JP7051454B2 - Amine Adduct and its uses - Google Patents

Description

The present invention is formed by an epoxy component (A) containing an epoxy component having a 9,9-bisarylfluorene skeleton and an amine component (B) containing an amine component having a heterocyclic skeleton containing a plurality of nitrogen atoms. The present invention relates to an amine adduct and a method for producing the same, a curable composition containing the amine adduct, and a cured product of the curable composition.

Epoxy resin compositions that have good storage stability and are cured by heating are in great demand in industrial fields such as semiconductor mounting because they lead to simplification of manufacturing processes. Various latent curing agents have been proposed in the production of such an epoxy resin composition, and among them, a latent curing agent using an amine adduct obtained by reacting an epoxy component and an amine component is known. There is.

Japanese Unexamined Patent Publication No. 8-27402 (Patent Document 1) discloses an epoxy resin powder coating composition containing an epoxy resin, an amine adduct, a boric acid ester, and a phenol compound. This document describes that the composition is capable of exhibiting good storage stability and excellent curing properties.

Further, Japanese Patent Application Laid-Open No. 2015-11426 (Patent Document 2) discloses a microcapsule type latent curing agent for epoxy resin in which a core containing an amine adduct is encapsulated in a shell formed of a resin. This document describes that the curing agent can be cured at a low temperature and has excellent storage stability.

Japanese Unexamined Patent Publication No. 8-27402 Japanese Unexamined Patent Publication No. 2015-11426

In the inventions described in Patent Documents 1 and 2, in order to obtain a curable epoxy resin composition having practical storage stability, other additives other than the amine adduct may be mixed, or the amine adduct may be further chemically treated. , Need to be physically modified. Therefore, the manufacturing process becomes complicated and the productivity tends to decrease.

Therefore, an object of the present invention is to provide an amine adduct which can be easily prepared and has excellent storage stability (or storage stability), a method for producing the same, and an application thereof.

Another object of the present invention is to provide an amine adduct, a method for producing the same, and an application thereof, which can achieve both high curing properties capable of rapidly curing an epoxy resin even at a relatively low temperature and high storage stability. ..

As a result of diligent studies to achieve the above problems, the present inventors can easily mix an epoxy component having a 9,9-bisarylfluorene skeleton and an amine component having a heterocyclic skeleton containing a plurality of nitrogen atoms. The present invention has been completed by finding that an amine adduct can be formed and that when this amine adduct is used as a curing agent and / or a curing accelerator for an epoxy resin, excellent storage stability is exhibited.

That is, the amine adduct of the present invention is an amine adduct formed by an epoxy component (A) and an amine component (B), and the epoxy component (A) has a 9,9-bisarylfluorene skeleton (an epoxy component). A1) is contained, and the amine component (B) contains an amine component (B1) having a heterocyclic skeleton containing a plurality of nitrogen atoms.

The epoxy component (A1) having a 9,9-bisarylfluorene skeleton may contain an epoxy component represented by the following formula (1) or a multimer thereof.

(In the formula, Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents that are non-reactive with an epoxy group, R ³ is a hydrogen atom or a methyl group, and A ¹ is a linear or branched alkylene. A group, k is an integer of 0 to 4, m and n are integers of 0 or more, and p is an integer of 1 or more).

In the above formula (1), Z is a benzene ring, a naphthalene ring or a biphenyl ring, R ² is a C _1-4 alkyl group or a C _6-10 aryl group, and A ¹ is a linear or branched C _2-4 alkylene. The group, k and m may be an integer of 0 to 2, n may be an integer of 0 to 10, and p may be 1 or 2. Further, in the above formula (1), Z may be a naphthalene ring, n may be 0, and p may be 1.

The amine component (B1) having a heterocyclic skeleton containing a plurality of nitrogen atoms may contain an amine component represented by the following formula (2).

(In the formula, R ⁴ indicates a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a cyanoethyl group, or a triazine-alkyl group; R ⁵ to R ⁷ are a hydrogen atom, a halogen atom, and a nitro group. , Alkyl group, cycloalkyl group, aryl group, aralkyl group or acyl group, the alkyl group may have a hydroxyl group, and ^R4 and ^R5 are bonded to each other and adjacent nitrogen atoms and carbon. A ring may be formed with an atom; q indicates an integer of 0 to 3; a double line of a solid line and a broken line indicates a single bond or a double bond).

The amine component (B1) having a heterocyclic skeleton containing a plurality of nitrogen atoms may contain an amine component represented by the following formulas (2a) and / or (2b).

(In the equation, r indicates an integer of 0 to 5; R ⁴ to R ⁷ and the double line of the solid line and the broken line are the same as described above).

In the amine adduct, the ratio of the amine component (B1) having a heterocyclic skeleton containing a plurality of nitrogen atoms is 0 with respect to 1 mol of the epoxy group of the epoxy component (A1) having a 9,9-bisarylfluorene skeleton. It may be 3 to 3 mol. The softening point of the amine adduct may be 50 to 180 ° C. The amine adduct may be a curing agent and / or a curing accelerator for curing the epoxy resin (C).

The present invention comprises an epoxy component (A) containing an epoxy component (A1) having a 9,9-bisarylfluorene skeleton and an amine component (B1) having an amine component (B1) having a heterocyclic skeleton containing a plurality of nitrogen atoms. ) And the above-mentioned method for producing an amine adduct.

The present invention also includes a curable composition containing the amine adduct and the epoxy resin (C). The epoxy resin (C) may be a liquid epoxy resin. The ratio of the amine adduct may be 1 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin.

The present invention also includes a cured product obtained by curing the curable composition and a method for producing the cured product by heating and curing the curable composition.

In the present specification and claims, "amine adduct" is a mixture of an epoxy component (A) and an amine component (B) to open (or consume) the epoxy group of the epoxy component (A). Means the cured product obtained. Therefore, the amine adduct is a combination of a form in which the amine component (B) is covalently incorporated into the cured product by reaction with an epoxy group or the like, and a form in which the amine component (B) is encapsulated in the cured product as a freeable guest compound. It may be held in a form or the like.

Further, in the present specification and claims, the number of carbon atoms of the substituent may be indicated by C ₁ , C ₆ , C ₁₀ , or the like. That is, for example, an alkyl group having 1 carbon atom is represented by "C ₁ alkyl", and an aryl group having 6 to 10 carbon atoms is represented by "C _6-10 aryl".

In the present invention, an amine adduct can be easily (or easily) or efficiently prepared by using a predetermined epoxy component (A) and a predetermined amine component (B). Further, probably because the epoxy component having a specific skeleton and the amine component having a specific skeleton are used in combination, the obtained amine adduct has excellent storage stability (or storage stability). Further, the amine adduct of the present invention can achieve both high curing properties capable of rapidly curing an epoxy resin even at a relatively low temperature and high storage stability.

FIG. 1 is a ¹ H-NMR spectrum of Amine Adduct of Example 1. FIG. 2 is a ¹ H-NMR spectrum of Amine Adduct of Example 2. FIG. 3 is a ¹ H-NMR spectrum of Amine Adduct of Example 3. FIG. 4 is a ¹ H-NMR spectrum of Amine Adduct of Example 4. FIG. 5 is a ¹ H-NMR spectrum of 9,9-bis (4-glycidyloxyphenyl) fluorene. FIG. 6 is a ¹ H-NMR spectrum of 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene. FIG. 7 is a ¹ H-NMR spectrum of 2-methylimidazole. FIG. 8 is a ¹ H-NMR spectrum of 2-ethyl-4-methylimidazole.

The amine adduct (also referred to as an adduct body, an epoxy adduct, an epoxyamine adduct, a modified amine, an amine-modified epoxy compound or an amine-modified epoxy resin) of the present invention is an amine formed by an epoxy component (A) and an amine component (B). Adduct, the amine component (B1) in which the epoxy component (A) contains an epoxy component (A1) having a 9,9-bisarylfluorene skeleton and the amine component (B) has a heterocyclic skeleton containing a plurality of nitrogen atoms. ) Is included.

[Epoxy component (A)]
(A1) Epoxy component having a 9,9-bisarylfluorene skeleton The epoxy component having a 9,9-bisarylfluorene skeleton (or the first epoxy component) (A1) includes the skeleton and an epoxy group (or oxylan skeleton). ), And may be a monofunctional epoxy component having one epoxy group, but a polyfunctional epoxy component having two or more epoxy groups is preferable. Typical examples of the first epoxy component (A1) include an epoxy component represented by the following formula (1) or a multimer thereof.

(In the formula, Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents that are non-reactive with an epoxy group, R ³ is a hydrogen atom or a methyl group, and A ¹ is a linear or branched alkylene. A group, k is an integer of 0 to 4, m and n are integers of 0 or more, and p is an integer of 1 or more).

In the above formula (1), the aromatic hydrocarbon ring (or arene ring) represented by the ring Z is roughly classified into a monocyclic aromatic hydrocarbon ring such as a benzene ring and a polycyclic aromatic hydrocarbon ring. Will be done. Examples of the polycyclic aromatic hydrocarbon ring include a fused polycyclic aromatic hydrocarbon ring (condensed polycyclic arene ring) and a ring-aggregated aromatic hydrocarbon ring (ring-aggregated arene ring).

Examples of the fused polycyclic arene ring include a fused bicyclic hydrocarbon ring (for example, a fused bicyclic _C8-20 arene ring such as an inden ring and a naphthalene ring, preferably a fused bicyclic C _10-16 arene. Rings and the like), fused bicyclic hydrocarbon rings such as fused tricyclic hydrocarbon rings (eg, anthracene rings, phenanthrene rings, etc.) and the like. Examples of the preferred fused polycyclic arene ring include a naphthalene ring and an anthracene ring, and a naphthalene ring is particularly preferable.

The ring-assembled arene ring includes a bi-C _6-12 arene ring such as a beerene ring, for example, a biphenyl ring, a binaphthyl ring, a phenylnaphthalene ring (1-phenylnaphthalene ring, 2-phenylnaphthalene ring, etc.), a tellarene ring, for example. Examples thereof include a tel C _6-12 arene ring such as a terphenylene ring. Preferred ring-set arene rings include biC _6-10 arene rings, particularly biphenyl rings and the like.

The types of the two rings Z may be the same or different from each other, and usually may be the same ring. Preferred ring Z includes C _6-12 arene rings such as benzene ring, naphthalene ring and biphenyl ring, and more preferably C _6-10 arene ring such as benzene ring and naphthalene ring, particularly naphthalene ring. Further, from the viewpoint of remarkably improving the storage stability, the ring Z is a polycyclic arene ring, particularly a fused polycyclic arene ring, particularly a fused polycyclic _C6-14 arene ring such as a naphthalene ring. Is preferable. The reason for this is not clear, but it is presumed that the 9,9-bis polycyclic arylfluorene skeleton is more likely to retain or encapsulate the amine component (B1) and the like.

The group R ¹ is not particularly limited as long as it is a substituent non-reactive to an epoxy group, but is, for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydrocarbon group [for example, an alkyl group. , Aryl group (C _6-10 aryl group such as phenyl group), etc.], etc., and in particular, it is often an alkyl group or the like. Examples of the alkyl group include a linear or branched C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a t-butyl group. Preferred alkyl groups are hereinafter, stepwise, linear or branched C _1-8 alkyl groups, linear or branched C _1-6 alkyl groups, and particularly C ₁ such as a methyl group. _-4 Alkyl groups are preferred.

When the number of substitutions k is a plurality (2 to 4), the types of the plurality of groups ^R1 may be different from each other or may be the same. Further, the types of the groups ^R1 substituted with different benzene rings forming the fluorene ring may be the same or different. The bonding position (substitution position) of the group ^R1 is not particularly limited, and examples thereof include the 2-position, the 7-position, the 2-position, and the 7-position of the fluorene ring. The preferred substitution number k is 0 to 1, especially 0. The two substitution numbers k may be the same or different from each other.

The substituent ^R2 to be substituted with ring Z may be a non-reactive group with respect to an epoxy group, for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a t-butyl group). Linear or branched C _1-12 alkyl groups such as, preferably C _1-8 alkyl groups, cycloalkyl groups (such as C _5-10 cycloalkyl groups such as cyclohexyl groups), aryl groups (such as cyclohexyl groups), aryl groups (such as For example, a C _6-10 aryl group such as a phenyl group, a trill group, a xylyl group or a naphthyl group), an aralkyl group (such as a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group or a phenethyl group), etc. Hydrocarbon group; alkoxy group (C _1-8 alkoxy group such as methoxy group and ethoxy group), cycloalkoxy group (C _5-10 cycloalkyloxy group such as cyclohexyloxy group), aryloxy group (phenoxy group) C 6-10 aryloxy group such as C _6-10 aryloxy group), aralkyloxy group (C _6-10 aryl-C _1-4 alkyloxy group such as benzyloxy group) and other groups-OR [In the formula, R is a hydrocarbon group (the above). An exemplary hydrocarbon group, etc.) is shown. ]; Groups such as alkylthio groups (C _1-8 alkylthio groups such as methylthio groups) -SR (in the formula, R is the same as above); acyl groups (C _1-6 acyl groups such as acetyl groups); Examples thereof include an alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); nitro group; cyano group and the like.

When the number of substitutions m is 1 or more, the preferred group R ² is a hydrocarbon group [for example, an alkyl group (for example, a linear or branched C _1-6 alkyl group), a cycloalkyl group (for example, C). _5-8 cycloalkyl groups), aryl groups (eg, C _6-10 aryl groups), aralkyl groups (eg, C _6-8 aryl-C _1-2 alkyl groups)], alkoxy groups (linear or branched). Chain-shaped C _1-4 alkoxy group, etc.) and the like. More preferred groups R ² are alkyl groups [C _1-4 alkyl groups (particularly methyl groups) and the like], aryl groups [eg, C _6-10 aryl groups (particularly phenyl groups) and the like], and in particular alkyl groups. May be. When the substituent R ² is an aryl group, the substituent R ² may form the ring-aggregated arene ring together with the ring Z.

Further, the substitution number m can be appropriately selected depending on the type of ring Z, and can be selected from, for example, in the range of about 0 to 8. The preferred number of substitutions m is, in stages, 0 to 4, 0 to 3, 0 to 2, and 0 or 1, particularly 0, is preferable. When the ring Z is a benzene ring and the repetition number n is 0, the preferred substitution number m is, stepwise, 1 to 4, 1 to 3, 1 to 2, and more preferably 1. May be good. The two m may be the same or different from each other.

When there are a plurality of (2 or more) m in the same ring Z, the types of the plurality of groups ^R2 may be different from each other or may be the same. Further, in the two rings Z, the types of the groups ^R2 may be the same or different. The substitution position of the group ^R2 is not particularly limited.

Examples of the alkylene group A ¹ include a linear or branched C _2-6 alkylene group such as an ethylene group, a propylene group, a trimethylene group, a 1,2-butanjiyl group and a tetramethylene group. The preferred A ¹ is a linear or branched C _2-3 alkylene group, and a linear or branched C _2-3 alkylene group, and an ethylene group is particularly preferable.

The number of repetitions n of the oxyalkylene group [OA ¹ ] may be an integer of 0 or more, and can be selected from the range of, for example, about 0 to 20. The preferred n is 0 to 15, 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 3, 0 to 2, and more preferably 0 to 1, in particular. , 0. In addition, n may be an average value (or the average number of added moles) in the molecular assembly, and the preferable range may be the same corresponding to the range of the integer.

When the repetition n of the oxyalkylene group [OA ¹ ] is 2 or more, the alkylene group A ¹ may be composed of different alkylene groups, or may be usually composed of the same alkylene group. Further, in the group corresponding to the substitution number p [-O- (A ¹ O) _n -CH ₂ -CR ³ (O-)-CH ₂ ] (hereinafter, also simply referred to as an epoxy-containing group), a different epoxy-containing group is used. ^The types of the alkylene group A1 to be formed may be the same or different, and may be usually the same.

The group R ³ may be either a hydrogen atom or a methyl group, but a hydrogen atom is preferable from the viewpoint of reactivity. The types of the ^two groups R3 may be the same or different from each other and are usually the same.

The number of substitutions p of the epoxy-containing group can be appropriately selected depending on the type of ring Z, and may be selected from the range of, for example, about 1 to 4. The preferred p is hereinafter, stepwise, 1 to 3, 1 to 2, and particularly preferably 1.

The substitution position of the epoxy-containing group is not particularly limited, and the epoxy-containing group can be substituted at an appropriate position on the ring Z. For example, when p is 1 and ring Z is a benzene ring, any of 2 to 6 positions may be used, and examples thereof include 2-position, 3-position, 4-position, and the like, preferably 3-position, 4-position, and particularly 4-position. It may be a place. When p is 1 and ring Z is a naphthalene ring, it is often the 5- to 8-position of the naphthyl group. For example, the 9-position of fluorene is replaced with the 1-position or 2-position of the naphthalene ring. (Replaced by the relationship of 1-naphthyl or 2-naphthyl), preferably in the relationship of 1,5, 2,6, etc., especially in the relationship of 2,6 for this replacement position. There are many. When p is 1 and ring Z is a biphenyl ring, it may be replaced with an arene ring bonded to the 9-position of fluorene or an arene ring adjacent to this arene ring. For example, the 3-position or 4-position of the biphenyl ring may be bonded to the 9-position of fluorene, and when the 3-position of the biphenyl ring Z is bonded to the 9-position of fluorene, the substitution position of the epoxy-containing group is 2. It may be any of ranks 4 to 6 and 2'to 6', and is usually 4th, 5th, 6th, 3', 4', preferably 4th, 6th, 4th. It may be replaced with a'position, especially the 6th position.

Typical epoxy components (or polyepoxy compounds) represented by the formula (1) include compounds in which (A1-1) n is 0 and compounds in which (A1-2) n is 1 or more. I can separate it. Examples of the compound (A1-1) in which n is 0 in the above formula (1) include 9,9-bis (glycidyloxyphenyl) fluorenes {for example, 9,9-bis (glycidyloxyphenyl) fluorene [for example. , 9,9-bis (4-glycidyloxyphenyl) fluorene, etc.]; 9,9-bis (alkyl-glycidyloxyphenyl) fluorene [eg, 9,9-bis (3-methyl-4-glycidyloxyphenyl) fluorene , 9,9-bis (3,5-dimethyl-4-glycidyloxyphenyl) fluorene, etc. 9,9-bis (mono or diC _1-4 alkyl-glycidyloxyphenyl) fluorene, etc.], 9,9-bis (Allyl-glycidyloxyphenyl) Fluorene [For example, 9,9-bis (mono or diC _6-10aryl -glycidyloxyphenyl) fluorene such as 9,9-bis (3-phenyl-4-glycidyloxyphenyl) fluorene Etc.], etc., 9,9-bis (glycidyloxy-substituted phenyl) fluorenes, etc.}; 9,9-bis (polyglycidyloxyphenyl) fluorenes {for example, 9,9-bis (polyglycidyloxyphenyl) fluorene [, etc.] 9,9-bis (di or triglycidyloxyphenyl) fluorene such as 9,9-bis (3,4-diglycidyloxyphenyl) fluorene, 9,9-bis (3,5-diglycidyloxyphenyl) fluorene, etc. ] Etc.}; 9,9-bis (glycidyloxynaphthyl) fluorenes {eg, 9,9-bis (glycidyloxynaphthyl) fluorene [eg, 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene, 9,9-Bis (5-glycidyloxy-1-naphthyl) fluorene, etc.], etc.}; Examples thereof include compounds in which the glycidyloxy group of these compounds is replaced with a 2-methylglycidyloxy group.

In the formula (1), as the compound (A1-2) having n of 1 or more, specifically, the compound having n of 1 or more corresponds to the compound exemplified as the compound (A1-1) having n of 0 or more. Certain compounds, such as 9,9-bis (glycidyloxy (poly) alkoxyphenyl) fluorene {9,9-bis (glycidyloxy (poly) alkoxyphenyl) fluorene [eg, 9,9-bis [4- (2) -Glysidyloxyethoxy) phenyl] 9,9-bis (glycidyloxy (poly) C _2-4 alkoxyphenyl) fluorene, etc.]; 9,9-bis (alkyl-glycidyloxy (poly) alkoxyphenyl) fluorene [ For example, 9,9-bis [4- (2-glycidyloxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-glycidyloxyethoxy) -3,5-dimethylphenyl] fluorene, etc. 9,9-Bis (mono or di C _1-4 alkyl-glycidyloxy (poly) C _2-4 alkoxyphenyl) fluorene, etc.]; 9,9-bis (aryl-glycidyloxy (poly) alkoxyphenyl) fluorene [ For example, 9,9-bis (mono or di C _6-10aryl -glycidyloxy (poly) C _2-4 , such as 9,9-bis [4- (2-glycidyloxyethoxy) -3-phenylphenyl] fluorene. Alkoxyphenyl) fluorene, etc.] etc.}; 9,9-bis (polyglycidyloxy (poly) alkoxyphenyl) fluorene {for example, 9,9-bis (polyglycidyloxyphenyl) fluorene [9,9-bis (3,9-bis) 9,9-bis (di or triglycidyloxy (poly), such as 4-di (2-glycidyloxyethoxy) phenyl) fluorene, 9,9-bis (3,5-di (2-glycidyloxyethoxy) phenyl) fluorene. ) C _2-4 alkoxyphenyl) fluorene, etc.] etc.}; 9,9-bis (glycidyloxy (poly) alkoxynaphthyl) fluorene {for example, 9,9-bis (glycidyloxy (poly) alkoxynaphthyl) fluorene [eg , 9,9-bis [6- (2-glycidyloxyethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-glycidyloxyethoxy) -1-naphthyl] fluorene, etc.]; Examples thereof include a compound in which the glycidyloxy group of the above compound is replaced with a 2-methylglycidyloxy group.

These epoxy components represented by the formula (1) can be used alone or in combination of two or more. Among these epoxy components represented by the formula (1), the compound (A1-1) in which n is 0 is preferable, and among them, 9,9-bis (glycidyloxyphenyl) fluorenes in which p is 1. 9,9-bis (glycidyloxynaphthyl) fluorenes are preferable, and 9,9-bis (glycidyloxynaphthyl) fluorenes such as 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene are particularly preferable.

The multimer of the epoxy component represented by the formula (1) may have a plurality of 9,9-bisarylfluorene skeletons, for example, two having two 9,9-bisarylfluorene skeletons. It may be a dimer or a decamer such as a trimer having three said skeletons and a tetramer having four said skeletons. The plurality of 9,9-bisarylfluorene skeletons are usually linked via a 2-hydroxypropane-1,3-diyl group or the like. Such a multimer may be prepared by a conventional method, for example, a polyhydroxy compound in which the glycidyl group having the group R3 in the above formula ( ¹ ) is replaced with a hydrogen atom, and epihalohydrin such as epichlorohydrin. The one-step method (tuffy method or direct method) in which and is reacted in the presence of a strong alkali such as sodium hydroxide; the epoxy component represented by the above formula (1) and the polyhydroxy compound are combined with an alkali metal salt ( Examples thereof include a two-step method (advanced method, melting method or indirect method) in which the reaction is carried out in the presence of an addition catalyst such as sodium hydroxide, sodium carbonate, lithium chloride, etc. The multimer of the epoxy component represented by the formula (1) may be used alone or in combination with the epoxy component (or monomer) represented by the formula (1). Usually, the epoxy component represented by the above formula (1) is widely used.

(A2) Other Epoxy Component The epoxy component (A) is not always necessary, but contains another epoxy component (or a second epoxy component) (A2) that does not belong to the first epoxy component (A1). You may.

The second epoxy component (A2) is not particularly limited, and is a conventional epoxy resin (or epoxy compound), for example, a glycidyl ether type epoxy resin (however, the epoxy component represented by the above formula (1) is excluded). , Glysidyl ester type epoxy resin, glycidyl amine type epoxy resin, epoxy resin obtained by oxidizing unsaturated double bonds to epoxidize, and the like. There may be. These second epoxy components (A2) can also be used alone or in combination of two or more.

The ratio of the first epoxy component (A1) may be selected from the range of, for example, about 10% by weight or more (for example, 30 to 100% by weight) with respect to the entire epoxy component (A). The preferred range may be 50% by weight or more (for example, 60 to 99% by weight) or 70% by weight or more (for example, 80 to 95% by weight) in a stepwise manner. Further, as a more preferable range, it may be 90% by weight or more (for example, 95 to 100% by weight), particularly 100% by weight (substantially only the first epoxy component (A1)).

The ratio of the total amount of the epoxy component of the formula (1) and its multimer is, for example, from a range of about 10% by weight or more (for example, 30 to 100% by weight) with respect to the entire first epoxy component (A1). You may choose. The preferred range may be 50% by weight or more (for example, 60 to 99% by weight) or 70% by weight or more (for example, 80 to 95% by weight) in a stepwise manner. Further, a more preferable range is 90% by weight or more (for example, 95 to 100% by weight), particularly 100% by weight (substantially only the epoxy component represented by the above formula (1) or a multimer thereof). May be good.

[Amine component (B)]
(B1) Amine component having a heterocyclic skeleton containing a plurality of nitrogen atoms An amine component having a heterocyclic skeleton containing a plurality of nitrogen atoms (also referred to as a first amine component) (B1) contains at least the skeleton. Just do it. The heterocyclic skeleton contains a plurality of nitrogen atoms (for example, basic nitrogen atoms) as constituent atoms. The number of nitrogen atoms (for example, basic nitrogen atoms) forming the heterocyclic skeleton may be, for example, 2 to 5, preferably 2 to 4, more preferably 2 to 3, and particularly 2. .. The number of atoms forming the heterocyclic skeleton is not particularly limited, but it is usually a 5- or 6-membered heterocycle. The heterocycle may be either an aliphatic heterocycle (non-aromatic heterocycle) or an aromatic heterocycle. Further, the heterocycle may be another hydrocarbon ring or a condensed polycyclic heterocycle condensed with the heterocycle.

Examples of such a first amine component (B1) include an amine component having a monocyclic heterocyclic skeleton {for example, piperazines [for example, piperazine; N, N'-N, N'-such as dimethyl piperazine. Dialkylpiperazin; N- (aminoethyl) piperazin; N-dialkylaminoethyl-N'-alkylpiperazin such as 1- (2-dimethylaminoethyl) -4-methylpiperazin], pyrazoles, pyrazines, pyrimidines, etc. Pyridazines, triazines (triazine, N, N', N "-tris (dimethylaminopropyl) hexahydro-s-triazine, etc.), pyrazolidines, pyrazolins, imidazolidines, frazanes, etc.}; Condensed polycyclic complex Amine components with a ring skeleton [eg, indazoles, purines, phthalazines, naphthylidines, quinoxalins, quinazolines, cinnolines, pteridines, perimidines, phenanthrolines, phenazines, triethylenediamine (DABCO; 1,4). -Diazabicyclo [2.2.2] octane) and the like] can be exemplified. The preferred first amine component (B1) may contain, for example, a compound represented by the following formula (2).

(In the formula, R ⁴ indicates a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a cyanoethyl group, or a triazine-alkyl group; R ⁵ to R ⁷ are a hydrogen atom, a halogen atom, and a nitro group. , Alkyl group, cycloalkyl group, aryl group, aralkyl group or acyl group, the alkyl group may have a hydroxyl group, and ^R4 and ^R5 are bonded to each other and adjacent nitrogen atoms and carbon. A ring may be formed with an atom; q indicates an integer of 0 to 3; a double line of a solid line and a broken line indicates a single bond or a double bond).

In the above formula (2), examples of the alkyl group represented by ^R4 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group and t-butyl. Examples thereof include a linear or branched C _1-10 alkyl group such as a group, an n-pentyl group, an n-hexyl group, a nonyl group, an isononyl group, and a decyl group. The preferred alkyl group may be a linear or branched C _1-6 alkyl group.

Examples of the cycloalkyl group represented by ^R4 include C _5-10 cycloalkyl groups such as cyclopentyl group and cyclohexyl group. Preferred cycloalkyl groups may be C _5-8 cycloalkyl groups, particularly C _5-6 cycloalkyl groups and the like.

The aryl group represented by ^R4 may be a monocyclic or polycyclic aryl group, and the polycyclic aryl group may be a partially saturated group as well as a completely unsaturated group. Examples of the aryl group include a _C6-16 aryl group such as a phenyl group, a naphthyl group, an azrenyl group, an indenyl group, an indanyl group and a tetralinyl group. The preferred aryl group may be a C _6-10 aryl group (phenyl group, naphthyl group, etc.).

The aralkyl group (arylalkyl group) represented by ^R4 is a group in which the above aryl group and the alkyl group are bonded, and for example, a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, and a 1-phenyl group. C6-12arylC such as -n-hexyl group, naphthalene-1-ylmethyl group, naphthalene-2- _ylethyl group, 1- (naphthalen-2-yl) -n-propyl group, inden-1-ylmethyl group Examples thereof include _1-6 alkyl groups. The preferred aralkyl group may be a C _6-10 aryl C _1-4 alkyl group (benzyl group, phenethyl group, etc.).

The alkyl group, cycloalkyl group, aryl group and aralkyl group may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, etc.), a hydroxyl group, an alkoxy group (C _1-6 alkoxy group such as methoxy group and ethoxy group), and an acyl group (formyl group; acetyl group, propionyl). C _1-10 alkyl-carbonyl group such as group), carboxyl group, alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group etc.), alkyl group (C _1-6 alkyl group such as methyl group, ethyl group etc.) Etc. can be exemplified.

In the triazine-alkyl group represented by ^R4 , triazine may be 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, or the like, and is a carbon atom of the triazine ring. May be substituted with an amino group, a hydroxyl group, or the like. Typical triazine-alkyl groups include, for example, 4,6-diamino-1,3,5-triazine-2-yl-methyl group and 4-amino-6-hydroxy-1,3,5-triazine-2. Examples thereof include 1,3,5-triazine-2-yl-C _1-4 alkyl groups such as -yl-methyl group and 4,6-dihydroxy-1,3,5-triazine-2-yl-methyl group. .. The preferred triazine-alkyl group may be a 4,6-diamino-1,3,5-triazine-2-yl- _C1-2 alkyl group.

When R ⁴ and R ⁵ do not form a ring, preferred R ^4s are hydrogen atom, C _1-4 alkyl group, C _6-10 aryl group, C _6-10 aryl C _1-4 alkyl group, cyanoethyl group. , Or 1,3,5-triazine-2-yl- _C1-2alkyl group, etc., usually a hydrogen atom, a cyanoethyl group, or the like.

The halogen atom represented by R ⁵ to R ⁷ includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl groups represented by R5 to ^R7 include a methyl group, an ethyl group, an n ^- propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group and an n-pentyl group. , N-hexyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, hexadecyl group (palmityl group), heptadecyl group, octadecyl group (stearyl group), etc. Examples thereof include a linear or branched C _1-20 alkyl group. Preferred alkyl groups include, stepwise, linear or branched C _1-18 alkyl groups, linear or branched C _1-12 alkyl groups, linear or branched C _1- . It may be a ₁₀ alkyl group, a linear or branched C _1-6 alkyl group, a linear or branched C _1-4 alkyl group.

Further, the alkyl group may have a hydroxyl group. Examples of the alkyl group having a hydroxyl group include hydroxy C _1-20 alkyl groups such as hydroxymethyl group and hydroxyethyl group. Preferred hydroxyalkyl groups include, stepwise, hydroxy C _1-18 alkyl group, hydroxy C _1-16 alkyl group, hydroxy C _1-12 alkyl group, hydroxy C _1-8 alkyl group, and hydroxy C _1-6 . It may be an alkyl group, more preferably a hydroxy C _1-4 alkyl group, still more preferably a hydroxy C _1-2 alkyl group, particularly a hydroxymethyl group.

Examples of the cycloalkyl group, aryl group, and aralkyl group represented by R5 to ^R7 include the ^same group as the substituent ^R4 , including preferred embodiments.

The acyl group represented by ^R5 to ^R7 may be a hydrogen atom; or a group in which an organic group such as an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group and a carbonyl group are bonded. .. Examples of the acyl group include a formyl group; an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyyl group, a 3-methylnonanoyl group and an 8-methylnonanoyl group. , 3-Ethyloctanoyl group, 3,7-dimethyloctanoyl group, undecanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, 1-methylpentadecanoyl group, 14 -Methylpentadecanoyl group, 13,13-dimethyltetradecanoyl group, heptadecanoyl group, 15-methylhexadecanoyl group, octadecanoyl group, 1-methylheptadecanoyl group, nonadecanoyle group, icosanoyl group, henaicosanoyl group, etc. Linear or branched C _1-26 alkyl-carbonyl group; C _2-6 alkenyl which may have a substituent (such as an aryl group) such as an acryloyl group, a methacryloyl group, an allylcarbonyl group and a cinnamoyl group. _-Carbonyl group; C _2-6 alkynyl-carbonyl group such as ethynylcarbonyl group, propynylcarbonyl group; C6-18aryl-carbonyl group such as benzoyl group, naphthylcarbonyl group, biphenylcarbonyl group, anthranylcarbonyl group; 2-pyridyl Examples thereof include a heteroaryl-carbonyl group such as a carbonyl group and a thienylcarbonyl group (for example, a non-aromatic or aromatic 5- to 6-membered heteroaryl-carbonyl group). The preferred acyl group may be a C _1-20 alkyl-carbonyl group, more preferably a C _1-6 alkyl-carbonyl group.

R ⁴ and R ⁵ may be bonded to each other to form a ring together with adjacent nitrogen and carbon atoms. The ring may be selected from the range of, for example, about 4 to 12 membered rings, and may be preferably 5 to 10 membered rings.

The repetition number q indicates 0 or an integer of 1 to 3, preferably 0 to 2, and more preferably 0 or 1.

The double line of the solid line and the broken line indicates a single bond or a double bond, and usually, when R ⁴ and R ⁵ are bonded to each other to form a ring (heterocycle), it may be a single bond, and R When ⁴ and R ⁵ do not form a ring (heterocycle), it is often a double bond.

When R ⁴ and R ⁵ do not form a ring, preferred R ⁵ includes a hydrogen atom, an alkyl group, and an aryl group, and more preferably an alkyl group.

Preferred R ⁶ and / or R ⁷ include a hydrogen atom, an alkyl group, a hydroxyalkyl group and the like.

More specifically, the first amine component (B1) may contain, for example, an amine component represented by the following formula (2a) and / or an amine component represented by the following formula (2b).

(In the formula, r indicates an integer of 0 to 5; R ⁴ to R ⁷ and the double line of the solid line and the broken line are the same as the above formula (2) including the preferable embodiment).

Further, in the above formula (2a), more preferable embodiments of ^R4 include a hydrogen atom, a cyanoethyl group and a triazine-alkyl group, and more preferably a hydrogen atom.

^In the above formula (2a), more preferable embodiments of R5 include a hydrogen atom, a linear or branched C _1-20 alkyl group, and a C _6-10 aryl group, and more preferably a linear or branched chain group. Among the branched C _1-12 alkyl groups, a linear or branched C _1-6 alkyl group is preferable, and a linear or branched C _1-4 alkyl group is particularly preferable.

In the above formula (2a), more preferable embodiments of R ⁶ include a hydrogen atom, a C _1-8 alkyl group, and a hydroxy C _1-4 alkyl group, and more preferably a hydrogen atom and a C _1-6 alkyl group. It may be present, and among them, a hydrogen atom and a C _1-4 alkyl group are preferable, and a _C1-2 alkyl group is particularly preferable.

In the above formula (2a), a hydrogen atom and a hydroxy C _1-4 alkyl group are mentioned as a more preferable embodiment of R ⁷ , and a hydrogen atom is more preferable.

In the formula (2a), the type of bond between the carbon atoms to which R ⁶ and R ⁷ are bonded may be a single bond (imidazoline compound), but a double bond (imidazole compound) is preferable.

In the above equation (2b), the preferred repetition number r is an integer of 1 to 5, more preferably an integer of 1 to 4, and particularly an integer of 1 to 3.

Typical examples of the compound represented by the formula (2a) include an imidazoline compound and an imidazole compound, and examples of the imidazoline compound include 2-methylimidazoline and 2-phenylimidazoline. Examples of the imidazole compound include 1-alkylimidazole such as 1-methylimidazole, 1-ethyl imidazole, 1-n-propyl imidazole, 1-isopropyl imidazole, 1-n-butyl imidazole and 1-isobutyl imidazole; 2 -2-alkyl imidazoles such as methyl imidazole, 2-ethyl imidazole, 2-n-propyl imidazole, 2-isopropyl imidazole, 2-n-butyl imidazole, 2-isobutyl imidazole, 2-undecyl imidazole, 2-heptadecyl imidazole 2-arylimidazole such as 2-phenylimidazole; 4-alkylimidazole such as 4-methylimidazole, 4-ethylimidazole; 1,2-dialkylimidazole such as 1,2-dimethylimidazole; 2,4-dimethylimidazole, 2,4-Dialkylimidazole such as 2-ethyl-4-methylimidazole; 2-aryl-4-alkylimidazole such as 2-phenyl-4-methylimidazole; 1-aralkyl such as 1-benzyl-2-methylimidazole- 2-Alkylimidazole; 1-aralkyl-2-arylimidazole such as 1-benzyl-2-phenylimidazole; 1-cyanoethyl-2-such as 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole; Alkylimidazole; 1-cyanoethyl-2-arylimidazole such as 1-cyanoethyl-2-phenylimidazole; 1-cyanoethyl-2,4-dialkylimidazole such as 1-cyanoethyl-2-ethyl-4-methylimidazole; 2-phenyl 2-aryl-4-alkyl-5-hydroxyalkylimidazole such as -4-methyl-5-hydroxymethylimidazole; 2-aryl-4,5- such as 2-phenyl-4,5-bis (hydroxymethyl) imidazole Examples thereof include bis (hydroxyalkyl) imidazole. In many cases, at least one group of R ⁴ to R ⁷ is a substituent other than a hydrogen atom in the imidazole compound, and preferably at least one group of R ⁴ to R ⁶ is a substituent other than a hydrogen atom. More preferably, at ^least one group of R5 or ^R6 is a substituent other than a hydrogen atom, and more preferably at ^least R5 is a substituent other than a hydrogen atom. When the amine adduct is used as a curing agent and / or a curing accelerator for the epoxy resin (C), it is easy to cure uniformly without agglomeration ⁽ gelation or separation of the gel phase), and thus R5 or R is particularly easy to cure. It is preferable that both of ⁶ are substituents other than hydrogen atoms.

Typical examples of the compound represented by the formula (2b) (cyclic amidine compound) include diazabicycloundecene (DBU: 1,8-diazabicyclo [5.4.0] -7-undecene) and diaza. Bicyclononene (DBN: 1,5-diazabicyclo [4.3.0] -5-nonene) and the like can be exemplified.

These first amine components (B1) can also be used alone or in combination of two or more. Of these first amine components (B1), the compound represented by the above formula (2a) is preferable, and the imidazole compound is particularly preferable. Preferred imidazole compounds include imidazole, alkyl imidazole, dialkyl imidazole, aryl imidazole, aralkyl-alkyl imidazole, aryl-alkyl-hydroxymethyl imidazole, aryl-bis (hydroxymethyl) imidazole, among others, imidazole, 1-methyl. Imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole 1-benzyl-2- Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis (hydroxymethyl) imidazole and the like are preferred. Usually, 2-C _1-6 alkyl imidazole such as 2-methylimidazole and 2-C _1-6 alkyl-4-C _1-6 alkyl imidazole such as 2-ethyl-4-methyl imidazole are widely used. When Amine Adduct is used as a curing agent and / or a curing accelerator for the epoxy resin (C), it is easy to cure uniformly without agglomeration (gelation or separation of the gel phase), and thus 2-ethyl-4 in particular. -2-C _1-4 alkyl-4-C _1-4 alkyl imidazoles such as methylimidazole are preferred.

These amine components may be salts with an acid, for example, an organic acid such as trimellitic acid, pyromellitic acid, isocyanuric acid or an inorganic acid such as hydrochloric acid.

(B2) Other Amine Component The amine component (B) is not always necessary, but contains another amine component (or a second amine component) (B2) that does not belong to the first amine component (B1). You may.

The second amine component (B2) is not particularly limited, and conventional amine compounds such as aliphatic amines, alicyclic amines, aromatic amines, and heterocyclic amines (provided that the first amine component) is used. Amine components, that is, excluding amine compounds having a heterocyclic skeleton containing a plurality of nitrogen atoms), modified amines, etc. are mentioned, and specific examples thereof include other curing agents and / or curing accelerators described later. Examples include amine-based compounds. These second amine components (B2) can also be used alone or in combination of two or more.

The ratio of the first amine component (B1) may be selected from the range of, for example, about 10% by weight or more (for example, 30 to 100% by weight) with respect to the entire amine component (B). The preferred range may be 50% by weight or more (for example, 60 to 99% by weight) or 70% by weight or more (for example, 80 to 95% by weight) in a stepwise manner. Further, as a more preferable range, it may be 90% by weight or more (for example, 95 to 100% by weight), particularly 100% by weight (substantially only the first amine component (B1)).

The ratio of the amine component represented by the formula (2) is selected from the range of, for example, about 10% by weight or more (for example, 30 to 100% by weight) with respect to the entire first amine component (B1). May be good. The preferred range may be 50% by weight or more (for example, 60 to 99% by weight) or 70% by weight or more (for example, 80 to 95% by weight) in a stepwise manner. Further, as a more preferable range, it may be 90% by weight or more (for example, 95 to 100% by weight), particularly 100% by weight (substantially only the amine component represented by the above formula (2)).

The ratio of the amine component represented by the formula (2a) is selected from the range of, for example, about 10% by weight or more (for example, 30 to 100% by weight) with respect to the entire first amine component (B1). May be good. The preferred range may be 50% by weight or more (for example, 60 to 99% by weight) or 70% by weight or more (for example, 80 to 95% by weight) in a stepwise manner. Further, as a more preferable range, it may be 90% by weight or more (for example, 95 to 100% by weight), particularly 100% by weight (substantially only the amine component represented by the above formula (2a)).

[Manufacturing method of amine adduct]
The amine adduct of the present invention contains an epoxy component (A) containing an epoxy component (A1) having a 9,9-bisarylfluorene skeleton and an amine component (B1) having a heterocyclic skeleton containing a plurality of nitrogen atoms. It can be prepared by mixing (or reacting with) the component (B).

The mixing of the epoxy component (A) and the amine component (B) may be carried out in the presence of a solvent, if necessary. Examples of the solvent include alcohols such as methanol, ethanol, propanol and butanol; ethers such as 2-methoxyethanol (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve) and ethylene glycol monobutyl ether (butyl cellosolve). Cellosolves, diethylene glycol monomethyl ether (methyl carbitol), diethylene glycol monoethyl ether (ethyl carbitol), carbitols such as diethylene glycol monobutyl ether (butyl carbitol), cyclic ethers such as dioxane and tetrahydrofuran, diethyl ether and the like. Chain ethers, etc .; Ketones, for example, chain ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 2-hexanone, cyclic ketones such as isophorone, cyclohexanone, etc .; methyl acetate, ethyl acetate, acetic acid, etc. Esters such as propyl, butyl acetate, isobutyl acetate; ethylene glycol monoethyl ether acetate (ethyl cellosolve acetate), diethylene glycol monoethyl ether acetate (ethyl carbitol acetate), propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, etc. Ether esters; aliphatic hydrocarbons such as heptane and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene; dimethyl Amidos such as formamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide can be exemplified. The solvent may be an aprotic polar solvent such as amides and sulfoxides. These solvents can be used alone or as a mixed solvent of two or more kinds. Of these solvents, a solvent in which both the epoxy component (A) and the amine component (B) are compatible or soluble is preferable. Usually, ketones such as methyl ethyl ketone are widely used.

The ratio of the amine component (B) is, for example, 0.5 to 5 mol, preferably 0.7 to 3 mol, more preferably 0.7 to 3 mol, based on 1 mol of the epoxy group (or oxylan ring) in the epoxy component (A). It may be 0.8 to 1.5 mol, more preferably 0.9 to 1.1 mol, particularly substantially equimolar.

The ratio of the first amine component (B1) is, for example, 0.5 to 5 mol, preferably 0.7 to 0.7 to 1 mol of the epoxy group (or oxylan ring) in the first epoxy component (A1). It may be 3 mol, more preferably 0.8 to 1.5 mol, even more preferably 0.9 to 1.1 mol, particularly substantially equimolar.

The ratio of the amine component (B) is, for example, 1 to 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 20 to 60 parts by weight, still more preferable, with respect to 100 parts by weight of the epoxy component (A). May be 25 to 50 parts by weight, particularly 30 to 45 parts by weight.

The ratio of the first amine component (B1) is, for example, 1 to 100 parts by weight, preferably 10 to 80 parts by weight, and more preferably 20 to 60 parts by weight with respect to 100 parts by weight of the first epoxy component (A1). Parts, more preferably 25 to 50 parts by weight, particularly 30 to 45 parts by weight.

The mixing or reaction may be carried out, for example, in the range of room temperature (about 25 ° C.) to about 180 ° C., preferably 50 to 150 ° C., more preferably 70 to 130 ° C., still more preferably 70 to 100 ° C., particularly 75. It may be up to 90 ° C.

The mixing or reaction time may be, for example, in the range of about 0.5 to 72 hours, preferably 1 to 48 hours, more preferably 2 to 24 hours, still more preferably 3 to 12 hours. ..

After the mixing or the reaction is completed, the solvent may be distilled off by a conventional method such as atmospheric distillation or vacuum distillation, if necessary.

The mixture or reaction product after distilling off the solvent may be further dried if necessary. As a drying method, vacuum drying is preferable. The drying temperature may be, for example, 50 to 100 ° C, preferably 70 to 90 ° C.

The dried mixture or reaction may be pulverized if necessary. The crushing method is not particularly limited, and for example, a conventional crushing method using a mortar, a ball mill, a bead mill, a jet mill, a hammer mill, or the like can be used.

The softening point of the amine adduct thus obtained can be selected from, for example, in the range of about 40 to 200 ° C., and the preferred range is as follows, stepwise, 50 to 180 ° C., 60 to 170 ° C., 70 to 160 ° C. ° C., especially 80-150 ° C. Among them, the more preferable softening points of the amine adduct are, in stages, 100 to 175 ° C, 110 to 165 ° C, 120 to 155 ° C, 125 to 145 ° C, and particularly 130 to 140 ° C. If the softening point is too low, the storage stability may decrease, and if the softening point is too high, the curability may decrease. In the present specification and claims, the softening point can be measured by the method described in Examples described later.

Further, in the formation of the amine adduct, the peak disappeared or shifted due to the opening of the oxylane ring (or epoxy group) of the epoxy component (A) by ¹ H-NMR or the like, or the first epoxy component (A1) ( Alternatively, it can be confirmed from the residual peaks derived from the 9,9-bisarylfluorene skeleton) and the first amine component (B1). For example, the peaks derived from the ring-opening of the oxylan ring (or epoxy group) of the epoxy component (A) are around 2.6 to 2.8 ppm, around 2.8 to 2.9 ppm, and 3.1 to 3,4 ppm. It is often observed in the vicinity, and the formation of amine epoxides may be confirmed by the disappearance or shift of these peaks.

[Cursable composition]
In the amine adduct of the present invention, a heterocyclic skeleton containing a plurality of nitrogen atoms of an amine component (B) that functions as a curing agent for an epoxy resin (epoxy compound) (C), particularly a first amine component (B1), is provided. Probably because the 9,9-bisarylfluorene skeleton of the epoxy component (A1) of 1 is stably encapsulated, it is stable for a long time at low temperature (normal temperature or storage temperature) even when mixed with an epoxy resin. On the other hand, the amine adduct can quickly cure the epoxy resin when heated to a predetermined temperature, probably because it releases the first amine component (B1) upon heating. Further, the amine adduct of the present invention functions as a curing agent for the epoxy resin, probably because it has a secondary amino group and / or a tertiary amino group as the heterocyclic skeleton of the first amine component (B1). It can also function as a curing accelerator. Therefore, the amine adduct of the present invention is useful as a curing agent and / or a curing accelerator for curing the epoxy resin (epoxy compound) (C). In addition, amine adducts (curing agents and / or curing accelerators) are useful in combination with epoxy resins (epoxy compounds) (C) to prepare curable compositions.

The curable composition may contain the amine adduct (also referred to as a first curing agent and / or a curing accelerator) and the epoxy resin (C), and if necessary, a conventional epoxy resin curing agent and /. Alternatively, it may contain a curing accelerator (also referred to as a second curing agent and / or a curing accelerator). Such a curing agent is not particularly limited as long as it is a compound that cures the epoxy resin by reacting with the oxylan ring (or epoxy group) of the epoxy resin, and the curing accelerator is also a compound that promotes the curing reaction of the epoxy resin. If there is, there is no particular limitation. Examples of such a curing agent or curing accelerator include amine compounds (aliphatic amines, alicyclic amines, aromatic amines, heterocyclic amines, modified amines, etc.), amide compounds, and the like. Ester-based compounds, phenol-based compounds, alcohol-based compounds, thiol-based compounds, ether-based compounds, thioether-based compounds, urea-based compounds, thiourea-based compounds, Lewis acid-based compounds, phosphorus-based compounds, acid anhydride-based compounds, onium salts. Examples thereof include a system compound (or a cationic polymerization initiator), an active silicon compound-aluminum complex, and the like.

Specific examples of the second curing agent and / or curing accelerator include the following compounds.

Examples of the aliphatic amines include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, pentanediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine and 2,5-dimethyl. Linear or branched alkylenediamines such as -2,5-hexanediamine; polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, pentamethyldiethylenetriamine; dimethylaminopropylamine, N, N-dialkylaminoalkylamines such as diethylaminopropylamine, dibutylaminopropylamine; (poly) etherdiamines such as bis (2-dimethylaminoethyl) ether, diethyleneglycolbispropylamine, polypropylene glycoldiamine; N, N , N', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N, N, N', N'-tetramethylpropylenediamine and other N-alkyl substituted alkylenediamines. Arcanol amines such as dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol; linear or branched alkylamines such as mono-t-alkylamines.

Examples of alicyclic amines include mensendiamine; isophoronediamine; dialkylcycloalkylamines such as dimethylcyclohexylamine; 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxa. Spiro [5.5] Spiro-ring or bridging ring amines such as undecane; hydrogenated products of aromatic amines described below [eg, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methyl). Bis (aminocyclohexyl) alkanes such as cyclohexyl) methane; cyclohexanediamines such as 1,2-cyclohexanediamine, 1,4-cyclohexanediamine; hydroxides of m-xylylene diamine; 1,3,5-tris (amino) Methyl) benzene hydrogenated products, etc.] and the like.

Examples of aromatic amines include phenylenediamine (o-phenylenediamine, m-phenylenediamine, p-phenylenediamine); m-xylylene diamine, 1,3,5-tris (aminomethyl) benzene and the like. Tri (aminomethyl) benzenes; mono-to-tri (dialkylaminomethyl) phenols such as 2- (dimethylaminomethyl) phenols, 2,4,6-tris (dimethylaminomethyl) phenols; bis (4-aminophenyl) Bis (aminophenyl) alkanes such as methane, bis (4-amino-3-methylphenyl) methane, bis (4-amino-3-ethylphenyl) methane; bis (amino) such as bis (4-aminophenyl) sulfone Phenyl) sulfones; phthalocyanine amines such as phthalocyanine tetramine; benzylalkylamines such as benzylmethylamine, benzyldimethylamine, (α-methylbenzyl) methylamine, (α-methylbenzyl) ethylamine and the like can be exemplified.

Examples of the heterocyclic amines include amines having a heterocyclic skeleton containing one nitrogen atom [pyridines such as pyridine and picolin; piperidine, 4-amino-2,2,6,6-tetramethylpiperidine and the like. Piperidins; Pyrols; Pyroleans such as 2H-Pyrol; Pyrrolidins; Pyrrolins; Indolins; Indols; Indols such as 3H-Indols; Isoindols; Indolins; Isoindrins; Isoquinolins; carbazoles; carbazoles such as 4H-carbazole; phenanthridins; acridins; phenoxazines; phenothiazines; quinuclydins; morpholins such as morpholins, methylmorpholins, ethylmorpholins, etc.]; first amines Amines having a heterocyclic skeleton containing a plurality of nitrogen atoms exemplified in the section of component (B) [Amine components having a monocyclic heterocyclic skeleton (piperazins, pyrazoles, pyrazines, pyrimidines, pyridazines, triazines) , Pyrazolidines, Pyrazolins, Imidazolynes, Frazans, Imidazolines exemplified as the compound represented by the formula (2a); Imidazoles exemplified as the compound represented by the formula (2a), etc.)]; Condensation Amine components with a polycyclic heterocyclic skeleton [indazoles, purines, phthalazines, naphthylidines, quinoxalins, quinazolines, cinnolines, pteridines, perimidines, phenanthrolines, phenazines, triethylenediamine (DABCO), Cyclic amidins (DBU, DBN, etc.) exemplified as the compound represented by the formula (2b)] and the like can be mentioned.

Examples of the modified amines include polyamines (or amine adducts) in which amines are added to epoxy compounds [excluding the amine adducts of the present invention], Michael-added polyamines, Mannich-added polyamines, thiourea-added polyamines, and ketone-blocking polyamines (excluding the amine adducts of the present invention). Ketimine), dicyandiamide, guanidine, organic acid hydrazide, diaminomaleonitrile, amineimide, boron trifluoride-piperidin complex, boron trifluoride-monoethylamine complex and the like can be exemplified.

Examples of the amide compound include condensation of dimer acid [polymerized fatty acid or multimerized fatty acid] (for example, dimer to tetramer of unsaturated higher fatty acid) and polyamine (for example, alkylenediamine, polyethylene polyamine, etc.). Examples thereof include a fatty acid (polyaminoamide) obtained by the above method.

These amine compounds may be salts with an acid, for example, an organic acid such as 2-ethylhexic acid, trimellitic acid, pyromellitic acid, isocyanuric acid or an inorganic acid such as hydrochloric acid.

Examples of the ester compound include active carbonyl compounds such as aryl and thioaryl esters of carboxylic acids.

Examples of the phenol-based compound include, as a phenol resin curing agent, an aralkyl-type phenol resin such as a phenol aralkyl resin and a naphthol aralkyl resin, a novolak-type phenol resin such as a phenol novolac resin and a cresol novolac resin, and modified resins thereof, for example. Phenol resins such as epoxidized or butylated novolak-type phenol resins; modified phenol resins such as dicyclopentadiene-modified phenol resins, paraxylene-modified phenol resins, triphenol alkane-type phenol resins, and polyfunctional phenol resins. It can be exemplified.

Examples of the alcohol-based compound, the thiol-based compound, and the thioether-based compound include polyols, polyethercaptans, and polysulfides.

Examples of the urea-based compound, thiourea-based compound, and Lewis acid-based compound include butylated urea, butylated melamine, butylated thiourea, and boron trifluoride.

Examples of the phosphorus-based compound include organic phosphine compounds such as alkyl phosphine such as ethyl phosphine and butyl phosphine, and primary phosphines such as aryl phosphine such as phenyl phosphine; dialkyl phosphine such as dimethyl phosphine, dipropyl phosphine and methyl ethyl phosphine. Second phosphines such as diarylphosphine such as diphenylphosphine; trialkylphosphines such as trimethylphosphine and triethylphosphine, and third phosphines such as triarylphosphine such as triphenylphosphine can be mentioned.

Examples of the acid anhydride-based compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimeritate), and glyceroltris (anhydrotrimeritate). Aromatic polycarboxylic acid anhydrides such as: tetrahydroanhydride, methyltetrahydroanhydride, trialkyltetrahydroanhydride, hexahydroanhydride, methylhexahydroanhydride, methylcyclohexcentricarboxylic acid anhydride, 5-( 2,5-Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, hymic anhydride, methylhymic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalanhydride Alicyclic polycarboxylic acid anhydrides such as acid (methylnagic anhydride); maleic anhydride, tetramethylene maleic anhydride, dodecenyl anhydride succinic acid, polyazipic acid anhydride, polyazereinic acid anhydride, polysevacinic acid anhydride, poly Alipid polycarboxylic acid anhydrides such as (ethyl octadecane diic acid) anhydrate, poly (phenylhexadecane diic acid) anhydrate; halogens such as het acid anhydride (chlorendic acid anhydride), tetrabromophthalic anhydride, tetrachlorophthalic anhydride Examples include acid anhydride.

Examples of the onium salt-based compound and the active silicon compound-aluminum complex include aryldiazonium salt, diallyliodonium salt, arylsulfonium salt, arylmethylsulfonium salt (benzylmethylsulfonium salt, etc.), diarylsulfonium salt, and triarylsulfonium salt. Examples thereof include a triphenylsilanol-aluminum complex, a triphenylmethoxysilane-aluminum complex, a silylperoxide-aluminum complex, and a triphenylsilanol-tris (salicil aldehyde) aluminum complex.

These curing agents and / or curing accelerators can be used alone or in combination of two or more. The ratio of the amine adduct (first curing agent and / or curing accelerator) of the present invention to the second curing agent and / or curing accelerator is, for example, the former / the latter (weight ratio) = 100/0. ~ 30/70, preferably 100/0 to 50/50, more preferably 100/0 to 70/30, even more preferably 100/0 to 90/10, especially 100/0 (substantially the amine adduct of the present invention). Only) is preferred.

(C) Epoxy resin As the epoxy resin (or epoxy compound) (C), for example, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, and an unsaturated double bond are oxidized and epoxidized. It may be an epoxy resin or the like.

Examples of the glycidyl ether type epoxy resin (or compound) include phenylglycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, s-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, and stearyl. Alcan monools such as glycidyl ethers Glysidyl ethers; Alcan polyols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiethylene glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol Polyglycidyl ether; mononuclear polyvalent phenols such as hydroquinone, resorcin, pyrocatechol, fluoroglucolinol or polyglycidyl ethers with alkylene oxide (ethylene oxide, etc.) adducts thereof; dihydroxynaphthalene, biphenol, bisphenols {for example, methylene bisphenol (Bisphenol F), Methylenebis (Orthocresol), Echilidenbisphenol (Bisphenol AD), Isopropyridenebisphenol (Bisphenol A), Isopropyridenebis (Orthocresol), Tetrabromobisphenol A, 1,3-Bis (4-hydroxycumyl) ) Benzene, 1,4-bis (4-hydroxycumyl) benzene, 9,9-bis (hydroxyaryl) fluorene [eg, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4) -Hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, etc.], Tris Or tetrakis (hydroxyphenyl) alkane [eg, 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, etc.], bis (hydroxyphenyl) ketone. , Bis (hydroxyphenyl) ether, bis (hydroxyphenyl) thioether, bis (hydroxyphenyl) sulfone, novolak or novolak resin (phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinnovora) Polyglycyl ethers of polynuclear polyhydric phenols such as terpenephenol or adducts thereof with an alkylene oxide (ethylene oxide or the like) adduct; polyglycyl ethers of heterocyclic compounds such as triglycidyl isocyanurate can be exemplified.

Examples of the glycidyl ester type epoxy resin (or compound) include monoglycidyl esters of monocarboxylic acids such as versatic acid glycidyl ester; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, Fat groups such as azelaic acid, sebasic acid, dimer acid, trimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid and endomethylenetetrahydrophthalic acid. , Glycidyl esters of alicyclic or aromatic polyvalent carboxylic acids, homopolymers or copolymers of glycidyl (meth) acrylate, and the like can be exemplified.

Examples of the glycidylamine type epoxy resin (or compound) include N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, N, N-diglycidyl toluidine, and tetraglycidyl. Examples thereof include diaminodiphenylmethane and triglycidylaminophenol.

Examples of the epoxy compound in which the unsaturated double bond is epoxidized include vinylcyclohexene epoxide, dicyclopentadiene epoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 3,4-epoxy-. Epoxides of cyclic olefins such as 6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, epoxidized styrene-butadiene copolymer, etc. The epoxidized conjugated diene polymer of the above can be exemplified.

These epoxy resins (or compounds) can be used alone or in combination of two or more. The epoxy resin (or compound) may be a monomer or may contain a multimer of about a dimer to a decamer. Further, mono or polyglycidyl ethers of alkane monools or alkane polyols, glycidyl esters of monocarboxylic acids, epoxidates of cyclic olefins and the like are often used as reactive diluents.

Preferred epoxy resins include polyglycidyl ethers having multiple epoxy groups (or oxylan rings) in the molecule, such as methylenebisphenol (bisphenol F), methylenebis (orthocresol), etylidenebisphenol (bisphenol AD), isopropyridene bisphenol ( Examples thereof include bisphenols such as bisphenol A), isopropylidenebis (orthocresol), and 9,9-bis (hydroxyaryl) fluorene, or polyglycidyl ethers having an alkylene oxide (ethylene oxide or the like) adduct thereof.

Further, the epoxy resin is a liquid having fluidity at about room temperature (for example, 10 to 30 ° C., preferably 15 to 20 ° C.), a highly viscous (or highly viscous) semi-solid or solid having poor fluidity. It may be a liquid epoxy resin which has fluidity at a temperature (mixing temperature or processing temperature) where it is usually mixed with Amin Adduct and is liquid or viscous at the mixing temperature.

In the curable composition of the present invention, the ratio of the curing agent and / or the curing accelerator can be appropriately selected depending on the curing method and the like, and is usually a ratio to which it is used as a curing agent and / or a curing accelerator. You may.

As a typical ratio of the total amount of the curing agent and / or the curing accelerator (the total amount of the first and second curing agents and / or the curing accelerator), typically, with respect to 100 parts by weight of the epoxy resin (C). For example, it may be selected from the range of about 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, still more preferably 10 to 30 parts by weight, and particularly 15 to 15 parts by weight. It may be 25 parts by weight.

The ratio of the amine adduct (first curing agent and / or curing accelerator) of the present invention is typically in the range of about 0.1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin (C). It may be selected from 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, still more preferably 10 to 30 parts by weight, and particularly 5 to 25 parts by weight.

The amine adduct of the present invention has a high compatibility with the epoxy resin (C), probably because it contains a 9,9-bisarylfluorene skeleton as the first epoxy component (A1), and is dispersed in an insoluble additive. The sex is also high. Therefore, even if the curable composition contains an amine adduct, it does not have a great adverse effect on the properties of the cured product.

The curable composition of the present invention can be produced by mixing a curing agent and / or a curing accelerator component containing the amine adduct of the present invention with an epoxy resin (C). For example, a curing agent and / or a curing accelerator component containing an amine adduct and an epoxy resin (C) are mixed with a homogenizer, a mixer or a mixer, a kneader (kneader, roll, extruder, etc.), or a raider (crusher). It may be prepared by mixing or kneading (for example, melt kneading) at a temperature and time at which a curing reaction (or gelation) does not occur or can be suppressed using a machine) or the like. Further, mixing or kneading may be performed under heating (for example, about 50 to 100 ° C.), and mixing or kneading at a low temperature (for example, about 0 to 50 ° C., preferably in an ice bath) and mixing under heating. Alternatively, kneading may be omitted. In addition, you may mix or knead in the presence of the solvent exemplified in the section of the said manufacturing method of amine adduct.

The curable composition of the present invention may contain various additives such as silane coupling agents, plasticizers, organic solvents, reactive diluents, fillers, reinforcing agents, colorants (pigments, etc.), if necessary. , Flame retardants, mold release agents, stabilizers (antioxidants, UV absorbers, etc.), bulking agents, thickeners and the like may be added.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-. Methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltri Examples thereof include ethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane.

Examples of the plasticizer include a phthalic acid-based plasticizer, an alkandicarboxylic acid-based plasticizer such as adipic acid, a phosphoric acid ester-based plasticizer, and a polyester-based plasticizer.

Examples of the organic solvent include the solvent exemplified in the section of the method for producing an amine adduct, and examples of the reactive diluent include the above-exemplified epoxy compounds such as n-butyl glycidyl ether, phenyl glycidyl ether, and styrene oxide. Examples thereof include epoxy compounds such as t-butylphenylglycidyl ether and dicyclopentadiene epoxide, and phenols such as phenol, cresol, and t-butylphenol.

Examples of the filler include calcium bicarbonate, light calcium carbonate, natural silica, synthetic silica, molten silica, titanium oxide, barium sulfate, zinc oxide, aluminum hydroxide, magnesium hydroxide, talc, kaolin, clay, mica, and wow. Examples thereof include lastnite, potassium titanate, aluminum borate, sepiolite, and zonotrite.

The colorant may be any of a black pigment such as carbon black, a white pigment such as titanium oxide, a yellow pigment, an orange pigment, a red pigment, a purple pigment, a blue pigment, and a green pigment.

Examples of the reinforcing agent include organic fibers [natural fibers such as cellulose fibers (cellulose nanofibers, etc.), polyalkylene allylate fibers, vinylon fibers, synthetic fibers such as aramid fibers, etc.], and inorganic fibers [glass fibers, carbon fibers, etc.]. Can be exemplified.

Examples of the flame retardant include hexabromocyclodecane, bis (dibromopropyl) tetrabromobisphenol A, tris (dibromopropyl) isocyanurate, tris (tribromoneopentyl) phosphate, decabromodiphenyloxide, and bis (pentabromo) phenylethane. , Tris (tribromophenoxy) triazine, ethylenebistetrabromophthalimide, polybromophenylindane, brominated polystyrene, tetrabromobisphenol A polycarbonate, brominated phenylene ethylene oxide, bromide such as polypentabromobenzyl acrylate, triphenyl phosphate, tri Cresyl phosphate, trixinyl phosphate, cresyldiphenyl phosphate, xylyldiphenyl phosphate, cresylbis (di-2,6-xylenyl) phosphate, 2-ethylhexyldiphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate , Bisphenol A bis (dicresyl) phosphate, resorcinol bis (di-2,6-xylenyl) phosphate, tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (tribromopropyl) phosphate, Phenyl esters such as diethyl-N, N-bis (2-hydrooxyethyl) aminomethylphosphonate, anionic oxalic acid-treated aluminum hydroxide, nitrate-treated aluminum hydroxide, high-temperature hot water-treated aluminum hydroxide, tinic acid surface treatment Examples thereof include a metal hydrate compound, a nickel compound surface-treated magnesium hydroxide, a silicone polymer surface-treated magnesium hydroxide, procobite, a multilayer surface-treated hydrated metal compound, and a cationic polymer-treated magnesium hydroxide.

Examples of the mold release agent include fatty acid-based mold release agents (higher fatty acid, higher fatty acid ester, higher fatty acid calcium, etc.), waxes (for example, carnauba wax, polyethylene-based wax, etc.), silicone oil, and the like.

Further, if necessary, the curable composition of the present invention contains an elastomer (or an elastomer modifier), for example, acrylonitrile butadiene rubber (NBR), liquid polybutadiene, polybutadiene (butadiene rubber, BR), in addition to the epoxy resin. Chloroprene rubber, silicone rubber, modified silicone rubber, cross-linked NBR, cross-linked BR, acrylic rubber (including core-shell type acrylic rubber), urethane rubber, polyester elastomer, functional group-containing liquid NBR, liquid polyester, liquid polysulfide, urethane prepolymer, etc. May include.

If necessary, in addition to the epoxy resin, other resins such as olefin resin (high density polyethylene, polypropylene, etc.), styrene resin (polystyrene, etc.), acrylic resin (polymethyl methacrylate, etc.), halogen are contained. It may contain a resin (polyvinyl chloride, etc.), a polyester resin (polyethylene terephthalate, etc.), a polycarbonate resin, a polyamide resin (nylon 6, nylon 66, etc.), a polyurethane resin, a silicone resin, etc., and the resin may contain. , Engineering plastic (polybutylene terephthalate, polyethylene naphthalate, bisphenol A type polycarbonate, polyacetal, polysulfone, polyethersulfone, polyetherimide, polyetheretherketone, etc.) may be used.

These additives, elastomers, and resins can be used alone or in combination of two or more. The ratio of these additives, elastomers and / or resins is not particularly limited and can be appropriately selected depending on the intended use.

The present invention also includes a cured product obtained by curing the curable composition. Such a cured product can be prepared by heating and curing the curable composition, depending on the use of the curable composition. For example, the curable composition may be applied to a substrate and cured, may be injected or sealed in a predetermined portion to be cured, may be cast and cured, or a substrate (fiber) may be applied. A prepreg may be prepared by impregnating the base material), and the prepreg may be laminated by a method such as laminating or winding, formed into a predetermined shape, and cured. The heating temperature for curing may be, for example, about 100 to 250 ° C, preferably 120 to 200 ° C, and more preferably 130 to 180 ° C. Since the curable composition of the present invention can be cured quickly even at a relatively low temperature, the heating temperature may be, for example, 70 to 150 ° C, preferably 80 to 120 ° C.

The gelation time of the curable composition of the present invention is, for example, 30 minutes or less (for example, 0 to 25 minutes), preferably 20 minutes or less (for example, 0.1 to 15 minutes) at a heating temperature of 100 ° C. , More preferably 13 minutes or less (for example, 1 to 10 minutes).

Although the curable composition of the present invention can be cured quickly at a low temperature, it has surprisingly high storage stability (or storage stability), and the pot life is, for example, one day or more (for example, one day to one day). Year), preferably 2 days or more (eg, 3 to 180 days), more preferably 5 days or more (eg, 7 to 120 days, especially 10 days or more (eg, 15 to 90 days).

In the present specification and claims, the gelation time and pot life can be measured by the method described in Examples described later.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the following examples and comparative examples, various characteristics were measured as follows.

( ^{1 1} H-NMR)
^{1 1} H-NMR was measured by dissolving amine adduct in deuterated chloroform and using "AVANCE III HD" ( ¹ H resonance frequency: 300 MHz) manufactured by Bruker Biospin.

(Softening point)
The softening point was measured using "M-565" manufactured by Nippon Buch Co., Ltd.

<Synthesis of amine adduct>
(Example 1) Amine adduct 2-methylimidazole of 9,9-bis (4-glycidyloxyphenyl) fluorene and 2-methylimidazole (“2MZ-H” manufactured by Shikoku Kasei Kogyo Co., Ltd., 8.2 g, 0. A solution of 9,9-bis (4-glycidyloxyphenyl) fluorene (23.0 g, 0.05 mol) of 9,9-bis (4-glycidyloxyphenyl) fluorene (23.0 g, 0.05 mol) in a 10 mol) methyl ethyl ketone (150 g) solution at 80 ° C. It was added dropwise with stirring over 160 minutes. After the dropping, the mixture was further stirred for 200 minutes and then cooled to room temperature. After cooling, methyl ethyl ketone was distilled off using a rotary evaporator. The obtained concentrate was dried under reduced pressure (80 ° C., overnight) and then ground in a mortar to obtain the title amine adduct as a yellowish white powder (yield 22.8 g, softening point 81.0 ° C.). ¹ H-NMR of the obtained amine adduct is shown in FIG.

In ¹ H-NMR of 9,9-bis (4-glycidyloxyphenyl) fluorene shown in FIG. 5, there are peaks corresponding to the oxylan ring near 2.7 ppm, 2.9 ppm and 3.3 ppm. In the ¹ H-NMR spectrum of Amin Adduct shown in FIG. 1, these peaks disappear. Further, in ¹ H-NMR of 2MZ-H shown in FIG. 7, a peak corresponding to a methyl group exists in the vicinity of 2.4 ppm, and this peak is also confirmed in the spectrum of amine adduct shown in FIG. From these facts, the formation of an amine adduct composed of 9,9-bis (4-glycidyloxyphenyl) fluorene and 2-methylimidazole was confirmed.

(Example 2) Amine adduct 2-ethyl-4-methylimidazole of 9,9-bis (4-glycidyloxyphenyl) fluorene and 2-ethyl-4-methylimidazole ("2E4MZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.), A solution of 9,9-bis (4-glycidyloxyphenyl) fluorene (23.0 g, 0.05 mol) in methyl ethyl ketone (150 g) in a solution of 11.0 g, 0.10 mol) in methyl ethyl ketone (150 g) at 80 ° C. 40. It was added dropwise with stirring over a minute. After the dropping, the mixture was further stirred for 240 minutes and then cooled to room temperature. After cooling, methyl ethyl ketone was distilled off using a rotary evaporator. The obtained concentrate was dried under reduced pressure (80 ° C., overnight) and then ground in a mortar to obtain the title amine adduct as a yellowish white powder (yield 23.0 g, softening point 81.2 ° C.). ¹ H-NMR of the obtained amine adduct is shown in FIG.

In ¹ H-NMR of 9,9-bis (4-glycidyloxyphenyl) fluorene shown in FIG. 5, there are peaks corresponding to the oxylan ring near 2.7 ppm, 2.9 ppm and 3.3 ppm. , These peaks disappear in the spectrum of Amin Adduct shown in FIG. Further, in ¹ H-NMR of 2-ethyl-4-methylimidazole shown in FIG. 8, there is a peak corresponding to a methyl group or an ethyl group near 1.3 ppm, around 2.2 ppm, and around 2.7 ppm. , These peaks are also confirmed in the spectrum of amine adduct shown in FIG. From these results, the formation of an amine adduct composed of 9,9-bis (4-glycidyloxyphenyl) fluorene and 2-ethyl-4-methylimidazole was confirmed.

(Example 3) In a solution of amine adduct 2MZ-H (8.2 g, 0.10 mol) of 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene and 2-methylimidazole in a methyl ethyl ketone (150 g) solution, 9 , 9-Bis (6-glycidyloxy-2-naphthyl) fluorene (28.1 g, 0.05 mol, manufactured by Osaka Gas Chemical Co., Ltd.) in a methylethylketone (150 g) solution at 80 ° C. for 150 minutes with stirring. Dropped. After the dropping, the mixture was further stirred for 180 minutes and then cooled to room temperature. After cooling, methyl ethyl ketone was distilled off using a rotary evaporator. The obtained concentrate was dried under reduced pressure (80 ° C., overnight) and then ground in a mortar to obtain the title amine adduct as a yellowish white powder (yield 25.5 g, softening point 144.8 ° C.). ¹ H-NMR of the obtained amine adduct is shown in FIG.

In ¹ H-NMR of 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene shown in FIG. 6, peaks corresponding to the oxylan ring were found near 2.8 ppm, 2.9 ppm and 3.4 ppm. Although present, these peaks have disappeared in the spectrum of Amin Adduct shown in FIG. Further, in ¹ H-NMR of 2-methylimidazole shown in FIG. 7, a peak corresponding to a methyl group exists near 2.4 ppm, and this peak is also confirmed in the spectrum of amine adduct shown in FIG. .. From these facts, the formation of an amine adduct composed of 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene and 2-methylimidazole was confirmed.

(Example 4) In a solution of 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene and 2-ethyl-4-methylimidazole in an amine adduct 2E4MZ (11.0 g, 0.10 mol) in a methyl ethyl ketone (150 g). , 9,9-Bis (6-glycidyloxy-2-naphthyl) fluorene (28.1 g, 0.05 mol) in a methylethylketone (150 g) solution was added dropwise at 80 ° C. over 140 minutes with stirring. After the dropping, the mixture was further stirred for 160 minutes and then cooled to room temperature. After cooling, methyl ethyl ketone was distilled off using a rotary evaporator. The obtained concentrate was dried under reduced pressure (80 ° C., overnight) and then ground in a mortar to obtain the title amine adduct as a yellowish white powder (yield 34.5 g, softening point 133.4 ° C.). ¹ H-NMR of the obtained amine adduct is shown in FIG.

In ¹ H-NMR of 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene shown in FIG. 6, peaks corresponding to the oxylan ring were found near 2.8 ppm, 2.9 ppm and 3.4 ppm. Although present, these peaks have disappeared in the spectrum of Amin Adduct shown in FIG. Further, in ¹ H-NMR of 2-ethyl-4-methylimidazole shown in FIG. 8, there is a peak corresponding to a methyl group or an ethyl group near 1.3 ppm, around 2.2 ppm, and around 2.7 ppm. , These peaks are also confirmed in the spectrum of amine adduct shown in FIG. From these results, the formation of an amine adduct composed of 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene and 2-ethyl-4-methylimidazole was confirmed.

<Preparation of curable composition and its characteristics>
(Example 5)
To 100 parts by weight of liquid epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation), 20 parts by weight of the amine adduct obtained in Example 1 is added to a homogenizer (“Ace Homogenizer AM-10” manufactured by Nissei Tokyo Office Co., Ltd.). , While cooling the container with ice water, stirred at a rotation speed of 15,000 rpm for 15 minutes to prepare a curable composition.

(Examples 6 to 8)
Instead of the amine adduct obtained in Example 1, the amine adduct obtained in Example 2 in Example 6, the amine adduct obtained in Example 3 in Example 7, and Example 4 in Example 8 A curable composition was prepared in the same manner as in Example 5 except that the amine adduct obtained in the above was used.

(Comparative Example 1)
Add 3 parts by weight of 2MZ-H to 100 parts by weight of liquid epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation), and use a homogenizer (“Ace Homogenizer AM-10” manufactured by Nissei Tokyo Office Co., Ltd.) in a container with ice water. Was stirred at a rotation speed of 15,000 rpm for 15 minutes while cooling to prepare a curable composition.

(Comparative Example 2)
Add 3 parts by weight of 2E4MZ to 100 parts by weight of liquid epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation), and cool the container with ice water using a homogenizer (“Ace Homogenizer AM-10” manufactured by Nissei Tokyo Office Co., Ltd.). While stirring at a rotation speed of 15,000 rpm for 15 minutes, a curable composition was prepared.

(Measurement of gelation time)
A glass sample tube and an aluminum block with a hole having the same outer diameter as the outer diameter were prepared. The aluminum block was preheated to a predetermined temperature on a hot plate. A sample was taken in a sample tube, and the sample tube was inserted into the hole of the aluminum block. Stir the inside of the sample tube with a spatula at a speed of about 60 times per minute in a circular shape (in a circular motion), and the end point is the point where the sample becomes gel and no longer adheres to the spatula or the stringing disappears. The time taken from the insertion of the sample tube to the end point was measured.

The results are summarized in Table 1. In addition, "aggregation" described in Table 1 indicates that gelation occurred and the gel phase and the liquid phase were separated while the temperature was raised to a predetermined temperature.

(Storage stability of curable composition)
The curable composition is stored at 25 ° C. in a closed container, and the viscosity (mPa. s / 25 ° C.) was measured. The time when the viscosity was doubled from the initial viscosity (viscosity measured immediately after preparation) was defined as the pot life. The results are shown in Table 2.

The curable composition using the amine adduct of the present invention has high curing properties at low temperatures (80 to 120 ° C.) and exhibits excellent storage stability.

The amine adduct of the present invention can significantly improve storage stability (or storage stability) in a curable composition containing an epoxy resin and the amine adduct, and exhibits a property of being rapidly cured by heating. Therefore, an epoxy resin is used. Can be effectively used as a curing agent or a curing accelerator. Therefore, the curable composition of the present invention has various uses to which an epoxy resin is applied, for example, an insulating material, a sealing material (a sealing material for electronic parts such as semiconductors and light emitting diodes, for example, a semiconductor sealing material, etc.). ), Epoxy resin laminated board (glass cloth, paper, synthetic fiber cloth, laminated board of base material such as copper foil and epoxy resin, for example, laminated board for printed wiring board), composite material (glass fiber, carbon fiber, Various fiber-reinforced composite materials with reinforcing fibers such as aramid fibers), casting materials, repair materials for concrete structures, adhesives, coating agents (eg, varnishes, paints (including powder paints), inks, etc.) Can be used for various purposes.

Claims (13)

An amine adduct formed by an epoxy component (A) and an amine component (B), wherein the epoxy component (A) contains an epoxy component (A1) having a 9,9-bisarylfluorene skeleton, and the amine component (B). ) Is an amine adduct containing an amine component (B1) having a heterocyclic skeleton containing a plurality of nitrogen atoms .
The amine component (B1) has the following formula (2a).

(In the formula, R ⁴ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a cyanoethyl group or a triazine-alkyl group; R ⁵ and R ⁶ are halogen atoms, nitro groups and alkyl groups. , Cycloalkyl group, aryl group, aralkyl group or acyl group, said alkyl group may have a hydroxyl group; R7 ^is a hydrogen atom, a halogen atom, a nitro group, an alkyl group, a cycloalkyl group, It represents an aryl group, an aralkyl group or an acyl group, and the alkyl group may have a hydroxyl group.)
Amine adduct containing an amine component represented by . The epoxy component (A1) has the following formula (1).

(In the formula, Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents that are non-reactive with an epoxy group, R ³ is a hydrogen atom or a methyl group, and A ¹ is a linear or branched alkylene. A group, k is an integer of 0 to 4, m and n are integers of 0 or more, and p is an integer of 1 or more.)
The amine adduct according to claim 1, which comprises an epoxy component represented by (1) or a multimer thereof. In formula (1), Z is a benzene ring, a naphthalene ring or a biphenyl ring, R ² is a C _1-4 alkyl group or a C _6-10 aryl group, and A ¹ is a linear or branched C _2-4 alkylene group. The amine adduct according to claim 2, wherein k and m are integers of 0 to 2, n is an integer of 0 to 10, and p is 1 or 2. The amine adduct according to claim 2 or 3, wherein in the formula (1), Z is a naphthalene ring, n is 0, and p is 1. The amine adduct according to any one of claims 1 to 4 , wherein the ratio of the amine component (B1) is 0.3 to 3 mol with respect to 1 mol of the epoxy group of the epoxy component (A1). The amine adduct according to any one of claims 1 to 5 , wherein the softening point is 50 to 180 ° C. The amine adduct according to any one of claims 1 to 6 , which is a curing agent and / or a curing accelerator for curing the epoxy resin (C). The method for producing an amine adduct according to any one of claims 1 to 7 , wherein the epoxy component (A) containing the epoxy component (A1) and the amine component (B) containing the amine component (B1) are mixed. A curable composition comprising the amine adduct according to any one of claims 1 to 7 and the epoxy resin (C). The curable composition according to claim 9 , wherein the epoxy resin (C) is a liquid epoxy resin. The curable composition according to claim 9 or 10 , which comprises 1 to 50 parts by weight of the amine adduct according to any one of claims 1 to 7 with respect to 100 parts by weight of the epoxy resin (C). A cured product obtained by curing the curable composition according to any one of claims 9 to 11 . A method for producing a cured product according to claim 12 , wherein the curable composition according to any one of claims 9 to 11 is heated and cured.

Images