CN109563017A

CN109563017A - Inclusion compound and preparation method thereof with and application thereof

Info

Publication number: CN109563017A
Application number: CN201780048521.6A
Authority: CN
Inventors: 山形宪; 山形宪一; 冢田慎郎; 冢田慎一郎; 安田祐郎; 安田祐一郎
Original assignee: Osaka Gas Chemicals Co Ltd
Current assignee: Osaka Gas Chemicals Co Ltd
Priority date: 2016-08-04
Filing date: 2017-07-31
Publication date: 2019-04-02
Also published as: TW201835146A; JP6985273B2; KR20190039165A; JPWO2018025799A1; WO2018025799A1

Abstract

Inclusion compound of the invention includes that formula (1) is represented, has 9 with phenolic hydroxyl, the compound of the bis- aryl fluorene skeletons of 9- includes that formula (2) is represented, the compound with 5 or 6 circle heterocyclic rings or its annelated heterocycles containing multiple nitrogen-atoms is as object as main body.Above-mentioned inclusion compound is useful as the curing agent and/or curing accelerator of epoxy resin.In formula, Ar¹、Ar²、Z¹And Z²Indicate monocyclic or fused polycyclic aromatic hydrocarbon ring；R¹、R²、R³And R⁴Indicate substituent group；N1 and n2 indicate 0~4 integer, among n1 and n2 at least one be 1 or more integer；M1, m2, p1 and p2 respectively it is identical or different indicate 0~4 integer；R⁵Indicate hydrogen atom, alkyl, cyano ethyl, triazine-alkyl etc.；R⁶~R⁸Indicate hydrogen atom, alkyl, aryl etc., R⁵With R⁶Can be bonding to each other and form ring；Q indicates 0 or 1~3 integer；The doublet of solid line and dotted line indicates singly-bound or double bond.

Description

Inclusion compound and preparation method thereof with and application thereof

Technical field

The present invention relates to novel inclusion compound using fluorene compound as main body and preparation method thereof, with and application thereof (curing agent and/or curing accelerator, solidification compound and its solidfied material).

Background technique

9,9- bis- arylfluorene compounds since heat resistance or optical characteristics (transparency, refractive index etc.) are excellent, by with Make the raw material of electronic material or optical material.For example, being described in Japanese Unexamined Patent Publication 2013-203695 bulletin (patent document 1): Epoxide with 9,9- bis- aryl fluorene skeletons and triazine skeleton has high-fire resistance and the dissolubility to organic solvent, It describes in Japanese Unexamined Patent Publication 2013-64119 bulletin (patent document 2): with the specific diol component with fluorene skeleton and having Polyester resin of the dicarboxylic acid component of fluorene skeleton as polymeric composition has high refractive index and low birefringence.

9,9- bis- arylfluorene compounds other than above-mentioned characteristic, specific volume from molecular structure (bulkiness, Bulkiness) have the function of including small molecule.For example, in Japanese Unexamined Patent Publication 2009-234998 bulletin (patent document 3) Describe: with the bis- arylfluorene compounds of 9,9- as host compound, with alcohols, ethers, ketone, esters, amides, nitrile, Or inclusion compound of the hydro carbons as guest compound, it describes in the embodiment of the document: double cresols fluorenes and leaf-alcohol (leafiness アルコー Le), 1- adamantanol, isoamyl acetate, acetone, isopropanol, diisopropyl ether etc. inclusion compound.Japanese Unexamined Patent Publication It is described in 6-166646 bulletin (patent document 4): with 1,1,2,2- tetra- (3,5- dimethyl -4- hydroxy phenyl) ethane etc. Inclusion compound of four phenol of alkane as host compound, can also example pyrrole other than alcohols etc. as guest compound The monocyclic nitrogen-containing heterocycle compound of pyridine, imidazoles etc. describes in embodiment: using diethylamine, triethylamine etc. as objectifying The example for closing object.Moreover, being proposed in Japanese Unexamined Patent Publication 11-71449 bulletin (patent document 5): will be with 1,1,2,2- tetra- (4- Hydroxy phenyl) ethane etc. four phenol of alkane as host compound and using imidazoles as the inclusion compound of guest compound Curing agent or curing accelerator as epoxy resin.

Such inclusion compound can make guest compound not volatilize, while improve chemical stability, and powder is made End and promoted operability.Furthermore it is possible to using guest compound release have temperature dependency responsive to temperature type material, It is used in the wide range of areas of separation material using selection separation property etc..However, since guest compound is restricted, packet The utilization of polymerisable compounds is limited.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2013-203695 bulletin (claims, embodiment)；

Patent document 2: Japanese Unexamined Patent Publication 2013-64119 bulletin (claims, embodiment)；

Patent document 3: Japanese Unexamined Patent Publication 2009-234998 bulletin (claims, embodiment)；

Patent document 4: Japanese Unexamined Patent Publication 6-166646 bulletin (claims, [0009], embodiment)；

Patent document 5: Japanese Unexamined Patent Publication 11-71449 bulletin (claims, embodiment).

Summary of the invention

Problems to be solved by the invention

Therefore, the object of the present invention is to provide comprising fluorene compound as the novel inclusion compound of main body and its preparation Method, with and application thereof.

Other objects of the present invention are, provide useful as the curing agent of epoxy resin and/or curing accelerator etc. Inclusion compound and preparation method thereof, with and application thereof.

Another other purposes of the invention are, provide have under the physical property for not reducing solidfied material high storage stability, And it can promptly cured solidification compound and its solidfied material by heating.

Means for solving the problems

The present inventor has made intensive studies to realize the above subject, as a result, it has been found that: have 9,9- with phenolic hydroxyl The compound of double aryl fluorene skeletons forms inclusion compound with the heterocyclic compound with multiple nitrogen-atoms, if by the inclusion chemical combination Object is used as the curing agent of epoxy resin, then storage stability is high, and by heating promptly cured epoxy resin, to complete The present invention.

That is, inclusion compound of the invention includes that compound represented by following formula (1) as host compound and includes With containing multiple nitrogen-atoms (for example, basic nitrogen atom) as ring atom 5 or 6 circle heterocyclic rings (for example, aliphatic or aromatics is miscellaneous Ring) or its annelated heterocycles compound as guest compound.

[chemical formula 1]

In formula, Ar¹、Ar²、Z¹And Z²Respective identical or different expression monocyclic aromatic hydrocarbon ring or polycycle aromatic hydrocarbon ring；R¹、R²、R³With R⁴Respective identical or different expression substituent group；N1 and n2 is identical or different indicate 0~4 integer, at least one among n1 and n2 It is at least 1 or more integer；M1, m2, p1 and p2 respectively it is identical or different indicate 0~4 integer.

In above-mentioned formula (1), ring Ar¹And Ar²Identical or different is phenyl ring or naphthalene nucleus；Ring Z¹And Z²It is identical or different to be Phenyl ring or naphthalene nucleus；R¹And R²It is identical or different for alkyl (alkyl, naphthenic base, aryl, aralkyl), alkoxy, cycloalkyloxy, Aryloxy group, aralkyl oxy, acyl group, alkoxy carbonyl, halogen atom, nitro, cyano or substituted-amino；R³And R⁴It is identical or different It can be alkyl (alkyl, naphthenic base, aryl, aralkyl), alkoxy, halogen atom, nitro, cyano or substituted-amino；N1 and n2 phase Same or difference can be 1~3 integer；The identical or different integer for being 0~2 of m1 and m2；P1 and p2 it is identical or different for 0~ 2 integer.

About aforementioned body compound, in formula (1), ring Ar¹And Ar²For phenyl ring；Ring Z¹And Z²For phenyl ring or naphthalene nucleus；N1 and N2 is 1 or 2；R¹And R²Identical or different is C_1-4Alkyl or C_6-10The integer that aryl, m1 and m2 are 0~2；The feelings that p1 and p2 is 0 Condition is more, in formula (1), R¹And R²For methyl or phenyl, the case where m1 and m2 are 1 or 2, is more.

Guest compound may include compound represented by following formula (2).

[chemical formula 2]

In formula, R⁵Indicate hydrogen atom, alkyl, naphthenic base, aryl, aralkyl, cyano ethyl or triazine-alkyl；R⁶~R⁸It indicates Hydrogen atom, halogen atom, nitro, alkyl, naphthenic base, aryl, aralkyl or acyl group, abovementioned alkyl can have hydroxyl, R⁵With R⁶It can It is bonding to each other and be formed together ring with adjacent nitrogen-atoms and carbon atom；Q indicates 0 or 1~3 integer；Pair of solid line and dotted line Weight line indicates singly-bound or double bond.

Above-mentioned guest compound may include compound represented by following formula (2a) and/or (2b).

[chemical formula 3]

In formula, r indicates 0~5 integer；R⁵~R⁸It is same as above with the doublet of solid line and dotted line.

In above-mentioned inclusion compound, about the ratio of guest compound, relative to 1 mole of host compound, can for 0.5~ 5 moles or so.

Above-mentioned inclusion compound can be by by compound represented by above-mentioned formula (1) and with containing multiple nitrogen-atoms (alkali Property nitrogen-atoms etc.) it is mixed as 5 or 6 circle heterocyclic rings (aliphatic series or aromatic heterocycle etc.) of ring atom or the compound of its annelated heterocycles It closes to prepare.

Above-mentioned heterocyclic compound contained in such inclusion compound, can be with due to secondary amino group or tertiary amino It is functioned as the curing agent or curing accelerator for making epoxy resin cure.Therefore, the invention also includes: comprising above-mentioned The curing agent or curing accelerator of inclusion compound；Solidification compound comprising above-mentioned inclusion compound and epoxy resin.It should In solidification compound, epoxy resin can be liquid-state epoxy resin.It should be noted that the usage amount of inclusion compound, relative to 100 parts by weight of epoxy resin can be 0.1~25 parts by weight or so.In addition, above-mentioned solidification compound can further include and be selected from At least one compound (the 2nd curing agent) of phenolic compound and anhydride compound.

The invention also includes: by solidfied material obtained by the solidification of above-mentioned solidification compound；Keep above-mentioned solidification compound solid The method for changing (for example, heat and solidify) to prepare solidfied material.

In this specification, sometimes by the above-mentioned compound with 5 or 6 circle heterocyclic rings or its annelated heterocycles containing multiple nitrogen-atoms It is abbreviated as " heterocyclic compound ".In addition, as described above, above-mentioned heterocyclic compound can be used as use with secondary amino group or tertiary amino It is functioned in the curing agent or curing accelerator for making epoxy resin cure.Therefore, sometimes by " curing agent or curing accelerator " It is abbreviated as " curing agent ".In addition, " inclusion compound " refers to, it is not limited to compound represented by above-mentioned formula (1) and above-mentioned heterocycle The inclusion compound of compound, also comprising by the compound represented by above-mentioned formula (1) phenolic hydroxyl and alkali be formed by salt.

Invention effect

The present invention can provide, and in the space formed by the fluorene compound with the bis- aryl fluorene skeletons of 9,9-, can will have more The heterocyclic compound of a nitrogen-atoms is incorporated to the novel inclusion compound of (intake, Qu り Write む) as guest compound.The inclusion Curing agent of the compound as epoxy resin etc. is useful.In addition, above-mentioned inclusion compound in composition epoxy resin, is not dropping There is high storage stability under the physical property of low solidfied material, and can promptly be solidified by heating.

Detailed description of the invention

[Fig. 1] is the inclusion compound of embodiment 1¹H-NMR spectrum.

[Fig. 2] is the TG-DTA chart of the inclusion compound of embodiment 1, and solid line indicates that TG, dotted line indicate DTA.

[Fig. 3] is the inclusion compound of embodiment 2¹H-NMR spectrum.

[Fig. 4] is the TG-DTA chart of the inclusion compound of embodiment 2, and solid line indicates that TG, dotted line indicate DTA.

[Fig. 5] is the inclusion compound of embodiment 3¹H-NMR spectrum.

[Fig. 6] is the TG-DTA chart of the inclusion compound of embodiment 3, and solid line indicates that TG, dotted line indicate DTA.

[Fig. 7] is the inclusion compound of embodiment 4¹H-NMR spectrum.

[Fig. 8] is the TG-DTA chart of the inclusion compound of embodiment 4, and solid line indicates that TG, dotted line indicate DTA.

[Fig. 9] is the inclusion compound of embodiment 5¹H-NMR spectrum.

[Figure 10] is the TG-DTA chart of the inclusion compound of embodiment 5, and solid line indicates that TG, dotted line indicate DTA.

[Figure 11] is the inclusion compound of embodiment 6¹H-NMR spectrum.

[Figure 12] is the TG-DTA chart of the inclusion compound of embodiment 6, and solid line indicates that TG, dotted line indicate DTA.

[Figure 13] is the DSC chart of the solidification compound of embodiment 7.

[Figure 14] is the DSC chart of the solidification compound of embodiment 8.

[Figure 15] is the DSC chart of the solidification compound of embodiment 9.

The DSC chart of the solidification compound of [Figure 16] comparative example 1.

Specific embodiment

(inclusion compound)

In inclusion compound, incorporate the small molecule as object in the space formed by host molecule, object independent of Covalent bond and steadily exist.

(host compound)

In inclusion compound of the invention, host compound includes compound represented by formula (1).

[chemical formula 4]

In above-mentioned formula (1), as ring Ar¹And Ar²Represented monocyclic aromatic hydrocarbon ring (monocyclic aromatics hydrocarbon ring), can example Phenyl ring etc..As polycycle aromatic hydrocarbon ring, can example fused polycyclic aromatic hydrocarbon ring (fused polycyclic hydrocarbon ring), as fused polycyclic Aromatic hydrocarbon ring, such as can enumerate: fused bicyclic formula aromatic hydrocarbons is (for example, the fused bicyclic formula C of naphthalene etc._10-16Aromatic hydrocarbons) ring, fused tricyclic formula Condensed two~tetra- ring type aromatic hydrocarbon rings of aromatic hydrocarbons (for example, anthracene, phenanthrene etc.) ring etc. etc..Preferred fused polycyclic aromatic hydrocarbon ring be naphthalene nucleus, Anthracene nucleus etc., especially naphthalene nucleus.

Preferred ring Ar¹And Ar²For phenyl ring or naphthalene nucleus (for example, phenyl ring).Ring Ar¹And Ar²It may be the same or different.For example, ring Ar¹And Ar²Both can be phenyl ring or naphthalene nucleus, can also be ring Ar¹For phenyl ring, ring Ar²For naphthalene nucleus.Ring Ar¹For phenyl ring, ring Ar² For the compound of naphthalene nucleus, benzo [a] fluorene compound, benzo [b] fluorene compound, benzo [c] fluorene compound can be formed.

As ring Z¹And Z²Represented monocyclic aromatic hydrocarbon ring, can example phenyl ring etc..Comprising condensed more in polycycle aromatic hydrocarbon ring Ring type aromatic hydrocarbon ring (fused polycyclic hydrocarbon ring), ring set aromatic hydrocarbon ring (ring set aromatics hydrocarbon ring) etc..As fused polycyclic aromatic hydrocarbons Ring, can example and above-mentioned ring Ar¹And Ar²Same condensed aromatics ring, such as can example naphthalene nucleus, anthracene nucleus etc..Preferred fused polycycle Formula aromatic hydrocarbon ring is naphthalene nucleus.Preferred ring Z¹And Z²For phenyl ring or naphthalene nucleus, phenyl ring generally can be.

It, can example as ring set aromatic hydrocarbon ring (ring set aromatics hydrocarbon ring aromatic hydrocarbon ring): biaryl hydrocarbon ring, such as cyclohexyl biphenyl, connection The connection C of naphthalene nucleus, phenyl naphthalene nucleus (1- phenyl naphthalene nucleus, 2- phenyl naphthalene nucleus etc.) etc._6-12Aromatic hydrocarbon ring, three aromatic hydrocarbon rings, such as Sanya phenyl ring Deng three C_6-12Aromatic hydrocarbon ring etc..As preferred ring set aromatic hydrocarbon ring, connection C can be enumerated_6-10Aromatic hydrocarbon ring, especially cyclohexyl biphenyl etc..

Substituent R¹、R²、R³And R⁴Type, be not particularly limited as long as the inclusion for not undermining guest compound, can be with From halogen atom, nitro, cyano, alkyl (alkyl, naphthenic base, aryl, aralkyl etc.), base-OR¹⁰, base-SR¹⁰, base-COOR¹⁰、 Base-COR¹⁰, base-CON (R¹⁰)₂(R¹⁰Indicate hydrogen atom, alkyl, naphthenic base, aryl, aralkyl etc.) etc. wide scope in select.

As R¹And R², such as can example: alkyl is (for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tertiary fourth The straight-chain or branch chain C of base etc._1-10Alkyl, preferably straight-chain or branch chain C_1-6Alkyl, further preferably straight chain Shape or branch chain C_1-4Alkyl etc.)；Naphthenic base is (for example, the C of cyclopenta, cyclohexyl etc._5-10Naphthenic base, preferably C_5-8Cycloalkanes Base, further preferably C_5-6Naphthenic base etc.)；Aryl (the C of phenyl, xenyl, naphthalene etc._6-12Aryl etc.)；Aralkyl (benzyl, The C of phenethyl etc._6-10Aryl-C_1-4Alkyl etc.)；Alkoxy is (for example, methoxyl group, ethyoxyl, propoxyl group, n-butoxy, isobutyl The straight-chain or branch chain C of oxygroup, tert-butoxy etc._1-10Alkoxy is (for example, C_1-8Alkoxy, preferably C_1-6Alkoxy) Deng)；Cycloalkyloxy is (for example, the C of cyclohexyl oxygroup etc._5-10Cycloalkyloxy etc.)；Aryloxy group is (for example, the C of phenoxy group etc._6-10Fragrant oxygen Base etc.)；Aralkyl oxy is (for example, the C of benzyloxy etc._6-10Aryl-C_1-4Alkoxy etc.)；Alkane sulphur corresponding to above-mentioned alkoxy Base (C_1-10Alkylthio group)；Cycloalkylthio (C corresponding to above-mentioned cycloalkyloxy_5-10Cycloalkylthio)；Virtue corresponding to above-mentioned aryloxy group Sulfenyl (C_6-10Arylthio)；Aromatic alkylthio (C corresponding to above-mentioned aralkyl_6-10Aryl-C_1-4Alkylthio group)；Acyl group is (for example, acetyl The C of base etc._1-6Acyl group etc.)；Carboxyl；Alkoxy carbonyl is (for example, the C of methoxycarbonyl etc._1-4Alkoxy-carbonyl etc.)；Halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom)；Nitro；Cyano；[dialkyl amido is (for example, dimethyl for substituted-amino Two C of amino etc._1-4Alkyl amino etc.), dialkylcarbonyl groups amino is (for example, the two (C of diacetyl amino etc._1-4Alkyl-carbonyl) Amino etc.)] etc..It should be noted that above-mentioned alkyl (alkyl, naphthenic base, aryl, aralkyl etc.) can have substituent group (alkyl, halogen Atom etc.), for example, alkyl phenyl (aminomethyl phenyl (toluene) base, 3,5-dimethylphenyl (dimethylbenzene) base etc.) can be formed.

These substituent Rs¹And R²Among, preferred substituent R¹And R²For alkoxy (straight-chain or branch chain C_1-6Alkane Oxygroup), alkyl (straight-chain or branch chain C_1-6Alkyl), aryl (C_6-12Aryl) etc..Especially preferred substituent R¹And R²For C_1-4Alkyl (the straight-chain or branch chain C of methyl etc._1-4Alkyl) or the aryl (C of phenyl etc._6-12Aryl).It should be noted that Substituent R¹And R²When for aryl, substituent R¹And R²It can be with ring Z¹And/or Z²It is formed together above-mentioned ring set aromatic hydrocarbon ring.These take For base R¹And R²Type, in identical or different ring Z¹And/or Z²In, it may be the same or different.

In the present invention, among substitution the number n1 and n2 of hydroxyl (phenolic hydroxyl OH) at least one be at least 1 or more integer. That is, in host compound of the invention, ring Z¹And/or ring Z²With phenolic hydroxyl.N1 and n2 can for 0~4 integer, preferably 1 ~3 integer, further preferably 1 or 2 (for example, 1).N1 and n2 is in ring Z¹And Z²In may be the same or different.

The position of substitution of hydroxyl (phenolic hydroxyl OH) is not particularly limited, can be in ring Z¹And/or Z²Appropriate location take Generation, for example, ring Z¹And Z²It can be 2~6- any positions when for phenyl ring, can be 2-, 3-, 4- etc..In addition, in ring Z¹And Z²In the case where for naphthalene nucleus, be naphthalene the position 5~8- the case where it is more, for example, relative to ring Ar is included¹And Ar²It is condensed Ring (for example, position 9- etc. of fluorenes), the position 1- of naphthalene nucleus or 2- substitutions (with the substitution of the relationship of 1- naphthalene or 2- naphthalene), relative to this The position of substitution is replaced with 1,5-, 2,6- etc. relationships (especially in the case where n1 and n2 is 1, with 2,6- relationships) The case where it is more.In addition, the position of substitution is not particularly limited in the case where n1 and n2 is 2 or more.In addition, in ring set virtue Hydrocarbon ring Z¹And/or Z²In, the position of substitution of hydroxyl is not particularly limited, for example, can with include ring Ar¹And Ar²Fused rings Replace in the aromatic hydrocarbon ring and/or the aromatic hydrocarbon ring adjacent with the aromatic hydrocarbon ring of (for example, position 9- etc. of fluorenes) bonding.For example, cyclohexyl biphenyl Z¹ And Z²The position 3- or 4- can with include ring Ar¹And Ar²Fused rings (for example, position 9- etc. of fluorenes) bonding, cyclohexyl biphenyl Z¹And/or Z² The position 3- and include ring Ar¹And Ar²Fused rings (for example, position 9- etc. of fluorenes) bonding when, with hydroxyl substituent group substitution position Setting can be for 2-, and 4~6-, any positions of 2 '~6 '-positions usually can be in 4-, 5-, 6-, 3 '-, 4 '-positions, preferably in 4-, 6- Position, the substitution of 4 '-positions (especially 6-).

Substituent R¹And R²Substitution number m1 and m2 can be left for 0~4 (for example, 0~3), preferably 0~2 (for example, 1 or 2) Right integer.Replacing number m1 and m2 is that the compound of the integer of 1 or more (for example, 1 or 2) can steadily include above-mentioned heterocyclic compound Object.M1 and m2 is in ring Z¹And Z²In may be the same or different.

As substituent R³And R⁴, such as can example: with above-mentioned substituent R¹And R²Same alkyl (alkyl, naphthenic base, Aryl, aralkyl), alkoxy, carboxyl or C_1-2Alkoxy-carbonyl, halogen atom, nitro, cyano or substituted-amino etc..

Replacing number p1 and p2 is the integer of 0~4 (for example, 0~3), preferably 0~2 (for example, 0 or 1) left and right, in particular 0.It should be noted that substitution number p1 and p2 can be mutually identical or difference, and in the case where p1 and p2 is 2 or more, substituent R³And R⁴ Type can be mutually identical or different.In addition, substituent R³And R⁴The position of substitution be not particularly limited, in ring Ar¹And Ar²For In the case where phenyl ring, it may be, for example, the position 2-~7- (2-, 3- and/or 7- etc.) of fluorenes ring.

It include following compounds in representative compound represented by above-mentioned formula (1).

(A) ring Ar¹And Ar²For the compound of phenyl ring

In the present invention, formula (1) is represented, in the representative compound as host molecule includes ring Ar¹And Ar²For phenyl ring Bis- (hydroxyaryl) the fluorenes classes of 9,9-.Include in such compound: in above-mentioned formula (1), (a1) ring Z¹And Z²For phenyl ring, n1 and n2 For 1 bis- (hydroxy phenyl) the fluorenes classes of 9,9-；(a2) ring Z¹And Z²Bis- (hydroxynaphenyl) the fluorenes classes of the 9,9- for being 1 for naphthalene nucleus, n1 and n2； (a3) ring Z¹And Z²Bis- (polyhydroxy phenyl) fluorenes classes of the 9,9- for being 2 or more for phenyl ring, n1 and n2 etc..

(a1) bis- (hydroxy phenyl) the fluorenes classes of 9,9-

As bis- (hydroxy phenyl) the fluorenes classes of 9,9-, it is suitble to use R¹And R²The compound for being 0 or 1 for alkyl, m1 and m2.

Specifically, as 9, bis- (hydroxy phenyl) the fluorenes classes of 9-, such as can enumerate: 9,9- bis- (4- hydroxy phenyl) fluorenes etc. Bis- (hydroxy phenyl) fluorenes of 9,9-；Bis- (the 4- hydroxy-2-methyl phenyl) fluorenes of 9,9-, 9,9- bis- (4- hydroxy-3-methyl phenyl) fluorenes, 9, Bis- (4- hydroxyl -3- ethylphenyl) fluorenes of 9-, bis- (3- hydroxyl -6- aminomethyl phenyl) fluorenes of 9,9-, bis- (the 2- hydroxy-4-methyl benzene of 9,9- Base) fluorenes, bis- (4- hydroxyl -3- tert-butyl-phenyl) fluorenes of 9,9- etc. bis- (alkyl hydroxy phenyl) fluorenes of 9,9- [for example, 9,9- bis- (C_1-6 Alkyl hydroxy phenyl) fluorenes etc.]；Bis- (4- hydroxyl -3,5- 3,5-dimethylphenyl) fluorenes of 9,9-, the bis- (4- hydroxyl -2,6- dimethyl benzenes of 9,9- Base) fluorenes, bis- (4- hydroxyl -3, the 5- di-t-butyl phenyl) fluorenes of 9,9- etc. bis- (dialkyl group hydroxy phenyl) fluorenes of 9,9- [for example, 9, Bis- (two C of 9-_1-6Alkyl hydroxy phenyl) fluorenes etc.]；Bis- (the naphthenic base hydroxyls of 9,9- of bis- (4- hydroxyl -3- cyclohexyl phenyl) fluorenes of 9,9- etc. Base phenyl) fluorenes is [for example, 9,9- bis- (C_5-10Naphthenic base hydroxy phenyl) fluorenes etc.]；Bis- (4- hydroxyl -3- phenyl) fluorenes of 9,9- etc. Bis- (aryl hydroxy phenyl) fluorenes of 9,9- [for example, 9,9- bis- (C_6-10Aryl hydroxy phenyl) fluorenes etc.] etc..

(a2) bis- (hydroxynaphenyl) the fluorenes classes of 9,9-

Include in above-mentioned bis- (hydroxynaphenyl) the fluorenes classes of 9,9-: the ring Z of foregoing illustrative bis- (hydroxy phenyl) the fluorenes classes of 9,9-¹And Z²For Bis- (hydroxynaphenyl) the fluorenes classes of 9,9- of naphthalene nucleus are { for example, 9,9- bis- (2- hydroxyl -6- naphthalene) fluorenes, bis- [1- (the 5- hydroxyl naphthalenes of 9,9- Base)] bis- (hydroxynaphenyl) fluorenes of 9,9- etc. of fluorenes etc. } etc..

(a3) bis- (polyhydroxy phenyl) the fluorenes classes of 9,9-

Moreover, including in above-mentioned bis- (polyhydroxy phenyl) the fluorenes classes of 9,9-: corresponding to bis- (hydroxy phenyl) the fluorenes classes [9,9- of above-mentioned 9,9- Bis- (monohydroxy phenyl) fluorenes classes] fluorenes class, such as 9, bis- (dihydroxy phenyl) fluorenes of 9- [9,9- bis- (3,4- dihydroxy phenyl) fluorenes (double catechol fluorenes) etc.]；Bis- (3,4- dihydroxy -5- aminomethyl phenyl) fluorenes of 9,9-, the bis- (3,4- dihydroxy -6- methylbenzenes of 9,9- Base) fluorenes etc. bis- (alkyl-dihydroxy phenyl) fluorenes of 9,9- [for example, 9,9- bis- (C_1-4Alkyl-dihydroxy phenyl) fluorenes etc.] etc. 9, Bis- (two or trihydroxy phenyl) the fluorenes classes of 9-.

(B) ring Ar¹With ring Ar²Among at least one be naphthalene nucleus compound

It include: (b1) ring Ar in compound represented by representative above-mentioned formula (1)¹For phenyl ring, another ring Ar²For The benzfluorene class of naphthalene nucleus；(b2) ring Ar¹And Ar²For the dibenzo fluorenes class etc. of naphthalene nucleus.

(b1) benzfluorene class

Include in benzfluorene class: bis- (hydroxyaryl) benzo [a] the fluorenes classes of such as 11,11-, bis- (hydroxyaryl) benzos of 11,11- Bis- (hydroxyaryl) benzo [c] the fluorenes classes of [b] fluorenes class, 7,7-.

Specifically include: in above-mentioned formula (1), Z¹And Z²The benzfluorene class for being 1 for phenyl ring, n1 and n2, such as 11,11- is bis- Bis- (hydroxy phenyl) benzo [b] the fluorenes classes of (hydroxy phenyl) benzo [a] fluorenes class, 11,11-, bis- (hydroxy phenyl) benzo [c] fluorenes of 7,7- Class；Z¹And Z²The benzfluorene class for being 1 for naphthalene nucleus, n1 and n2, such as 11, bis- (hydroxynaphenyl) benzo [a] the fluorenes classes of 11-, 11,11- are bis- Bis- (hydroxynaphenyl) benzo [c] the fluorenes classes of (hydroxynaphenyl) benzo [b] fluorenes class, 7,7-；Z¹And Z²It is 2 or more for phenyl ring, n1 and n2 Benzfluorene class, such as 11, bis- (polyhydroxy phenyl) benzo [a] the fluorenes classes of 11-, bis- (polyhydroxy phenyl) benzo [b] the fluorenes classes of 11,11-, 7,7- bis- (polyhydroxy phenyl) benzo [c] fluorenes class etc..

(b2) dibenzo fluorenes class

Include in representative dibenzo fluorenes class: bis- (hydroxyaryl) dibenzo [b, h] the fluorenes classes of 12,12-.

Specifically include: in above-mentioned formula (1), Z¹And Z²The dibenzo fluorenes class for being 1 for phenyl ring, n1 and n2, such as 12,12- Bis- (hydroxy phenyl) dibenzo [b, h] fluorenes classes；Z¹And Z²The dibenzo fluorenes class for being 1 for naphthalene nucleus, n1 and n2, such as 12, the bis- (hydroxyls of 12- Base naphthalene) dibenzo [b, h] fluorenes class；Z¹And Z²The dibenzo fluorenes class for being 2 or more for phenyl ring, n1 and n2, such as 12,12- is bis- (more Hydroxy phenyl) dibenzo [b, h] fluorenes class etc..

These host compounds can be used alone or two kinds of combination of the above use.

(guest compound)

In the present invention, the compound as guest molecule includes: having and is used as ring containing multiple nitrogen-atoms (for example, basic nitrogen atom) 5 or 6 circle heterocyclic rings of constituting atom or the heterocyclic compound of its annelated heterocycles.Heterocyclic compound can be (non-aromatic for aliphatic series heterocycle Property heterocycle) or aromaticity heterocycle is any.In heterocyclic compound, the number of the nitrogen-atoms (for example, basic nitrogen atom) of ring is formed It may be, for example, 2~5, preferably 2~4 or so.

In such heterocyclic compound, such as can example: piperazine, N- aminoethylpiperazine, diethylenetriamines, Sanya second Base diamines (DABCO；1,4- diazabicyclo [2.2.2] octane) etc..Preferably heterocyclic compound (guest compound) may include Such as compound represented by following formula (2).

[chemical formula 5]

As R⁵Represented alkyl, such as can example: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, The straight-chain or branch chain C of isobutyl group, tert-butyl, n-pentyl, n-hexyl, nonyl, isononyl, decyl etc._1-10Alkyl.It is preferred that Alkyl can be straight-chain or branch chain C_1-6Alkyl.

As R⁵Represented naphthenic base, such as can example: the C of cyclopenta, cyclohexyl etc._5-10Naphthenic base etc..Preferred ring Alkyl can be C_5-8Naphthenic base, especially C_5-6Naphthenic base etc..

R⁵Represented aryl can be monocyclic or polycycle aryl, and polycycle aryl can be not only complete unsaturation, go back It can be the group of fractional saturation.As aryl, such as can example: phenyl, naphthalene, azulene cyclopentacycloheptene base, indenyl, dihydro indenyl, four The C of hydrogen naphthalene etc._6-16Aryl etc..Preferred aryl can be C_6-10Aryl (phenyl, naphthalene etc.).

R⁵Represented aralkyl (aryl alkyl) is above-mentioned aryl and alkyl linked group, such as can example: benzyl, Phenethyl, 3- phenyl-n-propyl, 1- phenyl-n-hexyl, naphthalene -1- ylmethyl, naphthalene -2- base ethyl, 1- (naphthalene -2- base)-positive third The C of base, indenes -1- ylmethyl etc._6-12Aryl C_1-6Alkyl etc..Preferred aralkyl can be C_6-10Aryl C_1-4Alkyl (benzyl, benzene second Base etc.).

Abovementioned alkyl, naphthenic base, aryl and aralkyl can have substituent group.As substituent group, such as can example: halogen is former Sub (fluorine atom, chlorine atom etc.), hydroxyl, the alkoxy (C of methoxyl group, ethyoxyl etc._1-6Alkoxy etc.), acyl group (formoxyl, second The C of acyl group, propiono etc._1-10Alkyl-carbonyl etc.), carboxyl, alkoxy carbonyl (C_1-4Alkoxy-carbonyl etc.), alkyl (methyl, The C of ethyl etc._1-6Alkyl etc.) etc..

R⁵In represented triazine-alkyl, triazine can be 1,3,5-triazines, 1,2,4- triazines, 1,2,3- triazines etc., triazine The carbon atom of ring can be replaced with amino, hydroxyl etc..As representative triazine-alkyl, such as can example: 4,6- diaminostilbenes, 3,5- triazine -2- methyl, 4- amino -6- hydroxyl -1,3,5- triazine -2- methyl, 4,6- dihydroxy -1,3,5- triazine -2- methyl Deng 1,3,5- triazine -2-C_1-4Alkyl etc..Preferred triazine-alkyl can be 4,6- diaminostilbene, 3,5- triazine -2-C_1-2Alkane Base.

Preferred R⁵It can be hydrogen atom, C_1-4Alkyl, C_6-10Aryl, C_6-10Aryl C_1-4Alkyl, cyano ethyl or 1,3,5- Triazine -2-C_1-2Alkyl etc., in general, the situation for hydrogen atom, cyano ethyl etc. is more.

R⁶~R⁸Represented halogen atom includes fluorine atom, chlorine atom, bromine atom, iodine atom.As R⁶~R⁸Represented Alkyl, can example: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, just oneself Base, 2- ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, The straight-chain or branch chain C of heptadecyl, octadecyl etc._1-20Alkyl is (for example, C_1-18Alkyl).Preferably alkyl can be C_1-12Alkyl is (for example, C_1-10Alkyl).Alkyl can have hydroxyl.As the alkyl with hydroxyl, such as can example: methylol, hydroxyl The hydroxyl C of ethyl etc._1-20Alkyl is (for example, hydroxyl C_1-18Alkyl) etc..Preferred hydroxyalkyl can be the hydroxyl C of methylol etc._1-6Alkane Base is (for example, hydroxyl C_1-2Alkyl) etc..

As R⁶~R⁸Represented naphthenic base, aryl, aralkyl, can example: with above-mentioned substituent R⁵Same group.

R⁶~R⁸As long as the organic group of represented acyl group hydrogen atom, alkyl, alkenyl, alkynyl, aryl or heteroaryl etc. With the group of carbonyl linkage.As acyl group, such as can example: formoxyl；Acetyl group, propiono, bytyry, isobutyryl Base, valeryl, caproyl, heptanoyl group, caprylyl, pelargonyl group, capryl, 3- methyl pelargonyl group, 8- methyl pelargonyl group, 3- ethyl Caprylyl, 3,7- dimethyl-octa acyl group, undecanoyl base, dodecanoyl, tridecanoyl base, myristoyl base, pentadecanoyl base, palmityl Base, 1- methyl pentadecanoyl base, 14- methyl pentadecanoyl base, 13,13- dimethyl myristoyl base, heptadecanoyl base, 15- methyl palmityl The C of base, octadecanoyl, 1- methyl heptadecanoyl base, 19 acyl groups, 20 acyl groups, two undecanoyl bases etc._1-26Alkyl-carbonyl；Propylene The C of acyl group, methylacryloyl, allyl carbonyl, cinnamoyl etc._2-6Alkenyl-carbonyl；Acetenyl carbonyl, propinyl carbonyl etc. C_2-6Alkynyl-carbonyl；The C of benzoyl, naphthyl carbonyl, biphenylcarbonyl, anthrylcarbonyl etc._6-18Aryl-carbonyl；2- pyridine Heteroaryl-carbonylarnino (for example, the 5- or 6-membered heteroaryl-carbonylarnino of non-aromatic or aromatics) of base carbonyl, thienyl carbonyl etc. etc..It is preferred that Acyl group can be C_1-20Alkyl-carbonyl is (for example, C_1-6Alkyl-carbonyl etc.) etc..

R⁵With R⁶Can be bonding to each other and ring be formed together (for example, 4~12 member rings, preferably with adjacent nitrogen-atoms and carbon atom For 5~10 member rings).

Q indicates 0 or 1~3 integer, generally can be 0~2 (for example, 0 or 1).

The doublet of solid line and dotted line indicates singly-bound or double bond, in general, in R⁵With R⁶The feelings bonding to each other for forming ring (heterocycle) It can be singly-bound, in R under condition⁵In R⁶It can be double bond in the case where not forming ring (heterocycle).

Preferred R⁶It can be hydrogen atom, alkyl, aryl etc., can also be alkyl.Preferred R⁷And/or R⁸It can be hydrogen atom, alkane Base, hydroxyalkyl etc..

It more specifically, such as may include change represented by following formula (2a) as the heterocyclic compound of guest compound Close compound represented by object and/or following formula (2b).

[chemical formula 6]

R can be 0~5, for example, 1~5 (for example, 1~4) Zuo You integer.

It, can example specifically, as compound (imidazolium compounds) represented by formula (2a): imidazoles；1- methylimidazole Deng 1- alkyl imidazole；The 2- alkyl imidazole of 2-methylimidazole, 2- heptadecyl imidazole, 2- undecyl imidazole etc.；2- phenyl The 2- Aryimidazole of imidazoles etc.；The 4- alkyl imidazole of 4-methylimidazole etc.；The 1,2- dialkylimidazolium of DMIZ 1,2 dimethylimidazole etc.； 1- aralkyl -2- the alkyl imidazole of 1 benzyl 2 methyl imidazole etc.；1- cyano ethyl -2-methylimidazole, 1- cyano ethyl -2- 1- cyano ethyl -2- the alkyl imidazole of undecyl imidazole etc.；1- cyano ethyl-the 2- of 1- cyano ethyl -2- phenylimidazole etc. Aryimidazole；1- aralkyl -2- the Aryimidazole of 1- benzyl -2- phenylimidazole etc.；The 2,4- bis- of 2-ethyl-4-methylimidazole etc. Alkyl imidazole；2- aryl -4- the alkyl imidazole of 2- phenyl -4-methylimidazole etc.；1- cyano ethyl -2-ethyl-4-methylimidazole Deng 1- cyano ethyl -2,4- dialkylimidazolium；2- aryl -4- alkyl-the 5- of 2 phenyl 4 methyl 5 hydroxy methylimidazole etc. Hydroxyalkyl imidazoles；2- aryl -4,5- dihydroxyalkyl imidazoles of 2 pheny1 4,5 dihydroxymethyl imidazole etc. etc..It should be noted that miaow Azole compounds R⁵~R⁸Among at least one have the case where substituent group more.

Among these compounds, preferably imidazoles, 1- methylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2- ten Seven alkyl imidazoles, 2- undecyl imidazole, 4-methylimidazole, 1 benzyl 2 methyl imidazole, DMIZ 1,2 dimethylimidazole, 2- phenyl- 4- methyl -5- hydroxy methylimidazole, 2- phenylimidazole or 2 pheny1 4,5 dihydroxymethyl imidazole etc..

As compound represented by formula (2b) (cyclic annular amidine compound), such as can example: diazabicyclo endecatylene (DBU:1,8- diazabicyclo [5.4.0] -7- endecatylene), diazabicyclo-nonene (DBN:1,5- diazabicyclo [4.3.0] -5- nonene) etc..

These heterocyclic compounds can be and the sour organic acid such as trimellitic acid, pyromellitic acid, cyamelide or salt The salt of the inorganic acid of acid etc..

In inclusion compound, relative to 1 mole of host compound, the ratio of guest compound can for 0.5~5 mole, it is excellent It is selected as 0.7~2.5 mole (for example, 0.75~2.3 mole), further preferably 0.8~2.2 mole (for example, 1~2 mole) Left and right.

It should be noted that phenolic hydroxyl can forming salt (for example, salt with alkali) in inclusion compound of the invention.This hair Compound in bright inclusion compound, as long as having inclusion form, also comprising the such salt of formation.

(modulator approach of inclusion compound)

Inclusion compound of the invention can be by making compound (host compound) represented by above-mentioned formula (1) and above-mentioned heterocycle Compound (guest compound) mixing is reacted and is modulated.It should be noted that among host compound and guest compound extremely It, can be to for liquid in the case that the ingredient of few one is liquid under mixing temperature (for example, room temperature or 30~100 DEG C or so) Another ingredient is added in one ingredient and is mixed.For example, adding in the case where guest compound is liquid into guest compound Add host compound, mixing (or stirring), is recycled by leaching etc., it is possible thereby to obtain the inclusion generated as needed Compound.It is in the case where being mixed or stirred under heating, after cooling, is recycled, it is possible thereby to obtain inclusionization Close object.

Host compound and the mixing of guest compound or react as needed can be in the presence of a solvent.As molten Agent, such as can example: the alcohols of methanol, ethyl alcohol, propyl alcohol, butanol etc.；Ethers, such as 2-methyl cellosolve (methyl cellosolve), The dioxane of ethylene glycol monomethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve) etc., diglycol monotertiary first The card of base ether (methyl carbitol), carbiphene (ethyl carbitol), diethylene glycol monobutyl ehter (butyl carbitol) etc. Must alcohols, the cyclic ether of dioxanes, tetrahydrofuran etc., chain ether of Anaesthetie Ether etc. etc.；Acetone, methyl ethyl ketone, methyl-isobutyl The ketone of ketone, 2 pentanone, methyl-n-butyl ketone, isophorone, cyclohexanone etc.；Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, The esters of isobutyl acetate etc.；Ethylene glycol monomethyl ether acetate (ethyl cellosolve acetate), carbiphene acetic acid The ether-ether class of ester (ethylcarbitol acetate), propylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetic acid esters etc.；Heptan The aliphatic hydrocarbon of alkane, octane etc.；The alicyclic hydro carbons of hexamethylene etc.；The aromatic hydrocarbons of toluene, dimethylbenzene etc.；Methylene chloride, chlorine The halogenated hydrocarbons of imitative, chlorobenzene etc.；The amides of dimethylformamide, dimethyl acetamide etc.；The sulfoxide type of dimethyl sulfoxide etc. Deng.Solvent can be the aprotic polar solvent of amides, sulfoxide type etc..These solvents can be with independent or of more than two kinds mixed Bonding solvent form uses.

It can be guest compound relative to 1 mole of host compound about the ratio of host compound and guest compound 0.5~5 mole, preferably 0.7~3 mole, further preferably 0.8~2.5 mole or so.

It will can mix while stirring, lead to as needed with the mixture of host compound and guest compound comprising solvent The generated solid of recycling such as filter to take, thus to obtain inclusion compound.Above-mentioned mixed liquor can mix under heating, heating temperature For below the boiling point of solvent, may be, for example, 30~120 DEG C (preferably 50~100 DEG C) Zuo You.After heating, it can carry out as needed cold But, generated solid is recycled.

After reaction, solvent can utilize as needed the common side of air-distillation, vacuum distillation etc. before solid recycles Method evaporates.In addition, wrapping solvent-laden reaction mixture, the mixing of solvent that can be different from reaction dissolvent, and make inclusion compound It is precipitated.

The inclusion compound recycled can be washed or be dried as needed.

In inclusion compound of the invention, the ratio of components of host compound and guest compound can be by commonly analyzing Method, such as¹The integral of H-NMR spectrum is determined than easily.In addition, being based on companion using thermogravimetry (TG-DTA) The amount of the guest compound discharged from inclusion compound with heating can also determine host compound and guest compound Ratio of components.In the present invention, the host compound of inclusion compound and the ratio of components of guest compound are utilized¹H-NMR spectrum And/or TG-DTA, according to having analyzed as a result, simplest ratio of integers can also be determined as.

Moreover, the structure of inclusion compound of the invention can use Single Crystal X-ray structural analysis, powder x-ray diffraction Deng method be determined.

(solidification compound)

Inclusion compound of the invention due to steadily including the heterocyclic compound functioned as the curing agent of epoxy resin, Even if therefore mixing with epoxy resin, can also maintain to stablize for a long time under low temperature (room temperature or storage temperature).On the other hand, Inclusion compound is due to discharging heterocyclic compound along with heating, if being heated to predetermined temperature, can make asphalt mixtures modified by epoxy resin Rouge promptly solidifies.In addition, inclusion compound of the invention is due to primary amino group or secondary amino group and tertiary amino, in conduct Also it can be used as curing accelerator while the curing agent of epoxy resin functions to function.Therefore, inclusion of the invention Object is closed to be used as keeping cured (A) curing agent of (B) epoxy resin (epoxide) and/or curing accelerator useful.Moreover, (A) inclusion compound (curing agent and/or curing accelerator) is combined with (B) epoxy resin (epoxide) solidifies modulation Property composition is useful.

The solidification compound may include that above-mentioned inclusion compound and epoxy resin also may include as needed common The curing agent and/or curing accelerator (common curing agent and/or curing accelerator) of epoxy resin, as long as such curing agent It is the compound for reacting and making epoxy resin cure with the oxirane ring of epoxy resin (or epoxy group), then is not limited especially System, as long as curing accelerator promotes the compound of above-mentioned curing reaction, is also not particularly limited.As such curing agent or Curing accelerator, such as can example: aminated compounds (aliphatic amine, ester ring type and hetero ring type amine, aromatic amines, modified amine Class etc.), glyoxaline compound, imidazolines, amides compound, ester type compound, phenolic compound, alcohols chemical combination Object, sulfur alcohol compound, ether compound, thio-ether type compounds, carbamide compounds, thiourea, Louis's acids Close object, phosphorus species, anhydride compound, salt compounds (or cationic polymerization initiators), reactive silicon compound-aluminium Complex compound etc..

Specifically, as curing agent and curing accelerator, such as compound below can be enumerated.

It as aliphatic amine, such as can enumerate: ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, trimethylhexane diamine, penta 2 The straight-chain or branch chain of amine, 2,5- dimethylhexanediamine, trimethylhexane diamine, 2,5- dimethyl -2,5- hexamethylene diamine etc. are sub- Alkyl diamine class；Diethylenetriamines, trien, tetren, dipropylenediamine, pentamethyl diethylidene The polyalkylene polyamine class of triamine etc.；Dimethylamino propylamine, diethyl amino propylamine, dibutyl amino propyl amine, N, N- diformazan The N of basic ring hexylamine etc., N- dialkyl aminoalkyl amine or N, N- dialkyl amido naphthenic base amine；Bis- (2- dimethylaminos Ethyl) ether, diethylene glycol (DEG) double propylamine, polypropylene glycol diamines etc. (poly-) ether diamine class；N, N, N ', N '-tetramethylethylenediamine, N, N, N ', N ' -4-methyl hexamethylene diamine, N, N, N ', the N- alkyl substituted alkylene Diamines of N '-tetramethyl trimethylene diamine etc.；Diformazan The ethyl alcohol amine of base aminoethyloxyethyloxy ethyl alcohol, triethanolamine, dimethylamino hexanol etc.；Mono- alkyl amine etc..

As ester ring type and hetero ring type amine, such as can enumerate: piperidines, piperazine, menthene diamines, isophorone diamine, Methyl morpholine, ethyl morpholine, N- (amino-ethyl) piperazine, trimethylaminoethyl group piperazine, N, N '-dimethyl piperazine, 4- amino- The monocyclic amine of 2,2,6,6- tetramethyl piperidine etc.；Bis- (4- aminocyclohexyl) methane, bis- (4- amino -3- methylcyclohexyls) Bis- (aminocyclohexyl) alkanes of methane etc.；N, N ', the triazines of N "-three (dimethylaminopropyl) hexahydro-s- triazine etc.； Bis- four spiral shells [5,5] of (3- aminopropyl) -2,4,8,10- of 1,4- diazabicyclo (2,2,2) octane (triethylenediamine), 3,9- (1,5- diaza is double by hendecane or its additive compound, DBU (1,8- diazabicyclo [5.4.0] -7- endecatylene), DBN Ring [4.3.0] -5- nonene) etc. crosslinking ring type amine etc..

As aromatic amines, such as can example: o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, diaminodiphenyl-methane, Bis- (4- amino -3- aminomethyl phenyl) methane, bis- (4- amino -3- ethylphenyl) methane, diamino diphenyl sulfone, xyxylene Diamines, 1,3,5- tri- (amino methyl) benzene, 2- (dimethylaminomethyl) phenol, 2,4,6- tri- (dimethylaminomethyl) benzene Phenol, phthalocyanine tetramine, benzylmethylamine, dimethyl benzylamine, pyridine, picoline, α-methylbenzyl methylamine etc..

As modified amine, such as can example: there are polyamines (epoxy adduct), the Michael of amine in epoxide addition Addition polyamines, Mannich addition polyamines, thiocarbamide addition polyamines, ketone envelope chain polyamines (ketimide), dicyandiamide, guanidine, organic acid hydrazides, Diaminomaleonitrile, amine acid imide, boron trifluoride-piperidines complex compound, boron trifluoride-monoethylamine complex compound etc..

As glyoxaline compound, such as can example: imidazoles, 1- methylimidazole, 2-methylimidazole, 4-methylimidazole, 5- Methylimidazole, 1- ethyl imidazol(e), 2- ethyl imidazol(e), 4- ethyl imidazol(e), 5- ethyl imidazol(e), 1- n-propyl imidazoles, 2- n-propyl miaow Azoles, 1- isopropylimdazole, 2 isopropyl imidazole, 1- butylimidazolium, 2- butylimidazolium, 1- isobutyl group imidazoles, 2- isobutyl group Imidazoles, 2- undecyl -1H- imidazoles, 2- heptadecyl -1H- imidazoles, DMIZ 1,2 dimethylimidazole, 1,4- methylimidazole, 2,4- Methylimidazole, 2-ethyl-4-methylimidazole, 1- phenylimidazole, 2- phenyl -1H- imidazoles, 4- methyl -2- phenyl -1H- imidazoles, 2- phenyl -4-methylimidazole, 1 benzyl 2 methyl imidazole, 1- benzyl -2- phenylimidazole, 1- cyano ethyl -2-methylimidazole, 1- cyano ethyl -2-ethyl-4-methylimidazole, 1- cyano ethyl -2- undecyl imidazole, 1- cyano ethyl -2- phenylimidazole, 2- phenylimidazole cyamelide addition product, 2-methylimidazole cyamelide addition product, 2- phenyl -4,5- dihydroxymethyl miaow Azoles, 2 phenyl 4 methyl 5 hydroxy methylimidazole, two (2- cyanoethoxy) methylimidazole of 1- cyano ethyl -2- phenyl -4,5-, 1- dodecyl -2- methyl-3-benzyl imidazole chloride, 1- benzyl -2- phenylimidazole hydrochloride etc..

It as imidazolines, such as can enumerate: 2-methylimidazole quinoline, 2- benzylimidazoline etc..

It as amides compound, such as can enumerate: by dimeric dibasic acid [polymerized fatty acid or poly materialization fatty acid] (example Such as, dimer~tetramer of unsaturated high-grade fatty acid) it is condensed with polyamines (for example, Alkylenediamine, polyethylene polyamines etc.) Obtained by polyamide (polyamino amide) etc..

It as ester type compound, such as can enumerate: aryl and the active carbonyl compound of thioaryl ester etc. of carboxylic acid etc..

As phenolic compound, such as can example: as phenolic resin curing agent, phenol aralkyl resin, naphthols aralkyl The aralkyl-type phenol resin of base resin etc., the phenolic varnish type phenol of phenol resol resins, cresol novolac resin etc. Urea formaldehyde, these modified resins, such as can example: the phenolic aldehyde tree of epoxidation or butylated novolak phenolics etc. Rouge；Dicyclopentadiene-modified phenolic resin, paraxylene phenol-formaldehyde resin modified, trisphenol alkane type phenolic resin, multifunctional type The phenol-formaldehyde resin modified etc. of phenolic resin etc..In addition, as alcohol compound, sulfur alcohol compound, ether compound and thioether Class compound, such as can enumerate: polyalcohol, polymercaptan, polysulfide, 2- (dimethylaminomethyl), phenol 2,4,6- tri- (two Methylaminomethyl) phenol, 2,4,6- tri- (dimethylaminomethyl) phenol etc. three -2- ethylhexyl hydrochlorides etc..

It as carbamide compounds, thiourea, Louis's acid compounds, such as can enumerate: butylation urea, butyl Change melamine, butylation thiocarbamide, boron trifluoride etc..

It as phosphorus species, can enumerate: the alkylphosphines of organic phosphine compound, such as ethyl phosphine, butyl phosphine etc., Phenylphosphine Deng aryl phosphine etc. primary phosphine；The dialkyl phosphine of dimethyl phosphine, dipropyl phosphine, Methylethyl phosphine etc., diphenylphosphine etc. it is secondary Phosphine；Tertiary phosphine class of trimethyl-phosphine, triethyl phosphine, triphenylphosphine etc. etc..

It as anhydride compound, such as can enumerate: phthalic anhydride, trimellitic anhydride, chlorendic anhydride, pyromellitic acid The aromatics polycarboxylic acids of acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis- (trimellitic anhydrides), glycerol three (trimellitic anhydride) etc. Acid anhydride；Tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthaacid acid Acid anhydride (for example, 4- methylhexahydrophthalic anhydride etc.), carbic anhydride, methylendomethylene tetrahydro are adjacent Phthalate anhydride, methylcyclohexene tetracarboxylic acid anhydride, NA acid anhydrides (anhydrous Ha イミッ Network acid, Himic anhydride), methyl N A acid The alicyclic polycarboxylic acid anhydride of acid anhydride (anhydrous メチ Le Ha イミッ Network acid), methylnadic anhydride etc.；Maleic anhydride, dodecenyl succinic The aliphatic polycarboxylic acid anhydride etc. of succinic anhydride, polyadipate acid anhydride, poly- azelaic acid acid anhydride etc..

It as salt compounds and reactive silicon compound-aluminium complex, such as can enumerate: aryl diazonium salts, two virtues Base salt compounded of iodine, aryl sulfonium salt, aryl methyl sulfonium salt (benzyl methyl sulfonium salt etc.), diaryl sulfonium salt, triarylsulfonium salt, triphenyl silicon Alkanol-aluminium complex, triphenylmethoxy silane-aluminium complex, silicyl peroxide-aluminium complex, tri-phenyl-silane Alcohol-three (salicyl aldehydic acid salt) aluminium complex etc..

These curing agent and/or curing accelerator can be used alone or are applied in combination two kinds or more.These curing agent and Among curing accelerator, phenolic compound, anhydride compound etc. is widely used.Therefore, solidification compound of the invention can At least one kind of compound comprising being selected from phenolic compound (for example, novolak phenolics etc.), anhydride compound, from From the perspective of heat resistance [flexural properties etc. of (for example, 260 DEG C) under glass transition temperature, hot environment] can be promoted, Anhydride compound is preferably comprised (for example, hexahydrophthalic anhydride, 4- methylhexahydrophthalic anhydride and theirs is mixed Close object etc.).

The ratio of above-mentioned inclusion compound (the 1st curing agent) and above-mentioned curing agent and/or curing accelerator (the 2nd curing agent) Example, can according to suitable selections such as the type of above-mentioned 2nd curing agent or functional equivalent'ss (hydroxyl equivalent or anhydride group equivalent etc.), For example, can for the former/the latter's (weight ratio)=100/0~30/70, preferably 100/0~50/50, further preferably 100/0 ~70/30 or so.Above-mentioned 2nd curing agent be anhydride compound in the case where, above-mentioned inclusion compound (the 1st curing agent) with The ratio of above-mentioned 2nd curing agent, may be, for example, the former/the latter (weight ratio)=70/30~1/99 (for example, 50/50~3/97), Preferably 30/70~5/95 (for example, 20/80~7/93) left and right.In the case where above-mentioned 2nd curing agent is phenolic compound, The ratio of above-mentioned inclusion compound (the 1st curing agent) and above-mentioned 2nd curing agent, may be, for example, the former/the latter's (weight ratio)=70/ 30~1/99 (for example, 50/50~5/95), preferably 30/70~10/90 (for example, 20/80~12/88) left and right.

In addition, in the case where stating the 2nd curing agent in use, it can be with the functional group of the epoxy reaction in the 2nd curing agent The ratio of (for example, anhydride group, hydroxyl etc.) may be, for example, 0.7~1.3 equivalent relative to the epoxy group in (B) epoxy resin (for example, 0.8~1.2 equivalent), preferably 0.9~1.1 equivalent or so, generally can be 1 equivalent or so.

(B) epoxy resin can for diglycidyl ether type, glycidyl ester type, glycidic amine type, by unsaturated double-bond oxygen Change and epoxidised epoxide etc..

As the diglycidyl ether type epoxy compound (or resin) among (B) epoxy resin, such as can example: phenyl contracting Water glycerin ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, sec-butyl glycidol ether, 2- second The contracting of the alkane unary alcohol of base hexyl glycidyl ether, 2- Methyl Octyl glycidol ether, octadecyl glycidol ether etc. Water glycerol ether compound；Ethylene glycol, propylene glycol, butanediol, hexylene glycol, polyethylene glycol, thiodiglycol, glycerol, trihydroxy methyl third The epoxyalkane of the bisphenols of polyglycidyl ether, the bisphenol-A of alkane polyol class of alkane, pentaerythrite, D-sorbite etc. etc. The polyglycidyl ether of (ethylene oxide etc.) addition product；Quinhydrones (hydroquinone), resorcinol, catechol, phloroglucin etc. Monokaryon polyatomic phenol poly epihydric alcohol ether compound；Dihydroxy naphthlene, bis-phenol, diphenyl alkane [methylene bis-phenol (bis-phenol F), di-2-ethylhexylphosphine oxide (o-cresol), ethylidene bis-phenol (bisphenol-A D), isopropylidenediphenol (bisphenol-A), bis- (the adjacent first of isopropylidene Phenol), tetrabromobisphenol A, 1,3- bis- (4- hydroxyl cumenyl benzene), bis- (the hydroxyl virtues of 1,4- bis- (4- hydroxyl cumenyl benzene), 9,9- Base) fluorenes [for example, bis- (the 4- hydroxy-3-methyl phenyl) fluorenes of 9,9- bis- (4- hydroxy phenyl) fluorenes, 9,9-, 9,9- it is bis- (hydroxyl -3 4-, 5- 3,5-dimethylphenyl) fluorenes, bis- (6- hydroxyl -2- naphthalene) fluorenes of 9,9- etc.], 9,9- bis- (hydroxyl (single or poly-) alkoxy aryl) fluorenes [for example, 9,9- bis- (4- (2- hydroxyl-oxethyl) phenyl) fluorenes, bis- (6- (2- the hydroxyl-oxethyl) -2- naphthalene) fluorenes of 9,9- etc.] etc.], Three or tetraphenyl alkane [1,1,3- tri- (4- hydroxy phenyl) butane, 1,1,2,2- tetra- (4- hydroxy phenyl) ethane etc.], diphenyl Ketone, diphenyl ether, diphenylsulfide, diphenyl sulfone, novolaks or novolac resin (phenol novolacs, o-Hydroxytoluene Novolac, ethyl -phenol novolaks, butylphenol novolaks, octyl phenol novolaks, resorcinol novolaks Deng), the poly epihydric alcohol ether compound of the multicore polyatomic phenol of terpene phenol etc.；Cyamelide three-glycidyl ester etc. it is miscellaneous Poly epihydric alcohol ether compound of cycle compound etc..

As glycidyl ester type epoxy compound (or resin), such as can example: pivalic acid (バーサティッ Network acid) Single epihydric alcohol ester compound of the monocarboxylic acid class of ethylene oxidic ester etc.；Maleic acid, fumaric acid, itaconic acid, succinic acid, penta 2 Acid, suberic acid, adipic acid, azelaic acid, decanedioic acid, dimeric dibasic acid, trimer acid, phthalic acid, M-phthalic acid, terephthaldehyde Acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endo-methylene group tetrahydro neighbour's benzene Aliphatic, alicyclic or aromatic polycarboxylic acid class the glycidol esters and (methyl) glycidyl acrylate of dioctyl phthalate etc. Homopolymer or copolymer etc..

As glycidyl amine epoxy compound (or resin), such as can example: N, N- diglycidylaniline, double (4- (N- methyl-N- glycidyl-amino) phenyl) methane, N, N- diglycidyl toluidines, four glycidyl group diamino The glycidol amine compounds of amine etc. of base diphenyl methane, triglycidyl group amino-phenol etc..

As by the epoxidised epoxide of unsaturated double-bond, such as can example: vinylcyclohexene dicyclic oxide, Bicyclopentadiene dicyclic oxide, 3,4- epoxycyclohexyl-methyl -3,4- 7-oxa-bicyclo[4.1.0 formic acid esters, 3,4- epoxy -6- methyl The cyclic annular alkene of cyclohexyl methyl -6- cyclohexanecarboxylic acid ester, bis- (3,4- epoxy -6- methylcyclohexylmethyl) adipate esters etc. The epoxides of hydro carbons；The epoxidation polymerization of conjugated dienes of epoxidized polybutadiene, epoxidized styrene-butadiene copolymer etc. Object etc..

These epoxides (or resin) can be used alone or be applied in combination two kinds or more.It should be noted that epoxy Compound (or resin) can for monomer, also may include dimer~ten polymers or so polymer.In addition, alkane unary alcohol or The list or polyglycidyl ether of alkane polyol class, the ethylene oxidic ester of monocarboxylic acid class, the epoxides of cyclic olefin etc. The case where as reactive diluent, is more.

It, can example as preferred epoxide (or resin): there is multiple epoxy groups (or ethylene oxide in the molecule Ring) poly epihydric alcohol ether compound, for example, methylene bis-phenol (Bisphenol F), di-2-ethylhexylphosphine oxide (o-cresol), ethylidene bis-phenol are (double Phenol AD), isopropylidenediphenol (bisphenol-A), isopropylidene bis- (o-cresols), bis- (hydroxyaryl) fluorenes of 9,9-, the bis- (hydroxyls of 9,9- (single or poly-) alkoxy aryl) fluorenes etc. bisphenol compound polyglycidyl ether etc..

Moreover, epoxy resin can also can be shortage mobility to have the liquid of mobility under room temperature (15~20 DEG C) High viscosity (or highly viscous) semisolid or solid, in general, having at the temperature (processing temperature) mixed with inclusion compound There is mobility, it can be to be in a liquid state at the mixing temperature or sticky liquid-state epoxy resin, it can also be under room temperature (15~20 DEG C) It is in a liquid state or sticky epoxy resin.

In solidification compound of the invention, about the usage amount of inclusion compound, according to curing method, as objectifying The heterocyclic compound for closing object generally can be the usage amount as curing agent and/or curing accelerator.For example, for by with epoxy In the case that the reaction of base and making solidifies the add-on type curing agent that agent molecule must be incorporated in (group body Write まれ Ru) solidified resin, About the usage amount of inclusion compound, according to the characteristic of solidified resin, in general, rubbing relative to epoxy group (or oxirane ring) 1 You can be 0.1~1 mole in terms of the guest compound of inclusion or heterocyclic compound (curing agent and/or curing accelerator) conversion (for example, 0.2~0.8 mole, preferably 0.25~0.5 mole or so) left and right.In addition, being to be not incorporated in solidification in solidification agent molecule In resin and catalytic induce epoxy group open loop, generate epoxide between polymerization addition reaction aggretion type curing agent Or the case where in the case that light starts type curing agent or as curing accelerator, is inferior, about the usage amount of inclusion compound, phase It can be 1 mole or less (example in terms of guest compound or heterocyclic compound conversion for 1 mole of epoxy group (or oxirane ring) Such as, 0.001~0.5 mole, preferably 0.005~0.1 mole or so).

About the usage amount of inclusion compound, relative to 100 parts by weight of epoxy resin, as the object in inclusion compound Compound may be, for example, 0.1~25 parts by weight, preferably 0.5~15 parts by weight, further preferred 1~10 parts by weight (for example, 1.5 ~5 parts by weight) left and right.

It should be noted that the fluorene compound as host compound, high with the compatibility of epoxy resin, and to non-solubility The dispersibility of additive is also high.Therefore, even if hardening resin composition includes above-mentioned fluorene compound, also seldom to solidfied material Characteristic generates adverse effect.

Solidification compound of the invention can be prepared by mixing (A) ingredient and (B) ingredient.For example, will Such as (A) inclusion compound (curing agent and/or curing accelerator ingredient) and (B) epoxy resin (epoxide) [and root According to needs, above-mentioned 2nd curing agent or aftermentioned various additives etc.], (pinched using homogenizer, mixer or mixing machine, kneading machine Conjunction machine or roller, extruder etc.), mixing and kneading machine (mixing and kneading machine), do not generate or can inhibit curing reaction (or gelation) temperature, when Between under, (for example, melting mixing etc.) is mixed or is kneaded, it is possible thereby to modulate solidification compound of the invention.In addition, mixed Conjunction or mixing (for example, 50~100 DEG C or so) can carry out under heating, can also be in low temperature (for example, room temperature~50 DEG C, preferably Room temperature~40 DEG C or so) under mixed or be kneaded, and omit heating under mixing or mixing.It should be noted that can also with (A) ingredient and (B) ingredient are mixed or be kneaded in the presence of above-mentioned same organic solvent.

In solidification compound of the invention, as needed, various additives, such as silane coupling agent, increasing can also be added Mould agent, organic solvent, reactive diluent, filler, reinforcing agent, colorant (pigment etc.), fire retardant, release agent, stabilizer (antioxidant, ultraviolet absorbing agent etc.), incremental agent, thickener etc..

As silane coupling agent, such as can example: vinyltrimethoxysilane, vinyltriethoxysilane,γContracting Water glycerol oxygroup propyl trimethoxy silicane,γGlycidoxypropyl triethoxysilane,γMethacryloxy Propyl trimethoxy silicane,γMethacryloxypropyl,γTSL 8330,γAminopropyltriethoxywerene werene, N-β(amino-ethyl)γTSL 8330, N-β(amino-ethyl)γ- Aminopropyltriethoxywerene werene, N- phenyl-γTSL 8330, N- phenyl-γThree ethoxy of aminopropyl Base silane,γMercaptopropyi trimethoxy silane,γMercaptopropyltriethoxysilane etc..As plasticizer, such as can show Example: the alkane omega-dicarboxylic acids plasticizer of O-phthalic acids plasticizer, adipic acid etc., phosphate plasticizer, polyesters plasticising Agent etc..

As organic solvent, can example above-mentioned example solvent, as reactive diluent, can example above-mentioned example ring Oxygen compound, for example, n-butyl glycidyl ether, phenyl glycidyl ether, styrene oxide, tert-butyl-phenyl glycidol ether, The epoxide of bicyclopentadiene dicyclic oxide etc., the phenols etc. of phenol, cresols, tert-butyl phenol etc..

As filler, such as can example: calcium bicarbonate, precipitated calcium carbonate, native silicon dioxide, synthetic silica, Fused silica, titanium oxide, barium sulfate, zinc oxide, aluminium hydroxide, magnesium hydroxide, talcum, kaolin, clay, mica, calcium Silica, potassium titanate, aluminium borate, sepiolite, eakleite etc..Colorant can be carbon black Deng ?color pigment, titanium oxide etc. White pigment, yellow uitramarine, orange pigment, red pigment, violet pigment, blue pigment, viridine green etc. it is any.As Reinforcing agent, such as can example: the organic fiber [natural fiber, polyalkylene of cellulose fibre (cellulose nano-fibrous etc.) etc. The synthetic fibers etc. of aromatic ester fiber, vinylon fiber, aramid fiber etc.], inorfil [glass fibre, carbon fiber etc.].

As release agent, such as can example: fatty acid release agent (higher fatty acids, high-grade aliphatic ester, higher aliphatic Sour calcium etc.), wax class (for example, Brazil wax, polyethylene kind wax etc.), silicone oil etc..

As fire retardant, such as can example: hexabromo cyclodecane, bis- (dibromopropyl) tetrabromobisphenol As, three (dibromopropyls) three Polyisocyanate, three (tribromo neopentyl) phosphates, deca-BDE, bis- (pentabromo-) diphenylphosphino ethanes, three (tribromophenoxies) three Piperazine, ethylenebis tetrabromo phthalimide, more bromophenyl dihydroindene, brominated Polystyrene, the poly- carbonic acid of tetrabromobisphenol A Bromide, the triphenyl phosphate, tricresyl phosphate, phosphoric acid of ester, protobromide phenyl ethylene oxide, polyacrylic acid pentabromo- benzyl ester etc. Three (xylyl) esters (トリキシニ Le ホスフェート), cresyl diphenyl phosphate, xylyl diphenylphosphoric acid Bis- (two -2,6- xyxylenes) phosphates of ester, tolyl, 2- ethylhexyl diphenyl phosphate, resorcinol are bis- (diphenyl) Bis- (diphenyl) phosphates of phosphate, bisphenol-A, bis- (xylyl) phosphates of bisphenol-A, the bis- (two -2,6- benzene diformazans of resorcinol Base) phosphate, three (chloroethyl) phosphates, three (chloropropyl) phosphates, three (two chloropropyls) phosphates, three (three bromopropyls) phosphorus Phosphoric acid ester, the anion oxalic acid treatment hydroxide of bis- (2- hydroxyethyl) the aminomethylphosphonic acid esters of acid esters, diethyl-N, N- etc. Aluminium, nitrate treatment aluminium hydroxide, high-temperature-hot-water processing aluminium hydroxide, stannic acid are surface-treated hydrated metal compound, nickel chemical combination Object is surface-treated magnesium hydroxide, organosilicon polymer surface treatment magnesium hydroxide, phlogopite, multiple-level surface and handles hydrated metal Close object, cationic polymer processing magnesium hydroxide etc..

Moreover, in solidification compound of the invention, if it is desired, also may include elastomer other than epoxy resin (or elastomer modifier), for example, acrylonitrile butadiene rubber (NBR), liquid polybutadiene, polybutadiene (butadiene rubber, BR), neoprene, silicon rubber, modified silicon rubber, crosslinking NBR, crosslinking BR, acrylic rubber (include hud typed acrylic rubber Glue), polyurethane rubber, polyester elastomer, the liquid NBR containing functional group, liquid polyesters, liquid polysulfide compound, polyurethane prepolymer Object etc..

If desired, other resins, such as olefine kind resin (high-density polyethylene can also be contained other than epoxy resin Alkene, polypropylene etc.), styrene resin (polystyrene etc.), acrylic resin (polymethyl methacrylate etc.), contain halogen Resin (polyvinyl chloride etc.), polyester resin (polyethylene terephthalate etc.), polycarbonate resin, polyamide resin Rouge (nylon 6, nylon66 fiber etc.), polyurethane based resin, organic silicon resin etc., resin can be engineering plastics (poly- terephthaldehyde Sour butanediol ester, polyethylene naphthalate, bisphenol A polycarbonate, polyacetals, polysulfones, polyether sulfone, polyetherimide, Polyether-ether-ketone etc.).

The usage amount of these additives, elastomer and resin is not particularly limited, and can be selected depending on the application.

The present invention also includes solidfied material obtained by above-mentioned solidification compound solidification.Such solidfied material is according to curability group The purposes of object is closed, above-mentioned solidification compound can be heated and be allowed to solidify to modulate.For example, can be by above-mentioned solidification compound It is coated on substrate and is allowed to solidify, can also inject or be sealed in specified part and be allowed to solidify, can also cast and be allowed to solidify, it can also It is impregnated in substrate (fiber base material) modulation prepreg, which is laminated and is formed by the method for overlapping or winding etc. Regulation shape is processed as to be allowed to solidify again.Solidify can at a temperature of guest compound can be discharged from inclusion compound into Row may be, for example, 100~250 DEG C of (preferably 120~200 DEG C, further preferably 130~180 DEG C) left and right.

Although such resulting solidfied material includes the host compound as low molecular compound, can also be in various physical property (for example, the engineering properties of bending strength, bending modulus, dynamic viscoelastic etc., bending when glass transition temperature, high temperature is special Property etc. thermal property, the electrical property of dielectric constant, dielectric loss angle tangent etc., water absorption rate etc.) without significantling change under (or reduce) Keep (or maintenance).Therefore, solidification compound of the invention can inhibit the physical property of solidfied material to reduce, and with high stability Effectively store.

Embodiment

Hereinafter, based on embodiment, the present invention will be described in more detail, but the present invention is not limited to these Examples.It needs Bright, various characteristics are measured as follows in embodiment below and comparative example.

About¹Inclusion compound is dissolved in deuterated chloroform, deuterated methanol, deuterated dimethyl sulfoxide etc., makes by H-NMR With BrukerBioSpin society system " AVANCE III HD " (¹H resonant frequency: 300MHz) it is measured.

TG-DTA is measured using Seiko Instruments (strain) system " 6000 TG/DTA 6200 of EXSTAR ".

1. the modulation of inclusion compound

[embodiment 1] (synthesis of the inclusion compound of BCF:2E4MZ)

At 70 DEG C to bis- (the 4- hydroxy-3-methyl phenyl) fluorenes of 9,9- (BCF, Osaka Gas chemical (strain) system, 3.78g, In ethyl acetate (10mL) solution 10mol) be added 2-ethyl-4-methylimidazole (2E4MZ, four countries' chemical conversion industry (strain) system, 2.30g,2.1mmol).After stirring 1 hour, stops heating and being cooled to room temperature, generated solid leaching, drying obtain Obtained product (white solid, receipts amount 3.66g).Resulting inclusion compound passes through¹H-NMR and TG-DTA confirms as Host-guest ratio The inclusion compound of BCF:2E4MZ=1:1.

Fig. 1 shows the inclusion compounds of embodiment 1¹H-NMR spectrum, Fig. 2 indicate the inclusion compound of embodiment 1 TG-DTA chart.It should be noted that¹In H-NMR spectrum, the longitudinal axis indicates " intensity ", and horizontal axis indicates unit " ppm ", TG-DTA figure In table, horizontal axis indicates " temperature (DEG C) ", and the left longitudinal axis indicates " DTA ", and the right longitudinal axis indicates " TG ", indicates TG (thermogravimetric amount point with solid line Analysis) chart, it is represented by dotted lines DTA (differential thermal analysis) chart.In addition, " Cel " refers to " DEG C " in TG-DTA chart.

[embodiment 2] (synthesis of the inclusion compound of BXF:2E4MZ)

At 70 DEG C to bis- (4- hydroxyl -3,5- 3,5-dimethylphenyl) fluorenes of 9,9- (BXF, Osaka Gas chemical (strain) system, 4.05g, 10mmol) ethyl acetate (15mL) suspension in be added 2-ethyl-4-methylimidazole (2E4MZ, four countries' chemical conversion industry (strain) system, 2.26g, 2.1mmol), it in addition to this, operates similarly with example 1, obtains product (white solid, receipts amount 4.18g).Resulting inclusion compound passes through¹H-NMR and TG-DTA confirms as the inclusion of Host-guest ratio BXF:2E4MZ=1:1 Close object.

Fig. 3 indicates the inclusion compound of embodiment 2¹H-NMR spectrum, Fig. 4 indicate the inclusion compound of embodiment 2 TG-DTA chart.

[embodiment 3] (synthesis of the inclusion compound of BNF:2E4MZ)

To bis- (6- hydroxyl naphthalene -2- base) fluorenes of 9,9- (BNF, Osaka Gas chemical (strain) system, 907mg, 2mmol) at 60 DEG C Methanol (4mL) solution in be added 2-ethyl-4-methylimidazole (2E4MZ, four countries' chemical conversion industry (strain) system, 444mg, 4mmol). It after stirring 1 hour, is cooled down, reaction mixture is added in water (50mL), generated solid is filtered, is dry, Obtain product (white solid, receipts amount 712mg).Resulting inclusion compound passes through¹H-NMR and TG-DTA confirms as inclusion Inclusion compound than BNF:2E4MZ=1:1.

Fig. 5 indicates the inclusion compound of embodiment 3¹H-NMR spectrum, Fig. 6 indicate the inclusion compound of embodiment 3 TG-DTA chart.

[embodiment 4] (synthesis of the inclusion compound of BCF:2MZ-H)

At 70 DEG C into the solution of the ethyl acetate (15mL) of BCF (3.78g, 10mmol) be added 2-methylimidazole (2MZ-H, Four countries' chemical conversion industry (strain) system, 1.81g, 22mol).It after heating 5 minutes, is cooled down, by the filtering of generated solid, is done It is dry, obtain product (white solid, receipts amount 3.00g).Pass through¹H-NMR and TG-DTA confirms as Host-guest ratio BCF:2MZ-H= The inclusion compound of 1:2.

Fig. 7 indicates the inclusion compound of embodiment 4¹H-NMR spectrum, Fig. 8 shows the inclusion compounds of embodiment 4 TG-DTA chart.

[embodiment 5] (synthesis of the inclusion compound of BXF:2MZ-H)

At 70 DEG C into the solution of the ethyl acetate (15mL) of BXF (4.07g, 10mmol) be added 2-methylimidazole (2MZ-H, Four countries' chemical conversion industry (strain) system, 1.81g, 22mol).After heating 100 minutes, cooled down, generated solid is filtered, It is dry, obtain product (white solid, receipts amount 3.91g).Pass through¹H-NMR and TG-DTA confirms as Host-guest ratio BXF:2MZ-H The inclusion compound of=1:1.

Fig. 9 indicates the inclusion compound of embodiment 5¹H-NMR spectrum, Figure 10 indicate the inclusion compound of embodiment 5 TG-DTA chart.

[embodiment 6] (synthesis of the inclusion compound of BCF:DBU)

Diazabicyclo endecatylene (DBU, Tokyo are added into the solution of the ethyl acetate (8mL) of BCF (377mg, 1mmol) It is melted into (strain) system, 344g, 2.6mmol).While preventing the DBU from leaking out in a reservoir after 100 DEG C of heating stirrings, carry out cold But, by the filtering of generated solid, drying, product (white solid, receipts amount 660mg) is obtained.Pass through¹H-NMR and TG-DTA It confirms as the inclusion compound of Host-guest ratio BCF:DBU=1:2.

Figure 11 indicates the inclusion compound of embodiment 6¹H-NMR spectrum, Figure 12 indicate the inclusion compound of embodiment 6 TG-DTA chart.

Table 1 indicates the composition of each inclusion compound and the release temperature of guest compound.

[table 1]

2. the modulation and its characteristic of solidification compound

[embodiment 7: solidification compound]

Inclusionization obtained in embodiment 1 is added in 100 parts by weight of liquid-state epoxy resin (jER828, Mitsubishi Chemical's (strain) system) Object (BCF:2E4MZ) 13.3 parts by weight (2E4MZ is 3 parts by weight) is closed, (the smart mechanism of (strain) Japan makees made, Ace using homogenizer Homogenizer AM-10), with revolving speed 15000rpm stirring 10 minutes, modulate solidification compound.

[comparative example 1: solidification compound]

The 2E4MZ of 3 parts by weight is added in 100 parts by weight of liquid-state epoxy resin (jER828, Mitsubishi Chemical's (strain) system), with implementation Example 7 operates in the same way, and has modulated solidification compound.

[measurement of gelation time]

According to JIS C 2161, sample is placed on the stainless steel plate for being heated to predetermined temperature, with spatula (spatula) with every point The speed that clock is 60 times circularly mixes, and becomes gel-like sample, is not attached to the time point of spatula with sample or without wire drawing Time point as terminal.As shown in table 2, when the solidification compound of embodiment 7 shows the gelation same with comparative example 1 Between.

[table 2]

[DSC of solidification compound is measured]

It is provided using obtained in 100 parts by weight of liquid-state epoxy resin (jER 828, Mitsubishi Chemical's (strain) make) and embodiment 2~3 The inclusion compound (imidazoles is 3 parts by weight) of amount, operates similarly to Example 7, has modulated solidification compound (embodiment 8 With the solidification composition filling of embodiment 9).In addition, using the solidification compound of comparative example 1 as control.

Then, it takes a part of solidification compound to be placed in aluminum pot, uses differential scanning calorimetry DSC (Seiko Instruments (strain) makes " 6000 DSC 6220 of EXSTAR ") carry out heat analysis.It shows the result in table 3.In addition, Figure 13 Indicate that the DSC chart of the solidification compound of embodiment 7, Figure 14 indicate the DSC chart of the solidification compound of embodiment 8, figure 15 indicate that the DSC chart of the solidification compound of embodiment 9, Figure 16 indicate the DSC chart of the solidification compound of comparative example 1. It should be noted that " Cel " refers to " DEG C " in DSC chart.

[table 3]

By table 3 and Figure 13~Figure 16 it is found that showing sharp heat release using the solidification compound of the inclusion compound of embodiment Peak, and wide multiple exothermic peaks are shown using the solidification compound of the comparative example of imidazoles 1.

[storage stability of solidification compound]

After the container for accommodating above-mentioned solidification compound is kneaded while cooling with ice water, 20 minutes are stood at 25 DEG C, then Using a part of composition as sample, using E type viscosimeter (eastern machine industry (strain) makes " TVE-22L "), at 25 DEG C every Stipulated time determines viscosity (mPa s/25 DEG C).It shows the result in table 4.

[table 4]

As shown in Table 4, the solidification compound of embodiment 1 viscosity after 48 times is about 2 times of initial value, in contrast, than Compared with example 1 solidification compound after 24 times viscosity reach 7 times of initial value.

3. production and the physical property measurement of solidfied material

According to following step, solidfied material test film has been made.

[embodiment 10: the production of solidfied material test film]

Chemical combination will be included obtained in liquid-state epoxy resin (jER 828, Mitsubishi Chemical's (strain) system) 100 parts by weight and embodiment 1 10 parts by weight of object (BCF:2E4MZ) make to include using mixing and kneading machine (Ishikawa formula stirs mixing and kneading machine 18, (strain) Ishikawa workshop system) Compound is scattered in after epoxy resin, and vacuum defoamation is simultaneously injected into casting slot and [is being pasted with cellophane (cellophane) 2 aluminium sheets (3mm thick) between the slot that is interposed the silicon rubber of diameter of phi 3mm or 4mm as spacer and is fixed with clip] In, solidified in heated-air circulation oven according to condition documented by following table 5.It should be noted that the diameter root of spacer It carries out being suitable for change according to the size of test film.

[comparative example 2: the production of solidfied material test film]

Using spatula by 3 parts by weight of 100 parts by weight of liquid-state epoxy resin (jER 828) and 2-ethyl-4-methylimidazole (2E4MZ) It is sufficiently mixed.It by its vacuum defoamation and is injected into casting slot, according to recorded in following table 5 in heated-air circulation oven The condition stated is solidified.

[embodiment 11: the production of solidfied material test film]

By inclusion compound (BCF:2E4MZ) 10 obtained in 100 parts by weight of liquid-state epoxy resin (jER 828) and embodiment 1 Anhydride compound is added after being kneaded using mixing and kneading machine (Ishikawa formula stirs mixing and kneading machine 18, (strain) Ishikawa workshop system) in parts by weight (MH-700, new Japan Chemical (strain) system, anhydride equivalent 164g/eq.) 86.3 parts by weight, are mixed with spatula, carry out vacuum defoamation Afterwards, it is injected into casting slot, is solidified in heated-air circulation oven according to condition documented by following table 5.It should be noted It is that anhydride compound is with 1 mole of epoxy group relative to epoxy resin, the ratio that the anhydride group of anhydride compound is 1 mole Example is blended.

[comparative example 3: the production of solidfied material test film]

By 100 parts by weight of liquid-state epoxy resin (jER 828) and 3 parts by weight of 2-ethyl-4-methylimidazole (2E4MZ) and anhydride 86.3 parts by weight of compound (MH-700), are sufficiently mixed using spatula.By its vacuum defoamation and it is injected into casting slot, Solidified in heated-air circulation oven according to condition documented by following table 5.It should be noted that anhydride compound is with opposite In 1 mole of epoxy group of epoxy resin, the ratio that the anhydride group of anhydride compound is 1 mole is blended.

[embodiment 12: the production of solidfied material test film]

By phenolic compound (PSM-4261, group's honor chemical industry (strain) system, phenolic resin, hydroxyl equivalent 103g/eq.) 54.2 weights 10 parts by weight of inclusion compound (BCF:2E4MZ) obtained in part and embodiment 1 are measured, with double roller (6 inches of Mixing roll DY6-15, (strain) Daihan system) it is kneaded at 100 DEG C, further add liquid-state epoxy resin (jER 828) 100 weight Part be kneaded within about 5 minutes.After being taken out in roller, 100 DEG C are heated to, is injected into casting slot, in heated-air circulation oven In solidified according to condition documented by following table 5.It should be noted that phenolic compound is with the epoxy relative to epoxy resin 1 mole of base, the ratio that the hydroxyl of phenolic compound is 1 mole is blended.

[comparative example 4: the production of solidfied material test film]

By 54.2 parts by weight of 100 parts by weight of liquid-state epoxy resin (jER 828) and phenolic compound (PSM-4261), existed with double roller It is kneaded at 90~100 DEG C.After taking out in roller, 2-ethyl-4-methylimidazole (2E4MZ) 3 parts by weight are added, 100 DEG C baking oven in heating, after being mixed with spatula, be injected into casting slot, according to following tables in heated-air circulation oven Condition documented by 5 is solidified.It should be noted that phenolic compound is with 1 mole of epoxy group relative to epoxy resin, phenols The hydroxyl of compound is that 1 mole of ratio is blended.

Table 5 indicates the Blend proportion and condition of cure of each solidfied material.

[table 5]

The various physical property of solidfied material obtained in embodiment 10~12 and comparative example 2~4 are carried out using following documented method Measurement.

[bend test]

Test film: about 80mm × 10mm × 4.0mm

Determination condition: test speed 2mm/ minutes

Distance between the fulcrum 64mm

Test temperature room temperature or 260 DEG C

Measurement device: 5582 type of universal testing machine (Instron society system)

It should be noted that bending modulus is calculated according to the tangential elasticity modulus of initial stage straight line portion.

[dielectric constant, dielectric loss angle tangent measurement]

Test method: cavity resonator channel method (according to ASTM D 2520)

Test film: 80mm × 1.5mm × 1.5mm is thick

Determination condition: frequency 1GHz

23 ± 2 DEG C of experimental enviroment, 50 ± 5%RH

Measure number n=2

Measurement device: PNA-L Network Analyzer N5230A (Agilent Technologies (strain) system)

Cavity resonator CP431 ((strain) Northeast the development of electronics applied system).

[thermo-mechanical analysis (TMA) measurement]

Determination condition: measuring temperature room temperature~300 DEG C

5 DEG C/min of heating rate

In atmosphere nitrogen stream (50mL/ minutes)

Mode determination compact model (load 20mN)

Measurement device: TMA 8310 ((strain) Rigaku system).

[dynamic viscoelastic (DMA) measurement]

Measurement item: E ', E ", tanδ

Test film: band 50mm × 10mm × 3mm

Determination condition: measuring temperature room temperature~300 DEG C

4.0 DEG C/min of heating rate

Frequency 1Hz

In atmosphere nitrogen stream (300mL/ minutes)

Mode determination beam mode

Measurement device: EXSTAR DMS6100 ((strain) Hitachi High Tech Science system).

[water absorption rate measurement]

Test film: about 50mm × 50mm × 3.0mm

Test method: after test film is dried with following conditions, being impregnated in water, by the test sheet weight after impregnating and in advance The difference of test sheet weight after first drying is calculated divided by the test sheet weight after being pre-dried.

Determination condition: it is pre-dried 50 DEG C × 24 hours

Dipping in water 23 DEG C × 24 hours

Measure number n=3.

The measurement result of various physical property is shown in table 6 below.

[table 6]

As shown in Table 6, the solidfied material of the solidification compound comprising inclusion compound of the invention, and includes imidazoles The solidfied material of the solidification compound of monomer adduct is compared, and shows almost same physics value.Therefore, by using the present invention Inclusion compound, can obtain do not undermine substantially physical property and with high storage stability solidification compound.

In addition, the embodiment 11 comprising anhydride compound is different from other embodiments, compared with corresponding comparative example 3, Bending strength and bending modulus at 260 DEG C is high, and glass transition temperature also rises 10 DEG C or more, and heat resistance is promoted.

Industrial applicibility

It include that the storage stability of the solidification compound of epoxy resin mentions due to forming inclusion compound in the present invention It rises, and shows by heating promptly cured characteristic.Therefore, solidification compound of the invention can use in epoxy In the various uses that resin is applicable in, for example, insulating materials, sealing material (electronic component of semiconductor, light emitting diode etc. Sealing material, such as encapsulating semiconductor material etc.), plywood (epoxy resin plywood, with glass cloth, paper, synthetic fiber cloth, copper Plywood of the substrates such as foil, such as printed wiring board-use plywood etc.), composite material it is (fine with glass fibre, carbon fiber, aramid fiber The fiber reinforced composite material of the reinforcing fiber of dimension etc.), cast material, concrete body study for a second time courses one has flunked material, bonding agent, clear The various uses of the smears of paint, coating (including powdery paints), ink etc. etc..

Claims

1. inclusion compound, it includes compounds represented by following formula (1) as host compound, and includes to have containing multiple Nitrogen-atoms as 5 or 6 circle heterocyclic rings of ring atom or the compound of its annelated heterocycles as guest compound,

[chemical formula 1]

In formula, Ar¹、Ar²、Z¹And Z²Respective identical or different expression monocyclic aromatic hydrocarbon ring or polycycle aromatic hydrocarbon ring；R¹、R²、R³And R⁴ Respective identical or different expression substituent group；At least one is among the integer of the identical or different expression 0~4 of n1 and n2, n1 and n2 At least 1 or more integer；M1, m2, p1 and p2 respectively it is identical or different indicate 0~4 integer.

2. inclusion compound described in claim 1, wherein in formula (1), Ar¹And Ar²Identical or different is phenyl ring or naphthalene nucleus；Z¹ And Z²Identical or different is phenyl ring or naphthalene nucleus；R¹And R²Identical or different is alkyl, naphthenic base, aryl, aralkyl, alkoxy, ring Alkoxy, aryloxy group, aralkyl oxy, acyl group, alkoxy carbonyl, halogen atom, nitro, cyano or substituted-amino；R³And R⁴It is identical It or is not all alkyl, naphthenic base, aryl, aralkyl, alkoxy, halogen atom, nitro, cyano or substituted-amino；N1 is identical with n2 Or not be all 1~3 integer；The identical or different integer for being 0~2 of m1 and m2；The identical or different integer for being 0~2 of p1 and p2.

3. inclusion compound of any of claims 1 or 2, wherein in formula (1), Ar¹And Ar²For phenyl ring；Z¹And Z²For phenyl ring or naphthalene Ring；N1 and n2 is 1 or 2；R¹And R²Identical or different is C_1-4Alkyl or C_6-10The integer that aryl, m1 and m2 are 0~2；P1 and p2 It is 0.

4. inclusion compound according to any one of claims 1 to 3, wherein in formula (1), R¹And R²For methyl or phenyl, m1 It is 1 or 2 with m2.

5. inclusion compound according to any one of claims 1 to 4, wherein guest compound includes that following formula (2) are represented Compound,

[chemical formula 2]

In formula, R⁵Indicate hydrogen atom, alkyl, naphthenic base, aryl, aralkyl, cyano ethyl or triazine-alkyl；R⁶~R⁸It indicates Hydrogen atom, halogen atom, nitro, alkyl, naphthenic base, aryl, aralkyl or acyl group, abovementioned alkyl can have hydroxyl, R⁵With R⁶It can be mutual It is mutually bonded and is formed together ring with adjacent nitrogen-atoms and carbon atom；Q indicates 0 or 1~3 integer；Solid line and dotted line it is dual Line indicates singly-bound or double bond.

6. inclusion compound according to any one of claims 1 to 5, wherein guest compound include following formula (2a) and/or Compound represented by (2b),

[chemical formula 3]

In formula, r indicates 0~5 integer；R⁵~R⁸It is identical as claim 5 with solid line and the doublet of dotted line.

7. inclusion compound according to any one of claims 1 to 6, wherein relative to 1 mole of host compound, with 0.5~ 5 moles of ratio includes guest compound.

8. the method for preparing inclusion compound according to any one of claims 1 to 7, this method is will be described in claim 1 Formula (1) represented by compound, with have containing multiple nitrogen-atoms as 5 or 6 circle heterocyclic rings of ring atom or its condense it is miscellaneous The compound of ring mixes.

9. curing agent or curing accelerator are curing agent or curing accelerator for making epoxy resin cure, and include power Benefit require any one of 1~7 described in inclusion compound.

10. solidification compound, it includes inclusion compound according to any one of claims 1 to 7 and epoxy resin.

11. solidification compound described in any one of claim 10, wherein epoxy resin is liquid-state epoxy resin.

12. solidification compound described in claim 10 or 11, wherein relative to 100 parts by weight of epoxy resin, with 0.1~ The ratio of 25 parts by weight includes inclusion compound.

13. solidification compound described in any one of claim 10~12, further include selected from phenolic compound and At least one compound of anhydride compound.

14. solidfied material, being will be obtained by the solidification of solidification compound described in any one of claim 10~13.

15. the method for preparing solidfied material, this method is to add solidification compound described in any one of claim 10~13 Heat and solidify.