CN102037048B - Novel epoxy resin, method for producing the same, epoxy resin composition containing the epoxy resin as essential component, and cured product containing the epoxy resin as essential component - Google Patents
Novel epoxy resin, method for producing the same, epoxy resin composition containing the epoxy resin as essential component, and cured product containing the epoxy resin as essential component Download PDFInfo
- Publication number
- CN102037048B CN102037048B CN2009801181285A CN200980118128A CN102037048B CN 102037048 B CN102037048 B CN 102037048B CN 2009801181285 A CN2009801181285 A CN 2009801181285A CN 200980118128 A CN200980118128 A CN 200980118128A CN 102037048 B CN102037048 B CN 102037048B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- general formula
- essential component
- compound
- molecule
- 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.)
- Expired - Fee Related
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/31—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals in which the oxirane rings are condensed with a carbocyclic ring system having three or more relevant rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/44—Esterified with oxirane-containing hydroxy 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
- C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
- C08G59/186—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 using pre-adducts of epoxy compounds with curing agents with acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
Disclosed is a novel epoxy resin having excellent heat resistance and flexibility. The novel epoxy resin is represented by general formula (1). A method for producing the epoxy resin, an epoxy resin composition containing the epoxy resin as an essential component, and a cured product containing the epoxy resin as an essential component are also disclosed. In general formula (1), E1 and E3 represent, for example, a group represented by general formula (3); E2 represents, for example, a group represented by general formula (9); A1 and A2 represent an acid anhydride residue, namely a hydrocarbon which may contain a phosphorus, nitrogen or oxygen atom; and n represents an integer of 0-25. In general formulae (3) and (9), R represents a hydrocarbon group or a heterocyclic compound residue.
Description
Technical field
The present invention relates to epoxy resin, composition epoxy resin and epoxy resin cured product, neo-epoxy resin of the present invention, composition epoxy resin, epoxy resin cured product are useful to coating, tackiness agent, light appearance, sealing material, an injectable plastic material, electric and electronic circuit material, optical circuit material etc.
Background technology
The binding property of epoxy resin, thermotolerance, have excellent formability, so be used to scope widely such as electronic component, electric machine, auto parts, FRP, sporting goods.In recent years further require stable on heating raising, the demand that has the material of flexibility or obdurability simultaneously concurrently improves.
Generally speaking, the epoxy resin that thermotolerance is high has and in 1 molecule, has 2.1 above epoxy group(ing), so-called multifunctional type epoxy resin.As representational polyfunctional epoxy resin, YDPN-638 (Toto Kasei KK's system line style phenol aldehyde type epoxy resin), YDCN-700 (Toto Kasei KK's system cresol-novolac epoxy resin) etc. are arranged.But the cross-linking density after above-mentioned polyfunctional epoxy resin solidifies improves, though can access thermotolerance, flexibility reduces.
A kind of compsn is disclosed in the patent documentation 1; Be to use the Photocurable composition of epoxy functional resin; Comprise as the dihydroxyphenyl propane linear epoxy resin of multi-functional epoxy resin and performance as the mixture of the reactive diluent of the effect of softening agent and the compsn of cationic light trigger; Though thermotolerance is high, there is the inadequate problem of flexibility.
Patent documentation 1: the spy opens clear 62-102242 communique.
Summary of the invention
The inventor furthers investigate neo-epoxy resin; The neo-epoxy resin that discovery has an ad hoc structure of formula (1) expression can have the rerum natura of thermotolerance and flexibility concurrently; Accomplished the present invention, epoxy resin, composition epoxy resin, the epoxy resin cured product of the problem that can solve the rerum natura that has thermotolerance and flexibility concurrently is provided.
Neo-epoxy resin through using general formula (1) expression can solve above-mentioned problem.That is, the purport of the application's invention is the neo-epoxy resin of general formula (1) expression.
In the formula, E1 and E3 represent any in general formula (2)～general formula (7), and E2 representes any in general formula (8)～general formula (11), comprise at least one general formula (3), general formula (5) or the general formula (9) any in the general formula (1).A1, A2 are the acid anhydrides residue, and the expression hydrocarbon also can be phosphorous, nitrogen, Sauerstoffatom.N representes 0～25 integer.
In general formula (2)～(11) formula, R representes alkyl or hetero ring type compound residue.
Description of drawings
The MWD that obtains by GPC of the epoxy resin that Fig. 1 representes to obtain among the embodiment 1.
The mensuration result of the FTIR of the epoxy resin that Fig. 2 representes to obtain among the embodiment 1.
Embodiment
Below specify the present invention.
Neo-epoxy resin among the present invention is the epoxy resin of general formula (1) expression; E1 in the formula and E3 represent any in general formula (2)～general formula (7); E2 representes any in general formula (8)～general formula (11), but comprises at least a general formula (3), general formula (5) or the general formula (9) any in the general formula (1).
As a method making neo-epoxy resin of the present invention, the method that has the carboxyl that makes the compound that in 1 molecule, has 1 epoxy group(ing) and have 1 carboxyl all to react with epoxy resin.
Can use known epoxy resin with the epoxy resin that in 1 molecule, has 1 epoxy group(ing) and have a compound reaction of 1 carboxyl; Specifically can enumerate HBPA-DGE, DCPD-EP, MCPD-EP, TCPD-EP, CDA-EP, TD-EL, the system YX8000 of JAPAN EPOXY RESIN Co., Ltd., the YX8034 of aliphatic epoxy resins such as glycidyl ester type epoxy resins such as naphthalene diol type epoxy resin such as BPF type epoxy resin such as BPA type epoxy resin, Epo Tohto YDF-170, Epo Tohto YDF-8170, Epo Tohto YDF-870GS, Epo Tohto YDF-2001, Epo Tohto YDF-2004, Epo Tohto ZX-1355, Epo Tohto ZX-1711, Epo Tohto YD-171, Epo Tohto YD-172, Epo Tohto PG-207, Epo Tohto PG-207GS such as Epo Tohto YD-128, Epo Tohto YD-8125, Epo Tohto YD-127, Epo Tohto YD-825GS, Epo Tohto YD-134, Epo Tohto YD-011, Epo Tohto YD-012, Epo Tohto YD-013, Epo Tohto YD-901, Epo Tohto YD-902, Epo Tohto YD-903, Epo Tohto ST-3000, Epo Tohto ZX-1658 (diglycidyl ether of cyclohexanedimethanol), Epo Tohto ZX-1658GS, Epo Tohto ZX-1715, Epo Tohto FX-318, Maruzen Petrochemical Co., Ltd.'s system of Toto Kasei KK's system, the CELLOXIDE 2021 (3 of DICEL chemical industry Co., Ltd. system; 4-oxirane ring hexenyl methyl-3 ', 4 '-oxirane ring hexene carboxylicesters), CELLOXIDE 2021A, CELLOXIDE 2021P, CELLOXIDE 3000 (1; 2:8; The alicyclic epoxy resins such as epoxy resin of 9 diepoxy PC 560s, hydrogenated dimer acids glycol etc.; But be not limited thereto, can mix more than 2 kinds and use.
Reacting phase for 1.0 moles of carboxyls cooperate more than 1.1 moles, more preferably more than 2.0 moles, further preferred more than 3.0 moles epoxy group(ing) react.
In 1 molecule, have 1 epoxy group(ing) and have the compound of 1 carboxyl and the reaction of epoxy resin can adopt known compound method to carry out.That is, can heat and react through being engaged in the compound that has 1 epoxy group(ing) in 1 molecule and have 1 carboxyl and epoxy resin.Can use inert solvent or catalyzer etc. as required.Temperature of reaction is 50 ℃～200 ℃, more preferably 80 ℃～180 ℃.Reaction can be measured acid number, confirm that carboxyl disappears to confirm terminal point through the disappearance of machine analysis confirmation carboxyl or through chemical analysis.Reaction times is 1 hour～10 hours.
As the inert solvent that can use, preferably do not have the solvent of hydroxyl, specifically can enumerate benzene,toluene,xylene etc., but be not limited thereto, also can mix more than 2 kinds and use.
As the catalyzer that can use; Can enumerate imidazoles, triphenylphosphine, trimethylphenyl phosphines, three (2 such as glyoxal ethyline, 2-ethyl-4-methylimidazole; The 6-Dimethoxyphenyl) phosphorus
salts such as phosphine class, tetrabutyl phosphorus
bromide, tetrabutyl phosphorus
iodide, ethyl triphenyl phosphorus
bromide, ethyl triphenyl phosphorus
iodide such as phosphine etc.; But be not limited thereto, can mix more than 2 kinds and use.
The compound that in 1 molecule, has 1 epoxy group(ing) and have 1 carboxyl also can have 1 hydroxyl and has the compound of 1 epoxy group(ing) and comprise that the carboxylic-acid reaction of anhydrides obtains through making in 1 molecule; But be not limited thereto; So long as in 1 molecule, have 1 epoxy group(ing) and have the compound of 1 carboxyl, just unqualified.
During reaction, be to react below 1 equivalent, can access the compound that in 1 molecule, has 1 epoxy group(ing) and have 1 carboxyl through making anhydride equivalent with respect to 1 equivalent hydroxyl.With respect to 1 equivalent hydroxyl, anhydride equivalent is during greater than 1 equivalent, and acid anhydrides is residual, so might gelation when reacting with epoxy resin.With respect to 1 equivalent hydroxyl, anhydride equivalent is preferably smaller or equal to 1 equivalent to 0.5 equivalent.Can adjust hydroxyl arbitrarily through adjustment hydroxyl equivalent and anhydride equivalent.
As having 1 epoxy group(ing) in 1 molecule, having the compound of 1 hydroxyl; CDA-EP, TD-EL (the kind oil Co., Ltd. of ball system) or ZX-1658B (monoepoxide of Toto Kasei KK's preparing cyclohexane dimethanol), 3 are arranged, 4-epoxycyclohexyl methyl alcohol etc.In addition; Can enumerate through with a compound that the alcohol radical epoxidation obtains in the divalent alcohol such as terepthaloyl moietie, glycol ether, Ucar 35, dipropylene glycol, butanediol, NSC 6366, hexane diol, heptanediol, ethohexadiol, cyclohexanedimethanol, the spiroglycol; But be not limited thereto, can mix more than 2 kinds and use.
As anhydrides; Can enumerate itaconic anhydride, citraconic anhydride, 2-carboxyl-ethyl-methyl-phosphonic acid anhydride, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, methylhexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl norbornene dioic anhydride, dodecyl succinic anhydride, pyromellitic dianhydride, UVNUL MS-40 tetracarboxylic acid anhydride, ethylene glycol bis (trimellitic acid 1,2-anhydride), tetrahydrotoluene tetracarboxylic acid anhydride, trimellitic acid 1,2-anhydride, naphthalic anhydride, spy and open the acid anhydrides put down in writing among the flat 6-80765 etc.; But be not limited thereto, can mix more than 2 kinds and use.
The compound that have 1 epoxy group(ing) in 1 molecule, has 1 hydroxyl heats through each compound that adds specified amount with the reaction of the carboxylic-acid that comprises anhydrides, reacts.At this moment, can use inert solvent or catalyzer etc. as required.Temperature of reaction is 50 ℃～180 ℃, more preferably 80 ℃～150 ℃.Reaction can be through being disappeared by machine analysis confirmation acid anhydrides or utilizing chemical analysis to measure acid number, affirmation carboxyl disappearance decision terminal point.Reaction times is 1 hour～10 hours.
Operable inert solvent during as reaction needs the solubilizing reaction product, is preferably non-polar solvent, can enumerate benzene,toluene,xylene, MIBK etc.But, be not limited thereto, can mix more than 2 kinds and use.
Also can be through making the epoxy resin reaction that has 1 hydroxyl in the compound that has 2 above carboxyls in 1 molecule and 1 molecule and have 2 epoxy group(ing), the epoxy resin that synthetic 1 intramolecularly has 1 above hydroxyl and has 1 above epoxy group(ing).Wherein, ratio reacts to be 2 epoxy group(ing) with respect to 1 carboxyl.
As the compound that has 2 above carboxyls in 1 molecule, can enumerate oxalic acid, propanedioic acid, fumaric acid, succsinic acid, pentanedioic acid, hexanodioic acid, phthalic acid, toxilic acid, sebacic acid, methylene-succinic acid, citraconic acid, hexanaphthene tricarboxylic acid, naphthalic acid etc.In addition, through with alcohols that has 2 above hydroxyls in 1 molecule and the carboxylic-acid reaction that comprises anhydrides, can synthesize the compound that in 1 molecule, has 2 above carboxyls.In addition, this moment also can residual hydroxyl.
Alkali number or catalytic amount, temperature of reaction or reaction times that the epoxy resin that in 1 molecule, has 1 hydroxyl will use in the time of can will having the compound epoxidation of 2 above hydroxyls through adjustment synthesize.
In 1 molecule, having the compound of 2 above carboxyls and in 1 molecule, have 1 hydroxyl and have the epoxy resin of 1 epoxy group(ing) can be through known method reaction.That is, can heat and react through cooperating specified amount.Can use inert solvent or catalyzer etc. as required.Temperature of reaction is 50 ℃～200 ℃, more preferably 80 ℃～180 ℃.Reaction is through being disappeared by machine analysis confirmation carboxyl or confirming that by chemical analysis acid number decides terminal point.Reaction times is 1 hour～10 hours.The epoxy resin that obtains is the structure of general formula (1) expression, and n is 0～25 integer, and when reducing the viscosity of epoxy resin, n is 0～20.
Composition epoxy resin of the present invention also can cooperate other epoxy resin except neo-epoxy resin of the present invention.
The solidifying agent that uses in the composition epoxy resin of the present invention can be enumerated amine curing agent, acid anhydride type curing agent, phenol solidifying agent.In addition, also can enumerate Photoepolymerizationinitiater initiater.The concrete example of Photoepolymerizationinitiater initiater can be enumerated Lewis acid; Br; Sulfonium salt; Iodine
salt; Diazonium salt etc. various
salt etc.Wherein, preferred sulfonium salt, in the sulfonium salt, aromatic series sulfonium salt more preferably.Specifically can enumerate San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L (three new chemical industry Co., Ltd.), Adeka Optomer SP-150; Adeka Optomer SP-170 (Asahi Denka Kogyo K. K's system), CI-5102 (Tso Tat Co., Ltd., Japan's system), Cyracure UVI-6976; Cyracure UVI-6992 (Dow Chemical Co., Ltd. system) etc.; But be not limited thereto, can mix more than 2 kinds and use.
The use level of above-mentioned Photoepolymerizationinitiater initiater is 0.01 weight part～10 weight parts because of the thickness of the kind of the kind of rayed condition, epoxy resin or amount, Photoepolymerizationinitiater initiater, cured article or shape etc. are different with respect to 100 weight part epoxy resin.
Composition epoxy resin of the present invention can cooperate sensitizing agent, protective agent, stablizer, softening agent, wax, levelling agent, weighting agent, pigment, dyestuff, fire retardant, whipping agent, antistatic agent interfering, mould inhibitor, viscosity modifier, solvent etc. except that Photoepolymerizationinitiater initiater.In addition, also can in the scope of not destroying effect of the present invention, cooperate neo-epoxy resin of the present invention epoxy resin in addition.
Epoxy resin cured product of the present invention can and/or heat composition epoxy resin of the present invention through rayed and obtain.
The light of irradiation when composition epoxy resin of the present invention is solidified, so long as can get final product through the compsn that above-mentioned Photoepolymerizationinitiater initiater is cured, not special qualification can not used light arbitrarily according to the kind of Photoepolymerizationinitiater initiater.
The use ultraviolet ray is as the above-mentioned light time, and as light source, not special the qualification for example can be used common light source as the uviolizing source such as luminescent lamp, high voltage mercury lamp.And then, as light source, for example can use low pressure mercury lamp, xenon lamp, metal halide lamp, germicidal lamp, laser, LED light etc.
The illumination of above-mentioned light, irradiation dose, irradiation time can suitably be adjusted according to the cured article rerum natura according to the kind amount of Photoepolymerizationinitiater initiater, epoxy backbone of the present invention, additive, thickness etc. and different.
Can in photocuring system, as carrying out usually, before and after rayed, be heating and curing, and then promote its curing.
Find through use with neo-epoxy resin of the present invention serve as must composition composition epoxy resin, can access have concurrently thermotolerance and flexible, to useful composition epoxy resin and epoxy resin cured products such as coating, tackiness agent, light appearance, sealing material, an injectable plastic material, electric and electronic circuit material, optical circuit materials.
Embodiment
Below enumerate embodiment and illustrate in greater detail the present invention, the present invention not only is defined in these embodiment.
Embodiment 1
In being provided with the detachable flask of prolong, put into 164.5 parts of TD-EL (4; 7-methylene-2; 3-epoxy octahydro-1H-indenes-pure Maruzen Petrochemical Co., Ltd. system) and 160.2 parts of RIKACID MH-700 (methylhexahydrophthalic anhydride, New Japan Chem Co., Ltd's system) and 17.0 parts of toluene; Stir under nitrogen atmosphere on the limit, and heat temperature raising is carried out on the limit.This moment, the anhydride group with respect to hydroxyl was 0.951.The chemical formula of TD-EL is as follows.
This is reflected under 130 ℃ and carries out, and reaction proceeds to acid anhydrides and disappears.The compound that can obtain in 1 molecule, having 1 epoxy group(ing) and have 1 carboxyl through this reaction.Add CELLOXIDE 2021 (3 then; 4-oxirane ring hexenyl methyl-3 '; 4 '-oxirane ring hexene manthanoate) 374.4 parts of 300.8 parts, Epo Tohto ZX-1658 (diglycidyl ether of cyclohexanedimethanol) heat, and make it even.The chemical formula of CELLOXIDE 2021 is as follows.
As catalyzer; TPP-BB (normal-butyl triphenyl phosphorus
bromide, Hokko Chemical Industry Co., Ltd.'s system) is dissolved in 0.1 part of acetone, joins in the system.Under 130 ℃, react, confirm that acid number disappears, as reaction end.Obtain epoxy resin from the skeleton of employed TD-EL with general formula (3), general formula (5), general formula (9) expression.The epoxy equivalent (weight) of the epoxy resin that obtains is 210.4g/eq.Fig. 1 representes to measure the MWD that obtains by GPC, and Fig. 2 representes the mensuration result of FTIR.
Embodiment 2
Making TD-EL is that 227.9 parts, RIKACID MH-700 are that 222.2 parts, CELLOXIDE 2021 are that 200.7 parts, Epo Tohto ZX-1658 are 349.1 parts, does not use toluene.In addition, carry out the operation same with embodiment 1.Anhydride group with respect to hydroxyl is 0.952.The epoxy equivalent (weight) of the epoxy resin that obtains is 272.1g/eq.
Embodiment 3
Disposable 267.1 parts of TD-EL, 232.8 parts of RIKACID MH-700,2021,200.2 parts of Epo Tohto ZX-1658 of 299.9 parts of CELLOXIDE, 26.3 parts of toluene put in the detachable flask of record in embodiment 1; Stir, heat up, make it even.Temperature of reaction is remained on 90 ℃, be retained to and confirm that acid anhydrides disappears.Can access the compound that in 1 molecule, has 1 epoxy group(ing) and have 1 carboxyl through this reaction.As catalyzer, TPP-BB is dissolved in 0.1 part of acetone, join in the system.Under 130 ℃, react, confirm that acid number disappears, as reaction end.The epoxy equivalent (weight) of the epoxy resin that obtains is 313.9g/eq.
Embodiment 4
Making TD-EL is that 267.1 parts, RIKACID HNA-100 (methyl norbornene dioic anhydride, New Japan Chem Co., Ltd's system) are that 254.8 parts, CELLOXIDE 2021 are that 250.0 parts, Epo Tohto ZX-1658 are 228.1 parts, does not use toluene.In addition, carry out the operation same with embodiment 1.Anhydride group with respect to hydroxyl is 0.850.The epoxy equivalent (weight) of the epoxy resin that obtains is 342.1g/eq.
Embodiment 5
Making TD-EL is that 164.0 parts, RIKACID MH-700 are that 159.9 parts, CELLOXIDE 2021 are that 309.9 parts, HBPA-DGE (hydrogenation BPA type epoxy resin, Maruzen Petrochemical Co., Ltd.'s system) are that 366.1 parts, toluene are 36.0 parts; In addition, carry out the operation same with embodiment 3.Anhydride group with respect to hydroxyl is 0.799.The epoxy equivalent (weight) of the epoxy resin that obtains is 271.6g/eq.
Comparative example 1
In embodiment 1, put into 43.3 parts of tetramethylolmethanes (aerochemistry Co., Ltd. of Mitsubishi system), 170.9 parts of RIKACID MH-700 and 37.8 parts of toluene in the detachable flask of record, stir under nitrogen atmosphere on the limit, and heat temperature raising is carried out on the limit.At this moment, the anhydride group with respect to hydroxyl is 0.799.Under 130 ℃, react, confirm that acid anhydrides disappears, add 785.8 parts of HBPA-DGE, heat, make it even.As catalyzer, TPP-BB is dissolved in 0.1 part of acetone, join in the system.Under 150 ℃, react, confirm that acid number disappears, as reaction end.Obtain comprising the epoxy resin of the above polyfunctional epoxy resin of 3 officials ability through the tetramethylolmethane that uses.The epoxy equivalent (weight) of the epoxy resin that obtains is 420.8g/eq.
Comparative example 2
Making tetramethylolmethane is that 48.9 parts, RIKACID MH-700 are that 138.3 parts, HBPA-DGE are that 403.1 parts, CELLOXIDE 2021 are 403.1 parts, in addition, carries out the operation same with embodiment 1.At this moment, the anhydride group with respect to hydroxyl is 0.572.The epoxy equivalent (weight) of the epoxy resin that obtains is 273.5g/eq.
Comparative example 3
Making tetramethylolmethane is that 38.5 parts, RIKACID HNA-100 are that 207.6 parts, ZX-1658 are that 261.2 parts, CELLOXIDE 2021 are 492.8 parts, in addition, carries out the operation same with embodiment 1.At this moment, the anhydride group with respect to hydroxyl is 0.996.The epoxy equivalent (weight) of the epoxy resin that obtains is 252.6g/eq.
The epoxy resin that obtains in 100 parts of embodiment 1～5, the comparative example 1～3 is dissolved in the pimelinketone,, cooperates 0.5 part of Cyracure UVI-6976 (Dow Chemical corporate system) as Photoepolymerizationinitiater initiater.Being coated with machine with rod is coated on the mold release film; Under 150 ℃, remove and desolvated 30 minutes; With USHIO motor (strain) system Unicure system UVX-01212S1CS01 lamp pattern UVL-1500M2-N1, be that 10mV, accumulation light quantity are 8J/cm with the illumination under the wavelength 365nm
2Shine.And then under 150 ℃, carry out 60 minutes after fixing, obtain cured article.
Cured article is peeled off from mold release film, measured second-order transition temperature with the system EXSTAR6200DSC of SIINano Technology Co., Ltd..Condition determination is for to be warming up to 200 ℃ with 10 ℃/minute from room temperature, is second-order transition temperature with the initial flex point of the 2nd round-robin data.The result is shown in table 1.
The cured article of 50 μ m is peeled off from mold release film, be cut into the strip of 10mm * 50mm, carry out tension test with the system EZ-S of Shimadzu Scisakusho Ltd.Between chuck be to measure the elongation when measuring fracture under the 1mm/ condition of dividing for 30mm, draw speed.
Infrared extinction spectrum is measured with PERKIN ELMER JAPAN system 1760X.MWD is measured with the system liquid chromatography HLC-8120 of TOSOH Co., Ltd.
More than, by embodiment and comparative example can know have general formula (3), the neo-epoxy resin of the specific skeleton shown in the general formula (5), general formula (9) improved thermotolerance, flexible simultaneously.The second-order transition temperature of the epoxy resin that comparative example 1 such film elongation is high is low; If it is high as comparative example 3 second-order transition temperatures; Then the film elongation is low, but epoxy resin of the present invention can access second-order transition temperature height, cured article that the film elongation is also high shown in embodiment 1～embodiment 5.
Industrial applicability
Neo-epoxy resin of the present invention can improve thermotolerance through importing specific skeleton; Also can have the flexibility of cured article concurrently, so useful to coating, tackiness agent, light appearance, sealing material, an injectable plastic material, electric and electronic circuit material, optical circuit material etc.
Claims (6)
1. the neo-epoxy resin of general formula (1) expression,
In the formula; E1 and E3 represent any in general formula (2)～general formula (7), and E2 representes any in general formula (8)～general formula (11), comprise the skeleton of general formula (3), general formula (5) and general formula (9) expression in the general formula (1); A1, A2 are the acid anhydrides residue; The expression hydrocarbon also can be phosphorous, nitrogen, Sauerstoffatom, and n representes 0～25 integer;
In general formula (2)～(11) formula, R representes alkyl or hetero ring type compound residue.
2. neo-epoxy resin as claimed in claim 1, it obtains the compound and the epoxy resin reaction that in 1 molecule, have 1 epoxy group(ing) and have 1 carboxyl.
3. neo-epoxy resin as claimed in claim 1, it is through compound that in 1 molecule, has 1 hydroxyl and have 1 epoxy group(ing) and the carboxylic-acid that comprises anhydrides and epoxy resin reaction are obtained.
4. neo-epoxy resin as claimed in claim 1, it is to obtain through compound and the epoxy resin reaction that makes compound or the acid anhydrides that in 1 molecule, has 2 carboxyls and in 1 molecule, have 1 hydroxyl and have 1 epoxy group(ing).
5. composition epoxy resin, it is essential composition with each the described epoxy resin in the claim 1～4, contains solidifying agent.
6. cured article makes described composition epoxy resin thermofixation of claim 5 and/or photocuring and obtains.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008135629A JP5669289B2 (en) | 2008-05-23 | 2008-05-23 | Novel epoxy resin and method for producing the same, epoxy resin composition containing epoxy resin as essential component, and cured product containing epoxy resin as essential component |
| JP2008-135629 | 2008-05-23 | ||
| PCT/JP2009/059484 WO2009142317A1 (en) | 2008-05-23 | 2009-05-19 | Novel epoxy resin, method for producing the same, epoxy resin composition containing the epoxy resin as essential component, and cured product containing the epoxy resin as essential component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102037048A CN102037048A (en) | 2011-04-27 |
| CN102037048B true CN102037048B (en) | 2012-10-10 |
Family
ID=41340243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801181285A Expired - Fee Related CN102037048B (en) | 2008-05-23 | 2009-05-19 | Novel epoxy resin, method for producing the same, epoxy resin composition containing the epoxy resin as essential component, and cured product containing the epoxy resin as essential component |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5669289B2 (en) |
| KR (1) | KR101540831B1 (en) |
| CN (1) | CN102037048B (en) |
| WO (1) | WO2009142317A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5606752B2 (en) * | 2010-02-25 | 2014-10-15 | 株式会社ダイセル | Resin composition for optical semiconductor sealing and optical semiconductor device using the same |
| US10017601B2 (en) | 2013-07-04 | 2018-07-10 | Panasonic Intellectual Property Management Co., Ltd. | Resin composition, prepreg and laminate board |
| MA41308A (en) * | 2014-12-22 | 2017-11-14 | Nippon Soda Co | EPOXY RESIN COMPOSITION |
| KR102454213B1 (en) * | 2021-03-19 | 2022-10-14 | 한국화학연구원 | Novel acid anhydride-based epoxy compound, epoxy adhesive composition containing the same, and cured product prepared therefrom |
| KR102448685B1 (en) * | 2021-03-26 | 2022-09-29 | 한국화학연구원 | Epoxy adhesive composition containing acid anhydride-based epoxy compound modified with fatty acid and cured product prepared therfrom |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001047907A1 (en) * | 1999-12-27 | 2001-07-05 | Asahi Kasei Kabushiki Kaisha | Ester containing alicyclic epoxy and process for producing the same |
| JP3815605B2 (en) * | 2001-11-15 | 2006-08-30 | 日本化薬株式会社 | Optical waveguide resin composition and cured product thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0570559A (en) * | 1991-09-13 | 1993-03-23 | Toyo Ink Mfg Co Ltd | Curable resin composition |
| JP2003163169A (en) * | 2001-11-29 | 2003-06-06 | Sharp Corp | Vapor phase growth apparatus |
| JP3797348B2 (en) * | 2003-02-24 | 2006-07-19 | コニカミノルタホールディングス株式会社 | Active energy ray curable composition |
| JP5344789B2 (en) * | 2006-12-28 | 2013-11-20 | 新日鉄住金化学株式会社 | Novel epoxy resin, epoxy resin composition containing the epoxy resin as an essential component, and cured product containing the epoxy resin as an essential component |
-
2008
- 2008-05-23 JP JP2008135629A patent/JP5669289B2/en active Active
-
2009
- 2009-05-19 KR KR1020107026048A patent/KR101540831B1/en active IP Right Grant
- 2009-05-19 CN CN2009801181285A patent/CN102037048B/en not_active Expired - Fee Related
- 2009-05-19 WO PCT/JP2009/059484 patent/WO2009142317A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001047907A1 (en) * | 1999-12-27 | 2001-07-05 | Asahi Kasei Kabushiki Kaisha | Ester containing alicyclic epoxy and process for producing the same |
| JP3815605B2 (en) * | 2001-11-15 | 2006-08-30 | 日本化薬株式会社 | Optical waveguide resin composition and cured product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009142317A1 (en) | 2009-11-26 |
| JP2009280734A (en) | 2009-12-03 |
| CN102037048A (en) | 2011-04-27 |
| KR20110020233A (en) | 2011-03-02 |
| KR101540831B1 (en) | 2015-07-30 |
| JP5669289B2 (en) | 2015-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4977198A (en) | UV curable epoxy functional silicones | |
| CN102037048B (en) | Novel epoxy resin, method for producing the same, epoxy resin composition containing the epoxy resin as essential component, and cured product containing the epoxy resin as essential component | |
| KR101952321B1 (en) | Epoxy resin, epoxy resin composition and cured product | |
| CN1732199B (en) | Curable resin composition and products of curing thereof | |
| JP2004204228A (en) | Curable epoxy resin composition and cured material | |
| KR20030007515A (en) | Method 0f producing epoxy compound, epoxy resin compositi0n and its applications, ultraviolet rays-curable can-coating composition and method of producing coated metal can | |
| EP0859021A2 (en) | Epoxidised compositions | |
| KR20150030645A (en) | Epoxy resin composition, cured product thereof, and curable resin composition | |
| CN102803334A (en) | Thermosettable composition containing a half ester of a cycloaliphatic diol and a thermoset product therefrom | |
| KR20050076687A (en) | Non-ester type epoxy resin and resin composition | |
| Kumar et al. | Recent progress in bio‐based eugenol resins: From synthetic strategies to structural properties and coating applications | |
| KR101443406B1 (en) | Novel epoxy resin, epoxy resin composition essentially containing the epoxy resin, and cured product essentially containing the epoxy resin | |
| KR20060088123A (en) | Curable polyester having an oxetanyl group at end and process for preparing the same, resist composition, jet printing ink composition, curing methods and uses thereof | |
| JP4964498B2 (en) | Active energy ray-curable ink and printed matter | |
| KR20060041704A (en) | Thermosetting resin composition and cured coating film thereof | |
| JP2006169368A (en) | Resin composition, cured product and method for producing the same | |
| CN102414242B (en) | Thermosettable resin compositions | |
| JP5686629B2 (en) | Epoxy resin composition | |
| KR102021616B1 (en) | Process for producing phosphorus-containing epoxy resin | |
| JP2005206820A (en) | Inkjet ink composition for inkjet, method for curing the same, and use of the same | |
| JP4089562B2 (en) | Thermosetting composition | |
| JP2003041001A (en) | Thermosetting resin having dihydrobenzoxazine ring structure, resin composition and cured product | |
| JP2008239891A (en) | Novel epoxy resin, epoxy resin composition containing the same, and cured matter therefrom | |
| TWI557176B (en) | A thermosetting resin composition, a hardened product thereof, and a printed wiring board using the same | |
| JP6113454B2 (en) | Epoxy resin composition and cured product |
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 | ||
| C56 | Change in the name or address of the patentee |
Owner name: NIPPON STEEL + SUMITOMO METAL CORPORATION Free format text: FORMER NAME: NIPPON SEEL CHEMICAL CO., LTD. |
|
| CP03 | Change of name, title or address |
Address after: Tokyo, Japan, Japan Patentee after: Nippon Steel Chemical Co. Address before: Tokyo, Japan Patentee before: Nippon Seel Chemical Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121010 Termination date: 20170519 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |