JP3169051B2 - Room temperature curing type polyurethane composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention 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 can be cured by moisture at room temperature and has excellent properties such as elasticity and adhesiveness, and is therefore used as a sealing agent, a waterproofing agent, an adhesive and the like. Polyurethane-based sealing agents used in such applications include a one-pack type and a two-pack type, and the two-pack type requires that the main agent and the curing agent be mixed before use. Although there is an advantage that the time required for curing is short because it is uniformly mixed before use, the handling is complicated because the mixing process is performed on site at the time of construction. On the other hand, the one-pack type is easy to handle because there is no need to mix components at the time of construction, and the demand is increasing. One-component polyurethane compositions are mainly moisture-curable, and are cured by moisture in the air or moisture adsorbed on a compound compounded, so that crosslinking and curing starts from the surface of the composition and proceeds to the inside. . For this reason, it takes a long time from half a day to a whole day until the used composition is completely cured. As described above, the curability is inferior to that of the two-pack type, and there is a problem in storage stability because the curing reaction starts due to moisture in the air or moisture adsorbed to the components of the composition during storage. .

Oxazolidine-based, ketimine-based, enamine-based, and thiosilyl-based compounds are known as moisture-curable latent curing agents. Among them, oxazolidine-based compounds are particularly suitable for curing and storage stability. It is a hardener that has been removed, and the performance of the cured product is relatively good.
No. 7, JP-B-58-5913 and JP-B-58-59
No. 14), attempts have been made to control the ring-opening rate (activity) of the oxazolidine ring by changing the substituent at the 2-position carbon of oxazolidine.

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

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

The present inventors 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 requires a monoisocyanate compound as an essential component 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 the storage stability, and in some cases, a problem such as the possibility of gelation occurs.

[0007]

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

[0008]

That is, the present invention provides:
A) a polyisocyanate compound or a urethane prepolymer; B) an oxazolidine compound having at least one oxazolidine ring ; C) a hydrolyzable ester compound;
And Le isocyanate, oxygen-containing organic compound or a sulfur compound
Mixture or adduct with a substance; a sulfonamide derivative;
And organic bismuth compounds
A room temperature-curable polyurethane composition comprising a compound that promotes ring opening of at least one oxazolidine ring. A room temperature-curable polyurethane composition characterized by further comprising D) a modified carbodiimide compound in the composition. Here, the oxazolidine compound B) is a composition containing a reaction product of a polyisocyanate compound or a urethane prepolymer composed of an organic isocyanate and a polyol, and N-hydroxyalkyl oxazolidine, or the hydrolyzable ester compound is , A composition which is an orthoformate and / or an organic silicate, or a composition wherein the organic bismuth compound is an organic bismuth carboxylate 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 is crosslinked and cured to form a polymer while the isocyanate group part forms a urea bond due to the presence of water.

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

The polyol is a general term for alcohols in which a plurality of hydrogens of a hydrocarbon are substituted with hydroxyl groups. For example, one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran are used. A product obtained by addition polymerization of 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. As polyhydric alcohols, ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerin, hexanetriol, trimethylolpropane, pentaerythritol, etc., and as amines, ethylenediamine, hexamethylenediamine, etc., alkanolamines Examples thereof include ethanolamine and propanolamine, and examples of the polyhydric phenols include resorcinol 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 And lactone-based polyols and polyester-based polyols such as castor oil, and the like. These polyols can be used in combination as needed. These compounds may be used alone or in combination of two or more, but the weight average molecular weight is preferably about 100 to 10,000, more preferably about 500 to 7000.

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

In the production of the urethane prepolymer having an isocyanate group at the terminal, the ratio of the amount of the polyhydroxyl compound to the amount of the polyisocyanate compound is such that the number of hydroxyl groups in the polyhydroxyl compound is not more than 1 per isocyanate group in the polyisocyanate compound. The ratio is preferably 0.95 to 0.75. Also,
The production conditions for the urethane prepolymer may be the ordinary production conditions for 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 as the component B) of the present invention is a compound having a saturated 5-membered heterocyclic ring containing oxygen and nitrogen,
A compound having an oxazolidine ring, which is opened in the presence of moisture (water) and cured by reacting with an isocyanate group,
Specifically, N-hydroxyalkyloxazolidine,
And its polyisocyanate adducts, oxazolidine silyl ethers, carbonate oxazolidine, ester oxazolidine and the like.

The hydroxyalkyl oxazolidine is carried out, for example, by a dehydration condensation reaction between an alkanolamine and a ketone or aldehyde. Specific examples of hydroxyalkyloxazolidine include 2-isopropyl-3- (2
-Hydroxyethyl) oxazolidine (hereinafter referred to as hydroxyalkyloxazolidine (1)), 2- (1-
Methylbutyl) -3- (2-hydroxyethyl) oxazolidine (hereinafter, referred to as hydroxyalkyl oxazolidine (2)), 2-phenyl-3- (2-hydroxyethyl) oxazolidine (hereinafter, referred to as hydroxyalkyl oxazolidine (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]

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Oxazolidine silyl ether is obtained by mixing the above-mentioned N-hydroxyalkyloxazolidine with trimethoxysilane, tetramethoxysilane, triethoxysilane, dimethoxydimethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, and γ-glycidoxypropyltriyl. It is obtained by a reaction with an alkoxysilane such as methoxysilane and γ-glycidoxypropyltriethoxysilane. This reaction is carried out using titanium alkoxide, aluminum alkoxide or divalent Sn as a catalyst.
C. to 160.degree. C., particularly preferably 80.degree.

Specifically, the following oxazolidine silyl ethers (1) to (3) are mentioned.

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The carbonate oxazolidine is, for example,
And carbonate oxazolidine obtained by the method of 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 for 60 to 60
It is carried out at a temperature of 160 ° C, preferably in the range of 100 to 140 ° C. The amount of the catalyst to be added is preferably 50 to 1000 ppm based on the total amount of the hydroxyalkyl oxazolidine, carbonate and polyhydric alcohol.

Such a 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
d is each 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]

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Ester oxazolidine is described, for example, in US Pat. No. 3,661,923 and US Pat.
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. . Specific examples include the following ester oxazolidine (1). Further, a commercially available product such as a hardener OZ manufactured by Bayer and represented by the following ester oxazolidine (2) can also be used.

[0024]

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The content of the oxazolidine compound 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 balance between storage stability and curability.

An oxazolidine compound B) having three or more oxazolidine rings in one molecule may be used. This compound reacts an N-hydroxyalkyl oxazolidine represented by the following (b) with a polyisocyanate compound. As a result, the compound is synthesized as a compound having three or more oxazolidine rings in one molecule.

[0027]

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Here, R ¹ is a linear or branched divalent aliphatic hydrocarbon group having 2 to 3 carbon atoms, 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 the 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.

The N-hydroxyalkylamine includes
Bis-N- (2-hydroxyethyl) amine, bis-N
-(2-hydroxypropyl) amine and N- (2-
(Hydroxyethyl) -N- (2-hydroxypropyl)
Amines are preferred.

The above-mentioned aldehyde or ketone and the hydroxyalkylamine are reacted with an equimolar amount of nitrogen corresponding to the number of moles of the aldehyde or ketone. Is preferably used. 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 is preferably carried out in a solvent such as toluene or xylene under reflux conditions. The reaction time is
It is desirable to set it as 6 to 24 hours, and it is especially preferable to set it as 8 to 12 hours. The reason for setting the reaction time in this range is that the reaction is incomplete when the reaction time is less than 6 hours, and the reaction mixture is colored when the reaction time is more than 24 hours. Also,
The reaction is preferably performed in a normal atmosphere.

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

The polyisocyanate compound is a polyisocyanate having an organic group. Examples of the polyisocyanate compound include polyhydric alcohols such as glycerin, hexanetriol, trimethylolpropane, and polypropylene glycol, paraphenylene diisocyanate, tolylene diisocyanate, and tetramethylene. Reaction products of diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, octadecyl diisocyanate, naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate and modified products thereof, or tetramethylene diisocyanate, hexamethylene diisocyanate (HDI) The isocyanurate is obtained by trimerizing the diisocyanate compound in the presence of a catalyst. 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 can be obtained by reacting an 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. At the time of synthesis, a solvent such as toluene or xylene may be used for the purpose of decreasing the viscosity.

The molar ratio of N-hydroxyalkyl oxazolidine to polyisocyanate compound is preferably 1 mol of the polyisocyanate compound per 1 mol of hydroxyl group of N-hydroxyalkyl oxazolidine. When 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 becomes poor. If 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]

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The content of the oxazolidine compound having three or more oxazolidine rings in one molecule is determined by the fact that the number of moles of the oxazolidine ring in the curing agent is the polyisocyanate compound or the NC in 100 parts by weight of the urethane prepolymer A).
0.1 to 1.0 times the number of moles of O, preferably 0.2 to 1.0
It is preferable to use an amount that becomes 1.0 times. If an 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 which form an imino group and a hydroxyl group by opening a ring with water in the air to cause a crosslinking reaction. It is a curing agent. The generated imino group reacts with the isocyanate group to form a urea bond, and the hydroxyl group also reacts with the isocyanate group to form a urethane bond and promote crosslinking.

[0041]

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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 an oxazolidine compound having 2 carbon atoms. 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, 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 as long as it forms a skeleton of an isocyanate compound. It is preferable that the compound be a skeleton of a diisocyanate or triisocyanate compound. n is 1 to
It is an integer of 4 and preferably 2 or 3. In particular, when n is 2 or 3, a cured product having a good balance between tensile strength and tensile elongation can be obtained. If it exceeds 3, it becomes hard and brittle, and if it is less than 2, curing becomes insufficient.

Specific examples of the isocyanate oxazolidine compound include:

Embedded image TDI base, MDI base, XDI base, H
Polyfunctional oxazolidine such as DI base, etc.,
Commercial products such as Hardener OZ manufactured by Bayern can be used.

Another preferred example of the isocyanate oxazolidine compound is represented by the following formula (d):

Embedded image (Wherein, 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, n is 0 Oxazolidine compound represented by the formula:

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,
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 of 5-10 carbon atoms is preferable. And R
^When the substituent at position ¹ is an aliphatic hydrocarbon, both of the substituents are too fast to hydrolyze, resulting in poor storage stability. Also, R
^{When 1} is an aromatic group, hydrolysis is slow and curability is poor. Further, when the number of carbon atoms is 4 or less, hydrolysis is relatively fast and storage stability is poor. Conventionally, as oxazolidine compounds, compounds in which R ¹ is an alkyl group having 1 to 6 carbon atoms and the like are disclosed, but the effect as a latent curing agent is specifically determined by a difference in carbon number within this range. No technology recognizes the differences.

R ² is a residue obtained by removing an isocyanate group from an organic polyisocyanate, and may be any of aliphatic, alicyclic and 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 modified groups of isocyanurate and the like, and these are used alone or in combination of two or more.

M is an integer of 1 to 6, particularly preferably 2 to 3 in terms of curability and physical properties of the cured product. Also, n
Is preferably an integer of 0 to 4, particularly preferably 0 to 2 in terms of curability.

The process for producing the isocyanate oxazolidine compound of the formula (c) comprises the steps of: a. N-hydroxyethyl oxazolidine represented by the following formula (h) is synthesized from diethanolamine and the corresponding aldehyde,

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

B. The obtained N-hydroxyethyloxazolidine represented by the formula (h) and the organic polyisocyanate are synthesized. The method for producing the oxazolidine compound of the present invention comprises the steps a. And b. Even if step b. It may be only. a. At a reaction temperature of 70 to 150
The reaction is carried out dropwise at a temperature of 0 ° C. in the presence of an organic solvent such as benzene, toluene or xylene as a solvent. After completion of the dropwise addition, the reaction mixture is refluxed for 5 to 10 hours in an oil bath.
B. Is performed by mixing N-hydroxyethyl oxazolidine and an organic polyisocyanate,
The reaction is performed at a temperature of 5 to 10 hours. Also, if necessary,
The temperature may be changed during the reaction.

Examples of the aldehyde used include n-hexanal, 2-methylpentanal, 2-methylheptanal, n-octanal, 3,5,5-trimethylhexanal, n-decanal, n-undecanal and n-undecanal.
-Dodecanal, n-tridecanal, n-tetradecanal, n-pentadecanal and the like, and these aldehydes are commercially available.

As the organic polyisocyanate used for synthesizing the isocyanate oxazolidine compound, any of aliphatic, alicyclic and aromatic organic polyisocyanates 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. Used as one kind or a combination of two or more kinds.

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

Other preferred examples of component B) are oxazolidine silyl ethers, such as, for example, (i) obtained by reacting a oxazolidine containing a hydroxyl group with an alkoxysilane, or (ii) oxazolidine having a hydroxyl group and a halogen. It can be synthesized by a reaction with a silyl compound or the like. The reaction (i) is carried out at 40 to 160 ° C, particularly preferably at 80 to 140 ° C, using titanium alkoxide, aluminum alkoxide or a divalent tin compound (Sn ²⁺ ) as a catalyst. The catalyst may be used as it is, or may be used after being dissolved in a solution of an organic solvent such as xylene. The amount of such catalyst used is
The amount 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 the reaction time and the 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 represents 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, phenyl 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, An example is a mercaptopropyl group. When n is 2 or more, the R groups may be each independently another group or the same group.

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 each independently represent a hydrogen atom or a carbon atom
20 hydrocarbon groups. Furthermore, the number of carbon atoms is 3-12.
Is preferably at, specifically, an isopropyl group, an isopentyl group, a phenyl group, for example, an alkoxyphenyl group such as a methoxyphenyl group, among them R ^4,
One of R ⁵ is a hydrogen atom, which indicates storage stability;
It is preferable in terms of curability.

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

[0059]

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The amount of the oxazolidinyl silyl ether of the component B) relative to the urethane prepolymer of the component A) is such that the (Si-O) / NCO ratio of the silyl ether group in the oxazolidi compound to the isocyanate group in the urethane prepolymer is 1/1. To 1/20, especially 1/2 to 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, the suppression of foaming will be insufficient.

The compound for promoting ring-opening of the oxazolidine ring of the component C) of the present invention is a compound which is hydrolyzed mainly with water to generate a free acid to promote ring-opening of the oxazolidine ring. Preferably, component C) includes compounds of the following groups e), f) and g).

E) Hydrolyzable ester compound Orthoformate is exemplified, which is an alkyl ester of orthoformate, such as methyl orthoformate and ethyl orthoformate. The orthoformate is preferably present in an amount of from 0.01 to 100 parts by weight of the polyisocyanate compound of component A) or of the urethane prepolymer.
More preferably, the content is 0.1 to 5 parts by weight.
The reason for this range is that if an excessive amount is added, the resulting free acid may react with the isocyanate group itself.

The organic silicate has one of the following general formulas (j) and (k), and is produced from a carboxylic acid and a silanol. That is, the silyl ester compound used in the present invention is a siloxane-bonded Si—O—S
It is divided into a polymerized ester having i and a monomeric ester not having this structure, and any ester may be used.

The silyl ester compound acts as a source of free acid in the presence of water. The acid liberated here promotes the ring-opening of the oxazolidine compound, and serves as a cross-linking accelerator that promotes the polymerization of the oxazolidine compound with 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 an ester bond to release an acid. Acetic acid and propionic acid are preferred as the acid released. R ⁷ has 1 carbon atom
To 5 alkoxy groups, and preferably 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 R⁹Represents an alkyl group having 1 to 5 carbon atoms, an allyl group,
Or aralkyl group, R ^TenIs alkyl having 1 to 20 carbon atoms
Group, an aryl group or an aralkyl group, having up to 2 carbon atoms.
Or 3 is preferred. n is an integer of 1 to 4
You. Organic silicates are the polyisocyanates of component A)
To compound or urethane prepolymer 100 parts by weight
On the other hand, the content is 0.01 to 10 parts by weight and 0.1 to 5 parts by weight.
Let The reason for this range is that if an excessive amount is added,
Later free acids can react with the isocyanate groups themselves
This is because the nature occurs.

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

[0068]

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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 one of the two may be used.
More than one compound may be used in combination. 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, Alcohols, carboxylic acids and the like can be mentioned. Among them, it is preferable to use esters, acetals, orthoesters, etc. 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-dioxolan, or the following formula (n)

Embedded image Spiro orthocarbonates, bicycloorthoesters, 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, use of methyl formate, methyl acetate, methyl orthoformate, ethyl orthoformate, and the like is preferable in terms of storage stability.

The sulfur-containing organic compound is an organic compound having one or more sulfur atoms in the molecule, and specifically includes sulfides, thioacetals, thioketals, thioorthoesters, thioorthocarbonates, and the like. Thiols and the like can be mentioned. Specific examples include diethyl sulfide, propylene sulfide, thiirane, tetrahydrothiophene, propane thiol, benzyl mercaptan and the like. Among them, it is preferable to use tetrahydrothiophene, propylene sulfide, or 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 sulfur-containing organic compound is 0.1 to 20 parts by weight, preferably 0 to 20 parts by weight, per 100 parts by weight of the polyurethane component A). It is preferably from 0.5 to 5 parts by weight in terms 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) In the presence of moisture, it acts as a curing accelerator for a moisture-curable urethane resin comprising an isocyanate group-terminated polyurethane component and an oxazolidine component, and significantly 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,
Propyl group, butyl group, pentyl group, hexyl group, heptyl group, phenyl group, tolyl group, p- tolyl group, but xylyl group and the like, particularly preferred examples of R ¹ are,
A methyl group, p-toluyl and the like. R ² represents an organic group, and may contain nitrogen, sulfur, oxygen, and a 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 a cyanoethoxy group, a 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) by reacting a sulfonamide compound represented by the following formula (r) with an acid halide.

[0078]

Embedded image

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

When the compound represented by the formula (p) is obtained by the above 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) An isocyanate group in the sulfonyl isocyanate compound and an active group such as an alcohol, a mercaptan, an amine, an acid amide, and a silanol are mixed with a sulfonyl isocyanate compound and an active hydrogen compound so as to have an equivalent amount, and at −10 ° C. to room temperature, The reaction is carried out for 10 minutes to 2 hours.

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

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

The sulfonamide derivative represented by the formula (p) is used in an amount of 0.00
It is preferable to use it in the range of 5 to 10 parts by weight. 0.0
If the amount is less than 05 parts by weight, a sufficient accelerating effect cannot be obtained.
On the other hand, if the amount is more than 10 parts by weight, the storage stability is deteriorated. In addition, since many compounds of the formula (p) are crystalline compounds, it is preferable to add them to the polyurethane component after preparing a solution with a solvent such as toluene, xylene, acetonitrile, methyl ethyl ketone, or acetone. Such solvents are
The polyurethane component may contain 1 to 5% by weight.

G) Organic bismuth compound Preferably, it is an organic bismuth carboxylate compound. The organic bismuth compound is preferably contained in an amount of 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 the component A).

The carbodiimide compound of the component D) of the present invention is a general term for a compound represented by R ¹ NＣC ＝ NR ² and a polycarbodiimide compound and corresponds to a diimide form of carbon dioxide, and includes water, hydrogen sulfide, alcohol Nucleophiles such as thiol, ammonia and the like readily react, and particularly easily react with carboxylic acids.

(1) Examples of the monocarbodiimide compound 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 optionally substituted with an alkyl group, or a heterocyclic ring optionally substituted with an alkyl group. An alkyl group and an aralkyl group which may be substituted. Specifically, a methyl group,
Ethyl group, propyl group, isopropyl group, butyl group, p
A methylcyclohexane group, a p-dicyclohexylenemethyl group, a p-xylyl group, a cyclohexyl group, a morpholinoalkyl group and the like, and more preferably a cyclohexyl group and a morpholinoethyl group. Preferably, dicyclohexylcarbodiimide (DDC) represented by the following formula (s), trade name Stabacol I or the like is used.

[0087]

Embedded image

(2) The polycarbodiimide compound is obtained by carbodiimidating an aliphatic diisocyanate, and is a compound represented by the following general formula (t), and has a function of trapping 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
A 0 alkylene group, an alicyclic alkylene group which may be substituted with an alkyl group, an alkylene group containing a heterocyclic ring which may be substituted with an alkyl group, and an aralkyl group which may be substituted. Specifically, methylene, ethylene, propylene, isopropylene, butylene, p-methylenecyclohexane, p-dicyclohexylenemethylene, p-xylylene, cyclohexylene, morpholinoalkylene, etc. Preferably, they are a cyclohexylene group and a morpholinoethylene group. m is preferably 1 to 20, particularly preferably 1 to 5. Since m uses a polycarbodiimide having 1 to 20, water which affects storage stability in the system,
The carboxylic acid can be sufficiently captured.

Specific examples include polycarbodiimide derived from carbodiimidization of hydrogenated MDI, polycarbodiimide 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. For example, the polycarbodiimide compound may be obtained by reacting an aliphatic diisocyanate with carbodiimide at a high temperature, or may be prepared by reacting 3-methyl-1-phenyl-2. -Phosphorene-1-oxide and the like, and can be obtained by reacting at room temperature.

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 an aliphatic diisocyanate is used, the reactivity with water and a carboxyl compound is higher than that of an aromatic isocyanate, so that 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 based on 100 parts by weight of the polyisocyanate compound of component A) or the urethane prepolymer. , 1 to 4 parts by weight, the effect is remarkable. The blending amount is set within this range because if it is less than 0.1 part by weight or exceeds 10 parts by weight, the storage stability decreases.

In general, the one-pack type urethane composition may contain an acid or moisture generated in the production process of each component, or may add an acid as a catalyst. But,
Such acids and moisture reduce the storage stability of the composition. In the present invention, the composition is blended as a storage stabilizing agent by utilizing the properties of the polycarbodiimide compound, and contributes to the storage stability of the composition through the following two actions. The first is an action of trapping water contained in the compound compounded in the system. These moistures need to be captured by a carbodiimide compound and removed from the system in order to promote the cross-linking between the isocyanate groups and the opening of the oxazolidine ring and the formation of the cross-links accompanying storage during storage. The second is the action of trapping free carboxylic acids in the system. The free acid unnecessarily promotes the ring-opening of the oxazolidine ring during storage, and the cross-linking proceeds with this. Therefore, the free acid must be removed by capturing with a carbodiimide compound.

(3) The bisoxazolidine polycarbodiimide compound is obtained by blocking the terminal of a polycarbodiimide compound obtained by carbodiimidating 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 in 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 heterocyclic ring which may be substituted with an alkyl group. And an aralkyl group which may be substituted. Specifically, a methylene group, an ethylene group,
It is preferably 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 or the like, and more preferably cyclohexylene. A morpholinoethylene group.

R ⁷ is an alkylene group having 2 to 6 carbon atoms, 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, 6 to 10 carbon atoms.
Is an aryl group having m is 1 to 20, especially 1 to
It is preferably 5. Since polycarbodiimide having m of 1 to 20 is used, water affecting storage stability in the system,
The carboxylic acid can be sufficiently captured. Since the terminal is blocked with oxazolidine, the polymerization of polycarbodiimide can be stopped at a desired degree of polymerization, and the stability itself can be increased. In addition, since it has an oxazolidine group, it is incorporated into the system, so there is no fear of bleeding or the like.

A specific example is

Embedded image The terminal of polycarbodiimide derived from carbodiimide of hydrogenated MDI represented by
Oxazolidine compound-blocked (hydrogenated MDI-modified product) or polycarbodiimide derived from carbodiimidization of HDI with N-hydroxy-1,3-
Those blocked with oxazolidine compounds,

Embedded image A hydrogenated XDI modified product represented by

Embedded image Is mentioned. Among them, hydrogenated MDI modified product, hydrogenated XDI
Modified products are preferred.

The production of the bisoxazolidine polycarbodiimide compound is not particularly restricted but includes, for example, i) reaction of an aliphatic diisocyanate with carbodiimide at a high temperature, or 3-methyl-1-phenyl-2-phospholene-1-phosphate. An aliphatic diisocyanate is carbodiimidated by reacting at room temperature using a catalyst such as an oxide to synthesize a polycarbodiimide compound, and ii) the obtained polycarbodiimide compound and N-hydroxyalkyl-
1,3-oxazolidine compounds, for example, N-hydroxyethyl-1,3-oxazolidine compounds represented by the following formula (v)

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

Can be obtained by mixing and reacting the isocyanate groups of the polycarbodiimide compound with the oxazolidine compound so as to have an equivalent amount.

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 an aliphatic diisocyanate is used, the storage stability can be improved because the reactivity with water and a carboxyl compound is higher than that of an aromatic diisocyanate.

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 and the like.

The compounding amount of the bisoxazolidine polycarbodiimide compound is 0.1 part per 100 parts by weight of the polyisocyanate compound of component A) or the urethane prepolymer.
It is preferably from 1 to 10.0 parts by weight, particularly preferably from 0.3 to 3.0 parts by weight. The mixing amount was within this range because 0.1
If the amount is less than 10 parts by weight, the storage stability decreases, and if the amount exceeds 10.0 parts by weight, the storage stability also decreases.

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, quicklime, kaolin, zeolite, diatomaceous earth, vinyl chloride paste resin, glass balloon, vinylidene chloride resin balloon and the like. Alternatively, they can be used in combination.

The composition of the present invention may use a solvent, and preferably uses an aromatic hydrocarbon solvent. 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, and tris (chloroethyl). ) Phosphate, tris (dichloropropyl) phosphate, propylene glycol adipate polyester, butylene glycol adipate polyester, alkyl epoxystearate, epoxidized soybean oil, etc., and 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-pack urethane adhesive composition of the present invention is not particularly limited, but preferably includes
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 a urethane prepomarimer, B) an oxazolidine compound and a component C), a group e) an orthoformate and / or an organic silicate, a group f) p
A mixture or an adduct of toluenesulfonyl isocyanate with an oxygen-containing organic compound and a sulfur compound, and at least one compound of group g) an organic bismuth compound;
When the compound is selected from the above. This composition has properties such as excellent curability and good storage stability. Preferably, B) per 100 parts by weight of component A)
0.1 to 20 parts by weight, C) 0.1 to 5.0 parts by weight is desirable for obtaining stable and good curability.

[2] A composition containing the above-mentioned composition [1] and further containing a carbodiimide compound of component D). This composition has properties such as excellent curability and good storage stability. A preferred combination of component C) and component D) is to use component D) carbodiimide compound for component C) orthoformate and organosilicate, respectively. The reason is mainly to improve storage stability without impairing curability. Preferably, B) 0.1 to 20 parts per 100 parts by weight of component A)
Parts by weight, C) 0.1-5.0 parts by weight, D) 0.1-2.
It is desirable to use 5 parts by weight 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] In a 1 L three-necked flask, 100.1 g of diethanolamine and 100 ml of benzene were charged. 2-methylpentanal 100.2 was added to the resulting solution.
g was added dropwise. After 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
100 g of oxazolidine ethanol and 51.5 g of xylylene diisocyanate were mixed at room temperature and reacted at 50 ° C. for 1 hour and further at 80 ° C. for 8 hours. Yield 151 g.

[Latent curing agent II] Ester oxazolidine Hardener OZ (trade name, manufactured by Bayer AG), the aforementioned ester oxazolidine (2) (Examples 1-1 to 1-7, Comparative Examples 1-1 to 1-4) [Base] Examples of Resin Production] 57 parts by weight of polyoxypropylene triol having an average molecular weight of 5,000 having three hydroxyl groups (manufactured by Asahi Glass Co., Ltd.) and polypropylene ether diol having an average molecular weight of 2,000 having two hydroxyl groups of 23 parts by weight (Sanyo Chemical Co., Ltd.) 1) into a reaction vessel.
The solution 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) is added with stirring and reacted until free isocyanate is 2.2%. Thus, a polyurethane prepolymer TDI prepolymer having a terminal isocyanate group of 1.4% was obtained.

Next, this TDI prepolymer was added with 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 5,000 previously dehydrated, and 35 parts by weight of
Parts by weight of polypropylene ether diol having an average molecular weight of 2,000 were added, and at 80 ° C. the free isocyanate was 1.
The reaction was allowed to proceed to 8% to obtain a urethane prepolymer composition as an MDI prepolymer.

100 parts by weight of the urethane prepolymer was put into a kneading container filled with dry nitrogen gas, and 120 parts by weight of heavy calcium carbonate (Super 1500) manufactured by Maruo Calcium Co., Ltd. was added as a filler. Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.
Parts by weight, 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. Add 17 parts by weight of xylene manufactured by K.K. and knead well in a vacuum stirrer.
Master batch resin was used. Further, the following components shown in Table 1 were kneaded in respective amounts to obtain a one-component urethane composition. Methyl orthoformate: HC (OMe) ₃ organic silicate: manufactured by Shin-Etsu Chemical Co., Ltd .: 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 (Dismodule W manufactured by Bayer AG).
The mixture was stirred and dissolved, and tetraisopropoxytitanium (TPT-10 manufactured by Nippon Soda Co., Ltd.) was added thereto as a carbodiimidation catalyst.
0) was added and 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).

For each of the obtained urethane compositions, the initial viscosity immediately after kneading and the viscosity (storage stability) after standing at 60 ° C. for 3 days were measured with a B-type viscometer. Further, the urethane composition was applied on a glass plate, and was applied at 20 ° C. and a relative humidity of 65 ° C.
%, The time until the polyethylene terephthalate plate no longer adhered 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 cleavage promoting compound C) may be any of the aforementioned sulfonamide compounds (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 were mixed, and 134 g of diphenylmethane diisocyanate was further added.
The mixture was reacted at 80 ° C. for 10 hours with stirring to obtain a urethane prepolymer (2%) having an isocyanate group content of 1.1%.
-A) was synthesized. [Synthesis of Urethane Prepolymer (2-b)] After the synthesis of the urethane prepolymer (2-a), 7.0 g of the above-mentioned hydroxyalkyl oxazolidin (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) partially containing was synthesized.

(Examples 2-1 to 2-7) Urethane prepolymer (2-a) or urethane prepolymer (2-a)
b) To the [polyurethane component], the oxazolidine component, p-toluenesulfonyl isocyanate, the oxygen-containing organic compound, and other additives shown in Table 2 below were sequentially added in this order, followed by sufficient kneading 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 24 hours at 70 ° C. was measured. Further, each of the obtained compositions was 100 mm long.
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 of the composition were as shown in Table 2 below. Physical properties were measured. Table 2 shows the results.

[0124]

[Table 3]

[0125]

[Table 4]

Note) The amounts of each component are indicated by 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} : Oxazolidinesilyl 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 a 50% xylene solution of titanium tetraisopropoxide was reacted at 80 ° C. for 2 hours and at 140 ° C. for 3 hours while azeotropically producing by-produced ethanol with toluene. Thereafter, unreacted substances and toluene were distilled off under reduced pressure. The infrared absorption spectrum of the product confirmed that there was no hydroxyl group, and that no ethoxy group was present by ¹ HNMR. The product has a structural formula represented by the aforementioned 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 were mixed, and 124 g of diphenylmethane diisocyanate was further added.
The mixture was reacted at 80 ° C. for 10 hours with stirring to obtain a urethane prepolymer (3%) having an isocyanate group content of 0.7%.
-A) was synthesized.

Examples 3-1 to 3-6 and Comparative Examples 3-1 to 6-1
3-3) The components shown in Table 3 were kneaded with the urethane prepolymer (3-a) in amounts shown in Table 3 to obtain compositions.
The initial viscosity of the obtained composition was measured using a B-type viscometer. Further, the viscosities of these compositions after 7 days at 50 ° C. were measured. In addition, each of the obtained compositions was vertically
mm × 100mm × 5mm thick sheet shape,
The tack free time was measured. The tack-free time is indicated by the time (minutes) taken until the formed product does not stick to the finger even if the sheet-shaped molded product is pressed with the finger. Table 3 shows the results
Shown in

[0129]

[Table 5]

The components described in Table 3 are specifically as follows. Carbon black: Asahi Thermal Dioctyl phthalate manufactured by Asahi Carbon Co., Ltd .: Trade name Diasizer DOP ester oxazolidine manufactured by Mitsubishi Chemical Corporation: Hardener OZ manufactured by Bayer Corporation This is represented by the above-mentioned chemical formula ester oxazolidine (2).

Organic silicate ester: manufactured by Shin-Etsu Chemical Co., Ltd. KF910 Additive Ti (Ad-Ti): manufactured by Sumitomo Bayer Urethane Co., Ltd. (P-toluenesulfonyl isocyanate) Organic bismuth compound: manufactured by Nitto Kasei Co., Ltd.
t ^# 83 Carbodiimide compound: DCC reagent 2-Ethylhexanoic acid: Reagent

[0132]

The moisture-curable polyurethane resin composition of the present invention has excellent curability, excellent storage stability, and does not foam during curing. Also, there is no irritating odor or corrosion of the adherend as occurs when hydrogen chloride is used as a curing accelerator. Also, by appropriately selecting or combining oxazolidine ring cleavage promoting compounds, it is possible to design curability in accordance with the required performance of various products.

Continued on the front page (31) Priority claim number Japanese Patent Application No. 7-180040 (32) Priority date July 17, 1995 (July 17, 1995) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-220113 (32) Priority date August 29, 1995 (August 29, 1995) (33) Priority claim country Japan (JP) (31) Priority claim number 7-272370 (32) Priority Date October 20, 1995 (Oct. 20, 1995) (33) Priority Country Japan (JP) (72) Inventor Kazunori Ishikawa 2-1 Oiwake, Hiratsuka-shi, Kanagawa No. Yokohama Rubber Co., Ltd. Hiratsuka Works (72) Inventor Hiroyuki Okuhira No. 2-1 Oiwake, Hiratsuka-shi, Kanagawa Prefecture Yokohama Rubber Co., Ltd. Hiratsuka Works JP-A-2-233667 (JP, A) JP-A-50-89385 (JP, A) JP-A-52-65221 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G18 / 08

Claims (5)

(57) [Claims] 1. A) a polyisocyanate compound or urethane prepolymer; B) an oxazolidine compound having at least one oxazolidine ring ; C) a hydrolyzable ester compound; p-toluenesulfonate
And Le isocyanate, oxygen-containing organic compound or a sulfur compound
Mixture or adduct with a substance; a sulfonamide derivative;
And organic bismuth compounds
A room temperature-curable polyurethane composition comprising: a compound that promotes ring opening of at least one oxazolidine ring. 2. A room-temperature-curable polyurethane composition, which further comprises D) a modified carbodiimide compound in the composition of claim 1. 3. The method according to claim 1, wherein the oxazolidine compound B) comprises a reaction product of a polyisocyanate compound or a urethane prepolymer comprising an organic isocyanate and a polyol, and N-hydroxyalkyl oxazolidine. Room temperature-curable polyurethane composition. 4. The room temperature-curable polyurethane composition according to claim 1, wherein the hydrolyzable ester compound is an orthoformate and / or an organic silicate. 5. The method according to claim 1, wherein the organic bismuth compound is an organic bismuth compound.
The room temperature curing type polyurethane composition according to any one of claims 1 to 4, which is a carboxylate compound.