JPH09169829A - Cold-curing polyurethane composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a cold-curing polyurethane compsn. which is excellent in storage stability and curability, does not foam during curing, does not emit an irritant odor, and does not corrode an adherend by compounding a polyisocyanate compd. or a urethane prepolymer, an oxazolidine compd., and a compd. which accelerates the opening of an oxazolidine ring. SOLUTION: This compsn. is prepd. by compounding a polyisocyanate compd. or a urethane prepolymer (A), an oxazolidine compd. (B), and a compd. which accelerates the opening of an oxazolidine ring (C). Component A is pref. a urethane prepolymer formed from a polyol and a polyisocyanate in an equivalent ratio of hydroxyl group to isocyanate group of lower than 1, e.g. 0.95-0.75. Component B is pref. an isocyanatooxazolidine compd. (e.g. a compd. represented by formula I). Component C, when hydrolyzed, generates a free acid, which accelerates the opening of an oxazolidine ring, an example being methyl o- formate. The compsn. may further contain a modified carbodiimide compd. (D). The compounding ratio by wt. of A:B:C:D is 100:(0.1-200:(0.1-5.0):(0.1-2.5).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a room temperature curable urethane composition which is extremely useful as a polyurethane resin-based adhesive, coating material, sealing material, primer and the like.

[0002]

2. Description of the Related Art Polyurethane is used as a sealing agent, a waterproof agent, an adhesive agent, etc. because it can be cured by humidity at normal temperature and has various properties such as elasticity and adhesiveness. Polyurethane-based sealing agents used for such applications include a one-pack type and a two-pack type, and in the two-pack type, a main agent and a curing agent must be mixed before use. Although it has the advantage that the time required for curing is short because it is uniformly mixed before use, it is complicated to handle because the mixing step is performed on site during construction. On the other hand, the one-pack type does not require mixing of components at the time of construction, is easy to handle, and its demand is increasing. The one-pack type polyurethane composition is mainly a moisture-curable type, and is cured by moisture in the air or moisture adsorbed to a compounded compound, so that the crosslinking curing starts from the surface of the composition and proceeds to the inside. . Therefore, it takes a long time of half a day to a full day until the composition used is completely cured. As described above, the curability is inferior to that of the two-component type, and the curing reaction is started by the moisture in the air or the moisture adsorbed to the components of the composition during storage, so that there is a problem in storage stability. .

As the moisture-curable latent curing agent, oxazolidine type, ketimine type, enamine type, thiosilyl group type and the like have been known. Among them, oxazolidine type has a good balance of curability and storage stability. It is a curing agent that has been removed, and the performance of the cured product is relatively good (Japanese Patent Publication No. 55-3540).
No. 7, JP-B-58-5913 and JP-B-58-59
No. 14) has attempted to control the ring-opening rate (activity) of the oxazolidine ring by changing the substituent at the 2-carbon of oxazolidine.

Further, in Japanese Patent Laid-Open No. 2-55715, a one-pack type urethane composition is a composition in which an oxazolidine compound having two oxazolidine rings and an aromatic polyfunctional isocyanate are added to an isocyanate prepolymer for storage stability. However, it is not always sufficient. It is known that an acid such as 2-ethylhexanoic acid promotes the ring opening of the oxazolidine ring, but in the case of a one-pack type urethane composition, the acid itself reacts with urethane and the storage stability is poor. When a two-component urethane composition is used, problems such as foaming may occur due to the reaction between an acid and an isocyanate. Thus, the urethane prepolymer having an isocyanate group at the terminal generates carbon dioxide gas when the isocyanate group and water react,
When this amount exceeds a certain amount, bubbles are generated in the cured product.

As a method for solving such a problem, Japanese Patent Publication No. 62-9155 and Japanese Patent Publication No. 4-2796.
No. 2, Japanese Patent Laid-Open No. 4-226522, Japanese Patent Publication No. 5-
No. 8730 and the like are exemplified, but these describe a method of adding ketimine, aldimine or enamine into a urethane prepolymer. These methods are
Although it has a remarkable effect on the suppression of foaming, the compounds used in these methods increase the viscosity of the composition during long-term storage and cause a problem in storage stability. In order to improve the curability, hydrogen chloride or tin (IV) (J. Coatings Te
chnology, 49, 631 (1977). ), Or an organic compound of tin or lead, or a curing catalyst such as a tertiary amine has been disclosed, but when hydrogen chloride is used, irritating odor and corrosion of the adherend become problems. Further, tin (IV) compounds usually have very poor storage stability.

The inventors of the present invention have disclosed a urethane composition containing a urethane prepolymer, an oxazolidine compound, a silyl ester compound, and a monoisocyanate compound in JP-A-7-138336. This composition has a monoisocyanate compound as an essential constituent condition as a scavenger for water in the system, a ring-opened oxazolidine compound, or a free acid. However, the addition of monoisocyanate is not always effective in improving storage stability, and in some cases, problems such as gelation may occur.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems in the prior art and to provide a composition using an oxazolidine compound as a latent curing agent in which the rate and degree of ring opening of the oxazolidine ring are in a desired state. The present invention aims to provide a composition having a desired curing rate by controlling the temperature and controlling foaming of the composition during storage and curing. If the cured state of the urethane-based composition can be controlled as needed, one-component type and two-component type room-temperature-curable urethane-based compositions can be obtained, and adhesives, primers, coating agents, sealing materials, etc. It can be manufactured appropriately according to the purpose of use.

[0008]

Means for Solving the Problems That is, the present invention is based on A)
A room temperature curable polyurethane composition comprising a polyisocyanate compound or a urethane prepolymer, B) an oxazolidine compound having at least one oxazolidine ring, and C) an oxazolidine ring ring-opening promoting compound. In addition to the above composition,
D) A room temperature curable polyurethane composition comprising a modified carbodiimide compound. Here, the composition in which the oxazolidine compound B) contains a reaction product of a urethane prepolymer composed of a polyisocyanate compound or an organic isocyanate and a polyol, and N-hydroxylalkyloxazolidine, or the C) opening of the oxazolidine ring. The composition in which the ring promoting compound is a hydrolyzable ester compound, or the ring-opening promoting compound of the C) oxazolidine ring is p
A composition which is a mixture or an adduct of toluenesulfonyl isocyanate and an oxygen-containing organic compound or a sulfur compound, and a composition in which the C) oxazolidine ring ring-opening promoting compound is an organic bismuth compound.

Hereinafter, the present invention will be described in detail. The polyisocyanate compound or urethane prepolymer which is the component A) of the present invention is a compound which becomes a polymer by crosslinking and curing while the isocyanate group portion forms a urea bond in the presence of water.

The A) polyisocyanate compound or urethane prepolymer used in the present invention is not particularly limited as long as it is a urethane prepolymer produced from a polyol which is one of polyhydroxyl compounds and polyisocyanate.

The term "polyol" is a general term for alcohols obtained by substituting a plurality of hydrogen atoms of a hydrocarbon with hydroxyl groups. For example, one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran are used. It is a product obtained by addition-polymerizing a compound having two or more active hydrogens. Here, examples of the compound having two or more active hydrogens include polyhydric alcohols, amines, alkanolamines, and polyhydric phenols. Polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerin, hexanetriol, trimethylolpropane, pentaerythritol, etc., and amines include ethylenediamine, hexamethylenediamine, etc., alkanolamines. Examples thereof include ethanolamine and propanolamine, and examples of polyhydric phenols include resorcin and bisphenols.

Specifically, polyolefin polyols such as polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene glycol, polyoxybutylene glycol polyether polyol, polybutadiene polypolyol, polyisoprene polyol, and other adipate polyols. , Lactone-based polyols, polyester-based polyols such as castor oil, etc., and these polyols can be used in combination as necessary. These compounds may be used alone or in combination of two or more, but the weight average molecular weight thereof is preferably about 100 to 10,000, more preferably about 500 to 7,000.

As the polyisocyanate compound, there are various compounds used in the production of ordinary polyurethane resins. Specifically, 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate, diphenylmethane-4,4-diisocyanate and modified products thereof, 1,5-naphthalene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate. , Xylylene diisocyanate and the like. These polyisocyanate compounds may be used alone or in combination of two or more.

The amount ratio of the polyhydroxyl compound and the polyisocyanate compound in the production of the urethane prepolymer having an isocyanate group at the terminal is such that the number of the hydroxyl groups in the polyhydroxyl compound is 1 or less per isocyanate group in the polyisocyanate compound. However, it is preferably 0.95 to 0.75. Also,
The production conditions of the urethane prepolymer may be the usual production conditions of the urethane prepolymer. That is, the above-mentioned hydroxyl compound and polyisocyanate compound are reacted at a reaction temperature of 5
The reaction may be performed at about 0 to 100 ° C. under normal pressure.

The oxazolidine compound having at least one oxazolidine ring, which is the component B) of the present invention, is a compound having a saturated 5-membered heterocycle containing oxygen and nitrogen,
A compound having an oxazolidine ring that opens in the presence of moisture (water) and reacts with an isocyanate group to cure,
Specifically, N-hydroxyalkyl oxazolidine,
And polyisocyanate adducts thereof, oxazolidine silyl ether, carbonate oxazolidine, ester oxazolidine and the like.

The hydroxyalkyl oxazolidine is obtained by, for example, a dehydration condensation reaction between an alkanolamine and a ketone or an aldehyde. Specific examples of the hydroxyalkyl oxazolidine include 2-isopropyl-3- (2
-Hydroxyethyl) oxazolidine (hereinafter referred to as hydroxyalkyloxazolidine (1)), 2- (1-
Methylbutyl) -3- (2-hydroxyethyl) oxazolidine (hereinafter referred to as hydroxyalkyloxazolidine (2)), 2-phenyl-3- (2-hydroxyethyl) oxazolidine (hereinafter referred to as hydroxyalkyloxazolidine (3)) , 2- (p-methoxyphenyl) -3- (2-hydroxyethyl) oxazolidine (hereinafter referred to as hydroxyalkyloxazolidine (4)), 2- (2-methylbutyl) -3- (2-hydroxyethyl) -5. -Methyloxazolidine (hereinafter referred to as hydroxyalkyloxazolidine (5)).

[0017]

Embedded image

Oxazolidine silyl ethers are the above-mentioned N-hydroxyalkyl oxazolidines, trimethoxysilane, tetramethoxysilane, triethoxysilane, dimethoxydimethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane and γ-glycidoxypropyltriether. It is obtained by a reaction with an alkoxysilane such as methoxysilane or γ-glycidoxypropyltriethoxysilane. This reaction is performed using titanium alkoxide, aluminum alkoxide or divalent Sn as a catalyst in 40
C. to 160.degree. C., particularly preferably 80.degree. C. to 140.degree.

Specific examples include the following oxazolidine silyl ethers (1) to (3).

Embedded image

Carbonate oxazolidine is, for example,
Examples thereof include carbonate oxazolidine obtained by the method disclosed in JP-A-5-117252. Specifically, for example, by reacting a hydroxyalkyl oxazolidine such as the above-mentioned hydroxyalkyl oxazolidine (1) with a carbonate such as diallyl carbonate, dimethyl carbonate or dipropylene carbonate using a polyhydric alcohol such as diethylene glycol or glycerin. Obtainable. This reaction is carried out in the presence of a transesterification catalyst such as sodium methylate at 60-
It is carried out at a temperature in the range of 160 ° C, preferably 100-140 ° C. The addition amount of the catalyst is preferably 50 to 1000 ppm with respect to the total amount of hydroxyalkyl oxazolidine, carbonate and polyhydric alcohol.

Such carbonate oxazolidine is represented by the following formula (a).

Embedded image (In the formula, n is an integer of 1 to 10, R ^a and R ^b are each independently an organic group having 1 to 8 carbon atoms. R ^c and R ^c
Each ^d is independently a hydrogen atom or an organic group having 1 to 8 carbon atoms. And the like, and more specifically, the following carbonate oxazolidine (1).

[0022]

Embedded image

Ester oxazolidines are described, for example, in US Pat. No. 3,661,923 and US Pat. No. 4,138.
Various ester oxazolidines such as ester oxazolidine obtained by the method of JP-A No. 545 can be used, and for example, can be obtained by reacting the above-mentioned hydroxyalkyl oxazolidine (1) with a lower alkyl ether of dicarboxylic acid or polycarboxylic acid. . Specifically, the following ester oxazolidine (1) may be mentioned. Further, a commercially available product such as a hardener OZ represented by the following ester oxazolidine (2) manufactured by Bayer can be used.

[0024]

Embedded image

The content of these oxazolidine compounds B) is 1 to 20 parts by weight, particularly 2 to 10 parts by weight, based on 100 parts by weight of the urethane prepolymer A).
It is preferable in terms of the balance between storage stability and curability.

An oxazolidine compound B) having three or more oxazolidine rings in one molecule may be used, and this compound reacts an N-hydroxyalkyloxazolidine represented by the following (b) with a polyisocyanate compound. By doing so, it is synthesized as a compound having three or more oxazolidine rings in one molecule.

[0027]

[Chemical 6]

Here, R ¹ is a linear or branched divalent aliphatic hydrocarbon group having 2 to 3 carbon atoms, and is, for example, an alkylene group, an alkenylene group or an alkynylene group. R ² and R ³ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. The N-hydroxyalkyloxazolidine represented by the above formula (b) is synthesized from a corresponding aldehyde or ketone and N-hydroxyalkylamine by a known method.

As the aldehyde, formaldehyde,
Acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, 2
Aliphatic aldehydes such as -methylbutyraldehyde, 3-methylbutyraldehyde, hexylaldehyde, 2-methylpentylaldehyde, octylaldehyde, 3,5,5-trimethylhexylaldehyde; benzaldehyde, methylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, isopropyl Aromatic aldehydes such as benzaldehyde, isobutylbenzaldehyde, methoxybenzaldehyde, dimethoxybenzaldehyde, and trimethoxybenzaldehyde; acetone, methylethylketone, methylpropylketone, methylisopropylketone, diethylketone, methylbutylketone, methylisobutylketone, methyl-t-butylketone, diisobutyl Ketone, cyclopentanone, cyclohexanone Ketone is preferred.

As the N-hydroxyalkylamine,
Bis-N- (2-hydroxyethyl) amine, Bis-N
-(2-hydroxypropyl) amine and N- (2-
Hydroxyethyl) -N- (2-hydroxypropyl)
Amine is preferred.

The above-mentioned aldehyde or ketone and hydroxyalkylamine are reacted with an equimolar amount of nitrogen corresponding to the number of moles of the aldehyde or ketone, but the aldehyde or ketone is excessive in the range of 1.01 to 1.5. It is preferable to use Particularly preferably 1.01 to 1.1
Range. The reason for this is that unreacted N-hydroxyalkylamine is difficult to separate from the product and reacts with isocyanate, which causes a decrease in storage stability.

The reaction temperature is preferably refluxed in a solvent such as toluene or xylene. The reaction time is
The time is preferably 6 to 24 hours, and particularly preferably 8 to 12 hours. The reason for setting the reaction time in this range is that the reaction is incomplete when the time is less than 6 hours, and the reaction mixture is colored when the time exceeds 24 hours. Also,
The reaction is preferably carried out in a normal atmosphere.

As described above, 1.0% of the above aldehyde or ketone is added to the above hydroxyalkylamine.
It is used in the range of 1 to 1.5, preferably in 1.1 excess.
The reaction is carried out under reflux conditions for 6 to 24 hours, preferably 8 to 12 hours. After completion of the reaction, excess aldehyde or ketone is distilled off under reduced pressure to give N- represented by the above formula (b).
A hydroxyalkyl oxazolidine is obtained.

The polyisocyanate compound is a polyisocyanate having an organic group, and includes, for example, polyhydric alcohols such as glycerin, hexanetriol, trimethylolpropane or polypropylene glycol, and paraphenylene diisocyanate, tolylene diisocyanate, tetramethylene. Diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, octadecyl diisocyanate, naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate and reaction products with modified products thereof, or tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), etc. Trimerization of a diisocyanate compound in the presence of a catalyst gives isocyanurate Include compounds having 3 or more isocyanate groups in one molecule obtained by forming the door ring, these polyisocyanate compounds may be a single 2
More than one species may be used in combination.

The oxazolidine compound B) having three or more oxazolidine rings in one molecule is obtained by reacting the N-hydroxyalkyloxazolidine represented by the above formula (b) with a polyisocyanate compound at a reaction temperature of about 50 ° C to 100 ° C.
It is a reaction product that can be synthesized by reacting under normal pressure. A solvent such as toluene or xylene may be used for the purpose of decreasing the viscosity during the synthesis.

The amount ratio of N-hydroxyalkyl oxazolidine to polyisocyanate compound is preferably such that 1 mol of polyisocyanate compound reacts with 1 mol of hydroxyl group of N-hydroxyalkyl oxazolidine. If the amount of the polyisocyanate compound is more than 1 mol, the amount of unreacted organic polyisocyanate increases, and the curability when mixed with the urethane prepolymer deteriorates. When the amount of the polyisocyanate compound is less than 1 mol, the amount of unreacted N-hydroxyalkyloxazolidine that does not act as a trifunctional crosslinking agent in the reaction mixture increases, resulting in poor curability.

Specific examples of such a compound having three or more oxazolidine rings in one molecule include a polyfunctional oxazolidine compound (1) represented by the following formula and a polyfunctional oxazolidine compound (2 represented by the following formula: ) And the like.

[0038]

Embedded image

The content of the oxazolidine compound having three or more oxazolidine rings in one molecule is such that the number of moles of the oxazolidine ring in the curing agent is NC in 100 parts by weight of the polyisocyanate compound or urethane prepolymer A).
0.1 to 1.0 times the number of moles of O, preferably 0.2 to
It is preferable to use an amount of 1.0 times. This is because if the amount outside this range is used, the residual tack increases.

Particularly preferred is an isocyanate oxazolidine compound represented by the following formula (c), which has two or more functional groups capable of ring-opening with water in the air to form an imino group and a hydroxyl group and causing a crosslinking reaction. It is a curing agent. The generated imino group reacts with an isocyanate group to form a urea bond, and the hydroxyl group also reacts with an isocyanate group to form a urethane bond to accelerate crosslinking.

[0041]

Embedded image

Here, R ¹ is an alkylene group having 2 to 6 carbon atoms and is preferably a compound forming an oxazolidine ring having 2 or 3 carbon atoms. More preferably,
It is preferred to form a C2 oxazolidine compound. R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alicyclic alkyl group having 5 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R ⁴ is an alkylene group having 2 to 6 carbon atoms, an aryl group, or an alkylene group having 2 to 6 carbon atoms containing a urethane bond or an aryl group containing a urethane bond, and an alkyl group having 1 to 5 carbon atoms having a urethane bond. Alternatively, it is preferably an aryl group.

R ⁵ is a group obtained by removing an isocyanate group from n polyisocyanates, and may be any group which forms the skeleton of an isocyanate compound. It is preferable that the compound is a skeleton of a diisocyanate or triisocyanate compound. n is 1 to
It is an integer of 4, and is preferably 2 or 3. In particular, when n is 2 or 3, a cured product having a balanced tensile strength and tensile elongation can be obtained. If it exceeds 3, it will be hard and brittle, and if it is less than 2, curing will be insufficient.

Specific examples of the isocyanate oxazolidine compound include:

Embedded image Such as TDI base, MDI base, XDI base, H
Examples include polyfunctional oxazolidine such as DI base,
A commercially available product such as a hardener OZ manufactured by Bayern can be used.

Other preferable examples of the isocyanate oxazolidine compound are represented by the following formula (d):

Embedded image (In the formula, R ¹ is an aliphatic hydrocarbon group having 5 or more carbon atoms, R ² is a residue obtained by removing an isocyanate group from an organic polyisocyanate, m is an integer of 1 to 6, and n is 0. Is an integer of 4).

In the above formula, R ¹ is an aliphatic hydrocarbon group having 5 or more carbon atoms, preferably 5 to 15 carbon atoms, such as n-pentyl, 2-methylpentyl, 3-
Methylpentyl, 3,5,5-trimethylpentyl, n
-Heptyl, n-octyl, n-nonyl, n-decanyl, n-undecanyl, n-dodecanyl, n-tridecanyl, n-tetradecanyl and the like. Especially, the case where the number of carbon atoms is 5 to 10 is preferable. And R
^When the substituent at the ^1- position is an aliphatic hydrocarbon with two substituents, the hydrolysis is too fast and the storage stability is poor. Also, R
^{When 1} is an aromatic group, hydrolysis is slow and the curability is poor. Further, when the number of carbon atoms is 4 or less, the hydrolysis is relatively fast and the storage stability is poor. Further, conventionally, there are those which disclose a compound in which R ¹ is an alkyl group having 1 to 6 carbon atoms as an oxazolidine compound. Specifically, the effect as a latent curing agent depends on the difference in the number of carbon atoms within this range. There is no technology that recognizes the difference.

R ² is a residue obtained by removing an isocyanate group from an organic polyisocyanate, and may be aliphatic, alicyclic or aromatic. For example, aromatic groups such as tolylene, diphenylmethane, phenylene and polymethylene polyphenylene, aliphatic groups such as hexamethylene, alicyclic hydrocarbon groups such as isophorone, aromatic aliphatic groups such as xylene, and further carbodiimide modification thereof. Group or isocyanurate-modified group, and the like, and they are used as one kind or as a combination of two or more kinds.

It is preferable that m is an integer of 1 to 6, particularly 2 to 3 from the viewpoint of curability and physical properties of the cured product. Also, n
Is preferably an integer of 0 to 4, and more preferably 0 to 2 from the viewpoint of curability.

The method for producing the isocyanate oxazolidine compound represented by the formula (c) is as follows. N-hydroxyethyloxazolidine represented by the following formula (h) was synthesized from aldehyde corresponding to diethanolamine,

Embedded image (In the formula, R ¹ is an aliphatic hydrocarbon having 5 or more carbon atoms.)

B. The obtained N-hydroxyethyl oxazolidine represented by the formula (h) and an organic polyisocyanate are synthesized. The method for producing an oxazolidine compound of the present invention comprises steps a. And b. , Step b. It may be only. a. The reaction temperature is 70 to 150
The reaction is carried out by dropping in the presence of an organic solvent such as benzene, toluene or xylene as a solvent at ℃. After the addition is complete, the reaction mixture is refluxed for 5-10 hours in an oil bath.
Also, b. In the reaction of, N-hydroxyethyloxazolidine is mixed with organic polyisocyanate,
React at 5 ° C. for 5 to 10 hours. Also, if necessary,
The temperature may be changed during the reaction.

Aldehydes used include n-hexanal, 2-methylpentanal, 2-methylheptanal, n-octanal, 3,5,5-trimethylhexanal, n-decanal, n-undecanal, n.
-Dodecanal, n-tridecanal, n-tetradecanal, n-pentadecanal, etc. are mentioned, and these aldehydes are commercially available.

As the organic polyisocyanate used for synthesizing the isocyanate oxazolidine compound, any of aliphatic, alicyclic and aromatic can be used. For example, aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate and polymethylene polyphenylene polyisocyanate. Aliphatic polyisocyanates such as hexamethylene diisocyanate; Alicyclic polyisocyanates such as isophorone diisocyanate; Aromatic aliphatic polyisocyanates such as xylene diisocyanate; and carbodiimide-modified or isocyanurate-modified polyisocyanates thereof; They are used alone or in combination of two or more.

The isocyanate oxazolidine compound obtained as described above has properties such that various physical properties can be adjusted in relation to the component A).

Other preferred examples of component B) are oxazolidine silyl ethers, which are obtained, for example, by reacting (i) a hydroxyl group-containing oxazolidine with an alkoxysilane, or (ii) a hydroxyl group-containing oxazolidine and a halogen. It can be synthesized by a reaction with a silyl compound. Of these, the reaction (i) is carried out at 40 to 160 ° C, particularly preferably at 80 to 140 ° C, using a titanium alkoxide, an aluminum alkoxide or a divalent tin compound (Sn ²⁺ ) as a catalyst. The catalyst may be added as it is or may be used by dissolving it in a solution of an organic solvent such as xylene. The amount of such a catalyst used is
It is preferably 0.01 to 5 parts by weight, particularly 0.1 to 2 parts by weight, based on 100 parts by weight of oxazolidine, in view of reaction time and purity of the product.

Such an oxazolidine silyl ether is preferably a compound represented by the following formula (i).

Embedded image In the formula, n is an integer of 0 to 3.

R is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group, an alicyclic group, an alkoxy group, an acryloxyalkyl group, an aminoalkyl group or a mercaptoalkyl group; a vinyl group, a phenyl group. Examples include groups, amino groups, and the like, for example, methyl group, ethyl group, vinyl group, methacryloxypropyl group, epoxycyclohexyl group, glycidoxypropyl group, aminoethyl group, aminopropyl group, phenyl group, amino group, A mercaptopropyl group is exemplified. When n is 2 or more, the R groups may be independently different groups or the same groups.

R ² is preferably an alkyl group having 2 or 3 carbon atoms, particularly an ethyl group or an isopropyl group. R
³ is preferably a hydrogen atom or a methyl group.
R ⁴ and R ⁵ are each independently a hydrogen atom or a carbon number of 1 to
20 hydrocarbon groups. Further, the number of carbon atoms is 3 to 12
Are preferred, and specific examples thereof include an isopropyl group, an isopentyl group and a phenyl group, for example, an alkoxyphenyl group such as a methoxyphenyl group, among which R ⁴ ,
One of R ⁵ is a hydrogen atom, which means storage stability,
It is preferable in terms of curability.

Specific examples thereof include oxazolidine silyl ether compounds (1) to (7) represented by the following formula.

[0059]

Embedded image

The amount of the oxazolidine silyl ether of component B) relative to the urethane prepolymer of component A) is such that the (Si-O) / NCO ratio of the silyl ether groups in the oxazolidi compound and the isocyanate groups in the urethane prepolymer is 1/1. ˜1 / 30, especially ½˜1 / 20. If the amount of oxazolidine silyl ether is more than this range, curing will be insufficient, and if it is less than this range, foaming suppression will be insufficient.

The oxazolidine ring ring-opening promoting compound of the component C) of the present invention is a compound which promotes the ring opening of the oxazolidine ring mainly by hydrolysis with water to produce a free acid. Preferably, component C) includes compounds of groups e), f) and g) below.

E) Hydrolyzable Ester Compound Examples of the orthoformate ester include orthoformate alkyl esters such as methyl orthoformate and ethyl orthoformate. The orthoformate is preferably 0.01 or less with respect to 100 parts by weight of the polyisocyanate compound or urethane prepolymer of component A).
It is more preferably contained in an amount of 0.1 to 5 parts by weight.
The reason for setting this range is that if an excessive amount is added, the free acid generated thereafter may react with the isocyanate group itself.

The organic silicic acid ester has a structure represented by the following general formula (j) or (k) and is produced from a carboxylic acid and silanol. That is, the silyl ester compound used in the present invention is a siloxane-bonded Si-OS
The polymerized ester having i and the monomeric ester not having this structure can be divided into any ester.

The silyl ester compound acts as a source of free acid in the presence of water. The acid liberated here serves as a crosslinking accelerator that promotes ring opening of the oxazolidine compound and promotes polymerization of the oxazolidine compound and the urethane prepolymer.

[0065] Here, R ⁶ is an alkyl group, an aryl group or an aralkyl group having 1 to 20 carbon atoms, and the presence of water breaks the ester bond to release the acid. The liberated acid is preferably acetic acid or propionic acid. R ⁷ has 1 carbon atom
It is preferably an alkoxy group having 5 to 5 carbon atoms and 1 to 3 carbon atoms. R ⁸ is an alkyl group having 1 to 5 carbon atoms, an aryl group or an aralkyl group. m is an integer.

R⁹ _4-nSi (OCOR^Ten)_n ... (k) where R⁹Is an alkyl group or an allyl group having 1 to 5 carbon atoms.
Or aralkyl group, R ^TenIs alkyl having 1 to 20 carbons
Group, an aryl group or an aralkyl group, having 2 or less carbon atoms.
Or 3 is preferable. n is an integer of 1 to 4
You. Organosilicates are polyisocyanates of component A)
To 100 parts by weight of compound or urethane prepolymer
In contrast, 0.01 to 10 and 0.1 to 5 parts by weight are included.
Let The reason for setting this range is that if an excessive amount is added,
Free acid generated later can react with isocyanate group itself
This is because sex occurs.

F) A mixture or adduct of p-toluenesulfonyl isocyanate and an oxygen-containing organic compound or a sulfur compound p-toluenesulfonyl isocyanate is a compound represented by the following formula (m), and phosgene may be used. It can be obtained by a known isocyanate synthesis method by phosman decomposition, but a commercially available product such as Additive TI manufactured by Sumitomo Bayer Urethane Co., Ltd. can be used.

[0068]

Embedded image

As the oxygen-containing organic compound or the sulfur-containing organic compound, either one of the oxygen-containing organic compound and the sulfur-containing organic compound may be used, or both of them may be used.
You may use together a 1 or more type of compound. The oxygen-containing organic compound is an organic compound having one or more oxygen atoms in the molecule, and specifically includes epoxies, esters, ethers, acetals, orthoesters, orthocarbonates, carbonates, Examples thereof include alcohols and carboxylic acids. Among them, it is preferable to use esters, acetals, orthoesters and the like from the viewpoint of storage stability.

More specifically, methyl acetate, methyl formate, ethyl acetate, ethyl formate, methyl acrylate, dioctyl phthalate (DOP), diethyl ether, dioxane, tetrahydrofuran, phenyl glycidyl ether, butyl glycidyl ether, ethylene glycol dimethyl ether, Propylene glycol, polypropylene glycol, methyl orthoformate, ethyl orthoformate, diethyl acetal, 1,3-dioxolane, or the following formula (n)

Embedded image Spiro orthocarbonates, bicyclo orthoesters, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol,
Octanol, formic acid, acetic acid, propionic acid, octylic acid, stearic acid and the like are also exemplified. Among them, methyl formate, methyl acetate, methyl orthoformate, ethyl orthoformate and the like are preferable from the viewpoint of storage stability.

The sulfur-containing organic compound is an organic compound having one or more sulfur atoms in the molecule, and specifically, sulfides, thioacetals, thioketals, thioorthoesters, thioorthocarbonates, Examples thereof include thiols. Specific examples thereof include diethyl sulfide, propylene sulfide, thiirane, tetrahydrothiophene, propanethiol and benzyl mercaptan. Among them, it is preferable to use tetrahydrothiophene, propylene sulfide and the like from the viewpoint of storage stability.

The content of the mixture or adduct of p-toluenesulfonyl isocyanate and the oxygen-containing organic compound or the sulfur-containing organic compound is 0.1 to 20 parts by weight, especially 0% by weight based on 100 parts by weight of the polyurethane component A). It is preferably from 5 to 5 parts by weight from the viewpoint of storage stability and the like.

The group f) used in the present invention is preferably a compound (sulfonamide derivative) represented by the following formula (p): R ¹ —SO ₂ NHCO—R ² (p), which is used at room temperature. In the presence of moisture, it acts as a curing accelerator for a moisture-curable urethane resin composed of an isocyanate group-terminated polyurethane component and an oxazolidine component, and markedly improves the curability of the urethane resin composition of the present invention.

In the formula, R ¹ represents an organic group having 1 to 12 carbon atoms. Specific examples of R ¹ include a methyl group, an ethyl group,
Examples thereof include a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a phenyl group, a toluyl group, a p-toluyl group, and a xylyl group. Particularly preferred examples of R ¹ are:
Examples include a methyl group and p-toluyl. R ² represents an organic group and may contain nitrogen, sulfur, oxygen or silicon atom. Specific examples of R ² include a methyl group, an ethyl group, a propyl group, a propoxy group, a benzoyl group, a cyanoethoxy group, an n-butylimino group, a chloroethoxy group, a dichloroethoxy group and a trichloroethoxy group.
Particularly preferred examples of R ² are cyanoethoxy group, trichloroethoxy group and the like.

Specific examples of the compound represented by the formula (p) include compounds represented by the following sulfonamide compounds (1) to (4).

[0076]

Embedded image Among them, the sulfonamide compound (3) is excellent in curability.

The sulfonamide derivative represented by the formula (p) used in the present invention includes i) an isocyanate compound represented by the following formula (q) and an alcohol, a mercaptan, an amine,
It can be produced by reacting a compound having active hydrogen in the molecule such as acid amide or silanol, or ii) reacting a sulfonamide compound represented by the following formula (r) with an acid halide.

[0078]

Embedded image

Examples of the sulfonyl isocyanate compound represented by the following formula (q) include p-toluene sulfonyl isocyanate. Examples of the alcohol include methanol, ethanol, propanol, n-propyl alcohol, butanol, pentanol, hexanol, heptanol, octanol, ethylene cyanohydrin, monools such as trichloroethanol, ethylene glycol, propylene glycol, 1,4-butanediol. And diols such as polypropylene glycol. Examples of the mercaptan include methanethiol, ethanethiol, propanethiol, benzylmercaptan, triethylene glycol dimercaptan, polysulfide and the like. Examples of amines include ethylamine, propylamine, butylamine, n
-Butylamine, benzylamine, aniline, hexamethylenediamine and the like can be exemplified. Examples of acid amides include acetamide, propionamide, and stearic acid amide. Examples of silanols include trimethylsilanol and silanol-terminated polydimethylsiloxane.

When the compound represented by the formula (p) is obtained by the above-mentioned method i), the reaction between the sulfonyl isocyanate compound represented by the formula (q) and the active hydrogen compound is represented by the formula (q). Isocyanate group in the sulfonyl isocyanate compound and an active group such as alcohol, mercaptan, amine, acid amide, silanol, etc. are mixed with a sulfonyl isocyanate compound and an active hydrogen compound so that they are equivalent, and at -10 ° C to room temperature, It is carried out by reacting for 10 minutes to 2 hours.

When the sulfonamide derivative represented by the formula (p) is obtained by the above-mentioned method ii), p-toluenesulfonamide can be exemplified as the sulfonamide compound represented by the formula (r). Examples of acid halides include acetyl chloride, propionyl chloride, and benzoyl chloride.

The sulfonamide derivative represented by the formula (p) is obtained by mixing the sulfonylamine compound and the acid so that the amino group of the sulfonamide compound represented by the formula (r) and the halogen of the acid halide are equivalent. Mix the halides,
It is carried out by reacting at 50 to 100 ° C. for 2 to 10 hours.

The sulfonamide derivative represented by the formula (p) is 0.005 parts by weight based on 100 parts by weight of the polyurethane component.
It is preferably used in the range of 5 to 10 parts by weight. 0.0
If the amount is less than 05 parts by weight, a sufficient promoting effect cannot be obtained.
Further, if it is more than 10 parts by weight, the storage stability becomes poor. Also, since many compounds of the formula (p) are crystalline compounds, it is preferable to add them to the polyurethane component after forming a solution with a solvent such as toluene, xylene, acetonitrile, methyl ethyl ketone or acetone. Such solvents are
You may make it contain 1 to 5 weight% in a polyurethane component.

G) Organic bismuth compound It is preferably an organic bismuth carboxylate compound. The organic bismuth compound is contained in an amount of preferably 0.001 to 5.0, more preferably 0.1 to 2.0 parts by weight based on 100 parts by weight of the polyisocyanate compound or the urethane prepolymer of component A).

The carbodiimide compound of the component D) of the present invention is a general term for a compound represented by R ¹ N = C = NR ² and a polycarbodiimide compound, and corresponds to a diimide body of carbon dioxide, and includes water, hydrogen sulfide and alcohol. It easily attaches with nucleophiles such as thiol, and ammonia, and easily reacts especially with carboxylic acids.

Examples of (1) monocarbodiimide compounds include R ¹ N = C = NR ² . Here, R ¹ and R ² each independently include an alkyl group having 1 to 10 carbon atoms, an alicyclic alkyl group that may be substituted with an alkyl group, or a heterocycle that may be substituted with an alkyl group. An alkyl group and an optionally substituted aralkyl group. Specifically, a methyl group,
Ethyl group, propyl group, isopropyl group, butyl group, p
-Methylcyclohexane group, p-dicyclohexylenemethyl group, p-xylyl group, cyclohexyl group, morpholinoalkyl group and the like are preferable, and cyclohexyl group and morpholinoethyl group are more preferable. Preferably, dicyclohexylcarbodiimide (DDC) represented by the following formula (s), a trade name stavaxol I, or the like is used.

[0087]

Embedded image

The polycarbodiimide compound (2) is obtained by carbodiimidizing an aliphatic diisocyanate, is a compound represented by the following general formula (t), and has a function of capturing water in the system. ^{OCN- (R 6 -N = C =} N) m -R 7 -NCO ···· (t) where, R ^6, R ⁷ are each independently, a carbon number 1 to 1
0 is an alkylene group, an alicyclic alkylene group which may be substituted with an alkyl group, an alkylene group containing a heterocycle which may be substituted with an alkyl group, or an aralkyl group which may be substituted. Specifically, methylene group, ethylene group, propylene group, isopropylene group, butylene group, p-methylene cyclohexane group, p-dicyclohexylene methylene group, p-xylylene group, cyclohexylene group, morpholino alkylene group, etc. It is preferable, and a cyclohexylene group and a morpholinoethylene group are more preferable. m is preferably 1 to 20, particularly preferably 1 to 5. Since polycarbodiimide having m of 1 to 20 is used, the water content affecting the storage stability in the system,
The carboxylic acid can be sufficiently captured.

Specific examples are polycarbodiimides derived from carbodiimidization of hydrogenated MDI, polycarbodiimides derived from carbodiimidization of HDI,

Embedded image Is mentioned.

The production of the polycarbodiimide compound obtained by carbodiimidizing an aliphatic diisocyanate is not particularly limited, but for example, it can be obtained by reacting an aliphatic diisocyanate with carbodiimide at high temperature, or 3-methyl-1-phenyl-2. It can be obtained by reacting at room temperature using a catalyst such as -phospholen-1-oxide.

As the aliphatic diisocyanate used in the reaction, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenated MDI
(H ₁₂ MDI), xylylene diisocyanate (XD
I) and the like are typical. When the aliphatic diisocyanate is used, the reactivity with water and the carboxyl compound is higher than that of the aromatic isocyanate, so that the storage stability can be improved.

The amount of the polycarbodiimide compound derived from the carbodiimidization of the aliphatic diisocyanate is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyisocyanate compound or urethane prepolymer of component A). , 1 to 4 parts by weight, the effect is remarkable. The blending amount is set within this range because the storage stability decreases if it is less than 0.1 parts by weight or exceeds 10 parts by weight.

In general, in the one-pack type urethane composition, there are cases where an acid or water is produced in the production process of each composition component, or an acid is added as a catalyst. But,
Such acids and moisture reduce the storage stability of the composition. In the present invention, the properties of the polycarbodiimide compound are used to formulate the composition as a storage stabilizer in the composition, but the composition contributes to the storage stability of the composition through the following two actions. The first is the action of capturing the water contained in the compound compounded in the system. These waters need to be trapped with a carbodiimide compound and removed from the system in order to promote the crosslinking between isocyanate groups unnecessarily during storage and the ring opening of the oxazolidine ring and the formation of the crosslinking accompanied therewith. The second is the action of capturing the free carboxylic acid in the system. The free acid unnecessarily promotes the ring-opening of the oxazolidine ring during storage, and the cross-linking proceeds accordingly, so it is necessary to capture and remove it with a carbodiimide compound.

(3) The bisoxazolidine polycarbodiimide compound is obtained by blocking the end of a polycarbodiimide compound obtained by carbodiimidizing an aliphatic diisocyanate with an oxazolidine compound, and is a compound represented by the following formula (u). It has an acid scavenging effect and a water scavenging effect, and plays a role of improving the storage stability of the composition.

[0095]

Embedded image

Here, R ⁶ is an alkylene group having 1 to 10 carbon atoms, an alicyclic alkylene group which may be substituted with an alkyl group, or an alkylene group containing a heterocycle which may be substituted with an alkyl group. , An aralkyl group which may be substituted. Specifically, a methylene group, an ethylene group,
A propylene group, an isopropylene group, a butylene group, a p-methylenecyclohexane group, a p-dicyclohexylenemethylene group, a p-xylylene group, a cyclohexylene group, a morpholinoalkylene group and the like are preferable, and a cyclohexylene group is more preferable. And a morpholinoethylene group.

R ⁷ is an alkylene group having 2 to 6 carbon atoms, and particularly preferably an alkylene group having 2 or 3 carbon atoms. R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alicyclic alkyl group having 5 to 7 carbon atoms, and 6 to 10 carbon atoms.
Is an aryl group having. m is 1 to 20, especially 1 to
It is preferably 5. Since polycarbodiimide with m of 1 to 20 is used, the water content affecting the storage stability in the system,
The carboxylic acid can be sufficiently captured. Since the terminal is blocked with oxazolidine, the polymerization of the polycarbodiimide can be stopped at the desired degree of polymerization, and the stability of itself can be increased. Also, since it has an oxazolidine group, it is incorporated into the system, so there is no concern about bleeding.

A specific example is

Embedded image The end of the polycarbodiimide derived from the hydrogenated MDI carbodiimide represented by
N-hydroxy-1,3-terminated with oxazolidine compound blocked (hydrogenated MDI modified product) or polycarbodiimide derived from carbodiimidization of HDI
Capped with an oxazolidine compound,

Embedded image Hydrogenated XDI modified product represented by

Embedded image Is mentioned. Above all, hydrogenated MDI modified product, hydrogenated XDI
Modified products are preferred.

The production of the bisoxazolidine polycarbodiimide compound is not particularly limited. For example, i) an aliphatic diisocyanate can be obtained by reacting with a carbodiimide at high temperature, or 3-methyl-1-phenyl-2-phosphorene-1- A polycarbodiimide compound is synthesized by reacting an aliphatic diisocyanate with carbodiimidation at room temperature using a catalyst such as oxide, and ii) the obtained polycarbodiimide compound and N-hydroxyalkyl-
1,3-oxazolidine compound, for example, N-hydroxyethyl-1,3-oxazolidine compound represented by the following formula (v)

Embedded image(Where R⁷, R⁸And R⁹Is described in the above formula (v)
Of R⁷, R⁸And R ⁹Same as the definition of. )

And can be obtained by mixing and reacting the isocyanate group of the polycarbodiimide compound and the oxazolidine compound so that the amounts are approximately equal to each other.

As the aliphatic diisocyanate used in the reaction, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenated MDI
(H ₁₂ MDI), xylylene diisocyanate (XD
I) and the like are typical. When the aliphatic diisocyanate is used, the reactivity with water and the carboxyl compound is higher than that of the aromatic diisocyanate, so that the storage stability can be improved.

N-hydroxyalkyl-used in the reaction
As the 1,3-oxazolidine compound,

Embedded image N-hydroxyethyl-2- (1-methylbutyl) -1,3-oxazolidine represented by

Embedded image N-hydroxyethyl-2-phenyl-1, represented by
3-oxazolidine etc. are mentioned.

The blending amount of the bisoxazolidine polycarbodiimide compound is 0. 100 parts by weight based on 100 parts by weight of the polyisocyanate compound or the urethane prepolymer as the component A).
It is preferably from 1 to 10.0 parts by weight, particularly from 0.3 to 3.0 parts by weight. The compounding amount is set within this range is 0.1
This is because if it is less than 1 part by weight, the storage stability is lowered, and if it exceeds 10.0 parts by weight, the storage stability is also lowered.

The composition of the present invention comprises, in addition to the above compounds,
If necessary, filler, plasticizer, pigment, antistatic agent, flame retardant, thixotropic agent, silane coupling agent,
A dispersant, an antioxidant, a solvent and the like may be blended.

Examples of the filler include calcium carbonate, carbon black, clay, talc, titanium oxide, quick lime, kaolin, zeolite, diatomaceous earth, vinyl chloride paste resin, glass balloons, vinylidene chloride resin balloons and the like. Alternatively, they can be used as a mixture.

A solvent may be used in the composition of the present invention, and preferably an aromatic hydrocarbon solvent is used. As the aromatic solvent, xylene, toluene and the like are preferable.

Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP), dilauryl phthalate (DLP), dibutyl benzyl phthalate (BBP), dioctyl adipate, diisodecyl adipate, trioctyl phosphate, tris (chloroethyl). ) Phosphates, tris (dichloropropyl) phosphate, propylene glycol adipate propylene glycol polyester, butylene glycol adipate polyester, alkyl epoxystearate, epoxidized soybean oil, etc. can be used alone or in combination. . Examples of the pigment include organic pigments such as an azo pigment and a copper phthalocyanine pigment, and various inorganic pigments. Examples of the thixotropic agent include Aerosil (manufactured by Nippon Aerosil Co., Ltd.) and Dispalon (manufactured by Kusumoto Kasei Co., Ltd.).

Examples of the antistatic agent generally include ionic compounds such as quaternary ammonium salts and amines, and hydrophilic compounds such as polyethylene glycol and ethylene oxide derivatives. Examples of the adhesion-imparting agent include a terpene resin, a phenol resin, a terpene-phenol resin, a rosin resin, and a xylene resin.
Examples of the flame retardant include chloroalkyl phosphate, dimethylmethylphosphonate, bromine, phosphorus compounds, ammonium polyphosphate, diethylbishydroxyethylaminophosphate, and the like.

The method for producing the one-component urethane-based adhesive composition of the present invention is not particularly limited, but preferably, each component is
It is preferable to add other additives as necessary, knead the mixture sufficiently under reduced pressure or an inert atmosphere, and uniformly disperse the composition.

Preferred examples of the composition of the present invention include the following. [1] A) a polyisocyanate compound or urethane prepomarimer and B) an oxazolidine compound and component C) are combined in group e) orthoformate and / or organosilicate, group f) p.
At least one of a mixture or adduct of toluenesulfonyl isocyanate with an oxygen-containing organic compound and a sulfur compound, and a compound of group g) an organic bismuth compound
When the compound is selected above. This composition has properties such as very good curability and good storage stability. Preferably, B) to 100 parts by weight of component A)
0.1 to 20 parts by weight and C) 0.1 to 5.0 parts by weight are desirable for obtaining stable and good curability.

[2] A composition containing the carbodiimide compound of the component D) in addition to the above composition [1]. This composition has properties such as very good curability and good storage stability. A preferred combination of component C) and component D) is to use component D) a carbodiimide compound for component C) orthoformate ester and organosilicate ester, respectively. The reason is mainly to improve storage stability without impairing curability. Preferably, B) 0.1 to 20 relative to 100 parts by weight of component A).
Parts by weight, C) 0.1 to 5.0 parts by weight, D) 0.1 to 2.
5 parts by weight is desirable to obtain stable and good curability.

[0112]

The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited by these examples.

[1] Production and Evaluation of Compositions shown in Table 1 [Synthesis of Latent Curing Agent I] Diethanolamine (100.1 g) and benzene (100 ml) were placed in a 1 L three-necked flask. 2-Methylpentanal 100.2 was added to the obtained solution.
g was added dropwise. After completion of dropping, immerse the flask in an oil bath,
The reaction mixture was reacted under reflux conditions for 8 hours. Further, benzene was distilled off from the reaction mixture to obtain 187 g of N-hydroxyethyl-2- (1-methylbutyl) -1,3-oxazolidine, which was the above-mentioned hydroxyalkyl oxazolidine (2). This 2- (1-methylbutyl) -3
-Oxazolidine ethanol 100g and xylylene diisocyanate 51.5g were mixed at room temperature, and it was made to react at 50 degreeC for 1 hour, and also at 80 degreeC for 8 hours. Yield 151 g.

[Latent curing agent II] Ester oxazolidine Bayer Co., Ltd. trade name Hardener OZ, the aforementioned ester oxazolidine (2) (Examples 1-1 to 1-7, Comparative examples 1-1 to 1-4) [Base Production Example of Resin] 57 parts by weight of polyoxypropylene triol having 3 hydroxyl groups and an average molecular weight of 5000 (manufactured by Asahi Glass Co., Ltd.), and 23 parts by weight of polypropylene ether diol having 2 hydroxyl groups and an average molecular weight of 2000 (Sanyo Chemical Co., Ltd.) Put Kogyo Co., Ltd. into the reaction vessel, 1
It was dehydrated under reduced pressure at 10 ° C. and 50 mmHg for 2 hours. After this,
The reaction product was cooled to 80 ° C. and 9.1 parts by weight of 2,4-
Tolylene diisocyanate (2,4-TDI) and 2,6
-A mixture of tolylene diisocyanate (2,6-TDI) (2,4-TDI: 2,6-TDI = 80: 20) was added with stirring and reacted until the free isocyanate was 2.2%. A polyurethane prepolymer TDI prepolymer having a terminal isocyanate group of 1.4% was obtained.

Then, to this TDI prepolymer, 1
9.6 parts by weight of diphenylmethane-4,4'-diisocyanate (MDI, manufactured by MD Kasei Co., Ltd.) was added and stirred. Here, 85 parts by weight of polyoxypropylene triol having an average molecular weight of 5000, which had been dehydrated in advance, and 35
By weight, polypropylene ether diol having an average molecular weight of 2000 was added, and free isocyanate was 1.
The reaction was carried out to 8% to obtain a urethane prepolymer composition as an MDI prepolymer.

100 parts by weight of this urethane prepolymer was placed in a kneading container filled with dry nitrogen gas, and 120 parts by weight of heavy calcium carbonate (Super 1500) manufactured by Maruo Calcium Co. As silica, 10 Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.
40 parts by weight of dioctyl phthalate (DOP) manufactured by Mitsubishi Kasei Vinyl Co., Ltd. as a plasticizer, 1 part by weight of A-187 manufactured by Nippon Unicar Co., Ltd. as a silane coupling agent, and Kanto Chemical as a solvent. 17 parts by weight of xylene manufactured by K.K. is added and sufficiently kneaded in a vacuum stirrer.
It was a masterbatch resin. Further, the following components shown in Table 1 were kneaded in the respective amounts to obtain a one-component urethane composition. Methyl orthoformate: HC (OMe) ₃ organic silicate: manufactured by Shin-Etsu Chemical Co., Ltd .: trade name Kf
-910 Ad-Ti: manufactured by Sumitomo Bayer Urethane Co., Ltd .: trade name Additive Ti (P-toluenesulfonyl isocyanate) carbodiimide: dicyclohexylcarbodiimide (DDC), a compound of the above formula (S)

[Production of hydrogenated MDI-modified polycarbodiimide compound] 25 parts by weight of xylene was added to 100 parts by weight of hydrogenated MDI (Dismoder W manufactured by Bayer).
The solution was stirred and dissolved, and tetraisopropoxy titanium (TPT-10 manufactured by Nippon Soda Co., Ltd.) was used as a carbodiimidization catalyst.
0) (0.75 g) was added, and the mixture was refluxed at 120 ° C. for 15 hours. When the isocyanate content reached 4.2%, the heating was stopped and the mixture was allowed to cool, then 75 parts by weight of xylene was added to obtain a polycarbodiimide compound (CIHM).

With respect to each urethane composition obtained, the initial viscosity immediately after kneading and the viscosity (storage stability) after standing at 60 ° C. for 3 days were measured by a B-type viscometer. In addition, the urethane composition was applied on a glass plate, and the temperature was 20 ° C. and the relative humidity was 65.
%, The time until the polyethylene terephthalate plate did not adhere to the urethane composition was measured, and the tack free time (curing speed) was measured.

[0119]

[Table 1]

[0120]

[Table 2]

[2] The oxazolidine ring opening-promoting compound C) is the sulfonamide compound (1) to
Production and evaluation of the composition shown in Table 2 in the case of (4). [Synthesis of Urethane Prepolymer (2-a)] 850 g of polypropylene glycol having a number average molecular weight of 3000 and 150 g of polypropylene triol having a number average molecular weight of 3000
And 300 g of dioctyl phthalate are mixed, and further 134 g of diphenylmethane diisocyanate is added,
The reaction was carried out at 80 ° C. for 10 hours while stirring to give a urethane prepolymer (2% with an isocyanate group content of 1.1%).
-A) was synthesized. [Synthesis of Urethane Prepolymer (2-b)] After synthesizing the above urethane prepolymer (2-a), 7.0 g of the above-mentioned hydroxyalkyloxazolidine (2) was added, and the mixture was reacted at 80 ° C. for 8 hours to give an oxazolidine group terminal. A urethane prepolymer (2-b) containing a part of was synthesized.

(Examples 2-1 to 2-7) Urethane prepolymer (2-a) or urethane prepolymer (2-
b) [Polyurethane component], the oxazolidine component, p-toluenesulfonyl isocyanate, oxygen-containing organic compound, and other additives shown in Table 2 below were sequentially added in this order and sufficiently kneaded to obtain a composition. . The initial viscosity of the obtained composition was measured using a B type viscometer. Further, the viscosity of these compositions after 24 hours at 70 ° C. was measured. In addition, each of the obtained compositions was 100 mm in length.
The sheet was formed into a sheet having a width of 100 mm and a thickness of 5 mm, and the tack free time was measured. The tack-free time is indicated by the time (minutes) taken until the molded product does not adhere to the finger even when the molded product is pressed with a finger. Table 2 shows the results.

(Comparative Examples 2-1 to 2-6) A composition was obtained in the same manner as in Example 2-1 except that the components shown in Table 2 below were used. The physical properties were measured. Table 2 shows the results.

[0124]

[Table 3]

[0125]

[Table 4]

Note) The amount of each component means parts by weight. ^{* 1} : Super 1500 manufactured by Maruo Calcium Co., Ltd. ^{* 2} : Aerosil 200 manufactured by Nippon Aerosil Co., Ltd. ^{* 3} : Hardener OZ manufactured by Sumitomo Bayer Urethane Co., Ltd. ^{* 4} : Oxazolidine silyl ether (silicon III) 2- (2- Methylbutyl) -3- (2-hydroxyethyl) oxazolidine 100 g, tetraethoxysilane 3
A mixture of 2.7 g, 50 g of toluene and 0.5 g of 50% xylene solution of titanium tetraisopropoxide was reacted at 80 ° C. for 2 hours and at 140 ° C. for 3 hours while azeotropically distilling ethanol as a by-product. Then, unreacted materials and toluene were distilled off under reduced pressure. From the infrared absorption spectrum, it was confirmed that the product had no hydroxyl group, and ¹ HNMR confirmed that no ethoxy group was present. The product has the structural formula shown above for oxazolidine silyl ether (3). ^{* 5} : Additive Ti manufactured by Sumitomo Bayer Urethane Co., Ltd.

[3] Production and evaluation of other compositions shown in Table 3 [Synthesis of urethane prepolymer (3-a)] 850 g of polypropylene glycol having a number average molecular weight of 3000 and 150 g of polypropylene triol having a number average molecular weight of 3000
And 300 g of dioctyl phthalate are mixed, and further 124 g of diphenylmethane diisocyanate is added,
The reaction was carried out at 80 ° C. for 10 hours with stirring to give a urethane prepolymer (3% with an isocyanate group content of 0.7%).
-A) was synthesized.

(Examples 3-1 to 3-6, Comparative Examples 3-1 to 3-1)
3-3) The urethane prepolymer (3-a) was kneaded with the components shown in Table 3 in the amounts shown in Table 3 to obtain a composition.
The initial viscosity of the obtained composition was measured using a B type viscometer. Furthermore, the viscosity of these compositions after 50 days at 50 ° C. was measured. In addition, each of the obtained compositions was 100
mm × width 100 mm × thickness 5 mm,
The tack free time was measured. The tack-free time is indicated by the time (minutes) required until the formed article does not stick to the finger even if the sheet-shaped molded article is pressed with the finger. Table 3 shows the results
Shown in

[0129]

[Table 5]

The components shown in Table 3 are specifically as follows. Carbon black: manufactured by Asahi Carbon Co., Ltd. Asahi Thermal Dioctyl Phthalate: manufactured by Mitsubishi Chemical Co., Ltd., trade name: Diacizer DOP ester oxazolidine: Bayer Co., Ltd. trade name, Hardner OZ.

Organosilicate ester: Shin-Etsu Chemical Co., Ltd. trade name KF910 Additive Ti (Ad-Ti): Sumitomo Bayer Urethane Co., Ltd. (P-toluenesulphonyl isocyanate) Organic bismuth compound: Nitto Kasei Co. trade name
t ^# 83 carbodiimide compound: DCC reagent 2-ethylhexanoic acid: reagent

[0132]

The moisture-curable polyurethane resin composition of the present invention has excellent curability and storage stability, and does not foam when cured. Also, there is no irritating odor or corrosion of the adherend as occurs when hydrogen chloride is used as a curing accelerator. Further, by appropriately selecting or using a combination of oxazolidine ring opening-promoting compounds, curability can be designed according to the required performance of various products.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI technical display location C09K 3/10 C09K 3/10 D (31) Priority claim number Japanese Patent Application No. 7-180040 (32) Priority Sundaira 7 (1995) July 17 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-220113 (32) Priority Date Hei 7 (1995) August 29 (33) Priority Claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-272370 (32) Priority date Hei 7 (1995) October 20 (33) Priority claiming country Japan (JP) (72) Inventor Kazunori Ishikawa 2-1 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Hiratsuka Plant (72) Inventor Hiroyuki Okuhira Oiwake 2-1, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Hiratsuka Plant

Claims (7)

[Claims] 1. A room temperature curable composition comprising: A) a polyisocyanate compound or urethane prepolymer; B) an oxazolidine compound having at least one oxazolidine ring; and C) a compound for promoting ring opening of the oxazolidine ring. Polyurethane composition. 2. A room temperature curable polyurethane composition, which further comprises D) a modified carbodiimide compound in addition to the composition of claim 1. 3. The room temperature curing according to claim 1, wherein the oxazolidine compound B) contains a reaction product of a urethane prepolymer composed of a polyisocyanate compound or an organic isocyanate and a polyol, and N-hydroxylalkyloxazolidine. -Type polyurethane composition. 4. The room-temperature-curable polyurethane composition according to claim 1, wherein the C) ring-opening promoting compound for the oxazolidine ring is a hydrolyzable ester compound. 5. The compound according to claim 1, wherein the C) ring-opening promoting compound for the oxazolidine ring is a mixture or adduct of p-toluenesulfonyl isocyanate and an oxygen-containing organic compound or a sulfur compound. Room temperature curable polyurethane composition. 6. The room temperature curable polyurethane composition according to claim 1, wherein the C) ring-opening promoting compound of an oxazolidine ring is an organic bismuth compound. 7. A mixture or addition of C) an oxazolidine ring ring-opening promoting compound, group e) orthoformate ester and organic silicate ester, group f) p-toluenesulfonyl isocyanate, and oxygen-containing organic compound and sulfur compound. And a mixture of compounds each selected from at least one or more of each group of the group g) organic bismuth compound.
The room temperature curable polyurethane composition according to any one of 3 above.