CN102725273B - Inclusion compound and manufacture method thereof - Google Patents

Inclusion compound and manufacture method thereof Download PDF

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Publication number
CN102725273B
CN102725273B CN201180006305.8A CN201180006305A CN102725273B CN 102725273 B CN102725273 B CN 102725273B CN 201180006305 A CN201180006305 A CN 201180006305A CN 102725273 B CN102725273 B CN 102725273B
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Prior art keywords
acid
inclusion compound
compound
composition
methyl
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CN102725273A (en
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小野和男
龟谷直幸
天野仓夏树
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Nippon Soda Co Ltd
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Nippon Soda Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
    • C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The object of the present invention is to provide the 1:2 inclusion compound of highly purified aromatic carboxy acid compound and imidazolium compounds, and provide containing the composition epoxy resin of this inclusion compound as solidifying agent or curing catalyst.By adding aromatic carboxy acid compound to the alcohol liquid of imidazolium compounds or adding the alcoholic solution of aromatic carboxy acid compound to imidazolium compounds, aromatic carboxy acid compound (A) and imidazolium compounds (B) can be contained with high purity manufacture and the mol ratio of (A) and (B) is the inclusion compound of 1:2.The inclusion compound obtained like this can be used as solidifying agent or the curing catalyst of epoxy resin etc.

Description

Inclusion compound and manufacture method thereof
Technical field
The present invention relates to novel inclusion compound and manufacture method thereof, particularly relate to the inclusion compound be made up of aromatic carboxy acid compound and imidazolium compounds and manufacture method thereof that can be used as Epoxy cure catalysts etc. and the composition epoxy resin containing inclusion compound or its cured article.
Its content to the Japanese patent application 2010-228645 CLAIM OF PRIORITY of the Japanese patent application application on October 8th, No. 2010-10375 1 applied on January 20th, 2010, and is incorporated herein by the application.
Background technology
Epoxy resin is owing to having excellent mechanical characteristics, thermal property and be widely used in every field.As the solidifying agent for solidifying described epoxy resin, use imidazole compound, but the mixed solution of epoxy resin-imidazole compound exists, and solidification starts early, this problem of single liquid stability extreme difference.
Therefore, as solidifying agent, propose the salt (with reference to patent documentation 1) using and imidazole compound addition hydroxy-benzoic acid is formed, use four phenol system compounds (such as, 1,1,2,2 ,-four (4-hydroxy phenyl) ethane (hereinafter referred to as TEP)) with the inclusion compound of imidazole compound (with reference to patent documentation 2).This imidazoles acid salt and inclusion body can play certain effect, but wish to develop to have with the solidifying agent of its same function, carry H.D solidifying agent further.
Therefore, propose and develop the inclusion compound (patent documentation 3) of m-phthalic acid compound that contained (i) represent and the imidazolium compounds that formula (ii) represents.
[in formula, R 1represent C1 ~ C6 alkyl, C1 ~ C6 alkoxyl group, nitro or hydroxyl.]
[in formula, R 2represent hydrogen atom, C1 ~ C10 alkyl, aryl, arylalkyl or cyanoethyl, R 3~ R 5the acyl group of the C1 ~ C20 alkyl, aryl, arylalkyl or the C1 ~ C20 that represent hydrogen atom, nitro, halogen atom independently of one another, substituent C1 ~ C20 alkyl can be had, are optionally substituted by a hydroxyl group.]
The method for making of the inclusion compound in patent documentation 3 is added to after in solvent m-phthalic acid compound and imidazolium compounds, carries out heat treated or reflux process while stirring as required, make the method that it is separated out.In addition, if describe the dissolving easness considered solvent in the document, then the imidazolium compounds that the m-phthalic acid compound preferably formula (i) represented respectively and formula (ii) represent dissolves in a solvent, is mixed with each other by lysate.
But, in patent documentation 3, inclusion compound not only for 5-Hydroxy M Phthalic Acid and 2-phenyl-4-methyl-5-hydroxymethylimidazole is not specifically recorded, if the method utilizing this patent documentation to record makes 5-Hydroxy M Phthalic Acid and the reaction of 2-phenyl-4-methyl-5-hydroxymethylimidazole, then only can obtain the 1:1 inclusion compound of two compounds and the mixture of 1:2 inclusion compound.
Thereafter, the 1:1 inclusion compound (patent documentation 4) of 5-Hydroxy M Phthalic Acid and 2-phenyl-4-methyl-5-hydroxymethylimidazole can be manufactured with high purity, but 1:2 inclusion compound can not be manufactured with high purity.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Publication 4-2638 publication
Patent documentation 2: Japanese Unexamined Patent Publication 11-71449 publication
Patent documentation 3: International Publication No. 2008/075427 brochure
Patent documentation 4: International Publication No. 2009/037862 brochure
Summary of the invention
Therefore, problem of the present invention is the 1:2 inclusion compound obtaining the imidazoles such as the aromatic carboxy acid compounds such as 5-Hydroxy M Phthalic Acid and 2-phenyl-4-methyl-5-hydroxymethylimidazole with high purity.
The present inventor etc. conduct in-depth research, found that the blending means by inquiring into 5-Hydroxy M Phthalic Acid and 2-phenyl-4-methyl-5-hydroxymethylimidazole, the mol ratio that can obtain subject and object is the inclusion compound of 1 to 2 (hreinafter referred to as 1:2 inclusion compound).Repeatedly study further, the mol ratio that result is distinguished for just known subject and object be the inclusion compound of 1 to 1 (below, referred to as 1:1 inclusion compound) inclusion compound host compound and guest compound, 1:2 inclusion compound can be manufactured by utilizing the manufacturing process of the present application.In addition, the method of 1:2 inclusion compound can be manufactured and its Measures compare can not be manufactured in known manufacturing process, result distinguishes that known method can not manufacture 1:2 inclusion compound when the aromatic carboxy acid compound as host compound is to solvent poorly soluble.In a word, find the curable epoxy resin composition that can produce containing this 1:2 inclusion compound and cured article thereof, and find with containing compared with during 1:1 inclusion compound, its characteristic raising, thus complete the present invention.
That is, the present invention relates to:
(1) inclusion compound or its composition, containing following inclusion compound, this inclusion compound is 70 % by mole ~ 100 % by mole in containing total inclusion compound of (A) and (B),
Described inclusion compound contains compound (B) that aromatic carboxy acid compound (A) and formula (II) represent and (A) is 1:2 with the mol ratio of (B),
(in formula, R 2represent hydrogen atom, C1 ~ C10 alkyl, aryl, arylalkyl or cyanoethyl, R 3~ R 5the acyl group of C1 ~ C20 alkyl, aryl, arylalkyl or C1 ~ C20 represent hydrogen atom, nitro, halogen atom, C1 ~ C20 alkyl, being optionally substituted by a hydroxyl group.The part of mark dotted line represents singly-bound or double bond.)
(2) inclusion compound recorded according to above-mentioned (1) or its composition, it is characterized in that, aromatic carboxy acid compound is the compound that formula (III) or formula (IV) represent,
(in formula, n1 represents arbitrary integer in 1 ~ 4.N2 represents arbitrary integer in 0 ~ 4.R 6represent C1 ~ C6 alkyl, nitro or hydroxyl.)
(in formula, m1 represents arbitrary integer in 1 ~ 4.M2 represents arbitrary integer in 0 ~ 2.R 7represent the group that C1 ~ C6 alkyl, nitro, hydroxyl or following formula represent,
(in formula, q represents the integer of 1 or 2.* bonding position is represented))
(3) according to the inclusion compound recorded in above-mentioned (2) or its composition, it is characterized in that, formula (IV) is formula (I),
(in formula, R 1represent C1 ~ C6 alkyl, C1 ~ C6 alkoxyl group, nitro or hydroxyl.)
(4) inclusion compound recorded according to above-mentioned (3) or its composition, it is characterized in that, formula (I) is 5-Hydroxy M Phthalic Acid,
(5) inclusion compound recorded any one of above-mentioned (1) ~ (4) or its composition, it is characterized in that, formula (II) is 2-phenyl-4-methyl-5-hydroxymethylimidazole.
In addition, the present invention relates to:
(6) manufacture method of a kind of above-mentioned (1) inclusion compound of recording or its composition, it is characterized in that, the alcohol liquid to the compound of formula (II) adds aromatic carboxy acid compound,
(7) manufacture method of a kind of above-mentioned (1) inclusion compound of recording or its composition, it is characterized in that, the compound to formula (II) adds the alcoholic solution of aromatic carboxy acid compound.
In addition, also relate to:
(8) curable epoxy resin composition or its cured article, containing the inclusion compound recorded any one of above-mentioned (1) ~ (5) or its composition and epoxy resin.
Accompanying drawing explanation
Fig. 1 is the figure representing thermal analyses (DSC) chart that the inclusion compound obtained in synthetic example 1 measures based on temperature variation.
Fig. 2-1 is the figure representing thermal analyses (DSC) chart that the inclusion compound obtained in synthetic example 2 measures based on temperature variation.
Fig. 2-2 represents the inclusion compound that obtains in synthetic example 2 1the figure of H-NMR chart.
Fig. 3-1 is the figure representing thermal analyses (DSC) chart that the inclusion compound obtained in synthetic example 3 measures based on temperature variation.
Fig. 3-2 represents the inclusion compound that obtains in synthetic example 3 1the figure of H-NMR chart.
Fig. 4-1 is the figure representing thermal analyses (DSC) chart that the inclusion compound obtained in synthetic example 4 measures based on temperature variation.
Fig. 4-2 represents the inclusion compound that obtains in synthetic example 4 1the figure of H-NMR chart.
Fig. 5 is the figure representing thermal analyses (DSC) chart that the inclusion compound obtained in synthesized reference example 1 measures based on temperature variation.
Fig. 6 is the figure representing thermal analyses (DSC) chart that the inclusion compound obtained in synthesis comparative example 1 measures based on temperature variation.
Embodiment
(inclusion compound or its composition)
Inclusion compound of the present invention or its composition are (following with aromatic carboxy acid compound, referred to as " carboxylic acid cpd ") be host compound, the imidazolium compounds represented with formula (II) or imidazolinium compounds are (below, referred to as imidazolium compounds) be guest compound, the mol ratio of carboxylic acid cpd and imidazolium compounds is only the inclusion compound of 1:2 or contains the composition of the inclusion compound that mol ratio is 1:2 with high purity.
(in formula, R 2represent hydrogen atom, C1 ~ C10 alkyl, aryl, arylalkyl or cyanoethyl, R 3~ R 5the acyl group of C1 ~ C20 alkyl, aryl, arylalkyl or C1 ~ C20 represent hydrogen atom, nitro, halogen atom, C1 ~ C20 alkyl, being optionally substituted by a hydroxyl group.The part of mark dotted line represents singly-bound or double bond.)
Be the inclusion compound being sometimes mixed into the different mol ratio such as 1:1 in the inclusion compound of 1:2 in the mol ratio of carboxylic acid cpd and imidazolium compounds, in the present invention, be referred to as the composition of above-mentioned inclusion compound.
For inclusion compound of the present invention or its composition, in the inclusion compound entirety containing carboxylic acid cpd and imidazolium compounds, 1:2 inclusion compound containing proportional be more than 70 % by mole, be preferably more than 80 % by mole, more preferably more than 90 % by mole, be not preferably mixed with in fact the inclusion compound of other mol ratios such as 1:1 in addition.But inclusion compound of the present invention can containing the 3rd compositions such as solvents, and the 3rd composition is preferably less than 40 % by mole, is more preferably less than 10 % by mole, the inclusion compound most preferably not containing the 3rd composition.In the present invention, inclusion compound refers to that host compound forms cage type lattice (bag connects grid) and host compound and one kind or two or more guest compound carry out the compound of bonding by the key beyond covalent linkage, is more preferably called Crystalline Compound.Inclusion compound of the present invention containing carboxylic acid cpd and imidazolium compounds is alternatively the salt formed by carboxylic acid cpd and imidazolium compounds.
As abbreviation, 5-Hydroxy M Phthalic Acid is called " HIPA ", and 2-phenyl-4-methyl-5-hydroxymethylimidazole is called " 2P4MHZ ".
Here, cage type lattice refers to that host compound carries out bonding each other by the key beyond covalent linkage, space more than 2 molecules or 3 molecules of the host compound of bonding, by the structure of other molecule of key inclusion (object, solvent etc.) beyond covalent linkage or other molecule and host compound; Or host compound and other molecule (object, solvent etc.) carry out bonding by the key beyond covalent linkage, space more than 2 molecules or 3 molecules of the host compound with other molecular linkage, by the structure of the key inclusion host compound beyond covalent linkage and/or other molecule (object, solvent etc.).
Inclusion compound of the present invention can use as the resin curing agent of vibrin, epoxy resin, epoxy polyester resin etc., can particularly preferably use as the solidifying agent of epoxy resin.Composition epoxy resin of the present invention can be preferably used in the purposes of cured epoxy resin, such as epoxy resin tackiness agent, semiconductor-encapsulating material, sealing material for liquid crystal, the purposes such as printed wiring plywood, varnish, injectable plastic material, ink.In addition, inclusion compound of the present invention can be dissolve the fluent meterial formed in a solvent, but is preferably the material of (separating out in solvent) powder shaped.By being powder shaped, such as, can be used for powder coating.
The structure of inclusion compound can utilize thermal analyses (TG and DTA), infrared absorption spectrum (IR), X-ray diffraction (XRD) pattern, solid NMR spectrum etc. to confirm.In addition, the composition of inclusion compound can utilize thermal analyses, 1h-NMR spectrum, high performance liquid chromatography (HPLC), ultimate analysis etc. confirm.
In addition, such as, when the composition be made up of 1:1 inclusion compound and 1:2 inclusion compound, 1:2 inclusion compound can by inclusion compound containing proportional (purity) 1the integrated value of H-NMR calculates by purity (%)=1:2 inclusion compound/(1:1 inclusion compound+1:2 inclusion compound) × 100.As an example, for the purity of the 1:2 inclusion compound of HIPA and 2P4MHZ, at DMSO-d 6in, in the value (a) that 25 DEG C can use the integrated value of 2.1ppm to obtain divided by the integrated value of 7.5ppm, try to achieve by following formula.
Purity (%)=(2a/3-1) × 100 of 1:2 inclusion compound
(carboxylic acid cpd)
As aromatic carboxy acid compound, be not particularly limited, such as, can illustrate following compound.
Phenylformic acid, 2-tolyl acid, 3-tolyl acid, 4-tolyl acid, 2-ethyl benzoate, 3-ethyl benzoate, 4-ethyl benzoate, 2-n-propylbenzene formic acid, 3-n-propylbenzene formic acid, 4-n-propylbenzene formic acid, 2-butylbenzoic acid, 3-butylbenzoic acid, 4-butylbenzoic acid, 2-isopropyl acid, 3-isopropyl acid, 4-isopropyl acid, 2-isobutyl-benzene formic acid, 3-isobutyl-benzene formic acid, 4-isobutyl-benzene formic acid, 2 hydroxybenzoic acid, 3-hydroxy-benzoic acid, 4-HBA, 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, 2-nitrobenzene methyl, 3-nitrobenzene methyl, 4-nitrobenzene methyl, 2-ethyl nitrobenzoate, 3-ethyl nitrobenzoate, 4-ethyl nitrobenzoate, 2-nitrobenzoyl propyl propionate, 3-nitrobenzoyl propyl propionate, 4-nitrobenzoyl propyl propionate, 2-nitrobenzoyl acid butyl ester, 3-nitrobenzoyl acid butyl ester, 4-nitrobenzoyl acid butyl ester, 2，3-xylic acid, 2,4-mesitylenic acid, 2,5-mesitylenic acid, 2,6-mesitylenic acid, 3,4-mesitylenic acid, 3,5-mesitylenic acid, 3,6-mesitylenic acid, 4,5-mesitylenic acid, 4,6-mesitylenic acid, 2,3-diethylbenzene formic acid, 2,4-diethylbenzene formic acid, 2,5-diethylbenzene formic acid, 2,6-diethylbenzene formic acid, 3,4-diethylbenzene formic acid, 3,5-diethylbenzene formic acid, 3,6-diethylbenzene formic acid, 4,5-diethylbenzene formic acid, 4,6-diethylbenzene formic acid, 2,3-resorcylic acid, 2,4-resorcylic acid, DHB, 2,6-DHBA, PCA, 3,5-resorcylic acid, 3,6-resorcylic acid, 4,5-resorcylic acid, 4,6-resorcylic acid,
Phthalic acid, 3-methylphthalic acid, 4-methylphthalic acid, 5-methylphthalic acid, 6-methylphthalic acid, 3-ethyl phthalic acid, 4-ethyl phthalic acid, 5-ethyl phthalic acid, 6-ethyl phthalic acid, 3-n-propyl phthalic acid, 4-n-propyl phthalic acid, 5-n-propyl phthalic acid, 6-n-propyl phthalic acid, 3-butyl phthalic acid, 4-butyl phthalic acid, 5-butyl phthalic acid, 6-butyl phthalic acid, 3-sec.-propyl phthalic acid, 4-sec.-propyl phthalic acid, 5-sec.-propyl phthalic acid, 6-sec.-propyl phthalic acid, 3-isobutyl-phthalic acid, 4-isobutyl-phthalic acid, 5-isobutyl-phthalic acid, 6-isobutyl-phthalic acid, 3-hydroxyl phthalic, 4-hydroxyl phthalic, 5-hydroxyl phthalic, 6-hydroxyl phthalic, 3,4-dihydroxyl phthalic acid, 3,5-dihydroxyl phthalic acid, 3,6-dihydroxyl phthalic acid, 4,5-dihydroxyl phthalic acid, 4,6-dihydroxyl phthalic acid, 3-nitrophthalic acid, 4-nitrophthalic acid, 5-nitrophthalic acid, 6-nitrophthalic acid, 3,4-dimethyl phthalic acid, 3,5-dimethyl phthalic acid, 3,6-dimethyl phthalic acid, 4,5-dimethyl phthalic acid, 4,6-dimethyl phthalic acid,
M-phthalic acid, 2-methylresorcinol dioctyl phthalate, 4-methylresorcinol dioctyl phthalate, oreinol dioctyl phthalate, 6-methylresorcinol dioctyl phthalate, 2-ethyl resorcinol dioctyl phthalate, 4-ethyl resorcinol dioctyl phthalate, 5-ethyl resorcinol dioctyl phthalate, 6-ethyl resorcinol dioctyl phthalate, 2-n-propyl m-phthalic acid, 4-n-propyl m-phthalic acid, 5-n-propyl m-phthalic acid, 6-n-propyl m-phthalic acid, 2-sec.-propyl m-phthalic acid, 4-sec.-propyl m-phthalic acid, 5-sec.-propyl m-phthalic acid, 6-sec.-propyl m-phthalic acid, 2-butyl m-phthalic acid, 4-butyl m-phthalic acid, 5-butyl m-phthalic acid, 6-butyl m-phthalic acid, 2-isobutyl-m-phthalic acid, 4-isobutyl-m-phthalic acid, 5-isobutyl-m-phthalic acid, 6-isobutyl-m-phthalic acid, 4-tert-butyl isophthalic acid, 5-tert-butyl isophthalic acid, 6-tert-butyl isophthalic acid, 2-Hydroxy M Phthalic Acid, 4 hydroxyisophthalic acid, 5-Hydroxy M Phthalic Acid, 6-Hydroxy M Phthalic Acid, 2,4-dihydroxyl m-phthalic acid, 2,5-dihydroxyl m-phthalic acid, 2,6-dihydroxyl m-phthalic acid, 4,5-dihydroxyl m-phthalic acid, 4,6-dihydroxyl m-phthalic acid, 5,6-dihydroxyl m-phthalic acid, 2,4-dimethyl m-phthalic acid, 2,5-dimethyl m-phthalic acid, 2,6-dimethyl m-phthalic acid, 4,5-dimethyl m-phthalic acid, 4,6-dimethyl m-phthalic acid, 5,6-dimethyl m-phthalic acid, 2-nitroisophthalic acid, 4-nitroisophthalic acid, 5-nitroisophthalic acid, 6-nitroisophthalic acid, 2-methylterephthalic acid, 2-ethyl terephthalic acid, 2-n-propyl terephthalic acid, 2-sec.-propyl terephthalic acid, 2-butyl terephthalic acid, 2-isobutyl-terephthalic acid, 2-hydroxyterephthalic acid, 2,6-dihydric para-phthalic acid, 2,6-dimethyl terephthalic acid, 2-nitroterephthalic, 1,2,3-benzene tricarboxylic acid, 1,2,4-benzene tricarboxylic acid (trimellitic acid), 1,2,5-benzene tricarboxylic acid, 1,3,4-benzene tricarboxylic acid, 1,3,5-benzene tricarboxylic acid (trimesic acid), 4-hydroxyl-1,2,3-benzene tricarboxylic acid, 5-hydroxyl-1,2,3-benzene tricarboxylic acid, 3-hydroxyl-1,2,4-benzene tricarboxylic acid, 5-hydroxyl-1,2,4-benzene tricarboxylic acid, 6-hydroxyl-1,2,4-benzene tricarboxylic acid, 1,2,4,5-benzene tetracarboxylic acid (pyromellitic acid),
1-naphthoic acid, 2-naphthoic acid, 2-methyl isophthalic acid-naphthoic acid, 3-methyl isophthalic acid-naphthoic acid, 4-methyl isophthalic acid-naphthoic acid, 5-methyl isophthalic acid-naphthoic acid, 6-methyl isophthalic acid-naphthoic acid, 7-methyl isophthalic acid-naphthoic acid, 8-methyl isophthalic acid-naphthoic acid, 1-methyl-2-naphthoic acid, 3-methyl-2-naphthoic acid, 4-methyl-2-naphthoic acid, 5-methyl-2-naphthoic acid, 6-methyl-2-naphthoic acid, 7-methyl-2-naphthoic acid, 8-methyl-2-naphthoic acid, 1,2-naphthalic acid, 1,3-NDCA, Isosorbide-5-Nitrae-naphthalic acid, 1,5-naphthalic acid, 1,6-naphthalic acid, 1,7-naphthalic acid, 1,8-naphthalic acid, 2,3-naphthalic acid, 2,4-naphthalic acid, 2,5-naphthalic acid, NDA, 2,7-naphthalic acid, 2,8-naphthalic acid, 2-hydroxyl-1-naphthoic acid, 3-hydroxyl-1-naphthoic acid, 4-hydroxyl-1-naphthoic acid, 5-hydroxyl-1-naphthoic acid, 6-hydroxyl-1-naphthoic acid, 7-hydroxyl-1-naphthoic acid, 8-hydroxyl-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, 6-Hydroxy-2-naphthoic acid, 7-hydroxy-2-naphthoic acid, 8-hydroxy-2-naphthoic acid, 1,2,4,5-naphthalenetetracarbacidic acidic, 2,3-dihydroxyl-1-naphthoic acid, 2,4-dihydroxyl-1-naphthoic acid, 2,5-dihydroxyl-1-naphthoic acid, 2,6-dihydroxyl-1-naphthoic acid, 2,7-dihydroxyl-1-naphthoic acid, 2,8-dihydroxyl-1-naphthoic acid, 3,4-dihydroxyl-1-naphthoic acid, 3,5-dihydroxyl-1-naphthoic acid, 3,6-dihydroxyl-1-naphthoic acid, 3,7-dihydroxyl-1-naphthoic acid, 3,8-dihydroxyl-1-naphthoic acid, 4,5-dihydroxyl-1-naphthoic acid, 4,6-dihydroxyl-1-naphthoic acid, 4,7-dihydroxyl-1-naphthoic acid, 4,8-dihydroxyl-1-naphthoic acid, 5,6-dihydroxyl-1-naphthoic acid, 5,7-dihydroxyl-1-naphthoic acid, 5,8-dihydroxyl-1-naphthoic acid, 6,7-dihydroxyl-1-naphthoic acid, 6,8-dihydroxyl-1--naphthoic acid, 7,8-dihydroxyl-1-naphthoic acid, 1,3-dihydroxy-2-naphthoic acid, 1,4-dihydroxy-2-naphthsaisyuoic acid, 1,5-dihydroxy-2-naphthoic acid, 1,6-dihydroxy-2-naphthoic acid, 1,7-dihydroxy-2-naphthoic acid, 1,8-dihydroxy-2-naphthoic acid, 3,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid, 3,6-dihydroxy-2-naphthoic acid, 3,8-dihydroxy-2-naphthoic acid, 4,5-dihydroxy-2-naphthoic acid, 4,6-dihydroxy-2-naphthoic acid, 4,7-dihydroxy-2-naphthoic acid, 4,8-dihydroxy-2-naphthoic acid, 5,6-dihydroxy-2-naphthoic acid, 5,7-dihydroxy-2-naphthoic acid, 5,8-dihydroxy-2-naphthoic acid, 6,7-dihydroxy-2-naphthoic acid, 6,8-dihydroxy-2-naphthoic acid, 7,8-dihydroxy-2-naphthoic acid, hexahydrobenzoic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, 1,1-cyclohexane dicarboxylic acid, 1,2-perhydronaphthalene dioctyl phthalate, 1,3-perhydronaphthalene dioctyl phthalate, Isosorbide-5-Nitrae-perhydronaphthalene dioctyl phthalate, 1,5-perhydronaphthalene dioctyl phthalate, 1,6-perhydronaphthalene dioctyl phthalate, 1,7-perhydronaphthalene dioctyl phthalate, 1,8-perhydronaphthalene dioctyl phthalate etc.
These aromatic carboxy acid compounds can be used alone a kind, and also two or more kinds may be used.
Wherein, the aromatic carboxy acid compound that preferred formula (III) or formula (IV) represent,
(in formula, n1 represents arbitrary integer in 1 ~ 4.N2 represents arbitrary integer in 0 ~ 4.R 6represent C1 ~ C6 alkyl, nitro or hydroxyl.)
(in formula, m1 represents arbitrary integer in 1 ~ 4.M2 represents arbitrary integer in 0 ~ 2.R 7represent the group that C1 ~ C6 alkyl, nitro, hydroxyl or following formula represent
(in formula, q represents the integer of 1 or 2.* bonding position is represented).)
R 6, R 7c1 ~ C6 alkyl comprise cycloalkyl, specifically can enumerate methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, cyclobutyl, Cvclopropvlmethvl, n-pentyl, isopentyl, 2-methyl butyl, neo-pentyl, 1-ethyl propyl, n-hexyl, isohexyl, 4-methyl amyl, 3-methyl amyl, 2-methyl amyl, 1-methyl amyl, 3,3-dimethylbutyl, 2,2-dimethylbutyls etc.
In formula (III), the aromatic carboxy acid compound that further preferred formula (I) represents.
In formula, R 1represent C1 ~ C6 alkyl, C1 ~ C6 alkoxyl group or hydroxyl.
As C1 ~ C6 alkyl, preferred C1 ~ C4 alkyl, can have substituting group.C1 ~ C6 alkyl comprises cycloalkyl, specifically methyl can be enumerated, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, cyclobutyl, Cvclopropvlmethvl, n-pentyl, isopentyl, 2-methyl butyl, neo-pentyl, 1-ethyl propyl, n-hexyl, isohexyl, 4-methyl amyl, 3-methyl amyl, 2-methyl amyl, 1-methyl amyl, 3, 3-dimethylbutyl, 2, 2-dimethylbutyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 3-dimethylbutyl, 1-ethyl-butyl, 2-ethyl-butyl etc.
As C1 ~ C6 alkoxyl group, preferred C1 ~ C4 alkoxyl group, can have substituting group.As C1 ~ C6 alkoxyl group, specifically can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, isopentyloxy, 2-methylbutoxy group, 1-ethylpropoxy, 2-ethylpropoxy, neopentyl oxygen, positive hexyloxy, 4-methyl pentyloxy, 3-methyl pentyloxy, 2-methyl pentyloxy, 3,3-dimethyl butoxy, 2,2-dimethyl butoxy, 1,1-dimethyl butoxy, 1,2-dimethyl butoxy, 1,3-dimethyl butoxy, 2,3-dimethyl butoxy etc.
(imidazolium compounds)
The imidazolium compounds used in the present invention is the imidazolium compounds that represents of formula (II) and imidazolinium compounds.
Specifically, formula (II) is containing following structure.
In formula, R 2represent hydrogen atom, C1 ~ C10 alkyl, aryl, arylalkyl or cyanoethyl, preferred hydrogen atom.
As C1 ~ C10 alkyl, be preferably C1 ~ C6 alkyl, can substituting group be had.As C1 ~ C10 alkyl, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, nonyl, different nonyl, decyl etc. specifically can be enumerated.
Aryl refers to the meaning of monocycle or polyaromatic.Wherein, during for polyaromatic, except completely unsaturated, also comprise the group of fractional saturation.Such as can enumerate phenyl, naphthyl, base, indenyl, indanyl, tetrahydro naphthyl etc.In these groups, preferred C6 ~ C10 aryl.In addition, aryl can have substituting group.
Arylalkyl is above-mentioned aryl and alkyl linked group, can enumerate phenmethyl, styroyl, 3-phenyl-n-propyl, 1-phenyl-n-hexyl, naphthalene-1-ylmethyl, naphthalene-2-base ethyl, 1-naphthalene-2-base-n-propyl, indenes-1-ylmethyl etc.In these groups, preferred C6 ~ C10 aryl C1 ~ C6 alkyl.In addition, arylalkyl can have substituting group.
R 3~ R 5the acyl group of C1 ~ C20 alkyl, aryl, arylalkyl or C1 ~ C20 represent hydrogen atom, nitro, halogen atom, C1 ~ C20 alkyl independently of one another, being optionally substituted by a hydroxyl group.
As C1 ~ C20 alkyl, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, nonyl, different nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl etc. can be enumerated.Be preferably C1 ~ C10 alkyl.
Aryl and arylalkyl can be enumerated and R 2the same group of group.
As C1 ~ C20 acyl group, refer to the group of hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl or heteroaryl etc. and carbonyl bonding.Acyl group such as can enumerate formyl radical, ethanoyl, propionyl, butyryl radicals, pentanoyl, caproyl, oenanthyl, capryloyl, nonanoyl, decanoyl, 3-methyl nonanoyl, 8-methyl nonanoyl, 3-ethyl capryloyl, 3, 7-dimethyl-octa acyl group, undecanoyl, lauroyl, tridecanoyl, myristoyl, pentadecanoyl, palmitoyl, 1-methyl pentadecanoyl, 14-methyl pentadecanoyl, 13, 13-dimethyl myristoyl, heptadecanoyl base, 15-methyl palmitoyl, stearoyl, 1-methyl heptadecanoyl base, 19 acyl groups, the alkyl-carbonyls such as 20 acyl groups and two undecanoyl, acryl, methacryloyl, allyl group carbonyl, the alkenyl carbonyls such as cinnamoyl, ethynyl carbonyl, the alkynylcarbonyl groups such as proyl carbonyl, benzoyl, naphthoyl, dibenzoyl base, the sweet-smelling formacyls such as o-amino benzoyl acyl group, 2-PYRIDYLCARBONYL, the Heteroarylcarbonyl etc. such as thienyl carbonyl.In these groups, preferred C1 ~ C20 (comprising carbonyl) acyl group, particularly preferably C1 ~ C6 acyl group.
Specifically, as the imidazolium compounds that formula (II) represents, imidazoles can be enumerated, 2-ethyl-4-methylimidazole, glyoxal ethyline, 1 benzyl 2 methyl imidazole, 2-heptadecyl imidazole, 2-undecyl imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1, 2-methylimidazole, 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4, 5-bishydroxymethyl imidazoles etc., preferred 2-ethyl-4-methylimidazole, glyoxal ethyline, 1 benzyl 2 methyl imidazole, 2-heptadecyl imidazole, 2-undecyl imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole or 2-phenyl-4, 5-bishydroxymethyl imidazoles.
As the imidazolinium compounds that formula (II) represents, glyoxal ethyline quinoline, 2-benzylimidazoline, 2-undecyl imidazole quinoline, 2-heptadecyl imidazole quinoline, 2-ethyl imidazol(e) quinoline, 2 isopropyl imidazole quinoline, 2 can be enumerated, 4-methylimidazole quinoline, 2-phenyl-4-methylimidazole quinoline etc., preferred glyoxal ethyline quinoline or 2-benzylimidazoline.
(the 1:2 inclusion compound of carboxylic acid cpd and imidazolium compounds or the manufacture method of its composition)
The 1:2 inclusion compound of carboxylic acid cpd and imidazolium compounds or its composition can obtain by the following method etc. in fact.
(1) method of the alcoholic solution of carboxylic acid cpd is added to imidazolium compounds
(2) to the method for the alcohol liquid interpolation carboxylic acid cpd of imidazolium compounds
The detailed content of the method for (1) is below described.
In imidazolium compounds, add the alcoholic solution of carboxylic acid cpd as required while stirring.The interpolation of the alcoholic solution of carboxylic acid cpd is not particularly limited, but usually adds continuously or discontinuously through 5 ~ 120 minutes.
After adding the alcoholic solution of carboxylic acid cpd, place 0 ~ 5 hour in room temperature as required, heating 0 ~ 5 hour or reflux 0 ~ 5 hour in room temperature ~ 40 DEG C.
As the mixing ratio of carboxylic acid cpd and imidazolium compounds, relative to carboxylic acid cpd (main body) 1 mole, preferred imidazolium compounds (object) is 0.1 ~ 5.0 mole, is more preferably 0.5 ~ 3.0 mole.
As alcoholic solvent, the lower alcohols such as methyl alcohol, ethanol, n-propyl alcohol can be illustrated, be preferably methyl alcohol.It is 0.5 ~ 50 times amount that usage quantity converts relative to carboxylic acid cpd in weight usually.
For the operation after heat treated or reflux process, such as can only by stopping heating or reflux process make solid chemical compound separate out, but preferably after heating, room temperature placement one is late.After separating out solid chemical compound, such as, by filtration drying, obtain target compound.
The detailed content of the method for (2) is below described.
Imidazolium compounds is suspended or after being dissolved in alcohol (alcohol suspension and alcoholic solution are called alcohol liquid), adds carboxylic acid cpd while stirring as required.The interpolation of carboxylic acid cpd is not particularly limited, but usually adds continuously or discontinuously through 5 ~ 120 minutes.
Add after carboxylic acid cpd, place 0 ~ 5 hour in room temperature as required, DEG C heating 0 ~ 5 hour or reflux 0 ~ 5 hour in room temperature ~ 40.
As the mixing ratio of carboxylic acid cpd and imidazolium compounds, relative to 1 moles of carboxylic acids compound (main body), imidazolium compounds (object) is preferably 0.1 ~ 5.0 mole, is more preferably 0.5 ~ 3.0 mole.
As alcoholic solvent, the lower alcohols such as methyl alcohol, ethanol, n-propyl alcohol can be illustrated, be preferably methyl alcohol.It is 0.5 ~ 50 times amount that usage quantity converts relative to carboxylic acid cpd in weight usually.
As a reference, be the manufacture method of the inclusion compound of 1:1 in the mol ratio of following record HIPA and 2P4MHZ.
(mol ratio of HIPA and 2P4MHZ is the manufacture method of the inclusion compound of 1:1)
Be in fact only that the inclusion compound that forms of 1:1 can obtain by the following method etc. by the mol ratio of HIPA and 2P4MHZ.
After making HIPA be dissolved in alcohol, add 2P4MHZ while stirring as required.The interpolation of 2P4MHZ is not particularly limited, and usually through more than 5 minutes, preferably adds continuously or discontinuously through 5 minutes ~ 120 minutes.
Add after 2P4MHZ, place 0 ~ 5 hour in room temperature as required, DEG C heating 0 ~ 5 hour or reflux 0 ~ 5 hour in room temperature ~ 40.
As the mixing ratio of HIPA and the 2P4MHZ in the manufacture method of 1:1 inclusion compound, relative to 1 mole of HIPA (main body), 2P4MHZ (object) is preferably 0.1 ~ 5.0 mole, is more preferably 0.5 ~ 3.0 mole.
As the alcoholic solvent in the manufacture method of 1:1 inclusion compound, the lower alcohols such as methyl alcohol, ethanol, n-propyl alcohol can be illustrated, be preferably methyl alcohol.Usage quantity is generally 0.5 ~ 50 times amount relative to HIPA.
For the operation after heat treated or reflux process, such as, only by stopping heating or reflux process to make solid chemical compound separate out, but after preferably heating, an evening can be placed in room temperature.After separating out solid chemical compound, such as, by filtration drying, obtain target compound.
(curable epoxy resin composition)
Inclusion compound of the present invention or its composition can to mix with epoxy resin as epoxy curing agent or curing catalyst and be used as such as semiconductor encapsulant and use.
As the Cured epoxy resin compositions that semiconductor encapsulant etc. uses, containing epoxy resin, inclusion compound of the present invention and other additive of adding as required.
1) epoxy resin
As epoxy resin, known various polyepoxy compound can be used, such as, can enumerate two (4-hydroxy phenyl) propane diglycidylether, two (4-hydroxyl-3,5-dibromo phenyl) propane diglycidylether, two (4-hydroxy phenyl) ethane diglycidylether, two (4-hydroxy phenyl) methane diglycidylether, resorcinol diglycidyl ether, Phloroglucinol triglycidyl ether, trihydroxy-biphenyl triglycidyl ether, four glycidyl group benzophenone, two Resorcinol four glycidyl ether, tetramethyl-bisphenol A diglycidyl ether, bisphenol-c diglycidylether, bis-phenol HFC-236fa diglycidylether, 1,3-bis-﹝ 1-(2,3-glycidoxy)-1-trifluoromethyl-2,2,2-tri-Fu Yi Ji ﹞ benzene, Isosorbide-5-Nitrae-Shuan ﹝ 1-(2,3-glycidoxy)-1-trifluoromethyl-2,2,2-tri-Fu Jia Ji ﹞ benzene, 4,4 '-bis-(2,3-glycidoxy) octafluorobiphenyl, the fragrant family glycidyl ether compounds such as phenol novolak type diepoxides, alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxy carboxylate, the ester ring type polyepoxy compounds such as vinyl cyclohexene diepoxide, o-phthalic acid diglycidyl ester, tetrahydrophthalic acid 2-glycidyl ester, hexahydrophthalic acid 2-glycidyl ester, dimethyl glycidyl phthalic ester, dimethyl glycidyl hexahydrophthalic acid ester, diglycidyl p-Hydroxybenzoate, 2-glycidyl cyclopentane-1,3-dicarboxylic ester, the epihydric alcohol ester compounds such as dimer acid glycidyl ester, diglycidylaniline, diglycidyl Tolylamine, triglycidyl group amino-phenol, four glycidyl group diaminodiphenyl-methane, the glycidyl amine compound such as diglycidyl bromamide, diglycidylhydantoin, glycidyl epoxy allyloxyalkyl glycolylurea, the hetero ring type epoxy compoundss etc. such as triglycidyl isocyanurate.
In addition, as liquid-state epoxy resin, such as can enumerate (gathering) ethylene glycol diglycidylether, (gathering) polyalkylene ether such as propylene glycol diglycidylether, trihydroxymethylpropanyltri diglycidyl ether type epoxy compounds, glycidyl ester type epoxy compound, the homopolymer of (methyl) glycidyl acrylate, glycidyl allyl ether etc. or the multipolymers etc. of this monomer and other soft unsaturated monomer such as dimer acid diglycidyl ester, o-phthalic acid diglycidyl ester, tetrahydrophthalic acid 2-glycidyl ester.Soft unsaturated monomer refers to that the second-order transition temperature of its homopolymer is lower than the monomer of 60 DEG C, such as, methyl acrylate, ethyl propenoate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA, lauryl methacrylate etc.
2) inorganic filler
As long as composition epoxy resin of the present invention comprises above-mentioned inclusion compound and epoxy resin, also can be comprise the composition epoxy resin also comprising inorganic filler outside inclusion compound and epoxy resin in addition.
As inorganic filler, be not particularly limited, such as can enumerate silica glass, by carrying out the spherical silicon dioxide that flame melting obtains, the spherical silicon dioxide, crystalline silica, aluminum oxide, talcum, ammonium nitrides, silicon nitride, magnesium oxide, Magnesium Silicate q-agent etc. that utilize sol-gel method etc. to manufacture, they can be used alone and also can use two or more.
3) solidifying agent or effect promotor
In composition epoxy resin of the present invention, except above-mentioned inclusion compound, curing catalyst or solidifying agent can also be contained further.
As the solidifying agent that can contain in composition epoxy resin of the present invention, as long as make the compound of epoxy resin cure with the epoxy reaction in epoxy resin, be just not particularly limited.Similarly, as the curing catalyst that can contain in composition epoxy resin of the present invention, as long as promote the compound of above-mentioned curing reaction, be just not particularly limited.As such solidifying agent or curing catalyst, can arbitrary substance be selected use from the existing solidifying agent as epoxy resin or the usual material of curing catalyst.Such as, the amine compounds such as aliphatics amine, ester ring type and hetero ring type amine, aromatic amine, modified amine can be enumerated, imidazole compound, tetrahydroglyoxaline based compound, acid amides based compound, ester based compound, phenol system compound, alcohol based compound, mercaptan based compound, ether based compound, thioether based compound, urea based compound, thiocarbamide based compound, Lewis acid based compound, phosphorus series compound, acid anhydrides based compound, salt based compound, reactive silicon compound-aluminium coordination compound etc.
As solidifying agent or curing catalyst, specifically, such as following compound can be enumerated.
As aliphatics amine, such as, quadrol can be enumerated, trimethylene diamine, Triethylene Diamine, tetramethylene-diamine, hexamethylene-diamine, diethylenetriamine, Triethylenetetramine (TETA), tetren, dipropylenediamine, dimethylamino propylamine, diethyl amino propylamine, trimethylhexamethylenediamine, pentamethylene diamine, two (2-dimethyl aminoethyl) ether, five methyl diethylentriamine, alkyl-uncle-monoamine, 1, 4-diazabicyclo (2, 2, 2) octane (triethylenediamine), N, N, N', N'-tetramethyl-hexamethylene-diamine, N, N, N', N'-tetramethyl-trimethylene diamine, N, N, N', N'-Tetramethyl Ethylene Diamine, N, N-dimethylcyclohexylamine, dibutyl amino propyl amine, dimethylamino ethoxy ethoxy ethanol, trolamine, dimethylamino hexanol etc.
As ester ring type and hetero ring type amine, such as can enumerate piperidines, piperazine, alkane diamines, isophorone diamine, methylmorpholine, ethyl morpholine, N, N', N "-three (dimethylaminopropyl) perhydro-s-triazine, 3; two (the 3-aminopropyl)-2,4,8 of 9-; 10-tetra-oxaspiro (5; 5) undecane affixture, N-aminoethyl piperazine, trimethylaminoethyl group piperazine, two (4-aminocyclohexyl) methane, N, N'-lupetazin, 1,8-diazabicyclo [4.5.0] hendecene-7 etc.
As aromatic amine, such as, can enumerate O-Phenylene Diamine, mphenylenediamine, Ursol D, diaminodiphenyl-methane, diamino diphenyl sulfone, benzyimethylamine, dimethyl benzyl amine, m-xylene diamine, pyridine, picoline, α-methylbenzyl methylamine etc.
As modified amine, such as, can enumerate epoxy compounds addition polyamines, Michael addition polyamines, Mannich addition polyamines, thiocarbamide addition polyamines, ketone end-blocking polyamines, Dyhard RU 100, guanidine, organic acid hydrazides, Diaminomaleonitrile, aminimide, boron trifluoride-piperidines coordination compound, boron triflouride-mono aminoethane coordination compound etc.
As imidazole compound, such as imidazoles can be enumerated, 1-Methylimidazole, glyoxal ethyline, 3-Methylimidazole, 4-methylimidazole, 5-Methylimidazole, 1-ethyl imidazol(e), 2-ethyl imidazol(e), 3-ethyl imidazol(e), 4-ethyl imidazol(e), 5-ethyl imidazol(e), 1-n-propyl imidazoles, 2-n-propyl imidazoles, 1-isopropylimdazole, 2 isopropyl imidazole, 1-butylimidazolium, 2-butylimidazolium, 1-isobutyl-imidazoles, 2-isobutyl-imidazoles, 2-undecyl-1H-imidazoles, 2-heptadecyl-1H-imidazoles, 1,2 dimethylimidazole, 1,3-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, 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole isocyanuric acid adduct, glyoxal ethyline isocyanuric acid adduct, 2-phenyl-4,5-bis-(hydroxymethyl) imidazoles, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-bis-(2-cyanoethoxy) Methylimidazole, 1-dodecyl-2-methyl-3-benzyl imidazole muriate, 1-benzyl-2-phenylimidazole hydrochloride etc.
As tetrahydroglyoxaline based compound, such as, can enumerate glyoxal ethyline quinoline, 2-benzylimidazoline etc.
As acid amides based compound, such as, can enumerate the condensation by dimeracid and polyamines and the polymeric amide etc. obtained.
As ester based compound, such as, can enumerate the aryl of carboxylic acid and the such active carbonyl compound etc. of sulphur aryl ester.
As phenol system compound, alcohol based compound, mercaptan based compound, ether based compound and thioether based compound, such as can enumerate, as the phenol aralkyl resin of phenolic resin curative, the aralkyl-type phenol resin such as naphthols aralkyl resin, phenol resol resins, the novolak phenolics such as cresol novolac resin, their modified resin, such as epoxidation or butylated novolak phenolics etc., dicyclopentadiene-modified resol, p-Xylol modified phenolic resins, triphenol alkane type resol, multifunctional type resol etc.In addition, also can enumerate polyvalent alcohol, multi-thiol, polysulfide, 2-(dimethylaminomethylphenol), 2,4,6-tri-(dimethylamino methyl) phenol, 2, three-2-ethylhexyl the hydrochlorides etc. of 4,6-tri-(dimethylamino methyl) phenol.
As urea based compound, thiocarbamide based compound, Lewis acid based compound, such as, can enumerate butylation urea, butylated melamines, butylation thiocarbamide, boron trifluoride etc.
As phosphorus series compound, organic phosphoric compound can be enumerated, the uncle such as alkylphosphines, the Phenylphosphine phosphines such as such as ethyl phosphine, butyl phosphine; The secondary phosphines such as the dialkyl phosphines such as dimethyl phosphine, dipropyl phosphine, diphenylphosphine, methylethyl phosphine; The tertiary phosphines etc. such as trimethyl-phosphine, triethyl phosphine, triphenylphosphine.
As acid anhydrides based compound, such as Tetra hydro Phthalic anhydride can be enumerated, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, Nadic anhydride, methylendomethylenetetrahydrophthalic Tetra Hydro Phthalic Anhydride, maleic anhydride, tetramethylene maleic anhydride, trimellitic acid 1,2-anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride, pyromellitic acid dianhydride, dodecenyl succinic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bis (dehydration trimellitate), glycerine three (dehydration trimellitate), tetrahydrotoluene tetracarboxylic acid dianhydride, poly-nonane diacid acid anhydride etc.
In addition, as salt based compound and reactive silicon compound-aluminum complex, can enumerate such as aryldiazonium salt, Diaryl iodonium salt, triarylsulfonium salt, triphenyl silanol-aluminum complex, triphenylmethoxy silane-aluminum complex, silyl superoxide (silylperoxide)-aluminum complex, triphenyl silanol-three (salicylic aldehyde conjunction) aluminum complex etc.
As above-mentioned solidifying agent or curing catalyst, particularly preferably use amine compound, imidazole compound, phenol system compound.More preferably phenolic resin curative is used in phenol system compound.
4) other additive
In composition epoxy resin of the present invention in addition to the foregoing, the various additives such as softening agent, organic solvent, reactive diluent, extender, weighting agent, toughener, pigment, fire retardant, thickening material and releasing agent can be coordinated as required.As other additive, vinyltrimethoxy silane can be enumerated, vinyltriethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group triethoxyl silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl) γ aminopropyltriethoxy silane, N-phenyl-gamma-amino propyl trimethoxy silicane, N-phenyl-γ aminopropyltriethoxy silane, γ mercaptopropyitrimethoxy silane, the silane coupling agents such as γ-Mercaptopropyltriethoxysilane, the weighting agents such as Calcium hydrogen carbonate, light calcium carbonate, native silicon dioxide, synthetic silica, fused silica, kaolin, clay, titanium oxide, barium sulfate, zinc oxide, aluminium hydroxide, magnesium hydroxide, talcum, mica, wollastonite, potassium titanate, aluminum borate, sepiolite, xonotlite, NBR, polyhutadiene, neoprene, silicone, crosslinked NBR, crosslinked BR, acrylic acid series, core shell acrylic, urethanes, polyester elastomer, the elastomer modifier such as liquid NBR, liquid polybutadiene, liquid polyester, liquid polysulphides, modified silicone, polyurethane prepolymer containing functional group,
Hexabromo cyclodecane, two (dibromopropyl) tetrabromo-bisphenol, three (dibromopropyl) isocyanuric acid ester, three (tribromo neo-pentyl) phosphoric acid ester, decabromodiphynly oxide, two (pentabromo-) diphenylphosphino ethane, three (tribromophenoxy) triazine, the two tetrabromo phthalimide of ethylene, many bromophenyls indane, brominated Polystyrene, tetrabromobisphenol a polycarbonate, bromination penylene oxyethane (smelly elementization Off ェ ニ レ Application エ チ レ Application オ キ シ De), polyacrylic acid pentabromo-benzyl ester, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, cresyl diphenyl phosphate, xylyl diphenyl phosphoester, two (two-2, the 6-xylyls) phosphoric acid ester of tolyl, 2-ethylhexyl diphenyl phosphate, Resorcinol two [(phenylbenzene) phosphoric acid ester], dihydroxyphenyl propane two [(phenylbenzene) phosphoric acid ester], dihydroxyphenyl propane two [(diglycidyl) phosphoric acid ester], Resorcinol two [(two-2,6-xylyls) phosphoric acid ester], tricresyl phosphate (chloroethyl) ester, tricresyl phosphate (chloropropyl) ester, tricresyl phosphate (two chloropropyls) ester, tricresyl phosphate (three bromopropyls) ester, two (2-hydroxyethyl) the aminomethylphosphonic acid ester of diethyl-N, N-, negatively charged ion oxalic acid treatment aluminium hydroxide, nitrate process aluminium hydroxide, high-temperature-hot-water process aluminium hydroxide, stannic acid surface treatment hydrated metal compound, nickel compound surface treatment magnesium hydroxide, silicone polymer surface treatment magnesium hydroxide, phlogopite, multiple-level surface process hydrated metal compound, the fire retardants such as cationic polymers process magnesium hydroxide, the engineering plastics such as high density polyethylene(HDPE), polypropylene, polystyrene, polymethylmethacrylate, polyvinyl chloride, nylon 6,6, polyacetal, polyethersulfone, polyetherimide, polybutylene terephthalate, polyether-ether-ketone, polycarbonate, polysulfones, softening agent, the thinners such as n-butyl glycidyl ether, phenyl glycidyl ether, Styrene oxide 98min., tert-butyl-phenyl glycidyl ether, Dicyclopentadiene (DCPD) diepoxide, phenol, cresols, tert.-butyl phenol, extender, toughener, tinting material, thickening material, higher fatty acid, high-grade aliphatic ester, higher fatty acid calcium etc., the such as releasing agent such as carnauba wax, polyethylene-based wax, Deng.The use level of these additives is not particularly limited, and in the limit obtaining effect of the present invention, suitably can determine use level.
In addition, in composition epoxy resin of the present invention, except epoxy resin, also other resin can be contained.As other resin, vibrin, acrylic resin, silicon system resin, polyurethane series resin etc. can be enumerated.
5) preparation of composition epoxy resin and cured article thereof
For the mixing ratio of epoxy resin and inclusion compound of the present invention or its composition, relative to the oxirane ring 1 mole of epoxy resin, imidazolium compounds in inclusion compound or its composition is preferably containing 0.01 ~ 1.0 mole, more preferably containing 0.1 ~ 1.0 mole, further preferably containing 0.3 ~ 1.0 mole.
In addition, epoxy curing resin formation composition can be manufactured by blending epoxy and inclusion compound of the present invention or its composition, is usually heated to about 60 ~ 100 DEG C and carries out mixing to form sufficient admixture.In the manufacture of epoxy curing resin, single liquid stability of temperature now becomes important.The composition epoxy resin produced, according to its composition and manufacture method, can be solid-state, also can be liquid.
As the solidification method of epoxy curing resin formation composition, as long as epoxy curing resin formation composition to be carried out the method that heat treated makes it solidify, be just not particularly limited, usually, the Heating temperature of heat treated is 60 ~ 250 DEG C.
Embodiment
Below, embodiment is described, but technical scope of the present invention does not limit by these embodiments.
Should illustrate, in following examples, 1hNMR uses DMSO-d 6or MeOH-d 4as mensuration solvent, 25 DEG C of mensuration.
The manufacture of 1 inclusion compound
[synthetic example 1]
In flask, add the 2P4MHZ of 20.67g (109.8mmol), then add half 20g (109.8mmol) HIPA being dissolved into the liquid obtained in 170ml methyl alcohol while stirring.Use 11mL washed with methanol, after room temperature places 0.5 hour, add remaining HIPA methanol solution while stirring, use 11mL washed with methanol, after room temperature places 0.5 hour, reflux 3 hours.Thereafter, after room temperature places an evening, carry out filtering, vacuum-drying, obtain the resultant (yield 71%) of 28.89g thus.The resultant obtained is used 1hNMR, X-ray diffraction and thermal analyses (DSC) are analyzed, the crystallization of result to be HIPA:2P4MHZ the be inclusion compound of 1:2.In addition, the purity of 1:2 inclusion compound is 91%.Thermal analyses (DSC) figure measured based on temperature variation by the inclusion compound obtained is shown in Fig. 1.
[synthetic example 2]
In flask, drop into the methyl alcohol of 2P4MHZ and 130ml of 20.67g (109.8mmol), in the alcohol liquid be mixed to get, add the HIPA of 10g (54.9mmol) while stirring through 20 minutes.After room temperature places 0.5 hour, reflux 3 hours.Thereafter, after room temperature places an evening, carry out filtering, vacuum-drying, obtain 29.91g resultant (yield 97.5%) thus.The resultant obtained is used 1hNMR, X-ray diffraction and thermal analyses (DSC) are analyzed, the crystallization of result to be HIPA:2P4MHZ the be inclusion compound of 1:2.In addition, the purity of 1:2 inclusion compound is 97%.Thermal analyses (DSC) chart that the inclusion compound obtained is measured based on temperature variation and 1hNMR figure is shown in Fig. 2-1 and Fig. 2-2.
[synthetic example 3]
Add the 2P4MHZ of 20.67g (109.8mmol) in flask after, added through 15 minutes while stirring and 10g (54.9mmol) HIPA is dissolved into the liquid obtained in 130ml methyl alcohol.After room temperature places 0.5 hour, reflux 3 hours.Thereafter, after room temperature places an evening, carry out filtering, vacuum-drying, obtain 29.74g resultant (yield 97%) thus.The resultant obtained is used 1hNMR, X-ray diffraction and thermal analyses (DSC) are analyzed, the crystallization of result to be HIPA:2P4MHZ the be inclusion compound of 1:2.In addition, the purity of 1:2 inclusion compound is 99%.Thermal analyses (DSC) chart that the inclusion compound obtained is measured based on temperature variation and 1hNMR figure is shown in Fig. 3-1 and Fig. 3-2.
[synthetic example 4]
Replace 2P4MHZ to use 7.48g (109.8mmol) without the imidazoles (hereinafter referred to as Im) replaced, in addition, obtain the inclusion compound that HIPA:Im is 1:2 in the same manner as synthetic example 2.In addition, the purity of 1:2 inclusion compound is 77%.Thermal analyses (DSC) chart that the inclusion compound obtained is measured based on temperature variation and 1hNMR figure is shown in Fig. 4-1 and Fig. 4-2.
[synthesized reference example 1] (manufacture of 1:1 inclusion compound)
In flask, drop into the methyl alcohol of HIPA and 126ml of 20g (109.8mmol), in the solution be mixed to get, add the 2P4MHZ of 20.67g (109.8mmol) while stirring through 15 minutes.After room temperature places 2 hours, reflux 3 hours.Thereafter, after room temperature places an evening, carry out filtering, vacuum-drying, obtain 39.56g resultant (yield 97.3%) thus.The resultant obtained is used 1hNMR, X-ray diffraction and thermal analyses (DSC) are analyzed, the crystallization of result to be HIPA:2P4MHZ the be inclusion compound of 1:1.In addition, the purity of 1:2 inclusion compound is 0%.Thermal analyses (DSC) figure measured based on temperature variation by the inclusion compound obtained is shown in Fig. 5.
[synthesized reference example 2]
Replace 2P4MHZ to use the lm of 7.48g (109.8mmol), in addition, in the same manner as synthesized reference example 1, obtain the inclusion compound that HIPA:Im is 1:1.
[synthesis comparative example 1] (manufacture of the mixture of 1:1 and 1:2 inclusion compound)
In flask, drop into the methyl alcohol of 2P4MHZ and 230ml of HIPA, 37.65g (200mmol) of 36.43g (200mmol), stir, carry out the reflux of 3 hours.Thereafter, after room temperature places an evening, carry out filtering, vacuum-drying, obtain 64.41g resultant (yield 87.2%) thus.The resultant obtained is used 1hNMR, X-ray diffraction and thermal analyses (DSC) are analyzed, the data that result display is different from embodiment 1 and 2, and judgement is HIPA:2P4MHZ is the crystallization that the inclusion compound of 1:1 and the inclusion compound of 1:2 mix.In addition, the purity of 1:2 inclusion compound is 18%.Thermal analyses (DSC) figure measured based on temperature variation by the inclusion compound obtained is shown in Fig. 6.
The manufacture of 2 composition epoxy resins
The manufacture of 2-1 biphenyl type epoxy resin composition
[composition reference example 1]
By the inclusion compound obtained in synthesized reference example 1 method of the 0.249g that converts in imidazoles, 12.445g is as the YX4000H (Mitsubishi chemical Co., Ltd's system) of biphenyl type epoxy resin, 0.249g is as the TOWAX (registered trademark) 131 (East Asia changes into Co., Ltd.'s system) of releasing agent, 179.97g is as the FB-940 spherical silicon dioxide (Deuki Kagaku Kogyo Co., Ltd's system) of weighting agent, 0.383g is as the LS2940 (Shin-Etsu Chemial Co., Ltd's system) of silane coupling agent, 6.701g adds hot milling 5 minutes as the novolac phenol PSM-4261OH equivalent 103 (Gunsaka Chem. Industry Co., Ltd.'s system) of solidifying agent at 100 DEG C, after cooling, pulverize, manufacture biphenyl type epoxy resin composition.
[composition embodiment 1]
Use the inclusion compound obtained in synthetic example 1 method to replace the inclusion compound obtained in synthesized reference example 1 method, in addition, manufacture biphenyl type epoxy resin composition in the same manner as composition reference example 1.
The manufacture of 2-2 o-cresol phenolic epoxy varnish composition
[composition reference example 2]
By the inclusion compound obtained in synthesized reference example 1 method of the 0.378g that converts in imidazoles, 18.886g is as the EOCN-1020-55 epoxy equivalent (weight) 191 ~ 201 (Nippon Kayaku K. K's system) of o-cresol phenolic resin varnish, 0.378g is as the TOWAX (registered trademark) 131 (East Asia changes into Co., Ltd.'s system) of releasing agent, 169.97g is as the FB-940 spherical silicon dioxide (Deuki Kagaku Kogyo Co., Ltd's system) of weighting agent, 0.944g is as the LS-2940 (chemistry society of SHIN-ETSU HANTOTAI system) of silane coupling agent, 9.443g adds hot milling 5 minutes as the novolac phenol PSM-4261OH equivalent 103 (Gunsaka Chem. Industry Co., Ltd.'s system) of solidifying agent at 100 DEG C, after cooling, pulverize, manufacture biphenyl type epoxy resin composition.
[composition embodiment 2]
Use the inclusion compound obtained in synthetic example 1 method to replace the inclusion compound obtained in synthesized reference example 1 method, in addition, manufacture o-cresol phenolic epoxy varnish composition in the same manner as composition reference example 2.
The manufacture of 2-3 liquid epoxy resin composition
[composition reference example 3]
The inclusion compound obtained in synthesized reference example 1 method of the 0.4g that converts using imidazoles, 10g are mixed as the EPOTOHTOYD-128 (Toto Kasei KK's system) of liquid-state epoxy resin, manufactures liquid epoxy resin composition.
[composition embodiment 3]
Use the inclusion compound obtained in synthetic example 1 method to replace the inclusion compound obtained in synthesized reference example 1 method, in addition, manufacture liquid epoxy resin composition in the same manner as composition reference example 3.
[composition embodiment 4]
Use the inclusion compound obtained in synthetic example 4 method to replace the inclusion compound obtained in synthesized reference example 1 method, in addition, manufacture liquid epoxy resin composition in the same manner as composition reference example 3.
[composition reference example 4]
Use the inclusion compound obtained in synthesized reference example 2 method to replace the inclusion compound obtained in synthesized reference example 1 method, in addition, manufacture liquid epoxy resin composition in the same manner as composition reference example 3.
[test example 1]
(spiral flow test)
By the composition epoxy resin compressing tablet respectively obtained in the method for composition embodiment 1 and 2, composition reference example 1 and 2, be shaped to tablet.Use spiral of Archimedes mould and transfer molding machine, at 175 DEG C, pressure 70Kgf/cm 2condition under by these tablet injection moldings 3 minutes, measure the length of products formed obtained.For helicoidal flow value, measure initial value and 25 DEG C of values after 7 days, shown in the 1st table.
In spiral flow test, the larger expression mobility of its value is better.
[test example 2]
(gel time)
With metal superzapping spoon, the composition epoxy resin obtained in the method for appropriate composition embodiment 3 and 4, composition reference example 3 is placed on the hot plate of 175 DEG C, metal superzapping spoon is used to stir, the binding property of test portion disappears, and measures the time of time or the binding property disappearance can peeled off from hot plate.Show the result in the 2nd table.
Gel time is the time when certain temperature heat-sealable material to losing flowability, relevant to curing characteristics, can suitably select.Gel time is shorter, represent more early solidify, so particularly liquid-state epoxy resin time, the resin that preferred gel time is short.
(storage stability)
By the composition epoxy resin that obtains in the method for composition embodiment 3 and 4, composition reference example 3 30 DEG C of preservations, carry out visual observation, terminate as mensuration in the moment that have cured, evaluate storage stability.Show the result in the 2nd table.
[table 1]
1st table
[table 2]
2nd table
Industrial utilizability
According to the present invention, the 1:2 inclusion compound of aromatic carboxy acid compound and imidazolium compounds can be obtained with high purity.
In addition, in the present invention, because 1:2 inclusion compound can be manufactured with high purity, so can manufacture containing any one curable epoxy resin composition as solidifying agent or curing catalyst and cured article thereof in 1:1 inclusion compound and 1:2 inclusion compound.

Claims (4)

1. an inclusion compound or its composition, it is characterized in that, be the inclusion compound containing 5-Hydroxy M Phthalic Acid (A) and 2-phenyl-4-methyl-5-hydroxymethylimidazole (B) or its composition, the mol ratio containing (A) and (B) of 70 % by mole ~ 100 % by mole in containing total inclusion compound of (A) and (B) is the inclusion compound of 1:2.
2. a manufacture method for inclusion compound according to claim 1 or its composition, is characterized in that, the alcohol liquid to 2-phenyl-4-methyl-5-hydroxymethylimidazole adds 5-Hydroxy M Phthalic Acid.
3. a manufacture method for inclusion compound according to claim 1 or its composition, is characterized in that, adds the alcoholic solution of 5-Hydroxy M Phthalic Acid to 2-phenyl-4-methyl-5-hydroxymethylimidazole.
4. curable epoxy resin composition or its cured article, is characterized in that, containing inclusion compound according to claim 1 or its composition and epoxy resin.
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