CN102725273A - Clathrate and method for producing same - Google Patents
Clathrate and method for producing same Download PDFInfo
- Publication number
- CN102725273A CN102725273A CN2011800063058A CN201180006305A CN102725273A CN 102725273 A CN102725273 A CN 102725273A CN 2011800063058 A CN2011800063058 A CN 2011800063058A CN 201180006305 A CN201180006305 A CN 201180006305A CN 102725273 A CN102725273 A CN 102725273A
- Authority
- CN
- China
- Prior art keywords
- acid
- compound
- inclusion compound
- formula
- compsn
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
Landscapes
- 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
In order to provide a highly pure 1:2 clathrate of an aromatic carboxylic acid compound and an imidazole compound, and to provide an epoxy resin composition containing said clathrate as a curing agent or a curing promoter, it is possible to produce a highly pure clathrate that contains an aromatic carboxylic acid compound (A) and an imidazole compound (B) and where the mole ratio of (A) to (B) is 1:2, by means of adding the aromatic carboxylic acid compound to an alcohol solution of the imidazole compound, or by adding an alcohol solution of the aromatic carboxylic acid compound to the imidazole compound. The clathrate obtained thereby is useful as a curing agent or a curing promoter for epoxy resins or the like.
Description
Technical field
The present invention relates to novel inclusion compound and method of manufacture thereof, relate in particular to the inclusion compound and the method for manufacture and the composition epoxy resin or its cured article that contain inclusion compound that constitute by aromatic carboxy acid compound and imidazolium compounds that can be used as epoxy resin cure catalyzer etc.
The application advocates right of priority 2010-228645 number to the Japanese patent application of the Japanese patent application application on October 8th, 2010-10375 number 1 of application on January 20th, 2010, and its content is incorporated herein.
Background technology
Epoxy resin is widely used in every field owing to having excellent mechanical characteristics, thermal property.As being used to solidify said curing agent for epoxy resin, used imidazole compound, curing begins early, this problem of single liquid stability extreme difference but the mixed solution of epoxy resin-imidazole compound exists.
Therefore, as solidifying agent, proposed to use the salt (with reference to patent documentation 1) that imidazole compound addition hydroxy-benzoic acid is formed; Use four phenol system compounds (for example, 1,1; 2; 2 ,-four (4-hydroxy phenyl) ethane (below, be called TEP)) with the inclusion compound (with reference to patent documentation 2) of imidazole compound.This imidazoles acid salt and inclusion body can be brought into play certain effect, but hope to develop to have the solidifying agent that with the solidifying agent of its same function, further improves function.
Therefore, propose and developed the inclusion compound (patent documentation 3) of the imidazolium compounds that the m-phthalic acid compound that comprises formula (i) expression and formula (ii) represent.
In the formula, R
1Expression C1～C6 alkyl, C1～C6 alkoxyl group, nitro or hydroxyl.］
In the formula,
R2 expression Wasserstoffatomss, C1～C10 alkyl, aryl, arylalkyl or cyanoethyl, R
3～R
5Represent Wasserstoffatoms, nitro, halogen atom independently of one another, can have substituent C1～C20 alkyl, by the acyl group of the substituted C1 of hydroxyl～C20 alkyl, aryl, arylalkyl or C1～C20.］
The method for making of the inclusion compound in the patent documentation 3 is after adding to m-phthalic acid compound and imidazolium compounds in the solvent, carries out heat treated or reflux as required while stirring and handles the method that it is separated out.In addition, put down in writing in the document, after the imidazolium compounds of then preferably respectively the m-phthalic acid compound and the formula of formula (i) expression (ii) being represented is dissolved in the solvent, lysate has been mixed with each other if consider dissolving easness to solvent.
Yet; In the patent documentation 3; Not only for the not concrete record of the inclusion compound of 5-hydroxyl m-phthalic acid and 2-phenyl-4-methyl-5-hydroxymethyl imidazoles; If utilize the method for this patent documentation record to make 5-hydroxyl m-phthalic acid and 2-phenyl-4-methyl-5-hydroxymethyl imidazoles reaction, then only can access the 1:1 inclusion compound of two compounds and the mixture of 1:2 inclusion compound.
Can with high purity make the 1:1 inclusion compound (patent documentation 4) of 5-hydroxyl m-phthalic acid and 2-phenyl-4-methyl-5-hydroxymethyl imidazoles, but can not with high purity make 1:2 inclusion compound thereafter.
The prior art document
Patent documentation
Patent documentation 1: the special fair 4-2638 communique of Japan
Patent documentation 2: japanese kokai publication hei 11-71449 communique
Patent documentation 3: No. 2008/075427 pph of International Publication
Patent documentation 4: No. 2009/037862 pph of International Publication
Summary of the invention
Therefore, problem of the present invention is to obtain with high purity the 1:2 inclusion compound of aromatic carboxy acid compounds such as 5-hydroxyl m-phthalic acid and 2-phenyl-4-methyl-imidazoles such as 5-hydroxymethyl imidazoles.
The inventor etc. further investigate; The result finds through inquiring into the blending means of 5-hydroxyl m-phthalic acid and 2-phenyl-4-methyl-5-hydroxymethyl imidazoles; The mol ratio that can obtain subject and object is 1 to 2 inclusion compound (below, abbreviate the 1:2 inclusion compound as).Further study repeatedly; The result distinguish for the mol ratio that is known subject and object be 1 to 1 inclusion compound (below; Abbreviate the 1:1 inclusion compound as) inclusion compound host compound and guest compound, can make the 1:2 inclusion compound through the manufacturing process of utilizing the application to invent.In addition; The method that in known manufacturing process, can make the 1:2 inclusion compound compares with the method that can not make it; The result distinguishes that known method can not be made the 1:2 inclusion compound under the poorly soluble situation of aromatic carboxy acid compound to solvent as host compound.In a word, discovery can produce curable epoxy resin composition and the cured article thereof that contains this 1:2 inclusion compound, and finds to compare when containing the 1:1 inclusion compound, and its characteristic improves, thereby has accomplished the present invention.
That is, the present invention relates to:
(1) a kind of inclusion compound or its compsn contain following inclusion compound, and this inclusion compound is 70 moles of %～100 mole % in containing (A) and total inclusion compound (B),
Said inclusion compound contain the compound (B) of aromatic carboxy acid compound (A) and formula (II) expression and (A) and mol ratio (B) be 1:2,
(in the formula, R
2Expression Wasserstoffatoms, C1～C10 alkyl, aryl, arylalkyl or cyanoethyl, R
3～R
5Expression Wasserstoffatoms, nitro, halogen atom, C1～C20 alkyl, by the acyl group of the substituted C1 of hydroxyl～C20 alkyl, aryl, arylalkyl or C1～C20.The part of mark dotted line is represented singly-bound or two key.）
According to inclusion compound or its compsn of above-mentioned (1) record, it is characterized in that (2) aromatic carboxy acid compound is the compound of formula (III) or formula (IV) expression,
(in the formula, n1 representes arbitrary integer in 1～4.N2 representes arbitrary integer in 0～4.R
6Expression C1～C6 alkyl, nitro or hydroxyl.）
(in the formula, m1 representes arbitrary integer in 1～4.M2 representes arbitrary integer in 0～2.R
7The group that expression C1～C6 alkyl, nitro, hydroxyl or following formula are represented,
(in the formula, q representes 1 or 2 integer.* represent bonding position))
(3) according to inclusion compound or its compsn of record in above-mentioned (2), it is characterized in that formula (IV) is formula (I),
(in the formula, R
1Expression C1～C6 alkyl, C1～C6 alkoxyl group, nitro or hydroxyl.）
(4) according to inclusion compound or its compsn of above-mentioned (3) record, it is characterized in that formula (I) is a 5-hydroxyl m-phthalic acid,
According to inclusion compound or its compsn of each record in above-mentioned (1)～(4), it is characterized in that (5) formula (II) is 2-phenyl-4-methyl-5-hydroxymethyl imidazoles.
In addition, the present invention relates to:
(6) inclusion compound or the method for manufacture of its compsn of a kind of above-mentioned (1) record is characterized in that, add the aromatic carboxy acid compound to the pure liquid of the compound of formula (II),
(7) inclusion compound of a kind of above-mentioned (1) record or the method for manufacture of its compsn is characterized in that, add aromatic carboxy acid compound's alcoholic solution to the compound of formula (II).
In addition, also relate to:
(8) a kind of curable epoxy resin composition or its cured article contain inclusion compound or its compsn and the epoxy resin of each record in above-mentioned (1)～(5).
Description of drawings
The figure of Fig. 1 heat analysis (DSC) chart that to be the inclusion compound that obtains among the synthetic embodiment 1 of expression measure based on temperature variation.
Fig. 2-the 1st, the inclusion compound that obtains among the synthetic embodiment 2 of expression is based on the figure of heat analysis (DSC) chart of temperature variation mensuration.
Fig. 2-the 2nd, the inclusion compound that obtains among the synthetic embodiment 2 of expression
1The figure of H-NMR chart.
Fig. 3-the 1st, the inclusion compound that obtains among the synthetic embodiment 3 of expression is based on the figure of heat analysis (DSC) chart of temperature variation mensuration.
Fig. 3-the 2nd, the inclusion compound that obtains among the synthetic embodiment 3 of expression
1The figure of H-NMR chart.
Fig. 4-the 1st, the inclusion compound that obtains among the synthetic embodiment 4 of expression is based on the figure of heat analysis (DSC) chart of temperature variation mensuration.
Fig. 4-the 2nd, the inclusion compound that obtains among the synthetic embodiment 4 of expression
1The figure of H-NMR chart.
The figure of Fig. 5 heat analysis (DSC) chart that to be the inclusion compound that obtains in the expression synthesized reference example 1 measure based on temperature variation.
The figure of Fig. 6 heat analysis (DSC) chart that to be the inclusion compound that obtains in the synthetic comparative example 1 of expression measure based on temperature variation.
Embodiment
(inclusion compound or its compsn)
Inclusion compound of the present invention or its compsn be with the aromatic carboxy acid compound (below; Abbreviate " carboxylic acid cpd " as) be host compound; With the imidazolium compounds of formula (II) expression or imidazolinium compounds (below; Abbreviate imidazolium compounds as) be guest compound, the mol ratio of carboxylic acid cpd and imidazolium compounds is merely the inclusion compound of 1:2 or contains the compsn that mol ratio is the inclusion compound of 1:2 with high purity.
(in the formula, R
2Expression Wasserstoffatoms, C1～C10 alkyl, aryl, arylalkyl or cyanoethyl, R
3～R
5Expression Wasserstoffatoms, nitro, halogen atom, C1～C20 alkyl, by the acyl group of the substituted C1 of hydroxyl～C20 alkyl, aryl, arylalkyl or C1～C20.The part of mark dotted line is represented singly-bound or two key.）
In the mol ratio of carboxylic acid cpd and imidazolium compounds is the inclusion compound of 1:2, sneak into the inclusion compound of different mol ratio such as 1:1 sometimes, in the present invention, be referred to as the compsn of above-mentioned inclusion compound.
For inclusion compound of the present invention or its compsn; In the inclusion compound that contains carboxylic acid cpd and imidazolium compounds is all; The 1:2 inclusion compound to contain proportional be 70 moles more than the %; Be preferably 80 moles more than the %, further be preferably 90 moles more than the %, preferably be not mixed with the inclusion compound of other mol ratio such as 1:1 in addition in fact.But inclusion compound of the present invention can contain solvent grade in an imperial examination 3 compositions, and the 3rd composition is preferably 40 moles below the %, more preferably 10 moles below the %, does not most preferably contain the inclusion compound of the 3rd composition.Among the present invention, inclusion compound is meant that host compound forms cage type lattice (bag connects grid) and host compound and the guest compound more than a kind or 2 kinds and carries out the compound of bonding through covalent linkage key in addition, more preferably is called the crystallinity compound.The inclusion compound of the present invention that contains carboxylic acid cpd and imidazolium compounds also can be described as the salt that is formed by carboxylic acid cpd and imidazolium compounds.
As abbreviation, 5-hydroxyl m-phthalic acid is called " HIPA ", and 2-phenyl-4-methyl-5-hydroxymethyl imidazoles is called " 2P4MHZ ".
Here; The cage type lattice is meant that host compound carries out bonding through the key beyond the covalent linkage each other; In 2 molecules or the space more than 3 molecules of the host compound that bonding forms, through other molecule of key inclusion (object, solvent etc.) beyond the covalent linkage or the structure of other molecule and host compound; Perhaps host compound and other molecule (object, solvent etc.) carry out bonding through the key beyond the covalent linkage; In 2 molecules or the space more than 3 molecules of the host compound that forms with other molecular linkage, through the key inclusion host compound beyond the covalent linkage and/or the structure of other molecule (object, solvent etc.).
The resin curing agent that inclusion compound of the present invention can be used as vibrin, epoxy resin, epoxy polyester resin etc. uses, and especially preferably uses as curing agent for epoxy resin.Composition epoxy resin of the present invention preferably uses the purposes at cured epoxy resin, for example epoxy resin tackiness agent, semiconductor-encapsulating material, sealing material for liquid crystal, and printed wiring is with purposes such as plywood, varnish, an injectable plastic material, printing ink.In addition, inclusion compound of the present invention can be to be dissolved in the fluent meterial that forms in the solvent, but is preferably the material of (separating out in the solvent) powder shaped.Through being powder shaped, for example, can be used for powder coating.
The structure of inclusion compound heat capable of using is analyzed (TG and DTA), infrared absorption spectrum (IR), X-ray diffraction (XRD) pattern, solid NMR spectrum etc. and is confirmed.The composition of inclusion compound heat analysis capable of using in addition,,
1H-NMR spectrum, performance liquid chromatography (HPLC), ultimate analysis etc. are confirmed.
In addition, for example under the situation of the compsn that constitutes by 1:1 inclusion compound and 1:2 inclusion compound, what containing of 1:2 inclusion compound proportional (purity) can be by inclusion compound
1The integrated value of H-NMR is calculated 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,, try to achieve divided by the value (a) that the integrated value of 7.5ppm obtains in the 25 ℃ of integrated values that can use 2.1ppm by following formula.
The purity of 1:2 inclusion compound (%)=(2a/3-1) * 100
(carboxylic acid cpd)
As the aromatic carboxy acid compound, not special restriction, but the following compound of illustration for example.
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-hydroxy-benzoic acid, 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, 2-nitrobenzoic acid methyl esters, 3-nitrobenzoic acid methyl esters, 4-nitrobenzoic acid methyl esters, 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, 2,2,4-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, 2; 5-resorcylic acid, 2,6-resorcylic acid, 3,4-resorcylic acid, 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-methyl m-phthalic acid, 4-methyl m-phthalic acid, oreinol dioctyl phthalate, 6-methyl m-phthalic acid, 2-ethyl m-phthalic acid, 4-ethyl m-phthalic acid, 5-ethyl m-phthalic acid, 6-ethyl m-phthalic acid, 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-hydroxyl m-phthalic acid, 4 hydroxyisophthalic acid, 5-hydroxyl m-phthalic acid, 6-hydroxyl 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-methyl terephthalic acid, 2-ethyl terephthalic acid, 2-n-propyl terephthalic acid, 2-sec.-propyl terephthalic acid, 2-butyl terephthalic acid, 2-isobutyl-terephthalic acid, 2-hydroxyl terephthalic acid, 2,6-dihydric para-phthalic acid, 2,6-dimethyl terephthalic acid, 2-nitro terephthalic acid, 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 (PMA);
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-naphthalic acid, 1,4-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, 2,6-naphthalic acid, 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-hydroxyl-2-naphthoic acid, 3-hydroxyl-2-naphthoic acid, 4-hydroxyl-2-naphthoic acid, 5-hydroxyl-2-naphthoic acid, 6-hydroxyl-2-naphthoic acid, 7-hydroxyl-2-naphthoic acid, 8-hydroxyl-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-hydroxyl dihydroxy naphthlene formic 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-dihydroxyl-2-naphthoic acid, 1,4-dihydroxyl-2-naphthoic acid, 1; 5-dihydroxyl-2-naphthoic acid, 1,6-dihydroxyl-2-naphthoic acid, 1,7-dihydroxyl-2-naphthoic acid, 1,8-dihydroxyl-2-naphthoic acid, 3; 4-dihydroxyl-2-naphthoic acid, 3,5-dihydroxyl-2-naphthoic acid, 3,6-dihydroxyl-2-naphthoic acid, 3,8-dihydroxyl-2-naphthoic acid, 4; 5-dihydroxyl-2-naphthoic acid, 4,6-dihydroxyl-2-naphthoic acid, 4,7-dihydroxyl-2-naphthoic acid, 4,8-dihydroxyl-2-naphthoic acid, 5; 6-dihydroxyl-2-naphthoic acid, 5,7-dihydroxyl-2-naphthoic acid, 5,8-dihydroxyl-2-naphthoic acid, 6,7-dihydroxyl-2-naphthoic acid, 6; 8-dihydroxyl-2-naphthoic acid, 7,8-dihydroxyl-2-naphthoic acid, hexahydrobenzoic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1; 4-cyclohexane dicarboxylic acid, 1,1-cyclohexane dicarboxylic acid, 1,2-perhydronaphthalene dioctyl phthalate, 1; 3-perhydronaphthalene dioctyl phthalate, 1,4-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 use separately a kind also can and with more than 2 kinds.
Wherein, the aromatic carboxy acid compound of preferred formula (III) or formula (IV) expression,
(in the formula, n1 representes arbitrary integer in 1～4.N2 representes arbitrary integer in 0～4.R
6Expression C1～C6 alkyl, nitro or hydroxyl.）
(in the formula, m1 representes arbitrary integer in 1～4.M2 representes arbitrary integer in 0～2.R
7The group that expression C1～C6 alkyl, nitro, hydroxyl or following formula are represented
(in the formula, q representes 1 or 2 integer.* represent bonding position).）
R
6, R
7C1～C6 alkyl comprise naphthenic base; Particularly can enumerate methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-; Sec.-butyl, the tertiary butyl, cyclobutyl, cyclopropyl methyl; N-pentyl, isopentyl, 2-methylbutyl, 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 etc.
In the formula (III), the aromatic carboxy acid compound of further preferred formula (I) expression.
In the formula, R
1Expression 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 naphthenic base; Particularly can enumerate methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, sec.-butyl, the tertiary butyl, cyclobutyl, cyclopropyl methyl, n-pentyl, isopentyl, 2-methylbutyl, 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; Particularly can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec.-butoxy, tert.-butoxy, n-pentyloxy, isopentyloxy, 2-methyl butoxy, 1-ethyl propoxy-, 2-ethyl propoxy-, 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 that uses among the present invention is the imidazolium compounds and the imidazolinium compounds of formula (II) expression.
Particularly, formula (II) contains following structure.
In the formula, R
2Expression Wasserstoffatoms, C1～C10 alkyl, aryl, arylalkyl or cyanoethyl, preferred Wasserstoffatoms.
As C1～C10 alkyl, be preferably C1～C6 alkyl, can have substituting group.As C1～C10 alkyl, particularly can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec.-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, nonyl, different nonyl, decyl etc.
Aryl is meant the meaning of monocycle or polyaromatic.Wherein, during for polyaromatic, except unsaturated fully, also comprise the group of fractional saturation.For example can enumerate phenyl, naphthyl, Azulene 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 the alkyl linked group that forms, and 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
5Represent Wasserstoffatoms, nitro, halogen atom, C1～C20 alkyl independently of one another, by the acyl group of the substituted C1 of hydroxyl～C20 alkyl, aryl, arylalkyl or C1～C20.
As C1～C20 alkyl, can enumerate 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.Be preferably C1～C10 alkyl.
Aryl and arylalkyl can be enumerated and R
2The same group of group.
As C1～C20 acyl group, be meant the group that Wasserstoffatoms, alkyl, thiazolinyl, alkynyl, aryl or heteroaryl etc. and carbonyl bonding form.Acyl group for example can be enumerated formyl radical, ethanoyl, propionyl group, 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; Alkyl-carbonyls such as 13-dimethyl-myristoyl, heptadecanoyl base, 15-methyl palmitoyl, stearoyl, 1-methyl heptadecanoyl base, 19 acyl groups, 20 acyl groups and two undecanoyl; Alkenyl carbonyls such as acryl, methacryloyl, allyl group carbonyl, cinnamoyl; Alkynyl carbonyls such as ethynyl carbonyl, proyl carbonyl; Sweet-smelling formacyls such as benzoyl-, naphthoyl, dibenzoyl base, o-amino benzoyl acyl group, heteroaryl carbonyls such as 2-pyridyl carbonyl, thienyl carbonyl etc.In these groups, preferred C1～C20 (comprising carbonyl) acyl group, preferred especially C1～C6 acyl group.
Particularly; Imidazolium compounds as formula (II) expression; Can enumerate imidazoles, 2-ethyl-4-methylimidazole, glyoxal ethyline, 1 benzyl 2 methyl imidazole, 2-heptadecyl imidazoles, 2-undecyl imidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazoles, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1; The 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-dihydroxyl Methylimidazole etc.; Preferred 2-ethyl-4-methylimidazole, glyoxal ethyline, 1 benzyl 2 methyl imidazole, 2-heptadecyl imidazoles, 2-undecyl imidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazoles, 2-phenylimidazole or 2-phenyl-4,5-dihydroxyl Methylimidazole.
Imidazolinium compounds as formula (II) expression; Can enumerate glyoxal ethyline quinoline, 2-benzylimidazoline, 2-undecyl imidazole quinoline, 2-heptadecyl tetrahydroglyoxaline, 2-ethyl imidazol(e) quinoline, 2 isopropyl imidazole quinoline, 2; 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 method for manufacture of its compsn)
The 1:2 inclusion compound of carboxylic acid cpd and imidazolium compounds or its compsn can obtain by following method etc. in fact.
(1) adds the method for the alcoholic solution of carboxylic acid cpd to imidazolium compounds
(2) add the method for carboxylic acid cpd to the pure liquid of imidazolium compounds
The detailed content of the method for (1) below is described.
In imidazolium compounds, add the alcoholic solution of carboxylic acid cpd as required while stirring.The not special restriction of the interpolation of the alcoholic solution of carboxylic acid cpd, but added continuously or discontinuously through 5～120 minutes usually.
After adding the alcoholic solution of carboxylic acid cpd, placed 0～5 hour in room temperature as required, ℃ heating 0～5 hour or reflux are 0～5 hour in room temperature～40.
As the cooperate ratio of carboxylic acid cpd with imidazolium compounds, with respect to 1 mole of carboxylic acid cpd (main body), preferred imidazolium compounds (object) is 0.1～5.0 mole, more preferably 0.5～3.0 mole.
As alcoholic solvent, but lower alcohols such as illustration methyl alcohol, ethanol, n-propyl alcohol are preferably methyl alcohol.It is 0.5～50 times of amount that usage quantity converts with respect to carboxylic acid cpd in weight usually.
For the operation after heat treated or the reflux processing, for example can only solid chemical compound separated out, but behind preferred the heating, room temperature be placed an evening through stopping the processing of heating or reflux.After separating out solid chemical compound, for example, obtain target compound through filtration drying.
The detailed content of the method for (2) below is described.
After making the imidazolium compounds suspension or being dissolved in alcohol (pure suspension-s and alcoholic solution are called pure liquid), add carboxylic acid cpd as required while stirring.The not special restriction of the interpolation of carboxylic acid cpd, but added continuously or discontinuously through 5～120 minutes usually.
After adding carboxylic acid cpd, placed 0～5 hour in room temperature as required, ℃ heating 0～5 hour or reflux are 0～5 hour in room temperature～40.
As the cooperate ratio of carboxylic acid cpd with imidazolium compounds, with respect to 1 moles of carboxylic acids compound (main body), imidazolium compounds (object) is preferably 0.1～5.0 mole, more preferably 0.5～3.0 mole.
As alcoholic solvent, but lower alcohols such as illustration methyl alcohol, ethanol, n-propyl alcohol are preferably methyl alcohol.It is 0.5～50 times of amount that usage quantity converts with respect to carboxylic acid cpd in weight usually.
As a reference, the mol ratio at following record HIPA and 2P4MHZ is the method for manufacture of the inclusion compound of 1:1.
(mol ratio of HIPA and 2P4MHZ is the method for manufacture of the inclusion compound of 1:1)
Be that the inclusion compound that constitutes of 1:1 can obtain by following method etc. in fact only by the mol ratio of HIPA and 2P4MHZ.
After making HIPA be dissolved in alcohol, add 2P4MHZ as required while stirring.The interpolation of 2P4MHZ does not have special restriction, usually through more than 5 minutes, is preferably through 5 minutes～120 minutes continuously or interpolation discontinuously.
After adding 2P4MHZ, placed 0～5 hour in room temperature as required, ℃ heating 0～5 hour or reflux are 0～5 hour in room temperature～40.
As the cooperate ratio of the HIPA in the method for manufacture of 1:1 inclusion compound with 2P4MHZ, with respect to 1 mole of HIPA (main body), 2P4MHZ (object) is preferably 0.1～5.0 mole, more preferably 0.5～3.0 mole.
As the alcoholic solvent in the method for manufacture of 1:1 inclusion compound, but lower alcohols such as illustration methyl alcohol, ethanol, n-propyl alcohol are preferably methyl alcohol.Usage quantity is generally 0.5～50 times of amount with respect to HIPA.
For the operation after heat treated or the reflux processing, for example can only solid chemical compound be separated out, but behind preferred the heating, place an evening in room temperature through stopping the processing of heating or reflux.After separating out solid chemical compound, for example, obtain target compound through filtration drying.
(curable epoxy resin composition)
Inclusion compound of the present invention or its compsn can be used as epoxy curing agent or curing catalyst to be mixed with epoxy resin and for example is used as that semiconductor encapsulant uses.
As the Cured epoxy resin compositions of uses such as semiconductor encapsulant, other additive that contains epoxy resin, inclusion compound of the present invention and add as required.
1) epoxy resin
As epoxy resin; Can use known in the past various polyepoxy compounds; For example can enumerate two (4-hydroxy phenyl) propane diglycidylethers, two (4-hydroxyl-3; The 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 UVNUL MS-40, two Resorcinol four glycidyl ethers, tetramethyl-bisphenol A diglycidyl ether, bisphenol-c diglycidylether, bis-phenol HFC-236fa diglycidylether, 1; 3-Shuan ﹝ 1-(2; The 3-glycidoxy)-1-trifluoromethyl-2; 2; 2-San Fu Yi Ji ﹞ benzene, 1; 4-Shuan ﹝ 1-(2, the 3-glycidoxy)-1-trifluoromethyl-2,2; 2-San Fu Jia Ji ﹞ benzene, 4; Fragrant family glycidyl ether compounds such as 4 '-two (2, the 3-glycidoxy) octafluoro biphenyl, phenol phenolic varnish type diepoxides, ester ring type polyepoxy compounds such as alicyclic diepoxy acetal, alicyclic diepoxy adipic acid ester, alicyclic diepoxy carboxylicesters, VCH 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, diglycidyl pentamethylene-1; Epihydric alcohol ester compounds such as 3-dicarboxylic ester, dimeracid glycidyl ester, glycidyl amine compound such as diglycidylaniline, diglycidyl Tolylamine, triglycidyl group amino-phenol, four glycidyl group diaminodiphenyl-methane, diglycidyl bromamide, hetero ring type epoxy compoundss such as diglycidyl NSC 9226, glycidyl glycidoxyalkyl NSC 9226, triglycidyl isocyanurate etc.
In addition; As liquid-state epoxy resin; For example can enumerate polyalkylene ether type epoxy compoundss such as (gathering) ethylene glycol diglycidylether, (gathering) propylene glycol diglycidylether, trihydroxymethylpropanyltri diglycidyl ether; Glycidyl ester type epoxy compoundss such as dimeracid 2-glycidyl ester, o-phthalic acid diglycidyl ester, tetrahydrophthalic acid 2-glycidyl ester, the homopolymer of (methyl) glycidyl acrylate, glycidyl allyl ether etc. or the multipolymer of this monomer and other soft unsaturated monomer etc.Soft unsaturated monomer is meant that the second-order transition temperature of its homopolymer is lower than 60 ℃ monomer; For example, methyl acrylate, ethyl propenoate, (methyl) Bing Xisuandingzhi, (methyl) NSC 20949, (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 to comprise the composition epoxy resin that also comprises inorganic filler outside inclusion compound and the epoxy resin in addition.
As inorganic filler; Not special restriction; For example can enumerate silica glass, through carry out spherical silicon dioxide that the flame fusion obtains, utilize spherical silicon dioxide that sol-gel method etc. makes, crystalline silica, aluminum oxide, talcum, ammonium nitrides, silicon nitride, Natural manganese dioxide, Magnesium Silicate q-agent etc., they can use separately also and can use more than 2 kinds.
3) solidifying agent or effect promotor
In the composition epoxy resin of the present invention, except that above-mentioned inclusion compound, can also further contain curing catalyst or solidifying agent.
As the solidifying agent that can contain in the composition epoxy resin of the present invention, so long as with epoxy resin in epoxy reaction and make the compound of epoxy resin cure, just not special restriction.Likewise, as the curing catalyst that can contain in the composition epoxy resin of the present invention, so long as promote the compound of above-mentioned curing reaction, just not special restriction.As such solidifying agent or curing catalyst, can be from existing as selecting arbitrary substance to use the habitual material of curing agent for epoxy resin or curing catalyst.For example; Can enumerate amine compounds such as aliphatics amine, ester ring type and hetero ring type amine, aromatic amine, modified amine, imidazole compound, tetrahydroglyoxaline based compound, acid amides based compound, ester based compound, phenol system compound, pure 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, activated silica compound-aluminium coordination compound etc.
As solidifying agent or curing catalyst, particularly, for example can enumerate following compound.
As the aliphatics amine, for example, can enumerate quadrol, trimethylene diamines, Triethylene Diamine, tetramethylene-diamine; Hexamethylene-diamine, NSC 446, 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; For example can enumerate piperidines, piperazine,
alkane diamines, isophorone diamine, methylmorpholine, ethyl morpholine, N; N', N " three (dimethylaminopropyl) perhydro-s-triazine, 3, two (the 3-aminopropyls)-2 of 9-; 4; 8,10-four oxaspiros (5,5) undecane affixture, N-aminoethyl piperazine, trimethylammonium aminoethylpiperazine, two (4-aminocyclohexyl) methane, N; N'-lupetazin, 1,8-diazabicyclo ［ 4.5.0 ］ hendecene-7 etc.
As aromatic amine, for example can enumerate O-Phenylene Diamine, mphenylenediamine, Ursol D, diaminodiphenyl-methane, diamino diphenyl sulfone, benzyl methylamine, dimethyl benzyl amine, m-xylene diamine, pyridine, picoline, α-Jia Jibianji methylamine etc.
As modified amine, for example 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; Can enumerate for example imidazoles, 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-normal-butyl imidazoles, 2-normal-butyl imidazoles, 1-isobutyl-imidazoles, 2-isobutyl-imidazoles, 2-undecyl-1H-imidazoles, 2-heptadecyl-1H-imidazoles, 1; 2-methylimidazole, 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 affixture, glyoxal ethyline isocyanuric acid affixture, 2-phenyl-4; 5-two (hydroxymethyl) imidazoles, 2-phenyl-4-methyl-5-hydroxymethyl imidazoles, 1-cyanoethyl-2-phenyl-4,5-two (2-cyanic acid oxyethyl group) Methylimidazole, 1-dodecyl-2-methyl-3-benzyl imidazole
muriate, 1-benzyl-2-phenylimidazole hydrochloride etc.
As the tetrahydroglyoxaline based compound, for example can enumerate glyoxal ethyline quinoline, 2-benzylimidazoline etc.
As the acid amides based compound, for example can enumerate polymeric amide that the condensation through dimeracid and polyamines obtains etc.
As the ester based compound, for example can enumerate such active carbonyl compound of aryl and the sulphur aryl ester of carboxylic acid etc.
As phenol system compound, pure based compound, mercaptan based compound, ether based compound and thioether based compound; For example can enumerate; As phenolic varnish type resol such as aralkyl-type phenol resin, phenol novolac resin, cresols novolac resin such as the phenol aralkyl resin of phenolic resin curative, naphthols aralkyl resins; Their modified resin, for example epoxidation or butylated phenolic varnish type resol etc., Dicyclopentadiene (DCPD) modified phenolic resins, 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-three (dimethylamino methyl) phenol, 2,4, three-2-ethylhexyl hydrochloride of 6-three (dimethylamino methyl) phenol etc.
As urea based compound, thiocarbamide based compound, Lewis acid based compound, for example can enumerate butylation urea, butylation trimeric cyanamide, butylation thiocarbamide, boron trifluoride etc.
As phosphorus series compound, can enumerate organic phosphoric compound, for example uncle's phosphines such as alkylphosphines such as ethyl phosphine, butyl phosphine, Phenylphosphine; Secondary phosphines such as dialkyl phosphines such as dimethyl phosphine, dipropyl phosphine, diphenylphosphine, methylethyl phosphine; Tertiary phosphines such as trimethyl-phosphine, triethyl phosphine, triphenylphosphine etc.
As the acid anhydrides based compound, for example can enumerate methylene radical Tetra Hydro Phthalic Anhydride, maleic anhydride, tetramethylene maleic anhydride, trimellitic acid 1,2-anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride, pyromellitic acid dianhydride, dodecenyl succinic anhydride, UVNUL MS-40 tetracarboxylic acid dianhydride, ethylene glycol bis (dehydration trimellitate), glycerine three (dehydration trimellitate), tetrahydrotoluene tetracarboxylic acid dianhydride in Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, interior methylene radical Tetra Hydro Phthalic Anhydride, the methyl, gather nonane diacid acid anhydride etc.
In addition; As
salt based compound and activated silica compound-aluminum complex, can enumerate for example aryl diazonium
salt, diaryl iodine
salt, triarylsulfonium salt, triphenyl silanol-aluminum complex, triphenyl methoxy silane-aluminum complex, silyl superoxide (silyl peroxide)-aluminum complex, triphenyl silanol-three (salicylic aldehyde closes) aluminum complex etc.
As above-mentioned solidifying agent or curing catalyst, especially preferably use amine compound, imidazole compound, phenol system compound.More preferably use phenolic resin curative in the phenol system compound.
4) other additive
Except that above-mentioned substance, can cooperate various additives such as softening agent, organic solvent, reactive diluent, extender, weighting agent, toughener, pigment, fire retardant, thickening material and releasing agent as required in the composition epoxy resin of the present invention.As other additive, can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl) γ-An Jibingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane, N-phenyl-γ-An Jibingjisanyiyangjiguiwan, γ-Qiu Jibingjisanjiayangjiguiwan, γ-silane coupling agents such as sulfydryl propyl-triethoxysilicane; Weighting agents such as Calcium hydrogen carbonate, light calcium carbonate, native silicon dioxide, synthetic silica, fused silica, kaolin, clay, titanium oxide, permanent white, zinc oxide, white lake, Marinco H, talcum, mica, wollastonite, potassium titanate, aluminum borate, sepiolite, xonotlite; Elastomer modifiers such as NBR, polyhutadiene, neoprene, silicone, crosslinked NBR, crosslinked BR, acrylic acid series, nucleocapsid acrylic acid or the like, urethanes, polyester elastomer, the liquid NBR that contains functional group, liquid polybutadiene, liquid polyester, liquid polysulphides, modified silicone, polyurethane prepolymer;
Hexabromo cyclodecane, two (dibromopropyl) tetrabromo-bisphenol, three (dibromopropyl) isocyanuric acid ester, three (tribromo neo-pentyl) SULPHOSUCCINIC ACID ESTER, decabromodiphynly oxide, two (pentabromo-) diphenylphosphino ethane, three (tribromophenoxy) triazine, the two tetrabromo phthalimides of ethylene, many bromophenyls indane, brominated Polystyrene, tetrabromobisphenol a polycarbonate, bromination penylene oxyethane (smelly elementization Off エ ニ レ Application エ チ レ Application オ キ シ De), ROHM pentabromo-benzyl ester, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (YLENE) ester, tolyl diphenyl phosphoester, xylyl diphenyl phosphoester, tolyl two (two-2; The 6-xylyl) SULPHOSUCCINIC ACID ESTER, 2-ethylhexyl diphenyl phosphate, Resorcinol two [(phenylbenzene) SULPHOSUCCINIC ACID ESTER], dihydroxyphenyl propane two [(phenylbenzene) SULPHOSUCCINIC ACID ESTER], dihydroxyphenyl propane two [(diglycidyl) SULPHOSUCCINIC ACID ESTER], Resorcinol two [(two-2; The 6-xylyl) SULPHOSUCCINIC ACID ESTER], tricresyl phosphate (chloroethyl) ester, tricresyl phosphate (chloropropyl) ester, tricresyl phosphate (two chloropropyls) ester, tricresyl phosphate (three bromopropyls) ester, diethylammonium-N, two (2-hydroxyethyl) the aminomethylphosphonic acid esters of N-, negatively charged ion oxalic acid treatment white lake, nitrate salt are handled white lake, high-temperature-hot-water and are handled that white lake, stannic acid surface treatment hydrated metal compound, nickel compound surface treatment Marinco H, silicone polymer surface treatment Marinco H, phlogopite, multiple-level surface are handled hydrated metal compound, cationic polymers is handled fire retardants such as Marinco H; Engineering plastics such as high density polyethylene(HDPE), Vestolen PP 7052, PS, polymethylmethacrylate, SE, nylon 6,6, polyacetal, polyethersulfone, polyetherimide, polybutylene terephthalate, polyetheretherketone, polycarbonate, polysulfones; Softening agent; 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., for example releasing agent such as POLISHING WAX-103, polyethylene-based wax; Deng.The use level of these additives does not have special qualification, in obtaining the limit of effect of the present invention, can suitably confirm use level.
In addition, in the composition epoxy resin of the present invention, except that epoxy resin, also can contain other resin.As other resin, can enumerate vibrin, acrylic resin, silicon is resin, polyurethane series resin etc.
5) preparation of composition epoxy resin and cured article thereof
For the cooperation ratio of epoxy resin and inclusion compound of the present invention or its compsn; With respect to 1 mole of the oxirane ring of epoxy resin; Imidazolium compounds in inclusion compound or its compsn preferably contains 0.01～1.0 mole; More preferably contain 0.1～1.0 mole, further preferably contain 0.3～1.0 mole.
In addition, the curable epoxide resin formation can be made through blending epoxy and inclusion compound of the present invention or its compsn with compsn, is heated to usually and mixes about 60～100 ℃ can form sufficient admixture.In the manufacturing of curable epoxide resin, single liquid stability of the temperature of this moment becomes important.The composition epoxy resin that produces can also can be liquid state for solid-state according to its composition and method of manufacture.
As the solidification method of curable epoxide resin formation with compsn, so long as being carried out heat treated with compsn, the curable epoxide resin formation makes its solidified method, just not special restriction, usually, the Heating temperature of heat treated is 60～250 ℃.
Embodiment
Below, embodiment is described, but technical scope of the present invention is not limited by these embodiment.
Should explain, in following examples,
1HNMR uses DMSO-d
6Or MeOH-d
4As measuring solvent, 25 ℃ of mensuration.
The manufacturing of 1 inclusion compound
［ synthetic embodiment 1 ］
The 2P4MHZ that in flask, adds 20.67g (109.8mmol) adds while stirring that then 20g (109.8mmol) HIPA is dissolved into the half the of the liquid that obtains in the 170ml methyl alcohol.Use the 11mL washed with methanol, after room temperature is placed 0.5 hour, add remaining HIPA methanol solution while stirring, use the 11mL washed with methanol, after room temperature is placed 0.5 hour, reflux 3 hours., room temperature place an evening after, filter, vacuum-drying, obtain the resultant (yield 71%) of 28.89g thus thereafter.The resultant that obtains is used
1HNMR, X-ray diffraction and heat are analyzed (DSC) and are analyzed, and the result is that HIPA:2P4MHZ is the crystallization of the inclusion compound of 1:2.In addition, the purity of 1:2 inclusion compound is 91%.Heat analysis (DSC) figure that the inclusion compound that obtains is measured based on temperature variation is shown in Fig. 1.
［ synthetic embodiment 2 ］
In flask, drop into the 2P4MHZ of 20.67g (109.8mmol) and the methyl alcohol of 130ml, in the pure liquid that mixing obtains, added the HIPA of 10g (54.9mmol) while stirring through 20 minutes.Room temperature was placed after 0.5 hour, reflux 3 hours., room temperature place an evening after, filter, vacuum-drying, obtain 29.91g resultant (yield 97.5%) thus thereafter.The resultant that obtains is used
1HNMR, X-ray diffraction and heat are analyzed (DSC) and are analyzed, and the result is that HIPA:2P4MHZ is the crystallization of the inclusion compound of 1:2.In addition, the purity of 1:2 inclusion compound is 97%.Heat analysis (DSC) chart that the inclusion compound that obtains is measured based on temperature variation with
1HNMR figure is shown in Fig. 2-1 and Fig. 2-2.
[synthetic embodiment 3]
After in flask, adding the 2P4MHZ of 20.67g (109.8mmol), add through 15 minutes that while stirring 10g (54.9mmol) HIPA is dissolved into the liquid that obtains in the 130ml methyl alcohol.After room temperature is placed 0.5 hour, reflux 3 hours., room temperature place an evening after, filter, vacuum-drying, obtain 29.74g resultant (yield 97%) thus thereafter.The resultant that obtains is used
1HNMR, X-ray diffraction and heat are analyzed (DSC) and are analyzed, and the result is that HIPA:2P4MHZ is the crystallization of the inclusion compound of 1:2.In addition, the purity of 1:2 inclusion compound is 99%.Heat analysis (DSC) chart that the inclusion compound that obtains is measured based on temperature variation with
1HNMR figure is shown in Fig. 3-1 and Fig. 3-2.
［ synthetic embodiment 4 ］
Replace 2P4MHZ to use 7.48g (109.8mmol) not have substituted imidazoles (below, be called Im), in addition, likewise obtain the inclusion compound that HIPA:Im is 1:2 with synthetic embodiment 2.In addition, the purity of 1:2 inclusion compound is 77%.Heat analysis (DSC) chart that the inclusion compound that obtains is measured based on temperature variation with
1HNMR figure is shown in Fig. 4-1 and Fig. 4-2.
［ synthesized reference example 1 ］ (manufacturing of 1:1 inclusion compound)
In flask, drop into the HIPA of 20g (109.8mmol) and the methyl alcohol of 126ml, in the solution that mixing obtains, added the 2P4MHZ of 20.67g (109.8mmol) while stirring through 15 minutes.Room temperature was placed after 2 hours, reflux 3 hours., room temperature place an evening after, filter, vacuum-drying, obtain 39.56g resultant (yield 97.3%) thus thereafter.The resultant that obtains is used
1HNMR, X-ray diffraction and heat are analyzed (DSC) and are analyzed, and the result is that HIPA:2P4MHZ is the crystallization of the inclusion compound of 1:1.In addition, the purity of 1:2 inclusion compound is 0%.Heat analysis (DSC) figure that the inclusion compound that obtains is measured based on temperature variation is shown in Fig. 5.
［ synthesized reference example 2 ］
Replace 2P4MHZ to use the lm of 7.48g (109.8mmol), in addition, with synthesized reference example 1 likewise, obtain the inclusion compound that HIPA:Im is 1:1.
［ synthetic comparative example 1 ］ (manufacturing of the mixture of 1:1 and 1:2 inclusion compound)
In flask, drop into the HIPA of 36.43g (200mmol), the 2P4MHZ of 37.65g (200mmol) and the methyl alcohol of 230ml, stir, carry out 3 hours reflux., room temperature place an evening after, filter, vacuum-drying, obtain 64.41g resultant (yield 87.2%) thus thereafter.The resultant that obtains is used
1HNMR, X-ray diffraction and heat are analyzed (DSC) and are analyzed, and the result shows the data different with embodiment 1 and 2, and judgement is that HIPA:2P4MHZ is the crystallization that the inclusion compound of inclusion compound and the 1:2 of 1:1 mixes.In addition, the purity of 1:2 inclusion compound is 18%.Heat analysis (DSC) figure that the inclusion compound that obtains is measured based on temperature variation is shown in Fig. 6.
The manufacturing of 2 composition epoxy resins
The manufacturing of 2-1 biphenyl type epoxy resin compsn
［ compsn reference example 1 ］
To add hot milling 5 minute as the phenolic varnish phenol PSM-4261OH equivalent 103 (Gunsaka Chem. Industry Co., Ltd.'s system) of solidifying agent at 100 ℃ as LS2940 (Shin-Etsu Chemial Co., Ltd's system), the 6.701g of silane coupling agent as FB-940 spherical silicon dioxide (Deuki Kagaku Kogyo Co., Ltd's system), the 0.383g of weighting agent as TOWAX (registered trademark) 131 (East Asia changes into Co., Ltd.'s system), the 179.97g of releasing agent as YX4000H (Mitsubishi chemical Co., Ltd's system), the 0.249g of biphenyl type epoxy resin in imidazoles inclusion compound, the 12.445g that obtains in synthesized reference example 1 method of 0.249g that convert; After the cooling; Pulverize, make the biphenyl type epoxy resin compsn.
［ compsn embodiment 1 ］
Use the inclusion compound that obtains in synthetic embodiment 1 method to replace the inclusion compound that obtains in synthesized reference example 1 method, in addition, likewise make the biphenyl type epoxy resin compsn with compsn reference example 1.
The manufacturing of 2-2 o-cresol phenolic epoxy varnish compsn
［ compsn reference example 2 ］
To add hot milling 5 minute as the phenolic varnish phenol PSM-4261OH equivalent 103 (Gunsaka Chem. Industry Co., Ltd.'s system) of solidifying agent at 100 ℃ as LS-2940 (chemistry society of SHIN-ETSU HANTOTAI system), the 9.443g of silane coupling agent as FB-940 spherical silicon dioxide (Deuki Kagaku Kogyo Co., Ltd's system), the 0.944g of weighting agent as TOWAX (registered trademark) 131 (East Asia changes into Co., Ltd.'s system), the 169.97g of releasing agent as EOCN-1020-55 epoxy equivalent (weight) 191～201 (Nippon Kayaku K. K's system), the 0.378g of o-cresol phenolic resin varnish in imidazoles inclusion compound, the 18.886g that obtains in synthesized reference example 1 method of 0.378g that convert; After the cooling; Pulverize, make the biphenyl type epoxy resin compsn.
［ compsn embodiment 2 ］
Use the inclusion compound that obtains in synthetic embodiment 1 method to replace the inclusion compound that obtains in synthesized reference example 1 method, in addition, likewise make the o-cresol phenolic epoxy varnish compsn with compsn reference example 2.
The manufacturing of 2-3 liquid epoxy resin composition
［ compsn reference example 3 ］
To mix as the EPOTOHTO YD-128 (Toto Kasei KK's system) of liquid-state epoxy resin in imidazoles inclusion compound, the 10g that obtains in synthesized reference example 1 method of 0.4g that convert, make liquid epoxy resin composition.
［ compsn embodiment 3 ］
Use the inclusion compound that obtains in synthetic embodiment 1 method to replace the inclusion compound that obtains in synthesized reference example 1 method, in addition, likewise make liquid epoxy resin composition with compsn reference example 3.
［ compsn embodiment 4 ］
Use the inclusion compound that obtains in synthetic embodiment 4 methods to replace the inclusion compound that obtains in synthesized reference example 1 method, in addition, likewise make liquid epoxy resin composition with compsn reference example 3.
［ compsn reference example 4 ］
In addition the inclusion compound that obtains in inclusion compound replacement synthesized reference example 1 method that obtains in use synthesized reference example 2 methods likewise makes liquid epoxy resin composition with compsn reference example 3.
［ Test Example 1 ］
(spiral flow test)
The composition epoxy resin that obtains in the method with compsn embodiment 1 and 2, compsn reference example 1 and 2 is compressing tablet respectively, is shaped to tablet.Use spiral of Archimedes mould and transfer molding machine, at 175 ℃, pressure 70Kgf/cm
2Condition under with these tablet injection moldings 3 minutes, measure the length of resulting moulding article.For the helicoidal flow value, measure initial value and 25 ℃ of values after 7 days, shown in the 1st table.
The big more expression flowability of its value is good more in the spiral flow test.
［ Test Example 2 ］
(gel time)
Neutralizing the composition epoxy resin that obtains in the method for spoon with an amount of compsn embodiment 3 and 4, compsn reference example 3 with metal is placed on 175 ℃ the hot plate; Using metal to neutralize spoon stirs; The binding property of test portion disappears, and mensuration can be from the time that time that hot plate is peeled off or binding property disappear.The result is shown in the 2nd table.
Gel time be when certain temperature heated sealant material the time till lose flowability, relevant with curing characteristics, can suitably select.Gel time is short more, and expression is more early solidified, so particularly during liquid-state epoxy resin, the preferred gel time resin of lacking.
(storage stability)
The composition epoxy resin that obtains in the method with compsn embodiment 3 and 4, compsn reference example 3 carries out visual observation 30 ℃ of preservations, finishes as measuring in the moment of having solidified, and estimates storage stability.The result is shown in the 2nd table.
[table 1]
The 1st table
[table 2]
The 2nd table
Utilizability in the industry
According to the present invention, can obtain the 1:2 inclusion compound of aromatic carboxy acid compound and imidazolium compounds with high purity.
In addition, among the present invention,, contain in 1:1 inclusion compound and the 1:2 inclusion compound any as the curable epoxy resin composition and the cured article thereof of solidifying agent or curing catalyst so can make because can make the 1:2 inclusion compound with high purity.
Claims (8)
1. an inclusion compound or its compsn contain following inclusion compound, and this inclusion compound is 70 moles of %～100 mole % in containing (A) and total inclusion compound (B),
Said inclusion compound contain the compound (B) of aromatic carboxy acid compound (A) and formula (II) expression and (A) and mol ratio (B) be 1:2,
In the formula (II), R
2Expression Wasserstoffatoms, C1～C10 alkyl, aryl, arylalkyl or cyanoethyl, R
3～R
5Expression Wasserstoffatoms, nitro, halogen atom, C1～C20 alkyl, by the acyl group of the substituted C1 of hydroxyl～C20 alkyl, aryl, arylalkyl or C1～C20, the part of mark dotted line is represented singly-bound or two key.
2. inclusion compound according to claim 1 or its compsn is characterized in that, the aromatic carboxy acid compound is the compound of formula (III) or formula (IV) expression,
In the formula (III), n1 representes arbitrary integer in 1～4, and n2 representes arbitrary integer in 0～4, R
6Expression C1～C6 alkyl, nitro or hydroxyl,
In the formula (IV), m1 representes arbitrary integer in 1～4, and m2 representes arbitrary integer in 0～2, R
7The group that expression C1～C6 alkyl, nitro, hydroxyl or following formula are represented,
In the formula, q representes 1 or 2 integer, and * representes bonding position.
3. inclusion compound according to claim 2 or its compsn is characterized in that, formula (IV) is formula (I),
In the formula (I), R
1Expression C1～C6 alkyl, C1～C6 alkoxyl group, nitro or hydroxyl.
4. inclusion compound according to claim 3 or its compsn is characterized in that, formula (I) is a 5-hydroxyl m-phthalic acid.
5. according to each described inclusion compound or its compsn in the claim 1～4, it is characterized in that formula (II) is 2-phenyl-4-methyl-5-hydroxymethyl imidazoles.
6. the method for manufacture of the described inclusion compound of claim 1 or its compsn is characterized in that, adds the aromatic carboxy acid compound to the pure liquid of the compound of formula (II).
7. the method for manufacture of the described inclusion compound of claim 1 or its compsn is characterized in that, adds aromatic carboxy acid compound's alcoholic solution to the compound of formula (II).
8. a curable epoxy resin composition or its cured article contain each described inclusion compound or its compsn and epoxy resin in the claim 1～5.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010010375 | 2010-01-20 | ||
| JP2010-010375 | 2010-01-20 | ||
| JP2010228645 | 2010-10-08 | ||
| JP2010-228645 | 2010-10-08 | ||
| PCT/JP2011/000172 WO2011089874A1 (en) | 2010-01-20 | 2011-01-14 | Clathrate and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102725273A true CN102725273A (en) | 2012-10-10 |
| CN102725273B CN102725273B (en) | 2016-02-17 |
Family
ID=44306676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180006305.8A Expired - Fee Related CN102725273B (en) | 2010-01-20 | 2011-01-14 | Inclusion compound and manufacture method thereof |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5536108B2 (en) |
| CN (1) | CN102725273B (en) |
| BR (1) | BR112012016151A2 (en) |
| TW (1) | TWI525073B (en) |
| WO (1) | WO2011089874A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106604914A (en) * | 2014-09-08 | 2017-04-26 | 日本曹达株式会社 | Crystal polymorphism of inclusion compound and method for producing same, and curable resin composition |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012035755A1 (en) * | 2010-09-15 | 2012-03-22 | 日本曹達株式会社 | Liquid curable epoxy resin composition and adhesive agent containing same |
| JP6046894B2 (en) * | 2011-12-28 | 2016-12-21 | ナミックス株式会社 | Liquid encapsulant |
| JP5901349B2 (en) * | 2012-02-28 | 2016-04-06 | 古河電気工業株式会社 | Adhesive film, tape for wafer processing, and method for producing adhesive film |
| CN106589828A (en) * | 2016-12-22 | 2017-04-26 | 科化新材料泰州有限公司 | Environment-friendly epoxy resin composition and preparation method thereof |
| GB2576875B (en) | 2018-08-30 | 2022-08-31 | Hexcel Composites Ltd | Improvements in or relating to curing agents |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007191450A (en) * | 2006-01-20 | 2007-08-02 | Nippon Soda Co Ltd | Method for producing inclusion compound by slurry method |
| WO2009037862A1 (en) * | 2007-09-21 | 2009-03-26 | Nippon Soda Co., Ltd. | Inclusion complex containing epoxy resin composition for semiconductor encapsulation |
| CN101563326A (en) * | 2006-12-21 | 2009-10-21 | 日本曹达株式会社 | Clathrate compound, curing catalyst, composition for forming cured resin, and cured resin |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5000036B2 (en) * | 2000-12-11 | 2012-08-15 | 日本曹達株式会社 | Method for producing molecular compound |
-
2011
- 2011-01-14 BR BR112012016151A patent/BR112012016151A2/en not_active Application Discontinuation
- 2011-01-14 WO PCT/JP2011/000172 patent/WO2011089874A1/en active Application Filing
- 2011-01-14 CN CN201180006305.8A patent/CN102725273B/en not_active Expired - Fee Related
- 2011-01-14 JP JP2011550838A patent/JP5536108B2/en not_active Expired - Fee Related
- 2011-01-18 TW TW100101845A patent/TWI525073B/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007191450A (en) * | 2006-01-20 | 2007-08-02 | Nippon Soda Co Ltd | Method for producing inclusion compound by slurry method |
| CN101563326A (en) * | 2006-12-21 | 2009-10-21 | 日本曹达株式会社 | Clathrate compound, curing catalyst, composition for forming cured resin, and cured resin |
| WO2009037862A1 (en) * | 2007-09-21 | 2009-03-26 | Nippon Soda Co., Ltd. | Inclusion complex containing epoxy resin composition for semiconductor encapsulation |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106604914A (en) * | 2014-09-08 | 2017-04-26 | 日本曹达株式会社 | Crystal polymorphism of inclusion compound and method for producing same, and curable resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011089874A1 (en) | 2011-07-28 |
| JPWO2011089874A1 (en) | 2013-05-23 |
| TWI525073B (en) | 2016-03-11 |
| JP5536108B2 (en) | 2014-07-02 |
| TW201139358A (en) | 2011-11-16 |
| BR112012016151A2 (en) | 2015-09-15 |
| CN102725273B (en) | 2016-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101802049B (en) | Inclusion complex containing epoxy resin composition for semiconductor encapsulation | |
| CN102574988B (en) | Composition for formation of cured epoxy resin, and cured products thereof | |
| CN102356109B (en) | Inclusion complex, curing agent, cure accelerator, epoxy resin composition, and epoxy resin composition for encapsulation of semiconductor | |
| CN102341430B (en) | Epoxy resin composition, curing agent, and curing accelerator | |
| CN102725273A (en) | Clathrate and method for producing same | |
| JP6461170B2 (en) | Thermosetting resin composition | |
| CN102317343B (en) | Long chain alkylene group-containing epoxy compound | |
| CN103097427A (en) | Liquid curable epoxy resin composition and adhesive agent containing same | |
| KR20180127273A (en) | Epoxy resin composition comprising eco-friendly curing agent and cured product thereof | |
| JP2009091460A (en) | One-package cyanate-epoxy composite resin composition, cured product thereof, production method therefor, and sealing material and adhesive using the same | |
| CN102803334A (en) | Thermosettable composition containing a half ester of a cycloaliphatic diol and a thermoset product therefrom | |
| ES2706301T3 (en) | Composition that contains a polymer based on epoxy compounds | |
| KR20180130111A (en) | Epoxy resin composition comprising eco-friendly curing agent and cured product thereof | |
| JP2005008884A (en) | Curable epoxy resin composition, two-dimensional fabrication process using the same and shaped articles obtained therefrom | |
| GB2569614A (en) | A curative composition and a resin composition containing the curative composition | |
| KR20180041126A (en) | Use of low viscosity bis-anhydrohexitol ether compositions as reactive diluents for matrix compositions for crosslinkable resins, adhesives, coatings and composites | |
| CN105829388A (en) | Epoxy resin, method for producing same, epoxy resin composition, and cured product thereof | |
| JP4655490B2 (en) | Epoxy resin composition and cured product thereof | |
| KR20140041470A (en) | Use of epoxidized arylalkylphenols as reactive resin diluents | |
| WO2023127800A1 (en) | Epoxy resin composition, cured product, sealing material, and adhesive | |
| US3592823A (en) | N,n'-diglycidyl compounds | |
| JP3722582B2 (en) | Phosphorus-modified epoxy resin containing epoxy resin and phosphorus-containing compound | |
| KR102099795B1 (en) | Compound having anhydrosugar alcohol core and method for preparing the same | |
| KR20230024366A (en) | Aminimide compound, amineimide composition, curing agent, epoxy resin composition, method for preparing amineimide compound, sealing material, and adhesive | |
| US3480692A (en) | Mixtures of triglycidyl isocyanurate and other heterocyclic epoxides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160217 Termination date: 20190114 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |