WO2017047037A1 - Clathrate compound - Google Patents

Abstract

The present invention addresses the problem of providing a curing catalyst (clathrate compound) that suppresses a curing reaction at a low temperature, improving one-pack stability, and can effectively cure a resin by applying heat treatment. The clathrate compound according to the present invention contains a fluorene compound represented by formula (I) and an imidazole compound represented by formula (II).

Description

Inclusion compound

The present invention relates to a novel clathrate compound, a curing catalyst comprising the clathrate compound, a cured resin forming composition using the curing catalyst, a method for producing a cured resin using the cured resin forming composition, and the The present invention relates to a cured resin obtained by a production method.
This application claims priority to Japanese Patent Application No. 2015-182752 filed on September 16, 2015, the contents of which are incorporated herein by reference.

Epoxy resins are widely used in various fields because they have excellent mechanical and thermal properties. As a curing agent for curing such an epoxy resin, imidazole is used. However, the epoxy resin-imidazole mixed solution has a problem that the onset of curing is early and the stability of one solution is extremely poor.

Therefore, as the curing agent, an imidazolic acid addition salt obtained by adding hydroxybenzoic acid to imidazole (see Patent Document 1) or a tetrakisphenol compound (for example, 1,1,2,2-tetrakis (4-hydroxy) is used. It has been proposed to use an inclusion body of phenyl) ethane (hereinafter referred to as TEP)) and imidazole (see Patent Document 2). Such imidazole acid addition salts and clathrates have a certain effect, but development of those having the same function or further improved functions is desired.

Japanese Patent Publication No.4-2638 JP-A-11-71449

An object of the present invention is to suppress a curing reaction at a low temperature to improve the stability of one liquid and to cure the resin effectively by performing a heat treatment (cladding compound). Is to provide. Moreover, the subject of this invention provides the cured resin forming composition using this curing catalyst, the manufacturing method of the cured resin using this cured resin forming composition, and the cured resin obtained by this manufacturing method There is.

As a result of diligent research to solve the above problems, the present inventors have found that the above problems can be solved by using a clathrate compound of a specific fluorene compound and a specific imidazole compound, and to complete the present invention. It came.

That is, the present invention
(1) Formula (I)

(In the formula, each X ¹ independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or Represents a cyano group.
m represents any integer from 0 to 4, and n represents any integer from 0 to 4.
X ² each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group. .
p represents any integer from 0 to 4, and q represents any integer from 0 to 4. And a fluorene compound represented by formula (II)

(Wherein R ¹ represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group.
R ² to R ⁴ each independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, a nitro group, or a cyano group. To express. An inclusion compound containing an imidazole compound represented by:
(2) The clathrate compound according to (1), wherein the fluorene compound represented by the formula (I) is 9,9-bis (4-hydroxyphenyl) fluorene,
(3) A curing catalyst for epoxy resin comprising the clathrate compound according to (1) or (2),
(4) A composition for forming an epoxy cured resin containing the following component (A) and component (B):
(A) Epoxy resin (B) Formula (I)

(In the formula, each X ¹ independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or Represents a cyano group.
m represents any integer from 0 to 4, and n represents any integer from 0 to 4.
X ² each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group. .
p represents any integer from 0 to 4, and q represents any integer from 0 to 4. And a fluorene compound represented by formula (II)

(Wherein R ¹ represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group.
R ² to R ⁴ each independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, a nitro group, or a cyano group. To express. Imidazole represented by the formula (II) in the component (B) with respect to 1 mole of the epoxy ring of the epoxy resin as the component (A) component. The composition for forming an epoxy cured resin according to (4), containing 0.01 to 1.0 mol of the compound,
(6) The epoxy cured resin forming composition according to (4) or (5), wherein the fluorene compound represented by the formula (I) is 9,9-bis (4-hydroxyphenyl) fluorene,
(7) A method for producing an epoxy cured resin by heating and curing the epoxy cured resin forming composition according to any one of (4) to (6),
(8) An epoxy cured resin obtained by heat-treating the composition for forming an epoxy cured resin according to any one of (4) to (6),
(9) Further, it contains one or more epoxy resin curing catalysts selected from cyclic amidine compounds, acid anhydrides, quinone compounds, tertiary amine compounds, aromatic amine compounds, imidazole compounds and organic phosphine compounds (4 ) Composition for forming an epoxy cured resin,
(10) The composition for forming an epoxy cured resin according to (4), further containing a curing agent, and (11) the composition for forming an epoxy cured resin according to (4), further containing a filler.

According to the curing catalyst (cladding compound) of the present invention, the curing reaction at low temperature is suppressed to improve the one-component stability, and the resin can be effectively cured by performing a heat treatment. it can.

2 is a graph showing the XRD measurement results of inclusion compound A obtained in Example 1. FIG. FIG. 3 is a view showing a TG-DSC measurement result of inclusion compound A obtained in Example 1. 1 is a diagram showing a ¹ H-NMR spectrum of inclusion compound A obtained in Example 1. FIG. It is a figure which shows the DSC measurement result of the composition A for epoxy cured resin formation obtained in Example 2. FIG. FIG. 4 is a diagram showing the XRD measurement results of inclusion compound B obtained in Example 3. FIG. 6 is a view showing a TG-DSC measurement result of inclusion compound B obtained in Example 3. It is a diagram showing ^{1 H-NMR} spectrum of the resulting inclusion compound B in Example 3. It is a figure which shows the DSC measurement result of the composition for epoxy cured resin formation obtained in Example 4. FIG. FIG. 6 is a view showing an XRD measurement result of an inclusion compound C obtained in Example 5. FIG. 6 is a view showing a TG-DSC measurement result of inclusion compound C obtained in Example 5. 6 is a diagram showing a ¹ H-NMR spectrum of inclusion compound C obtained in Example 5. FIG. It is a figure which shows the DSC measurement result of the composition for epoxy cured resin formation obtained in Example 6. FIG. FIG. 6 is a view showing an XRD measurement result of an inclusion compound D obtained in Example 7. FIG. 6 is a view showing a TG-DSC measurement result of inclusion compound D obtained in Example 7. 4 is a diagram showing a ¹ H-NMR spectrum of inclusion compound D obtained in Example 7. FIG. It is a figure which shows the DSC measurement result of the composition for epoxy cured resin formation obtained in Example 8. FIG.

[Fluorene compound]
The fluorene compound represented by the formula (I) will be described. First, in the present invention, the term “unsubstituted” means only a group serving as a mother nucleus. When there is no description of “having a substituent” and only the name of the group serving as a mother nucleus is used, it means “unsubstituted” unless otherwise specified.
On the other hand, the term “having a substituent” means that any hydrogen atom of a group serving as a mother nucleus is substituted with a group having the same or different structure from the mother nucleus. Accordingly, the “substituent” is another group bonded to a group serving as a mother nucleus. The number of substituents may be one, or two or more. Two or more substituents may be the same or different.
Terms such as “C1-6” indicate that the group serving as the mother nucleus has 1 to 6 carbon atoms. This number of carbon atoms does not include the number of carbon atoms present in the substituent. For example, a butyl group having an ethoxy group as a substituent is classified as a C2 alkoxy C4 alkyl group.

The “substituent” is not particularly limited as long as it is chemically acceptable and has the effects of the present invention. Examples of groups that can be “substituents” are shown below.
Halogeno groups such as fluoro, chloro, bromo and iodo groups;
C1-6 such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc. An alkyl group;
Vinyl group, 1-propenyl group, 2-propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, etc. A C2-6 alkenyl group of
C2-6 alkynyl groups such as ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group;
A C3-8 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group;
A C6-10 aryl group such as a phenyl group or a naphthyl group;
A C6-10 aryl C1-6 alkyl group such as a benzyl group or a phenethyl group;
3-6 membered heterocyclyl group;
A 3-6 membered heterocyclyl C1-6 alkyl group;

Hydroxyl group;
C1-6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group;
C2-6 alkenyloxy groups such as vinyloxy group, allyloxy group, propenyloxy group, butenyloxy group;
C6-10 aryloxy groups such as phenoxy group and naphthoxy group;
A C6-10 aryl C1-6 alkoxy group such as a benzyloxy group or a phenethyloxy group;
A 3-6 membered heterocyclyloxy group;
A 3-6 membered heterocyclyl C1-6 alkoxy group;
C1-6 haloalkyl groups such as chloromethyl group, chloroethyl group, trifluoromethyl group, 1,2-dichloro-n-propyl group, 1-fluoro-n-butyl group, perfluoro-n-pentyl group;
A C1-6 haloalkoxy group such as a trifluoromethoxy group, 2-chloro-n-propoxy group, 2,3-dichlorobutoxy group;

An amino group;
A C1-6 alkylamino group such as a methylamino group, a dimethylamino group, a diethylamino group;
C6-10 arylamino groups such as anilino group and naphthylamino group;
A C6-10 aryl C1-6 alkylamino group such as a benzylamino group or a phenethylamino group;
A mercapto group;
C1-6 alkylthio groups such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group;
A C1-6 alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, a t-butylsulfonyl group;
A C6-10 arylthio group such as a phenylthio group or a naphthylthio group;
A 3-6 membered heterocyclylthio group;
A C6-10 arylsulfonyl group such as a phenylsulfonyl group;
A 3-6 membered heterocyclylsulfonyl group;
A cyano group;
Nitro group.
In these “substituents”, any hydrogen atom in the substituent may be substituted with a group having a different structure. In this case, examples of the “substituent” include a halogeno group, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a cyano group, and a nitro group.

In addition, the “3- to 6-membered heterocyclyl group” is a cyclic group containing 1 to 4 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom as constituent atoms of the ring. Examples of the “3- to 6-membered heterocyclyl group” include a 3- to 6-membered saturated heterocyclyl group, a 5- to 6-membered heteroaryl group, and a 5- to 6-membered partially unsaturated heterocyclyl group.

Examples of the 3- to 6-membered saturated heterocyclyl group include aziridinyl group, epoxy group, pyrrolidinyl group, tetrahydrofuranyl group, thiazolidinyl group, piperidyl group, piperazinyl group, morpholinyl group, dioxolanyl group, dioxanyl group and the like.
Examples of 5-membered heteroaryl groups include pyrrolyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl Can do.
Examples of the 6-membered heteroaryl group include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, and a triazinyl group.
Examples of the 5-membered partially unsaturated heterocyclyl group include a pyrrolinyl group, a dihydrofuranyl group, an imidazolinyl group, a pyrazolinyl group, and an oxazolinyl group.
Examples of the 6-membered partially unsaturated heterocyclyl group include an isoxazolinyl group and a dihydropyranyl group.

[X ¹ , X ² ]
In formula (I), each X ¹ independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, or a nitro group. Or a cyano group. m represents any integer from 0 to 4, and n represents any integer from 0 to 4.
X ² each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group. . p represents any integer from 0 to 4, and q represents any integer from 0 to 4.

Examples of the “halogeno group” in X ¹ and X ² include a fluoro group, a chloro group, a bromo group, and an iodo group.

The “C1-6 alkyl group” in X ¹ and X ² may be linear or branched. Examples of the C1-6 alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, s-butyl group, t -Butyl group, i-pentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, i-hexyl group and the like can be mentioned.
The substituent on the “C1-6 alkyl group” is preferably a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, or a cyano group.

As the “C1-6 alkyl group having a substituent”, specifically,
Fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2,2,2-trifluoroethyl group, 2, 2,2-trichloroethyl group, pentafluoroethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 3,3,3-trifluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl A C1-6 haloalkyl group such as a group, perfluorohexyl group, perchlorohexyl group, 2,4,6-trichlorohexyl group;
Hydroxy C1-6 alkyl groups such as hydroxymethyl group, 2-hydroxyethyl group;
Methoxymethyl group, ethoxymethyl group, methoxyethyl group, ethoxyethyl group, methoxy-n-propyl group, ethoxymethyl group, ethoxyethyl group, n-propoxymethyl group, i-propoxyethyl group, s-butoxymethyl group, t A C1-6 alkoxy C1-6 alkyl group such as a butoxyethyl group;
C3-8 cycloalkyl C1-6 alkyl groups such as cyclopropylmethyl group, 2-cyclopropylethyl group, cyclopentylmethyl group, 2-cyclohexylethyl group, 2-cyclooctylethyl group;
A C7-11 aralkyl group such as a benzyl group or a phenethyl group;
A cyano C1-6 alkyl group such as a cyanomethyl group and a cyanoethyl group;
And so on.

As the “C1-6 alkoxy group” in X ¹ and X ² , a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an i-propoxy group, Examples include i-butoxy group, s-butoxy group, t-butoxy group, i-hexyloxy group and the like.
The substituent on the “C1-6 alkoxy group” is preferably a halogeno group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, or a C6-10 aryl group.

Specific examples of the “substituted C1-6 alkoxy group” include chloromethoxy group, dichloromethoxy group, difluoromethoxy group, trichloromethoxy group, trifluoromethoxy group, 1-fluoroethoxy group, 1,1- Examples thereof include C1-6 haloalkoxy groups such as difluoroethoxy group, 2,2,2-trifluoroethoxy group, and pentafluoroethoxy group.

Specific examples of the fluorene compound represented by the formula (I) include 9,9-bis (4-hydroxyphenyl) fluorene <9,9-Bis (4-hydroxyphenyl) fluorene>, 9,9-bis ( 4-hydroxy-3-methylphenyl) fluorene <9,9-Bis (4-hydroxy-3-methylphenyl) fluorene>, 2,7-dibromo-9,9-bis (4-hydroxyphenyl) fluorene <2,7 -Dibromo-9,9-bis (4-hydroxyphenyl) fluorene>, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene <9,9-Bis (3-amino-4-hydroxyphenyl) fluorene>, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene <9,9-Bis (4-hydroxy-3,5-dimethylphenyl) fluorene>, 9,9-bis (4-hydroxy-2, 6-dibromophenyl) fluorene <9,9-Bis (4-hydroxy-2,6-dibromolphenyl) fluorene>.

[Imidazole compound]
Next, the imidazole compound represented by the formula (II) will be described.
[R ¹ ]
In formula (II), R ¹ represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group.

Examples of the “C1-6 alkyl group” for R ¹ include the same groups as those exemplified for X ¹ above. The substituent on the “C1-6 alkyl group” is preferably a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, or a cyano group.

The “C6-10 aryl group” in R ¹ may be monocyclic or polycyclic. In the polycyclic aryl group, if at least one ring is an aromatic ring, the remaining ring may be a saturated alicyclic ring, an unsaturated alicyclic ring, or an aromatic ring.
Examples of the “C6-10 aryl group” in R ¹ include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.
Examples of the substituent on the “C6-10 aryl group” include halogeno group, C1-6 alkyl group, hydroxyl group, C1-6 alkoxy group, C1-6 haloalkoxy group, cyano group, nitro group and the like.

[R ² to R ⁴ ]
In the formula (II), R ² to R ⁴ each independently represent a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, nitro Represents a group or a cyano group.

Examples of the “halogeno group”, “C1-6 alkyl group”, and “C6-10 aryl group” in R ² to R ⁴ are the same as those exemplified for X ¹ above.
The substituent on the “C1-6 alkyl group” is preferably a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, or a cyano group. Examples of the substituent on the “C6-10 aryl group” include halogeno group, C1-6 alkyl group, hydroxyl group, C1-6 alkoxy group, C1-6 haloalkoxy group, cyano group, nitro group and the like.

Specific examples of the imidazole compound represented by the formula (II) include imidazole, 2-ethyl-4-methylimidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 1-benzyl-2- Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl Examples include -2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and the like.

[Inclusion compound]
The clathrate compound of the present invention is not particularly limited as long as it is a clathrate compound containing a fluorene compound represented by the formula (I) and an imidazole compound represented by the formula (II). The clathrate compound of the present invention may contain a third component such as a solvent, and the third component is preferably 40 mol% or less, more preferably 20 mol% or less, and more preferably 10 mol% or less. It is particularly preferred that
The clathrate compound of the present invention can be used as a resin curing agent such as a polyester resin, an epoxy resin, an epoxy-polyester resin, or a urethane resin, and can be particularly preferably used as a curing agent for an epoxy resin. The clathrate compound of the present invention may be in the form of a liquid dissolved in a solvent, but is preferably in the form of a powder (deposited in the solvent). By being in a powder form, it can be used for, for example, a powder coating.

The clathrate compound of the present invention is subjected to a heat treatment or a heat reflux treatment while adding a fluorene compound represented by the formula (I) and an imidazole compound represented by the formula (II) to the solvent and stirring as necessary. And can be obtained by recrystallization and precipitation. In consideration of ease of dissolution in a solvent, the fluorene compound represented by the formula (I) and the imidazole compound represented by the formula (II) may be dissolved in the solvent and then mixed with each other. preferable.
Solvents include water, methanol, ethanol, isopropyl alcohol, ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, acetonitrile, benzene, toluene, hexane, chloroform, dichloromethane, tetrachloride. Carbon or the like can be used. The addition ratio of the fluorene compound represented by the formula (I) and the imidazole compound represented by the formula (II) during the production of the clathrate compound of the present invention is the fluorene compound (host) represented by the formula (I). The amount of the imidazole compound (guest) represented by the formula (II) is preferably 0.1 to 5.0 mol, more preferably 0.5 to 3.0 mol, relative to 1 mol.

[Epoxy cured resin forming composition]
The epoxy cured resin forming composition of the present invention is particularly limited as long as it contains an epoxy resin (component (A)) and the inclusion compound of the present invention (component (B)). Instead, component (B) is as described above.

〔Epoxy resin〕
As the epoxy resin of component (A), various conventionally known polyepoxy compounds can be used. For example, bis (4-hydroxyphenyl) propane diglycidyl ether, bis (4-hydroxy-3,5-dibromophenyl) propanedi Glycidyl ether, bis (4-hydroxyphenyl) ethane diglycidyl ether, bis (4-hydroxyphenyl) methane diglycidyl ether, resorcinol diglycidyl ether, phloroglicinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, tetraglycidyl benzophenone, Bisresorcinol tetraglycidyl ether, tetramethylbisphenol A diglycidyl ether, bisphenol C diglycidyl ether, bisphenol hexafluoropropane Glycidyl ether, 1,3-bis [1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoroethyl] benzene, 1,4-bis [1- (2,3 -Epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl] benzene, 4,4'-bis (2,3-epoxypropoxy) octafluorobiphenyl, phenol novolac bisepoxy compounds, etc. Alicyclic glycidyl ether compounds; alicyclic diepoxy acetals, alicyclic diepoxy adipates, alicyclic diepoxy carboxylates, vinylcyclohexene dioxide, and other alicyclic polyepoxy compounds; diglycidyl phthalate, diglycidyl tetrahydrophthalate, Diglycidyl hexa Glycidyl ester compounds such as hydrophthalate, dimethyl glycidyl phthalate, dimethyl glycidyl hexahydrophthalate, diglycidyl-p-oxybenzoate, diglycidyl cyclopentane-1,3-dicarboxylate, dimer acid glycidyl ester; diglycidyl aniline, diglycidyl toluidine Glycidylamine compounds such as triglycidylaminophenol, tetraglycidyldiaminodiphenylmethane, diglycidyltribromoaniline; heterocyclic epoxy compounds such as diglycidylhydantoin, glycidylglycidoxyalkylhydantoin, and triglycidylisocyanurate .

The ratio of the imidazole compound represented by the formula (II) in the component (A) and the component (B) in the epoxy cured resin forming composition of the present invention is 1 mol of the epoxy ring of the epoxy resin as the component (A). On the other hand, the imidazole compound represented by the formula (II) in the component (B) is preferably contained in an amount of 0.01 to 1.0 mol, more preferably 0.1 to 1.0 mol, More preferably, the content is from 3 to 1.0 mol.

The composition for forming an epoxy cured resin of the present invention can be produced by mixing the component (A) and the component (B). Usually, a room temperature to 100 so as to form a sufficiently mixed state. Heat to about ℃ and mix. In the production of an epoxy cured resin, the stability of one liquid at this temperature is important.

In addition to the above components, the following components can be added to the composition of the present invention for the purpose of imparting desired properties.
(1) Curing Catalyst for Epoxy Resin In addition to the above curing catalyst, a known curing catalyst can be used in combination with the composition of the present invention.
For example, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 5,6-dibutylamino-1,8-diazabicyclo [5.4.0] Cyclic amidine compounds such as undec-7-ene; acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, trimellitic anhydride; 1,4- Benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4benzoquinone, 2,3-dimethoxy-1 Quinone compounds such as 1,4-benzoquinone and phenyl-1,4-benzoquinone; triethylenediamine, benzyldimethylamine, triethanolamine, Tertiary amine compounds such as methylaminoethanol and tris (dimethylaminomethyl) phenol; aromatic amines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and m-xylenediamine Compounds; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; And organic phosphine compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenyl (p-tolyl) phosphine.

(2) Curing agent Further known curing agents for curing the epoxy resin can be used. For example, compounds having two phenolic hydroxyl groups in one molecule such as resorcin, catechol, bisphenol A, bisphenol F; phenol novolak resin, cresol novolak resin, cresol aralkyl resin, phenol aralkyl resin, biphenyl aralkyl resin, dicyclopentadiene Polyphenol resin such as a type phenol resin and a naphthol aralkyl resin; and the like.

(3) Filler In addition, a filler may be blended in order to control the viscosity and physical properties of the cured product. As the filler, an insulating inorganic filler, whisker, or resin filler can be used. Examples of the insulating inorganic filler include glass, silica, alumina, titanium oxide, carbon black, mica, and boron nitride. Examples of whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride. A polyurethane resin, a polyimide resin, or the like can be used as the resin filler.
In addition, metal particles such as gold, silver, copper, nickel, solder, and conductive fillers such as carbon can also be used when constituting an adhesive for joining electronic components.

(4) Other additives In addition, the release agent, leveling agent, silane coupling agent, flame retardant, antioxidant, colorant, silicone-based flexibility, as long as the desired properties of the present invention are not impaired. Known additives such as an agent and an ion trapping agent can be blended.

[Epoxy cured resin]
The method for producing the epoxy curable resin of the present invention is not particularly limited as long as it is a method of curing the epoxy curable resin-forming composition by heat treatment. Usually, the heating temperature of the heat treatment is 60 It is preferably from 250 to 250 ° C., and preferably from 100 to 200 ° C., and it is preferably cured at such temperature for a short time.

〔Use applications〕
The clathrate of the present invention is an epoxy resin curing catalyst with excellent latency. The composition for forming an epoxy cured resin containing this is stable for a long time when stored near room temperature, and can be quickly cured at a relatively low temperature during curing.
The use of the composition for forming an epoxy curable resin of the present invention is not particularly limited, and examples thereof include underfill, thermosetting prepreg, casting material, structural adhesive, and powder coating. Can do. In particular, regarding electrical materials, printed circuit board prepregs, semiconductor / electronic component sealing materials, electronic component adhesives, conductive adhesives, resist inks, insulating materials, and the like can be given.

Hereinafter, the present invention will be described more specifically by way of examples. However, the technical scope of the present invention is not limited to these examples.

[Example 1]
(Preparation of inclusion compound)
4.40 g of 9,9-bis (4-hydroxyphenyl) fluorene, 2.76 g of 2-ethyl-4-methylimidazole (hereinafter 2E4MZ), and 43.0 g of hexane-ethyl acetate mixed solvent were added to the flask, The mixture was heated to reflux with stirring for 3 hours. After cooling to room temperature, filtration and drying under reduced pressure were performed to obtain 6.46 g of product. The obtained product is an inclusion compound A in which the molar ratio of 9,9-bis (4-hydroxyphenyl) fluorene to 2E4MZ is 1: 2 based on XRD, TG-DSC and ¹ H-NMR measurements. It was confirmed. 1A to 1C show the measurement results.

The measurement conditions for each spectrum are as follows (the same applies to other examples).
[XRD measurement]
Device: Ultimate IV (Rigaku)
X-ray source: Cu 40 kV / 40 mA
Measurement method: Concentration method Filter: Kβ filter Scan speed: 5 ° / min.
[TG-DSC measurement]
Equipment: TGA-DSC1 (manufactured by METTLER TOLEDO)
Al PAN seal measurement temperature range: room temperature to 500 ° C
Temperature increase rate: 20 ° C / min
Sample amount: about 3mg
[ ¹ H-NMR measurement]
Device: JNM-AL400 (manufactured by JEOL Ltd.)
Heavy solvent: CD ₃ OD
Integration count: 16 times

(XRD measurement)
Since the diffraction patterns of 9,9-bis (4-hydroxyphenyl) fluorene and 2E4MZ, which are raw materials, disappeared and a new diffraction pattern was observed, inclusion was confirmed (FIG. 1A).
(TG-DSC measurement)
The onset temperature of the endothermic peak accompanying melting was 221 ° C. for 9,9-bis (4-hydroxyphenyl) fluorene and 48 ° C. for 2E4MZ, whereas it was 120 ° C. for the inclusion compound. The onset temperature in weight reduction is 326 ° C. for 9,9-bis (4-hydroxyphenyl) fluorene and 162 ° C. for 2E4MZ, whereas the weight loss derived from 2E4MZ is 165 ° C. for inclusion compounds. It was found that the thermal stability of 2E4MZ was improved by inclusion. (Fig. 1B)
⁽¹ H-NMR measurement)
From the peak integration values attributed to 9,9-bis (4-hydroxyphenyl) fluorene and 2E4MZ, it was found that 9,9-bis (4-hydroxyphenyl) fluorene and 2E4MZ were included in a one-to-two manner. (FIG. 1C).

[Example 2]
(Preparation of composition for forming epoxy cured resin)
After adding inclusion compound A to 5 g of epoxy resin (trade name: Epototo (registered trademark) YD-128, manufactured by Toho Kasei Co., Ltd.) so as to be 0.2 g (equivalent to 4 phr) in terms of 2E4MZ, The composition A for epoxy cured resin formation was obtained by knead | mixing for 10 minutes at 25 degreeC.
(DSC measurement of epoxy cured resin forming composition)
Using a DSC measuring device (DSC1, manufactured by METTLER TOLEDO), weigh the composition A for forming an epoxy cured resin into an aluminum container so that the amount is about 8 to 10 mg, and under nitrogen purge (nitrogen flow rate: 50 mL / min) The temperature was raised from 30 ° C. to 250 ° C. (temperature increase rate: 10 k / min), and the heat generation based on the curing reaction of the epoxy cured resin forming composition A was measured. FIG. 1D shows the measurement results with time and temperature taken on the horizontal axis.
Compared to the composition for forming an epoxy cured resin consisting of only 2E4MZ, the composition A for forming an epoxy cured resin comprising an inclusion compound A has a higher exothermic peak rising temperature due to epoxy curing and is thermally stable by inclusion. The improvement of the property was confirmed (FIG. 1D).

[Example 3]
(Preparation of inclusion compound)
Example 1 was carried out in the same manner except that 2E4MZ was changed to 2.06 g of 1-methylimidazole (hereinafter, 1MZ) and the solvent was changed from a hexane-ethyl acetate mixed solvent to hexane to obtain 5.86 g of a product. . XRD of the product obtained, from TG-DSC and ¹ H-NMR measurement, 9,9-bis 1 as (4-hydroxyphenyl) fluorene and 1MZ molar ratio: inclusion compound was clathration with 2 B It was confirmed that. The measurement results are shown in FIGS. 2A to 2C.
(XRD measurement)
Since the diffraction pattern of 9,9-bis (4-hydroxyphenyl) fluorene as a raw material disappeared and a new diffraction pattern was observed, inclusion was confirmed (FIG. 2A).
(TG-DSC measurement).
1MZ is a liquid, and the onset temperature of the endothermic peak accompanying decomposition was 117 ° C., whereas the endothermic peak accompanying crystal melting of the clathrate compound was 122 ° C. In addition, the onset temperature in weight reduction was seen from around room temperature in 1MZ, whereas in the inclusion compound, the weight loss derived from 1MZ shifted to 113 ° C to the high temperature side, and thermal stabilization was achieved by inclusion. It was found that the property was improved (FIG. 2B).
⁽¹ H-NMR measurement)
From the peak integral values attributed to 9,9-bis (4-hydroxyphenyl) fluorene and 1MZ, it was found that 9,9-bis (4-hydroxyphenyl) fluorene and 1MZ were included in a 1: 2 ratio. (FIG. 2C).

[Example 4]
(Preparation of composition for forming epoxy cured resin)
About the preparation of the composition for epoxy cured resin formation of Example 2, it carried out similarly except having changed the clathrate compound A into the clathrate compound B, and obtained the composition B for epoxy cured resin formation.
(DSC measurement of epoxy cured resin forming composition)
The DSC measurement of the epoxy cured resin forming composition of Example 2 was performed in the same manner except that the epoxy cured resin forming composition A was changed to the epoxy cured resin forming composition B, and the heat generation based on the curing reaction was measured. . FIG. 2D shows the measurement results with time and temperature taken on the horizontal axis.
Compared with the composition for forming an epoxy cured resin consisting of only 1MZ, the composition B for forming an epoxy cured resin comprising the inclusion compound B has a slow rise temperature of the exothermic peak accompanying the epoxy curing, and is thermally stable by inclusion. The improvement of the property was confirmed (FIG. 2D).

[Example 5]
(Preparation of inclusion compound)
Example 1 was performed in the same manner as in Example 1 except that 2E4MZ was changed to 2.06 g of 2-methylimidazole (hereinafter, 2MZ) and the solvent was changed from a hexane-ethyl acetate mixed solvent to toluene to obtain 5.96 g of a product. The resulting product, XRD, the molar ratio of the TG-DSC and at the ¹ H-NMR measurement of 9,9-bis (4-hydroxyphenyl) fluorene and 2MZ 1: it is 2. The term inclusion compound C It was confirmed. The measurement results are shown in FIGS. 3A to 3C.
(XRD measurement)
The diffraction patterns of 9,9-bis (4-hydroxyphenyl) fluorene and 2MZ, which are raw materials, disappeared, and a new diffraction pattern was observed, confirming inclusion (FIG. 3A).
(TG-DSC measurement).
The onset temperature of the endothermic peak accompanying melting was 141 ° C. at 2 MZ, whereas it was 169 ° C. when the clathrate compound was used. The onset temperature for weight reduction is 162 ° C. for 2MZ, whereas for inclusion compounds, the weight loss derived from 2MZ shifts to 169 ° C. on the high temperature side, and thermal stability is improved by inclusion. It was found to improve (FIG. 3B).
⁽¹ H-NMR measurement)
From the peak integral values attributed to 9,9-bis (4-hydroxyphenyl) fluorene and 2MZ, it was found that 9,9-bis (4-hydroxyphenyl) fluorene and 2MZ were included in a one-to-two manner. (FIG. 3C).

[Example 6]
(Preparation of composition for forming epoxy cured resin)
About the preparation of the composition for epoxy cured resin formation of Example 2, it carried out similarly except having changed the clathrate compound A into the clathrate compound C, and obtained the composition C for epoxy cured resin formation.
(DSC measurement of epoxy cured resin forming composition)
The DSC measurement of the epoxy cured resin forming composition of Example 2 was performed in the same manner except that the epoxy cured resin forming composition A was changed to the epoxy cured resin forming composition C, and the heat generation based on the curing reaction was measured. . FIG. 3D shows the measurement results with time and temperature taken on the horizontal axis.
Compared with 2MZ, the composition C for epoxy cured resin formation had a slower rise temperature of the exothermic peak accompanying epoxy curing, confirming improvement in thermal stability due to inclusion (FIG. 2D).

[Example 7]
Example 1 was carried out in the same manner except that the amount of 2E4MZ added was changed from 2.76 g to 2.08 g, to obtain 6.27 g of the product. According to XRD, TG-DSC and ¹ H-NMR measurement of the obtained product, it is inclusion compound D in which 9,9-bis (4-hydroxyphenyl) fluorene and 2E4MZ are included in 2 to 3. It was confirmed. The measurement results are shown in FIGS. 4A to 4C.
(XRD measurement)
Since the diffraction pattern derived from the raw material disappeared and a new diffraction pattern was observed in the same manner as in Example 1, inclusion was confirmed (FIG. 4A).
(TG-DSC measurement).
As in Example 1, the endothermic peak accompanying the melting of the crystal and the onset temperature in weight reduction shifted to a higher temperature than 2E4MZ alone, and the thermal stability of 2E4MZ was improved by inclusion. (FIG. 4B).
⁽¹ H-NMR measurement)
As in Example 1, the peak integration value revealed that 9,9-bis (4-hydroxyphenyl) fluorene and 2E4MZ were included in a 2-to-3 manner (FIG. 4C).

[Example 8]
(Preparation of composition for forming epoxy cured resin)
Example 2 Preparation of the epoxy cured resin forming composition was performed in the same manner except that the clathrate compound A was changed to the clathrate compound D to obtain an epoxy cured resin forming composition B.
(DSC measurement of epoxy cured resin forming composition)
Example 2 DSC measurement of the epoxy cured resin forming composition was performed in the same manner except that the epoxy cured resin forming composition A was changed to the epoxy cured resin forming composition D, and DSC measurement was performed. FIG. 4D shows the measurement results with time and temperature taken on the horizontal axis.
As in Example 2, the epoxy cured resin forming composition D comprising the clathrate compound D has a high rise temperature of the exothermic peak accompanying epoxy curing, and the thermal stability to the resin is improved by inclusion (FIG. 4D). ).

Claims (11)

1. Formula (I)
   

   

   (In the formula, each X ¹ independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or Represents a cyano group.
   m represents any integer from 0 to 4, and n represents any integer from 0 to 4.
   X ² each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group. .
   p represents any integer from 0 to 4, and q represents any integer from 0 to 4. And a fluorene compound represented by formula (II)
   

   

   (Wherein R ¹ represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group.
   R ² to R ⁴ each independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, a nitro group, or a cyano group. To express. The inclusion compound containing the imidazole compound represented by this.
2. The clathrate compound according to claim 1, wherein the fluorene compound represented by the formula (I) is 9,9-bis (4-hydroxyphenyl) fluorene.
3. A curing catalyst for epoxy resin comprising the clathrate compound according to claim 1 or 2.
4. The composition for epoxy cured resin formation containing the following (A) component and (B) component.
   (A) Epoxy resin (B) Formula (I)
   

   

   (In the formula, each X ¹ independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or Represents a cyano group.
   m represents any integer from 0 to 4, and n represents any integer from 0 to 4.
   X ² each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group. .
   p represents any integer from 0 to 4, and q represents any integer from 0 to 4. And a fluorene compound represented by formula (II)
   

   

   (Wherein R ¹ represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group.
   R ² to R ⁴ each independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, a nitro group, or a cyano group. To express. ) An inclusion compound mainly composed of an imidazole compound
5. The imidazole compound represented by the formula (II) in the component (B) is contained in an amount of 0.01 to 1.0 mol per mol of the epoxy ring of the epoxy resin as the component (A). Composition for forming an epoxy cured resin.
6. The composition for forming an epoxy cured resin according to claim 4 or 5, wherein the fluorene compound represented by the formula (I) is 9,9-bis (4-hydroxyphenyl) fluorene.
7. A method for producing an epoxy cured resin by heat-treating and curing the epoxy cured resin forming composition according to any one of claims 4 to 6.
8. An epoxy curable resin obtained by curing the composition for forming an epoxy curable resin according to any one of claims 4 to 6 by heat treatment.
9. Furthermore, the curing catalyst for 1 or more types of epoxy resins chosen from a cyclic amidine compound, an acid anhydride, a quinone compound, a tertiary amine compound, an aromatic amine compound, an imidazole compound, and an organic phosphine compound is contained. An epoxy cured resin forming composition.
10. Furthermore, the composition for epoxy cured resin formation of Claim 4 containing a hardening | curing agent.
11. Furthermore, the composition for epoxy cured resin formation of Claim 4 containing a filler.
    

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