JPH09143174A - Enamine compound, production of urethane prepolymer modified with enamine, urethane resin composition and composition for waterproofing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new enamine compound providing a moisture-curable urethane resin excellent in storage stability in a closed container, curable with moisture in the atmosphere free from foaming of a cured material. SOLUTION: This enamine compound is a compound which has an alicyclic enamine structure containing an N atom of an aliphatic tertiary amine as a constituent site in the molecular structure of the amine and another substituent group bonded to the N atom, as a functional group having a structure of a hydroxyl group and an alkylene group, such as a compound of the formula (R1 and R2 are each a hydroxyl group-containing hydrocarbon, another hydrocarbon, the sum of the carbon atoms of the hydrocarbon is 3-32, R1 and R2 are not another hydrocarbon at the same time; Y is a straight-chain or branched- chain 2-8C alkylene; E is an electrophilic compound residue; B is H, a 1-6C alkyl, etc.) such as diethyl-2-(N-methyl-3-amino-1-propanol-N-yl)-1- cyclohexenyl-1,3-dipropionate. The compound, for example, is obtained by reacting a condensation product of an aliphatic cyclic secondary amino-alcohol and an alicyclic ketone with an electrophilic compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an enamine compound which is a novel substance capable of producing a secondary amino alcohol by hydrolysis, a urethane resin composition using the compound, and a composition for a waterproof material using the composition. Regarding things.

Further, the present invention relates to an enamine compound, which is a compound which produces a secondary amino alcohol by hydrolysis, and is useful as a curing agent for epoxy resins or urethane resins. Further, the present invention relates to moisture in air. Is a moisture-curable urethane resin composition that utilizes a reaction of hydrolyzing with water to generate a secondary amino group, and is used as a sealing material for construction or vehicles, wall material, waterproof material, paint, or adhesive. The present invention relates to a urethane resin composition that is useful for industrial purposes, and further, the present invention is a waterproof composition which is a mixture of the urethane resin composition and a filler and is moisture-curable and excellent in storage stability. It is about things.

[0003]

2. Description of the Related Art Urethane resins are excellent in various properties such as rubber elasticity, abrasion resistance and durability and are used as sealing materials, wall materials, waterproof materials, paints or adhesives.

Such a urethane resin is a one-pack type in which a polyurethane prepolymer having a terminal isocyanate group is cured by water in the atmosphere after construction, and a curing agent containing a main chain containing a polyurethane prepolymer having a terminal isocyanate group and a polyol chain. The agent is roughly divided into a two-component type that mixes and cures at the time of construction, but the former one-component polyurethane can be used by anyone because of the simple construction method.
Recently, it has become particularly noticeable.

This one-pack type polyurethane is called a moisture-curable polyurethane, and the most common one is a method of reacting polyisocyanate with moisture (moisture). In this method, the addition of isocyanate and moisture is used. In addition to the problem that carbon dioxide gas was generated and the cured product foamed, the curability was also extremely poor.

Therefore, conventionally, as a moisture-curable urethane resin composition having good curability without generating gas during curing, Japanese Patent Laid-Open No. 4-279620 discloses a polyamine and an aromatic aldehyde. There is disclosed a moisture-curable urethane resin composition in which a polyaldimine obtained by reacting with is mixed with a urethane resin as a curing agent.

[0007]

However, the above-mentioned Japanese Patent Application Laid-Open No.
The moisture-curable urethane resin composition described in JP-A-279620 has good curability and can prevent foaming of the cured product, but has poor storage stability in a closed container and gel. However, there is a problem in that it leads to increase in viscosity and increase in viscosity.

[0008] The problem to be solved by the present invention is that the curing in an atmospheric humidity is moderately fast, it is not accompanied by foaming, and it is stored in a closed container for a long time with a constant viscosity. The present invention provides a moisture-curable urethane resin composition which is excellent in so-called storage stability, a novel enamine compound constituting the composition, an enamine-modified urethane prepolymer, and a waterproof material composition.

[0009]

Means for Solving the Problems As a result of intensive studies by the present inventors, a urethane resin composition was obtained by modifying a urethane polymer with an enamine compound, which is a novel substance that produces a secondary amino group by hydrolysis. It was found that the above problem can be solved by using one component, and the present invention has been completed.

That is, the present invention has an alicyclic enamine structure having a nitrogen atom of the amine as a constituent site in the molecular structure of the aliphatic tertiary amine, and is bonded to the nitrogen atom. A novel enamine compound, wherein the other substituent is a functional group having a structure having a hydroxyl group and an alkylene group,

A method for producing an enamine-modified urethane prepolymer, which comprises reacting the novel enamine compound with a urethane prepolymer,

A urethane resin composition comprising the enamine-modified urethane prepolymer and the urethane prepolymer as essential components, and the urethane resin composition and a filler as essential components. The present invention relates to a waterproof material composition.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The enamine compound which is a novel substance of the present invention has an alicyclic enamine structure having a nitrogen atom of the amine as a constituent site in the molecular structure of the aliphatic tertiary amine. Further, the other substituent bonded to the nitrogen atom is a functional group having a structure having a hydroxyl group and an alkylene group. In the enamine compound, the hydroxyl group reacts with isocyanate groups present at both ends of the urethane polymer to form a urethane bond, and the alicyclic enamine structure is hydrolyzed by moisture (water) to give a secondary amino group. Is generated. That is, the novel enamine compound in the present invention can modify the isocyanate groups at both terminals of the urethane prepolymer to generate a prepolymer having an enamine structure at both terminals, and by coexisting this with the urethane prepolymer. The urethane resin composition that exhibits the above-described excellent performance can be obtained.

Such a novel enamine compound is preferably one in which the carbon atom forming the enamine structure does not have an active hydrogen atom from the viewpoint of good storage stability particularly when it is used as a urethane resin composition. .

As a specific example thereof, particularly preferably, one represented by the following general formula 1 or general formula 2 can be mentioned.

[0016]

Embedded image

(In the formula, R1 and R2 are a hydroxyl group-containing hydrocarbon group or another hydrocarbon group, and the total number of carbon atoms thereof is 3 to 22.
However, R1 and R2 do not become other hydrocarbon groups at the same time. Y is a linear or branched alkylene group having 2 to 8 carbon atoms, E is a residue of an electrophilic compound, B is a hydrogen atom, a linear branched group having 1 to 6 carbon atoms. Alternatively, it is a cyclic alkyl group or a residue of an electrophilic compound. )

[0018]

Embedded image

(In the formula, R3 and R4 are each a carbon atom number of 1 to 1.
3 is a hydrocarbon group, and R5 is a hydrocarbon group having 1 to 15 carbon atoms. X is a carbon atom or a nitrogen atom, Y is a linear or branched alkylene group having 2 to 8 carbon atoms, E is a residue of an electrophilic compound,
B is a hydrogen atom, a linear branched or cyclic alkyl group having 1 to 6 carbon atoms, or a residue of an electrophilic compound. )

Specific examples of the structure represented by the general formula 1 or the general formula 2 are not particularly limited and may include all the structures derived from the raw material components described below. First, as general formula 1, diethyl-
2- (N-methyl-3-amino-1-propanol-N
-Yl) -1-cyclohexenyl-1,3-dipropionate, diethyl-2- (N-methyl-3-amino-2)
-Methyl-1-propanol-N-yl) -1-cyclohexenyl-1,3-dipropionate, diethyl-2
-(N-methyl-4-amino-1-butanol-N-yl) -1-cyclohexenyl-1,3-dipropionate, diethyl-2- (N-methyl-4-amino-2-methyl-1-propanol) -N-yl) -1-cyclohexenyl-1,3-dipropionate, diethyl-2-
(N-Methyl-3-amino-1-propanol-N-yl) -1-methylcyclohexenyl-1,3-dipropionate, diethyl-2- (N-methyl-3-amino-)
2-Methyl-1-propanol-N-yl) -1-methylcyclohexenyl-1,3-dipropionate, N,
N'-diphenyl-2- (N-methyl-3-amino-1
-Propanol-N-yl) -1-cyclohexenyl-
1,3-dicarboxamide, N, N'-diphenyl-
2- (N-methyl-3-amino-2-methyl-1-propanol-N-yl) -1-cyclohexenyl-1,3
-Dicarboxamide, etc., and the general formula 2
As diethyl-2- (1- (N-hydroxyethyl) piperazinyl) -1-cyclohexenyl-1,3
-Dipropionate, diethyl-2- (4-hydroxypiperidinyl) -1-cyclohexenyl-1,3-dipropionate, diethyl-2- (2,2,6,6-tetramethyl-4-hydroxypiperidine) -1- Cyclohexenyl-1,3-dipropionate, diethyl-2
-(1- (N-hydroxyethyl) piperazinyl)-
1-methylcyclohexenyl-1,3-dipropionate, diethyl-2- (4-hydroxypiperidinyl)
-1-Methylcyclohexenyl-1,3-dipropionate, dimethyl-2- (1- (N-hydroxyethyl)
Piperazineyl) -1-cyclohexenyl-1,3-dipropionate, N, N′-diphenyl-2- (1-
(N-Hydroxyethyl) piperazineyl) -1-cyclohexenyl-1,3-carboxamide, N, N′-
Diphenyl-2- (4-hydroxypiperidinyl)-
1-cyclohexenyl-1,3-dicarboxamide and the like can be mentioned.

The method for producing such a novel enamine compound is not particularly limited, but it is a condensate obtained by reacting an aliphatic branched or cyclic secondary amino alcohol with an alicyclic ketone. And a method of reacting an electrophilic compound.

The branched or cyclic secondary amino alcohol used in the production of the novel enamine compound of the present invention, for example, the branched secondary amino alcohol, has 3 to 22 carbon atoms. N-alkyl-substituted alkanolamines are preferred, specifically N-methyl-3-amino-1-propanol, N-methyl-4-amino-1.
-Butanol, N-methyl-3-amino-2-methyl-
1-propanol, N-methyl-4-amino-2-methyl-1-butanol, N-methyl-6-amino-1-hexanol and the like can be mentioned. However, when produced from N-alkyl-substituted amino (alkyl) ethanol, isomer 1,3-oxazolidine may be produced.

As the cyclic secondary amino alcohol,
An alicyclic aminoalcohol having 1 to 15 carbon atoms constituting the alcohol moiety and having 3 to 22 total carbon atoms is preferable, and specifically, 4-hydroxypiperidine, 2,2,2. Amino alcohols having an alicyclic structure such as 6,6-tetramethyl-4-hydroxypiperidine and piperidine-4-carboxylic acid, 1-hydroxyalkyl (C2-3) -2-alkyl (C0-1) piperazine, N -(Hydroxyethyl) piperazine, N- [2-
Examples thereof include amino alcohols having a nitrogen atom in the cyclic structure such as [2- (hydroxyethoxy) ethyl]] piperazine.

Next, the cyclic ketone used in the reaction with the secondary amino alcohol is not particularly limited, but those having 4 to 10 carbon atoms are used as the hydrolyzate of the obtained novel enamine compound. Preferred from the viewpoint of easy decomposition, such alicyclic ketone compounds include, for example, specifically cyclopentanone, methylcyclopentanone,
Examples include monoalicyclic ketones such as dimethylcyclopentanone, cyclohexanone, methylcyclohexanone, dimethylhexanone, ethylhexanone, cycloheptanone, methylcycloheptanone, dimethylcycloheptanone (including isomers and various mixtures of isomers). To be Among these, those having a cyclohexane ring such as cyclohexanone, methylcyclohexanone, dimethylhexanone, and ethylhexanone are preferable because the above-mentioned hydrolyzability becomes better.

Next, as the electrophilic compound used in the reaction, a compound having an acrylic group such as (meth) acrylic acid or its ester or acrylonitrile,
Examples thereof include isocyanate compounds, acetyl compounds, alkyl halides, allyl halides and acid halides.

Specific examples of the compound having an acrylic group include acrylic acid, methacrylic acid, acrylic acid or methacrylic acid methyl ester, ethyl ester, propyl ester, butyl ester or allyl ester,
Acrylonitrile and the like can be mentioned. Further, in these compounds, the hydrogen atom on the carbon at the 1-position or 2-position of the acrylic group may be substituted with a methyl group, a nitro group, a cyano group or the like.

Specific examples of the isocyanate compound include monoisocyanates such as phenyl isocyanate, o-tolyl isocyanate, P-tolyl isocyanate, methyl isocyanate and butyl isocyanate,
Aromatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, partially carbodiimidated diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, and fats Use is made of a monoisocyanate obtained by reacting an aromatic diisocyanate, an alicyclic diisocyanate, or a mixture of two or more thereof with a compound having active hydrogen, such as a secondary amine or a primary or secondary alcohol. it can.

Examples of the acetyl compound include acetic anhydride. Further, as the alkyl halide, the allyl halide, and the acid halide, the respective residues are -R (R
Represents an alkyl _{group), - CH 2 CH = CH} 2, -CO
R (R represents an alkyl group) is mentioned.

Among these electrophilic compounds, esters of (meth) acrylic acid are particularly preferable because they are excellent in storage stability in the case of a urethane resin composition.

As a specific method for producing the novel enamine compound of the present invention, for example, the above secondary amino alcohol and the above alicyclic ketone are used in a solvent such as cyclohexane, benzene, toluene or xylene. An alicyclic enamine, which is a condensate, is obtained by performing a dehydration reaction by azeotropic distillation, and the above electrophilic compound is further added dropwise with stirring to carry out the reaction. In this case, the substituents corresponding to the substituent E and the substituent B in the general formula 1 and the general formula 2 are introduced into two carbon atoms adjacent to the 1-position of the cycloalkene ring of the alicyclic enamine. When the alicyclic ketone already has a substituent on one of the two carbon atoms adjacent to the 1-position, for example, when methylhexanone is used, the methyl group corresponds to the substituent B. Therefore, only the substituent E is introduced by the electrophilic compound.

As described above, the urethane prepolymer used in the present invention is used as an enamine-modified prepolymer by reacting with the novel enamine compound, and at the same time, as a urethane resin composition, it is used in combination with the enamine-modified prepolymer. Urethane prepolymer is used. in this case,
The modifying urethane prepolymer and the urethane prepolymer used as one component of the composition may be the same or different.

As such a urethane prepolymer,
It is a compound having two or more isocyanate groups, and a prepolymer prepared by a conventional method with an organic polyisocyanate and an organic polyhydroxyl compound in excess of isocyanate, and the organic polyisocyanate itself can be used, but viscosity, cured product strength From the standpoint of the performance of the cured product such as elongation, and the like, a prepolymer prepared by the conventional method using the former organic polyisocyanate and organic polyhydroxyl compound in excess of isocyanate is preferred.

As the organic polyisocyanate, 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, partially carbodiimidated diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene Aromatic diisocyanates such as diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate and cyclohexane diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate and alicyclic diisocyanates. These organic polyisocyanates can be used as one kind or as a mixture of two or more kinds in any case where they are reacted with an organic polyhydroxyl compound and when they are used as a prepolymer component as they are.

Examples of the organic polyhydroxyl compound used in the present invention include polyether polyol, polyester polyol and other polyols. Also,
For example, a polyol produced using a metal cyanide compound as a catalyst can also be used. These organic polyhydroxyl compounds can be arbitrarily selected and used according to the intended use of the composition, but particularly when used as the waterproofing material composition of the present invention, viscosity, cured product strength, elongation, etc. From the viewpoint of the characteristics of (1), it is preferable to use the polyether polyol in combination with another polyol.

Examples of the polyether polyol include one or more polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, glucose, sorbitol and sucrose, and propylene oxide and ethylene. Examples thereof include polyols obtained by adding one kind or two or more kinds of oxide, butylene oxide, styrene oxide and the like. Among these, a polyether polyol obtained by adding ethylene oxide to propylene glycol is preferable because it has a low viscosity when formed into a composition and has excellent elongation of a cured product.

As the polyester polyol, ethylene glycol, propylene glycol, butanediol,
One or more of pentanediol, hexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane or other low molecular weight polyols and glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, Dimer acid,
Examples thereof include condensation polymers with hydrogenated dimer acid or one or more low molecular weight dicarboxylic acids and oligomer acids, and ring-opening polymers such as propiolactone, caprolactone and valerolactone.

Other polyols include polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, acrylic polyol and the like. Further, low molecular weight polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol glycerin, trimethylolpropane, glucose, sorbitol and sucrose are also included. Among these, ethylene glycol, diethylene glycol, and trimethylolpropane are preferable because the cured product has particularly good strength.

The urethane prepolymer obtained by reacting the above-mentioned organic polyisocyanate with an organic polyhydroxyl compound preferably has an average molecular weight of 500 to 10,000. That is, when the average molecular weight is 500 or more, the cured product has excellent elongation and strength, while when the average molecular weight is 10,000 or less, the viscosity of the composition is low.

Next, in the present invention, an enamine-modified urethane prepolymer can be obtained by reacting the above-mentioned novel enamine compound with a urethane prepolymer. The reaction conditions are not particularly limited, but the equivalent ratio of the hydroxyl group and the isocyanate group (OH /
NCO) = 0.5 to 2 is preferable from the viewpoint of curability and storage stability.

The urethane resin composition of the present invention contains the reaction product of the novel enamine compound described above and the urethane prepolymer and the urethane prepolymer as essential components. The reaction method of the novel enamine compound and the urethane prepolymer is not particularly limited, and examples thereof include a method of mixing and heating theoretical amounts of both.

In the composition of the present invention, the abundance ratio of the reaction product of the enamine compound and the urethane prepolymer to the urethane prepolymer is not particularly limited, but is not limited to the isocyanate group in the urethane prepolymer. , The equivalent ratio with the amino group in the enamine compound, NCO
It is preferable that the ratio is /N=0.1 to 100.

The urethane resin composition of the present invention comprises a plasticizer,
You may use together a stabilizer, a hardening catalyst, etc. As a plasticizer,
Examples thereof include dibutyl phthalate and dioctyl phthalate, and examples of the stabilizer include antioxidants, ultraviolet absorbers and the like. Examples of the catalyst include tertiary amines and organometallic compounds.

The polyurethane resin composition of the present invention is used as a sealing material for construction or vehicles, wall material, waterproof material, paint,
Alternatively, it can be used as an adhesive or the like. It is especially useful as a waterproof material.

The waterproof material composition of the present invention contains the above-mentioned urethane resin composition and a filler as an essential component.

Examples of the filler include calcium carbonate, titanium oxide, calcium hydroxide, calcium oxide, talc, clay, aluminum sulfate, vinyl chloride paste resin and the like. These may be surface-treated,
They can be used alone or in combination.

[0046]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples. Parts in Examples are parts by weight.

<Synthesis of Urethane Prepolymer> Synthesis Example 1 1501 parts of polyoxypropylene glycol (molecular weight 3000) and 3095 parts of polyoxypropylene triol (molecular weight 5000) produced with potassium hydroxide catalyst and 2,4-tolylene diisocyanate 404 copies and 10
A urethane prepolymer was obtained by reacting at 0 ° C. for 10 hours. Hereinafter, this is referred to as a urethane prepolymer a. Terminal N
CO group is 1.5%, viscosity is 59,000 cps / 25 ° C
Met.

Synthesis Example 2 Polyoxypropylene glycol (molecular weight 2000) 1750 produced using a complex metal cyanide complex as a catalyst
Parts and polyoxyethylene propylene triol (molecular weight 7000) 1990 parts, diphenylmethane diisocyanate 655 parts and xylene 489 parts at 100 ° C.
The reaction was carried out for a time to obtain a urethane prepolymer. Hereinafter referred to as urethane prepolymer b. The terminal NCO group is 2.3%,
The viscosity was 5000 cps / 25 ° C.

<Synthesis of Enamine Derivative Intermediate> Synthesis Example 3 130.2 parts (1.0 mol) of N- (hydroxyethyl) piperazine, 117.8 parts (1.2 mol) of cyclohexanone and 220 parts of toluene were mixed, and water drops were added. Heat under nitrogen using a separator. After 20 hours half of the water had separated and after 35 hours the calculated amount of water had separated. When the solvent toluene was distilled off, a brown transparent liquid was obtained. When the infrared absorption spectrum was measured, characteristic absorption of enamine was observed at 1640 cm ^-1 . The amine equivalent weight was 210. The purity is 9 by gas chromatography.
2.3%. This product is N-cyclohexenyl-N- (hydroxyethyl) piperazine, abbreviated as CPE.

Synthetic Example 4 The procedure of CPE was repeated except that N-methyl-3-amino-1-propanol was used instead of N- (hydroxyethyl) piperazine of Synthetic Example 3, and a brown transparent liquid was obtained. was gotten. When the infrared absorption spectrum was measured, characteristic absorption of enamine was observed at 1640 cm ^-1 . The amine equivalent weight was 169. The purity was 93.2% as determined by gas chromatography. The product is N-cyclohexenyl-N-methyl-3-amino-1-propanol, abbreviated as CPA.

<Synthesis of Comparative Ketimine Compound> Synthesis Example 5 The same operation as in CPE was performed except that ethylenediamine was used in place of N- (hydroxyethyl) piperazine in Synthesis Example 3 and salicylaldehyde was used in place of cyclohexanone. As a result, a brown transparent liquid was obtained. When the infrared absorption spectrum was measured, a characteristic absorption of aldimine was observed at 1670 cm ^-1 . The amine equivalent weight was 134. The purity is 9 by gas chromatography.
2.2%. This product is N, N'-disalicylidene ethylenediamine, and is abbreviated as SEA.

<Synthesis of Enamine Compound> Example 1 CPE 202.1 parts (0.96 mol) and methanol 4
Add 00 parts to the reaction vessel and add ethyl acrylate 230.8
Part (2.31 mol) was added to the dropping funnel, the dropping was started while stirring at 60 ° C. in a nitrogen stream while paying attention to heat generation, and the dropping was carried out for 0.5 hours. After the dropping, stirring was continued under reflux for 24 hours. When cooled to room temperature and desolvated under reduced pressure, a brown transparent liquid was obtained. Measurement of the infrared absorption spectrum, was observed a characteristic absorption of an ester to ^1740cm-1, characteristic absorption of enamine was observed in ^1640cm-1. The amine equivalent weight was 411. This infrared absorption spectrum is shown in FIG. The abbreviation of this product, diethyl-2- (1- (N-hydroxyethyl) piperazinyl) -1-cyclohexenyl-1,3-dipropionate, is CPE-EA.

Example 2 In Example 1, phenylisocyanate was used in place of ethyl acrylate, toluene was used in place of methanol, and the same reaction was carried out to obtain a brown transparent liquid. . When the infrared absorption spectrum was measured, characteristic absorption of enamine was observed at 1640 cm ^-1 .
The amine equivalent weight was 449. This product, N, N'-
The abbreviation for diphenyl-2- (1- (N-hydroxyethyl) piperazinyl) -1-cyclohexenyl-1,3-carboxamide is CPE-PI.

Example 3 The same operation as in Example 1 was carried out except that CPA was used instead of CPE, and a brown transparent liquid was obtained. Measurement of the infrared absorption spectrum, characteristic absorption of enamine obtained ^1640cm-1, hydroxyl group characteristic absorption was observed at 3350 cm ^-1. The amine equivalent weight was 369. This product, diethyl-2-
The abbreviation for (N-methyl-3-amino-1-propanol-N-yl) -1-cyclohexenyl-1,3-dipropionate is CPA-EA.

<Reaction of Enamine Compound with Urethane Prepolymer> Example 4 411 parts (1 equivalent) of the CPE-EA obtained above and 2800 parts (1 equivalent) of the urethane prepolymer a were mixed to obtain 10
Heated at 0 ° C. for 2 hours. The obtained enamine-modified urethane prepolymer is designated as CPE-EA-a.

Examples 5 to 9 In the same manner as in Example 4, those obtained from CPE-EA and urethane prepolymer b were designated as "CPE-EA-b",
The one obtained from CPE-PI and urethane prepolymer a is "CPE-PI-a", and the one obtained from CPE-PI and urethane prepolymer b is "CPE-PI-."
b ", those obtained from CPA-EA and urethane prepolymer a are" CPA-EA-a ", those obtained from CPA-EA and urethane-b are" CPA-EA-b ".
And

<Preparation and Evaluation of Urethane Resin Composition> Example 10 CPE-EA-a (1 equivalent), urethane prepolymer a (1 equivalent) and salicylic acid (0.3 equivalent) were mixed, sealed and sealed at room temperature for 6 months. It was stored, but no change was observed. After storage, it was applied on a glass plate and left at room temperature in a room with a relative humidity of 50% to cure in 2 hours.

Examples 11 to 15 Similar to Example 10, CPE-EA-b and CPE-PI.
-A, CPE-PI-b, CPA-EA-a, CPA-E
1 equivalent each of A-b and urethane prepolymer a, b
The ingredients were blended according to Table 1 so that the ratio of each was 1 equivalent and 0.3 equivalent of salicylic acid. For each of the formulations of Examples, the increase in viscosity was measured when the container was sealed and stored at room temperature for 6 months. On the other hand, each formulation was applied on a glass plate immediately after the formulation, allowed to stand at room temperature in a room with a relative humidity of 50%, and the curing time was measured. The results are shown in Table 1.

Comparative Examples 1 and 2 According to Table 1, 1 equivalent of SEA obtained in Synthesis Example 5, 1 equivalent of each of urethane prepolymers a and b, and 0.3 equivalent of salicylic acid were mixed. did. For each formulation, the increase in viscosity and the curing time were measured as in Examples 11-15. Table 1 shows the results.

[0060]

[Table 1] (The compounding amount in Table 1 is based on weight.)

<Preparation and Evaluation of Composition for Waterproofing Material> Example 16 1250 parts of calcium carbonate, 144 parts of titanium oxide and 16 parts of weathering stabilizer were charged, and the mixture was stirred at room temperature for 15 minutes, and subsequently at 100 ° C. While kneading by kneading, dehydration operation was carried out for 1 hour. Next, 607 parts of polyurethane prepolymer a, C
696 parts of PE-EA-a and 9 parts of salicylic acid were charged and kneaded at room temperature for 15 minutes. Further, 255 parts of xylene was charged and stirred to obtain a one-pack type polyurethane composition. Table 2 shows the results of storage stability and sheet properties after curing of this composition.

The storage stability was determined by measuring the viscosity with a BM type rotational viscometer after the one-pack type polyurethane composition was sealed and stored for a certain period. After the construction, the physical properties of the cured sheet were measured according to JIS-K6301.

That is, the hardness, the tensile strength and the elongation were measured when the sample was left for 7 days at 23 ° C. and 50% relative humidity after the construction and further left at 50 ° C. for 7 days.

Examples 17 and 18 As in Example 16, adjustment was carried out using CPE-PI-a and CPA-EA-a instead of CPE-EA-a. Table 2 shows the storage stability of the composition and the physical properties of the sheet after curing.

Comparative Example 3 A similar preparation was carried out by using SEA obtained in Synthesis Example 5 instead of CPE-2EA-a in Example 16. Table 2 shows the storage stability of the composition and the physical properties of the sheet after curing.

The storage stability in the table shows the stability after 14 days.

[0067]

[Table 2]

[0068]

EFFECTS OF THE INVENTION According to the present invention, curing by moisture in the atmosphere is moderately fast, and without foaming, it can be stored for a long time in a closed container with a constant viscosity. It is possible to provide a moisture-curable urethane resin composition which is remarkably excellent in so-called storage stability, a novel enamine compound constituting the composition, an enamine-modified urethane prepolymer, and a waterproof material composition.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum diagram of the enamine compound “CPE-EA” of the present invention obtained in Example 1.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C09K 3/18 101 C09K 3/18 101

Claims (10)

[Claims] 1. A substituent having an alicyclic enamine structure in which the nitrogen atom of the amine is a constituent site in the molecular structure of the aliphatic tertiary amine, and which is bonded to the nitrogen atom. Is a functional group having a structure having a hydroxyl group and an alkylene group. 2. The compound according to claim 1, wherein the carbon atom forming the enamine structure has no active hydrogen atom. 3. The method according to claim 1 or 2 represented by the following general formula 1.
The enamine compound described. Embedded image (In the formula, R1 and R2 are a hydroxyl group-containing hydrocarbon group or another hydrocarbon group, and the total number of carbon atoms thereof is 3 to 22. provided that R1 and R2 are the same. It does not become another hydrocarbon group.
Y is a linear or branched alkylene group having 2 to 8 carbon atoms, E is a residue of an electrophilic compound, B is a hydrogen atom, a linear branched group having 1 to 6 carbon atoms. Alternatively, it is a cyclic alkyl group or a residue of an electrophilic compound. ) 4. The method according to claim 1, which is represented by the following general formula 2.
The enamine compound described. Embedded image (In the formula, R3 and R4 are hydrocarbon groups having 1 to 3 carbon atoms, R5 is a hydrocarbon group having 1 to 15 carbon atoms, X is a carbon atom or a nitrogen atom, and Y is A linear or branched alkylene group having 2 to 8 carbon atoms, E is a residue of an electrophilic compound, B is a hydrogen atom,
It is a linear branched or cyclic alkyl group having 1 to 6 carbon atoms, or a residue of an electrophilic compound. ) 5. A method for producing an enamine-modified urethane prepolymer, which comprises reacting the enamine compound according to any one of claims 1 to 4 with a urethane prepolymer. 6. A urethane resin composition comprising the reaction product according to claim 5 and a urethane prepolymer as essential components. 7. The average molecular weight of the urethane prepolymer is
The composition according to claim 5, which is 500 to 10,000. 8. The reaction product of the enamine compound and the urethane prepolymer, and the abundance ratio of the urethane prepolymer are the equivalent ratios of the isocyanate groups in the urethane prepolymer and the amino groups in the enamine compound as NCO / N =
The composition according to claim 4 or 5, which has a ratio of 0.1 to 100. 9. The composition according to claim 5, 6 or 7, wherein the urethane prepolymer is terminated with an isocyanate group obtained by reacting an organic polyisocyanate with an organic polyhydroxyl compound. 10. A waterproofing material composition comprising the urethane resin composition according to claim 6 and a filler as essential components.