sorbitol, dextrose, fructose or sucrose. Saccharides and derivatives thereof, such as polyethylene oxide, polypropylene oxide and copolymers thereof, having 2 to 8 terminals and having a molecular weight of 100 to 50, having 1 to 8 hydroxyl groups at the terminals. 000 polyalkylene oxides, for example, ethylenediamine, di (2-aminoethyl) amine, hexamethylenediamine, 4,4 ′
-Diaminodiphenylmethane, tri (2-aminoethyl) amine, N, N'-dimethylethylenediamine,
N, N'-diethylethylenediamine or poly (amine) having 2 to 3 carbon atoms and having 2 or 3 primary or secondary amino groups such as di (2-methylaminoethyl) amine, for example, pyrrolidine, piperidine , Morpholine or 1,2,3,4-tetrahydroquinoline or other saturated cyclic secondary amines having 4 to 20 carbon atoms, such as piperazine, pyrazine or 1,4,7-triazacyclononane. Cyclic polyvalent amines containing 4 to 20 2 to 3 secondary amino groups.

Among these active hydrogen compounds, water is more preferable, for example, methanol, ethanol, normal-propanol, isopropanol, normal-
Butyl alcohol, sec-butyl alcohol, ter
t-butyl alcohol, isopentyl alcohol, te
alcohols having 1 to 10 carbon atoms, such as rt-pentyl alcohol and normal-octyl alcohol;
For example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4
-Polyhydric alcohols having 2 to 10 carbon atoms and having 2 to 4 hydroxyl groups, such as butanediol, trimethylolpropane, glycerin or pentaerythritol, such as polyethylene oxide, polypropylene oxide or copolymers thereof; 2 to 6
Polyalkylene oxides having a molecular weight of 100 to 10,000 and having 2 to 6 hydroxyl groups at the terminals, such as N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine or di ( Polyhydric amines having 2 to 3 carbon atoms and having 2 to 3 secondary amino groups such as 2-methylaminoethyl) amine, such as piperazine, pyrazine,
4 to 20 carbon atoms such as 4,7-triazacyclononane
Cyclic polyamines containing two or three secondary amino groups.

Among these active hydrogen compounds, water is more preferable, and examples thereof include water such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, trimethylolpropane, glycerin, and pentaerythritol. Polyhydric alcohols having 2 to 4 hydroxyl groups having 2 to 10 carbon atoms, such as polyethylene oxide, polypropylene oxide or copolymers thereof, having 2 to 6 terminals and having 2 to 6 terminals Having a molecular weight of 100 to 10,000 having one hydroxyl group
00 polyalkylene oxides.

As the alkylene oxide compound in the present invention, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methylglycidyl Epoxy compounds such as ether, allyl glycidyl ether and phenyl glycidyl ether. These may be used in combination of two or more. When used in combination, a method of simultaneously using a plurality of alkylene oxide compounds,
A method of sequentially using the method or a method of repeating the method may be employed. Among these alkylene oxide compounds, ethylene oxide, propylene oxide, 1,2
-Butylene oxide or styrene oxide is preferred, ethylene oxide and propylene oxide are more preferred.

For the polymerization reaction of the alkylene oxide compound,
The amount of the phosphazenium compound used is not particularly limited.
However, the amount is not limited to 1 mole of the alkylene oxide compound.
Always 1 × 10^-15~ 5 × 10^-1Mol, preferably 1 × 10
^-7~ 1 × 10^-2Range of moles. In addition, the reaction of the polymerization reaction
The reaction temperature depends on the alkylene oxide compound used and other
Although not uniform depending on the type and amount of the components, usually 150 ° C
Or less, preferably 10 to 130 ° C., more preferably
Is in the range of 50 to 120C. The pressure during the reaction is
Types of alkylene oxide compounds and other components used
Or not uniform depending on the amount or polymerization temperature,
Normally, the pressure during the polymerization reaction is 30 kg / cm ^Two(Absolute
Pressure, hereinafter the same), preferably 0.1 to 15 k
g / cm^Two, More preferably 1 to 10 kg / cm^TwoRange
It is.

The latent curing agent which forms an amine by hydrolysis in the present invention is, for example, enamine (UK Patent 1).
575666), polyaldimine or polyketimine (British Patent No. 1064841, German Patent No. 313369)
JP-A-2-283710, JP-A-4-279
620), β-lactam (JP-A-2-168) and oxazolidine (JP-A-2-55715).
And so on. In particular, a polyaldimine represented by the following general formula (4) disclosed in JP-A-4-279620 is a one-pack moisture-curable urethane composition containing the same as a latent curing agent. Is excellent in the balance of properties such as curability, storage properties and physical properties of the cured product, and is most preferable.

[0039]

Embedded image Y-(— N ＝ CH—X) n (4) (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 a divalent or trivalent polyoxyalkylene group having a molecular weight of 70 to 6000. n represents 2 or 3. )

The polyaldimine represented by the general formula (4) is obtained by subjecting a polyamine and an aldehyde described in detail below to an azeotropic dehydration reaction using a solvent such as toluene or xylene under an acid catalyst. This is obtained by performing the reaction and continuing the reaction until the distillation of water into the water droplet separator stops. The ratio of the polyamine to the aldehyde is preferably from 1 to 2 equivalents of the aldehyde to the amine equivalent.

The polyamine used for producing the polyaldimine represented by the general formula (4) includes: 1) ethylenediamine, 1,3-diaminopropane, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine , Decamethylenediamine, etc., aliphatic diamines, 4,4′-diaminodicyclohexylmethane, isophoronediamine, bisaminomethylcyclohexane, 2,5- or 2,6-
Diamino methyl bicyclo [2.2.1] heptane, diaminocyclohexane, 3 (4), 8 (9) - bis (aminomethyl) - tricyclo [5.2.1.0 ^2.6] alicyclic diamines decane, Propylene oxide and / or aromatic diamine such as diaminodiphenylmethane, diaminodiphenylether, xylylenediamine, phenylenediamine, 3,5-diethyltoluene-2,4- or 2,6-diamine, water, ethylene glycol, propylene glycol, etc. Diamines such as polyoxyalkylene diamines obtained by converting hydroxyl groups of polyoxyalkylene glycols obtained by addition polymerization of ethylene oxide into amino groups, 2) 1,3,5-tris (aminomethyl) benzene,
Conversion of hydroxyl groups of polyoxyalkylene triols obtained by addition polymerization of propylene oxide and / or ethylene oxide to triamine such as 1,3,5-tris (aminomethyl) cyclohexane, glycerin, trimethylolpropane, etc., to amino groups And triamines such as polyoxyalkylene triamines.

Examples of the aldehyde to be reacted with the polyamine include, for example, benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde,
-Ethylbenzaldehyde, 4-propylbenzaldehyde, 4-butylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde, p-anisaldehyde, p-ethoxybenzaldehyde and the like.

In the present invention, the one-pack moisture-curable urethane composition contains a latent curing agent for producing an amine by hydrolysis and a polyurethane prepolymer having an isocyanate group. The latent curing agent and the polyurethane prepolymer having an isocyanate group have a ratio of the number of amino groups of the polyamine formed by hydrolysis of the latent curing agent to the number of isocyanate groups contained in the polyurethane prepolymer having the isocyanate group. (The number of amino groups / the number of isocyanate groups) is blended at a ratio of 0.5 to 2.0, preferably 0.7 to 1.5.

The one-part moisture-curable urethane composition used in the present invention may contain a filler, a thixotropy-imparting agent, a plasticizer, a solvent, an adhesion-imparting agent, and a coloring agent for adjusting viscosity, resin properties, resistance and curing speed. By mixing agents, stabilizers, fungicides, organic acids, and the like, products such as sealing materials, waterproofing materials, wall materials, flooring materials, paints, and adhesives can be obtained.

The method of blending these is not particularly limited, and may be simply mixed or other known methods such as adding necessary additives such as a filler, a plasticizer, a thixotropic agent, and other auxiliaries. After stirring and mixing using a mixer such as a planetary mixer or a dissolver, a polyurethane prepolymer having an isocyanate group and a latent curing agent may be added and sufficiently mixed. When the water content of various additives is high, it is necessary to perform dehydration in advance or to add a dehydrating agent such as zeolite. The one-pack moisture-curable urethane composition thus obtained is stored in a sealed can in a nitrogen atmosphere.

[0046]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In addition, in an Example, a part shows a weight part.

[Production of Polyol] The polyols used are shown below. The polyols A to F use a phosphazenium compound catalyst, the polyols G and H use a hexacyanocobalt zinc complex catalyst, the polyols I and J use a cesium hydroxide catalyst, and the polyols K and L use a potassium hydroxide catalyst. It is a polyol produced by the above method.

484 g of dipropylene glycol (3.6 g) was placed in a 1-L eggplant-shaped flask equipped with a polyol A stirrer, a nitrogen inlet tube and a thermometer.
1 mol), and dimethylaminotris [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide {[(Me ₂ N) ₃ P =
_{N] 3 (Me 2 N)} P + OH -} and 27.01 g (0.0
43 mol). This was heated to 100 ° C., the pressure was reduced to 5 mmHg while stirring, and water produced by the reaction was removed by flowing dry nitrogen. Mono {dimethylaminotris [tris (dimethylamino) phosphoranylideneamino] phosphonium} salt} [(Me ₂ N) ₃ P = N of excess dipropylene glycol and the phosphazenium compound contained therein, dipropylene glycol ]
^{_{3 (Me 2 N) P +}} Dpg -} to give a mixture of (Dpg ^-
Represents a monovalent anion of dipropylene glycol).

The entire mixture was charged into a similar 5 L autoclave. After that, the inside of the reactor was replaced with dry nitrogen,
The temperature was raised to 80 ° C. and 2920 g of propylene oxide (5
The reaction was carried out at 80 ° C. for 12 hours while intermittently supplying 0.34 mol) to keep the pressure during the reaction at about 3.8 kg / cm ² (absolute pressure, the same applies hereinafter). Then 10m at the same temperature
After reducing the pressure to mHg and maintaining this pressure for 30 minutes to remove residual propylene oxide, the pressure was returned to normal pressure with dry nitrogen, and the content was cooled to room temperature (first stage). In order to further increase the molecular weight, 828 g of a part of the content was transferred to a similar 5 L autoclave, the inside of the reactor was replaced with dry nitrogen, the temperature was raised to 80 ° C., and 1932 g of propylene oxide (33 .30 mol) at a reaction pressure of 3.8 k
g / cm ² while intermittently supplying 80
The reaction was carried out at 24 ° C. for 24 hours (second stage). Then at the same temperature 3
It was kept at 10 mmHg for 0 minutes. Thereafter, the inside of the reactor was replaced with dry nitrogen to return to normal pressure. As a result of the two-stage reaction, 2,721 g of polyoxypropylene diol (polyol A), which is a polymer of propylene oxide, was obtained.
The hydroxyl value of the polyol was 37.3 mgKOH / g, and the total degree of unsaturation was 0.011 meq / g.

Polyol B 428 g of catalyst-containing polyoxypropylene diol obtained in the first stage polymerization reaction of polyol A was transferred to a similar 5 L autoclave, and 2478 g of propylene oxide (42. 73mo
l) was reacted at 80 ° C. for 24 hours while intermittently supplying so that the pressure during reaction was maintained at about 3.8 kg / cm ² . Then, the temperature was kept at 10 mmHg for 30 minutes at the same temperature. afterwards,
The inside of the reactor was replaced with dry nitrogen to return to normal pressure, and 2807 g of polyoxypropylene diol (polyol B) which was a polymer of propylene oxide was obtained. The polyol has a hydroxyl value of 18.7 mgKOH / g and a total unsaturation of 0.0
It was 21 meq / g.

Polyol C 423 g of catalyst-containing polyoxypropylene diol obtained in the first-stage polymerization reaction of polyol A was transferred to a similar 5 L autoclave, and in order to increase the molecular weight,
The reaction was carried out at 80 ° C. for 24 hours while intermittently supplying 2158 g (37.20 mol) of propylene oxide so as to keep the reaction pressure around 3.8 kg / cm ² . Then, the temperature was kept at 10 mmHg for 30 minutes at the same temperature. Thereafter, the inside of the reactor was replaced with dry nitrogen to return to normal pressure (second stage). To further increase the molecular weight, 834 g of part of the contents
Was transferred to a similar 5 L autoclave, the inside of the reactor was replaced with dry nitrogen, the temperature was raised to 80 ° C., and 1557 g (26.85 mol) of propylene oxide was further kept at about 3.8 kg / cm ² during the reaction. At 80 ° C. for 24 hours with intermittent supply as described above. Then at the same temperature 30
It was kept at 10 mmHg for minutes. Thereafter, the inside of the reactor was replaced with dry nitrogen to return to normal pressure (third stage). Thus, in a three-stage reaction, 2298 polyoxypropylene diol (polyol C), which is a polymer of propylene oxide, was added.
g was obtained. The hydroxyl value of the polyol is 7.5 mg KOH /
g, the total degree of unsaturation was 0.033 meq / g.

In a 300 ml eggplant flask equipped with a polyol D stirrer and a thermometer, 112 g (1.22 mol) of glycerin was weighed, and 1- (1,1,3,3-tetramethylbutyl manufactured by Fluka) was added thereto. ) -2,2-Bis [tris (dimethylamino) phosphoranylideneamino] -4,4,4-tris (dimethylamino) -2λ ⁵ , 4λ ⁵ -catenadi (phosphazene) ｛[(Me ₂ N) ₃ P = N] ₃ P = Nt-
After adding 10.1 g (0.015 mol) of C ₈ H ₁₇ }, the mixture was heated and stirred at 80 ° C. for 2 hours to obtain an excess of glycerin and glycerin mono {1,1,3,3, a phosphazenium compound contained therein. 3-tetramethylbutyl amino tris [tris (dimethylamino) phosphoranylideneamino Rani isopropylidene amino] phosphonium} salt _{{[(Me 2 N) 3} P = N] 3
A mixture of (tC ₈ H ₁₇ NH) P ⁺ Gly ⁻を 得 was obtained (Gly ⁻ represents a monovalent anion of glycerin).

The whole amount of the mixture was subjected to 2 liters equipped with a temperature measuring tube, a pressure gauge, a stirrer, and an alkylene oxide introducing tube.
In an autoclave. The inside of the reactor was replaced with dry nitrogen, and the temperature was raised to 80 ° C.
g (18.10 mol) at a reaction pressure of 3.8 kg / cm
² at 80 ° C with intermittent supply to keep around ²
Allowed to react for hours. Then, at the same temperature, 10 mmHg for 30 minutes
Then, the pressure was returned to normal pressure with dry nitrogen, and the content was cooled to room temperature (first stage). To further increase the molecular weight, the contents were transferred to a 5 L autoclave equipped with a temperature measuring tube, a pressure gauge, a stirrer, and an alkylene oxide introducing tube, and the inside of the reactor was replaced with dry nitrogen, and the temperature was raised to 80 ° C. do it,
Further, 2619 g of propylene oxide (45.16 mo
l) was reacted at 80 ° C. for 24 hours while intermittently supplying so that the pressure during reaction was maintained at about 3.8 kg / cm ² . Then, it was kept at 10 mmHg at the same temperature for 30 minutes (second
Stage). Thereafter, the inside of the reactor was replaced with dry nitrogen to return to normal pressure. As a result of the two-stage reaction, 3669 g of polyoxypropylene triol (polyol D), which is a polymer of propylene oxide, was obtained. The polyol has a hydroxyl value of 55.9 mgKOH / g and a total unsaturation of 0.007.
meq / g.

355 g (3.86 mol) of glycerin was weighed and placed in a 1-L eggplant-shaped flask equipped with a polyol E stirrer, a nitrogen inlet tube and a thermometer, and tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium was added thereto. Converting the hydroxide {[(Me ₂ N) ₃ P = N] ₄ P ⁺ OH ⁻ } to 34.
97 g (0.046 mol) were added. This was heated to 100 ° C., and while being stirred, the pressure was reduced to 5 mmHg, and dried nitrogen was passed to remove generated water. Mono {tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium} salt [[(Me ₂ N) ₃ P = N] ₄ P ⁺ Gly ^{− of} excess glycerin and phosphazenium compound glycerin contained therein Was obtained.

The entire amount of the mixture was charged into a similar 5 L autoclave. After that, the inside of the reactor was replaced with dry nitrogen,
The temperature was raised to 80 ° C. and 3170 g of propylene oxide (5
(4.66 mol) at 80 ° C. for 12 hours while intermittently supplying so as to maintain a pressure during reaction at about 3.8 kg / cm ² . Then, the temperature was maintained at 10 mmHg at the same temperature for 30 minutes, and the pressure was returned to normal pressure with dry nitrogen, and the content was cooled to room temperature (first stage). To further increase the molecular weight, 216 g of a part of the content was transferred to a similar 5 L autoclave, the inside of the reactor was replaced with dry nitrogen, the temperature was raised to 80 ° C., and 2329 g of propylene oxide (40 .16m
ol) at 80 ° C. for 24 hours while intermittently supplying so as to maintain a pressure during reaction at about 3.8 kg / cm ² .
Then, the temperature was kept at 10 mmHg for 30 minutes at the same temperature. Thereafter, the inside of the reactor was replaced with dry nitrogen to return to normal pressure (second pressure).
Stage). As a result of the two-stage reaction, 2,429 g of polyoxypropylene triol (polyol E), which is a polymer of propylene oxide, was obtained. The polyol has a hydroxyl value of 16.8 mg KOH / g and a total unsaturation of 0.024.
meq / g.

Polyol F 409 g of catalyst-containing polyoxypropylene triol obtained in the first stage polymerization reaction of polyol E was transferred to a similar 5-liter autoclave, and the molecular weight was increased in order to increase the molecular weight.
The reaction was carried out at 80 ° C. for 24 hours while intermittently supplying 1886 g (32.51 mol) of propylene oxide so as to maintain a pressure during reaction at about 3.8 kg / cm ² . Then, the temperature was kept at 10 mmHg for 30 minutes at the same temperature. Thereafter, the inside of the reactor was replaced with dry nitrogen to return to normal pressure (second stage). To further increase the molecular weight, 826 g of a part of the contents
Was transferred to the same 5 L autoclave, the inside of the reactor was replaced with dry nitrogen, the temperature was raised to 80 ° C., and 1831 g (31.57 mol) of propylene oxide was further kept at about 3.8 kg / cm ² during the reaction. At 80 ° C. for 24 hours with intermittent supply as described above. Then at the same temperature 30
It was kept at 10 mmHg for minutes. Thereafter, the inside of the reactor was replaced with dry nitrogen to return to normal pressure (third stage). Thus, in a three-stage reaction, polyoxypropylene triol (polyol F), which is a polymer of propylene oxide, was added to 254
7 g were obtained. The hydroxyl value of the polyol is 11.3 mg KO
H / g and the total degree of unsaturation were 0.030 meq / g.

Polyol G Polyoxypropylene diol (polyol G) having a hydroxyl value of 19.1 mgKOH / g and a total degree of unsaturation of 0.009 meq / g was obtained by a known method using a hexacyanocobalt zinc complex catalyst.

Polyol H Polyoxypropylene triol (polyol H) having a hydroxyl value of 22.5 mgKOH / g and a total degree of unsaturation of 0.011 meq / g was obtained by a known method using a hexacyanocobalt zinc complex catalyst.

Polyol I A hydroxyl value of 19.3 mg KOH / g and a total degree of unsaturation of 0.048 me were obtained by a known method using a cesium hydroxide catalyst.
q / g of polyoxypropylene diol (polyol I) was obtained.

Polyol J A hydroxyl value of 17.2 mg KOH / g and a total degree of unsaturation of 0.056 me were obtained by a known method using a cesium hydroxide catalyst.
q / g of polyoxypropylene triol (polyol J) was obtained.

Polyol K A hydroxyl value of 37.1 mg KOH / g and a total degree of unsaturation of 0.050 me by a known method using a potassium hydroxide catalyst.
q / g of polyoxypropylene diol (polyol K) was obtained.

Polyol L A hydroxyl value of 32.2 mgKOH / g and a total degree of unsaturation of 0.053 me were obtained by a known method using a potassium hydroxide catalyst.
q / g of polyoxypropylene triol (polyol L) was obtained.

[Evaluation Method] The storability was evaluated by placing the one-part moisture-curable urethane composition in a closed container, storing it at 50 ° C. for 30 days, and measuring the viscosity with a B-type rotational viscometer.

The mechanical properties of the cured composition after application were determined by JI
It was measured by S-K6301. That is, 23 ° C after construction,
Tensile strength and elongation were measured when left for 7 days in a relative humidity of 50% and further left for 7 days at 50 ° C.

Example 1 According to the method described in JP-A-4-279620, tetramethylenediamine and p-tolualdehyde were subjected to a dehydration-condensation reaction, and dialdimine (A-1: an amine value of 381 mg) was used.
KOH / g). Next, 36 parts of 2,4-tolylene diisocyanate, 215 parts of polyol C, and 749 parts of polyol F were reacted at 100 ° C. for 10 hours,
A polyurethane prepolymer (P-1) having an isocyanate group was obtained. The terminal NCO groups of the prepolymer were 1.0% by weight.

In a 3 liter planetary mixer, 200 parts of dioctyl phthalate, 650 calcium carbonate
The mixture was kneaded at room temperature for 20 minutes, followed by dehydration for 1 hour under reduced pressure while kneading at 100 ° C. next,
700 parts of the polyurethane prepolymer (P-1) and 24 parts of dialdimine (A-1) were added and kneaded at room temperature for 20 minutes. Further, 10 parts of an antisettling agent (hydrophobic silica manufactured by Nippon Aerosil Co., Ltd .: trade name Aerosil # R-972),
150 parts of xylene was added and kneaded at room temperature under reduced pressure for 20 minutes to obtain a one-part moisture-curable urethane composition of the present invention.

The one-part moisture-curable urethane composition had a low viscosity after storage at 50 ° C. for 30 days as shown in Table 1, and was excellent in long-term storage at high temperatures. In addition, mechanical properties such as tensile strength and elongation were also good.

Example 2 According to the method described in JP-A-4-279620, polyoxypropylene triamine (Texaco Che
manufactured by Medical Company, trademark: JEFFAMI
(NET-403, molecular weight 440) and p-isopropylbenzaldehyde were subjected to a dehydration condensation reaction to obtain trialdimine (A-2: an amine value of 304 mgKOH / g).

Next, 51 parts of 2,4-tolylene diisocyanate, 579 parts of polyol G,
371 parts with 100 ° C. for 10 hours to give a polyurethane prepolymer having isocyanate groups (P-2)
I got 1.0% by weight of terminal NCO groups of the prepolymer
Met.

The procedure of Example 1 was repeated except that 700 parts of (P-2) were used as the polyurethane prepolymer and 30 parts of (A-2) were used as the latent curing agent.
To obtain a one-part moisture-curable urethane composition of the present invention.

As shown in Table 1, the one-part moisture-curable urethane composition had a low viscosity after storage at 50 ° C. for 30 days, and was excellent in long-term storage at high temperatures. In addition, mechanical properties such as tensile strength and elongation were also good.

Example 3 According to the method described in JP-A-2-168,
Bis {3,3-dimethyl-2-oxo-1- [3- (2
-(2-ethoxyethoxy) ethoxycarbonylaminomethyl) benzyl] azetidin-4-yl} piperazine was synthesized, and β-lactam (A-3: amine value 133 mg)
KOH / g).

Next, 67 parts of 2,4-tolylene diisocyanate, 432 parts of polyol B,
501 parts was reacted at 100 ° C. for 10 hours, and a polyurethane prepolymer having an isocyanate group (P-3)
I got 2.0% by weight of terminal NCO groups of the prepolymer
Met.

Next, in the same manner as in Example 1 except that 700 parts of (P-3) was used as the polyurethane prepolymer and 140 parts of (A-3) was used as the latent curing agent. Thus, a one-part moisture-curable urethane composition of the present invention was obtained.

As shown in Table 1, the one-part moisture-curable urethane composition had a low viscosity after storage at 50 ° C. for 30 days and was excellent in long-term storage at high temperatures. In addition, mechanical properties such as tensile strength and elongation were also good.

Example 4 According to the method described in JP-A-4-279620, diaminomethylbicyclo [2.2.1] which is a mixture of about 60% of the 2,5-isomer and about 40% of the 2,6-isomer is used. Heptane and benzaldehyde were subjected to a dehydration condensation reaction to obtain dialdimine (A-4: amine value: 337 mgKOH / g).

Next, 67 parts of 2,4-tolylene diisocyanate, 285 parts of polyol I, and polyol J
648 parts at 100 ° C. for 10 hours, and a polyurethane prepolymer having an isocyanate group (P-4)
I got 2.0% by weight of terminal NCO groups of the prepolymer
Met.

Next, the procedure of Example 1 was repeated except that 700 parts of (P-4) were used as the polyurethane prepolymer and 55 parts of (A-4) were used as the latent curing agent.
To obtain a one-part moisture-curable urethane composition of the present invention.

As shown in Table 1, the one-part moisture-curable urethane composition had a low viscosity after storage at 50 ° C. for 30 days, and was excellent in long-term storage at high temperatures. In addition, mechanical properties such as tensile strength and elongation were also good.

Example 5 137 parts of 2,4-tolylene diisocyanate, 713 parts of polyol A, and 150 parts of polyol D
The reaction was carried out at 00 ° C. for 10 hours to obtain a polyurethane prepolymer (P-5) having an isocyanate group. The terminal NCO groups of the prepolymer were 4.0% by weight.

Next, in Example 1, 700 parts of (P-5) was used as a polyurethane prepolymer, and bisoxazolidine (A-5: manufactured by MILES, trade name HARDENER OZ, amine number 230 m) was used as a latent curing agent.
(gKOH / g) Except for using 162 parts, a one-part moisture-curable urethane composition of the present invention was obtained in the same manner as in Example 1.

As shown in Table 1, the one-part moisture-curable urethane composition had a low viscosity after storage at 50 ° C. for 30 days and was excellent in long-term storage at high temperatures. In addition, mechanical properties such as tensile strength and elongation were also good.

Comparative Example 1 70 parts of 2,4-tolylene diisocyanate, 404 parts of polyol K, and 525 parts of polyol L
The reaction was carried out at 0 ° C. for 10 hours to obtain a polyurethane prepolymer (P-6) having an isocyanate group. The terminal NCO groups of the prepolymer were 1.0% by weight.

Next, the procedure of Example 1 was repeated except that 700 parts of (P-6) were used as the polyurethane prepolymer and 24 parts of (A-1) were used as the latent curing agent.
To obtain a one-part moisture-curable urethane composition.

As shown in Table 1, this one-part moisture-curable urethane composition has a high viscosity after being stored at 50 ° C. for 30 days, and its workability is extremely poor when stored for a long time at a high temperature. there were. Also, mechanical properties such as tensile strength and elongation were inferior.

Comparative Example 2 90 parts of 2,4-tolylene diisocyanate, 387 parts of polyol K, and 523 parts of polyol L
The reaction was carried out at 0 ° C. for 10 hours to obtain a polyurethane prepolymer (P-7) having an isocyanate group. The terminal NCO groups of the prepolymer were 2.0% by weight.

Next, the procedure of Example 1 was repeated except that 700 parts of (P-7) were used as the polyurethane prepolymer and 55 parts of (A-4) were used as the latent curing agent.
To obtain a one-part moisture-curable urethane composition.

As shown in Table 1, this one-part moisture-curable urethane composition has a high viscosity after being stored at 50 ° C. for 30 days, and its workability is extremely poor when stored at a high temperature for a long period of time. there were. Also, mechanical properties such as tensile strength and elongation were inferior.

Comparative Example 3 129 parts of 2,4-tolylene diisocyanate, 345 parts of polyol K, and 526 parts of polyol L
The mixture was reacted at 00 ° C. for 10 hours to obtain a polyurethane prepolymer (P-8) having an isocyanate group. The terminal NCO groups of the prepolymer were 4.0% by weight.

Next, in the same manner as in Example 1, except that 700 parts of (P-8) was used as the polyurethane prepolymer and 162 parts of (A-5) were used as the latent curing agent. Thus, a one-part moisture-curable urethane composition was obtained.

As shown in Table 1, this one-part moisture-curable urethane composition has a high viscosity after being stored at 50 ° C. for 30 days, and its workability is extremely poor when stored for a long time at a high temperature. there were. Also, mechanical properties such as tensile strength and elongation were inferior.

[0092]

[Table 1]

[0093]

[Table 2]

[0094]

According to the present invention, in a one-pack moisture-curable urethane composition containing a latent curing agent which produces an amine by hydrolysis and a polyurethane prepolymer having an isocyanate group, a polyisocyanate compound is used. ,
A hydroxyl value OHV (mgKOH / g) of 5 to 60,
And the total degree of unsaturation USV (meq / g) is USV ≦ 1.2
/ OHV polyoxyalkylene polyol,
Alternatively, in the presence of a phosphazenium compound, by using a polyurethane prepolymer having an isocyanate group obtained by the reaction with a polyoxyalkylene polyol produced by polymerizing an alkylene oxide compound, the composition for a long time at high temperature Even when stored,
Since the viscosity does not increase and the viscosity is kept low, a one-part moisture-curable urethane composition that is easy to discharge from a container, easy to apply, and has excellent cured properties after application can be obtained.
In addition, even when stored at a high temperature for a long period of time, it is not necessary to store in a low-temperature warehouse or the like, which is excellent in economy.

Claims (4)

[Claims] 1. A polyisocyanate compound having a hydroxyl value OHV (mg KOH / g) of 5 to 60 and a total unsaturation USV (meq / g) of the following formula (1): ## STR1 ## Embedded image A polyurethane prepolymer having an isocyanate group obtained by a reaction with a polyoxyalkylene polyol satisfying USV ≦ 1.2 / OHV (1), and (b) a latent curing agent that forms an amine by hydrolysis. And a one-part moisture-curable urethane composition. 2. A polyisocyanate compound (a) and the following general formula (2) [formula 2] or general formula (3) [formula 3] Embedded image (However, a, b and c in the general formula (2) or d, e, f and g in the general formula (3) are each 0 or 3
The following positive integers are not all 0 at the same time. R
Is a same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. x represents the number of phosphazenium cations, and Z ^x- represents the x-valent anion of the active hydrogen compound. A) a polyurethane prepolymer having an isocyanate group obtained by reaction with a polyoxyalkylene polyol produced by polymerizing an alkylene oxide compound in the presence of a phosphazenium compound represented by One-part moisture-curable urethane composition comprising: a latent curing agent; (A) a polyisocyanate compound and the following general formula (2) [formula 4] or general formula (3) [formula 5] Embedded image (However, a, b and c in the general formula (2) or d, e, f and g in the general formula (3) are each 0 or 3
The following positive integers are not all 0 at the same time. R
Is a same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. x represents the number of phosphazenium cations, and Z ^x- represents the x-valent anion of the active hydrogen compound. ) Is a polyoxyalkylene polyol produced by polymerizing an alkylene oxide compound in the presence of a phosphazenium compound represented by the formula (I), wherein the hydroxyl value OHV (mgK
OH / g) is 5 to 60, and the total degree of unsaturation is USV
A polyurethane prepolymer having an isocyanate group obtained by reaction with a polyoxyalkylene polyol whose (meq / g) satisfies the following formula (1): [Chemical formula 6] USV ≦ 1.2 / OHV (1) A one-part moisture-curable urethane composition comprising: (b) a latent curing agent that produces an amine by hydrolysis. 4. A latent curing agent which generates an amine by hydrolysis is represented by the following general formula (4): ## STR7 ## Y-(-N = CH-X) n (4) (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 a divalent or trivalent polyoxyalkylene group having a molecular weight of 70 to 6000. n represents 2 or 3. The one-part moisture-curable urethane composition according to any one of claims 1 to 3, which is a polyaldimine represented by the following formula: