JP2019123795A - Amine adduct and use thereof - Google Patents

Abstract

To provide an amine adduct which can be easily prepared and has excellent storage stability (or preservation stability), a method for producing the same, and a use thereof.SOLUTION: The amine adduct contains an epoxy component (A1) having a 9,9-bisarylfluorene skeleton and an amine component (B1) having a heterocyclic skeleton. The epoxy component (A1) having the 9,9-bisarylfluorene skeleton may contain an epoxy component represented by formula (1) or a multimer thereof. (In the formula, Z represents an aromatic hydrocarbon ring; Rand Reach represent a non-reactive substituent; Rrepresents a hydrogen atom or a methyl group; Arepresents an alkylene group; k represents an integer of 0-4; m and n each represent an integer of 0 or more; and p represents an integer of 1 or more.)SELECTED DRAWING: None

Description

  The present invention is formed of 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.

  An epoxy resin composition having good storage stability and cured by heating is in great demand in the industrial field such as semiconductor mounting because it leads to simplification of the production process. In the production of such epoxy resin compositions, various latent curing agents have been proposed, among which latent curing agents using an amine adduct obtained by reacting an epoxy component and an amine component are known. There is.

  JP-A-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. The document states that the composition can exhibit good storage stability and excellent curing properties.

  Moreover, the microcapsule type latent curing agent for epoxy resins which included the core which contains an amine adduct in the shell formed with resin is disclosed by Unexamined-Japanese-Patent No. 2015-113426 (patent document 2). The document states that the curing agent can be cured at low temperatures and has excellent storage stability.

JP-A-8-27402 JP, 2015-113426, A

  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 may be mixed in addition to the amine adduct, or the amine adduct may be further chemically modified. It is necessary to do physical modification. For this reason, the manufacturing process is complicated, and the productivity is easily reduced.

  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 a use thereof.

  Another object of the present invention is to provide an amine adduct capable of achieving both high curing characteristics capable of rapidly curing an epoxy resin even at relatively low temperatures and high storage stability, a method for producing the same and applications thereof. .

  As a result of intensive studies to achieve the above problems, the present inventors have found it convenient to mix an epoxy component having a 9,9-bisarylfluorene skeleton with an amine component having a heterocyclic skeleton containing a plurality of nitrogen atoms. It has been found that it is possible to form an amine adduct and that the amine adduct exhibits excellent storage stability when used as a curing agent and / or a curing accelerator for an epoxy resin, and completed the present invention.

  That is, the amine adduct of the present invention is an amine adduct formed of the epoxy component (A) and the amine component (B), and the epoxy component (A) is an epoxy component having a 9,9-bisarylfluorene skeleton ( A1) is included, and the amine component (B) includes 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.

(Wherein, Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents nonreactive to the epoxy group, R ³ is a hydrogen atom or a methyl group, and A ¹ is a linear or branched alkylene 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. 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).

(Wherein 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 to} R ⁷ represent a hydrogen atom, a halogen atom, a nitro group , An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an acyl group, and the alkyl group may have a hydroxyl group, and R ⁴ and R ⁵ are bonded to each other to form an adjacent nitrogen atom and carbon The ring may be formed with the atom; q represents an integer of 0 to 3; a double line of a solid line and a broken line represents 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 formula (2a) and / or (2b).

(Wherein, r represents 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 above).

  In the amine adduct, the proportion of the amine component (B1) having a heterocyclic skeleton containing a plurality of nitrogen atoms is 0 with respect to 1 mole of the epoxy group of the epoxy component (A1) having a 9,9-bisarylfluorene skeleton. It may be 3 to 3 moles. 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 provides an amine component (B) containing 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. And a method of producing the amine adduct by mixing

  The present invention also encompasses a curable composition comprising the above amine adduct and an epoxy resin (C). The epoxy resin (C) may be a liquid epoxy resin. The proportion 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 encompasses a cured product obtained by curing the curable composition, and a method of heating and curing the curable composition to produce the cured product.

  In the present specification and claims, the "amine adduct" is prepared by mixing the amine component (B) with the epoxy component (A) and opening (or consuming) the epoxy group of the epoxy component (A). It means a cured product obtained by Therefore, the amine adduct has a form in which the amine component (B) is covalently incorporated into the cured product by reaction with an epoxy group or the like, a form in which the amine component is included in the cured product as a liberateable guest compound, or a combination thereof. You may hold | maintain by a form etc.

In the specification and claims of the present application, the number of carbon atoms of a 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 prepared conveniently (or easily) or efficiently using a predetermined epoxy component (A) and a predetermined amine component (B). In addition, the amine adduct obtained has excellent storage stability (or storage stability) probably because it is used in combination with an epoxy component having a specific skeleton and an amine component having a specific skeleton. Furthermore, the amine adduct of the present invention is compatible with high curing properties that can rapidly cure epoxy resins even at relatively low temperatures, and high storage stability.

FIG. 1 is a ¹ H-NMR spectrum of the amine adduct of Example 1. FIG. 2 is a ¹ H-NMR spectrum of the amine adduct of Example 2. FIG. 3 is a ¹ H-NMR spectrum of the amine adduct of Example 3. FIG. 4 is a ¹ H-NMR spectrum of the 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 of the present invention (also referred to as adduct, epoxy adduct, epoxyamine adduct, modified amine, amine modified epoxy compound or amine modified epoxy resin) is an amine formed of epoxy component (A) and amine component (B). An adduct, wherein the epoxy component (A) contains an epoxy component (A1) having a 9,9-bisarylfluorene skeleton, and the amine component (B) has an heterocyclic structure containing a plurality of nitrogen atoms (B1) Contains).

[Epoxy component (A)]
(A1) Epoxy component having 9,9-bisarylfluorene skeleton Epoxy component (or first epoxy component) having 9,9-bisarylfluorene skeleton (A1) includes the above-mentioned skeleton and epoxy group (or oxirane skeleton) And may be a monofunctional epoxy component having one epoxy group, but is preferably a polyfunctional epoxy component having two or more epoxy groups. As a 1st epoxy component (A1), the epoxy component represented by following formula (1) or its multimer etc. are mentioned typically, for example.

(Wherein, Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents nonreactive to the epoxy group, R ³ is a hydrogen atom or a methyl group, and A ¹ is a linear or branched alkylene 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 ring Z is roughly classified into monocyclic aromatic hydrocarbon rings such as benzene ring and polycyclic aromatic hydrocarbon rings Be done. Examples of the polycyclic aromatic hydrocarbon ring include a fused polycyclic aromatic hydrocarbon ring (fused polycyclic arene ring), a ring-aggregated aromatic hydrocarbon ring (ring-assembled arene ring) and the like.

As the fused polycyclic arene ring, for example, a fused bicyclic hydrocarbon ring (eg, fused bicyclic C _8-20 arene ring such as indene ring, naphthalene ring, etc., preferably fused bicyclic C _10-16 arene) And rings such as fused tricyclic hydrocarbon rings (eg, anthracene ring, phenanthrene ring and the like) and the like. As preferable fused polycyclic arene rings, naphthalene ring, anthracene ring and the like can be mentioned, and in particular, naphthalene ring is preferable.

As the ring assembly arene ring, biarene ring, for example, bi-C _6-12 arene ring such as biphenyl ring, binaphthyl ring, phenyl naphthalene ring (1-phenyl naphthalene ring, 2-phenyl naphthalene ring etc.), terarene ring, for example, Examples include ter C _6-12 arene rings such as a terphenylene ring. As a preferable ring assembly arene ring, a bi-C _6-10 arene ring, especially a biphenyl ring and the like can be mentioned.

The two ring Z types may be the same or different rings, and usually the same ring. Preferred examples of the ring Z include C _6-12 arene rings such as benzene ring, naphthalene ring and biphenyl ring, and more preferred are C _6-10 arene rings such as benzene ring and naphthalene ring, and particularly preferred is a naphthalene ring. Further, from the viewpoint of being able to remarkably improve the storage stability, ring Z is a polycyclic arene ring, particularly a fused polycyclic C _6-14 arene ring such as a fused polycyclic arene ring, particularly a naphthalene ring, Is preferred. The reason for this is not clear, but it is presumed that the 9,9-bispolycyclic arylfluorene skeleton more easily holds or clasps the amine component (B1) and the like.

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

In the case the substitution number k is plural (2 to 4), the type of a plurality of groups R ¹ may be different from each other, it may be identical. Further, the types of the group R ¹ substituted on different benzene rings forming the fluorene ring may be the same or different. Further, the bonding position (substituting position) of the group R ¹ is not particularly limited, and examples thereof include the 2-, 7-, 2- and 7-positions of the fluorene ring. The preferred substitution number k is 0 to 1, in particular 0. The two substitution numbers k may be identical to or different from one another.

The substituent R ² to be substituted on the ring Z may be any non-reactive group to the epoxy group, for example, an alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group) linear or branched _{C 1-12} alkyl group such as, preferably such as _{C 1-8} alkyl group), a cycloalkyl group (the cycloalkyl such as _{C 5-10} cycloalkyl group such as cyclohexyl group), an aryl group ( For example, C _6-10 aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group etc., aralkyl group (C _6-10 aryl-C _1-4 alkyl group such as benzyl group, phenethyl group etc.), etc. hydrocarbon group; an alkoxy group C _5-1, such as (methoxy group, C _1-8, etc. alkoxy group such as ethoxy group), cycloalkoxy (hexyloxy group cycloheteroalkyl Cycloalkyl such as alkyl group), _{C 6-10} aryloxy groups such as an aryloxy group (phenoxy group), a group such as an aralkyl group _{(C 6-10} aryl _{-C 1-4} alkyl group such as a benzyl group) -OR, wherein R represents a hydrocarbon group (such as the above-mentioned hydrocarbon group). A group -SR (wherein R is as defined above) such as an alkylthio group (such as a C _1-8 alkylthio group such as a methylthio group); an acyl group (such as a C _1-6 acyl group such as an acetyl group); Alkoxy carbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group etc.); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.); nitro group; cyano group etc. may be mentioned.

When m is 1 or more, preferred examples of R ² include a hydrocarbon group [eg, an alkyl group (eg, a linear or branched C _1-6 alkyl group), a cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, C _6-10 aryl group), aralkyl group (eg, C _6-8 aryl-C _1-2 alkyl group), etc.], alkoxy group (linear or branched) A chain C _1-4 alkoxy group and the like can be mentioned. More preferable group R ² is an alkyl group [C _1-4 alkyl group (especially methyl group etc.)], an aryl group [eg C _6-10 aryl group (especially phenyl group etc.) etc.], and in particular, an alkyl group It may be When the substituent R ² is an aryl group, the substituent R ² may form the above-mentioned ring assembly arene ring together with the ring Z.

  The number of substitutions m can be appropriately selected according to the type of ring Z, and can be selected, for example, from the range of about 0 to about 8. The preferable substitution number m is 0 to 4, 0 to 3, 0 to 2, and more preferably 0 or 1, and particularly 0, in stages. In addition, when the ring Z is a benzene ring and the number of repetitions n is 0, the preferable number of substitutions m is, in the following, stepwise 1-4, 1-4, 1-3, 1-2, and more preferably 1. It is also good. In addition, two m may mutually be same or different.

In the same ring Z, when m is a plurality (2 or more), the types of the plurality of groups R ² may be different from each other or may be the same. Also, in two rings Z, the type of group R ² may be the same or different. The substitution position of the group R ² is not particularly limited.

The alkylene group A ^1, for example, ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, a linear or branched C _2-6 alkylene group such as tetramethylene group. The preferable A ¹ is a linear or branched C _2-4 alkylene group or a linear or branched C _2-3 alkylene group in a stepwise manner, particularly preferably an ethylene group.

The repeating number n of the oxyalkylene group [OA ¹ ] may be an integer of 0 or more, and can be selected, for example, from the range of about 0 to 20. The preferable 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, and particularly 0 to 5, in a stepwise manner. , 0 may be. In addition, n may be an average value (or average addition mole number) in the molecular assembly, and the preferable range may be the same corresponding to the range of the integer.

Note that when repeated n of the oxyalkylene group [OA ^1] is 2 or more, the alkylene group A ¹ may be composed of different alkylene group, typically, it may be composed of the same alkylene group. Further, in the group [—O— (A ¹ O) _n —CH ₂ —CR ³ (O —) — CH ₂ ] (hereinafter, also simply referred to as “epoxy-containing group”) corresponding to the substitution number p, different epoxy-containing groups The type of alkylene group A ^{1 to be} formed may be the same or different, and may usually be 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 radicals R ³ may be identical or different from one another and are usually identical.

  The substitution number p of the epoxy-containing group can be appropriately selected according to the type of the ring Z, and may be selected, for example, from the range of about 1 to 4. The preferred value of p is 1 to 3 or 1 to 2 in a stepwise manner, and 1 is particularly preferable.

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

As an epoxy component (or polyepoxy compound) represented by a typical formula (1), a compound in which (A1-1) n is 0 and a compound in which (A 1-2) n is 1 or more are widely used. It can be different. As the compound (A1-1) in which n is 0 in the formula (1), for example, 9,9-bis (glycidyloxyphenyl) fluorenes {eg, 9,9-bis (glycidyloxyphenyl) fluorene [eg 9,9-bis (4-glycidyloxyphenyl) fluorene and the like]; 9,9-bis (alkyl-glycidyloxyphenyl) fluorene [eg, 9,9-bis (3-methyl-4-glycidyloxyphenyl) fluorene 9,9-bis (mono or di C _1-4 alkyl-glycidyloxyphenyl) fluorene etc., such as 9,9-bis (3,5-dimethyl-4-glycidyloxyphenyl) fluorene], 9,9-bis (Aryl-glycidyloxyphenyl) fluorene [eg, 9,9-bis (3-phenyl-4-glycidyl oxy) Phenyl) fluorene such as 9,9-bis (mono- or _{di-C 6-10} aryl - glycidyloxyphenyl) fluorene, etc.] such as 9,9-bis (glycidyloxy - and substituted phenyl) fluorenes}; 9,9 Bis (polyglycidyloxyphenyl) fluorenes {eg, 9,9-bis (polyglycidyloxyphenyl) fluorene [9,9-bis (3,4-diglycidyloxyphenyl) fluorene, 9,9-bis (3,3 9,9-bis (di or triglycidyl oxyphenyl) fluorene etc, such as 5-diglycidyloxyphenyl) fluorene 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.}; compounds obtained by substituting a glycidyloxy group of these compounds to 2-methylglycidyl group, and the like.

Specific examples of the compound (A1-2) in which n is 1 or more in the formula (1) correspond to the compounds exemplified as the compound (A1-1) in which the n is 0. Certain compounds, such as 9,9-bis (glycidyloxy (poly) alkoxyphenyl) fluorenes {9,9-bis (glycidyloxy (poly) alkoxyphenyl) fluorene [eg, 9,9-bis [4- (2) -9,9-bis (glycidyl oxy (poly) C _2-4 alkoxy phenyl) fluorene etc, such as glycidyloxy ethoxy) phenyl] fluorene]; 9, 9-bis (alkyl glycidyl oxy (poly) alkoxy phenyl) fluorene [ For example, 9,9-bis [4- (2-glycidyloxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-) Glycidyl oxy) -3,5-dimethylphenyl] fluorene such as 9,9-bis (mono- or _{di-C 1-4} alkyl - glycidyloxy _{(poly) C 2-4} alkoxyphenyl) fluorene]; 9,9 -Bis (aryl-glycidyloxy (poly) alkoxyphenyl) fluorene [eg, 9,9-bis (mono or di or such as 9,9-bis [4- (2-glycidyloxyethoxy) -3-phenylphenyl] fluorene C _6-10 aryl-glycidyloxy (poly) C _2-4 alkoxyphenyl) fluorene etc], etc.}; 9,9-bis (polyglycidyloxy (poly) alkoxyphenyl) fluorenes {eg, 9,9-bis ( Polyglycidyloxyphenyl) fluorene [9,9-bis (3,4-di (2-glycidyl oxy) Ethoxy) phenyl) fluorene, 9,9-bis (3,5-di (2-glycidyloxy) phenyl) fluorene such as 9,9-bis (di or tri glycidyloxy _{(poly) C 2-4} alkoxyphenyl) Fluorene and the like] and the like}; 9,9-bis (glycidyloxy (poly) alkoxynaphthyl) fluorenes {eg, 9,9-bis (glycidyloxy (poly) alkoxynaphthyl) fluorene [eg, 9,9-bis [6 -(2-glycidyl oxyethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-glycidyl oxyethoxy) -1-naphthyl] fluorene etc], etc.}; glycidyl oxy groups of these compounds -The compound etc. which were substituted by the methyl glycidyloxy group are mentioned.

  The epoxy component represented by these said Formula (1) can also be used individually or in combination of 2 or more types. Among the epoxy components represented by the above formula (1), compounds (A1-1) in which n is 0 are preferable, and in particular, 9,9-bis (glycidyloxyphenyl) fluorenes in which p is 1. 9,9-bis (glycidyloxynaphthyl) fluorenes are preferred, and 9,9-bis (glycidyloxynaphthyl) fluorenes such as 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene are particularly preferred.

The multimer of the epoxy component represented by the formula (1) may have a plurality of 9,9-bisarylfluorene skeletons, for example, two diethylene glycol having two 9,9-bisarylfluorene skeletons It may be a dimer, a decamer such as a trimer, a trimer having the three backbones, or a tetramer having the four backbones. 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 a glycidyl group having a group R ³ in the above formula (1) is replaced by a hydrogen atom, and an epihalohydrin such as epichlorohydrin A single-step method (Taffy method or direct method) of reacting in the presence of a strong alkali such as sodium hydroxide; an epoxy component represented by the formula (1) and the polyhydroxy compound; A two-step method (Advanced method, melting method or indirect method) in which reaction is performed in the presence of an addition catalyst such as sodium hydroxide, sodium carbonate, lithium chloride and the like) can be mentioned. The multimer of the epoxy component represented by said Formula (1) may be used independently, and may be used in combination with the epoxy component (or monomer) represented by said Formula (1). Usually, the epoxy component represented by said Formula (1) is used widely.

(A2) Other Epoxy Component The epoxy component (A) is not necessarily required, but contains other epoxy component (or second epoxy component) (A2) not belonging to the first epoxy component (A1). It may be

  The second epoxy component (A2) is not particularly limited, and a conventional epoxy resin (or epoxy compound), for example, a glycidyl ether type epoxy resin (with the exception of the epoxy component represented by the above formula (1)) And glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, epoxy resin oxidized and epoxidized unsaturated double bond, etc., and specifically, epoxy components exemplified in epoxy resin (C) described later It may be. These second epoxy components (A2) can also be used alone or in combination of two or more.

  The proportion of the first epoxy component (A1) may be selected, for example, from the range of about 10% by weight or more (for example, 30 to 100% by weight) with respect to the entire epoxy component (A). As a preferable range, 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) may be provided stepwise. Further, as a further preferable range, 90% by weight or more (for example, 95 to 100% by weight), particularly 100% by weight (substantially only the first epoxy component (A1)) may be used.

  The ratio of the total amount of the epoxy component of the formula (1) and the multimer thereof is, for example, in the 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. As a preferable range, 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) may be provided stepwise. Further, as a further preferable range, it 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 its multimer) It is also 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) at least contains 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 (eg, 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 ring is not particularly limited, but usually it is usually a 5- or 6-membered heterocyclic ring. The heterocyclic ring may be either an aliphatic heterocyclic ring (non-aromatic heterocyclic ring) or an aromatic heterocyclic ring. The heterocycle may also be a fused polycyclic heterocycle fused to another hydrocarbon ring or heterocycle.

  As such a first amine component (B1), for example, an amine component having a monocyclic heterocyclic skeleton {eg, piperazines [eg, piperazine; N, N'- such as N, N'-dimethylpiperazine, etc. N- (aminoethyl) piperazine; N-dialkylaminoethyl-N'-alkyl piperazine such as 1- (2-dimethylaminoethyl) -4-methylpiperazine; etc., pyrazoles, pyrazines, pyrimidines, Pyridazines, triazines (triazine, N, N ', N "-tris (dimethylaminopropyl) hexahydro-s-triazine, etc.), pyrazolidines, pyrazolines, imidazolidines, furanazines, etc.}; Amine components having a ring skeleton [eg, indazoles, purines, phthalazines, Examples thereof include phyllidines, quinoxalines, quinazolines, cinnolines, pteridines, perimidines, phenanthrolines, phenazines, triethylenediamine (DABCO; 1,4-diazabicyclo [2.2.2] octane) and the like. As a preferable 1st amine component (B1), the compound represented by following formula (2) may be included, for example.

(Wherein 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 to} R ⁷ represent a hydrogen atom, a halogen atom, a nitro group , An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an acyl group, and the alkyl group may have a hydroxyl group, and R ⁴ and R ⁵ are bonded to each other to form an adjacent nitrogen atom and carbon The ring may be formed with the atom; q represents an integer of 0 to 3; a double line of a solid line and a broken line represents a single bond or a double bond).

In the above formula (2), examples of the alkyl group represented by R ⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl and t-butyl A linear or branched C _1-10 alkyl group such as a group, n-pentyl group, n-hexyl group, nonyl group, isononyl group, decyl group and the like can be exemplified. The preferred alkyl group may be a linear or branched C _1-6 alkyl group.

The cycloalkyl group represented by R ^4, for example, C _5-10 cycloalkyl groups such as cyclopentyl group, cyclohexyl group can be exemplified. Preferred cycloalkyl groups may be C _5-8 cycloalkyl groups, in particular C _5-6 cycloalkyl groups.

The aryl group represented by R ⁴ may be a monocyclic or polycyclic aryl group, and the polycyclic aryl group may be a group not only fully unsaturated but also partially saturated. Examples of the aryl group include a phenyl group, a naphthyl group, azulenyl group, indenyl group, indanyl group, a C _6-16 aryl group such as tetralinyl group can be exemplified. The preferred aryl group may be a C _6-10 aryl group (such as a phenyl group or a naphthyl group).

The aralkyl group (arylalkyl group) represented by R ⁴ is a group in which the above aryl group and an alkyl group are bonded, and examples thereof include a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, and a 1-phenyl group. C _6-12 aryl C such as -n-hexyl group, naphthalen-1-ylmethyl group, naphthalen-2-ylethyl group, 1- (naphthalen-2-yl) -n-propyl group, inden-1-ylmethyl group and the like _{A 1-6} alkyl group etc. can be illustrated. 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. As a substituent, for example, halogen atom (fluorine atom, chlorine atom, etc.), hydroxyl group, alkoxy group (C _1-6 alkoxy group such as methoxy group, ethoxy group etc.), acyl group (formyl group; acetyl group, propionyl Groups such as C _1-10 alkyl-carbonyl group), carboxyl group, alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group etc.), alkyl groups (C _1-6 alkyl group such as methyl group and ethyl group) Etc. can be illustrated.

In the triazine-alkyl group represented by R ⁴ , the triazine may be 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine or the like, and a carbon atom of the triazine ring May be substituted with an amino group, a hydroxyl group or the like. As a representative triazine-alkyl group, for example, 4,6-diamino-1,3,5-triazin-2-yl-methyl group, 4-amino-6-hydroxy-1,3,5-triazine-2 -1, ₄ -triazin-2-yl-C _1-4 alkyl group such as -yl-methyl group, 4,6-dihydroxy-1,3,5-triazin-2-yl-methyl group, etc. can be exemplified . Preferred triazine-alkyl groups may be 4,6-diamino-1,3,5-triazin-2-yl-C _1-2 alkyl groups.

When R ⁴ and R ⁵ do not form a ring, preferred R ⁴ is a hydrogen atom, a C _1-4 alkyl group, a C _6-10 aryl group, a C _6-10 aryl C _1-4 alkyl group, a cyanoethyl group Or a 1,3,5-triazin-2-yl-C _1-2 alkyl group etc., and usually a hydrogen atom, a cyanoethyl group etc. in many cases.

The halogen atom represented by R ^{5 to} R ⁷ includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group represented by R ^{5 to} R ⁷ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group and 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. A linear or branched _C1-20 alkyl group etc. can be illustrated. Preferred examples of the alkyl group include a linear or branched C _1-18 alkyl group, a linear or branched C _1-12 alkyl group, and a linear or branched C ₁ -C alkyl group in the following. ₁₀ alkyl group, linear or branched C _1-6 alkyl group may be straight-chain or branched-chain C _1-4 alkyl group.

In addition, the alkyl group may have a hydroxyl group. As an alkyl group which has a hydroxyl group, hydroxy _C1-20 alkyl groups, such as a hydroxymethyl group and a hydroxyethyl group, etc. can be illustrated, for example. Preferred examples of the hydroxyalkyl group include, in the following, 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, 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, especially a hydroxymethyl group.

Examples of the cycloalkyl group, aryl group and aralkyl group represented by R ^{5 to} R ⁷ include the same groups as those of the above-mentioned substituent R ⁴ and preferable embodiments.

The acyl group represented by R ^{5 to} R ⁷ may be a group in which a hydrogen atom; or 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: formyl group; acetyl group, propionyl group, butyryl group, isobutyryl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, 3-methylnonanoyl group, 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, nonadecanoyl group, eicosanoyl group, henicosanoyl group, etc. Linear or branched C _1-26 alkyl - carbonyl group; an acryloyl group, a methacryloyl group, an allyl group, a substituent (aryl group) optionally C _2-6 alkenyl optionally having a cinnamoyl group - Carbonyl group; C _2-6 alkynyl-carbonyl group such as ethynyl carbonyl group and propynyl carbonyl group; C _6-18 aryl-carbonyl group such as benzoyl group, naphthyl carbonyl group, biphenyl carbonyl group and anthranyl carbonyl group; 2-pyridylcarbonyl group And heteroaryl-carbonyl groups such as thienylcarbonyl group (eg, non-aromatic or aromatic 5- to 6-membered heteroaryl-carbonyl group etc.) and the like. A preferred acyl group is a C _1-20 alkyl-carbonyl group, more preferably a C _1-6 alkyl-carbonyl group.

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

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

A double line of a solid line and a broken line indicates a single bond or a double bond, and in general, when R ⁴ and R ⁵ bond together to form a ring (heterocycle), it may be a single bond, R ^{When 4} and R ⁵ do not form a ring (heterocycle), they are often double bonds.

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.

As preferable R ⁶ and / or R ⁷ , a hydrogen atom, an alkyl group, a hydroxyalkyl group and the like can be mentioned.

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

(In the formula, r represents an integer of 0 to 5; R ^{4 to} R ⁷ and the double line of a solid line and a broken line are the same as the formula (2) including the preferred embodiment).

Further, in the formula (2a), a more preferred embodiment of R ^4, a hydrogen atom, cyanoethyl group, a triazine - alkyl group, and more preferably include a hydrogen atom.

In the above formula (2a), more preferable embodiments of R ⁵ 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 group. Among them, a branched or branched C _1-12 alkyl group is preferable, and 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), as a more preferable embodiment of R ⁶ , a hydrogen atom, a C _1-8 alkyl group, a hydroxy C _1-4 alkyl group can be mentioned, and a hydrogen atom or a C _1-6 alkyl group is more preferable. Among them, a hydrogen atom and a C _1-4 alkyl group are preferable, and a C _1-2 alkyl group is particularly preferable.

In the formula (2a), a more preferred embodiment of R ^7, a hydrogen atom, a hydroxy C _1-4 alkyl group, and more preferably a hydrogen atom.

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

  In the formula (2b), the preferable number of repetitions r is an integer of 1 to 5, more preferably an integer of 1 to 4, and particularly an integer of 1 to 3.

As a compound represented by Formula (2a), an imidazoline compound and an imidazole compound are mentioned typically, For example, 2-methyl imidazoline, 2-phenyl imidazoline etc. are mentioned as an imidazoline compound. Examples of the imidazole compound include imidazole; 1-alkylimidazole such as 1-methylimidazole, 1-ethylimidazole, 1-n-propylimidazole, 1-isopropylimidazole, 1-n-butylimidazole and 1-isobutylimidazole; 2-alkylimidazole such as -methylimidazole, 2-ethylimidazole, 2-n-propylimidazole, 2-isopropylimidazole, 2-n-butylimidazole, 2-isobutylimidazole, 2-undecylimidazole, 2-heptadecylimidazole 2-arylimidazole such as 2-phenylimidazole; 4-alkylimidazole such as 4-methylimidazole, 4-ethylimidazole; 1 such as 1,2-dimethylimidazole; 2-dialkylimidazole; 2,4-dialkylimidazole such as 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole; 2-aryl-4-alkylimidazole such as 2-phenyl-4-methylimidazole; 1- 1-aralkyl-2-alkylimidazole such as benzyl-2-methylimidazole; 1-aralkyl-2-arylimidazole such as 1-benzyl-2-phenylimidazole; 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2 1-cyanoethyl-2-alkylimidazole such as undecylimidazole; 1-cyanoethyl-2-arylimidazole such as 1-cyanoethyl-2-phenylimidazole; 1-cyanoethyl-2-ethyl-4-methylimidazole 1-cyanoethyl-2,4-dialkylimidazole; 2-aryl-4-alkyl-5-hydroxyalkylimidazole such as 2-phenyl-4-methyl-5-hydroxymethylimidazole; 2-phenyl-4,5-bis Examples include 2-aryl-4,5-bis (hydroxyalkyl) imidazole such as (hydroxymethyl) imidazole. In many cases, in the imidazole compound, at least one of R ^{4 to} R ⁷ is a substituent other than a hydrogen atom, preferably at least one of R ^{4 to} R ⁶ is a substituent other than a hydrogen atom. More preferably, at least one of R ⁵ or R ⁶ is a substituent other than a hydrogen atom, and at least R ⁵ is preferably a substituent other than a hydrogen atom. When an amine adduct is used as a curing agent and / or a curing accelerator for an epoxy resin (C), in particular, R ⁵ or R ^{5 in} that it is easily cured uniformly without aggregation (gelling or separation of gel phase). ^It is preferred that both of ^{6 be} a substituent other than hydrogen atom.

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

These first amine components (B1) can also be used alone or in combination of two or more. Among these first amine components (B1), compounds represented by the above formula (2a) are preferable, and in particular, imidazole compounds are preferable. Preferred imidazole compounds include imidazole, alkylimidazole, dialkylimidazole, arylimidazole, aralkyl-alkylimidazole, aryl-alkyl-hydroxymethylimidazole, aryl-bis (hydroxymethyl) imidazole, among which imidazole, 1-methylimidazole 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, or 2-phenyl-4,5-bis (hydroxymethyl) imidazole It is preferred. Normally, _{2-C 1-6} alkyl imidazoles such as 2-methylimidazole, _{2-ethyl-4-2-C 1-6} alkyl _{-4-C 1-6} alkyl imidazoles such as methylimidazole is generic. When an amine adduct is used as a curing agent and / or a curing accelerator for an epoxy resin (C), in particular, 2-ethyl-4 is particularly preferable in that it is easily cured uniformly without aggregation (gelling or separation of gel phase). 2-C _1-4 alkyl-4-C _1-4 alkylimidazole such as -methylimidazole is preferred.

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

(B2) Other Amine Component The amine component (B) may, but need not, contain other amine component (or second amine component) (B2) not belonging to the first amine component (B1). It may be

  The second amine component (B2) is not particularly limited, and commonly used amine compounds such as aliphatic amines, alicyclic amines, aromatic amines, heterocyclic amines (however, the first one) Amine components, that is, amine compounds having a heterocyclic skeleton containing a plurality of nitrogen atoms are excluded, modified amines and the like, and specifically exemplified as other curing agents and / or curing accelerators described later An amine compound etc. are mentioned. These second amine components (B2) can also be used alone or in combination of two or more.

  The proportion of the first amine component (B1) may be selected, for example, from the range of about 10% by weight or more (for example, 30 to 100% by weight) with respect to the entire amine component (B). As a preferable range, 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) may be provided stepwise. Further, as a further preferable range, 90% by weight or more (for example, 95 to 100% by weight), particularly 100% by weight (substantially only the first amine component (B1)) may be used.

  The proportion of the amine component represented by the above formula (2) is, for example, selected from the range of about 10% by weight or more (for example, 30 to 100% by weight) with respect to the entire first amine component (B1) It is also good. As a preferable range, 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) may be provided stepwise. Further, as a more preferable range, 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)) may be used.

  The proportion of the amine component represented by the above formula (2a) is, for example, selected from the range of about 10% by weight or more (for example, 30 to 100% by weight) with respect to the entire first amine component (B1) It is also good. As a preferable range, 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) may be provided stepwise. Further, as a more preferable range, 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)) may be used.

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

  The mixing of the epoxy component (A) and the amine component (B) may optionally be carried out in the presence of a solvent. As the solvent, for example, alcohols such as methanol, ethanol, propanol and butanol; ethers, such as 2-methoxyethanol (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve) and the like 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, etc. Linear ethers and the like; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pe Chain ketones such as tanone and 2-hexanone, cyclic ketones such as isophorone, cyclohexanone and the like; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate etc. esters; ethylene glycol monoethyl ether acetate (ethyl cellosolve Acetate), Diethylene glycol monoethyl ether acetate (ethyl carbitol acetate), Propylene glycol monomethyl ether acetate, Ether esters such as dipropylene glycol monomethyl ether acetate; Aliphatic hydrocarbons such as heptane and octane; Alicyclics such as cyclohexane Hydrocarbons; Aromatic hydrocarbons such as toluene and xylene; Halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene; Dimethyl Formamide, amides such as dimethylacetamide; sulfoxides such as dimethyl sulfoxide, and others. The solvent may be an aprotic polar solvent such as amides, sulfoxides and the like. These solvents can be used alone or as a mixture of two or more. Among these solvents, preferred are solvents in which both the epoxy component (A) and the amine component (B) are compatible or soluble. Usually, ketones such as methyl ethyl ketone are widely used.

  The proportion of the amine component (B) is, for example, 0.5 to 5 mol, preferably 0.7 to 3 mol, more preferably 1 mol of the epoxy group (or oxirane ring) in the epoxy component (A). It may be 0.8 to 1.5 moles, more preferably 0.9 to 1.1 moles, and in particular substantially equimolar.

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

  The proportion 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, and more preferably 100 parts by weight of the epoxy component (A). May be 25 to 50 parts by weight, in particular 30 to 45 parts by weight.

  The proportion 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 per 100 parts by weight of the first epoxy component (A1). It may be part, more preferably 25 to 50 parts by weight, especially 30 to 45 parts by weight.

  The mixing or reaction may be carried out, for example, at 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 -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, and still more preferably 3 to 12 hours. .

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

  The mixture or the reaction product after evaporation of 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 reactant may be milled as required. The grinding method is not particularly limited, and, for example, a conventional grinding 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, for example, from the range of about 40 to 200 ° C., and the preferable range is 50 to 180 ° C., 60 to 170 ° C., 70 to 160 ° C. in stages. C., in particular 80.degree. To 150.degree. Among them, the softening point of the amine adduct is more preferably 100 to 175 ° C., 110 to 165 ° C., 120 to 155 ° C., 125 to 145 ° C., particularly 130 to 140 ° C. If the softening point is too low, the storage stability may be reduced, and if the softening point is too high, the curability may be reduced. In the present specification and the claims, the softening point can be measured by the method described in the examples below.

In addition, the formation of the amine adduct may be caused by disappearance or shift of the peak derived from the ring opening of the oxirane ring (or epoxy group) of the epoxy component (A) by ¹ H-NMR or the like, or the first epoxy component (A1) (A1) Alternatively, it can be confirmed from the remaining of the peak derived from the 9,9-bisarylfluorene skeleton) and the first amine component (B1). For example, as peaks derived from the ring opening of the oxirane ring (or epoxy group) of the epoxy component (A), the peaks are around 2.6 to 2.8 ppm, 2.8 to 2.9 ppm and 3.1 to 3,4 ppm Often observed in the vicinity, the disappearance or shift of these peaks may confirm the formation of amine adducts.

[Curable composition]
In the amine adduct of the present invention, an amine component (B) that functions as a curing agent for the epoxy resin (epoxy compound) (C), particularly a heterocyclic skeleton containing a plurality of nitrogen atoms of the first amine component (B1), It is stable for a long time at a low temperature (ordinary temperature or storage temperature) even if it is mixed with an epoxy resin probably because the 9,9-bisarylfluorene skeleton of the epoxy component (A1) of 1 is stably included. On the other hand, the amine adduct can rapidly cure the epoxy resin when heated to a predetermined temperature, in order to release the first amine component (B1) with heating. Also, the amine adduct of the present invention functions as a curing agent for 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 (hardeners and / or accelerators) are useful for preparing curable compositions in combination with epoxy resin (epoxy compound) (C).

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

  As a specific 2nd hardening | curing agent and / or a hardening accelerator, the following compounds etc. are mentioned, for example.

  Examples of aliphatic amines include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, pentanediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, and 2,5-dimethylene. Linear or branched alkylene diamines such as 2,5-hexane diamine; Polyalkylene polyamines such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, dipropylene triamine, pentamethyl diethylene triamine, dimethylaminopropylamine, N, N-dialkylaminoalkylamines such as diethylaminopropylamine and dibutylaminopropylamine; bis (2-dimethylaminoethyl) (Poly) ether diamines such as tellurium, diethylene glycol bispropylamine, polypropylene glycol diamine, etc .; N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N N-alkyl-substituted alkylene diamines such as N, N ', N'- tetramethylpropylene diamine; alkanolamines such as dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol; mono-t-alkylamine etc. Linear or branched alkylamines and the like can be mentioned.

  As alicyclic amines, for example, mensene diamine; isophorone diamine; dialkyl cycloalkyl amines such as dimethylcyclohexylamine; 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxa Spiro ring or bridged cyclic amines such as spiro [5.5] undecane; hydrogenated products of aromatic amines described later [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; hydrogenated products of m-xylylenediamine; 1,3,5-tris (amino) (Methyl) benzene, etc.] and the like.

  As the aromatic amines, for example, phenylenediamine (o-phenylenediamine, m-phenylenediamine, p-phenylenediamine); m-xylylenediamine, mono- or tri- (1,5-tris (aminomethyl) benzene etc .; Tri (aminomethyl) benzenes; mono- to tri (dialkylaminomethyl) phenols such as 2- (dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol; bis (4-aminophenyl) Bis (aminophenyl) alkanes such as methane, bis (4-amino-3-methylphenyl) methane, bis (4-amino-3-ethylphenyl) methane and the like; bis (amino) such as bis (4-aminophenyl) sulfone Phenyl) sulfones; phthalocyanines such as phthalocyaninetetramine N'amin like; benzyl methylamine, benzyl dimethylamine, (alpha-methylbenzyl) methylamine, can be exemplified benzyl alkyl amines such as (alpha-methylbenzyl) ethylamine.

  Examples of the heterocyclic amines include amines having a heterocyclic skeleton containing one nitrogen atom [pyridines such as pyridine and picoline; piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, etc. Pyrroles, such as pyrrole, 2H-pyrrole, pyrrolidines, pyrrolines, indolizines, indoles, such as indole, 3H-indole, isoindoles, indolines, isoindolines, quinolizines, quinolines Isoquinolines; carbazoles such as carbazole and 4H-carbazole; phenanthridines; acridines; phenoxazines; phenothiazines; quinuclidines; morpholines such as morpholine, methylmorpholine, ethylmorpholine etc .; first amine An example in the component (B) section Amines having a heterocyclic skeleton containing a plurality of nitrogen atoms [amine components having a monocyclic heterocyclic skeleton (piperazines, pyrazoles, pyrazines, pyrimidines, pyridazines, triazines, pyrazolidines, pyrazolines, Imidazolidines, furazans, imidazolines exemplified as the compound represented by the formula (2a); imidazoles exemplified as the compound represented as the compound represented by the formula (2a), etc. and the like]; having a fused polycyclic heterocyclic skeleton Amine component [indazoles, purines, phthalazines, naphthyridines, quinoxalines, quinazolines, cinnolines, pteridines, perimidines, phenanthrolines, phenazines, triethylenediamine (DABCO), represented by the formula (2b) Cyclic amidines exemplified as compounds (DBU, DBN ), Etc.] and the like.

  As modified amines, for example, polyamines (or amine adducts) where amines are added to epoxy compounds (but excluding the amine adducts of the present invention), Michael addition polyamines, Mannich addition polyamines, thiourea addition polyamines, ketone blocking polyamines ( Ketimine), dicyandiamide, guanidine, organic acid hydrazide, diaminomaleonitrile, amine imide, boron trifluoride-piperidine complex, boron trifluoride-monoethylamine complex and the like.

  As the amide compound, for example, 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, alkylene diamine, polyethylene polyamine etc.) And polyamides (polyaminoamides) obtained by

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

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

  Examples of phenol compounds include, as phenol resin curing agents, aralkyl type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins, novolac type phenol resins such as phenol novolac resins and cresol novolac resins, modified resins thereof, for example Phenolated resin such as epoxidized or butylated novolak type phenolic resin; modified resin such as dicyclopentadiene modified phenolic resin, paraxylene modified phenolic resin, triphenol alkane type phenolic resin, polyfunctional phenolic resin etc It can be illustrated.

  Moreover, as an alcohol type compound, a thiol type compound, and a thioether type compound, a polyol, polymercaptan, a polysulfide etc. are mentioned, for example.

  Examples of urea compounds, thiourea compounds and Lewis acid compounds include butylated urea, butylated melamine, butylated thiourea and boron trifluoride.

  As the phosphorus compound, organic phosphine compounds, for example, alkyl phosphines such as ethyl phosphine and butyl phosphine, primary phosphines such as aryl phosphines such as phenyl phosphine; dialkyl phosphines such as dimethyl phosphine, dipropyl phosphine and methyl ethyl phosphine, Secondary phosphines such as diaryl phosphines such as diphenyl phosphine; trialkyl phosphines such as trimethyl phosphine and triethyl phosphine; and tertiary phosphines such as triaryl phosphines such as triphenyl phosphine.

  As an acid anhydride type compound, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (an hydro trimellitate) And aromatic polycarboxylic acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexenic carboxylic anhydride, 5- ( 2,5-Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, hymic acid anhydride, methyl hymic acid anhydride, endo methylene tetrahydrophthalic anhydride, methyl endo methylene tetraphenyl Alicyclic polycarboxylic acid anhydrides such as phthalic anhydride (methyl nadic acid anhydride); maleic anhydride, tetramethylene maleic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, etc. , Aliphatic polycarboxylic acid anhydrides such as poly (ethyloctadecanedioic acid) anhydride and poly (phenylhexadecanedioic acid) anhydride; Hetic anhydride (chlorendic anhydride), tetrabromophthalic anhydride, tetrachlorophthalic anhydride And the like.

  Examples of onium salt compounds and active silicon compound-aluminum complexes include aryldiazonium salts, diaryliodonium salts, arylsulfonium salts, arylmethylsulfonium salts (benzylmethylsulfonium salts etc.), diarylsulfonium salts, triarylsulfonium salts, Examples include triphenylsilanol-aluminum complex, triphenylmethoxysilane-aluminum complex, silylperoxide-aluminum complex, triphenylsilanol-tris (salicylaldehyde) aluminum complex and the like.

  These curing agents and / or curing accelerators can be used alone or in combination of two or more. The ratio of the amine adduct of the present invention (the first curing agent and / or the curing accelerator) to the second curing agent and / or the 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, still 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 epoxy resin (or epoxy compound) (C), for example, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, unsaturated double bond oxidized and epoxidized It may be an epoxy resin or the like.

  Examples of glycidyl ether type epoxy resins (or compounds) include phenyl glycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, s-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, stearyl Glycidyl ethers of alkane monools such as glycidyl ether; of alkane polyols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiethylene glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol Polyglycidyl ether; hydroquinone, resorcinol, pyrocatechol, furo Polyglycidyl ethers of mononuclear polyhydric phenols such as glucosinol or adducts thereof with alkylene oxides (such as ethylene oxide); dihydroxynaphthalene, biphenols, bisphenols {eg, methylene bisphenol (bisphenol F), methylene bis (ortho cresol), ethylidene bisphenol ( Bisphenol AD), isopropylidene bisphenol (bisphenol A), isopropylidene bis (ortho cresol), 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], etc.}, tris or tetrakis (hydroxyphenyl) ) Alkanes [eg, 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, etc.], bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) ) Ether, bis (hydroxyphenyl) thioether, bis (hydroxyphenyl) sulfone, novolak or novolak resin (phenol novolak, ortho cresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novola And polyglycidyl ethers of polynuclear polyhydric phenols such as terpene phenols or adducts thereof with alkylene oxides (such as ethylene oxide); polyglycidyl ethers of heterocyclic compounds such as triglycidyl isocyanurate; and the like.

  Examples of glycidyl ester type epoxy resins (or compounds) 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, Aliphatic acids such as azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid And glycidyl esters of alicyclic or aromatic polyhydric carboxylic acids, and homopolymers or copolymers of glycidyl (meth) acrylate.

  Examples of glycidyl amine type epoxy resins (or compounds) include N, N-diglycidyl aniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, N, N-diglycidyl toluidine, tetraglycidyl Diaminodiphenylmethane, triglycidyl aminophenol and the like can be exemplified.

  Examples of the epoxy compound in which unsaturated double bond is epoxidized include vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy- Epoxides of cyclic olefins such as 6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, epoxidized styrene-butadiene copolymer and the like And epoxidized conjugated diene polymers of

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

  Preferred epoxy resins are polyglycidyl ethers having a plurality of epoxy groups (or oxirane rings) in the molecule, for example, methylene bisphenol (bisphenol F), methylene bis (ortho cresol), ethylidene bisphenol (bisphenol AD), isopropylidene bisphenol ( Examples thereof include bisphenols such as bisphenol A), isopropylidene bis (orthocresol), and 9,9-bis (hydroxyaryl) fluorene, or polyglycidyl ethers of alkylene oxide (such as ethylene oxide) adducts thereof.

  Furthermore, the epoxy resin is a liquid having fluidity at about room temperature (for example, 10 to 30 ° C., preferably 15 to 20 ° C.), a semi-solid or solid of low flowability, high viscosity (or high viscosity), The epoxy resin is generally fluid at a temperature (mixing temperature or processing temperature) to be mixed with the amine adduct, and may be a liquid epoxy resin which 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 according to the curing method etc., and is usually a ratio of the degree used as the curing agent and / or the curing accelerator. May be

  The representative proportion 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) is typically based on 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, especially 15 to It may be 25 parts by weight.

  The proportion of the amine adduct (first curing agent and / or curing accelerator) of the present invention is typically, for example, about 0.1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin (C). And 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 preferably 15 to 25 parts by weight.

  The amine adduct of the present invention is highly compatible with the epoxy resin (C), probably because it contains a 9,9-bisarylfluorene skeleton as the first epoxy component (A1), and the dispersion to the non-soluble additive is also possible. Sex is also high. Therefore, even if the curable composition contains an amine adduct, the characteristics of the cured product are not adversely affected.

  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), a homogenizer, a mixer or a mixer, a kneader (a kneader, a roll, an extruder, etc.) Machine or the like, may be prepared by mixing or kneading (for example, melt-kneading, etc.) at a temperature and time at which a curing reaction (or gelation) does not occur or can be suppressed. Also, mixing or kneading may be performed under heating (for example, about 50 to 100 ° C.), or mixing or kneading is performed 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 | mix in presence of the solvent illustrated to the term of the manufacturing method of the said amine adduct.

  In the curable composition of the present invention, various additives, for example, a silane coupling agent, a plasticizer, an organic solvent, a reactive diluent, a filler, a reinforcing agent, a coloring agent (pigment, etc.), if necessary. Flame retardants, mold release agents, stabilizers (antioxidants, UV absorbers, etc.), extenders, thickeners, etc. may be added.

  As a silane coupling agent, for example, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyl tri Examples include ethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane.

  Examples of the plasticizer include phthalic acid plasticizers, alkanedicarboxylic acid plasticizers such as adipic acid, phosphoric acid ester plasticizers, polyester plasticizers, and the like.

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

  As the filler, for example, calcium bicarbonate, light calcium carbonate, natural silica, synthetic silica, fused silica, titanium oxide, barium sulfate, zinc oxide, aluminum hydroxide, magnesium hydroxide, talc, kaolin, clay, mica, woca The last night, potassium titanate, aluminum borate, sepiolite, sonotolite etc. can be illustrated.

  The colorant may be any of black pigments such as carbon black, white pigments such as titanium oxide, yellow pigments, orange pigments, red pigments, purple pigments, blue pigments, green pigments and the like.

  As the reinforcing agent, for example, organic fibers [natural fibers such as cellulose fibers (cellulose nanofibers, etc.), polyalkylene arylate fibers, synthetic fibers such as vinylon fibers, aramid fibers, etc.], inorganic fibers [glass fibers, carbon fibers, etc.] Can be illustrated.

  Examples of the flame retardant include hexabromocyclodecane, bis (dibromopropyl) tetrabromobisphenol A, tris (dibromopropyl) isocyanurate, tris (tribromoneopentyl) phosphate, decabromodiphenyl oxide, bis (pentabromo) phenylethane Tris (tribromophenoxy) triazine, ethylene bistetrabromophthalimide, polybromophenylindane, brominated polystyrene, tetrabromobisphenol A polycarbonate, brominated phenylene ethylene oxide, brominated polypentabromobenzyl acrylate etc., triphenyl phosphate, triphenyl phosphate Cresyl phosphate, trixinyl phosphate, cresyl diphenyl phosphate, xylyl diphenyl phosphate, Zyl bis (di-2,6-xylenyl) phosphate, 2-ethylhexyl diphenyl 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, diethyl-N, N-bis (2-hydroxyethyl) amino methylphosphonate and the like Phosphates, anion oxalic acid treated aluminum hydroxide, nitrated aluminum hydroxide, high temperature hydrothermally treated aluminum hydroxide, tin acid surface treated hydrated metal compound , Surface treated magnesium hydroxide a nickel compound, a silicone polymer surface treatment of magnesium hydroxide, procolipase bytes, multilayer surface-treated hydrated metal compound, such as a cationic polymer treatment magnesium hydroxide can be exemplified.

  Examples of the release agent include fatty acid-based release agents (higher fatty acids, higher fatty acid esters, higher fatty acid calcium and the like), waxes (for example, carnauba wax and polyethylene waxes), silicone oils and the like.

  Furthermore, the curable composition of the present invention may, if necessary, contain an elastomer (or elastomer modifier), for example, acrylonitrile butadiene rubber (NBR), liquid polybutadiene, polybutadiene (butadiene rubber, BR), in addition to epoxy resin. Chloroprene rubber, silicone rubber, modified silicone rubber, crosslinked NBR, crosslinked BR, acrylic rubber (including core-shell acrylic rubber), urethane rubber, polyester elastomer, functional NBR liquid, liquid polyester, liquid polysulfide, urethane prepolymer, etc. May be included.

  If necessary, in addition to epoxy resins, other resins, for example, olefin resins (such as high density polyethylene and polypropylene), styrene resins (such as polystyrene), acrylic resins (such as polymethyl methacrylate), and halogen containing Resin (polyvinyl chloride etc.), polyester resin (polyethylene terephthalate etc.), polycarbonate resin, polyamide resin (nylon 6, nylon 66 etc.), polyurethane resin, silicone resin etc. may be contained, and the resin And engineering plastics (polybutylene terephthalate, polyethylene naphthalate, bisphenol A polycarbonate, polyacetal, polysulfone, polyether sulfone, polyether imide, polyether ether ketone, etc.) .

  These additives, elastomers, and resins may be used alone or in combination of two or more. The proportions of these additives, elastomers and / or resins are not particularly limited, and can be appropriately selected according to the application.

  The present invention also encompasses a cured product obtained by curing the curable composition. Such a cured product can be prepared by heating and curing the curable composition according to the application of the curable composition. For example, the curable composition may be applied to a substrate and cured, or may be injected or sealed in a predetermined portion and cured, or may be cast and cured, a substrate (fiber (fiber) The base material may be impregnated to prepare a prepreg, and this prepreg may be laminated by a method such as superposition or winding, molded 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. The heating temperature may be, for example, 70 to 150 ° C., preferably 80 to 120 ° C., since the curable composition of the present invention can be cured quickly even at a relatively low temperature.

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

  Although the curable composition of the present invention can be rapidly cured at low temperature, the storage stability (or storage stability) is unexpectedly high, and the pot life is, for example, 1 day or more (eg, 1 day to 1 day) Year), preferably 2 days or more (e.g. 3 to 180 days), more preferably 5 days or more (e.g. 7 to 120 days, especially 10 days or more (e.g. 15 to 90 days).

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

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

( ¹ H-NMR)
¹ H-NMR was prepared 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 Buchi Co., Ltd.

<Synthesis of amine adduct>
Example 1 Amine adduct of 9,9-bis (4-glycidyloxyphenyl) fluorene and 2-methylimidazole 2-Methylimidazole ("2MZ-H" manufactured by Shikoku Kasei Kogyo Co., Ltd., 8.2 g, 0. 0). A solution of 9,9-bis (4-glycidyloxyphenyl) fluorene (23.0 g, 0.05 mol, manufactured by Osaka Gas Chemicals Co., Ltd., 23.0 g, 0.05 mol) in a solution of 10 mol of methyl ethyl ketone (150 g) at 80 ° C. Under stirring over 160 minutes. After 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 give the title amine adduct as a pale yellow powder (yield 22.8 g, softening point 81.0 ° C.). The 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, peaks corresponding to the oxirane ring exist near 2.7 ppm, 2.9 ppm and 3.3 ppm. These peaks have disappeared in the ¹ H-NMR spectrum of the amine adduct shown in FIG. Moreover, in ¹ H-NMR of 2MZ-H shown in FIG. 7, a peak corresponding to a methyl group is present around 2.4 ppm, and this peak is also confirmed in the spectrum of the amine adduct shown in FIG. 1. From these facts, the formation of an amine adduct consisting of 9,9-bis (4-glycidyloxyphenyl) fluorene and 2-methylimidazole was confirmed.

(Example 2) Amine adduct of 9,9-bis (4-glycidyloxyphenyl) fluorene and 2-ethyl-4-methylimidazole 2-ethyl-4-methylimidazole ("2E4MZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.) A solution of 11.0 g, 0.10 mol) in methyl ethyl ketone (150 g), 9,9-bis (4-glycidyloxyphenyl) fluorene (23.0 g, 0.05 mol) in methyl ethyl ketone (150 g) It was added dropwise with stirring over a minute. After 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 give the title amine adduct as a pale yellow powder (yield 23.0 g, softening point 81.2 ° C.). The 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, peaks corresponding to the oxirane ring exist near 2.7 ppm, 2.9 ppm and 3.3 ppm. In the spectrum of the amine adduct shown in FIG. 2, these peaks disappear. Further, in the ¹ H-NMR of 2-ethyl-4-methylimidazole shown in FIG. 8, peaks corresponding to a methyl group or an ethyl group are present in the vicinity of 1.3 ppm, 2.2 ppm, and 2.7 ppm. These peaks are also confirmed in the spectrum of the amine adduct shown in FIG. From these facts, formation of an amine adduct consisting of 9,9-bis (4-glycidyloxyphenyl) fluorene and 2-ethyl-4-methylimidazole was confirmed.

EXAMPLE 3 Amine adduct of 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene and 2-methylimidazole 2MZ-H (8.2 g, 0.10 mol) in methyl ethyl ketone (150 g) solution 9 While stirring methyl ethyl ketone (150 g) solution of 1,9-bis (6-glycidyloxy-2-naphthyl) fluorene (28.1 g, 0.05 mol, manufactured by Osaka Gas Chemical Co., Ltd.) over 150 minutes at 80 ° C. It dripped. After 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 pale yellow powder (yield 25.5 g, softening point 144.8 ° C.). The 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 oxirane ring are around 2.8 ppm, 2.9 ppm and 3.4 ppm. Although present, these peaks have disappeared in the spectrum of the amine adduct shown in FIG. Also, in ¹ H-NMR of 2-methylimidazole shown in FIG. 7, a peak corresponding to a methyl group is present around 2.4 ppm, and this peak is also confirmed in the spectrum of the amine adduct shown in FIG. . From these facts, formation of an amine adduct consisting of 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene and 2-methylimidazole was confirmed.

Example 4 Amine adduct of 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene and 2-ethyl-4-methylimidazole 2E4 MZ (11.0 g, 0.10 mol) in methyl ethyl ketone (150 g) solution A methyl ethyl ketone (150 g) solution of 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene (28.1 g, 0.05 mol) was added dropwise with stirring at 80 ° C. over 140 minutes. After 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 give the title amine adduct as a pale yellow powder (yield 34.5 g, softening point 133.4 ° C.). The 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 oxirane ring are around 2.8 ppm, 2.9 ppm and 3.4 ppm. Although present, these peaks have disappeared in the spectrum of the amine adduct shown in FIG. Further, in the ¹ H-NMR of 2-ethyl-4-methylimidazole shown in FIG. 8, peaks corresponding to a methyl group or an ethyl group are present in the vicinity of 1.3 ppm, 2.2 ppm, and 2.7 ppm. These peaks are also confirmed in the spectrum of the amine adduct shown in FIG. From these facts, formation of an amine adduct consisting of 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene and 2-ethyl-4-methylimidazole was confirmed.

<Preparation of a curable composition and its characteristics>
(Example 5)
20 parts by weight of the amine adduct obtained in Example 1 is added to 100 parts by weight of liquid epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation), and a homogenizer ("Ace Homogenizer AM-10" manufactured by Nippon Seiki Co., Ltd.) The composition was stirred at a rotational speed of 15000 rpm for 15 minutes while cooling the container with ice water to prepare a curable composition.

(Examples 6 to 8)
Instead of the amine adduct obtained in Example 1, in Example 6, the amine adduct obtained in Example 2 is used. In Example 7, the amine adduct obtained in Example 3 is obtained. 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)
3 parts by weight of 2MZ-H is added to 100 parts by weight of liquid epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation), and the container is made of ice water using a homogenizer ("Ace Homogenizer AM-10" manufactured by Nippon Seiki Co., Ltd.) The composition was stirred at a rotational speed of 15000 rpm for 15 minutes while cooling to prepare a curable composition.

(Comparative example 2)
3 parts by weight of 2E4MZ was added to 100 parts by weight of liquid epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation), and the container was cooled with ice water using a homogenizer ("Ace Homogenizer AM-10" manufactured by Nippon Seiki Co., Ltd.) The mixture was stirred for 15 minutes at a rotation number of 15000 rpm to prepare a curable composition.

(Measurement of gelation time)
A glass sample tube and an aluminum block having a hole of the same diameter as the outer diameter of the sample tube were prepared. The aluminum block was preheated to a predetermined temperature on a hot plate. The sample was taken into a sample tube, and the sample tube was inserted into the hole of the aluminum block. Stir in the sample tube with a spatula at a rate of about 60 times per minute (in a circular manner), and let the end point be the point at which the sample becomes gelled and no longer adheres to the spatula, or the point where stringing does not occur. 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" as described in Table 1 shows that it gelled while the temperature was raised to a predetermined temperature and the gel phase and the liquid phase were separated.

(Storage stability of curable composition)
The curable composition is stored at 25 ° C. in a closed container, and the viscosity (mPa ··· The s / 25 ° C. was measured. The time which showed twice the viscosity from the initial viscosity (the viscosity measured immediately after preparation) was taken 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 a low temperature (80 to 120 ° C.) and exhibits excellent storage stability.

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

Claims (15)

  An amine adduct formed of 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 an amine component (B) Amine adducts comprising an amine component (B1) having a heterocyclic skeleton containing multiple nitrogen atoms). The epoxy component (A1) has the following formula (1)

(Wherein, Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents nonreactive to the epoxy group, R ³ is a hydrogen atom or a methyl group, and A ¹ is a linear or branched alkylene 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, comprising an epoxy component represented by or a multimer thereof. In formula (1), Z is a benzene ring, naphthalene ring or 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 component (B1) is represented by the following formula (2)

(Wherein 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 to} R ⁷ represent a hydrogen atom, a halogen atom, a nitro group , An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an acyl group, and the alkyl group may have a hydroxyl group, and R ⁴ and R ⁵ are bonded to each other to form an adjacent nitrogen atom and carbon The ring may be formed with the atom; q is 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 adduct according to any one of claims 1 to 4, which comprises an amine component represented by The amine component (B1) has the following formula (2a) and / or (2b)

(Wherein, r represents an integer of 0 to 5; R ^{4 to} R ⁷ and double lines of a solid line and a broken line are the same as in claim 5)
The amine adduct according to any one of claims 1 to 5, comprising an amine component represented by   The amine adduct according to any one of claims 1 to 6, wherein the proportion of the amine component (B1) is 0.3 to 3 moles relative to 1 mole of the epoxy group of the epoxy component (A1).   The amine adduct according to any one of claims 1 to 7, which has a softening point of 50 to 180 ° C.   The amine adduct according to any one of claims 1 to 8, which is a curing agent and / or a curing accelerator for curing the epoxy resin (C).   The method of manufacturing the amine adduct according to any one of claims 1 to 9 by mixing an epoxy component (A) containing an epoxy component (A1) and an amine component (B) containing an amine component (B1).   The curable composition containing the amine adduct in any one of Claims 1-9, and an epoxy resin (C).   The curable composition according to claim 11, wherein the epoxy resin (C) is a liquid epoxy resin.   The curable composition according to claim 11 or 12, which comprises the amine adduct according to any one of claims 1 to 9 in a proportion of 1 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin (C).   The hardened | cured material which the curable composition in any one of Claims 11-13 hardened | cured.   A method for producing a cured product according to claim 14, wherein the curable composition according to any one of claims 11 to 13 is heated and cured.

Images