JP2006193629A - Curable composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition achieving a cured product having high modulus. <P>SOLUTION: The curable composition contains a conjugated diene compound obtained by reacting an alkoxysilane compound having one silicon atom and two or more alkoxy groups in one molecule, with a compound represented by formula (1): R<SP>1</SP>-XH (1) (wherein, R<SP>1</SP>is a monovalent hydrocarbon group having a conjugated diene structure; and X is an oxygen atom or a sulfur atom), and a dienophile compound having two or more α,β-unsaturated bonds in one molecule. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curable composition and a cured product thereof.

A fiber reinforced composite material composed of a reinforced fiber and a matrix resin is lightweight and excellent in mechanical strength, and thus is widely used in aerospace applications, general industrial applications, sports equipment applications, and the like.
As the matrix resin, a thermosetting resin or a thermoplastic resin represented by an epoxy resin is used. Among them, the epoxy resin has good adhesion to the reinforcing fiber, the cured product has a high elastic modulus, and is excellent in heat resistance and moisture resistance.
As the reinforcing fiber, carbon fiber, aramid fiber, glass fiber, boron fiber, or the like is used, and among them, carbon fiber that is excellent in specific strength and specific elastic modulus and can obtain a high-performance composite material is often used.
As a typical fiber reinforced composite material, a fiber reinforced composite material using a combination of an epoxy resin and carbon fiber can be given. The fiber-reinforced composite material has high heat resistance and high compressive strength in a high-temperature atmosphere even in a state where moisture is absorbed in the air and the glass transition temperature is lowered.

It is known that the compressive strength of the fiber-reinforced composite material depends on the elastic modulus (storage elastic modulus: G ′) of the matrix resin, and the higher the elastic modulus of the matrix resin, the higher the compressive strength. However, it is difficult to increase the elastic modulus of the matrix resin itself. At present, the elastic modulus in the fiber direction of the fiber-reinforced composite material is controlled by the characteristics of the reinforcing fiber.
The present applicant has previously noted that the adduct obtained by the Diels-Alder reaction between a conjugated diene compound and a dienophile compound exhibits thermoreversibility by a retro-Diels-Alder reaction, and has a heat reversibility. Research on curable resins is ongoing. Among them, a number of epoxy resins containing a conjugated diene structure have been successfully developed (see, for example, Patent Document 1).

JP 2003-183348 A

  The objective of this invention is providing the curable composition which implement | achieves the hardened | cured material which has a high elasticity modulus.

As a result of earnest research on the curable composition for realizing a cured product having a high elastic modulus, the present inventor has a specific conjugated diene compound and two or more α, β-unsaturated bonds in one molecule. It has been found that a cured product comprising a curable composition containing a dienophile compound has a high elastic modulus.
And this inventor completed this invention based on this knowledge.
That is, the present invention provides the following (i) to (xii).

(I) a conjugated diene compound obtained by a reaction between an alkoxysilane compound having one silicon atom and two or more alkoxy groups in one molecule, and a compound represented by the following formula (1):
A curable composition containing a dienophile compound having two or more α, β-unsaturated bonds in one molecule (the curable composition according to the first aspect of the present invention).

R ¹ -XH (1)

(In the formula, R ¹ represents a monovalent hydrocarbon group containing a conjugated diene structure. X represents an oxygen atom or a sulfur atom.)
(Ii) The curable composition according to the above (i), wherein the conjugated diene structure is a furan ring and the X is an oxygen atom.

(Iii) a conjugated diene compound represented by the following formula (2);
A curable composition containing a dienophile compound having two or more α, β-unsaturated bonds in one molecule (the curable composition of the second aspect of the present invention).

SiR ² _n (XR ¹ ) _4-n (2)

(In the formula, each R ¹ independently represents a monovalent hydrocarbon group containing a conjugated diene structure. Each R ² is independently substituted with a functional group in which a hydrogen atom reacts with a thermosetting resin. And n represents an integer of 0 to 2. X independently represents an oxygen atom or a sulfur atom.)
(Iv) The curable composition according to (iii) above, wherein all of the conjugated diene structures are furan rings and all of the X are oxygen atoms.

(V) a conjugated diene compound obtained by a reaction between an epoxy compound having two or more epoxy groups in one molecule and a compound represented by the following formula (3);
A curable composition containing a dienophile compound having two or more α, β-unsaturated bonds in one molecule (the curable composition of the third aspect of the present invention).

R ¹ -XH (3)

(In the formula, R ¹ represents a monovalent hydrocarbon group containing a conjugated diene structure. X represents an oxygen atom or a sulfur atom.)
(Vi) The curable composition according to (v) above, wherein the conjugated diene structure is a furan ring and the X is a sulfur atom.

(Vii) a conjugated diene compound obtained by reacting a compound having two or more α, β-unsaturated bonds in one molecule with a compound represented by the following formula (4);
A curable composition containing a dienophile compound having two or more α, β-unsaturated bonds in one molecule (the curable composition according to the fourth aspect of the present invention).

R ¹ -XH (4)

(In the formula, R ¹ represents a monovalent hydrocarbon group containing a conjugated diene structure. X represents an oxygen atom or a sulfur atom.)
(Viii) The curable composition according to (vii) above, wherein the conjugated diene structure is a furan ring and the X is a sulfur atom.

(Ix) Any of the above (i) to (viii), wherein the α, β-unsaturated bond contained in the dienophile compound is an acryloyloxy group in which the hydrogen atom at the α-position may be substituted with a hydrocarbon group A curable composition according to any one of the above.
(X) The curable composition according to any one of (i) to (ix), further containing a thermosetting resin.
(Xi) The curable composition according to (x), wherein the thermosetting resin is an epoxy resin and further contains a curing agent.
(Xii) A cured product obtained by forming a bond by a Diels-Alder reaction between the conjugated diene compound and the dienophile compound of the curable composition according to any one of the above (i) to (xi). .

  According to the present invention, a curable composition capable of producing a cured product having a high elastic modulus is provided.

The present invention is described in detail below.
First, the curable composition of this invention is demonstrated.
The curable composition of the present invention contains a specific conjugated diene compound and a dienophile compound having two or more α, β-unsaturated bonds in one molecule. Examples of the curable composition of the present invention include the following four embodiments, all of which contain a common dienophile compound.

The curable composition of the first aspect of the present invention comprises an alkoxysilane compound having one silicon atom and two or more alkoxy groups in one molecule, and a compound represented by the following formula (1): A conjugated diene compound obtained by reaction;
It is a curable composition containing a dienophile compound having two or more α, β-unsaturated bonds in one molecule.

R ¹ -XH (1)

(In the formula, R ¹ represents a monovalent hydrocarbon group containing a conjugated diene structure. X represents an oxygen atom or a sulfur atom.)

  The conjugated diene compound contained in the curable composition of the first aspect of the present invention includes an alkoxysilane compound having one silicon atom and two or more alkoxy groups in one molecule, and a formula (1) It is a conjugated diene compound obtained by reaction with the represented compound.

An alkoxysilane compound having one silicon atom and two or more alkoxy groups in one molecule will be described below.
The alkoxysilane compound having one silicon atom and two or more alkoxy groups in one molecule is not particularly limited, and for example, conventionally known compounds can be used.
The number of alkoxy groups contained in the alkoxysilane compound is preferably 2 to 4, more preferably 3 or 4.
In one preferred embodiment, the alkoxy group is an alkoxy group having 1 to 6 carbon atoms.
Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. In addition, an alkoxy group having 3 or more carbon atoms includes each isomer (for example, an isopropoxy group).

One preferred aspect of the alkoxysilane compound is that the substituent other than the alkoxy group bonded to the silicon atom is an alkyl group in which a hydrogen atom may be substituted with a functional group that reacts with the thermosetting resin. It is.
The number of alkyl groups is preferably 0 to 2, and more preferably 0 to 1.
Examples of the alkyl group include a linear alkyl group having 1 to 10 carbon atoms and a branched alkyl group having 3 to 10 carbon atoms, and among these, a linear alkyl group having 1 to 10 carbon atoms is preferable. One of the embodiments.
Examples of the linear alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Examples include an octyl group, an n-nonyl group, and an n-decyl group.
Examples of the branched alkyl group having 3 to 10 carbon atoms include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, isohexyl group, isoheptyl group, isooctyl group, isononyl group, and isodecyl group. Can be mentioned.

The alkyl group may be substituted with a functional group in which a hydrogen atom reacts with the thermosetting resin.
Examples of the functional group include an isocyanate group, a blocked isocyanate group, an epoxy group, an amino group, a mercapto group, a vinyl group, a carboxy group, a vinyl group, a methacryloxy group, and a halogen atom. Of these, an epoxy group is one of the preferred embodiments.
The blocked isocyanate group is a group in which the isocyanate group is blocked with a protective group, and the isocyanate group can be generated by removing the block by, for example, heat or moisture. Specific examples of the blocked isocyanate group include isocyanate groups blocked with a blocking agent such as alcohols, phenols, oximes, triazoles, and caprolactams.
The functional groups can be used alone or in combination of two or more.
The functional group is preferably bonded to the terminal of the alkyl group from the viewpoint of reactivity.

The alkyl group can contain an ether bond, an imino group, and the like. Among them, it is one of preferred embodiments that an ether bond is contained.
Examples of the alkyl group include a linear alkyl group containing an ether bond in which a terminal hydrogen atom is substituted with an epoxy group.
Examples of the linear alkyl group containing an ether bond in which the terminal hydrogen atom is substituted with an epoxy group include γ-glycidoxymethyl group, γ-glycidoxyethyl group, and γ-glycidoxypropyl. Group and γ-glycidoxybutyl group, among which γ-glycidoxypropyl group is preferable.

Examples of the alkoxysilane compound as a raw material include a tetraalkoxysilane compound, a trialkoxysilane compound, and a dialkoxysilane compound.
Examples of the tetraalkoxysilane compound include tetramethoxysilane and tetraethoxysilane.

  Examples of trialkoxysilane compounds include epoxy group-containing trialkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyl Isocyanate group-containing trialkoxysilane compounds such as triethoxysilane, γ-isocyanatoethyltrimethoxysilane, γ-isocyanatoethyltriethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltri Methoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropylto Examples include amino group-containing trialkoxysilane compounds such as limethoxysilane; mercapto group-containing trialkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  Examples of dialkoxysilane compounds include γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylethyldimethoxysilane, and γ-glycidoxypropylethyldiethoxysilane. Epoxy group-containing dialkoxysilane compounds such as γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatoethylmethyldiethoxysilane, γ-isocyanatoethylmethyldimethoxysilane, etc. Silane compounds; amino acids such as γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane Group-containing dialkoxy silane compound; .gamma.-mercaptopropyl methyl dimethoxy silane, mercapto group-containing dialkoxy silane compound such as .gamma.-mercaptopropyl methyl diethoxy silane.

The compound represented by Formula (1) is demonstrated below.
The compound represented by the following formula (1) is a raw material for the conjugated diene compound contained in the curable composition of the first aspect of the present invention.

R ¹ -XH (1)

R ¹ in the formula (1) represents a monovalent hydrocarbon group containing a conjugated diene structure.
Examples of the conjugated diene structure include a chain conjugated diene structure and a cyclic conjugated diene structure. From the viewpoint of excellent stability against heat and the like, a monovalent hydrocarbon group containing a cyclic conjugated diene structure is preferable. Examples of monovalent hydrocarbon groups containing specific conjugated diene structures are listed in Table 1.

(In Table 1, R ^{3 to} R ⁸ each independently represents a hydrogen atom, an alkyl group or an alkylene group.)
In Table 1, examples of the alkyl group represented by R ^{3 to} R ⁸ include a linear alkyl group having 1 to 10 carbon atoms and a branched alkyl group having 3 to 10 carbon atoms. Among these, a linear alkyl group having 1 to 10 carbon atoms is one of preferred embodiments.
Examples of the linear alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Examples include an octyl group, an n-nonyl group, and an n-decyl group.
Examples of the branched alkyl group having 3 to 10 carbon atoms include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, isohexyl group, isoheptyl group, isooctyl group, isononyl group, and isodecyl group. Can be mentioned.

In Table 1, examples of the alkylene group represented by R ^{3 to} R ⁸ include a linear alkylene group having 1 to 10 carbon atoms and a branched alkylene group having 3 to 10 carbon atoms. A linear alkylene group having 1 to 10 carbon atoms is one preferred embodiment. Among these, a linear alkylene group having 1 to 4 carbon atoms is preferable.
Examples of the linear alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group, and a methylene group is one of the preferred embodiments.
Examples of the conjugated diene structure contained in the monovalent hydrocarbon group include a cyclic conjugated diene structure represented in Table 1. Among them, a cyclic conjugated diene structure having a hetero atom is preferable. Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. Among these, an oxygen atom is preferable. The cyclic conjugated diene structure having an oxygen atom is preferably a furan ring.
Examples of the monovalent hydrocarbon group containing a furan ring include a monovalent hydrocarbon group represented by the following formula (5).

(In the formula, R ^{3 to} R ⁶ each independently represents a hydrogen atom, an alkyl group or an alkylene group.)
The alkyl group represented by R ^{3 to} R ⁶ in Formula (5) is the same as the alkyl group represented by R ^{3 to} R ⁸ in Table 1.
The alkylene group represented by R ^{3 to} R ⁶ in Formula (5) is the same as the alkylene group represented by R ^{3 to} R ⁸ in Table 1.

The substitution position at which the alkylene group is bonded to the furan ring is the 2-position or the 3-position. The substitution position at which the alkylene group is bonded to the furan ring is preferably the 2-position from the viewpoint that it can prevent a decrease in reactivity due to steric hindrance in the Diels-Alder reaction to be performed later, and is easily available.
In addition, the substituents other than the alkylene group bonded to the furan ring can prevent a decrease in reactivity due to steric hindrance in the subsequent Diels-Alder reaction, and are all hydrogen atoms because they are easily available. Is preferred.

Specific examples of the structure of R ¹ include a furfuryl group, a 3-furylmethyl group, a 2-furylethyl group, a 3-furylethyl group, a 2-furylpropyl group, and a 3-furylpropyl group. Groups are preferred.
X in Formula (1) represents an oxygen atom or a sulfur atom, and preferably an oxygen atom.
The compound represented by Formula (1) is not specifically limited. For example, furfuryl alcohol, furfuryl thiol, 3-furyl methyl alcohol, and 3-furyl methyl thiol are mentioned. Among them, furfuryl alcohol is one of the preferred embodiments.

The conjugated diene compound contained in the curable composition of the first aspect of the present invention is prepared by an alkoxysilane compound having one silicon atom and two or more alkoxy groups in one molecule, If it uses the compound represented by (1), it will not specifically limit. For example, it can be produced by the following reaction.
Specifically, the reaction is an exchange reaction between two or more alkoxy groups contained in the alkoxysilane compound and the compound represented by the formula (1). As such an exchange reaction, for example, a conventionally known method can be used.
A catalyst can be used for the reaction. As a catalyst used for reaction, acidic catalysts, such as hydrochloric acid, a sulfuric acid, an organic acid, or a basic catalyst can be used, for example, It is one of the preferable aspects to use a basic catalyst.
Examples of the basic catalyst include ammonia, primary amines, secondary amines, and tertiary amines, and tertiary amines are one preferred embodiment.
Tertiary amines include, for example, monoamines, diamines, triamines, polyamines, aliphatic amines, aromatic amines, cyclic amines, alcohol amines, ether amines, among which aliphatic amines, aromatic amines. A group amine is mentioned as a preferred embodiment.

Specific tertiary aliphatic amines include, for example, triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane -1,3-diamine, tetramethylguanidine, N, N'-dimethylpiperazine, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 1,4-diazabicyclo [2.2.2 ] Octane (DABCO) and bis (2-dimethylaminoethyl) ether.
Specific examples of the tertiary aromatic amine include pyridine.

Among these, 1,8-diazabicyclo [5,4,0] -7-undecene is mentioned as one of preferred embodiments.
A catalyst can be used individually or in combination of 2 or more types, respectively.
It is preferable that the usage-amount of a catalyst is 0.01-20 mass parts with respect to 100 mass parts of alkoxysilane compounds as a raw material, More preferably, it is 0.5-2 mass parts.

The reaction can be performed using a solvent or without a solvent, and is preferably performed without a solvent.
When a solvent is used, a compound azeotroped with an alcohol (for example, methanol or ethanol) produced by the reaction can be used. Examples of such compounds include ether compounds such as methyl propyl ether, methyl butyl ether, ethyl propyl ether, methyl-t-butyl ether, ethoxymethoxymethane; n-pentane, n-hexane, 2,3,3-trimethylbutane. Aliphatic hydrocarbons such as cyclopentane, cyclohexane and trans-1,3-dimethylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene.
The reaction is preferably carried out while distilling off alcohol (eg, methanol, ethanol) produced by the reaction to the outside of the reaction system.

The reaction temperature is preferably 30 to 100 ° C, more preferably 60 to 80 ° C.
The reaction is usually carried out at normal pressure, but can be carried out under reduced pressure or under pressure as necessary.
Reaction time is not specifically limited, For example, it is 1 to 10 hours normally, and 3 to 5 hours are preferable.

The conjugated diene compound contained in the curable composition of the first aspect of the present invention is preferably, for example, the conjugated diene compound contained in the curable composition of the second aspect of the present invention. The specific structure of the conjugated diene compound contained in the curable composition of the second aspect of the present invention will be described later.
The conjugated diene compounds contained in the curable composition of the first aspect of the present invention can be used alone or in combination of two or more.

The dienophile compound contained in the curable composition of the 1st aspect of this invention is demonstrated below.
The dienophile compound contained in the curable composition of the first aspect of the present invention is a dienophile compound having two or more α, β-unsaturated bonds in one molecule.
In the dienophile compound having two or more α, β-unsaturated bonds in one molecule, examples of the α-position functional group include a carbonyl group, a carbonyloxy group, an amino group, an imino group, an amide group, and a thiocarbonyl group. , A sulfonyl group, an oxy group, and a thio group. Of these, a carbonyloxy group is preferable.

In the dienophile compound having two or more α, β-unsaturated bonds in one molecule, examples of the β-position group include a single bond, a hydrogen atom, and a functional group. Examples of the functional group at the β-position include those similar to the functional group at the α-position described above. Among these, a hydrogen atom is preferable from the reactivity with the compound represented by the formula (1).
In the α, β-unsaturated bond, the carbon-carbon unsaturated bond between the α-position and the β-position is a double bond or a triple bond. Among these, a double bond is one of preferred embodiments.
The carbon-carbon unsaturated bond of the α, β-unsaturated bond is preferably at the end of the compound in order to increase the reactivity.

Examples of the α, β-unsaturated bond include an acryloyloxy group in which the hydrogen atom at the α-position may be substituted with a hydrocarbon group.
An acryloyloxy group is a group represented by —O—CO—CH═CH ₂ .
Examples of the hydrocarbon group include an aliphatic hydrocarbon group such as a methyl group, an ethyl group, and a propyl group; and an aromatic hydrocarbon group such as a phenyl group, and among them, a methyl group is one preferred embodiment.
Examples of the acryloyloxy group in which the hydrogen atom at the α-position is substituted with a hydrocarbon group include, for example, a methacryloyloxy group (—O—CO—CCH ₃ ═CH ₂ ), —O—CO—C (CH ₂ CH ₃ ). = CH _2, include _{-O-CO-CPh = CH 2} .
The acryloyloxy group in which the α-position hydrogen atom may be substituted with a hydrocarbon group can be bonded to an alkylene group having 1 to 4 carbon atoms. Moreover, it is mentioned as one of the suitable aspects that the acryloyloxy group (the hydrogen atom has couple | bonded with (alpha) position) has couple | bonded with the C1-C4 alkylene group.

As the acryloyloxy group to which an alkylene group having 1 to 4 carbon atoms is bonded and the hydrogen atom at the α-position may be substituted with a hydrocarbon group, for example, —CH ₂ —O—CO—CH═CH ₂ , _{-CH 2 -O-CO-C (} CH 3) = CH 2, -CH 2 -O-CO-C (CH 2 CH 3) = CH 2, -CH 2 CH 2 -O-CO-CH = CH 2 , —CH ₂ CH ₂ —O—CO—C (CH ₃ ) ═CH ₂ , —CH ₂ CH ₂ —O—CO—C (CH ₂ CH ₃ ) = CH ₂ , —CH ₂ CH ₂ CH ₂ —O _{-CO-CH = CH 2, -CH} 2 CH 2 CH 2 -O-CO-C (CH 3) = CH 2, -CH 2 CH 2 CH 2 -O-CO-C (CH 2 CH 3) = CH _{2, -CH 2 CH 2 CH 2} CH 2 -O-CO-CH = CH 2, -CH 2 CH 2 CH 2 CH 2 -O-CO-C (CH 3) = CH 2, - _{H 2 CH 2 CH 2 CH 2} -O-CO-C (CH 2 CH 3) = CH 2 and the like. Among these, —CH ₂ —O—CO—CH═CH ₂ is preferable.

In the dienophile compound having two or more α, β-unsaturated bonds in one molecule, how the α, β-unsaturated bond is bonded in one molecule of the dienophile compound is not particularly limited. For example, a structure in which an α, β-unsaturated bond is bonded as a repeating unit, a structure in which an α, β-unsaturated bond is bonded to a different atom in the compound, and an α, β-unsaturated bond is 1 Examples include structures that are bonded to one atom. Among them, a structure in which an α, β-unsaturated bond is bonded on one atom is preferable.
Examples of the atom to which the α, β-unsaturated bond is bonded include a carbon atom, a nitrogen atom, and a sulfur atom, and among them, a carbon atom is preferable.
The number of α, β-unsaturated bonds in one molecule is 2 or more, preferably 2 to 4, more preferably 3.

The dienophile compound having two or more α, β-unsaturated bonds in one molecule is not particularly limited, and for example, conventionally known compounds can be used.
Examples of the dienophile compound having two or more α, β-unsaturated bonds in one molecule include three acryloyloxy groups in which the hydrogen atom at the α-position may be substituted with a hydrocarbon group, one carbon Examples include dienophile compounds bonded on the atom. Specifically, the dienophile compound represented by following formula (6) is mentioned, for example.

(Wherein R ^{9 to} R ¹¹ each independently represents a hydrogen atom or a methyl group.)
Examples of the dienophile compound represented by the formula (6) include a triacrylate compound in which R ^{9 to} R ¹¹ are all hydrogen atoms, a triacrylate compound in which R ⁹ is all methyl groups, and R ^{10 to} R ¹¹ are all hydrogen atoms. A methacrylate compound is mentioned. Among these, from the reactivity with the compound represented by the formula (1), a triacrylate compound in which R ^{9 to} R ¹¹ are all hydrogen atoms can be mentioned as one of preferred embodiments.
The triacrylate compound in which R ^{9 to} R ^{11 in} formula (6) are all hydrogen atoms is specifically a triacrylate compound represented by the following formula (7).

The dienophile compounds contained in the curable composition of the first aspect of the present invention can be used alone or in combination of two or more.
The dienophile compound contained in the curable composition of the 1st aspect of this invention is not restrict | limited in particular about the manufacturing method. For example, it can be produced according to a conventionally known method.
The curable composition of the first aspect of the present invention preferably contains 0.3 to 2 equivalents, more preferably 0.8 to 1.2 equivalents of the dienophile compound with respect to 1 equivalent of the conjugated diene compound. To do.

Next, the curable composition of the 2nd aspect of this invention is demonstrated.
The curable composition of the second aspect of the present invention contains a conjugated diene compound represented by the following formula (2) and a dienophile compound having two or more α, β-unsaturated bonds in one molecule. It is a curable composition.

SiR ² _n (XR ¹ ) _4-n (2)

(In the formula, each R ¹ independently represents a monovalent hydrocarbon group containing a conjugated diene structure. Each R ² is independently substituted with a functional group in which a hydrogen atom reacts with a thermosetting resin. And n represents an integer of 0 to 2. X independently represents an oxygen atom or a sulfur atom.)

The conjugated diene compound contained in the curable composition of the 2nd aspect of this invention is demonstrated below.
The conjugated diene compound contained in the curable composition of the second aspect of the present invention is a conjugated diene compound represented by the formula (2).
In formula (2), each R ¹ independently represents a monovalent hydrocarbon group containing a conjugated diene structure, and a monovalent hydrocarbon containing a conjugated diene structure represented by R ¹ in formula (1). It is the same as the hydrocarbon group. Among them, it is preferable that all the conjugated diene structures in R ^{1 of the} formula (2) are furan rings.
X in Formula (2) represents an oxygen atom or a sulfur atom each independently, and is preferably an oxygen atom. Especially, it is preferable that all X of Formula (2) is an oxygen atom.

Examples of the substituent XR ¹ in the formula (2) include a furfuryloxy group, a 3-furylmethoxy group, a 2-furylethoxy group, a 3-furylethoxy group, a 2-furylpropoxy group, and a 3-furylpropoxy group. A furan ring such as a furfurylthio group, a 3-furylmethylthio group, a 2-furylethylthio group, a 3-furylethylthio group, a 2-furylpropylthio group, and a 3-furylpropylthio group. An alkylenethio group containing is preferable, and a furfuryloxy group is particularly preferable.

In formula (2), each R ² independently represents an alkyl group in which a hydrogen atom may be substituted with a functional group that reacts with the thermosetting resin.
The alkyl group optionally substituted with a functional group in which the hydrogen atom represented by R ² in the formula (2) reacts with the thermosetting resin is contained in the curable composition of the first aspect of the present invention. In the conjugated diene compound, the hydrogen atom is the same as the alkyl group which may be substituted with a functional group that reacts with the thermosetting resin, which is described in the alkoxysilane compound as a raw material.

N in the formula (2) is an integer of 0 to 2, and preferably 0 or 1.
Since the conjugated diene compound contained in the curable composition of the second aspect of the present invention contains (4-n) substituents XR ¹ , it contains (4-n) conjugated diene structures. .
In the conjugated diene compound contained in the curable composition of the second aspect of the present invention, the number of conjugated diene structures is 2 to 4, preferably 3 to 4. In particular, in the case of a conjugated diene compound having three or more conjugated diene structures, a cured product having a three-dimensional network structure is obtained by a Diels-Alder reaction with a dienophile compound having two or more dienophile structures in one molecule. Obtainable.

Here, the relationship between the conjugated diene compound contained in the curable composition of the 1st aspect of this invention and the conjugated diene compound contained in the curable composition of the 2nd aspect of this invention is demonstrated.
The conjugated diene compound contained in the curable composition of the 1st aspect of this invention is a conjugated diene compound obtained by reaction of the said alkoxysilane compound and the compound represented by Formula (1).
At this time, the alkoxysilane compound as a raw material may be substituted with one silicon atom in one molecule, 2 to 4 alkoxy groups, and a functional group in which a hydrogen atom reacts with a thermosetting resin. It may have an alkyl group.
Then, the the alkoxysilane compound is reacted with a compound represented by formula (1), compounds represented by alkoxy groups of formula of the alkoxysilane compound (1) (Formula (1): R ¹ -XH) Exchange reaction, and in one molecule, 2 to 4 substituents XR ¹ and ^one alkyl group optionally substituted with a functional group in which a hydrogen atom reacts with a thermosetting resin are formed on one silicon atom. It becomes the conjugated diene compound which has couple | bonded.
Here, the alkyl group which may be substituted with a functional group in which a hydrogen atom reacts with the thermosetting resin is identical to R ² in the formula (2).
That is, when the conjugated diene compound contained in the curable composition of the first aspect of the present invention is obtained from the above alkoxysilane compound, the resulting conjugated diene compound is the curable characteristic of the second aspect of the present invention. It corresponds to the conjugated diene compound contained in the composition.

  The conjugated diene compound contained in the curable composition of the second aspect of the present invention is a silane compound containing four conjugated diene structures in one molecule, a silane compound containing three conjugated diene structures, Examples include silane compounds containing two conjugated diene structures, and among them, silane compounds containing four conjugated diene structures and silane compounds containing three conjugated diene structures are preferred.

  Examples of the silane compound containing four conjugated diene structures include tetraalkoxy such as tetrafurfuryloxysilane, tetra (3-furylmethoxy) silane, tetra (2-furylethoxy) silane, and tetra (3-furylethoxy). Silane compounds; tetraalkylthiosilane compounds such as tetrafurfurylthiosilane, tetra (3-furylmethylthio) silane, tetra (2-furylethylthio) silane, tetra (3-furylethylthio) silane, etc. Tetrafurfuroxysilane represented by (8) is one of the preferred embodiments.

Examples of the silane compound containing three conjugated diene structures include γ-glycidoxypropyltrifurfuryloxysilane, γ-glycidoxypropyltri (3-furylmethoxy) silane, γ-glycidoxypropyltri ( Epoxy group-containing trialkoxysilane compounds such as 2-furylethoxy) silane and γ-glycidoxypropyltri (3-furylethoxy) silane;
γ-glycidoxypropyltrifurfurylthiosilane, γ-glycidoxypropyltri (3-furylmethylthio) silane, γ-glycidoxypropyltri (2-furylethylthio) silane, γ-glycidoxypropyltri ( Epoxy group-containing trialkylthiosilane compounds such as 3-furylethylthio) silane;

Methyltrifurfuryloxysilane, methyltri (3-furylmethoxy) silane, methyltri (2-furylethoxy) silane, methyltri (3-furylethoxy) silane, ethyltriflufuryloxysilane, ethyltri (3-furylmethoxy) silane, ethyltri ( Alkyltrialkoxysilane compounds such as 2-furylethoxy) silane and ethyltri (3-furylethoxy) silane;
Methyltrifurfurylthiosilane, methyltri (3-furylmethylthio) silane, methyltri (2-furylethylthio) silane, methyltri (3-furylethylthio) silane, ethyltrifurfurylthiosilane, ethyltri (3-furylmethylthio) silane, Examples include alkyltrialkylthiosilane compounds such as ethyltri (2-furylethylthio) silane and ethyltri (3-furylethylthio) silane. Among them, γ-glycidoxypropyltriflufuroxy represented by the following formula (9) Silane is one of the preferred embodiments.

Examples of the silane compound containing two conjugated diene structures include di-groups containing an epoxy group and an alkyl group such as γ-glycidoxypropylmethyldiflufuryloxysilane and γ-glycidoxypropylethyldiflufuryloxysilane. Alkoxysilane compounds;
a dialkylthiosilane compound containing an epoxy group and an alkyl group, such as γ-glycidoxypropylmethyldifurfurylthiosilane, γ-glycidoxypropylethyldiflufurthiosilane;
Dialkyl dialkoxysilane compounds such as dimethyldiflufuroxysilane, ethylmethyldiflufuroxysilane, diethyldiflufuroxysilane;
Examples thereof include dialkyldialkylthiosilane compounds such as dimethyldifurfurylthiosilane, ethylmethyldifurfurylthiosilane, and diethyldifurfurthiothiosilane.

The production method of the conjugated diene compound contained in the curable composition of the second aspect of the present invention is not particularly limited. For example, it can be produced according to a method for producing a conjugated diene compound contained in the curable composition of the first aspect of the present invention.
Examples of the alkoxysilane compound used as a raw material include tetramethoxysilane, tetraethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane.
The conjugated diene compounds contained in the curable composition of the second aspect of the present invention can be used alone or in combination of two or more.

The dienophile compound contained in the curable composition of the 2nd aspect of this invention is demonstrated below.
The dienophile compound contained in the curable composition of the second aspect of the present invention is a dienophile compound having two or more α, β-unsaturated bonds in one molecule. The dienophile compound contained in the curable composition of the second aspect of the present invention is the same as the dienophile compound contained in the curable composition of the first aspect of the present invention.
The dienophile compound contained in the curable composition of the 2nd aspect of this invention can be used individually or in combination of 2 or more types, respectively.
The curable composition according to the second aspect of the present invention preferably contains 0.3 to 2 equivalents, more preferably 0.8 to 1.2 equivalents of the dienophile compound with respect to 1 equivalent of the conjugated diene compound. To do.

Next, the curable composition of the 3rd aspect of this invention is demonstrated.
The curable composition of the third aspect of the present invention is
A conjugated diene compound obtained by reaction of an epoxy compound having two or more epoxy groups in one molecule with a compound represented by the following formula (3);
It is a curable composition containing a dienophile compound having two or more α, β-unsaturated bonds in one molecule.

R ¹ -XH (3)

(In the formula, R ¹ represents a monovalent hydrocarbon group containing a conjugated diene structure. X represents an oxygen atom or a sulfur atom.)

The conjugated diene compound contained in the curable composition of the third aspect of the present invention is a reaction between an epoxy compound having two or more epoxy groups in one molecule and a compound represented by the following formula (3) It is a conjugated diene compound obtained by the following.
An epoxy compound having two or more epoxy groups in one molecule will be described below.
As an epoxy compound, a conventionally well-known epoxy resin can be used, for example. As the epoxy compound, for example, an epoxy resin having an epoxy equivalent of 100 to 1000 can be used.

Examples of the epoxy resin include glycidyl ether type, glycidyl ester type, and glycidyl amino type epoxy resins.
Examples of the glycidyl ether type epoxy resin include bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, and biphenyl type epoxy compounds having a bisphenyl group, Polyalkylene glycol type, alkylene glycol type epoxy compound, epoxy compound having naphthalene ring, bifunctional epoxy compound having fluorene group, epoxy compound represented by the following formula (10), represented by the following formula (11) Tetraphenylolethane type epoxy compounds, phenol novolak type, orthocresol novolak type, DPP novolak type, and tris-hydroxyphenylmethane type epoxy compounds.

Examples of the glycidyl ester type epoxy resin include epoxy resins of synthetic fatty acids such as dimer acid.
Examples of the glycidylamino epoxy resin include N, N-diglycidylaniline, triglycidyl isocyanurate (TGIC), triglycidyl-p-aminophenol, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM). ), Tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane.

Of these, trifunctional or tetrafunctional glycidylamino type epoxy resins are preferred because of their high heat resistance and relatively low viscosity.
Examples of the trifunctional glycidylamino epoxy resin include triglycidyl isocyanurate (TGIC) and triglycidyl-p-aminophenol.
Examples of the tetrafunctional glycidylamino type epoxy resin include N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM), tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-di). Glycidylaminomethyl) cyclohexane, among which N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM) is preferred.

The compound represented by Formula (3) is demonstrated below.
The compound represented by the following formula (3) is a raw material for the conjugated diene compound contained in the curable composition of the third aspect of the present invention.

R ¹ -XH (3)

R ¹ in the formula (3) represents a monovalent hydrocarbon group containing a conjugated diene structure is the same as R ¹ in the formula (1).
X in Formula (3) represents an oxygen atom or a sulfur atom, and a sulfur atom is preferable.
The compound represented by the formula (3) is not particularly limited, and for example, conventionally known compounds can be used. Specifically, for example, furfuryl alcohol, furfuryl thiol, 3-furylmethyl alcohol, and 3-furylmethyl thiol are exemplified, and among these, furfuryl thiol is preferable.

  Examples of the conjugated diene compound contained in the curable composition according to the third aspect of the present invention include N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM) and a formula (3). And a conjugated diene compound represented by the following formula (12) obtained by reacting with a compound.

(In the formula, R ¹ represents a monovalent hydrocarbon group containing a conjugated diene structure. X represents an oxygen atom or a sulfur atom.)
R ¹ in the formula (12) represents a monovalent hydrocarbon group containing a conjugated diene structure is the same as R ¹ in the formula (3).
X in Formula (12) represents an oxygen atom or a sulfur atom, and a sulfur atom is preferable.

Examples of the substituent XR ¹ in the formula (12) include a furfuryloxy group, a 3-furylmethoxy group, a 2-furylethoxy group, a 3-furylethoxy group, a 2-furylpropoxy group, and a 3-furylpropoxy group. An alkyleneoxy group containing a furan ring; a furan ring such as a furfurylthio group, a 3-furylmethylthio group, a 2-furylethylthio group, a 3-furylethylthio group, a 2-furylpropylthio group, or a 3-furylpropylthio group; Examples thereof include an alkylenethio group, and among them, a furfurylthio group is preferable.
The conjugated diene compound in the case where the substituent XR ¹ in the formula (12) is a furfurylthio group is represented by the following formula (13).

The conjugated diene compounds contained in the curable composition of the third aspect of the present invention can be used alone or in combination of two or more.
The conjugated diene compound contained in the curable composition of the 3rd aspect of this invention is the compound represented by the epoxy compound which has 2 or more epoxy groups in 1 molecule about the manufacturing method, and Formula (3) If it uses, it will not specifically limit. For example, it can be produced according to the following production method.
The production method of the conjugated diene compound can be carried out using a solvent or without a solvent, and among them, it is preferably carried out without a solvent.
When using a solvent, the solvent used is not particularly limited as long as it uniformly dissolves the raw material epoxy compound and the compound represented by formula (3). For example, methanol, Alcohols such as ethanol, propanol, isopropanol and butanol; esters such as ethyl acetate, propyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as tetrahydrofuran and diethylene glycol dimethyl ether; benzene, toluene, Aromatic hydrocarbons such as xylene; and aliphatic hydrocarbons such as pentane, hexane, and cyclohexane.

Examples of the catalyst used include acidic catalysts such as hydrochloric acid, sulfuric acid, and organic acids, and basic catalysts. Among these, basic catalysts are preferable.
Examples of basic catalysts include ammonia, primary amines, secondary amines, and tertiary amines. Among them, tertiary amines are one of the preferred embodiments.
Examples of the tertiary amine include monoamines, diamines, triamines, polyamines, aliphatic amines, aromatic amines, cyclic amines, alcohol amines, ether amines, etc. Among them, aliphatic amines Aromatic amines are preferred.

Specific tertiary aliphatic amines include, for example, triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane -1,3-diamine, tetramethylguanidine, N, N'-dimethylpiperazine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), 1,4-diazabicyclo [2,2,2 ] Octane (DABCO) and bis (2-dimethylaminoethyl) ether.
Specific examples of the tertiary aromatic amine include pyridine.

Among these, 1,8-diazabicyclo [5,4,0] -7-undecene and triethylamine are preferable.
These catalysts can be used alone or in combination of two or more.
The amount of the catalyst used is preferably 0.01 to 20 parts by mass, more preferably 0.5 to 2 parts by mass, with respect to 100 parts by mass of the raw material epoxy compound.
The reaction temperature is preferably 30 to 100 ° C, more preferably 60 to 80 ° C.
The reaction is usually performed at normal pressure, and can be performed under reduced pressure or increased pressure as necessary.
The reaction time is not particularly limited, and is usually 1 to 10 hours, preferably 3 to 5 hours.
The conjugated diene compounds contained in the curable composition of the third aspect of the present invention can be used alone or in combination of two or more.

The dienophile compound contained in the curable composition of the 3rd aspect of this invention is demonstrated below.
The dienophile compound contained in the curable composition of the third aspect of the present invention is a dienophile compound having two or more α, β-unsaturated bonds in one molecule. The dienophile compound contained in the curable composition of the third aspect of the present invention is the same as the dienophile compound contained in the curable composition of the first aspect of the present invention.
The dienophile compound contained in the curable composition of the 3rd aspect of this invention can be used individually or in combination of 2 or more types, respectively.
The curable composition according to the third aspect of the present invention preferably contains 0.3 to 2 equivalents, more preferably 0.8 to 1.2 equivalents of the dienophile compound with respect to 1 equivalent of the conjugated diene compound. To do.

Subsequently, the curable composition of the 4th aspect of this invention is demonstrated.
The curable composition of the fourth aspect of the present invention is
A conjugated diene compound obtained by reacting a compound having two or more α, β-unsaturated bonds in one molecule with a compound represented by the following formula (4);
It is a curable composition containing a dienophile compound having two or more α, β-unsaturated bonds in one molecule.

R ¹ -XH (4)

(In the formula, R ¹ represents a monovalent hydrocarbon group containing a conjugated diene structure. X represents an oxygen atom or a sulfur atom.)

The conjugated diene compound contained in the curable composition of the fourth aspect of the present invention includes a compound having two or more α, β-unsaturated bonds in one molecule and a compound represented by the formula (4) It is a conjugated diene compound obtained by reaction.
A compound having two or more α, β-unsaturated bonds in one molecule will be described below.
In a compound having two or more α, β-unsaturated bonds in one molecule, examples of the α-position functional group include a carbonyl group, a carbonyloxy group, an amino group, an imino group, an amide group, a thiocarbonyl group, Examples include a sulfonyl group, an oxy group, and a thio group, and among them, a carbonyloxy group is preferable.
Examples of the remaining substituent bonded to the α-position include a hydrogen atom; an aliphatic hydrocarbon group such as a methyl group, an ethyl group, and a propyl group; and an aromatic hydrocarbon group such as a phenyl group. A methyl group is preferred.

In a compound having two or more α, β-unsaturated bonds in one molecule, examples of the β-position group include a single bond, a hydrogen atom, and a functional group. Examples of the functional group at the β-position include those similar to the functional group at the α-position described above. Among these, a hydrogen atom is preferable from the reactivity with the compound represented by the formula (4).
In the α, β-unsaturated bond, the carbon-carbon unsaturated bond between the α-position and the β-position is a double bond or a triple bond. Of these, a double bond is one of the preferred embodiments.
The α, β-unsaturated bond is preferably a carbon-carbon unsaturated bond at the terminal of the compound in order to increase the reactivity.
Examples of the α, β-unsaturated bond include an acryloyloxy group in which the hydrogen atom at the α-position may be substituted with a hydrocarbon group.
An acryloyloxy group is a group represented by —O—CO—CH═CH ₂ .
Examples of the hydrocarbon group include an aliphatic hydrocarbon group such as a methyl group, an ethyl group, and a propyl group; and an aromatic hydrocarbon group such as a phenyl group, and among them, a methyl group is one preferred embodiment.
Examples of the acryloyloxy group in which the α-position hydrogen atom is substituted with a hydrocarbon group include, for example, a methacryloyloxy group (—O—CO—CCH ₃ ═CH ₂ ), —O—CO—C (CH ₂ CH ₃ ). = CH _2, include _{-O-CO-CPh = CH 2} .
The acryloyloxy group in which the α-position hydrogen atom may be substituted with a hydrocarbon group can be bonded to an alkylene group having 1 to 4 carbon atoms. Moreover, it is mentioned as one of the suitable aspects that the acryloyloxy group (alpha position has the hydrogen atom couple | bonded) has couple | bonded with the C1-C4 alkylene group.

As the acryloyloxy group to which an alkylene group having 1 to 4 carbon atoms is bonded and the hydrogen atom at the α-position may be substituted with a hydrocarbon group, for example, —CH ₂ —O—CO—CH═CH ₂ , _{-CH 2 -O-CO-C (} CH 3) = CH 2, -CH 2 -O-CO-C (CH 2 CH 3) = CH 2, -CH 2 CH 2 -O-CO-CH = CH 2 , —CH ₂ CH ₂ —O—CO—C (CH ₃ ) ═CH ₂ , —CH ₂ CH ₂ —O—CO—C (CH ₂ CH ₃ ) = CH ₂ , —CH ₂ CH ₂ CH ₂ —O _{-CO-CH = CH 2, -CH} 2 CH 2 CH 2 -O-CO-C (CH 3) = CH 2, -CH 2 CH 2 CH 2 -O-CO-C (CH 2 CH 3) = CH _{2, -CH 2 CH 2 CH 2} CH 2 -O-CO-CH = CH 2, -CH 2 CH 2 CH 2 CH 2 -O-CO-C (CH 3) = CH 2, - _{H 2 CH 2 CH 2 CH 2} -O-CO-C (CH 2 CH 3) = CH 2 . Among these _{-CH 2 -O-CO-CH =} CH 2 are preferred.

In a compound having two or more α, β-unsaturated bonds in one molecule, how the α, β-unsaturated bond is bonded in one molecule of the compound is not particularly limited. For example, a structure in which an α, β-unsaturated bond is bonded as a repeating unit, a structure in which an α, β-unsaturated bond is bonded to a different atom in the compound, and an α, β-unsaturated bond is 1 Examples include structures that are bonded to one atom. Among these, a structure in which an α, β-unsaturated bond is bonded on one atom is one of more preferable embodiments. Examples of the atom to which the α, β-unsaturated bond is bonded include a carbon atom, a nitrogen atom, and a sulfur atom, and among them, a carbon atom is preferable.
The number of α, β-unsaturated bonds in one molecule is 2 or more, preferably 2 to 4, more preferably 3.

The compound having two or more α, β-unsaturated bonds in one molecule is not particularly limited, and for example, conventionally known compounds can be used.
As a compound having two or more α, β-unsaturated bonds in one molecule, for example, in one molecule, the double bond is located at the terminal, the α-position substituent is a carbonyloxy group, and the carbonyloxy group And a compound in which three of the α, β-unsaturated bonds are bonded to one carbon atom. Specifically, the compound represented by following formula (14) is mentioned, for example.

(In formula, R < ¹² > -R < ¹⁴ > represents a hydrogen atom, a methyl group, or an ethyl group each independently.)
Trimethacrylate Examples of the compound represented by the formula (14), for example, triacrylate compounds R ¹² to R ¹⁴ are all hydrogen atoms, R ¹² are all methyl groups R ¹³ to R ¹⁴ are all hydrogen atoms Compounds.
The triacrylate compound in which R ^{12 to} R ^{14 in the} formula (14) are all hydrogen atoms is specifically a compound represented by the following formula (15).

The compound represented by Formula (4) is demonstrated below.
The compound represented by the formula (4) is used as a raw material for the conjugated diene compound contained in the curable composition of the fourth aspect of the present invention.

R ¹ -XH (4)

R ¹ in the formula (4) represents a monovalent hydrocarbon group containing a conjugated diene structure is the same as R ¹ in the formula (1).
X in Formula (4) represents an oxygen atom or a sulfur atom, and a sulfur atom is preferable.
Examples of the compound represented by the formula (4) include furfuryl alcohol, furfuryl thiol, 3-furyl methyl alcohol, and 3-furyl methyl thiol, and furfuryl thiol is preferable.

  The conjugated diene compound contained in the curable composition according to the fourth aspect of the present invention is represented, for example, by the formula (15) as a compound having two or more α, β-unsaturated bonds in one molecule. And a conjugated diene compound represented by the following formula (16) obtained by reacting the compound represented by formula (4) with the compound represented by formula (4).

(In the formula, R ¹ represents a monovalent hydrocarbon group containing a conjugated diene structure. X represents an oxygen atom or a sulfur atom.)
R ¹ in formula (16) represents a monovalent hydrocarbon group containing a conjugated diene structure, and is the same as R ¹ in the compound represented by formula (4).
X in Formula (16) represents an oxygen atom or a sulfur atom, preferably a sulfur atom.
Examples of the substituent XR ¹ in the formula (16) include a furfuryloxy group, a 3-furylmethoxy group, a 2-furylethoxy group, a 3-furylethoxy group, a 2-furylpropoxy group, and a 3-furylpropoxy group. An alkyleneoxy group containing a furan ring; a furan ring such as a furfurylthio group, a 3-furylmethylthio group, a 2-furylethylthio group, a 3-furylethylthio group, a 2-furylpropylthio group, or a 3-furylpropylthio group; The alkylene thio group to contain is mentioned, A furfuryl thio group is especially preferable.
The conjugated diene compound when the substituent XR ¹ in the formula (16) is a furfurylthio group is a conjugated diene compound represented by the following formula (17).

The conjugated diene compound contained in the curable composition according to the fourth aspect of the present invention is a compound having two or more α, β-unsaturated bonds in one molecule and a formula (4). If it uses the compound represented, it will not specifically limit. For example, it can be produced according to the method for producing a conjugated diene compound contained in the curable composition of the third aspect of the present invention.
The conjugated diene compounds contained in the curable composition of the fourth aspect of the present invention can be used alone or in combination of two or more.

The dienophile compound contained in the curable composition of the 4th aspect of this invention is demonstrated below.
The dienophile compound contained in the curable composition of the fourth aspect of the present invention is a dienophile compound having two or more α, β-unsaturated bonds in one molecule. The dienophile compound contained in the curable composition of the fourth aspect of the present invention is the same as the dienophile compound contained in the curable composition of the first aspect of the present invention.
The dienophile compound contained in the curable composition of the 4th aspect of this invention can be used individually or in combination of 2 or more types, respectively.
The curable composition according to the fourth aspect of the present invention preferably contains the dienophile compound in an amount of 0.3 to 2 equivalents, more preferably 0.8 to 1.2 equivalents with respect to 1 equivalent of the conjugated diene compound. To do.

The curable composition of the present invention may further contain a thermosetting resin in the curable composition of any one of the first to fourth aspects of the present invention.
The thermosetting resin used is not particularly limited, and for example, a conventionally known one can be used. Among them, those that are two-dimensionally or three-dimensionally cross-linked are preferable. Specific examples of the thermosetting resin include an epoxy resin, an acrylic resin, a modified silicone resin, a urethane resin, and a polyimide resin. Of these, an epoxy resin is preferable.

The epoxy resin is not particularly limited, and examples thereof include those having two or more epoxy groups in one molecule. It is preferable that the epoxy equivalent of an epoxy resin is 100-1000.
Examples of the epoxy resin include epoxy compounds having a bisphenyl group such as bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, and biphenyl type, polyalkylene glycol Type, alkylene glycol type epoxy compound, epoxidized resin having naphthalene ring, bifunctional glycidyl ether type epoxy resin such as epoxy compound having fluorene group;
Tri- or higher functional glycidyl ether type epoxy resin such as phenol novolac type, orthocresol novolak type, DPP novolak type, tris-hydroxyphenylmethane type, trifunctional type represented by formula (10), tetraphenylolethane type, etc .;
Glycidyl ester type epoxy resin of synthetic fatty acid such as dimer acid;
Glycidyl such as N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM), triglycidyl isocyanurate, tetraglycidyl-m-xylylenediamine, N, N-diglycidylaniline, triglycidyl-p-aminophenol An amino type epoxy resin is mentioned.

An epoxy resin that is liquid at room temperature (15 to 30 ° C.) is preferable because it enables the curable composition to be cured without using a solvent component.
Among these, bisphenol A type, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM), and triglycidyl-p-aminophenol are preferable because of their high heat resistance and relatively low viscosity.
A thermosetting resin can be used individually or in combination of 2 types or more, respectively.

  The blending ratio of the thermosetting resin is preferably 50 to 500 parts by mass, more preferably 400 to 500 parts by mass with respect to 100 parts by mass of the conjugated diene compound. When the blending ratio of the thermosetting resin to the conjugated diene compound is within this range, the elastic modulus of the resulting cured product can be increased.

The curable composition of this invention can improve the elasticity modulus of the hardened | cured material obtained rather than adjusting the compounding ratio of a conjugated diene compound and a dienophile compound freely.
Moreover, when the curable composition of this invention further contains a thermosetting resin, a conjugated diene compound, a dienophile compound, and a thermosetting resin can be mix | blended as a separate compound. Therefore, the curable composition of the present invention can freely and easily change the compounding ratio of the conjugated diene compound, the dienophile compound, and the thermosetting resin.
On the other hand, conventionally, as a compound blended in a curable composition capable of Diels-Alder reaction, a functional group derived from a thermosetting resin, a conjugated diene structure and / or a dienophile structure are contained in one molecule. And the compounding ratio of the conjugated diene structure, the dienophile structure, and the functional group derived from the thermosetting resin cannot be easily changed, and the elastic modulus of the cured product is improved. It was difficult.

When the thermosetting resin is an epoxy resin, the curable composition of the present invention preferably further contains a curing agent.
The curing agent to be used is not particularly limited, and for example, a conventionally known one can be used. Specific examples include amine curing agents, acid or acid anhydride curing agents, polymercaptan curing agents, dicyandiamides, imidazole compounds, phenol resins, urea resins, melamine resins, and Lewis acids.

  Examples of the amine curing agent include butylamine, hexylamine, octylamine, dodecylamine, oleylamine, ethylenediamine, propylenediamine, 1,2-diaminopropane, butylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, tetraethylenepenta Chain aliphatic amines such as amine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, guanidine, cyclohexylamine, triethylenediamine, morpholine N-methylmorpholine, 1,8-diazabicyclo [5.4.0] -7-undecene, isophor Diamine, 1,3-bisaminomethylcyclohexane, N-aminoethylpiperazine, 3,3-dimethyl-4,4-diaminodicyclohexylmethane, mensendiamine, 4,4-diaminodicyclohexylmethane, 1,3-bisaminomethyl Cycloaliphatic amines such as cyclohexane and aliphatic amines such as aliphatic aromatic amines such as benzylamine and m-xylenediamine;

aromatic amines such as m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diphenylguanidine;
Amine adduct (polyamine epoxy resin adduct), polyamine-ethylene oxide adduct, ketimine which is a reaction product of aliphatic amine and ketone;
Secondary or tertiary amines such as dibutylamine, benzyldimethylamine, diethanolamine, triethanolamine, tetramethylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, piperidine, pyridine;
Carboxylates of these amine compounds;
A polyamidoamine obtained by reacting dimer acid with a polyamine such as diethylenetriamine or triethylenetetramine;
And quaternary ammonium salts such as benzyltriethylammonium acetate.

Examples of the acid or acid anhydride curing agent include polycarboxylic acids such as adipic acid, azelaic acid, and decanedicarboxylic acid;
Phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (andro trimellitate), pyromellitic anhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic anhydride Aromatic anhydrides such as;
Cyclic aliphatic acid anhydrides such as maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride;
Aliphatic acid anhydrides such as polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride, dodecenyl succinic anhydride, poly (ethyloctadecanedioic acid) anhydride;
Halogenated acid anhydrides such as tetrabromophthalic anhydride and het anhydride are listed.

Examples of the polymercaptan curing agent include esters of thioglycolic acid such as pentaerythritol tetrathioglycolate and dipentaerythritol hexathioglycolate; compounds having a mercapto group such as a polysulfide rubber having a mercapto group at the terminal. .
Examples of dicyandiamides include dicyandiamide and reaction adducts of dicyandiamide and aromatic amine.
Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, and 1-benzyl-2-methylimidazole.
Examples of the phenol resin include novolac type phenol resins and phenol polymers.
Examples of the Lewis acid include BF ₃ monoethylamine and BF ₃ piperazine.

Among them, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, diaminodiphenylmethane, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, imidazole compound, novolac type phenol resin, BF ₃ mono Ethylamine is preferable, and 4,4′-diaminodiphenyl sulfone and 3,3′-diaminodiphenyl sulfone are more preferable.
These curing agents can be used alone or in combination of two or more.
The blending ratio of the curing agent is preferably 0.3 to 2 equivalents, more preferably 0.8 to 1.2 equivalents with respect to 1 equivalent of the epoxy resin.

When the conjugated diene compound and the curable resin contained in the curable composition of the present invention are liquid at room temperature, the conjugated diene compound and the curable resin are mixed and, for example, are not cured unless heated, so handling is very Easy to.
The curable composition of the present invention is used as a two-component curable composition in which a main component other than the curing agent is used as a main component, and the main component and the curing agent are mixed according to a conventional method before use. It can also be used as a one-component curable composition.
The curable composition of the present invention includes various fillers, plasticizers, curing catalysts, dehydrating agents, softeners, stabilizers, colorants, difficult additives, as long as the object of the present invention is not impaired. Known additives such as a flame retardant, a reinforcing agent, an anti-aging agent, an antioxidant, an ultraviolet absorber, a dye, and a pigment can be blended.
Further, the curable composition of the present invention is not particularly limited with respect to the production method thereof, and in addition to the conjugated diene compound and the dienophile compound, a thermosetting resin, a curing agent, various additives, for example, a roll, a kneader, an extrusion And mixing with a universal agitator.

The method for curing the curable composition of the present invention is not particularly limited. For example, it can be cured under the conditions used for the curing reaction of ordinary curable resins.
The reaction pressure is preferably atmospheric pressure.
The reaction temperature is preferably room temperature to 200 ° C, more preferably 120 to 180 ° C.
The reaction time is preferably 0.5 to 10 hours, more preferably 1 to 2 hours.
The reaction is preferably performed in the presence of moisture or a curing agent when the curable composition contains a thermosetting resin.
The curable composition of the present invention can be used in a very wide range. Specific applications include, for example, matrix resins for fiber reinforced composite materials, prepregs, adhesives (for civil engineering, concrete, wood, metal, glass, plastic, etc.), sealants, waterproofing agents, paints, Examples include foams and hot melt materials (hot melt adhesives, hot melt paints, etc.). A matrix resin for fiber-reinforced composite materials and a prepreg are preferable examples.

Below, the hardened | cured material of this invention is demonstrated.
The cured product of the present invention is a cured product obtained by curing by forming a bond between the conjugated diene compound and the dienophile compound of the curable composition by a Diels-Alder reaction.

When the curable composition of the present invention is heated, for example, the conjugated diene compound and the dienophile compound undergo a Diels-Alder reaction, a bond is formed between the conjugated diene compound and the dienophile compound, and is cured to produce a cured product. The produced cured product has a chain structure or a three-dimensional structure. For example, when two conjugated dienes are contained in one conjugated diene compound and two dienes are contained in one dienophile compound, the resulting cured product has a chain structure. In addition, when there are 3 or more conjugated dienes contained in one conjugated diene compound and 2 or more dienes contained in one dienophile compound, and conjugated dienes contained in one conjugated diene compound Is 2 or more, and when the diene contained in one dienophile compound is 3 or more, the resulting cured product has a three-dimensional structure.
When the curable composition of the present invention further contains a thermosetting resin, when the curable composition is heated in the presence of moisture or a curing agent, the conjugated diene compound and the dienophile compound undergo a Diels-Alder reaction, A bond is formed between the conjugated diene compound and the dienophile compound, and the thermosetting resin undergoes a curing reaction to produce a cured product. The resin obtained by curing the thermosetting resin has a chain structure or a three-dimensional structure depending on the number of functional groups of the thermosetting resin. Thus, when the curable composition of the present invention further contains a thermosetting resin, the resulting cured product has a chain structure or a three-dimensional structure obtained by Diels-Alder reaction (hereinafter referred to as “Diels-Alder reaction”). Structure ") and the chain structure or three-dimensional structure of the thermosetting resin obtained by the curing reaction of the thermosetting resin (hereinafter referred to as" the structure by the curing reaction of the thermosetting resin ") There is.)

In addition, the bond formed between the conjugated diene compound and the dienophile compound of the cured product of the present invention is unlikely to dissociate even at a temperature at which the thermosetting resin decomposes, and the structure due to the Diels-Alder reaction is considered to be strong. It is done.
From this, when the curable composition of the present invention contains a thermosetting resin and the blending ratio of the conjugated diene compound and the dienophile compound to the thermosetting resin is low, the structure by Diels-Alder reaction is within the cured product. In other words, it plays the role of a framework, and as a result, it is considered that the elastic modulus of the cured product is improved.
Note that the mechanism as described above for the cured product of the present invention is the inventor's guess, and even if the mechanism is different from the above, it is within the scope of the present invention.
The cured product of the present invention can be used in a very wide range. Specific applications include, for example, matrix resins for fiber reinforced composite materials, prepregs, adhesives (for civil engineering, concrete, wood, metal, glass, plastic, etc.), sealants, waterproofing agents, paints, Examples include foams and hot melt materials (hot melt adhesives, hot melt paints, etc.). A matrix resin for fiber-reinforced composite materials and a prepreg are preferable examples.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these. The physical properties of the cured product were evaluated by the following methods.

(Elastic modulus)
For the cured products synthesized in the following examples and comparative examples, G ′ (storage modulus) of each cured product was measured by the DMA method. The measurement conditions for G ′ (storage modulus) are as follows. The results are shown in Table 2.
-Measuring device: ARES (manufactured by TA-instruments)
-Test method: Torsion test-Test piece: Strip-like test piece of length 32 mm x width 12 mm x thickness 1 mm of each of the following cured products-strain: 0.01%
・ Frequency: 1 Hertz ・ Measurement temperature: 40 ℃
・ Heating rate: 5 ° C / min
-Measurement temperature range: 30-300 ° C

(Synthesis Example 1) Preparation of tetrafurfuryloxysilane Basic to 20 g (96.0 mol) of tetraethoxysilane (Shin-Etsu Chemical Co., Ltd.) and 37.67 g (384.0 mmol) of furfuryl alcohol (Kanto Chemical Co., Ltd.) 0.5 g (3.3 mmol) of 1,8-diazabicyclo [5,4,0] -7-undecene (manufactured by Kanto Chemical Co.) as a catalyst was added, heated under reduced pressure, and then at 60 ° C. for 3 hours, And reacted at 90 ° C. for 1 hour. After the reaction, it was confirmed by ¹ H-NMR analysis that the ethoxy group had disappeared almost completely, and tetrafurfuroxysilane represented by the formula (8) was obtained almost quantitatively. Tetrafurfuroxysilane was liquid at 20 ° C.
The obtained tetraflufuryloxysilane was subjected to IR analysis, ¹ H-NMR analysis, and FAB-MS analysis.
FIG. 1 is a chart showing an IR spectrum measured for tetraflufuryloxysilane by IR analysis.
As a result of measurement (CDCl ₃ , 270 MHz) for tetraflufuryloxysilane by ¹ H-NMR analysis, signals of δ = 4.72 ppm, 6.23 ppm, 6.35 ppm, and 7.39 ppm were obtained. The obtained signals are expressed as follows: δ = 4.72 ppm (Ha), δ = 6.23 ppm (Hc), δ = 6, where each proton of tetrafurfuryloxysilane is represented by Ha to Hd represented by the following formula (18). .35 ppm (Hb) and δ = 7.39 ppm (Hd).
Moreover, the mass spectrometry value by FAB-MS analysis was 415.6 (exact mass number 416.09).

(Example 1) Preparation of cured product 1 1.0 g (2.4 mmol) of tetraflufuryloxysilane prepared in Synthesis Example 1 and triacrylate represented by formula (7) (M-309, manufactured by Toagosei Co., Ltd.) The same applies hereinafter) 0.95 g (3.2 mmol) was cured at 180 ° C. for 2 hours to obtain a cured product 1.
About the obtained hardened | cured material 1, IR spectrum was measured. As a result, it was confirmed that the absorption of the furan ring (1504 cm ⁻¹ ) decreased.

(Example 2) Preparation of cured product 2 1.0 g (2.4 mmol) of tetraflufuroxysilane prepared in Synthesis Example 1 and 0.95 g (3.2 mmol) of triacrylate represented by the formula (7) Further, bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd., YD-128, the same applies below) 9.12 g (24.0 mmol) and 4,4′-diaminodiphenyl sulfone (manufactured by Wakayama Seika Kogyo Co., Ltd., applies hereinafter) 2.98 g (12.0 mmol) was subjected to a curing reaction at 180 ° C. for 2 hours to obtain a cured product 2.
About the obtained hardened | cured material 2, IR spectrum was measured. As a result, it was confirmed that the absorption of the furan ring (1504 cm ⁻¹ ) decreased.

Example 3 Preparation of Cured Product 3 1.2 g (2.88 mmol) of tetraflufuryloxysilane prepared in Synthesis Example 1 and 1.14 g (3.85 mmol) of triacrylate represented by the formula (7) N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM) (manufactured by HUNTSMAN, MY-721) 12.9 g (epoxy equivalent 0.115 mol) and triglycidyl-p-aminophenol 7.1 g (67.6 mmol as epoxy equivalent) (manufactured by HUNTSMAN, MY-0500, the same applies below) and 6.44 g (26 W), 3,3′-diaminodiphenylsulfone (manufactured by Wakayama Seika Kogyo Co., Ltd., the same applies hereinafter) 0.0 mol) was cured at 180 ° C. for 2 hours to obtain a cured product 3.
About the obtained hardened | cured material 3, IR spectrum was measured. As a result, it was confirmed that the absorption of the furan ring (1504 cm ⁻¹ ) decreased.

(Comparative Example 1) Preparation of Cured Material 4. Bisphenol A type epoxy resin 9.12 g (24.0 mmol) and 4,4′-diaminodiphenylsulfone 2.98 g (12.0 mmol) were cured at 180 ° C. for 2 hours. Cured product 4 was obtained.

Comparative Example 2 Preparation of Cured Product 5 12.9 g (0.115 mol as epoxy equivalent) of N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol 1 g (67.6 mmol as an epoxy equivalent) and 6.44 g (26.0 mmol) of 3,3′-diaminodiphenylsulfone were subjected to a curing reaction at 180 ° C. for 2 hours to obtain a cured product 5.

  As apparent from Table 2, the G ′ (storage elastic modulus) of the cured product (cured product 2) obtained from the curable composition of the present invention is higher than that of the cured product 4, and the G of the cured product 3 It turned out that '(storage elastic modulus) is high compared with the hardened | cured material 5. The curable composition of the present invention can provide a cured product having a high G ′ (storage modulus) near room temperature. Thus, since the cured product obtained from the curable composition of the present invention has a large G ′ (storage elastic modulus), it can be said that the cured product has a high crosslinking density and a high compressive strength.

FIG. 1 is a chart showing an IR spectrum measured by IR analysis for tetrafurfuryloxysilane obtained in Synthesis Example 1.

Claims (12)

A conjugated diene compound obtained by reacting an alkoxysilane compound having one silicon atom and two or more alkoxy groups in one molecule with a compound represented by the following formula (1);
A curable composition containing a dienophile compound having two or more α, β-unsaturated bonds in one molecule.
R ¹ -XH (1)
(In the formula, R ¹ represents a monovalent hydrocarbon group containing a conjugated diene structure. X represents an oxygen atom or a sulfur atom.)   The curable composition according to claim 1, wherein the conjugated diene structure is a furan ring and the X is an oxygen atom. A conjugated diene compound represented by the following formula (2);
A curable composition containing a dienophile compound having two or more α, β-unsaturated bonds in one molecule.
SiR ² _n (XR ¹ ) _4-n (2)
(In the formula, each R ¹ independently represents a monovalent hydrocarbon group containing a conjugated diene structure. Each R ² is independently substituted with a functional group in which a hydrogen atom reacts with a thermosetting resin. And n represents an integer of 0 to 2. X independently represents an oxygen atom or a sulfur atom.)   The curable composition according to claim 3, wherein all of the conjugated diene structures are furan rings and all of the X are oxygen atoms. A conjugated diene compound obtained by reaction of an epoxy compound having two or more epoxy groups in one molecule with a compound represented by the following formula (3);
A curable composition containing a dienophile compound having two or more α, β-unsaturated bonds in one molecule.
R ¹ -XH (3)
(In the formula, R ¹ represents a monovalent hydrocarbon group containing a conjugated diene structure. X represents an oxygen atom or a sulfur atom.)   The curable composition according to claim 5, wherein the conjugated diene structure is a furan ring and the X is a sulfur atom. A conjugated diene compound obtained by reacting a compound having two or more α, β-unsaturated bonds in one molecule with a compound represented by the following formula (4);
A curable composition containing a dienophile compound having two or more α, β-unsaturated bonds in one molecule.
R ¹ -XH (4)
(In the formula, R ¹ represents a monovalent hydrocarbon group containing a conjugated diene structure. X represents an oxygen atom or a sulfur atom.)   The curable composition according to claim 7, wherein the conjugated diene structure is a furan ring, and the X is a sulfur atom.   The curability according to any one of claims 1 to 8, wherein the α, β-unsaturated bond contained in the dienophile compound is an acryloyloxy group in which a hydrogen atom at the α-position may be substituted with a hydrocarbon group. Composition.   Furthermore, the curable composition in any one of Claims 1-9 containing a thermosetting resin.   The curable composition according to claim 10, wherein the thermosetting resin is an epoxy resin and further contains a curing agent.   A cured product obtained by forming a bond by a Diels-Alder reaction between the conjugated diene compound and the dienophile compound of the curable composition according to any one of claims 1 to 11.

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