JP2003137960A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition with extremely good storage stability and low-temperature curability compatible with each other, and to provide another version of the curable resin composition retaining extremely good storage stability and low-temperature curability and having high weatherability as well. SOLUTION: This curable resin composition comprises a compound with the isocyanate groups blocked with a blocking agent, having at least two blocked isocyanate groups <=140 deg.C in the dissociation temperature for the isocyanate groups and the blocking agent and a nylon salt of specific structure. A 2nd version of the composition comprises a compound having at least two isocyanate groups, a compound having at least two vinyl(thio)ether groups and the nylon salt of specific structure. A 3rd version of the composition comprises either one of the above two compositions and a compound having at least two epoxy groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable urethane resin composition containing a thermal latent curing agent, and more particularly to a thermal latent curing agent having a specific nylon salt structure and a compound having a blocked isocyanate group. It contains a compound having an active isocyanate group and a compound having a specific functional group, and has excellent storage stability and heat curing at 140 ° C. or lower, preferably 100 to 120 ° C. (hereinafter, referred to as “low temperature curing” in the present specification). "Curability"). Moreover, when a compound having an epoxy group is contained in these compositions, it relates to a curable resin composition having both excellent storage stability and low temperature curability, and further excellent weather resistance.

[0002]

2. Description of the Related Art Isocyanate group-containing compounds used as thermosetting urethane compositions are not active isocyanate group-containing compounds because isocyanate groups have high reactivity even at low temperatures such as room temperature. Blocked isocyanate compounds in which isocyanate groups are blocked with a blocking agent such as alcohol are used. The blocked isocyanate compound pre-blocked with the blocking agent is heated in the presence of a so-called active hydrogen compound to thermally dissociate the blocking agent to regenerate the isocyanate group, whereby curing is started.

However, if a highly reactive active hydrogen compound is selected to enhance the curability of the urethane composition, the reactivity of the isocyanate group itself is high,
The urethane composition is highly likely to react with each other during storage, and lacks storage stability. On the other hand, when a compound with low reactivity or a compound with a high thermal dissociation temperature between an isocyanate group and a blocking agent is selected with an emphasis on storage stability, curing at low temperatures becomes difficult, and storage stability and low temperature curability There is a problem that it is not possible to achieve both.

In order to solve the above problems, various thermosetting urethane resin compositions have been proposed. For example, JP-A-5
JP-A-86164 discloses a thermosetting composition comprising a blocked polyisocyanate blocked with a specific blocking agent and a polyamine. In the same publication,
In order to avoid a reaction between a highly reactive polyamine and a blocked polyisocyanate, the blocked polyisocyanate is a blocked polyisocyanate blocked with a specific blocking agent, and is substantially the same as room temperature or at an appropriately elevated temperature. It is insoluble in, which ensures storage stability.

Further, Japanese Unexamined Patent Publication No. 10-158353 discloses a one-pack type thermosetting urethane composition containing a blocked isocyanate compound and an amine as main components. In this publication, in order to avoid the reaction between a highly reactive amine and a blocked isocyanate group and to secure the storage stability of the urethane composition, the active amine group on the surface is used as a curing agent, and the central particle size is 2 μm or less. The fine powder coating amine coated with the fine powder of is used.

However, storage stability of these compositions is good under relatively mild storage conditions at room temperature or 40 ° C. Therefore, the storage stability is still unsatisfactory when the temperature becomes high in summer or in the environment in which it is actually used.

The applicant of the present invention has also filed Japanese Patent Laid-Open No. 2001-4894.
In JP-A No. 8-, a one-pack type thermosetting urethane resin composition containing a prepolymer having a tertiary blocked isocyanate group having a large steric hindrance and a carboxylate of polyamine can achieve both storage stability and low temperature curability. It has been described. However, due to recent technological innovation and the like, a composition having physical properties more suitable for a manufacturing process, a manufacturing method, physical properties required for products, and the like has been demanded. The curable composition described in JP 2001-48948 A has both storage stability and low temperature curability, but further improvement in storage stability is required while maintaining the low temperature curability.

On the other hand, in the urethane composition, the heat resistance,
Other resin components such as epoxy resin may be added to the composition in order to improve weather resistance and the like. Then, studies have been carried out on the one-pack type epoxy resin composition to make the storage stability and the low temperature curability compatible with each other, and as its thermal latent curing agent, diamine having a piperazine ring and dicarboxylic acid having a long chain methylene group are used. It is also known that the following specific nylon salt is effective in heat resistance adhesion, adhesion resistance and storage stability (Journal of the Japan Adhesion Society Vol. 1, No. 1,
1965).

However, although the nylon salt curing agent has effective curability and storage stability in epoxy resin, storage stability is not sufficient in thermosetting resins other than epoxy resin such as urethane resin and urea resin. Moreover, the curing temperature is very high, which is not practical.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems. That is, the present invention includes a compound having a blocked isocyanate group and a thermal latent curing agent composed of a specific nylon salt, and has extremely excellent storage stability and 140 ° C. or less, preferably 100 to 12.
A first object of the present invention is to provide a cured resin composition capable of satisfying both the property of being heat-cured at 0 ° C. (referred to as “low temperature curability” in the present specification).

The present invention also provides an isocyanate group containing a compound having an unblocked active isocyanate group, a compound having a vinyl (thio) ether group, and a thermal latent curing agent comprising a specific nylon salt. A second object is to provide a cured resin composition that can achieve both excellent storage stability and low temperature curability without blocking.

Further, the present invention provides a curable resin composition which has excellent weather resistance while maintaining storage stability and low temperature curability even in the above composition system, and which has these three properties in a well-balanced manner. Is the third purpose.

[0013]

As a result of years of research on thermal latent curing agents used for urethane resins and the like, the inventors have found that an isocyanate compound having an isocyanate group blocked with a blocking agent and a specific structure are The present inventors have found that a composition containing a thermal latent curing agent comprising a nylon salt has extremely excellent storage stability while maintaining low temperature curability, and completed the present invention.

Further, the composition containing the specific compound as the third crosslinking component other than the nylon salt has both excellent storage stability and low temperature curability even if the isocyanate group of the isocyanate compound is not blocked. Knowing that
The present invention has been completed.

It has been found that a composition further containing an epoxy compound in addition to the above-mentioned components retains extremely excellent storage stability and low temperature curability and has improved weather resistance, and thus the present invention is completed. I arrived.

That is, the present invention is: 1) a compound having two or more blocked isocyanate groups in which the isocyanate group is blocked with a blocking agent and the dissociation temperature between the isocyanate group and the blocking agent is 140 ° C. or lower;
A curable resin composition comprising: one or more selected from the group consisting of the following nylon salts (I), (II) and (III): A nylon salt (I) comprising a primary diamine represented by the following general formula (1) and a dicarboxylic acid represented by the following general formula (2),

[Chemical 4] (In the formula, R ¹ is a hydrocarbon group having 8 to 37 carbon atoms in which a nitrogen atom of an amino group is directly bonded to a carbon atom of an aliphatic hydrocarbon; R ² is a linear group having 8 to 15 carbon atoms. Nylon salt (II) comprising a piperazine derivative represented by the following general formula (3) and a dicarboxylic acid represented by the following general formula (2),

[Chemical 5] (In the formula, R ² is a linear hydrocarbon group having 8 to 15 carbon atoms; R 2
^{3 to} R ⁶ are, independently of each other, a hydrogen atom or a carbon number of 1.
~ 4 alkyl groups. ) 1 shown in the following general formula (1)
A nylon salt (III) comprising a primary diamine and a monocarboxylic acid represented by the following general formula (4).

[Chemical 6] (In the formula, R ¹ is a hydrocarbon group having 8 to 37 carbon atoms in which the nitrogen atom of the amino group is directly bonded to the carbon atom of the aliphatic hydrocarbon; R ⁷ and R ¹¹ are H or OH independently of each other. ;
R ⁸ , R ¹⁰ are Cl, Br, I, COOR independently of each other.
¹⁷ , COR ¹⁷ , CF ₃ , CN, SO ₂ R ¹⁷ , NO ₂ or H; R ⁹ is Cl, Br, I, COOR ¹⁷ , COR ¹⁷ ,
CF _3, CN, a ^{_{SO 2 R 17, H, OH}} , NR 17 2 or OR ^17, wherein at least one of R ⁷ to R ¹¹ have the substituent other than hydrogen atom. Here, R ¹⁷ has 1 to 5 carbon atoms
Is a hydrocarbon group. This makes it possible to provide a cured resin composition having extremely excellent storage stability and low-temperature curability even in a urethane resin having a blocked isocyanate group, and the first object of the present invention can be achieved. In the present invention, the nylon salt is a general term for a salt composed of a diamine capable of widely producing a polyamide and a monocarboxylic acid having a specific substituent or a dicarboxylic acid having a long-chain methylene group. It does not mean a polyamide compound formed by dehydration condensation with an acid. The nylon salt is defined as an equimolar salt, but may be continuously bound by a salt bond, and is a salt (compound or mixture) which becomes a polyamide compound when heated and condensed.

The present invention provides 2) a compound having at least one blocked isocyanate group and at least one epoxy group in the molecule, or a compound having at least two blocked isocyanate groups and at least two epoxy groups in the molecule. A curable resin composition comprising: a mixture; and one or more selected from the group consisting of nylon salts (I), (II) and (III) described in 1). This makes it possible to provide a curable resin composition that has excellent weather resistance while maintaining storage stability and low-temperature curability, and that has these three properties in a well-balanced manner, and can achieve the third object of the present invention. .

The present invention comprises 3) a compound having two or more isocyanate groups; a compound having two or more vinyl (thio) ether groups; and the nylon salt (I) or (I) according to 1).
And at least one selected from the group consisting of I) and (III). This makes it possible to provide a cured resin composition that can achieve both excellent storage stability and low-temperature curability without blocking isocyanate groups, and can achieve the second object of the present invention.

The present invention further provides 4) an isocyanate group,
A compound having at least one vinyl (thio) ether group and an epoxy group in its molecule, or a compound having two or more of the isocyanate groups, a compound having two or more of the vinyl (thio) ether groups, and the epoxy group. And a mixture of compounds having two or more of: and one or more selected from the group consisting of nylon salts (I), (II) and (III) according to 1); . This makes it possible to provide a curable resin composition that has excellent weather resistance while maintaining storage stability and low-temperature curability, and that has these three properties in a well-balanced manner, and can achieve the third object of the present invention. .

[0020]

DETAILED DESCRIPTION OF THE INVENTION The present invention is described in detail below.
The invention according to claim 1 is a compound (A) which blocks an isocyanate group with a blocking agent and has two or more blocked isocyanate groups whose dissociation temperature between the isocyanate group and the blocking agent is 140 ° C. or lower. And at least one member selected from the group consisting of the above-mentioned nylon salts (I), (II) and (III);

The isocyanate compound (a) used for producing the compound (A) having two or more blocked isocyanate groups needs to be a compound having two or more active isocyanate groups (at its terminal). This is because if it has two or more isocyanate groups, the crosslinking reaction proceeds intramolecularly and / or intermolecularly, the crosslinking density becomes sufficiently high, and the physical properties of the cured product are excellent. Such an isocyanate compound (a) includes a-1) a polyisocyanate compound a-2) a mixture of a polyisocyanate compound and a polyol compound (monomer) a-3) a polyol compound (polymer) having a hydroxyl group at the terminal and a hydroxyl group. On the other hand, it is a urethane prepolymer having an active isocyanate group at the end, which is obtained by reacting an excess polyisocyanate compound. Here, the “active isocyanate group” used in the present specification refers to an isocyanate group (—NCO group) in which the isocyanate group is not blocked by a phenol group or the like, and does not mean the activity of the isocyanate group itself. It is used as a meaning for the above-mentioned “blocked isocyanate group”.

The polyisocyanate compound a-1) and the mixture a-2) of the polyisocyanate compound and the polyol compound (monomer) used in the present invention will be described. Examples of the polyisocyanate compound a-1) include various compounds used in ordinary production of polyurethane resins. Specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate,
Examples thereof include naphthalene-1,5-diisocyanate, compounds hydrogenated to these, and ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, and the like.

As the polyisocyanate compound used in the mixture a-2) of the polyisocyanate compound and the polyol compound (monomer), all the above polyisocyanate compounds a-1) can be used. As the polyol compound (monomer), ethylene glycol,
Diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-
Dihydric alcohols such as butanediol, 4,4'-dihydroxyphenylpropane, 4,4'-dihydroxyphenylmethane; glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, pentaerythritol, etc. And polyhydric alcohols thereof.

The mixing ratio of the polyisocyanate compound and the polyol compound (monomer) is such that the ratio of isocyanate groups to hydroxyl groups and the NCO / OH ratio are 1.4 to 3.0, preferably 1.7 to 2.5. is there. NCO / OH ratio is 1.4
If it is less than the above range, the polymer may have a high molecular weight and the polymer viscosity may be very high. In addition, the strength of the cured product may decrease. On the other hand, if the NCO / OH ratio is more than 3.0, foaming may occur during curing or the cured product often becomes brittle, and adjustment with another material such as an epoxy group-containing compound may be necessary.

The urethane prepolymer a- used in the present invention
3) will be described. Urethane prepolymer a-3)
Is composed of a polyol compound and an isocyanate compound. Examples of the polyol compound, which is one of the raw materials for producing the urethane prepolymer, include polyether polyol, polyester polyol, other polyols, and mixed polyols thereof, as in the case of ordinary polyurethane resin compositions.

Examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 4,4'-dihydroxyphenylpropane and 4,4'-dihydroxy. Dihydric alcohols such as phenylmethane; glycerin, 1,1,1-
Polyhydric alcohols such as trimethylolpropane, 1,2,5-hexanetriol and pentaerythritol; Diamines such as ethylenediamine and aromatic diamines; One or more kinds of saccharides such as sorbitol, ethylene oxide, propylene oxide, Butylene oxide,
Examples thereof include polyols obtained by adding one or more alkylene oxides such as styrene oxide.

As the polyester polyol, one or two of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane, or other low molecular weight polyol is used. Condensation polymer of one or more species and one or more species of glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, or other low molecular carboxylic acid or oligomeric acid A ring-opening polymer such as propion lactone or valerolactone.

Other polyols include a polyol having a carbon-carbon bond in the main chain, for example, acrylic polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, etc .; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol. Preferable examples include low molecular weight polyols such as pentanediol and hexanediol.

These polyol compounds may be used singly or in a mixture of two or more when producing the urethane prepolymer. The mixing ratio in this case is
Any mixing ratio can be used depending on the use, storage stability, low temperature curability, physical properties of the cured product, and the like.

As the polyisocyanate compound which is the other raw material for producing the urethane prepolymer, all of the above polyisocyanate compounds a-1) can be used. These polyisocyanate compounds a-1)
Is used in the production of the urethane prepolymer, either one or two.
A mixture of two or more species can be used. In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature curability and physical properties of the cured product.

In the production of the urethane prepolymer, the raw material amount ratio is the equivalent ratio of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the polyol (NCO
/ OH ratio) is 1.4 to 3.0, and it is preferable to set the amount ratio to 1.7 to 2.5. Within this range, foaming due to the remaining polyisocyanate compound, the viscosity of the urethane prepolymer due to molecular chain extension does not increase, the physical properties of the cured product are good, and storage stability and low temperature curability are excellent. .

As the urethane prepolymer, those having a number average molecular weight of 400 to 10,000 (GPC method) are preferably used, and those having a number average molecular weight of 2000 to 7,000 are particularly preferable. This is because the viscosity of the urethane prepolymer does not increase and the physical properties of the cured product are excellent.

The production conditions of the urethane prepolymer are not particularly limited, and the usual production conditions of the urethane prepolymer can be mentioned. That is, the reaction temperature is 50 to 10
The reaction can be carried out under atmospheric pressure at about 0 ° C. Further, a urethane-forming catalyst such as an organic tin compound or an organic bismuth compound can also be used.

In the composition of the present invention, one type of urethane prepolymer a-3) or a mixture of two or more types can be used. In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature curability and physical properties of the cured product. In the composition of the present invention, one or more of the polyisocyanate compound a-1) and / or one or more mixture a-2) of the polyisocyanate compound and the polyol compound (monomer) and / or the urethane prepolymer. It can also be used as a mixture with a-3) one or more kinds. In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature curability and physical properties of the cured product.

The compound (A) having two or more blocked isocyanate groups used in the present invention is a compound obtained by blocking the active isocyanate group of the isocyanate compound (a) with a blocking agent.

The blocking agent is not particularly limited as long as it is generally used for blocking isocyanate groups and the like, and examples thereof include phenols, lactams, oximes, active methylenes, alcohols, benzotriazoles, mercaptans, Examples thereof include acid amide type, imide type, amine type, imidazole type, and urea type.
Phenol-based blocking agents include phenol, cresol, xylenol, and ethylphenol; lactam-based blocking agents include ε-caprolactam and δ-
Valerolactam, β-butyrolactam, β-propiolactam and the like; oxime type blocking agents include formamide oxime, acetamide oxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, cyclohexanone oxime, etc .; active methylene type As the blocking agent, diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone, etc .; as the alcohol-based blocking agent, methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, ethylene. Examples thereof include glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether. Phenol-based, lactam-based, and oxime-based blocking agents are preferred.

The dissociation temperature between the isocyanate group of the blocked isocyanate compound used in the present invention and the blocking agent is 140 ° C. or lower. Within this range, a composition having extremely excellent storage stability and low temperature curability can be obtained.
The dissociation temperature is preferably 120 ° C. or lower, particularly preferably 100 ° C. or lower. Examples of the blocking agent having such a dissociation temperature include ε-caprolactam and methyl ethyl ketoxime.

Further, the compound (A) having two or more blocked isocyanate groups may contain an unblocked isocyanate group as long as the storage stability and the early curability which are the objects of the present invention can be secured. it can. Although it cannot be generally stated depending on the isocyanate compound used, the nylon salt, the required physical properties, etc., the blocking rate of the active isocyanate group is specifically 0.5 to 1.0 equivalent with respect to 1 equivalent of the active isocyanate group. Yes, and preferably
0.7 to 1.0 equivalent, and particularly preferably 0.8 to
It is 1.0 equivalent. If the active isocyanate group is blocked within this range, extremely excellent storage stability can be obtained while maintaining low temperature curability.

The production conditions for the blocking are not particularly limited, and the production conditions used for ordinary blocking can be mentioned. That is, it can be obtained by setting the reaction temperature to about 50 to 100 ° C. and stirring the reaction.

The compound (A) having two or more blocked isocyanate groups of the present invention can be blocked by mixing one or more of the above blocking agents.
Further, two or more compounds having two or more blocked isocyanate groups blocked with different blocking agents can be mixed and used. The mixing ratio in these cases depends on the application,
An arbitrary mixing ratio can be used depending on storage stability, low temperature curability and physical properties of the cured product.

The nylon salt used in the present invention will be described. In the present invention, the nylon salt is a general term for a salt composed of a diamine capable of widely producing a polyamide and a monocarboxylic acid having a specific substituent or a dicarboxylic acid having a long-chain methylene group. It does not mean a polyamide compound formed by dehydration condensation with an acid. Nylon salt is defined as a salt composed of equimolar amount, but may be continuously bonded by a salt bond,
It is a salt (compound or mixture) which becomes a polyamide compound when heated and condensed.

<Nylon Salt (I)> The primary diamine which is one of the raw materials for producing the nylon salt (I) is represented by the general formula (1).
Is a diamine in which the nitrogen atom of the amino group is directly bonded to the carbon atom of the aliphatic hydrocarbon in the hydrocarbon group having 8 to 37 carbon atoms. The hydrocarbon group having 8 to 37 carbon atoms is a linear hydrocarbon group or an alicyclic hydrocarbon group, and these groups may contain an aromatic ring. Also, the nitrogen atom of the amino group does not directly bond to these aromatic rings.

When it is a primary diamine, nylon salt (I)
It is easy to produce, and both storage stability and low temperature curability can be achieved. When the diamine is directly bonded to the carbon atom of the aliphatic hydrocarbon, the nylon salt (I) can undergo a crosslinking reaction at a low temperature after thermal dissociation and has excellent storage stability. Also,
When the number of carbon atoms of the hydrocarbon group is within this range, excellent storage stability and low temperature curability can be obtained.

The amine is not particularly limited and includes, for example, 1,8-diaminooctane; 1,9-diaminononane; 1,10-diaminodecane; 1,11-diaminoundecane; 1,12-diaminododecane. ; 1,
3-cyclohexanebis (methylamine); 1,3-cyclohexanebis (ethylamine); o, m or p-
Xylylenediamine; bisphenol A, bisphenol F, glycerin, neopentyl glycol, propylene glycol and the like, a so-called adduct modified amine obtained by reacting the glycidyl ether type epoxy resin obtained by the reaction with epichlorohydrin, and the like. . These adduct-modified amines can be used alone or as a mixture with the amine. In order to achieve both excellent storage stability and low temperature curability, o, m or p
-Xylylenediamine, 1,8-diaminooctane,
1,10-diaminodecane, 1,12-diaminododecane, 1,3-cyclohexanebis (methylamine) used alone or bisphenol A of these amines
Glycidyl ether and neopentyl glycidyl ether adduct modified products are preferably mixed and used, and m- or p-xylylenediamine having an aromatic ring is preferable, and m- or p-xylylenediamine having an aromatic ring is particularly preferable. preferable.

The dicarboxylic acid, which is the other raw material for producing the nylon salt (I), has 8 to 1 carbon atoms represented by the general formula (2).
It is an aliphatic dicarboxylic acid having a total carbon number of 10 to 17, in which a carboxyl group is bonded to both ends of a linear hydrocarbon group R ² of 5.

When the hydrocarbon group has a long-chain methylene group having 8 to 15 carbon atoms, the nylon salt (I) can be easily produced, and both storage stability and low temperature curability can be achieved.

The dicarboxylic acid is not particularly limited, and specifically, sebacic acid (decanedioic acid), undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecane. Examples thereof include diacid and heptadecanedioic acid. From the viewpoints of storage stability, low temperature curability, and availability, etc., the hydrocarbon group has an even number of carbon atoms, sebacic acid, dodecanedioic acid, tetradecanedioic acid, and hexadecanedioic acid are preferable, and dodecanedioic acid is particularly preferable. Is preferred.

The nylon salt (I) may be any combination of the above-mentioned dicarboxylic acid and diamine. For example, p-xylylenediamine and sebacic acid, p-xylylenediamine and dodecanedioic acid, p-xylylenediamine and tetradecanedioic acid, p-xylylenediamine and hexadecanedioic acid; 1,8-octanediamine and sebacic acid. , 1,8-octanediamine and dodecanedioic acid, 1,8
-Octanediamine and tetradecanedioic acid, 1,8-octanediamine and hexadecanedioic acid; 1,10-diaminodecane and sebacic acid, 1,10-diaminodecane and dodecanedioic acid, 1,10-diaminodecane and tetradecanedioic acid , 1,10-diaminodecane and hexadecanedioic acid;
1,12-diaminododecane and sebacic acid, 1,12-
Diaminododecane and dodecanedioic acid, 1,12-diaminododecane and tetradecanedioic acid, 1,12-diaminododecane and hexadecanedioic acid; 1,3-cyclohexanebis (ethylamine) and sebacic acid, 1,3-cyclohexanebis (ethylamine ) And dodecanedioic acid, 1,3-cyclohexanebis (ethylamine) and tetradecanedioic acid,
Examples include 1,3-cyclohexanebis (ethylamine) and hexadecanedioic acid. From the viewpoints of storage stability, low temperature curing property, availability, and the like, m-xylylenediamine and sebacic acid, m-xylylenediamine and dodecanedioic acid, m-xylylenediamine and tetradecanedioic acid, m-xylylenediamine.
Xylylenediamine and hexadecanedioic acid; p-xylylenediamine and sebacic acid, 1,8-octanediamine and sebacic acid, 1,10-diaminodecane and sebacic acid,
1,12-Diaminododecane and sebacic acid, 1,3-cyclohexanebis (ethylamine) and sebacic acid are preferred, and m-xylylenediamine and dodecanedioic acid are particularly preferred.

<Nylon Salt (II)> Nylon Salt (I
The diamine, which is one of the starting materials for I), is the piperazine derivative represented by the general formula (3). When it is a piperazine derivative, the nylon salt (II) can be easily produced, and both storage stability and low temperature curability can be achieved. In addition, nylon salt (I
After the thermal dissociation of I), a crosslinking reaction can be carried out at a low temperature.

The piperazine derivative is not particularly limited, and examples thereof include piperazine, 2-methylpiperazine, 2-ethylpiperazine, 2-propylpiperazine, 2-butylpiperazine, 2,5-dimethylpiperazine and 2,6. -Dimethylpiperazine, 2-aminomethylpiperazine, homopiperazine and the like (including various isomers) can be mentioned. Piperazine, 2-methylpiperazine, and 2-aminomethylpiperazine are particularly preferable for achieving both excellent storage stability and low-temperature curability.

The other dicarboxylic acid of the nylon salt (II) is the same as the dicarboxylic acid having a long chain methylene group of the nylon salt (I) (general formula (2)). Specifically, all the dicarboxylic acids exemplified above can be used.

The nylon salt (II) can be used in any combination of the piperazine derivative and the dicarboxylic acid. Examples thereof include piperazine and sebacic acid, piperazine and dodecanedioic acid, piperazine and tetradecanedioic acid, piperazine and hexadecanedioic acid, and 2-methylpiperazine and dodecanedioic acid. From the viewpoints of storage stability, low-temperature curability, availability, and the like, piperazine and sebacic acid, piperazine and dodecanedioic acid, and 2-methylpiperazine and dodecanedioic acid are preferable.

<Nylon Salt (III)> Nylon Salt (I
The primary diamine, which is one of the raw materials for producing II), is the same as the diamine of the general formula (1) used for the nylon salt (I). Specifically, all the diamines exemplified above can be used. When the diamine of the general formula (1) is used, the nylon salt (II) can be easily produced, and both storage stability and low temperature curability can be achieved. When the diamine is directly bonded to the carbon atom of the aliphatic hydrocarbon, the nylon salt (I
After the thermal dissociation of I), a crosslinking reaction can be carried out at a low temperature.

The monocarboxylic acid having a specific substituent, which is the other raw material for producing the nylon salt (III), is the benzoic acid derivative represented by the general formula (4). The substituent on the phenyl group of benzoic acid is not particularly limited, but the ortho position (R ⁷ and R ^{11 in} the general formula (4)) is preferably a hydrogen atom or a hydroxyl group capable of forming a hydrogen bond with a carboxyl group, and the meta position ( R ⁸ and R ^{10 in} the general formula (4) are preferably hydrogen atoms or electron withdrawing groups, and are in the para position (R in the general formula (4)).
⁹ ) is preferably an electron-withdrawing group, an alkoxy group, or an electron-donating group such as a hydroxyl group. With such a benzoic acid derivative, both excellent storage stability and low temperature curability can be achieved. When such a substituent is introduced, the acidity (dissociation property) of benzoic acid increases or the steric hindrance increases, so that the reactivity between the nylon salt forming site and the active group such as an isocyanate group decreases, which is excellent. It is considered that both storage stability and low temperature curability are compatible.

Such benzoic acid is not particularly limited, and salicylic acid, 3-chlorobenzoic acid, 3-methylcarbonylbenzoic acid, 3-trifluorobenzoic acid, 4-anisic acid, 4-chlorobenzoic acid, 4 -Nitrobenzoic acid, 4
-Methylcarbonylbenzoic acid, 4-cyanobenzoic acid, 4
-Trifluorobenzoic acid, 3,5-dichlorobenzoic acid,
3,4-dichlorobenzoic acid and the like can be mentioned. From the viewpoint of storage stability, low temperature curing property and easy availability, 4-chlorobenzoic acid, 4-anisic acid, 4-nitrobenzoic acid, 4
-Cyanobenzoic acid is preferred, and 4-chlorobenzoic acid is particularly preferred.

The nylon salt (III) may be any combination of the above monocarboxylic acid and diamine. For example, m-xylylenediamine and 4-anisic acid,
Examples thereof include m-xylylenediamine and 4-chlorobenzoic acid, and m-xylylenediamine and salicylic acid. From the viewpoint of storage stability, low temperature curability, and availability, m
-Xylylenediamine and 4-anisic acid, m-xylylenediamine and 4-chlorobenzoic acid are preferred.

In the present invention, nylon salts (I) and (II) are used.
And at least one nylon salt selected from the group consisting of (III) is used as a thermal latent curing agent. That is,
The nylon salt (I) can be used alone or in combination of two or more, and the nylon salt (II) or (II
The same applies to I). Nylon salt (I),
A mixture of (II) and (III) can also be used. The mixing ratio in these cases may be any mixing ratio depending on the application, storage stability, low temperature curability, physical properties of the cured product, and the like.

The method for producing the nylon salt is not particularly limited. For example, a diamine and a carboxylic acid are mixed in water or an alcohol such as methanol. Nylon salt precipitates when left to stand or cooled. Nylon salt is water-soluble, but it is very stable even at room temperature, does not dissociate with water in the atmosphere, and does not deliquesce.

The nylon salt (I) contained in the curable resin composition according to claim 1 is 2 to 100 parts by mass of the compound (A) having two or more blocked isocyanate groups.
The amount is 60 parts by mass, preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass. Nylon salt (II) is a compound (A) 1 having two or more blocked isocyanate groups.
2 to 60 parts by mass, preferably 5 to 100 parts by mass
50 parts by mass, more preferably 10 to 30 parts by mass.
Nylon salt (III) is 2 to 100 parts by mass of the compound (A) having two or more blocked isocyanate groups.
The amount is 60 parts by mass, preferably 5 to 50 parts by mass, more preferably 5 to 30 parts by mass. Within this range, both excellent storage stability and low temperature curability can be achieved.

The curable resin composition of the present invention may contain one or more polymers other than the compound of the present invention within the range of not impairing the object of the present invention. Plasticizer, filler, catalyst, solvent, UV absorber, dye, pigment, flame retardant, reinforcing agent, antioxidant, antioxidant, thixotropic agent, surfactant (including leveling agent), dispersant, A dehydrating agent, a rust preventive agent, an adhesion-imparting agent, an antistatic agent and the like may be contained.

Polymers other than the compound of the present invention are not particularly limited, but specifically, thermoplastic resins such as polyethylene (PE), polypropylene (PP), polystyrene (PS), and thermosetting resin such as phenol resin, Epoxy resin, polyurethane resin, etc., styrene type, vinyl chloride type, urethane type, etc. thermoplastic elastomer, silicone type, urethane type, etc. thermosetting elastomer, natural rubber,
Synthetic rubber such as isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber (IIR), chloroprene rubber (CR), ethylene propylene rubber (EPM, EPDM), and special rubber. Acrylonitrile-butadiene rubber (NB
R) and the like. Since the present invention is a curable resin composition containing a crosslinking agent, the polymer other than the compound of the present invention is preferably a thermosetting resin that is cured with a diamine or a carboxylic acid. The content of these polymers is the compound (A) 1 having two or more blocked isocyanate groups.
2 to 100 parts by mass, preferably 5 to 100 parts by mass
˜50 parts by mass.

Examples of the plasticizer include benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citric acid, and other polyesters, polyethers, Epoxy-based, paraffin-based, naphthene-based and aromatic process oils and the like can be mentioned. The content thereof is 5 to 100 parts by mass, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the compound having two or more blocked isocyanate groups.

As the filler, titanium dioxide, carbon black, fumed silica, pyrogenic silica, precipitated silica, crushed silica, fused silica, silicic acid derivative, diatomaceous earth, talc, metal powder, iron oxide, zinc oxide, oxidation Titanium,
Examples thereof include barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, wax stone clay, kaolin clay, calcined clay, and surface-treated products thereof. The content is 1 to 100 parts by mass with respect to 100 parts by mass of the compound having two or more blocked isocyanate groups,
It is preferably 5 to 50 parts by mass.

Examples of the catalyst include metal catalysts such as dibutyltin dilaurate, dioctyltin laurate, zinc octylate and organic bismuth compounds, amine catalysts such as triethylenediamine and morpholine amine. The content is 0.01 to 3 parts by mass with respect to 100 parts by mass of the compound having two or more blocked isocyanate groups,
It is preferably 0.05 to 1 part by mass.

Examples of the antioxidant include hindered phenol compounds; aliphatic and aromatic hindered amine compounds. Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA). Pigments include titanium dioxide, zinc oxide, ultramarine blue, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum,
Inorganic pigments such as hydrochloride and sulfate; azo pigments, phthalocyanine pigments, quinacridone pigments, quinacridone quinone pigments,
Dioxazine pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, quinonaphthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindoline pigments, Examples include organic pigments such as carbon black. Examples of the thixotropic agent include bentone, silicic acid anhydride, silicic acid derivatives, and urea derivatives. Examples of the ultraviolet absorber include 2-hydroxybenzophenone type, benzotriazole type, salicylate type and the like. As the flame retardant, phosphorus such as TCP, chlorinated paraffin,
Examples thereof include halogen type such as perchlorpentacyclodecane, antimony type such as antimony oxide, and aluminum hydroxide.

Examples of the solvent include hydrocarbons such as hexane and toluene; halogenated hydrocarbons such as tetrachloromethane; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; esters such as ethyl acetate. An alcohol type such as methanol and ethanol. Examples of the surfactant (leveling agent) include polybutyl acrylate, polydimethyl siloxane, modified silicone compounds, fluorine-based surfactants and the like. Vinylsilane or the like can be used as the dehydrating agent. Examples of the rust preventive agent include zinc phosphate, tannic acid derivative, phosphoric acid ester, basic sulfonate, and various rust preventive pigments. Examples of the adhesion-imparting agent include known silane coupling agents, silane compounds having an alkoxysilyl group, titanium coupling agents, zirconium coupling agents and the like. For example, trimethoxyvinylsilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane,
3-glycidoxy propyl trimethoxysilane etc. are mentioned. As the antistatic agent, a quaternary ammonium salt or a hydrophilic compound such as polyglycol or ethylene oxide derivative is generally used. The content of various additives, etc. described from antiaging agent to antistatic agent,
Compound 100 having two or more blocked isocyanate groups
0.01 to 5 parts by weight, preferably 0.
05 to 2 parts by mass.

Method 1 for producing the curable resin composition of the present invention
For example, a compound (A) having two or more blocked isocyanate groups is put in a kneading machine filled with nitrogen gas,
Furthermore, after adding a plasticizer, a filler, etc., if necessary,
Nylon salt is added, and the mixture is sufficiently kneaded at low temperature (room temperature to 40 ° C) under reduced pressure. The obtained curable resin composition can be used as it is, or can be stored in a container after cooling and sealing after being poured into a container.

Applications of the curable resin composition according to claim 1 are paints, adhesives, sealing agents, and other molded products. In particular, since it has a low temperature curability, it is preferably used as an adhesive composition for attaching interior parts such as plastic parts to steel plates in automobile manufacturing.

In the thermosetting resin composition of the present invention, when the composition is heated, all of the nylon salts (I), (II) and (III) are thermally dissociated at about 80 to 100 ° C. to diamine. And a carboxylic acid are released, and the blocked isocyanate group is thermally dissociated into an active isocyanate group and a blocking agent at 140 ° C or lower, and an active isocyanate group generated from a compound having two or more blocked isocyanate groups and three-dimensional crosslinking It is a thermosetting resin composition which becomes a urethane polymer by reacting, that is, the blocked isocyanate compound functions as a thermal latent isocyanate group-containing compound and the nylon salt functions as a thermal latent curing agent. Thus, the nylon salt (I) in the composition,
The thermal dissociation of (II) and (III) occurs at a low temperature of about 80 to 100 ° C., and the three-dimensional cross-linking reaction is caused by adjusting the blocked isocyanate group to also thermally dissociate near this temperature. Has excellent low temperature curability.

Further, the conventionally known curing agent which thermally dissociates at a low temperature is inferior in storage stability because the three-dimensional cross-linking reaction gradually progresses before reaching the thermal curing temperature. When the temperature is lower than the dissociation temperature, thermal dissociation is difficult and a three-dimensional cross-linking reaction does not occur, so that the storage stability is excellent. Furthermore, because the isocyanate groups are blocked, the storage conditions of the composition become severe, and the three-dimensional cross-linking reaction does not proceed even if some of the nylon salt is thermally dissociated, exhibiting extremely excellent storage stability. .

The invention according to claim 2 is a compound (b) having at least one blocked isocyanate group and at least one epoxy group in its molecule, or a compound (A) having two or more blocked isocyanate groups. A mixture of compounds (c) having two or more epoxy groups;
A curable resin composition comprising: one or more selected from the group consisting of the above-mentioned nylon salts (I), (II) and (III). Here, the compound (b) having at least one blocked isocyanate group and at least one epoxy group in the molecule means the compound (monomer, b-1) having these groups in the molecule and / or these groups. Is a prepolymer b-2) having in the molecule. Also,
Compound (A) having two or more blocked isocyanate groups
And the mixture of the compound (c) having two or more epoxy groups means a mixture of the compound (A) and the compound (c) having two or more epoxy groups.

At least one epoxy group and blocked isocyanate group used in the present invention are contained in the molecule.
If the compound (b) has the same properties, it can be cured by undergoing a cross-linking reaction with each other intramolecularly and / or intermolecularly. The compound (b)
Examples of the monomer include a monomer b-1) obtained by blocking a reaction product of a hydroxyl group-containing epoxy compound and a polyisocyanate compound with a blocking agent. The polyisocyanate compound is the polyisocyanate compound a-
All of 1) can be used. The hydroxyl group-containing epoxy compound is not particularly limited, and examples thereof include glycidol, glycerol diglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane diglycidyl ether, polypropylene glycol monoglycidyl ether, polyethylene glycol monoglycidyl ether, glycerol diglycidyl ether, bisphenol A. Examples thereof include monoglycidyl ether, bisphenol S monoglycidyl ether, diglycidyl aminophenol, (2S, 3S) -3-phenylglycidol. Among these, glycidol and glycerol diglycidyl ether are preferable. Monomer b-1) with low viscosity and high reactivity with isocyanate compounds
Is obtained. In order to obtain an unblocked form of the monomer b-1) by the reaction of the polyisocyanate compound a-1) and the hydroxyl group-containing epoxy compound,
The polyisocyanate compound may be used in a large excess to carry out the reaction under ordinary conditions. The blocking can be performed under the above conditions.

Examples of the compound (b) include prepolymer b-2) having at least one epoxy group and at least one blocked isocyanate group in its molecule. Such polymers are obtained by using epoxy polyols and blocking active isocyanate groups with blocking agents in the production of urethane prepolymers. The modified prepolymer may be prepared by grafting a prepolymer having one group with a side chain containing the other group, or both prepolymers may be copolymerized.

The epoxy polyol is not particularly limited,
Specifically, bisphenol A-based, glycidyl ether-based epoxy polyols; the hydroxyl group-containing epoxy compounds, and the like can be used. The production method is also not particularly limited, and specifically, a bisphenol A-based or glycidyl ether-based epoxy resin having epoxy groups at both ends is reacted with monoethanolamine, diethanolamine or the like under normal reaction conditions.

The isocyanate compound to be reacted with the epoxy polyol is the above-mentioned polyisocyanate compound a-
All of 1) can be used.

As the blocking agent in the compounds b-1) and b-2), all the blocking agents described above can be used. Further, the blocking rate of the isocyanate group by the blocking agent is 0.5 to 0.99 equivalents relative to 1 equivalent of the active isocyanate group, and preferably 0.
7 to 0.98 equivalent, particularly preferably 0.8 to 0.98
It is equivalent. Within this range, both excellent storage stability and low temperature curability can be achieved.

The prepolymer b-2) having at least one epoxy group and at least one blocked isocyanate group in its molecule has a number average molecular weight of 400-400.
It is preferable to use 10000 (GPC method),
In particular, it is preferable to use those of 2000 to 7000. This is because the viscosity of the prepolymer does not increase and the cured physical properties are excellent. The prepolymer may be used alone or in combination of two or more. In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature curability and physical properties of the cured product.

The production conditions of the prepolymer are not particularly limited, and the usual production conditions of urethane prepolymer can be mentioned. That is, the reaction temperature can be about 50 to 100 ° C. and the reaction can be performed under normal pressure. Further, a urethane-forming catalyst such as an organic tin compound or an organic bismuth compound can also be used. Then, the blocked urethane prepolymer can be obtained by reacting with the blocking agent under the blocking conditions.

The modified prepolymer obtained by grafting the side chain containing the other group on the prepolymer having one group and the prepolymer for copolymerizing both prepolymers are not particularly limited. The manufacturing conditions may be those usually used. For example, 2 equivalents of bisphenol A type glycidyl ether and monoethanolamine or diethanolamine are added in an equivalent amount or less to extend the chain. There may be mentioned a method of reacting the hydroxyl group thus generated with a polyisocyanate compound and finally blocking the active isocyanate group with a blocking agent.

The compound (b) having at least one epoxy group and at least one blocked isocyanate group in its molecule includes at least one compound b-1) having each of these groups in the molecule, and One or more prepolymers b-2) each having these groups in the molecule can be mixed and used. In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature curability and physical properties of the cured product.

The mixture of the compound (A) having two or more blocked isocyanate groups and the compound (c) having two or more epoxy groups means the compound (A) and the compound (A) having two or more epoxy groups ( As the compound having two or more blocked isocyanate groups, which is a mixture with c), all the compounds (A) described above can be used. In the compound having two or more blocked isocyanate groups, when the blocking rate of the isocyanate group by the blocking agent is 1.0 equivalent (100%) to 1 equivalent of the active isocyanate group, the above-mentioned active isocyanate group is used. It is also possible to newly add a compound (a) having two or more of the above as long as the object of the present invention is not impaired.

The compound (c) having two or more epoxy groups means a polyepoxy compound (monomer, c-1) and a prepolymer c-2) having two or more epoxy groups. The compound (c) needs to have two or more epoxy groups for the above reason. Polyepoxy compound (monomer,
c-1)) is not particularly limited, and specifically includes phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, N, N-diglycidyl amine, tetraglycidyl diaminodiphenylmethane. , Diglycidyl bisphenol A, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether and the like. Among these, diglycidyl bisphenol A and glycerol triglycidyl ether are preferable. This is because it has low viscosity and high reactivity.

Prepolymer c having two or more epoxy groups
-2) is not particularly limited, and specifically, an epoxy resin can be used. For example, bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, pyrocatechol, resorcinol, cresol novolac, tetrabromobisphenol A, trihydroxybiphenyl, bisresorcinol, bisphenol hexafluoroacetone, tetramethylbisphenol G, glycidyl ether type obtained by reaction of polyphenols such as F and bixylenol with epichlorohydrin; aliphatic such as glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol Polyglycidyl obtained by reaction of polyhydric alcohols with epichlorohydrin Ether type; glycidyl ether ester type obtained by reaction of hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid with epichlorohydrin; phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexa Polyglycidyl ester type derived from polycarboxylic acid such as hydrophthalic acid, endomethylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid, and polymerized fatty acid; glycidylamino derived from aminophenol, aminoalkylphenol, etc. Glycidyl ether type; Glycidylaminoglycidyl ester type derived from aminobenzoic acid; Aniline, toluidine, tribromoaniline, xylylenediamine, diaminocyclohexane, bisami Glycidylamine type derived from nomethylcyclohexane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone and the like; further epoxidized polyolefin, glycidylhydantoin, glycidylalkylhydantoin, triglycidyl cyanurate, etc .; butylglycidyl ether , Phenyl glycidyl ether, alkyl phenyl 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. In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature curability and physical properties of the cured product.

Among these, glycidyl ether type epoxy resins (bisphenol A type polyglycidyl ether, bisphenol F type polyglycidyl ether) obtained by reaction with bisphenol A and bisphenol F are preferable because of low viscosity and high reactivity. .

It is also possible to use an epoxy-modified prepolymer having a side chain grafted with a compound containing an epoxy group.

Such an epoxy prepolymer or epoxy modified prepolymer has a number average molecular weight of 400.
It is preferable to use the one of 10,000 to 10,000 (GPC method), and it is particularly preferable to use the one of 2000 to 7,000. This is because the viscosity is easy to handle and the cured product has good physical properties.

As the mixture of the compound (A) having two or more blocked isocyanate groups and the compound (c) having two or more epoxy groups, a compound (a-1) having two or more blocked isocyanate groups, a-2) and a
Compounds obtained by blocking -3)) and epoxy compounds (monomer c-1) and prepolymer c-2)) can be used each alone or in combination of two or more. In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature curability and physical properties of the cured product. In the present invention, a compound (b) having at least one epoxy group and at least one blocked isocyanate group in the molecule; and a compound (A) having two or more blocked isocyanate groups and two epoxy groups. A mixture of the compounds (c) having the above can be further mixed and used. In this case, the mixing ratio is also
An arbitrary mixing ratio can be used depending on the physical properties of the cured product.

The content of the compound (c) having two or more epoxy groups contained in the curable resin composition of the present invention is such that the mixture of the compounds (A) and (c) (when the compound (a) is contained, Further, it is 1 to 95 parts by mass, preferably 1 to 70 parts by mass, and more preferably 2 to 100 parts by mass of the compound (A) containing the compound (a) and the mixture of (a) and (c). 40 parts by mass, particularly preferably 5 to 20 parts by mass. Within this range, excellent weather resistance can be obtained by mixing the epoxy compound, and excellent storage stability and low temperature curability of the composition can be maintained even when the epoxy compound is mixed. The "content of the compound (c) having two or more epoxy groups" as used herein is applied to a composition containing the compound (A) having no blocked epoxy group and not having an epoxy group. Of course, it does not apply to a composition containing only the compound (b) having at least one isocyanate group in its molecule.

The nylon salts (I), (II) and (III) can be used in the composition according to the second aspect. By using these nylon salts, both excellent storage stability and low temperature curability can be achieved. Nylon salt (I),
(II) or (III) may be used alone or in combination of two or more, and may be used as the nylon salt (I) or (II).
It is also possible to mix and use (III). In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature curability and physical properties of the cured product.

The nylon salt (I) contained in the curable resin composition according to claim 2 is a compound (b) or compound (A) having at least one of the epoxy group and the blocked isocyanate group in the molecule. ) And (c) (when the compound (a) is contained, the mixture of the compound (A), (a) and (c) which further contains the compound (a))
2 to 60 parts by mass, preferably 5 to 100 parts by mass
˜50 parts by mass, more preferably 10 to 30 parts by mass. The nylon salt (II) is a compound (b) or a compound (A) and (c) having at least one epoxy group and one blocked isocyanate group in the molecule.
2 to 60 parts by mass, preferably 100 parts by mass of the mixture (when the compound (a) is contained, the mixture of the compounds (A), (a) and (c) containing the compound (a)). It is 5 to 50 parts by mass, more preferably 10 to 30 parts by mass. The nylon salt (III) is a compound (b) having at least one of the epoxy group and the blocked isocyanate group in the molecule, or a mixture of the compounds (A) and (c) (when the compound (a) is contained, Further, 2 to 60 parts by mass, preferably 5 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the compound (A) containing the compound (a) and the mixture of (a) and (c). Parts by mass. Within this range, both excellent storage stability and low temperature curability can be achieved.

The composition according to claim 2 may contain one or more polymers other than the compound used in the present invention within the range that does not impair the object of the present invention. , Plasticizers, fillers, catalysts, solvents, UV absorbers, dyes, pigments, flame retardants, reinforcing agents, antioxidants, antioxidants, thixotropic agents, surfactants (including leveling agents), dispersants , A dehydrating agent, a rust preventive agent, an adhesion-imparting agent, an antistatic agent and the like can also be contained. Polymers other than the compound used in the present invention, plasticizers, fillers, catalysts, solvents, UV absorbers, dyes, pigments, flame retardants, reinforcing agents, antioxidants, antioxidants, thixotropic agents, surfactants ( As the leveling agent), the dispersant, the dehydrating agent, the rust preventive, the adhesion-imparting agent, the antistatic agent, and the like, all of the above can be used.

Method 1 for producing a curable resin composition of the present invention
For example, put a prepolymer having two or more epoxy groups and a prepolymer having two or more blocked isocyanate groups in a kneading machine filled with nitrogen gas, and further add a plasticizer, a filler, etc., if necessary. After that, nylon salt is added, and the mixture is sufficiently kneaded at low temperature (room temperature to 40 ° C.) under reduced pressure.
The obtained composition can be used as it is, or after being poured into a container, it can be stored by cooling and sealing.

The use of the curable resin composition according to the second aspect is a paint, an adhesive, a sealing agent, and other molded articles. In particular, since it contains an epoxy component, it is a low-temperature curable composition having durability, heat resistance and the like, and is suitably used as an adhesive when attaching interior parts such as plastic parts to steel plates in automobile manufacturing.

The composition of the present invention can be used not only in a compound having a blocked isocyanate group but also in a compound having a blocked isocyanate group and an epoxy group, or in a mixture of a compound having a blocked isocyanate group and a compound having an epoxy group. By including the nylon salt as a thermal latent curing agent, the composition has both excellent low temperature curability and storage stability, and exhibits excellent weather resistance.

In the invention described in claim 3, the compound (a) having two or more isocyanate groups; the compound (d) having two or more vinyl (thio) ether groups; the nylon salt (I), ( II) and one or more kinds selected from the group consisting of (III), and a curable resin composition containing;

As the compound (a) having two or more isocyanate groups, all the above-mentioned isocyanate compounds (a) can be used. In addition, a part of the isocyanate group of the compound (a) may be blocked by the blocking agent.

In the present invention, the “vinyl (thio) ether group” means either a vinyl ether group, a vinyl thioether group or a group having both of them. That is,
The "compound (d) having two or more vinyl (thio) ether groups" is a compound having two or more vinyl ether groups, a compound having two or more vinyl thioether groups, or a combination of two vinyl ether groups and two vinyl thioether groups. It is a compound that has the above.

The "compound (d) having two or more vinyl (thio) ether groups" is a compound having two or more functional groups represented by the following general formula (5) in one molecule.

[Chemical 7] (In the formula, R¹²~ R¹⁶Are hydrogen atom or carbon number, respectively
1 to 18 organic groups, R ¹²Or R¹³And R¹⁵Or R¹⁶
May combine with each other to form a heterocycle containing X.
R¹⁵Or R¹⁶Is X along with the carbon to which they are attached
You may form the ring which does not contain. X is an oxygen atom or
It is an ou atom. ) Here, the organic group means a cycloalkyl group or an alkoxyl group.
Group, cycloalkoxy group, aryl group, aryloxy
Groups, alkanoyloxy groups, aralkyloxy groups and
At least one selected from the group consisting of halogen atoms
Whether substituted with an atomic group or not
Good alkyl group, cycloalkyl group, aryl group,
A alkylene group, a cycloalkylene group or an arylene group
is there.

The functional group represented by the general formula (5) is not particularly limited, and examples thereof include a methyl vinyl ether group, an ethyl vinyl ether group, an isopropyl vinyl ether group, an n-propyl vinyl ether group, and an n-butyl vinyl ether group. , An isobutyl vinyl ether group, a 2-ethylhexyl vinyl ether group, a cyclohexyl vinyl ether group and other vinyl ether groups and vinyl thioether groups corresponding thereto; 2,3-dihydrofuranyl group, 3,4-dihydro-2H-pyranyl group, 3,4 2-position such as -dihydro-2-methoxy-2H-pyranyl group, 3,4-dihydro-2-ethoxy-2H-pyranyl group, 2,3-dihydrobenzopyranyl group, 2,3-dihydrobenzofuranyl group Cyclic vinyl ether groups and their corresponding cyclic groups Two thioether groups, and the like.

In the general formula (5), R ^{12 to} R ¹⁴ are preferably hydrogen atoms or alkyl groups having 1 to 18 carbon atoms, and R ¹⁵ or R ¹⁶ are hydrogen atoms or C 1 to 18 carbon atoms, respectively. An alkyl group or an alkylene group is preferable. (R ¹² or R ¹³ and R ¹⁵ or R ¹⁶ may be bonded to each other to form a heterocycle containing X, and R ¹⁵ or R ¹⁶ is a ring not containing X together with the carbon to which they are bonded. In particular, R ^{12 to} R ¹⁴ are each preferably a hydrogen atom, and one of R ^{15 and} R ¹⁶ is a hydrogen atom, and the other is a hydrogen atom or a methyl group, an ethyl group or the same. Is preferably part of a cyclohexane ring that forms a cyclohexane ring with the carbon to which it is attached. Reactivity is improved,
This is because the raw materials are easily available.

When one or more of the above functional groups are present in one molecule, a crosslinking reaction occurs and the cured product has excellent physical properties. When a polymer vinyl ether compound or the like (including a prepolymer) to be described later is used, depending on the application, required physical properties of the cured product, etc.
The number of functional groups can be set arbitrarily.

Compound (d) having two or more functional groups
Is not particularly limited, and a low molecular weight (monomer) compound or a high molecular compound (including a prepolymer) can be used. Specific examples include the compounds shown below. d-1) ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, propylene glycol divinyl ether, butanediol divinyl ether, butanediol diisopropenyl ether, pentanediol divinyl ether, hexanediol divinyl ether Vinyl ether, neopentyl glycol diisopropenyl ether, nonanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether,
Low molecular weight polyvalent vinyl ethers such as 2,2-bis [p- (2-vinyloxyethoxy) phenyl] propane, cyclohexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and acetic acid diisocyanate ester, and vinyl ethers thereof. Examples thereof include vinyl thioethers in which some or all of the oxygen atoms of the group are replaced with sulfur atoms.

D-2) A vinyl ether and / or a vinyl thioether compound obtained by reacting the polyvalent vinyl ether or vinyl thioether described in d-1) with a polyol in an excess such as a vinyl ether group. Here, the polyols specifically include ethanediol, propanediol, butanediol, pentanediol, octanediol or their homologues and corresponding oligomer ethers; glycerin, trimethylolethane, trimethylolpropane, hexanetriol, penta Erythritol, dipentaerythritol, sorbitol, polyvinyl alcohol, bisphenol A, resorcin, hydroquinone or derivatives thereof; trishydroxyethyl isocyanurate; hydroxyl group-containing epoxide; hydroxyl group-containing polyether; hydroxyl group-containing polyester; hydroxyl group-containing polyacryl; And other polyols.

D-3) Addition product of hydroxyl group-containing monovinyl ether and / or monovinyl thioether with polyvalent isocyanate compound, for example, ethylene glycol monovinyl ether, propylene glycol monovinyl ether, 1,4-butylene glycol monovinyl ether, methanol dihydropyran. , Hydroxyethyl vinyl ether, hydroxybutyl vinyl ether,
9-hydroxynonyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, triethylene glycol monovinyl ether and the like and vinyl thioether compounds corresponding thereto, tetramethylene diisocyanate,
Hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclohexane-1,3- or 1,4-diisocyanate, isophorone diisocyanate, perhydro-2,4'- or -4,4 '-Diphenylmethane diisocyanate, 1,3- and 1,4
-Phenylene diisocyanates, 2,4- and 2,6
-Tolylene diisocyanate, diphenylmethane-2,
4'- or -4,4'-diisocyanate, 3,2-
Or 3,4-diisocyanate-4′-methyldiphenylmethane, naphthalene-1,5-diisocyanate,
Xylylene diisocyanate, tetramethyl xylylene diisocyanate, norbornane diisocyanate, triphenylmethane-4,4 ', 4''-triisocyanate or isocyanurate type, burette type or polyol addition type polyisocyanates of these low molecular weight polyisocyanates , And an adduct with a high molecular weight polyisocyanate compound (including a prepolymer). Here, as the high molecular weight polyisocyanate compound (including prepolymer), tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, polypropylene glycol, polytetramethylene ether glycol, polyester polyol Examples include urethane prepolymers synthesized from and.

Among these compounds (d), in particular,
From the viewpoint of cost reduction, low molecular weight polyvalent vinyl ethers and low molecular weight polyvalent vinyl thioethers corresponding thereto are easy to adjust physical properties of hydroxyl group-containing monovinyl ethers and / or adducts of monovinyl thioethers with polyvalent isocyanate compounds. Therefore, it is preferably used.

The molecular weight of the main chain when the above-mentioned polymer compound or the like is used as the compound (d) is not particularly limited, and may be any molecular weight depending on the performance of the composition, the application and the like. The compound (d) having two or more vinyl (thio) ether groups can be used alone or in combination of two or more. In this case, the mixing ratio can be any ratio depending on the physical properties required for the cured product, the application, and the like.

As the mixture of the compound (a) having two or more active isocyanate groups and the compound (d) having two or more vinyl (thio) ether groups, a compound having two or more active isocyanate groups (the above a-1), a-2)
And a-3)) and vinyl (thio) ether compounds (monomers d-1), d-2) and d-3)) may be used alone or in combination of two or more. In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature curability and physical properties of the cured product.

The content of the compound (d) having two or more vinyl (thio) ether groups contained in the curable resin composition of the present invention is 100% of the compound (a) having two isocyanate groups.
1 to 50 parts by weight, preferably 2
˜30 parts by mass, particularly preferably 3 to 10 parts by mass.
Within this range, both excellent storage stability and low temperature curability can be achieved.

The composition according to claim 3 comprises the above-mentioned nylon salts (I), (II) and (I) as thermal latent curing agents.
II) can be used. By using these nylon salts, both excellent storage stability and low temperature curability can be achieved.
These nylon salts (I), (II) or (III)
Can be used alone or in combination of two or more,
Nylon salts (I), (II) and (III) can also be mixed and used. In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature curability and physical properties of the cured product.

The nylon salt (I) contained in the curable resin composition according to claim 3 is 2 to 60 parts by mass, preferably 5 parts by mass with respect to 100 parts by mass of the mixture of the compounds (a) and (d). ˜50 parts by mass, more preferably 10 to 30 parts by mass. The amount of the nylon salt (II) is 2 to 60 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the mixture of the compounds (a) and (d). Nylon salt (III) includes compounds (a) and (d)
2 to 60 parts by mass, preferably 5 to 50 parts by mass, and more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the mixture. Within this range, both excellent storage stability and low temperature curability can be achieved.

The composition according to claim 3 comprises a polymer other than the compound of the present invention within a range not impairing the object of the present invention.
One kind or two or more kinds may be contained, and if necessary, further, a plasticizer, a filler, a catalyst, a solvent, an ultraviolet absorber, a dye, a pigment, a flame retardant, a reinforcing agent, an antioxidant, an antioxidant. It may also contain a thixotropic agent, a surfactant (including a leveling agent), a dispersant, a dehydrating agent, a rust preventive agent, an adhesion imparting agent, an antistatic agent and the like. Polymers other than the compound of the present invention, plasticizers, fillers, catalysts, solvents, ultraviolet absorbers,
Dyes, pigments, flame retardants, reinforcing agents, antiaging agents, antioxidants, thixotropic agents, surfactants (including leveling agents), dispersants, dehydrating agents, rust preventives, adhesion imparting agents, antistatic agents For example, all of the above can be used.

Method 1 for producing the curable resin composition of the present invention
For example, a kneader filled with nitrogen gas was charged with a prepolymer having two or more isocyanate groups and a prepolymer having two or more vinyl ether groups, and further a plasticizer, a filler, etc. were added as needed. After that, nylon salt is added, and the mixture is sufficiently kneaded at low temperature (room temperature to 40 ° C.) under reduced pressure. The obtained composition can be used as it is, or after being poured into a container, it can be stored by cooling and sealing.

Applications of the curable resin composition according to claim 3 are paints, adhesives, sealing agents, and other molded products. In particular, since it has a low temperature curability, it is preferably used as an adhesive composition for attaching interior parts such as plastic parts to steel plates in automobile manufacturing.

When a compound having a vinyl (thio) ether group is used, the compound also participates in the three-dimensional crosslinking reaction and the physical properties of the cured product are improved. In particular, dicarboxylic acid generated by thermal dissociation of nylon salt is generally less likely to react with an isocyanate group than diamine, and even if a part of it remains, it reacts with a compound having a vinyl (thio) ether group and participates in a crosslinking reaction. it can. Then, it is considered that the amount of the free dicarboxylic acid present in the composition after curing is reduced, which improves the physical properties of the cured product. Also, vinyl (thio)
By including a compound having an ether group and a nylon salt as a thermal latent curing agent, even if the nylon salt is thermally dissociated during storage to generate a diamine and a dicarboxylic acid, the vinyl (thio) ether group can be supplemented. The composition can be used as it is as a main agent without blocking the isocyanate group, and the composition has excellent workability and cost reduction, and has excellent low temperature curability and storage stability.

The invention according to claim 4 is the compound (e) having at least one isocyanate group, vinyl (thio) ether group and epoxy group in the molecule, or the compound having two or more isocyanate groups. (A), a compound (d) having two or more vinyl (thio) ether groups and a compound (c) having two or more epoxy groups
A mixture of the above; and one or more selected from the group consisting of the above-mentioned nylon salts (I), (II) and (III);

The compound (e) having at least one isocyanate group, vinyl (thio) ether group and epoxy group in the molecule means the compound (monomer, e-1) having these groups in the molecule and Or or the prepolymer e-2) having these groups in the molecule. A compound or prepolymer having these trifunctional groups in the molecule can be crosslinked intramolecularly and / or intermolecularly with each other to be cured.

The compound (monomer, e-1)) having at least one isocyanate group, vinyl (thio) ether group and epoxy group in the molecule is, for example,
Examples include a reaction product of a polyisocyanate compound, a hydroxyl group-containing vinyl (thio) ether compound, and a hydroxyl group-containing epoxy compound. The polyisocyanate compound is all the compounds of the above a-1), the hydroxyl group-containing vinyl (thio) ether compound is all the compounds exemplified in the above compound d), and the hydroxyl group containing epoxy compound is the above compound b-1). All the compounds exemplified in 1) can be used. As the reaction conditions, the above-mentioned usual production conditions for urethane prepolymer can be mentioned.

The above-mentioned prepolymer e-2) having a trifunctional group in the molecule is used in the production of a urethane prepolymer.
Isocyanate compound (a), epoxy polyol (hydroxyl group-containing epoxy compound), and compound (d-2) having the vinyl (thio) ether group (react with excess hydroxyl groups compared to isocyanate groups) or d-3)
It is obtained by using. A modified prepolymer obtained by grafting a side chain containing the remaining functional group onto a prepolymer having any functional group can be used, or a prepolymer having each functional group can be copolymerized.

As the epoxy polyol, any of those mentioned above in the invention of claim 2 can be used, and the compound d- having the vinyl (thio) ether group can be used.
The same applies to 2), d-3) and a hydroxyl group-containing epoxy compound. The manufacturing method thereof is also as described above.

Although the above-mentioned polyisocyanate compound a) can be used as the isocyanate compound of the present invention, it is not necessary to block the isocyanate group in the present invention. Since it has a vinyl (thio) ether group in its molecule, both excellent storage stability and low temperature curability can be achieved without blocking the isocyanate group.

The number average molecular weight of the prepolymer e-2) is preferably 400 to 10,000 (GPC method), and particularly preferably 2,000 to 7,000. This is because the viscosity of the prepolymer does not increase and the cured physical properties are excellent. The prepolymer may be used alone or in combination of two or more. In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature curability and physical properties of the cured product.

The production conditions of the prepolymer are not particularly limited, and the usual production conditions of urethane prepolymer can be mentioned. That is, the reaction temperature can be about 50 to 100 ° C. and the reaction can be performed under normal pressure. Further, a urethane-forming catalyst such as an organic tin compound or an organic bismuth compound can also be used.

The modified prepolymer prepared by grafting a side chain containing the remaining functional group on the prepolymer having any functional group and the prepolymer for copolymerizing both prepolymers are not particularly limited. The manufacturing conditions may be those usually used. For example, there may be mentioned a method in which a urethane prepolymer is synthesized under the above-mentioned conditions and the terminal isocyanate group is partially added with an epoxy polyol and a hydroxyl group-containing vinyl (thio) ether compound.

The compound (e) having at least one of these three functional groups in its molecule is a compound (monomer, e) having each of the above-mentioned groups in its molecule.
-1) One or more kinds and prepolymer e-2) having one or more of the above groups in the molecule can be mixed and used. In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature curability and physical properties of the cured product.

The mixture of the compound (a) having two or more isocyanate groups, the compound (d) having two or more vinyl (thio) ether groups and the compound (c) having two or more epoxy groups is as described above. All of the compounds (a), (c) and (d) can be used, one of each compound
It is also possible to use one kind or a mixture of two or more kinds. In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature curability and physical properties of the cured product. In the present invention, the compound (e) having at least one trifunctional group in its molecule; and the mixture of the compounds (a), (c) and (d) described above are mixed and used. You can The mixing ratio in this case can also be an arbitrary mixing ratio depending on the application, the physical properties of the cured product, and the like.

The respective contents of the compounds (a), (c) and (d) contained in the curable resin composition of the present invention are 100 parts by mass of the mixture of the compounds (a), (c) and (d). On the other hand, the compound (a) is 30 to 97.5 parts by mass, preferably 60 to 96 parts by mass, particularly preferably 75.
˜94.5 parts by mass. The compound (c) is 2 to 50 parts by mass, preferably 3 to 30 parts by mass, and particularly preferably 4 to 20 parts by mass. Compound (d) is 0.5 to 2
It is 0 parts by mass, preferably 1 to 10 parts by mass, particularly preferably 1.5 to 5 parts by mass. Within this range,
This is because excellent weather resistance can be obtained by mixing the epoxy compound, and excellent storage stability of the composition can be maintained even when the epoxy compound is mixed.

In the composition according to claim 4, the nylon salts (I), (II) and (I) are used as the thermal latent curing agent.
II) can be used. By using these nylon salts, both excellent storage stability and low temperature curability can be achieved.
The nylon salts (I), (II) or (III) can be used alone or in combination of two or more, and the nylon salts (I), (II) and (III) can also be used in combination. it can. In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature curability and physical properties of the cured product.

The nylon salt (I) contained in the curable resin composition according to claim 4 has a compound (e) or a compound (a) or (c) having at least one trifunctional group in its molecule. 2 to 60 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the mixture of the above) and (d). Nylon salt (I
I) is 2 to 60 parts by mass with respect to 100 parts by mass of the compound (e) or the mixture of the compounds (a), (c) and (d) each having at least one trifunctional group in its molecule. Preferably 5 to 50 parts by mass, more preferably 10
˜30 parts by mass. Nylon salt (III) is 3
2 to 60 parts by mass, preferably 5 to 50 parts by mass with respect to 100 parts by mass of the compound (e) or the mixture of the compounds (a), (c) and (d) each having at least one functional group in its molecule. Parts, more preferably 5 to 30 parts by mass. Within this range, both excellent storage stability and low temperature curability can be achieved.

The composition according to claim 4 contains 1 polymer other than the compound of the present invention within a range not impairing the object of the present invention.
One kind or two or more kinds may be contained, and if necessary, further, a plasticizer, a filler, a catalyst, a solvent, an ultraviolet absorber, a dye, a pigment, a flame retardant, a reinforcing agent, an antioxidant, an antioxidant. It may also contain a thixotropic agent, a surfactant (including a leveling agent), a dispersant, a dehydrating agent, a rust preventive agent, an adhesion imparting agent, an antistatic agent and the like. Polymers other than the compound of the present invention, plasticizers, fillers, catalysts, solvents, ultraviolet absorbers,
Dyes, pigments, flame retardants, reinforcing agents, antiaging agents, antioxidants, thixotropic agents, surfactants (including leveling agents), dispersants, dehydrating agents, rust preventives, adhesion imparting agents, antistatic agents For example, all of the above can be used.

Method 1 for producing a curable resin composition of the present invention
For example, the compounds (a), (c) and (d) are put into a kneading machine filled with nitrogen gas, and further, a plasticizer, a filler and the like are added if necessary, and then a nylon salt is added. Knead thoroughly at low temperature (room temperature to 40 ° C) under reduced pressure. The obtained composition can be used as it is, or after being poured into a container, it can be stored by cooling and sealing.

Applications of the curable resin composition according to claim 4 are paints, adhesives, sealing agents, and other molded products. In particular, since it contains an epoxy component, it is a low-temperature curable composition having durability, heat resistance and the like, and is suitably used as an adhesive when attaching interior parts such as plastic parts to steel plates in automobile manufacturing.

When a compound having a vinyl (thio) ether group is used, this compound also participates in the three-dimensional crosslinking reaction and the physical properties of the cured product are improved. In particular, dicarboxylic acid generated by thermal dissociation of nylon salt is generally less likely to react with an isocyanate group than diamine, and even if a part of it remains, it reacts with a compound having a vinyl (thio) ether group and participates in a crosslinking reaction. it can. Then, it is considered that the amount of the free dicarboxylic acid present in the composition after curing is reduced, which improves the physical properties of the cured product.

By incorporating a compound having a vinyl (thio) ether group and a nylon salt as a thermal latent curing agent, even if the nylon salt is thermally dissociated to generate a diamine and a dicarboxylic acid, the vinyl (thio) ether is produced. Since it can be supplemented with a group, the composition has both excellent low temperature curability and storage stability without blocking the isocyanate group. As described above, the use of the compound having a vinyl (thio) ether group improves the physical properties of the cured product. Further, even if the isocyanate group is not blocked by using this compound,
The storage stability is improved while maintaining the low temperature curability of the composition. Further, this compound does not affect the improvement of weather resistance by the compound having an epoxy group. That is, a compound having an active isocyanate group, a vinyl (thio) ether group and an epoxy group in the molecule, respectively, or a compound having an active isocyanate group, a compound having a vinyl (thio) ether group and a compound having an epoxy group When the mixture contains the nylon salt as a thermal latent curing agent, the composition has both excellent low temperature curability and storage stability, and exhibits excellent weather resistance.

[0134]

EXAMPLES The present invention will be specifically described by showing examples, but the present invention is not limited thereto.

A mixing ratio of 1000 g of trifunctional PPG (manufactured by Asahi Glass Co., Ltd., Exenol 5030, number average molecular weight 5000) and tolylene diisocyanate (2,4- and 2,6-tolylene diisocyanate is 80/20, manufactured by Mitsui Chemicals, Inc. , TDI-80 / 20) 103 g (NCO / OH =
2.0) was reacted with stirring at 70 ° C. for 17 hours to obtain urethane prepolymer 1 (number average molecular weight 5350).
(GPC method)).

1000 g of trifunctional PPG (Asahi Glass Co., Ltd., Exenol 5030, number average molecular weight 5000) and meta-
Tetramethylxylylene diisocyanate (TMXD
I, manufactured by Mitsui Cytec Co., Ltd.) 142 g (NCO / OH =
2.0) at 80 ° C. for 17 hours with stirring,
Urethane prepolymer 2 was obtained (number average molecular weight 5500).
(GPC method)). Next, add 15 g of ethylmethylketoxime, which is 1.5 times the equivalent of the NCO group, and add 1 at 60 ° C.
The mixture was heated and stirred for 7 hours to obtain a block prepolymer having an average molecular weight of 5,700.

Epoxy resin is commercially available bisphenol A.
And a bisphenol A type epoxy resin composed of epichlorohydrin (model name EP410 manufactured by Asahi Denka Co., Ltd.).
0E).

As the vinyl ether compound, commercially available cyclohexanedimethanol divinyl ether was used (manufactured by Nippon Carbide Industry Co., Ltd., model number CHDVE).

230 g (1 mol) of dodecanedioic acid was dissolved in anhydrous isopropyl alcohol by heating, and the mixture was added dropwise to a solution of 136 g (1 mol) of 1,3-xylylenediamine in anhydrous isopropyl alcohol at room temperature. 70 after mixing
The mixture was stirred at ℃, allowed to cool, and the precipitated white crystals were filtered, washed with 500 ml of anhydrous isopropyl alcohol, and dried (760 mmHg, room temperature, 17 hours) to obtain nylon salt A.
350 g (yield 95%) was obtained. This was ground in a mortar and used.

230 g (1 mol) of dodecanedioic acid was dissolved in anhydrous isopropyl alcohol with heating to give piperazine 86.
It was put and mixed in a solution of g (1 mol) of anhydrous isopropyl alcohol at room temperature. After mixing, the mixture is stirred at 70 ° C., allowed to cool, and the precipitated white crystals are filtered, washed with 500 ml of anhydrous isopropyl alcohol, and dried (760 mmH
g, room temperature, 17 hours) to obtain 300 g of nylon salt B (yield 95%). This was similarly ground and used.

312 g (2 mol) of 4-chlorobenzoic acid
Is dissolved in anhydrous isopropyl alcohol by heating, and 1,3-
A solution of 136 g (1 mol) of xylylenediamine in an anhydrous isopropyl alcohol solution was added dropwise at room temperature. After mixing, the mixture was stirred at 70 ° C., allowed to cool, and the precipitated white crystals were filtered, washed with 500 ml of anhydrous isopropyl alcohol, and dried (760 mmHg, room temperature, 17 hours) to give 430 g of nylon salt C (yield 96%). Obtained.

230 g (1 mol) of dodecanedioic acid was dissolved in anhydrous isopropyl alcohol by heating, and the mixture was put and mixed in a solution of 112 g (1 mol) of triethylenediamine in anhydrous isopropyl alcohol at room temperature. After mixing, the mixture was stirred at 70 ° C., allowed to cool, and the precipitated white crystals were filtered, washed with 500 ml of anhydrous isopropyl alcohol, and dried (76
0mmHg, room temperature, 17 hours) and then nylon salt D310
g (yield 91%) was obtained. Grind this in the same way,
used.

230 g (2 mol) of benzoic acid was dissolved in anhydrous isopropyl alcohol by heating, and the mixture was added dropwise to a solution of 136 g (1 mol) of 1,3-xylylenediamine in anhydrous isopropyl alcohol at room temperature. After mixing, the mixture was stirred at 70 ° C., allowed to cool, and the precipitated white crystals were filtered, washed with 500 ml of anhydrous isopropyl alcohol, and dried (76
0mmHg, room temperature, 17 hours) and then nylon salt E340
g (yield 93%) was obtained. Grind this in a mortar,
used.

The following compositions were prepared and various tests were conducted. (Preparation method) A universal mixing stirrer (manufactured by Dalton Co., 50MV-C1, 50 to 10) at each component ratio shown in Table 1.
At 0 rpm), the mixture was stirred at room temperature for 0.5 hours.

50 g of each composition of Examples and Comparative Examples was placed in a metal container and heated to a thickness of 3 mm, and the curing temperature was measured. 10 ℃ from 80 ℃ to 160 ℃
It was carried out by heating every 30 minutes and observing the state of the cured coating film. The test results are shown in Table 1.

Each of the compositions of Examples and Comparative Examples was filled in a closed container, purged with nitrogen, and left at room temperature and 70 ° C. for 1 day. The viscosity was measured with an E-type viscometer, and the viscosity increase ratio of 70 ° C. standing relative to the initial viscosity of standing at room temperature was determined. The test results are shown in Table 1. When the viscosity increase ratio is 2.0 times or less, it can be generally said that the storage stability is excellent. In Table 1, “gelling” means gelling when left at 70 ° C., and “curing” means curing after standing at 70 ° C.

[0147]

[Table 1]

[0148]

Industrial Applicability According to the present invention, there is provided a cured resin composition containing a compound having a blocked isocyanate group and a thermal latent curing agent composed of a specific nylon salt and capable of achieving both excellent storage stability and low temperature curability. Can be provided.

Further, according to the present invention, an isocyanate group containing a compound having an unblocked active isocyanate group, a compound having a vinyl (thio) ether group, and a thermal latent curing agent containing a specific nylon salt is used. It is possible to provide a cured resin composition that can achieve both excellent storage stability and low temperature curability without blocking.

Further, according to the present invention, it is possible to provide a curable resin composition which has excellent weather resistance while maintaining storage stability and low temperature curability, and which has these three properties in a well-balanced manner even in the above composition system.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J034 CA01 CA04 CB03 CC01 CC08                       DB04 DF01 DF14 DF16 DF17                       DG01 DG03 DG04 DG05 DG06                       DK00 DL01 DL03 FE06 HA01                       HA07 HA08 HC03 HC12 HC13                       HC17 HC22 HC64 HC67 HC71                       HC73 HD03 HD04 HD05 HD06                       HD07 HD08 HD12 JA42 RA07                       SA02

Claims (4)

[Claims] 1. A compound having two or more blocked isocyanate groups in which an isocyanate group is blocked with a blocking agent and the dissociation temperature between the isocyanate group and the blocking agent is 140 ° C. or lower; and the following nylon salt (I). ,
1 selected from the group consisting of (II) and (III)
And a curable resin composition containing; The following general formula (1)
A nylon salt (I) comprising a primary diamine represented by the formula (1) and a dicarboxylic acid represented by the following general formula (2): (In the formula, R ¹ is a hydrocarbon group having 8 to 37 carbon atoms in which a nitrogen atom of an amino group is directly bonded to a carbon atom of an aliphatic hydrocarbon; R ² is a linear carbon atom having 8 to 15 carbon atoms. A hydrogen group.) A nylon salt (II) comprising a piperazine derivative represented by the following general formula (3) and a dicarboxylic acid represented by the following general formula (2): (In the formula, R ² is a linear hydrocarbon group having 8 to 15 carbon atoms; R 2
^{3 to} R ⁶ are independently a hydrogen atom or a carbon number of 1 to
4 is an alkyl group. ) A nylon salt (III) comprising a primary diamine represented by the following general formula (1) and a monocarboxylic acid represented by the following general formula (4). [Chemical 3] (In the formula, R ¹ is a hydrocarbon group having 8 to 37 carbon atoms in which the nitrogen atom of the amino group is directly bonded to the carbon atom of the aliphatic hydrocarbon; R ⁷ and R ¹¹ are H or OH independently of each other. ;
R ⁸ , R ¹⁰ are Cl, Br, I, COOR independently of each other.
¹⁷ , COR ¹⁷ , CF ₃ , CN, SO ₂ R ¹⁷ , NO ₂ or H; R ⁹ is Cl, Br, I, COOR ¹⁷ , COR ¹⁷ ,
CF _3, CN, a ^{_{SO 2 R 17, H, OH}} , NR 17 2 or OR ^17, wherein at least one of R ⁷ to R ¹¹ have the substituent other than hydrogen atom. Here, R ¹⁷ has 1 to 5 carbon atoms
Is a hydrocarbon group. ) 2. A compound having at least one blocked isocyanate group and at least one epoxy group in the molecule, or a mixture of a compound having two or more blocked isocyanate groups and a compound having two or more epoxy groups; Nylon salt (I), (II) according to item 1.
And one or more selected from the group consisting of (III); 3. A compound having two or more isocyanate groups; a compound having two or more vinyl (thio) ether groups; and the nylon salts (I), (II) and (III) according to claim 1. Curable resin composition containing 1 or more types selected from the group; 4. A compound having at least one isocyanate group, vinyl (thio) ether group and epoxy group in the molecule, or 2 compounds having the isocyanate group.
A compound with two or more, two vinyl (thio) ether groups
A mixture of one or more compounds and a compound having two or more epoxy groups; and one or more selected from the group consisting of nylon salts (I), (II) and (III) according to claim 1. Curable resin composition containing.