JP2003321665A - Adhesion-giving agent and curable resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesion-giving agent capable of being cured by moisture, etc., without being affected by an alcohol formed out of a modified silicone resin, etc., which is coated, and having excellent adhesive properties, even when the modified silicone resin, etc., is not removed, and to provide a curable resin composition containing the same. <P>SOLUTION: This adhesion-giving agent has an isocyanate group bonded to a tertiary carbon atom, and further has an alkoxysilyl group. The curable resin composition contains the adhesion-giving agent, an amine-based latent curing agent, and a urethane prepolymer having isocyanate groups bonded to the tertiary carbon atoms. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a building adhesive,
Regarding the curable resin composition used as a sealing agent and the like and the adhesion-imparting agent contained therein, in particular, a urethane resin (composition) and a resin (composition) having an alkoxysilyl group at the end can be overcoated to improve adhesiveness. To a curable resin composition excellent in heat resistance and an adhesion-imparting agent contained therein.

[0002]

2. Description of the Related Art Epoxy adhesive compositions have been widely used as building adhesives, and their improvements have been actively made. For example, a composition in which modified silicone (including a resin having an alkoxysilyl group at the terminal described later) is blended to develop rubber elasticity is disclosed in JP-A-61-2687.
No. 20, JP-A-4-1220, JP-A-4-10087.
No. 8, JP-A-7-42349, JP-A-7-15824.
3, JP-A-10-237408, and JP-A-10-30.
It is described in each publication of No. 6273.

This epoxy adhesive composition is excellent in heat resistance, water resistance, etc., but is inferior in impact resistance, workability, etc., and is poor in flexibility and brittle. In addition, the “Act on Ensuring Housing Quality Assurance” requires the provision of adhesives that can meet long-term guarantees. That is,
There is a demand for a more reliable adhesive that can withstand various environmental changes such as temperature and humidity and deformation such as vibration.

As such a more reliable building adhesive, a polyurethane resin and a modified silicone resin which are excellent in impact resistance and water resistance, which have a low elongation at low temperature to a high temperature, little change in strength, are highly flexible. Etc. have become popular in recent years.

However, a base material (adherend) for which an adhesive for construction, particularly an adhesive for exterior materials (for example, tiles) is used.
In some cases, modified silicone resin, urethane resin or the like is coated (including undercoating, coating as a primer, etc.) in order to secure water resistance, adjust unevenness (unevenness), and the like. The coated modified silicone resin produces alcohol from an alkoxysilyl group (hydrolyzable silyl group) contained therein when it is cured or deteriorated. Then, this alcohol easily reacts with the isocyanate group of the urethane resin (urethane prepolymer) and inactivates the isocyanate group, so that the adhesion between the urethane resin and the modified silicone resin coated is impaired. Therefore, when a modified silicone resin or the like is coated on the base material, a urethane-based adhesive or the like cannot be used, and even if it is used, the isocyanate group is deactivated by the alcohol and the adhesive strength is poor, It does not function as an adhesive agent, a sealing agent or the like having higher reliability than the above.

[0006]

SUMMARY OF THE INVENTION The present invention is a cure that can be cured by moisture or the like without being affected by alcohol produced from a modified silicone resin coated (including coating as a primer, a primer, etc. herein). The purpose of the present invention is to provide a resin composition. More specifically, the present invention, in the case where the adherend is a modified silicone resin or the like coated on a base material or the like, the adhesiveness with the modified silicone resin or the like is not required even if the modified silicone resin or the like is not removed. An object of the present invention is to provide a curable resin composition having excellent properties. The present invention also provides an adhesion-imparting agent and an adhesion-imparting agent composition contained in the curable resin composition having excellent adhesive strength.

[0007]

Means for Solving the Problems As a result of intensive investigations by the present inventors regarding building adhesives, sealing agents, etc., particularly adhesives for exterior materials (such as tiles), tertiary isocyanate groups and alkoxysilyl groups have been obtained. It was found that when a compound having a group is used, it does not easily react with an alcohol produced from a resin having an alkoxysilyl group at the terminal, and when cured, it has excellent adhesiveness to a resin having an alkoxysilyl group at the terminal. . In addition, when an amine-based latent curing agent (particularly, ketimine or an oxazolidine compound) is used in the urethane-based composition, the reaction with the alcohol generated from the alkoxysilyl group is suppressed in the composition with the above-mentioned compound, and it may be caused by moisture or the like. Curing easily and quickly, and ensuring sufficient pot life (reactivity adjustment)
Found. Furthermore, in the urethane-based composition, when the above compound and / or the amine-based latent curing agent (particularly, ketimine and oxazolidine compound) are used, a resin having an alkoxysilyl group at the terminal and a urethane resin, which have been conventionally considered difficult, Overcoating becomes more possible, and
It was found that the adhesiveness between both resins is also extremely excellent. The present invention is based on the above findings.

That is, the present invention provides the following inventions. 1) An adhesion promoter having an isocyanate group bonded to a tertiary carbon atom and an alkoxysilyl group. 2) Here, the adhesion-imparting agent is (a) tetramethylxylylene diisocyanate (TM)
XDI); and (b) adhesion imparting obtained by reacting a compound containing an alkoxysilyl group with one or more groups selected from the group consisting of a secondary amino group, a mercapto group and an epoxy group; Agents (type 1) are preferred.

The adhesion-imparting agent is (a) a urethane prepolymer obtained by reacting tetramethylxylylene diisocyanate with a polyol; and (b) a group consisting of a secondary amino group, a mercapto group and an epoxy group. Also preferred is an adhesion promoter (type 2) obtained by reacting a compound containing one or more selected groups with an alkoxysilyl group. By using a urethane prepolymer or a compound having a skeleton similar to that of a resin having an alkoxysilyl group at the end as the raw material polyol of the type 2 adhesion-imparting agent, a curable composition (a coating agent applied to an adherend is Compatibility) with the urethane prepolymer (urethane resin) or a resin having an alkoxysilyl group at its end, and the adhesiveness is improved. Preferable examples of the polyol used for the urethane prepolymer include low molecular weight compounds such as ethylene glycol, butanediol, trimethylolpropane, polyoxyalkylene polyol, polyester polyol, polyacrylic polyol and the like.

3) A curable resin composition containing the adhesion-imparting agent described in 1) above. 4) The curable resin composition according to 3), which further contains a resin having an alkoxysilyl group at the terminal. 5) The curable resin composition according to 4), which further contains an epoxy resin and an amine-based latent curing agent. The compositions of the above 3) to 5) are suitably used for adhering adherends coated with a urethane resin.

6) A curable resin composition containing the adhesion-imparting agent described in 1) above and an amine-based latent curing agent. 7) The curable resin composition according to 6), further containing a urethane prepolymer having an isocyanate group bonded to a tertiary carbon atom. 8) The curable resin composition according to 7), which further contains an epoxy resin. 9) The curable resin composition according to 7) or 8), which further contains a resin having an alkoxysilyl group at the terminal. The compositions of 6) to 9) are preferably used for adhesion of adherends coated with a resin having an alkoxysilyl group at the terminal. In particular, since the composition described in 8) above contains an epoxy resin, weather resistance, heat resistance, water resistance, adhesiveness, strength and the like are improved.

10) A agent containing an amine-based latent curing agent and a urethane prepolymer having an isocyanate group bonded to a tertiary carbon atom; B agent containing a resin having an alkoxysilyl group at the end; Consists of 1) above
A curable resin composition comprising the adhesion-imparting agent according to 5. and / or the curable resin composition according to 5) above in an agent A and / or an agent B. The present invention can provide a two-pack type composition in addition to the one-pack type composition described in 9) above, and a one-pack type composition or a two-pack type composition can be appropriately selected depending on storage conditions and the like.

11) Furthermore, an epoxy resin is added to the above A
The curable resin composition according to 10), which is contained in the agent and / or the agent B. This improves the weather resistance, heat resistance, water resistance, adhesiveness, strength, etc. of the two-part composition described in 10) above.

12) The amine-based latent curing agent is a ketimine comprising a ketone represented by the following general formula (1) or (2) and a polyamine, and / or a general formula (5) or (6) below. The curable resin composition according to any one of 5) to 11), which is an oxazolidine compound composed of a hydroxyl group-containing oxazolidine and a polyisocyanate compound.

[0015]

[Chemical 3] (In the formula, R ¹ , R ⁴ , R ⁵ and R ⁶ are independently of each other a hydrocarbon group having 1 to 6 carbon atoms, R ² is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R ³ is hydrogen. Atom, methyl group or ethyl group.)

[0016]

[Chemical 4] (In the formula, R ^{3 to} R ⁶ are as described above, R ⁷ and R ⁸ are independently of each other a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, and R ⁷ and R ⁸ are bonded to each other. R ⁹ may form a ring, and R ⁹ is a hydrocarbon group having 1 to 6 carbon atoms.) According to the present invention, storage stability, deep curability, etc. are excellent,
Even if the adherend is a base material coated with modified silicone resin, etc., it is not affected by the alcohol produced from the modified silicone resin, and can be overcoated without removing the modified silicone resin etc. Is also excellent.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the adhesion-imparting agent of the present invention and the curable resin composition containing them will be described.
The adhesion promoter of the present invention has an isocyanate group bonded to a tertiary carbon atom and an alkoxysilyl group. In addition,
In the present invention, the adhesion-imparting agent, which does not include a constituent component that constitutes the main chain of the urethane prepolymer or the resin having an alkoxysilyl group at the terminal, in the bonding group that bonds the isocyanate group and the alkoxysilyl group described below is type 1, The adhesion-imparting agent containing the constituents is called type 2. It suffices that each of the isocyanate group and the alkoxysilyl group has at least one in the molecule. Since the adhesion-imparting agent of the present invention has an isocyanate group and an alkoxysilyl group, it exhibits adhesiveness by binding with both a urethane resin and a resin having an alkoxysilyl group at the terminal, but the adhesion-imparting agent is An isocyanate group is bonded to a tertiary carbon atom. As a result, the reactivity of the isocyanate group is suppressed, so that the reaction with the alcohol produced from the modified silicone resin or the like is suppressed, and it becomes possible to overcoat the modified silicone resin or the like, which has been difficult in the past.

The carbon atom to which the isocyanate group of the adhesion promoter of the present invention is bound is not particularly limited as long as it is a tertiary carbon atom, and may be an aliphatic carbon atom or an aromatic carbon atom. Aliphatic carbon atoms are preferable because they are suitable for reactivity with the modified silicone resin. As the isocyanate group bonded to such an aliphatic carbon atom, for example, an isocyanate group derived from a polyisocyanate compound such as tetramethylxylylene diisocyanate (TMXDI) can be used.

The alkoxysilyl group of the adhesion-imparting agent of the present invention is not particularly limited as long as it has at least one alkoxy group. The alkoxy group bonded to the silicon atom of the alkoxysilyl group is not particularly limited, but a methoxy group, an ethoxy group or a propoxy group is preferable because the raw materials are easily available. The group other than the alkoxy group bonded to the silicon atom of the alkoxysilyl group is not particularly limited, and examples thereof include a hydrogen atom or a carbon group such as a methyl group, an ethyl group, a propyl group, and an isopropyl group having 20 or less carbon atoms,
Preferable examples are an alkyl group, an alkenyl group and an arylalkyl group.

Examples of the alkoxysilyl group include a methyldimethoxysilyl group, a dimethylmethoxysilyl group,
Examples thereof include trimethoxysilyl group, ethyldiethoxysilyl group, diethylethoxysilyl group, triethoxysilyl group, tris (2-methoxyethoxy) silyl group, ethyldimethoxysilyl group and methyldiethoxysilyl group. Among them, those having two or more alkoxy groups in the alkoxysilyl group are preferable in terms of excellent physical properties of the cured product after the alkoxysilyl group is crosslinked, and examples thereof include a methyldimethoxysilyl group, a trimethoxysilyl group, and ethyldiethoxy. Silyl group, triethoxysilyl group, tris (2
Preferable examples thereof include -methoxyethoxy) silyl group and the like.

As long as the adhesion-imparting agent of the present invention has the above-mentioned isocyanate group and alkoxysilyl group, the bonding group for bonding these groups is not particularly limited. The bonding group can be arbitrarily selected so that the adhesion-imparting agent (Type 1) can be easily synthesized. For example, as described below, a polyisocyanate compound and a compound having an active hydrogen such as an amino group or a mercapto group, or Examples thereof include a residue (urethane bond or the like) obtained by reaction with a compound having an epoxy group or the like that reacts with an isocyanate group.

The type 2 adhesion-imparting agent comprises (a) a urethane prepolymer obtained by reacting tetramethylxylylene diisocyanate with a polyol; and (b) a group consisting of a secondary amino group, a mercapto group and an epoxy group. It is obtained by reacting one or more selected groups with a compound containing an alkoxysilyl group. The polyol used for the urethane prepolymer (a) is not particularly limited, but suitable examples include low molecular compounds such as ethylene glycol, butanediol, trimethylolpropane, polyoxyalkylene polyols, polyester polyols, polyacrylic polyols and the like. Since the adhesiveness imparting agent type 2 has a skeleton similar to a urethane prepolymer (including urethane resin) or a resin having an alkoxysilyl group at the terminal in the skeleton, the compatibility with the resin is improved and the adhesion is improved. The property is improved.

The adhesion-imparting agent can be manufactured by the following method. The type 1 adhesion-imparting agent produces a urethane prepolymer described later by using a polyisocyanate compound having an isocyanate group bonded to a tertiary carbon atom and a compound having an alkoxysilyl group in excess of the polyisocyanate compound. It can be obtained by reacting under the conditions. For example, the type 1 adhesion-imparting agent is a compound containing tetramethylxylylene diisocyanate, one or more groups selected from the group consisting of a secondary amino group, a mercapto group and an epoxy group, and an alkoxysilyl group. It is obtained by reacting. here,
As the amino group, a "secondary amino group" is used. With a primary amino group, the reaction with the isocyanate group is too fast, so that the desired structure may not be obtained in some cases.

Examples of the polyisocyanate compound used for the adhesion-imparting agent include TMXDI and polyisocyanate compounds obtained by polymerizing an isocyanate compound (TMI) having an α-methylstyrene skeleton. Examples of the compound containing a secondary amino group or the like and an alkoxysilyl group include N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β. (Aminoethyl)
Secondary amino group-containing silane compounds such as γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyl Mercapto group-containing silane compounds such as dimethoxysilane and γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β Examples thereof include epoxy group-containing silane compounds such as-(3,4 epoxycyclohexyl) ethyltrimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane. Among them, the amino group-containing silane compound is preferable from the viewpoint of easy availability and reaction, and the secondary amino group-containing silane compound is easy to synthesize the adhesion promoter in the composition of the present invention. It is particularly preferable in terms of points.

The type 2 adhesion-imparting agent comprises (a) a urethane prepolymer obtained by reacting tetramethylxylylene diisocyanate with a polyol; and (b) a group consisting of a secondary amino group, a mercapto group and an epoxy group. It can be obtained by reacting a compound containing one or more selected groups with an alkoxysilyl group under the conditions for producing the urethane prepolymer described later by using the urethane prepolymer in excess. As the polyol, a polyol used when producing a urethane prepolymer described later can be used.

The adhesion-imparting agent of the present invention is inferior in the reactivity of the isocyanate group and can suppress the reaction with the alcohol produced from the modified silicone resin or the like even when it is overcoated on the modified silicone resin or the like. However, since the adhesion-imparting agent does not deactivate the isocyanate group and can bond to both the urethane resin and the resin having an alkoxysilyl group at the terminal, it is possible to firmly bond these resins and to provide an excellent overcoating. Shows sex. That is, it has been difficult in the past, recoating a modified silicone resin or the like with a urethane-based resin composition,
And, the reverse coating is possible.

Next, the curable resin composition of the present invention will be described. The composition of the present invention is each composition described below,
First, each component (resin component and curing agent) contained in these compositions will be described.

(I) Resin having an alkoxysilyl group at the terminal The resin having an alkoxysilyl group at the terminal is a prepolymer having an average of one or more alkoxysilyl groups in the molecule, and is a conventionally known so-called "modified silicone resin". Can be used.

The alkoxysilyl group causes a condensation reaction in the presence of moisture or a cross-linking agent, if necessary, by using a catalyst or the like.

The alkoxysilyl group is preferably a methoxy group, an ethoxy group or a propoxy group as the alkoxy group bonded to the silicon atom, as described in the adhesion-imparting agent of the present invention. The alkoxysilyl group is methyldimethoxy. A silyl group, a trimethoxysilyl group, an ethyldiethoxysilyl group, a triethoxysilyl group, a tris (2-methoxyethoxy) silyl group and the like are preferable. The groups other than the alkoxy group bonded to the silicon atom of the alkoxysilyl group are the same as those described above, and a hydrogen atom or an alkyl group, an alkenyl group or an arylalkyl group having 20 or less carbon atoms can be preferably mentioned. .

In the present invention, the alkoxysilyl group may be present at the terminal in the molecule, on the side chain, or on both.

Examples of the main chain of the resin having an alkoxysilyl group at the terminal include polyethers such as alkylene oxide polymers, polyesters, ether / ester block copolymers, vinyl polymers, vinyl copolymers, and diene polymers. Examples thereof include polymers and saturated hydrocarbons. Examples of the polyether include those having a repeating unit represented by the following formula.

[0033]

[Chemical 5]

The polyether may be composed of only one kind of these repeating units or may be composed of two or more kinds thereof.

The vinyl polymer, vinyl copolymer, diene polymer and saturated hydrocarbon include, for example, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-butadiene copolymer, Ethylene-propylene copolymer, ethylene-
Vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, polyisoprene, styrene-isoprene copolymer, isobutylene-isoprene copolymer, polychloroprene, styrene-chloroprene copolymer, acrylonitrile-chloroprene copolymer, poly Examples include isobutylene, polyacrylic acid ester, and polymethacrylic acid ester.

The resin main chain having an alkoxysilyl group at the terminal may be used alone or in combination of two or more kinds.

The resin having an alkoxysilyl group at the terminal is preferably bifunctional or more, that is, alkoxysilanes having two or more alkoxysilyl groups in the molecule are preferred.
-20 functional alkoxysilanes are more preferable because the raw materials are easily available.

The resin having an alkoxysilyl group at the terminal may be used alone or in combination of two or more. When two or more kinds are mixed and used, it is preferable to contain 10% by mass or more of a compound having a polyether main chain and / or a compound having a saturated hydrocarbon main chain.

The molecular weight of the resin having an alkoxysilyl group at the terminal is not particularly limited, but a high molecular weight resin has a high viscosity and is difficult to handle in some cases, so that the number average molecular weight is preferably 50,000 or less. The resin having an alkoxysilyl group at such an end can be produced by a known method. Examples of commercially available products include MS polymer, EPaON manufactured by Kanegafuchi Chemical Co., Ltd .; Exestar manufactured by Asahi Glass Co., Ltd.

(II) Urethane Prepolymer The urethane prepolymer used in the present invention is not particularly limited as long as it is a urethane prepolymer having an isocyanate group bonded to a tertiary carbon atom, but the carbon atom to which the isocyanate group is bonded is aromatic. It is preferable not to form a ring, and specifically, a urethane prepolymer having an isocyanate group bonded to a carbon atom which is a tertiary carbon atom and does not form an aromatic ring. Here, the "carbon atom which is a tertiary carbon atom and does not form an aromatic ring" is an aliphatic carbon atom which is a tertiary carbon atom and may contain a hetero atom,
A carbon atom forming an aliphatic ring or a carbon atom forming an aliphatic ring containing a hetero atom. Therefore, the urethane prepolymer used in the present invention is, for example, diphenylmethane diisocyanate (MDI) or tolylene diisocyanate (TD) in which a nitrogen atom of an isocyanate group is directly bonded to a carbon atom of a phenyl group constituting an aromatic ring.
It does not include phenylisocyanate compounds such as I).
The urethane prepolymer used in the present invention has two or more of the above isocyanate groups in the molecule. Such a urethane prepolymer is obtained by reacting a polyisocyanate having an isocyanate group bonded to a carbon atom which is a tertiary carbon atom and does not form an aromatic ring, with a polyol.

The polyisocyanate is not particularly limited as long as it is a compound having an isocyanate group bonded to a carbon atom which is a tertiary carbon atom and does not form an aromatic ring,
Such polyisocyanates may be used alone or in combination of two or more. Specifically, tetramethyl xylene diisocyanate (TMXD
I), polyisocyanates such as isocyanate compounds obtained by polymerizing an isocyanate compound (TMI) having an α-methylstyrene skeleton, and isocyanurate bodies and burette bodies of these polyisocyanates. Preferable examples of the isocyanurate body of polyisocyanate include isocyanurate bodies such as tetramethylxylylene diisocyanate.

As the polyol used for synthesizing the urethane prepolymer, polyether polyol, polyester polyol and other polyols and mixed polyols thereof can be used. Examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 4,4′-dihydroxyphenylpropane,
4,4'-dihydroxyphenylmethane, glycerin,
One or more polyhydric alcohols such as 1,1,1-trimethylolpropane, 1,2,5-hexanetriol and pentaerythritol, and one of propylene oxide, ethylene oxide, butylene oxide, styrene oxide and the like. Another example is a polyether polyol obtained by adding two or more kinds. In particular,
Examples thereof include polyoxypropylene glycol, polyoxyethylene glycol, polyoxypropylene triol, and polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran.

The polyester polyol is, for example, one or two of low molecular weight polyols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane and other low molecular weight polyols. Above, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid,
Examples thereof include condensation polymers with dimer acid and one or more low molecular weight carboxylic acids and oligomer acids; ring-opening polymers such as propionlactone, valerolactone and caprolactone.

Other polyols include polymer polyols; polycarbonate polyols; polybutadiene polyols; hydrogenated polybutadiene polyols; acrylic polyols; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, etc. A low molecular weight polyol is mentioned.

Among these, a polyether polyol having a number average molecular weight of 500 to 15,000, particularly a polyether polyol having a number average molecular weight of 1,000 to 10,000 is preferable because the physical properties after curing are particularly excellent. These polyols may be used alone or in combination of two or more.

The urethane prepolymer is obtained by reacting a polyol with an excess of polyisocyanate. The mixing ratio of polyol and polyisocyanate is
The ratio of isocyanate groups in polyisocyanate to hydroxyl groups in polyol (NCO / OH) is 1.3-2.
It is preferably 5 and more preferably 1.5 to 2.0. Within this range, the urethane prepolymer has an appropriate viscosity and the cured product exhibits excellent elongation.

As the method for producing the urethane prepolymer, the same method as that for the ordinary urethane prepolymer can be used. For example, it can be obtained by heating and stirring the above-mentioned quantitative ratio of the polyol and the polyisocyanate at 50 to 100 ° C. If necessary, a urethane-forming catalyst such as an organic tin compound, organic bismuth, or amine may be used.

Thus, a urethane prepolymer having an isocyanate group bonded to a carbon atom which is a tertiary carbon atom and does not form an aromatic ring is obtained. These urethane prepolymers may be used alone or in combination of two or more.

In the present invention, a urethane prepolymer having an isocyanate group bonded to a carbon atom which is a tertiary carbon atom and does not form an aromatic ring is used. However, all the isocyanate groups contained in the urethane prepolymer are It does not have to be bonded to a carbon atom that is a tertiary carbon atom and does not form an aromatic ring. The urethane prepolymer may partially have an isocyanate group bonded to a primary or secondary elementary atom. Preferably, 20 mol% or less of an isocyanate group bonded to a primary or secondary carbon atom or an aromatic carbon atom may be contained with respect to all the isocyanate groups contained in the urethane prepolymer.
In the present invention, the isocyanate group of the urethane prepolymer does not have to be protected (blocked), but it may be protected if necessary. The protection in this case is
Usually used amines, phenols, oximes and the like can be used.

(III) Epoxy resin The epoxy resin is
It is not particularly limited, and examples thereof include bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, pyrocatechol, resorcinol, cresol novolac, tetrabromobisphenol A, trihydroxybiphenyl, bisresorcinol, bisphenol hexafluoro. Glycidyl ether type obtained by the reaction of polychlorophenol such as acetone, tetramethylbisphenol F, bixylenol and epichlorohydrin; glycerin, neopentylglycol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, polypropylene Obtained by reacting an aliphatic polyhydric alcohol such as glycol with epichlorohydrin Polyglycidyl ether type; p-
Glycidyl ether ester type obtained by the reaction of hydroxycarboxylic acids such as oxybenzoic acid and β-oxynaphthoic acid with epichlorohydrin; phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endo Polyglycidyl ester type derived from polycarboxylic acid such as methylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid and polymerized fatty acid; glycidylaminoglycidyl ether type derived from aminophenol, aminoalkylphenol, etc .; amino Glycidyl aminoglycidyl ester type derived from benzoic acid; aniline, toluidine, tribromoaniline,
Glycidylamine type derived from xylylenediamine, diaminocyclohexane, bisaminomethylcyclohexane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, etc .; further epoxidized polyolefin, glycidylhydantoin, glycidylalkylhydantoin, tri Glycidyl cyanurate and the like; butyl glycidyl ether, phenyl glycidyl ether, alkylphenyl glycidyl ether, benzoic acid glycidyl ester, monoepoxy compounds such as styrene oxide, and the like, and one or a mixture of two or more thereof can be used. .

Of these, bisphenol A and bisphenol F type epoxy resins are preferable because they are easily available and have a good balance of properties (performance) of the cured product. The epoxy resin or its prepolymer may be a commercially available product or may be produced. The production conditions are not particularly limited, and it can be carried out under commonly used conditions.

The (IV) and (V) amine-based latent curing agents are not particularly limited, and the curing agents used in urethane-based compositions and epoxy-based compositions can be used. In the urethane-based composition, when an amine-based latent curing agent (particularly, ketimine and oxazolidine compound described below) is used,
In the composition with the adhesion-imparting agent of the present invention, the reaction with the alcohol generated from the alkoxysilyl group is suppressed, the composition is easily and quickly cured by moisture, etc., and the pot life can be sufficiently secured (reactivity adjustment). . Further, in the urethane-based composition, when the adhesion-imparting agent and / or the amine-based latent curing agent of the present invention (particularly, ketimine and oxazolidine compound described below) are used, an alkoxysilyl group is added to the terminal, which was conventionally considered difficult. It becomes possible to apply multiple coatings of the resin and the urethane resin (improvement of overlaying property),
Moreover, the adhesiveness between both resins is also extremely excellent.

The urethane composition (including epoxy resin) of the present invention usually contains a latent curing agent. The latent curing agent can be used without particular limitation as long as it is generally contained in the one-pack type moisture-curable urethane composition or the one-pack type moisture-curable epoxy composition. For example, oxazolidine compounds, ketimines (including aldimines), enamines, JP-B-5-75035, JP-B-7-9882.
Examples thereof include morpholine compounds disclosed in Japanese Patent Laid-Open Publications and the like. In the present invention, among these, the moisture potential which is substantially inactive in the absence of moisture, but produces a primary or secondary amino group by contact with the moisture (hydrolysis) A curing agent is preferable, and specifically, an oxazolidine compound, ketimine, and enamine are preferable. These can be used without particular limitation as long as they are moisture-latent compounds having skeletons of oxazolidine compounds, ketimines or enamines. Hereinafter, the ketimine and oxazolidine compounds suitable for the composition of the present invention will be described.

(IV) Ketimine Among ketimines, ketone (1) having an aromatic group at one of the α-positions of the following carbonyl group or α of the carbonyl group
A ketimine composed of a ketone (2) having a substituent having a large steric hindrance on one of the positions and a polyamine is preferable.

[0055]

[Chemical 6] (In the formula, R ¹ , R ⁴ , R ⁵ and R ⁶ are independently of each other a hydrocarbon group having 1 to 6 carbon atoms, R ² is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R ³ is hydrogen. Atom, methyl group or ethyl group.)

Ketimine does not function as a curing agent until the amine is regenerated by a hydrolysis reaction with water, and is hydrolyzed by water in the air or water contained in the composition,
It is a latent curing agent that regenerates amines.

(IV-1) Ketimine (A) The ketimine (A) composed of the above ketone (1) and polyamine will be described.

The ketimine used in the composition of the present invention is
It is a ketimine (A) obtained from a polyamine and a ketone represented by the following general formula (1).

[Chemical 7] (In the formula, R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, R ² is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) Here, R ¹ and R ² have 1 to 6 carbon atoms. The hydrocarbon group of, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl , 2-ethylbutyl group,
Alkyl groups such as 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group and 1-ethyl-2-methylpropyl group, and these alkyl groups, respectively. And an alkylene group corresponding to

When the composition contains the ketimine (A) consisting of the ketone (1) having an aromatic group at one of the α-positions of the carbonyl group, it has excellent storage stability, and the reactivity is adjusted and overcoating is performed. You can improve your sex.

The ketone represented by the above general formula (1), which is a raw material of the ketimine (A), is not particularly limited as long as it has an aromatic group and an aliphatic group at the α-position of the carbonyl group. Acetophenone, 1'or 2'-acetonaphthone and alkyl group-substituted products thereof are mentioned. When such a ketone is used, the stability of ketimine is improved, and when it is made into a composition, it has excellent storage stability, and it is possible to adjust the reactivity and improve the recoatability.

Among these ketones, valerophenone,
Isovalerophenone, n-hexanophenone, n-heptanophenone, 2'-ethylpropiophenone, 4'-
Ethylpropiophenone, 4'-n-butylacetophenone, 4'-isobutylacetophenone, 4'-t-butylpropiophenone, 4'-n-pentylacetophenone are easily available and the stability of ketimine (A) is high. It is excellent because it is preferable. Particularly, acetophenone and propiophenone are preferable as general-purpose products.

The amine used for the synthesis of ketimine (A) can be used without particular limitation as long as it is a polyamine having two or more primary amino groups, but it is directly bonded to an aromatic ring because of its excellent curing rate. An aliphatic polyamine (which may contain an aromatic ring in its skeleton) which is a polyamine having two or more primary amino groups which is not used is preferable. As the aliphatic polyamine, 2,5-dimethyl-2,5-
Hexamethylenediamine, Mensendiamine, 1,4-
Bis (2-amino-2-methylpropyl) piperazine,
Polypropylene glycol in which an amino group is bonded to propylene branched carbon at both ends of the molecule (diamine having a propylene skeleton, for example, "Jefamine D230", "Jeffamine D400" manufactured by San Techno Chemical Co., triamine having a propylene skeleton, for example, "Jeffamine T40
3 "etc.), ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethylpiperazine,
1,2-diaminopropane, iminobispropylamine, methyliminobispropylamine, H ₂ N (CH ₂
CH ₂ O) ₂ (CH ₂ ) ₂ NH ₂ (“Jefamine EDR 148” (diamine having ethylene glycol skeleton manufactured by San Techno Chemical Co., Ltd.)) and the like. Diamino-2-methylpentane ("M" manufactured by DuPont Japan
PMD ”), metaxylylenediamine (MXDA), polyamidoamine (“ X2000 ”manufactured by Sanwa Chemical Co., Ltd.), isophoronediamine, 1,3-bisaminomethylcyclohexane (“ 1,3BAC ”manufactured by Mitsubishi Gas Chemical Co., Inc.), 1 -Cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine, dimethyleneamine having a norbornane skeleton ("NBDA" manufactured by Mitsui Chemicals, Inc.) and the like can be mentioned. Among these, 1,3-bisaminomethylcyclohexane, dimethyleneamine having a norbornane skeleton, metaxylylenediamine, H ₂ N (CH ₂ C) because of its particularly high curing rate.
H ₂ O) ₂ (CH ₂ ) ₂ NH ₂ (diamine having ethylene glycol skeleton), diamine having propylene skeleton, triamine having propylene skeleton, polyamidoamine (trade name: X2
000) is preferred.

The ketimine (A), which is a reaction product of a polyamine and a ketone (1), is preferably used in combination with acetophenone or propiophenone and 1, from the viewpoint of stability, adjustment of reactivity and recoatability. Obtained from 3-bisaminomethylcyclohexane; Obtained from acetophenone or propiophenone and dimethyleneamine (NBDA) having a norbornane skeleton; Obtained from acetophenone or propiophenone and metaxylylenediamine; Acetophenone Or propiophenone and diamine of ethylene glycol skeleton or propylene skeleton, Jeffamine EDR148,
Those obtained from Jeffamine D230, Jeffamine D400 and the like or Jeffamine T403 which is a propylene skeleton triamine; and the like. Among these, those obtained from acetophenone or propiophenone and 1,3-bisaminomethylcyclohexane and acetophenone or propiophenone are particularly excellent in stability, reactivity adjustment and recoatability. Dimethyleneamine with a norbornane skeleton (N
BDA) and those obtained from acetophenone or propiophenone and metaxylylenediamine are preferred.

The ketimine (A) may be used alone or in combination of two or more kinds. Such ketimine (A) is obtained by mixing a ketone and a polyamine without solvent or with benzene, toluene,
It can be obtained by heating under reflux in the presence of a solvent such as xylene, and reacting while removing the water that is eliminated by azeotropic distillation.

(IV-2) Ketimine (B) The ketimine (B) comprising the following ketone (2) and polyamine will be described. The ketimine (B) composed of the ketone (2) having a substituent having a large steric hindrance on one of the α-positions of the carbonyl group is stable and has excellent storage stability when formed into a composition with a urethane prepolymer or the like. Have
The reactivity can be adjusted and the recoatability can be improved. The ketone used for the synthesis of the ketimine compound is a ketone having a substituent at the α-position and having large steric hindrance. The ketone having a substituent at the α-position is a ketone having a substituent at the α-position counted from the carbonyl group, and by using a ketimine synthesized using such a ketone as a latent curing agent, The composition of the present invention can increase the curing speed while maintaining good storage stability and deep curability.
Furthermore, the reactivity can be adjusted and the overcoating property can be improved.

[0066]

[Chemical 8] (In the formula, R ³ is a hydrogen atom, a methyl group or an ethyl group;
⁴ , R ⁵ and R ⁶ are independently of each other a hydrocarbon group having 1 to 6 carbon atoms. Here, the hydrocarbon group having 1 to ⁶ carbon atoms of R ^{4 to} R ⁶ is the same as described for R ¹ and R ² of the above ketone (1). In addition, R ⁴ and R ⁵ may combine to form a ring, and R ⁵ and R ⁶ may combine to form a ring. Preferred examples of such a compound include methyl isopropyl ketone (MIPK), methyl t-butyl ketone (MTBK), methyl cyclohexyl ketone, and methyl cyclohexanone.

As the polyamine which is the other raw material of the ketimine (B), the same polyamine as the ketimine (A) can be used.

The ketimine (B) is preferably used as MIPK or MTBK and H ₂ N (CH ₂ CH ₂₎ from the viewpoint of stability, adjustment of reactivity and recoatability.
₂ O) ₂ (CH ₂ ) ₂ NH ₂ and obtained, MI
Obtained from PK or MTBK and 1,3-bisaminomethylcyclohexane, MIPK or MTBK
Obtained from dimethylene amine (NBDA) having a norbornane skeleton, MIPK or MTBK and MXDA
And those obtained from MIPK or MTBK and polyamidoamine. Among them, those obtained from MIPK or MTBK and dimethyleneamine (NBDA) having a norbornane skeleton, those obtained from MIPK or MTBK and 1,3-bisaminomethylcyclohexane, those obtained from MIPK or MTBK and MXDA. Are preferable, and MIPK or MTB is preferable because the adhesiveness is particularly excellent.
Those obtained from K and polyamidoamine are preferred.
The ketimine (B) may be used alone or in combination of two or more. The method for producing ketimine (B) is the same as that for ketimine (A).

The ketimines (A) and (B) may be combined, and the combination is not particularly limited, and any ketimine may be used together. A latent curing agent (hereinafter, referred to as a “ketimine mixed-type latent curing agent”) by optionally combining one or more ketimines preferable as ketimines (A) and one or more ketimines preferable as ketimines (B). Yes, it is preferable.

For example, those obtained from acetophenone or propiophenone and 1,3-bisaminomethylcyclohexane, dimethyleneamine (NBDA) having acetophenone or propiophenone and norbornane skeleton.
And one or more ketimines (A) selected from the group consisting of: MIPK or MTBK and dimethyleneamine having a norbornane skeleton (NBDA); MIPK or MTBK and 1,3-bis Obtained from aminomethylcyclohexane, MIPK
Or obtained from MTBK and MXDA, MIP
K or MTBK and at least one ketimine (B) selected from the group consisting of polyamidoamines
It is particularly preferable to use and; in combination.

In the ketimine-mixed latent curing agent,
The ratio (molar ratio) of ketimine (A) and ketimine (B) is
It is not particularly limited and can be appropriately adjusted depending on the purpose, application, required physical properties and the like.

(V) Oxazolidine Compound Among oxazolidine compounds, oxazolidine synthesized from a ketone (2) or (4) having a substituent having a large steric hindrance on one side of the α-position of a carbonyl group and an amino alcohol is further added to polyisocyanate. An oxazolidine compound obtained by reacting with a compound is preferable.

[0073]

[Chemical 9] (In the formula, R ^{3 to} R ⁶ are as described above, and R ⁷ and R ⁸ are independently of each other a hydrogen atom or a carbon number of 1 to 15).
R ⁷ and R ⁸ may combine with each other to form a ring. ) The oxazolidine compound is obtained by adding the oxazolidine described below to some or all of the isocyanate groups both when the polyisocyanate described below is used for the raw material polyisocyanate compound and when the urethane prepolymer is used. Although they are compounds, they are collectively referred to as oxazolidine compounds in the present invention.

The oxazolidine compound does not function as a curing agent until the amine is regenerated by a hydrolysis reaction with water, and is hydrolyzed by water in the air or water contained in the composition to regenerate the amine. It is a latent curing agent.

(V-1) Oxazolidine Compound (A) Regarding the oxazolidine compound (A) used in the present invention,
explain. The oxazolidine compound (A) of the present invention comprises a hydroxyl group-containing oxazolidine represented by the following general formula (5) and a polyisocyanate compound.

[Chemical 10] (In the formula, R ^{3 to} R ⁶ are as described above.)

R ⁴ , R ⁵ and R ⁶ of the oxazolidine (5) are hydrocarbons having 1 to ⁶ carbon atoms and are the same as those described for R ¹ and R ² of the ketone (1).

The substituents R ^{3 to} R ⁶ further improve the curing rate of the curable resin composition using the oxazolidine compound (A) as a latent curing agent, and are excellent in reactivity adjustment and recoatability, and oxazolidine. From the viewpoint of accelerating the hydrolysis of the compound (A), a compound in which R ³ , R ⁵ and R ⁶ are methyl groups and R ⁴ is a hydrogen atom is preferable. The oxazolidine (5) may be used alone or in combination of two or more.

Oxazolidine (5) can be obtained by reacting a ketone represented by the following general formula (2) with a diethanolamine represented by the following general formula (3).

[Chemical 11] The synthesis is carried out, for example, by reacting the ketone (2) and the diethanolamine (3) in the absence of a solvent or in the presence of a solvent such as benzene, toluene, xylene, etc., while heating and refluxing, while removing the desorbed water by azeotropic distillation. Can be obtained.

The polyisocyanate compound used for producing the oxazolidine compound (A) is not particularly limited as long as it is a compound having two or more isocyanate groups. For example, polyisocyanate used for producing a usual urethane prepolymer, Alternatively, a usual urethane prepolymer may be used. Examples of the polyisocyanate used for producing a normal urethane prepolymer include, for example,
2,4-Tolylene diisocyanate (2,4-TD
I), 2,6-tolylene diisocyanate (2,6-T
DI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), p-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate ( XD
I), tetramethylxylylene diisocyanate (TM)
XDI), aromatic polyisocyanate such as 1,5-naphthalene diisocyanate; hexamethylene diisocyanate (HDI), aliphatic polyisocyanate such as norbornane diisocyanatomethyl (NBDI); isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenation) X
DI), H ₁₂ MDI (hydrogenated MDI), and other alicyclic polyisocyanates; carbodiimide-modified polyisocyanates of the above polyisocyanates, or isocyanurate-modified polyisocyanates thereof.

Examples of the ordinary urethane prepolymer include urethane prepolymers obtained by reacting the polyisocyanate used for producing the above ordinary urethane prepolymer with the above polyol. Reaction conditions and the like in the production of the urethane prepolymer are as described above. The polyisocyanate compound may be used alone or in combination of two or more.

The oxazolidine compound (A) is obtained by reacting the hydroxyl group of the hydroxyl group-containing oxazolidine with the isocyanate group of the polyisocyanate compound. For the reaction, the conditions for producing an ordinary urethane can be selected, but at room temperature to 150 ° C., particularly 50 to 90 ° C., 1 to 2
It is preferably carried out for 0 hours.

Since the oxazolidine compound (A) functions as a latent curing agent, it has two or more oxazolidine residues (oxazolidine ring moieties). The reaction rate and the introduction rate of the oxazolidine and the polyisocyanate compound are not particularly limited as long as they have two or more oxazolidine residues (oxazolidine ring moieties).

Since the oxazolidine compound (A) thus obtained has a bulky group around the nitrogen in the heterocycle, the nitrogen in the heterocycle is protected by the steric hindrance of the substituent, and its base The sex is significantly weakened. Therefore, the moisture-curable resin composition using the oxazolidine compound (A) of the present invention as a latent curing agent is particularly excellent in storage stability and can adjust reactivity and improve recoatability. Further, the moisture-curable resin composition using the oxazolidine compound (A) of the present invention as a latent curing agent has a long so-called tack free time, and the time required for allowing water necessary for hydrolysis of oxazolidine to penetrate into the coating surface is Can be long. For this reason, it is very excellent in deep-part curability, and the cured film can be easily thickened. Therefore,
The oxazolidine compound (A) of the present invention can be suitably used as a latent curing agent for a moisture curable resin composition.

(V-2) Oxazolidine Compound (B) Regarding the oxazolidine compound (B) used in the present invention,
explain. The oxazolidine compound (B) of the present invention comprises a hydroxyl group-containing oxazolidine represented by the following general formula (6) and a polyisocyanate compound.

[Chemical 12] (In the formula, R ⁷ and R ⁸ are independently of each other a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, R ⁷ and R ⁸ may combine to form a ring, and R ⁹ is a carbon atom. It is a hydrocarbon group of the numbers 1 to 6.)

The substituent R ⁹ of the oxazolidine (6) represents a hydrocarbon group having 1 to 6 carbon atoms, specifically, 1 carbon atom.
Examples thereof include an alkyl group of 6 to 6 and an alkenyl group corresponding to the alkyl group, and are the same as those described for R ¹ and R ² . Among them, it is preferable that R ⁹ is a methyl group or an ethyl group because the surface curability of the composition is particularly excellent.

R ⁷ and R ⁸ independently of each other represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms. Carbon number 1
As the hydrocarbon group of 15 to 15, for example, 1 to 15 carbon atoms
Linear or branched alkyl group, alkenyl group, aryl group optionally substituted by 1 or 2 substituents, arylalkyl group, cycloalkyl group optionally substituted by 1 or 2 substituents Etc. Specifically, as the alkyl group, for example, a methyl group, an ethyl group,
Propyl group, butyl group, pentyl group, octyl group, dodecyl group, lauryl group, isopropyl group, isobutyl group,
sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 1-methylheptyl group, etc .; As the alkenyl group, for example, vinyl group, allyl group, isopropenyl group, 2-methylallyl group and the like; aryl group such as tolyl group (o-, m-, p-), dimethylphenyl group, mesityl group and the like; arylalkyl group such as benzyl group, phenethyl group and α- Methylbenzyl group and the like; Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group and the like.

Further, R ⁷ and R ⁸ are bonded to each other to form a compound having 4 to 4 carbon atoms.
10 alicyclic or aromatic rings may be formed. Examples of such an alicyclic ring having 4 to 10 carbon atoms include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. 4 to 4 carbon atoms
Examples of the aromatic ring of 10 include a phenyl group, a benzyl group, a tolyl group (o-, m-, p-), a xylyl group, and the like.

Among these functional groups, R ⁷ is a branched hydrocarbon group, a hydrocarbon group containing an alicyclic ring or an aromatic ring, for example,
When a branched alkyl group such as an isopropyl group or a bulky group such as an aryl group, an arylalkyl group, or a cycloalkyl group, the nitrogen atom in the heterocycle (oxazolidine ring) is protected by the steric hindrance of the substituent, Since the basicity of the nitrogen atom is significantly weakened, the resulting composition of the present invention is preferable because it has good storage stability, reactivity adjustment, and recoatability.

Among the above-mentioned functional groups as R ⁷ , particularly when the carbon at the 1-position is a branched carbon or a ring member carbon, the composition of the present invention obtained has storage stability, reactivity adjustment and overcoating. It is preferable because it has particularly good properties. Specific examples of R ⁷ in which the 1-position carbon is a branched carbon include, for example, isopropyl group, s-butyl group, t-butyl group, t-pentyl group, 1-methylbutyl group, 1-methylheptyl group,
Examples thereof include an isopropenyl group. Specific examples of R ⁷ in which the 1-position carbon is a ring member carbon include, for example, a phenyl group,
Tolyl group (o-, m-, p-), dimethylphenyl group,
Examples thereof include aryl groups such as α-methylbenzyl group, and cycloalkyl groups such as cyclopentyl group, cyclohexyl group and methylcyclohexyl group. Among these, R ⁷ is particularly preferably an isopropyl group, a t-butyl group, or a cyclohexyl group from the viewpoint of easy availability of raw materials and easy synthesis.

Among the oxazolidine compounds (B) used in the present invention, preferred oxazolidines include, for example, oxazolidines represented by the following formulas (7), (8) and (9).

[Chemical 13]

Oxazolidine (6) is represented by the following general formula (1
It can be produced using the amino alcohol represented by 0) and the ketone represented by the following general formula (4) in the same manner as the production of oxazolidine used for the oxazolidine compound (A).

[0092]

[Chemical 14] (In the formula, R ^{7 to} R ⁹ are as described above.)

Polyisocyanate compound used for producing oxazolidine compound (B), reaction conditions with the polyisocyanate compound, having two or more oxazolidine residues (oxazolidine ring moieties), reaction between oxazolidine compound and polyisocyanate compound The rate and the introduction rate are similar to those of the oxazolidine compound (A).

Since the oxazoline compound (B) has a substituent around the nitrogen atom of its heterocycle, preferably a bulky group in which the 1-position carbon is a branched carbon or a ring member carbon, the oxazolidine compound (B) The composition using as a latent curing agent is excellent in storage stability, adjustment of reactivity and recoatability. Further, an oxazolidine compound (B)
Acts as a latent curing agent by ring-opening by hydrolysis in the presence of moisture (moisture). By containing the oxazolidine compound (B), the so-called tack free time is reasonably long, and the time required for the water required for the hydrolysis of the oxazolidine compound to penetrate into the composition can be lengthened.
Therefore, the oxazolidine compound (B) of the present invention can be suitably used as a latent curing agent for a moisture curable resin composition.

The oxazolidine compound (A) may be used alone or in combination of two or more kinds, and the oxazolidine compound (B) may be used alone or in combination of two or more kinds. Furthermore, the oxazolidine compounds (A) and (B) may be combined, and the combination is not particularly limited, and any oxazolidine compound may be used together. A latent curing agent (hereinafter, referred to as “oxazolidine mixed-type latent curing agent”) is optionally combined with one or more kinds of oxazolidine compounds preferable as the oxazolidine compound (A) and one or more kinds of oxazolidine compounds preferable as the oxazolidine compound (B). It may be said that it is).

For example, an oxazolidine compound (A) in which the substituents R ³ , R ⁵ and R ⁶ are methyl groups and R ⁴ is a hydrogen atom, and the substituent R ⁷ is an isopropyl group, a t-butyl group, a cyclohexyl group. It is particularly preferable to use a combination of the oxazolidine compound (B) which is and the one selected from the group consisting of the oxazolidine compound (B) represented by the above formulas (7), (8) and (9).

In the oxazolidine mixed latent curing agent, the ratio (molar ratio) of the oxazolidine compound (A) and the oxazolidine compound (B) is not particularly limited, and may be appropriately selected depending on the purpose, application, required physical properties and the like. Can be adjusted.

As the amine-based latent curing agent, the ketimines (A) and (B) or the oxazolidine compounds (A) and (B) may be used alone or in combination of two or more as described above. Further, a ketimine mixed latent curing agent and an oxazolidine mixed latent curing agent may be used in combination, and in this case, the ratio (molar ratio) of the ketimine mixed latent curing agent and the oxazolidine mixed latent curing agent is: Not particularly limited,
It can be appropriately prepared depending on the purpose, application, required physical properties and the like.

Next, the curable resin composition of the present invention will be described. The 1st aspect of the curable resin composition of this invention is a curable resin composition containing the said adhesion promoter. A second aspect thereof is a curable resin composition containing the above adhesion-imparting agent and a resin having an alkoxysilyl group at the terminal. A third aspect thereof is a curable resin composition containing the adhesion-imparting agent, a resin having an alkoxysilyl group at the terminal, an epoxy resin, and an amine-based latent curing agent. The compositions of the second and third aspects, in the case where the adherend is a urethane resin coated on a base material or the like, have a curability excellent in adhesiveness with the urethane resin or the like without removing the urethane resin. It is intended to provide a resin composition. The compositions of the second and third aspects solve the above problems, and specifically, when the adherend is a urethane resin or the like coated on a base material,
A modified silicone-based curable resin composition having excellent adhesiveness to a urethane resin, simply by recoating without removing the urethane resin. The composition of the third aspect is
Since the composition of the second aspect contains the epoxy resin and the curing agent, the weather resistance, heat resistance, water resistance, adhesiveness, strength and the like are further improved.

A fourth aspect is a curable resin composition containing the above-mentioned adhesion-imparting agent and an amine-based latent curing agent. A fifth aspect thereof is a curable resin composition containing the above-mentioned adhesion-imparting agent, an amine-based latent curing agent, and a urethane prepolymer having an isocyanate group bonded to a tertiary carbon atom. A sixth aspect thereof is a curable resin composition containing the above-mentioned adhesion promoter, an amine-based latent curing agent, a urethane prepolymer having an isocyanate group bonded to a tertiary carbon atom, and an epoxy resin. A seventh aspect thereof is a curable resin composition containing the above-mentioned adhesion-imparting agent, amine-based latent curing agent, urethane prepolymer having an isocyanate group bonded to a tertiary carbon atom, and a resin having an alkoxysilyl group at the end. is there. An eighth aspect thereof is a curable resin containing the above-mentioned adhesion-imparting agent, an amine-based latent curing agent, a urethane prepolymer having an isocyanate group bonded to a tertiary carbon atom, an epoxy resin and a resin having an alkoxysilyl group at the end. It is a composition.

In the compositions of the fourth to eighth aspects, when the adherend is a modified silicone resin or the like coated on a base material or the like, which produces alcohol by curing or the like,
A urethane-based curable resin composition having excellent adhesiveness to a modified silicone resin or the like by simply applying multiple layers without removing the modified silicone resin or the like. In addition, when an amine-based latent curing agent is used in the urethane-based composition, it is generated from the amine-based latent curing agent due to moisture before the reaction between the alcohol generated from the modified silicone resin of the adherend and the isocyanate group of the urethane. The amine and isocyanate groups are easily and quickly cured, and the pot life can be sufficiently secured (reactivity adjustment). Further, since the compositions of the sixth aspect and the eighth aspect contain an epoxy resin, the compositions of the fifth aspect and the seventh aspect further have weather resistance, heat resistance, water resistance, adhesiveness, strength and the like. Be improved. Further, since the compositions of the seventh and eighth aspects contain a urethane prepolymer having a tertiary isocyanate group and a resin having an alkoxysilyl group at the terminal, it is conventionally difficult to overcoat, prepare, etc. A type curable resin composition,
It has excellent adhesiveness and workability, and is very useful for construction (for exterior materials).

A ninth aspect thereof is an agent A containing an amine-based latent curing agent and a urethane prepolymer having an isocyanate group bonded to a tertiary carbon atom; and a resin having an alkoxysilyl group at the terminal. B agent; and the above-mentioned adhesion-imparting agent, or the above-mentioned adhesion-imparting agent and amine-based latent curing agent, together with A agent and / or B
The curable resin composition contained in the agent. A tenth aspect thereof is the composition of the ninth aspect, wherein the agent A and / or the agent B contains an epoxy resin. 9th
The composition of the tenth aspect is a two-component composition of the one-component composition of the seventh and eighth aspects, and can be stored for a long time under more severe conditions (for example, under high temperature and high humidity).
In addition, when an amine-based latent curing agent is used in the urethane-based composition, it is generated from the amine-based latent curing agent due to moisture before the reaction between the alcohol generated from the modified silicone resin of the adherend and the isocyanate group of the urethane. The amine and isocyanate groups are easily and quickly cured, and the pot life can be sufficiently secured (reactivity adjustment). The effect of the epoxy resin is similar to the above.

In an eleventh aspect thereof, the amine-based latent curing agent of the third to tenth aspects is the above general formula (1) or (2).
A ketimine composed of a ketone and a polyamine represented by the formula, and / or an oxazolidine compound composed of a hydroxyl group-containing oxazolidine represented by the general formula (5) or (6) and a polyisocyanate compound. It is a thing. When a ketimine or oxazolidine compound is used as the amine-based latent curing agent in the urethane-based composition, before the reaction between the alcohol produced from the modified silicone resin of the adherend and the isocyanate group of the urethane,
The amine and isocyanate groups generated from the amine-based latent curing agent are easily and quickly cured by moisture and the like, and the pot life can be sufficiently secured (reactivity adjustment). The composition (3rd to 10th embodiments) using a ketimine and an oxazolidine compound as an amine-based latent curing agent is excellent in storage stability, deep-curing property, and the like, and the ketimine and the oxazolidine compound are stable. The overall reactivity is worse,
Even if a modified silicone resin coated on a base material is overcoated, the modified silicone resin is not affected by alcohol derived from the modified silicone resin, and the adherend is a modified silicone resin coated on the base material. Further, it can be overcoated without removing the modified silicone resin and the like, and is particularly suitably used for a building (for exterior material) adhesive used for the adherend.

In the composition of the present invention, the content of each component is not particularly limited, and the characteristics required for the composition,
The content can be appropriately adjusted according to the purpose of use, but the following content is preferable. In the description of the content of each component, “resin” is included in the composition,
The term refers to a resin having an alkoxysilyl group at the terminal, an epoxy resin, a urethane prepolymer having an isocyanate group bonded to a tertiary carbon atom, and other polymers described later.

The content of the adhesion-imparting agent of the present invention is 0.1 to 50 relative to 100 parts by mass of all the resins contained in the composition.
Parts by mass, more preferably 0.5 to 30 parts by mass, 1
-20 parts by mass is particularly preferable. Below 0.1 parts by mass,
In some cases, the effect of the adhesion-imparting agent of the present invention cannot be expected,
If it exceeds 50 parts by mass, the physical properties after curing may deteriorate.

The content of the epoxy resin is 1 to 200 parts by mass, preferably 2 to 100 parts by mass, and more preferably 3 to 50 parts by mass, relative to 100 parts by mass of the other resins contained in the composition.
Part by weight is especially preferred. If it is less than 1 part by mass, the effect of the epoxy resin (high adhesiveness, high strength, etc.) may not be expected, and if it exceeds 200 parts by mass, the flexibility may be poor.

In the one-part compositions of the seventh and eighth aspects, which contain a resin having an alkoxysilyl group at the terminal and a urethane prepolymer having an isocyanate group bonded to a tertiary carbon atom, the use and the composition are It may be appropriately prepared according to the required properties and the like, and may be used as it is or may be stored.

The content of the amine-based latent curing agent in the composition is not particularly limited as long as it is a content generally used. When the amine-based latent curing agent is the above-described ketimine, all the isocyanate groups (NCO) in the urethane prepolymer and all the epoxy groups in the epoxy resin with respect to the amino groups (NH ₂ ) contained in these hydrolyzed polyamines. The molar ratio of the total amount of epoxy groups (E) ((NCO +
E) / (NH ₂ )) is 0.5 to 10, preferably 0.8 to 5, and more preferably 0.9 to 3.

When the amine-based latent curing agent is the above-mentioned oxazolidine compound, all isocyanate groups (NCO) in the urethane prepolymer and unreacted isocyanate groups in the oxazolidine compound with respect to the oxazolidine ring (ox) of the oxazolidine compound. The molar ratio ((NCO + NCO _ox + E) / (ox)) of the total amount of (NCO _ox ) and all epoxy groups (E) in the epoxy resin is 0.5 to
It is 20, preferably 0.8 to 10, and more preferably 0.9 to 5.

When the above-mentioned ketimine and the oxazolidine compound are used in combination as the amine-based latent curing agent, the molar ratio of the amino group (NH ₂ ) contained in the hydrolyzed polyamine to the oxazolidine ring of the oxazolidine compound ( o
x) the total amount of all isocyanate groups (NCO) in the urethane prepolymer, unreacted isocyanate groups (NCO _ox ) in the oxazolidine compound and all epoxy groups (E) in the epoxy resin (molar ratio). (NC
O + NCO _ox + E) / (NH ₂ + ox)) is 0.5 to
It is 20, preferably 0.8 to 10, and more preferably 0.9 to 5. When the content of the amine-based latent curing agent is within the above range, it is excellent in storage stability and deep curability, and is more excellent in adjusting the reactivity and improving the recoatability.

The composition of the present invention (compositions of the first to eleventh aspects) has the following essential components in each aspect,
Other additives, compounding agents, polymers and the like may be contained as necessary within a range not impairing the object of the present invention. Additive,
Examples of the compounding agent include a reinforcing agent (filler), an antioxidant, an antioxidant, a pigment (dye), a plasticizer, a thixotropic agent, an ultraviolet absorber, a flame retardant, a solvent, and a surfactant (leveling agent). , A dispersant, a dehydrating agent, a rust preventive, an adhesion imparting agent, an antistatic agent, a thixotropy imparting agent, and the like. As these additives, compounding agents, polymers, etc., those commonly used in compositions such as sealing agents and adhesives can be used.
It can be added to the composition of the present invention in a usual content, and can be appropriately changed depending on the purpose, application, required performance and the like.

The composition of the present invention is produced by thoroughly kneading the above-mentioned components under reduced pressure or in the presence of nitrogen using a stirring device such as a mixing mixer and uniformly dispersing them. The compositions of the ninth aspect and the tenth aspect may be prepared by separately preparing the agent A and the agent B by the above method or the like, and further preparing them by the above method or the like at the time of use.

The composition of the present invention is suitable as a sealing material, an adhesive, a coating material, a primer, a paint and the like, and is more suitable when an undercoat material coated with a modified silicone resin is an adherend. In particular, it is suitable for construction (for exterior materials) sealing materials, adhesives, coating materials, primers, paints, etc. (which may be simply referred to as "adhesives and the like" in the present specification) used for the adherend. Used. The composition containing the epoxy resin (third, sixth to eighth, tenth aspects) is a sealing material, an adhesive, a coating material, a primer which is required to have weather resistance, heat resistance, high adhesiveness, high strength and the like. It is suitable for paints and the like, and is more suitable when a base material coated with a modified silicone resin or the like is an adherend, and particularly for a building (exterior material) adhesive or the like used for the adherend. It is preferably used. The composition (3rd to 10th embodiments) using a ketimine and an oxazolidine compound as an amine-based latent curing agent is excellent in storage stability, deep-curing property, and the like, and the ketimine and the oxazolidine compound are stable. The overall reactivity is poorer, and even when it is overcoated on a modified silicone resin coated on a base material or the like, it is not affected by the alcohol derived from the modified silicone resin, and the adherend is the modified silicone resin or the like. However, it is possible to apply multiple layers without removing the modified silicone resin or the like, and it is particularly suitably used for a building (for exterior material) adhesive or the like used for the adherend. Since the composition of the present invention can be overcoated with a modified silicone resin or the like and a urethane prepolymer, the compositions of the seventh aspect and the eighth aspect, which are one-component compositions, are stable and have excellent adhesiveness. Further, it is excellent in workability and is suitably used for an adhesive for construction (for exterior materials) and the like.

The compositions according to the first to sixth aspects of the present invention are
It is suitable for use as an adherend already coated with urethane resin, modified silicone resin and the like. The composition of the present invention is applied onto the resin coated on the adherend by a conventional method, and is adhered to the other adherend. The compositions of the seventh and eighth aspects of the present invention are suitably used for an adherend already coated with a urethane resin, a modified silicone resin or the like, or an adherend not coated with a resin or the like. The composition of the present invention is applied to a resin coated on the adherend or a resin not coated with the resin by a conventional method, and is adhered to the other adherend.

The compositions of the seventh and eighth aspects of the present invention are suitably used for an adherend coated with a urethane resin, a modified silicone resin or the like or an adherend not coated with a resin or the like. . One of the agent A and the agent B is applied on a resin coated on the adherend or on an adherend not coated with the resin by a usual method, and the other is further coated thereon by a usual method. It is applied and adhered to the other adherend. Here, agent A and B
The agent may be applied multiple times. In addition, when using A and B
Mix the agents to form a one-part composition, apply by a conventional method,
It may be bonded to the other adherend.

[0116]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

Urethane prepolymers, ketimine derivatives, adhesion promoters and the like, which are raw materials for the compositions of Examples 1 to 5 and Comparative Examples 1 and 2, were synthesized as follows. In addition, the compound used for the synthesis used the commercial item. (1) Synthesis of urethane prepolymer Tetramethyl xylylene diisocyanate (manufactured by Mitsui Cytec Co., Ltd.) and trifunctional polypropylene glycol (“EXCENOL 5030” manufactured by Asahi Glass Co., Ltd.) were mixed at a ratio of NCO / OH of 1.5, and 80 The desired urethane prepolymer was obtained by heating with stirring at ℃ overnight. (2) Synthesis of ketimine 100 g of norbornanediamine (NBDA) and 145 g of methyl isopropyl ketone were put into a flask together with 100 g of toluene, and the reaction was carried out for 15 hours while removing water produced by azeotropic distillation. Then, toluene and excess ketone were distilled off. Removal gave the desired ketimine. (3) Synthesis of adhesion promoter 1 (type 1) 52.3 g of N-phenyl-γ-aminopropyltrimethoxysilane (manufactured by Nippon Unicar, Y9669) and tetramethylxylylene diisocyanate (manufactured by Mitsui Cytec) Were mixed at a ratio of NCO / NH of 1.0, and heated and stirred at 80 ° C. overnight to obtain an adhesion promoter 1. (4) Synthetic PPG of adhesion-imparting agent 2 (type 2) (average molecular weight 2000, excenol 2020,
Asahi Glass Co., Ltd.) 501 g and TMXDI 123.3 g N
CO / OH was mixed at a ratio of 2.0 and heated and stirred at 80 ° C. overnight to obtain a urethane prepolymer. 200 g of this urethane prepolymer and 20.3 g of N-phenyl-γ-aminopropyltrimethoxysilane were mixed at a ratio of NCO / NH of 1.0, and the mixture was heated and stirred at 80 ° C. overnight to form the adhesion promoter 2. Obtained. (5) Synthesis of adhesion-imparting agent 3 50 g of mercaptopropyltrimethoxysilane (A189, manufactured by Nippon Unicar Co., Ltd.) and 62.2 g of TMXDI are N
CO / SH was mixed at a ratio of 1.0, dibutyltin diacetate was further mixed in a catalytic amount, and the mixture was stirred at 100 ° C. for 24 hours to obtain an adhesion promoter 3. (6) Epoxy resin is manufactured by Asahi Denka (EP-4100E,
A bisphenol A type epoxy resin having an epoxy equivalent of 190) was used. (7) As the resin having an alkoxysilyl group at the end (modified silicone resin), MS polymer, manufactured by Kanebuchi Chemical Co., Ltd. (S302, main chain is PPG) was used.

As the other additives and resins, the following commercially available products were used. The plasticizer used was diisononyl adipate (manufactured by Mitsubishi Chemical Corporation), the calcium carbonate was used by Maruo Calcium Co., and the tin catalyst was dibutyltin acetate (reagent).

The curable resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were produced with the compounding amounts (parts by mass) shown in Table 1,
The adhesiveness and recoatability were evaluated. (Example 1) A composition was obtained by thoroughly kneading the mixture in the amounts shown in Table 1 using a mixing mixer under reduced pressure and uniformly dispersing the mixture. In this composition, all isocyanate groups (NCO) in the urethane prepolymer with respect to amino groups (NH ₂ ) contained in the polyamine after hydrolysis of ketimine
The ratio (NCO / NH ₂ ) was 1.0. (Example 2) A composition was obtained in the same manner as in Example 1 with the compounding amounts (parts by mass) shown in Table 1. The ratio ((NCO + E) / NH ₂ ) of urethane prepolymer and epoxy resin to ketimine of this composition was 1.0. (Example 3) A composition was obtained in the same manner as in Example 2. The ratio ((NCO + E) / NH ₂ ) of urethane prepolymer and epoxy resin to ketimine of this composition was 1.0. (Example 4) A composition was obtained in the same manner as in Example 1 with the compounding amounts (parts by mass) shown in Table 1. This composition does not contain ketimine. (Example 5) A composition was obtained in the same manner as in Example 2. The ratio ((NCO + E) / NH ₂ ) of urethane prepolymer and epoxy resin to ketimine of this composition was 1.0.

Comparative Example 1 A composition was obtained in the same manner as in Example 1 except that the adhesion promoter 1 was not used. (Comparative Example 2) A composition was obtained in the same manner as in Example 2 except that the adhesion promoter 1 was not used.

<Adhesion Test (Overcoating Property)> (Examples 1 to 5 and Comparative Examples 1 and 2) The above-mentioned modified silicone was uniformly applied to adherends (mortar) and left at room temperature for 1 week. And cured. After confirming the curing, the urethane compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were applied in a bead shape (linear shape) and cured at room temperature for 1 week (on the urethane composition. The other adherend is not glued). After confirming the curing, the composition cured into a bead shape was pulled by hand to evaluate the adhesiveness. The results are shown in Table 1.

Example 4 The urethane prepolymer was uniformly applied to an adherend (mortar) and cured in the same manner. Then, the modified silicone resin composition of Example 4 was applied and cured in the same manner, and the adhesiveness was evaluated in the same manner. The results are shown in Table 1.

[0123]

[Table 1]

As can be seen from Table 1, in the examples using the adhesion-imparting agent of the present invention, even if the modified silicone resin was overcoated with the urethane resin composition, the urethane resin was overcoated with the modified silicone resin composition. However, in both cases, cohesive failure occurred, the adhesiveness was excellent, and the recoatability was remarkably improved without being affected by the alcohol derived from the modified silicone resin. On the other hand, in the comparative example in which the adhesion-imparting agent of the present invention is not used, interfacial peeling occurs and the adhesiveness is poor,
Due to the influence of alcohol, the recoatability is extremely poor.

[0125]

According to the present invention, a coating (undercoat,
It is possible to provide a curable resin composition that can be cured by moisture or the like without being affected by alcohol produced from a modified silicone resin (including a coating as a primer). More specifically, according to the present invention, in the case where the adherend is a base material coated with a modified silicone resin or the like, the adhesiveness with the modified silicone resin or the like can be obtained without removing the modified silicone resin or the like. A curable resin composition having excellent properties can be provided. Further, it is possible to provide an adhesion-imparting agent and an adhesion-imparting agent composition contained in the curable resin composition having excellent adhesive strength.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 101/10 C08L 101/10 C09J 11/06 C09J 11/06 163/00 163/00 175/04 175 / 04 201/10 201/10 F-term (reference) 4J002 AA031 AC061 AC091 BB061 BB071 BB101 BB151 BB171 BB201 BC051 BG041 BG061 BG101 BL011 CD011 CD021 CD031 CD041 CD051 CD061 CA0614J0414J041614014 DG02 DG03 DG04 DG05 DG06 DG08 DK02 DK05 DK06 DK08 HA04 HA07 HB16 HC03 HC12 HC46 HC52 HC61 HC64 HC67 HC71 HC73 JA42 MA17 QB11 RA08 4J040 CA031 CA051 CA071 CA141 DA051 DA061 DA121 DA141 DB051 DF031 EC001 EC061 EC071 EC161 ED061 EE051 EF001 EF052 EF111 EF112 EF121 EF131 EF132 EF182 EF291 EF302 EF321 EF322 EK072 GA31 HC01 HC05 HC06 HC26 HD03 HD36 JB04 KA26 LA06 PA34

Claims (7)

[Claims] 1. An adhesion promoter having an isocyanate group bonded to a tertiary carbon atom and an alkoxysilyl group. 2. The adhesion-imparting agent is (a) tetramethylxylylene diisocyanate; (b) at least one group selected from the group consisting of secondary amino groups, mercapto groups and epoxy groups, and an alkoxysilyl group. The adhesion-imparting agent according to claim 1, which is obtained by reacting a compound containing; 3. A curable resin composition containing the adhesion promoter according to claim 1 or 2 and a resin having an alkoxysilyl group at the terminal. 4. A curable resin composition containing the adhesion-imparting agent according to claim 1 or 2, an amine-based latent curing agent, and a urethane prepolymer having an isocyanate group bonded to a tertiary carbon atom. 5. The curable resin composition according to claim 4, which further contains an epoxy resin. 6. The curable resin composition according to claim 4, further comprising a resin having an alkoxysilyl group at the terminal. 7. A ketimine composed of a ketone represented by the following general formula (1) or (2) and a polyamine, wherein the amine-based latent curing agent is: (In the formula, R ¹ , R ⁴ , R ⁵ and R ⁶ are independently of each other a hydrocarbon group having 1 to 6 carbon atoms, R ² is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R ³ is hydrogen. Atom, a methyl group or an ethyl group) and / or a hydroxyl group-containing oxazolidine represented by the following general formula (5) or (6) and a polyisocyanate compound: (In the formula, R ^{3 to} R ⁶ are as described above, R ⁷ and R ⁸ are independently of each other a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, and R ⁷ and R ⁸ are bonded to each other. A curable resin composition according to any one of claims 4 to 6, which may form a ring, and R ⁹ is a hydrocarbon group having 1 to 6 carbon atoms.