CN102083881B - Modified epoxy resin, epoxy resin compositions and cured articles - Google Patents
Modified epoxy resin, epoxy resin compositions and cured articles Download PDFInfo
- Publication number
- CN102083881B CN102083881B CN200980107601.XA CN200980107601A CN102083881B CN 102083881 B CN102083881 B CN 102083881B CN 200980107601 A CN200980107601 A CN 200980107601A CN 102083881 B CN102083881 B CN 102083881B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- epoxy
- resins
- composition epoxy
- solidifying agent
- 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.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- 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
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
- H01L2924/097—Glass-ceramics, e.g. devitrified glass
- H01L2924/09701—Low temperature co-fired ceramic [LTCC]
Landscapes
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
The present invention discloses a modified epoxy resin which exhibits excellent handleability in a solid state at ordinary temperatures and exerts an excellently low viscosity at a molding temperature; epoxy resin compositions which each comprise the modified epoxy resin and an inorganic filler and which can give cured articles exhibiting high thermal conductivity, low thermal expansion, and excellent heat resistance and moisture resistance; and cured epoxy resin articles made by using the compositions. The modified epoxy resin can be prepared by reacting a mixture of hydroquinone and 4, 4'-dihydroxybiphenyl at a weight ratio of 0.1 to 10.0 with epichlorohydrin, and is in a crystalline state at ordinary temperatures. The epoxy resin compositions each comprises (A) an epoxy resin component, (B) a curing agent, and (C) an inorganic filler as the main components, with the epoxy resin component (A) containing the modified epoxy resin in an amount of 50wt% or above.
Description
Technical field
The present invention relates to the reliability excellence the electrical/electronic parts such as encapsulating semiconductor, plywood, heat-radiating substrate in insulating material under the useful normal temperature as solid-state operability crystalline modified epoxy, the composition epoxy resin that uses it and the cured article therefrom of the low viscosity excellence during excellent and moulding.
Background technology
In the past, sealing method as the electrical/electronic parts such as diode, transistor, unicircuit, semiconductor device etc., utilize sealing method that Resins, epoxy, silicone resin etc. carry out, use the vacuum sealing method of glass, metal, pottery etc. such as employing, but in recent years, the resin-sealed main flow that occupies of utilizing transfer formation to carry out of cost advantage can be produced, have in addition simultaneously to Reliability Enhancement in a large number.
In the resin combination that uses in the above-mentioned method of resin-sealing that utilizes transfer formation to carry out, normal operation is by with Resins, epoxy and the sealing material that consists of as the resin combination of the principal constituent of resinous principle as the resol of solidifying agent.
In addition, as the method for mounting electronic parts on printed base plate, insert mode from the past pin underway to the transfer of surface mounting mode.In the surface mounting mode, because whole packing is heated to the scolding tin temperature, so the packing crack that thermal shocking causes becomes large problem, as the strong method that prevents from packing the crack, has the height of inorganic filling material to fill rate.In addition, as the sealing material of power unit etc. and the composition epoxy resin that uses, a large amount of heat of emitting in order to tackle element requires the high-density fillingization of inorganic filling material.
In order to overcome the problems referred to above, the Resins, epoxy of expectation low viscosity excellence.As low viscosity epoxy resin, generally be widely used bisphenol A type epoxy resin, bisphenol f type epoxy resin etc., the low-viscosity epoxy resin is liquid at normal temperatures in these Resins, epoxy, is difficult to operation.And then these Resins, epoxy are insufficient aspect thermotolerance, physical strength, toughness.
In view of the foregoing, recently motion has a lot of composition epoxy resins that use under the normal temperature as the crystalline Resins, epoxy of solid.Motion has that pair operation task, thermotolerance, toughness etc. have improved in the patent documentation 1 with biphenyl be Resins, epoxy as the epoxy resin composition for encapsulating semiconductor of host, but insufficient aspect low water absorbable, low viscosity, solidified nature.In addition, in the patent documentation 2 motion host is arranged is the solid epoxy resin of Bisphenol F type.Bisphenol f type epoxy resin has the feature of low viscosity excellence, but thermotolerance, solidified nature existing problems.In addition, the composition epoxy resin that uses the Resins, epoxy with Resorcinol structure is disclosed in the patent documentation 3, it has the alkyl substituent of carbon number 3～6, because substituent sterically hindered, exist reactive low or solidify after the accumulation of molecule be subject to hindering the problems such as caused thermal conductivity is low.In addition, disclose in the patent documentation 7 and mixed the composition epoxy resin that the Resins, epoxy with Resorcinol structure and the Resins, epoxy with biphenyl structural form, but be not the target that is rendered as with high thermal conductivity.In the patent documentation 7, as the Resins, epoxy with biphenyl structural, the Resins, epoxy that uses tetramethyl-to replace, but find according to the inventor's etc. additional experiment, there is the problem that thermal conductivity is reduced in the Resins, epoxy with alkyl substituent.
In addition, as the gimmick for thermal conductivity is improved, use crystalline silica, silicon nitride, aluminium nitride, the such trial (patent documentation 4,5) of spherical alumina powder, but when improving the containing ratio of inorganic filling material, the viscosity rise when producing moulding, while flowability descend, formability suffers damage such problem.Therefore, the method that only improves the containing ratio of inorganic filling material is conditional.
In view of above situation, utilize the method for the high heat conductance of matrix resin itself also to obtain research, for example motion has the resin combination of the liquid-crystalline resin that uses the mesomorphic group with rigidity in patent documentation 6 and the patent documentation 8.But, these Resins, epoxy with mesomorphic group are the high crystalline with upright and outspoken structure of biphenyl structural, azomethine structure etc., the single in fact epoxy compounds that does not have the distribution of dystectic molecular weight, therefore have the poor shortcoming of workability when forming composition epoxy resin.And then, under solid state, effectively be orientated in order to make molecule, need to apply powerful magnetic field and make its curing, in order extensively to utilize industrial, there is very large restriction on the equipment.In addition, present case is, with the mixed system of inorganic filling material in, compare with the thermal conductivity of matrix resin, the thermal conductivity of inorganic filling material is large overwhelmingly, even improve the thermal conductivity of matrix resin itself, the thermal conductivity raising as matrix material there is not too large contribution yet, can not get sufficient thermal conductivity and improve effect.And general understanding is: it is the heat conductivity raising of resin that heat conductivity is improved what study, for the situation of the mixed system of filler under, when filler fully exists, the heat conductivity of filler is high overwhelmingly, no matter so the heat conductivity of resin height, effect is all little.
In the patent documentation 9, following composition epoxy resin is disclosed: connection to semiconductor device that semiconductor element is installed by the flip-chip mode is dispersed in the sealing resin layer effectively with electrode part institute applying load alleviates, even under the severe environmental conditions such as temperature cycle, also can guarantee the conduction of semiconductor device, but as Resins, epoxy, the Resorcinol type Resins, epoxy with tertiary butyl and the biphenyl type epoxy resin with methyl etc. are only disclosed.In the patent documentation 10, the highly heat-conductive epoxy resin composition that a kind of good fluidity, die wear are few, contain the spherical cristobalite that the cured article with high thermal conductivity can be provided is disclosed, obtaining its method for the improvement packing material, is not to want modified resin.In the patent documentation 11, disclose a kind of composition epoxy resin of filling a large amount of inorganic filling materials, can obtain the forming composition of heat conductivity excellence, the method that obtains it is the improvement packing material, but is not to want modified resin.
Patent documentation 1: JP 4-7365 number
Patent documentation 2: Unexamined Patent 6-345850 number
Patent documentation 3: Unexamined Patent 6-145293 communique
Patent documentation 4: Unexamined Patent 11-147936 communique
Patent documentation 5: JP 2002-309067 communique
Patent documentation 6: Unexamined Patent 11-323162 communique
Patent documentation 7: Unexamined Patent 6-184272 communique
Patent documentation 8: Unexamined Patent 2004-331811 communique
Patent documentation 9: JP 2001-207031 communique
Patent documentation 10: JP 2001-172472 communique
Patent documentation 11: JP 2001-348488 communique
Summary of the invention
The problem that invention will solve
Therefore, the object of the invention is to address the above problem, provide under the normal temperature that operability as solid is excellent, the modified epoxy of the low viscosity excellence under the mold temperature simultaneously, and use it to be provided at composition epoxy resin and the cured article thereof of the cured article of thermal conductivity in the situation with the inorganic filling material Composite high and low heat expansion property, thermotolerance and excellent moisture resistance.Be used for solving the means of problem
Carried out various researchs in order to solve above-mentioned problem, found that following phenomenon: in the situation that specific resin, when containing certain a certain amount of above inorganic filling material, the heat conductivity raising of resin is reflected on the final cured article.And find, mixture and Epicholorohydrin reaction by making the compound that specifically has phenolic hydroxyl group have crystallinity, operability excellence at normal temperatures, and the thermal conductivity as matrix material improves especially simultaneously, finishes thus the present invention.
The present invention has crystalline modified epoxy under the normal temperature, it is characterized in that, its be make with respect to Resorcinol 1 weight part be mixed with 4,4 '-mixture and the Epicholorohydrin reaction of dihydroxybiphenyl 0.1～10 weight part obtain.
In addition, the present invention is composition epoxy resin, its be with (A) Resins, epoxy, (B) solidifying agent, and (C) inorganic filling material it is characterized in that as the composition epoxy resin of main component, use above-mentioned modified epoxy more than the 50wt% as Resins, epoxy.
The optimal way of above-mentioned composition epoxy resin is as follows.
1) containing ratio of inorganic filling material is 80～96wt%.
2) solidifying agent is that phenol is solidifying agent.
3) be solidifying agent as phenol, use the above difunctionality phenolic compound of 50wt%.
4) above-mentioned difunctionality phenolic compound is for being selected from Resorcinol, 4,4 '-dihydroxybiphenyl, 4,4 '-dihydroxy diphenyl ether, 1, two (4-hydroxyphenoxy) benzene, 4 of 4-, 4 '-dihydroxyl ditan, 4,4 '-dihydroxyl diphenyl sulfide, 1,5-naphthalene glycol, 2, at least a in 7-naphthalene glycol and 2, the 6-naphthalene glycol.
5) as inorganic filling material, use the above spherical aluminum oxide of 50wt% of inorganic filler.
And then the present invention is above-mentioned composition epoxy resin, it is characterized in that the composition epoxy resin that it is used for encapsulating semiconductor.
The present invention is cured article in addition, it is characterized in that, it is above-mentioned composition epoxy resin to be solidified obtain, and thermal conductivity is more than the 4W/mK.
Here, for cured article, the caloric receptivity that the resinous principle of the peak of the fusing point in its differential scanning calorimeter in the differential scanning calorimeter of 120 ℃～280 ℃ scope, other cured article converts is to get final product more than the 10J/g.
Embodiment
Modified epoxy of the present invention, can by make Resorcinol and 4,4 '-mixture and the Epicholorohydrin of dihydroxybiphenyl react to make.This reaction can equally with common epoxidation reaction be carried out.Modified epoxy of the present invention be except the epoxide that contains Resorcinol and 4,4 '-epoxide of dihydroxybiphenyl beyond, contain have in a part from Resorcinol and 4,4 '-mixture of the epoxide of the unit of dihydroxybiphenyl.And as known, the epoxide that the reaction of dihydroxy compound and Epicholorohydrin obtains is 0 the epoxide (n=0 body) except containing the polymerization degree, also contains the polymers such as n=1 (dimer), n=2 (tripolymer).
Resorcinol and 4,4 '-blending ratio of dihydroxybiphenyl with weight ratio count Resorcinol/4,4 '-scope of dihydroxybiphenyl=0.1～10.0, be preferably 0.2～5.0 scope.During less than this scope, because 4,4 '-impact of the high-melting-point of the epoxy compounds of dihydroxybiphenyl, the operability variation, during greater than this scope, the characteristics such as the thermotolerance of cured article reduce.
For example can enumerate following methods: with Resorcinol and 4,4 '-phenolic hydroxyl group that the mixture of dihydroxybiphenyl is dissolved in relatively them is with after in the Epicholorohydrin of molar ratio computing excess quantity, makes its reaction 1～10 hour in the presence of the alkali metal hydroxides such as sodium hydroxide, potassium hydroxide under 50～150 ℃, the temperature of preferred 60～100 ℃ scope.The usage quantity of the alkali metal hydroxide of this moment with respect to Resorcinol and 4,4 '-1 mole of hydroxyl in the dihydroxybiphenyl is 0.8～1.2 mole, preferred 0.9～1.0 mole scope.Epicholorohydrin with respect to Resorcinol and 4,4 '-hydroxyl in the dihydroxybiphenyl is that excess quantity ground uses, usually with respect to Resorcinol and 4,4 '-1 mole of hydroxyl in the dihydroxybiphenyl is 1.5～15 moles.After reaction finished, superfluous Epicholorohydrin was removed in distillation, and residue is dissolved in toluene, the methyl iso-butyl ketone (MIBK) equal solvent, filters, washes, removes inorganic salt, then distills desolventizing, can obtain thus the Resins, epoxy of target.
When the manufacturing of modified epoxy of the present invention, can use further mixed except the essential composition as raw material be Resorcinol and 4,4 '-material of the phenoloid of other kind beyond the dihydroxybiphenyl.But, in this case, Resorcinol and 4,4 '-to be that above, the preferred 70wt% of 50wt% of whole phenoloids is above, more preferably 90wt% is above get final product for the total amount of dihydroxybiphenyl.
The epoxy equivalent (weight) of modified epoxy of the present invention is considered from high fill-ratio and the mobile viewpoint that improves of mineral filler usually in 110～300 scope, the Resins, epoxy of preferred low viscosity, and preferred epoxy equivalent (weight) is at the Resins, epoxy of 110～160 scope.
Modified epoxy of the present invention has crystallinity at normal temperatures.Crystalline present can be in differential scanning calorimetric analysis as the endotherm(ic)peak of the melting of accompanying crystallization and confirm.Need to prove, because modified epoxy of the present invention is mixture, therefore, the endotherm(ic)peak of this moment is generally observed is not 1 peak but a plurality of peak.As the fusing point of in differential scanning calorimetric analysis, observing, for coming free Resorcinol and 4,4 '-endotherm(ic)peak of the derivative modified epoxy of dihydroxybiphenyl, the endotherm(ic)peak of minimum temperature is more than 50 ℃, be preferably more than 70 ℃, the endotherm(ic)peak of top temperature is preferably below 130 ℃ below 150 ℃.When lower than it, form in the situation of powder, caking etc. occurs, the operability as solid reduces at normal temperatures, when higher than it, has the problem such as poorly soluble with solidifying agent etc.In addition, the melt viscosity under preferred 150 ℃ is more low better, usually below 0.1Pas, preferably below 0.01Pas, more preferably below 0.005Pas.
The content of the purity of modified epoxy of the present invention, particularly water-disintegrable chlorine is considered from the viewpoint of the Reliability Enhancement of applicable electronic component, is advisable less.Be not particularly limited, be preferably below the 1000ppm, more preferably below the 500ppm.Need to prove, water-disintegrable chlorine of the present invention refers to the value measured by the following method.Be the following value that obtains: sample 0.5g is dissolved in 30ml two
Behind the alkane, add the 1N-KOH of 10ml, boiling reflux was cooled to room temperature after 30 minutes, and then added 80% acetone water 100ml, at 0.002N-AgNO
3The value of carrying out the potential difference titration in the aqueous solution and obtaining.
Composition epoxy resin of the present invention take (A) Resins, epoxy, (B) solidifying agent, and (C) inorganic filling material as Resins, epoxy, contain the above above-mentioned modified epoxy of 50wt% of Resins, epoxy composition as main component.That is, all the 50wt% of Resins, epoxy is above is above-mentioned modified epoxy.Advantageously, all the 70wt% of Resins, epoxy is above, more preferably 90wt% is above is above-mentioned modified epoxy.The usage ratio of modified epoxy is than above-mentioned scope hour, and the raising effect of the thermal conductivity when forming cured article etc. is little.
In the composition epoxy resin of the present invention, except the above-mentioned modified epoxy that uses as essential component of the present invention, can also be also with common other Resins, epoxy that has the epoxy group(ing) more than 2 in the molecule.For example can enumerate: dihydroxyphenyl propane, Bisphenol F, 3,3 ', 5,5 '-tetramethyl--4,4 '-the dihydroxyl ditan, 4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-the dihydroxyl diphenyl sulfide, 4,4 '-dihydroxy benzophenone, bisphenol fluorene, 4,4 '-xenol, 3,3 ', 5,5 '-tetramethyl--4,4 '-dihydroxybiphenyl, 2,2 '-xenol, Resorcinol, pyrocatechol, tert-butyl catechol, Tert. Butyl Hydroquinone, 1, the 2-dihydroxy naphthlene, 1, the 3-dihydroxy naphthlene, 1, the 4-dihydroxy naphthlene, 1, the 5-dihydroxy naphthlene, 1, the 6-dihydroxy naphthlene, 1, the 7-dihydroxy naphthlene, 1, the 8-dihydroxy naphthlene, 2, the 3-dihydroxy naphthlene, 2, the 4--dihydroxy naphthlene, 2, the 5-dihydroxy naphthlene, 2, the 6-dihydroxy naphthlene, 2, the 7-dihydroxy naphthlene, 2, the 8-dihydroxy naphthlene, the allylate of above-mentioned dihydroxy naphthlene or poly-allylat thing, the allylation dihydroxyphenyl propane, the allylation Bisphenol F, 2 yuan of phenols such as allylation phenol phenolic varnish, or phenol phenolic varnish, bisphenol-A phenolic varnish, the o-Hydroxytoluene Novolac, the meta-cresol phenolic varnish, the p-cresol phenolic varnish, the xylenol phenolic varnish, poly(4-hydroxystyrene), three (4-hydroxy phenyl) methane, 1,1,2,2-four (4-hydroxy phenyl) ethane, Phloroglucinol, pyrogallol, the tert-butyl o benzenetriol, the allylation pyrogallol, the poly-allylat pyrogallol, 1,2,4-benzene triol, 2,3,4-trihydroxybenzophenone, phenol aralkyl (Off ェ ノ one Le ァ ラ Le キ Le Trees fat) resin, naphthols aralkyl resin, Dicyclopentadiene (DCPD) is the phenols more than 3 yuan such as resin, or by the derivative glycidyl ether compound of the halogenation bisphenols such as tetrabromo-bisphenol etc.These Resins, epoxy can 1 kinds or are mixed more than 2 kinds and use.
As the solidifying agent that uses in the composition epoxy resin of the present invention, general as epoxy curing agent and known solidifying agent can use.Preferred solidifying agent is that phenol is solidifying agent.Phenol is that phenoloid is arranged in the solidifying agent, and phenoloid also comprises resol except the phenolic compound as single compound.
Be the concrete example of solidifying agent as phenol, can enumerate: dihydroxyphenyl propane, Bisphenol F, 4,4 '-the dihydroxyl ditan, 4,4 '-dihydroxy diphenyl ether, 1, two (4-hydroxyphenoxy) benzene of 4-, 1, two (4-hydroxyphenoxy) benzene of 3-, 4,4 '-the dihydroxyl diphenyl sulfide, 4,4 '-the dihydroxyl diphenylketone, 4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-dihydroxybiphenyl, 2,2 '-dihydroxybiphenyl, 10-(2, the 5-dihydroxy phenyl)-10H-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, the phenol phenolic varnish, bisphenol-A phenolic varnish, the o-Hydroxytoluene Novolac, the meta-cresol phenolic varnish, the p-cresol phenolic varnish, the xylenol phenolic varnish, poly(4-hydroxystyrene), Resorcinol, Resorcinol, pyrocatechol, tert-butyl catechol, Tert. Butyl Hydroquinone, Off Le ォ ロ グ リ シ ノ one Le, pyrogallol, the tert-butyl o benzenetriol, the allylation pyrogallol, the poly-allylat pyrogallol, 1,2,4-benzene triol, 2,3, the 4-trihydroxybenzophenone, 1, the 2-dihydroxy naphthlene, 1, the 3-dihydroxy naphthlene, 1, the 4-dihydroxy naphthlene, 1, the 5-dihydroxy naphthlene, 1, the 6-dihydroxy naphthlene, 1, the 7-dihydroxy naphthlene, 1, the 8-dihydroxy naphthlene, 2, the 3-dihydroxy naphthlene, 2, the 4-dihydroxy naphthlene, 2,5-dihydroxy naphthlene, 2,6-dihydroxy naphthlene, 2, the 7-dihydroxy naphthlene, 2,8-dihydroxy naphthlene, the allylate of above-mentioned dihydroxy naphthlene or poly-allylat thing, the allylation dihydroxyphenyl propane, the allylation Bisphenol F, allylation phenol phenolic varnish, allylation pyrogallol etc.
The solidifying agent that solidifying agent can mix more than 2 kinds uses.Preferred solidifying agent contains the above difunctionality phenolic compound of 50wt% in the solidifying agent, preferably contains more than the 70wt%.As difunctionality phenolic compound in this case, be preferably selected from 4,4 '-dihydroxybiphenyl, 4,4 '-dihydroxy diphenyl ether, Isosorbide-5-Nitrae-two (4-hydroxyphenoxy) benzene, 4,4 '-dihydroxyl ditan, 4,4 '-dihydroxy benaophenonel, 4,4 '-dihydroxyl diphenyl sulfide, 1,5-naphthalene glycol, 2,7-naphthalene glycol, 2,6-naphthalene glycol, Resorcinol, and Resorcinol in phenolic compound.Wherein, preferred 4,4 '-dihydroxybiphenyl, 4,4 '-dihydroxy diphenyl ether or 4,4 '-the dihydroxyl ditan.
As the solidifying agent that uses in the composition epoxy resin of the present invention, except above-mentioned phenol is solidifying agent, can use as the common known solidifying agent of solidifying agent.If can enumerate: Ammonia solidifying agent, acid anhydride type curing agent, phenol are solidifying agent, polythiol class solidifying agent, polyaminoamide class cured article, isocyanates solidifying agent, blocked isocyanate class solidifying agent etc. for example.The use level of these solidifying agent is considered the physical property of the kind of the solidifying agent that cooperates, the heat conductivity molding for epoxy resin body that obtains and is suitably set.
As the concrete example of Ammonia solidifying agent, can enumerate: aliphatics amine, polyether polyamine class, ester ring type amine, aromatic amine etc.As the aliphatics amine, can enumerate: quadrol, 1,3-diaminopropanes, 1,4-diaminopropanes, hexamethylene-diamine, 2,5-dimethyl hexamethylene-diamine, trimethylhexamethylenediamine, diethylenetriamine, the two propylamine of imino-, two (hexa-methylene) triamine, Triethylenetetramine (TETA), tetren, penten, N-hydroxyethyl ethylene diamine, four (hydroxyethyl) ethylene diamine etc.As the polyether polyamine class, can enumerate: triethylene glycol diamine, Tetraglycol 99 diamines, glycol ether two (propylamine), polyoxygenated trimethylene diamines, polyoxygenated propylidene three amines etc.As the ester ring type amine, can enumerate: isophorone diamine, メ タ セ Application ジ ァ ミ Application, N-aminoethyl piperazine, two (4-amino-3-methyl bicyclic hexyl) methane, two (amino methyl) hexanaphthene, 3, two (the 3-aminopropyls)-2 of 9-, 4,8,10-four oxaspiros (5,5) undecane, norbornylene diamines (ノ Le ボ Le ネ Application ジ ァ ミ Application) etc.As aromatic amine, can enumerate: tetrachloro p-Xylol diamines, m-xylene diamine, the p-Xylol diamines, mphenylenediamine, O-Phenylene Diamine, Ursol D, 2, the 4-diamino anisole, 2, the 4-tolylene diamine, 2, the 4-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminostilbene, the 2-diphenylethane, 2, the 4-diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfone, Metha Amino Phenon, between amino-benzylamine, benzyl dimethyl amine, 2-dimethylaminomethyl phenol, trolamine, methylbenzylamine, α-(m-aminophenyl base) ethamine, α-(p-aminophenyl) ethamine, diamino diethyl-dimethyl ditan, α, α '-two (4-aminophenyl)-to diisopropyl benzene etc.
Concrete example as acid anhydride type curing agent, can enumerate: dodecenylsuccinic anhydride, poly-adipic acid acid anhydride, poly-nonane diacid acid anhydride, poly sebacic polyanhydride, poly-(ethyl octadecyl diacid) acid anhydride, poly-(phenyl hexadecyl diacid) acid anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, the acid of hexahydrophthalic anhydride No water メ チ Le Ha ィ ミ ッ Network, Tetra Hydro Phthalic Anhydride, the trialkyl Tetra Hydro Phthalic Anhydride, the tetrahydrotoluene dicarboxylic anhydride, the tetrahydrotoluene tetracarboxylic anhydride, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, the pyromellitic acid acid anhydride, the benzophenone tetracarboxylic anhydride, the ethylene glycol bis trimellitate, the hexachloro endoethylene tetrahydrophthalic acid acid anhydride, carbic anhydride, the methyl carbic anhydride, 5-(2,5-dioxa tetrahydrochysene-3-furyl)-3-methyl-3-hexanaphthene-1, the 2-dicarboxylic anhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, 1-methyl-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride etc.
Functional group in the preferred epoxy group(ing) of the mixing ratio of Resins, epoxy and solidifying agent and the solidifying agent counts 0.8～1.5 scope with equivalence ratio.In the time of outside this scope, the also epoxy group(ing) of remained unreacted or the functional group in the solidifying agent after the curing, low about the reliability of sealing function, therefore not preferred.
The addition of the inorganic filling material in the composition epoxy resin of the present invention is 80～96wt% with respect to composition epoxy resin, is preferably 84～96wt%.When lacking than this scope, can not give full play to high thermal conductivity, low heat expansion property, the such target effect of the present invention of high heat resistance.More these effects of the addition of inorganic filling material are better, but are not to improve according to volume fraction, and leap improves from specific addition.Their physical property depends on the effect that the higher order structure under the control polymer state is controlled, and this higher order structure is mainly in the realization of inorganic filling material surface, and therefore thinking needs the inorganic filling material of specified quantitative.On the other hand, when the addition of inorganic filling material manyed than above-mentioned scope, viscosity uprised, and the formability variation is therefore not preferred.
Above-mentioned inorganic filling material is preferably spherical packing material, and also comprising section is elliptoid packing material, so long as spherically just be not particularly limited, considers from the viewpoint that flowability is improved, and is particularly preferably as far as possible the packing material near spherical shape.Thus, easily obtain the closeest interstitital textures such as face-centred cubic structure, the dense structure of six sides, can obtain sufficient loading level.Not that when loading level increased, the mutual friction of packing material increased in the spherical situation, reach before the above-mentioned upper limit that flowability is extremely low and viscosity uprises, the formability variation, therefore not preferred.
Consider from the viewpoint that thermal conductivity improves, in the inorganic filling material, preferably use the above thermal conductivity of 50wt% to be the inorganic filling material more than the 5W/mK, preferably use aluminum oxide, aluminium nitride, crystalline silica etc.Wherein, spherical alumina particularly preferably.In addition, also can be as required with shape irrespectively and with amorphous inorganic filling material such as fused silica, crystalline silica etc.
The median size of inorganic filling material is preferably below the 30 μ m.When median size is larger than this scope, composition epoxy resin mobile impaired, intensity also reduces in addition, and is therefore not preferred.
Can cooperate known curing catalyst in the composition epoxy resin of the present invention.If for example, Ammonia, imidazoles, organic phosphine class, Lewis acid etc. are arranged, specifically have: 1,8-diazabicyclo (5,4,0) tertiary amines such as hendecene-7, triethylenediamine, benzyldimethylamine, trolamine, dimethylaminoethanol, three (dimethylaminomethyl) phenol; The imidazoles such as glyoxal ethyline, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl imidazoles; The organic phosphine classes such as tributylphosphine, methyldiphenyl base phosphine, triphenylphosphine, diphenylphosphine, Phenylphosphine; Tetraphenylphosphonium
Tetraphenyl borate salts, tetraphenylphosphonium
Ethyl triphenyl borate, tetrabutyl phosphorus
Tetrabutyl borates etc. four replace phosphorus
Four substituted boracic acid salt; The tetraphenyl boron salt such as 2-ethyl-4-methylimidazole tetraphenyl borate salts, N-methylmorpholine tetraphenyl borate salts etc.As addition, be the scope of 0.2～10 weight part with respect to Resins, epoxy 100 weight parts usually.These can use separately, also may be used.
The addition of above-mentioned curing catalyst is preferably 0.1～10.0wt% with respect to Resins, epoxy (in situation about cooperating as the halogen-containing Resins, epoxy of fire retardant, comprise it) and the total of solidifying agent.During less than 0.1wt%, gelation time postpones, and the rigidity when causing owing to curing reduces the operability that causes and reduces, and on the contrary, when surpassing 10.0wt%, curing is accelerated in the moulding on the way, and filling easily occurs.
In the composition epoxy resin of the present invention, can use paraffin as the releasing agent of normal operation in the composition epoxy resin.As paraffin, can example such as stearic acid, montanic acid, montanate, phosphoric acid ester etc.
In the composition epoxy resin of the present invention, in order to improve the bonding force of inorganic filling material and resinous principle, can use the coupling agent of normal operation in the composition epoxy resin.As coupling agent, can example such as epoxy silane.The addition of coupling agent is 0.1～2.0wt% with respect to composition epoxy resin preferably.During less than 0.1wt%, the affinity of resin and base material is poor, the formability variation, and when surpassing 2.0wt% on the contrary, the products formed of continuously shaped property is contaminated.
In addition in composition epoxy resin of the present invention, the flowability during from the improvement moulding and consider with the viewpoint that the adaptation of the base material such as lead frame improves can be added thermoplastic oligopolymer class.As thermoplastic oligopolymer class, can illustration: C5 petroleum resin, styrene resin, indene resin, indenes styrene copolymerized resin, indenes vinylbenzene phenol copolymer resins, the indenes of system and C9 system. coumarone copolymer resins, indenes thionaphthene copolymer resins etc.As addition, be the scope of 2～30 weight parts with respect to Resins, epoxy 100 weight parts usually.
And then in composition epoxy resin of the present invention, can suitably cooperate in the general composition epoxy resin operable one-tenth to assign to use.Such as using the fire retardants such as phosphorus flame retardant, bromine compounds, ANTIMONY TRIOXIDE SB 203 99.8 PCT, reaching the tinting materials such as carbon black, organic dye etc.
Composition epoxy resin of the present invention with Resins, epoxy, solidifying agent and inorganic filling material as main component.In the resinous principle of having removed packing material, the mixing ratio of Resins, epoxy and solidifying agent is more than the 50wt%, is preferably more than the 70wt%, and more preferably 80wt% is above gets final product.Need to prove, the resinous principle of having removed packing material refers to solidify rear all the components as the composition beyond the packing material.Perhaps, refer to all the components beyond the packing material in the cured article.
After composition epoxy resin of the present invention mixed other homogeneous chemical composition beyond Resins, epoxy, solidifying agent, inorganic filling material and the coupling agent by mixing machine etc., the interpolation coupling agent carried out mixing the manufacturing by warming mill, kneader etc.The cooperation of these compositions does not sequentially have specific restriction.And, also can carry out the pulverizing of melting mixing thing after mixing, carry out powdered, sheet.
Composition epoxy resin of the present invention is particularly suitable for using as sealing in semiconductor device.
Cured article of the present invention obtains by making above-mentioned composition epoxy resin thermofixation.In order to obtain cured article with composition epoxy resin of the present invention, methods such as applicable transfer formation, press compression molding, cast molding, injection molding, extrusion moulding is considered from the viewpoint of mass productivity, preferred transfer formation.
Cured article of the present invention considers to be preferably to have crystalline cured article from the viewpoint of high thermal conductivity.The crystalline of cured article presents, and can observe the endotherm(ic)peak of melting of accompanying crystallization as fusing point in differential scanning calorimeter, confirms thus.Preferred fusing point is 120 ℃～280 ℃ scope, more preferably 150 ℃～250 ℃ scope.In addition, the preferred thermal conductivity of cured article is more than the 4W/mK, to be particularly preferably more than the 6W/mK.
The degree of crystallinity of cured article of the present invention is more high better, and the degree of crystallization can be estimated by the caloric receptivity that accompanying crystallization in differential scanning calorimeter melts.Preferred caloric receptivity is more than the 10J/g for the resinous principle of having removed packing material of per unit weight.More preferably more than the 15J/g, be particularly preferably more than the 30J/g.Than this scope hour, improve effect as the thermal conductivity of epoxy resin cured product little.In addition, consider from the viewpoint of low heat expansion property and thermotolerance raising, crystallinity is more high more preferred.Need to prove, said caloric receptivity refers to by differential thermal analysis meter here, use accurate weighing approximately the sample of 10mg under nitrogen gas stream, measure and the caloric receptivity that obtains with the condition of 10 ℃/minute of heat-up rates.
Epoxy resin cured product of the present invention, can obtain by utilizing above-mentioned forming method to be heating and curing, usually, be 80 ℃～250 ℃ as mold temperature, in order to improve the degree of crystallinity of epoxy resin cured product, be desirably in than the fusing point of cured article and also be cured under the low temperature.Preferred solidification value is 100 ℃～200 ℃ scope, more preferably 130 ℃～180 ℃.In addition, be 30 seconds～1 hour preferred set time, more preferably 1 minute～30 minutes.And then after the moulding, by after fixing, can further improve degree of crystallinity.Usually, the after fixing temperature is 130 ℃～250 ℃, and the time is 1 hour～20 hours scope, preferably, be desirably in than under the temperature of low 5 ℃～40 ℃ of the endotherm peak temperature in the differential thermal analysis with carrying out after fixing in 1 hour～24 hours.
Embodiment
By the following examples the present invention is carried out more specific description.
Reference example 1
Resorcinol 150.0g is dissolved among Epicholorohydrin 1260g, the diglyme 120g, stirred 1 hour at 60 ℃ of lower 48% sodium hydroxide 22.7g of adding.Under reduced pressure afterwards, (approximately 130Torr) is with dripping 48% aqueous sodium hydroxide solution 204.5g in 3 hours.During this, the water of generation is discharged to outside the system by the azeotropic with Epicholorohydrin, and the Epicholorohydrin that distills out turns back in the system.After dropping finishes, continue reaction again and dewatered in 1 hour, then Epicholorohydrin is removed in distillation, behind the adding methyl iso-butyl ketone (MIBK) 600g, washes except desalting.Afterwards, stirred 1 hour at 85 ℃ of lower 48% sodium hydroxide 20.0g of interpolation, with the washing of 200mL warm water.Afterwards, except after anhydrating, methyl iso-butyl ketone (MIBK) is removed in underpressure distillation, obtains the Resins, epoxy 278g of white crystals shape by separatory.Epoxy equivalent (weight) is 117, and water-disintegrable chlorine is 310ppm, and the fusing point that utilizes capillary tube technique to measure is 84 ℃～101 ℃, and the viscosity under 120 ℃ is 1.8mpas.The resin that obtains by each composition ratio that GPC measures the Resins, epoxy that is obtained by Resorcinol try to achieve is: n=0 (monomer) is 85.7%, n=1 (dimer) is 9.1%, n=2 (tripolymer) is 1.6%.Here, water-disintegrable chlorine is by carrying out the following value of measuring: sample 0.5g is dissolved in two
After among the alkane 30ml, then the 1N-KOH boiling reflux of adding 10ml 30 minutes is cooled to normal temperature, adds 80% acetone water 100ml again, uses 0.002N-AgNO
3The aqueous solution carries out the potential difference titration to the solution that obtains.In addition, fusing point is with 2 ℃ of/minute values that obtain of heat-up rate by capillary tube technique.Viscosity uses the CAP2000H of BROOKFIELD system to measure, and softening temperature is measured with ring and ball method according to JIS K-6911.In addition, GPC measures according to following condition: device: Japanese ゥ ォ one タ, one ズ (strain) system, 515A type, post: TSK-GEL2000 * 3 piece and TSK-GEL4000 * 1 piece (Jun Wei East ソ one (strain) system), solvent: tetrahydrofuran (THF), flow: 1ml/min, temperature: 38 ℃, detector: RI.
Reference example 2
With 4,4 '-dihydroxybiphenyl 100.0g is dissolved among Epicholorohydrin 700g, the diglyme 105g, and then under reduced pressure (approximately 130Torr) is lower to 3 hours dropping 48% aqueous sodium hydroxide solution 87.8g at 60 ℃.During this, the water of generation is discharged to outside the system by the azeotropic with Epicholorohydrin, and the Epicholorohydrin that distills out turns back in the system.After dripping end, continue again reaction and dewatered in 1 hour, then be cooled to normal temperature, filter and reclaim precipitate.Afterwards, the washing precipitate removes and desalts, and then dry, obtains the Resins, epoxy 137g of crystalline powder shape.Epoxy equivalent (weight) is 163, and the fusing point that utilizes capillary tube technique to measure is 169 ℃～175 ℃.Each composition ratio that the resin that obtains is measured in the general formula (1) of obtaining by GPC is: n=0 is that 93.7%, n=1 is 5.9%.
Embodiment 1
Resorcinol 50.0g, 4,4 '-dihydroxybiphenyl 100.0g is dissolved among Epicholorohydrin 1000g, the diglyme 150g, stirred 1 hour at 60 ℃ of lower 48% sodium hydroxide 16.5g of adding.Under reduced pressure afterwards, (approximately 130Torr) is with dripping 48% aqueous sodium hydroxide solution 148.8g in 3 hours.During this, the water of generation is discharged to outside the system by the azeotropic with Epicholorohydrin, and the Epicholorohydrin that distills out turns back in the system.After dropping finishes, continue reaction again and dewatered in 1 hour, Epicholorohydrin is removed in distillation, behind the adding methyl iso-butyl ketone (MIBK) 600g, washes except desalting.Afterwards, stirred 1 hour at 85 ℃ of lower 48% sodium hydroxide 13.5g of interpolation, with the washing of 200mL warm water.Afterwards, except anhydrating, then methyl iso-butyl ketone (MIBK) is removed in underpressure distillation, obtains modified epoxy (Resins, epoxy A) 224g of white crystals shape by separatory.Epoxy equivalent (weight) is 139, and water-disintegrable chlorine is 320ppm, utilizes fusing point that capillary tube technique measures at 104 ℃～141 ℃, and the viscosity under 150 ℃ is 3.4mPas.The n=0 (monomer) that measures the Resins, epoxy that is obtained by Resorcinol obtain by GPC is 23.1%, n=1 (dimer) is 2.2%.In addition, by 4,4 '-n=0 (monomer) of the Resins, epoxy that dihydroxybiphenyl obtains is 67.2%, n=1 (dimer) is 4.1%.
Embodiment 2
Resorcinol 75.0g, 4,4 '-dihydroxybiphenyl 75.0g is dissolved among Epicholorohydrin 1000g, the diglyme 150g, stirred 1 hour at 60 ℃ of lower 48% sodium hydroxide 18.1g of adding.Under reduced pressure afterwards, (approximately 130Torr) is with dripping 48% aqueous sodium hydroxide solution 162.7g in 3 hours.During this, the water of generation is discharged to outside the system by the azeotropic with Epicholorohydrin, and the Epicholorohydrin that distills out turns back in the system.After dripping end, continue reaction dehydration in 1 hour, then Epicholorohydrin is removed in distillation again, after the adding 540g methyl iso-butyl ketone (MIBK), washes except desalting.Afterwards, stirred 1 hour at 85 ℃ of lower 48% sodium hydroxide 13.5g of interpolation, with the washing of 200mL warm water.Afterwards, except anhydrating, then methyl iso-butyl ketone (MIBK) is removed in underpressure distillation, obtains modified epoxy (Resins, epoxy B) 214g of white crystals shape by separatory.Epoxy equivalent (weight) is 135, and water-disintegrable chlorine is 380ppm, and the fusing point that utilizes capillary tube technique to measure is 108 ℃～119 ℃, and the viscosity under 150 ℃ is 2.3mPas.The n=0 (monomer) that measures the Resins, epoxy that is obtained by Resorcinol obtain by GPC is 53.1%, n=1 (dimer) is 34.2%.In addition, by 4,4 '-n=0 (monomer) of the Resins, epoxy that dihydroxybiphenyl obtains is 7.2%, n=1 (dimer) is 4.3%.
Embodiment 3
Resorcinol 125.0g, 4,4 '-dihydroxybiphenyl 25.0g is dissolved among Epicholorohydrin 1200g, the diglyme 180g, stirred 1 hour at 60 ℃ of lower 48% sodium hydroxide 21.2g of adding.Under reduced pressure afterwards, (approximately 130Torr) is with dripping 48% aqueous sodium hydroxide solution 190.6g in 3 hours.During this, the water of generation is discharged to outside the system by the azeotropic with Epicholorohydrin, and the Epicholorohydrin that distills out turns back in the system.After dripping end, continue reaction dehydration in 1 hour, Epicholorohydrin is removed in distillation again, after the adding 560g methyl iso-butyl ketone (MIBK), washes except desalting.Afterwards, stirred 1 hour at 85 ℃ of lower 48% sodium hydroxide 13.5g of interpolation, with the washing of 200mL warm water.Afterwards, except anhydrating, then methyl iso-butyl ketone (MIBK) is removed in underpressure distillation, obtains modified epoxy (Resins, epoxy C) 265g of white crystals shape by separatory.Epoxy equivalent (weight) is 124, and water-disintegrable chlorine is 390ppm, and the fusing point that utilizes capillary tube technique to measure is 86 ℃～105 ℃, and the viscosity under 150 ℃ is 0.8mPas.The n-0 (monomer) that measures the Resins, epoxy that is obtained by Resorcinol obtain by GPC is 80.1%, n=1 (dimer) is 2.2%.In addition, by 4,4 '-n=0 (monomer) of the Resins, epoxy that dihydroxybiphenyl obtains is 13.1%, n=1 (dimer) is 3.0%.
Embodiment 4～8, comparative example 1～5
As the Resins, epoxy composition, use modified epoxy (order by the embodiment numbering is Resins, epoxy A, Resins, epoxy B, Resins, epoxy C), the Resins, epoxy (Resins, epoxy D) of reference example 1, the Resins, epoxy (Resins, epoxy E) of reference example 2, biphenyl based epoxy resin (the Resins, epoxy F: ジ ャ パ Application ェ Port キ シ レ ジ Application system, YX-4000H of embodiment 1～embodiment 3; Epoxy equivalent (weight) 195); As solidifying agent, use phenol aralkyl resin (solidifying agent A: Mitsui Chemicals system, XL-225-LL; 75 ℃ of OH equivalent 174, softening temperatures), Resorcinol (solidifying agent B), 4,4 '-dihydroxy diphenyl ether (solidifying agent C); As curing catalyst, use triphenylphosphine, as inorganic filling material, use spherical alumina (median size 12.2 μ m), cooperate composition and the amount shown in the table 1, after fully mixing with mixing machine, use mixing approximately 5 minutes of warming mill, to obtain institute's material cooling, pulverize, obtain respectively the composition epoxy resin of embodiment 4～8, comparative example 1～5.Use this composition epoxy resin behind 170 ℃, 5 minutes condition compacted under, under 170 ℃, carry out 12 hours after fixing, obtain the curing molding thing, estimate its physical property.The result of embodiment gathered be shown in table 1, with the table 2 that the results are shown in of comparative example.Need to prove the numeral weight part of each title complex in table 1 and the table 2.In addition, comparative example 5 is because moulding is bad, physical property that therefore can not the evaluate cure forming composition.
Evaluation method as shown below.
(1) thermal conductivity is used NETZSCH LFA447 type processed thermal conductivity meter, measures with astable heat-pole method (non-permanent ripe Line method).
(2) fusing point, Heat of fusion (DSC method) are used differential scanning calorimetric analysis device (セ ィ コ one ィ Application ス ッ Le DSC6200 type processed), with 10 ℃ of/minute mensuration of heat-up rate.
(3) linear expansivity, second-order transition temperature use セ ィ コ one ィ Application ス ッ Le (strain) TMA120C type processed heat engine tool determinator, with 10 ℃ of/minute mensuration of heat-up rate.
(4) water-intake rate is shaped to the disk of diameter 50mm, thickness 3mm, behind the after fixing, and the weight rate of moisture absorption after 100 hours under 85 ℃, the condition of relative humidity 85%.
[table 1]
| Embodiment | 4 | 5 | 6 | 7 | 8 |
| Resins, epoxy A | 66.5 | 107.5 | 87.0 | ||
| Resins, epoxy B | 65.5 | ||||
| Resins, epoxy C | 62.5 | ||||
| Solidifying agent A | 83.5 | 84.5 | 87.5 | ||
| Solidifying agent B | 42.5 | ||||
| Solidifying agent C | 63.0 | ||||
| Inorganic filling material | 1000 | 1000 | 1000 | 1000 | 1000 |
| Curing catalyst | 1.6 | 1.6 | 1.6 | 1.6 | 1.6 |
| Gel time (sec) | 33 | 34 | 37 | 45 | 42 |
| Eddy flow (cm) | 101 | 110 | 114 | 130 | 127 |
| Second-order transition temperature (℃) | 134 | 132 | 131 | 87 | 89 |
| Thermal expansivity (ppm,＜Tg) | 13.0 | 14.0 | 14.0 | 11.0 | 10.0 |
| Thermal expansivity (ppm,＞Tg) | 56.0 | 57.0 | 60.0 | 53.0 | 52.0 |
| Heat-drawn wire (℃) | 144 | 142 | 141 | 167 | 172 |
| Water-intake rate (wt%, 100h) | 0.14 | 0.15 | 0.14 | 0.12 | 0.11 |
| Thermal conductivity (W/mK) | 4.3 | 4.2 | 4.2 | 5.0 | 5.2 |
| Fusing point (℃) | - | - | - | 166.3 | 199.5 |
| Heat of fusion (J/g-resin) | 0 | 0 | 0 | 15 | 26 |
[table 2]
| Comparative example | 1 | 2 | 3 | 4 | 5 |
| Resins, epoxy D | 60.0 | 34.0 | 33.0 | ||
| Resins, epoxy E | 33.0 | ||||
| Resins, epoxy F | 34.0 | 79.0 | 117.0 | ||
| Solidifying agent A | 90.0 | 82.0 | 71.0 | 84.0 | |
| Solidifying agent B | 33.0 | ||||
| Inorganic filling material | 1000 | 1000 | 1000 | 1000 | 1000 |
| Curing catalyst | 1.6 | 1.6 | 1.6 | 1.6 | 1.6 |
| Gel time (sec) | 44 | 49 | 35 | 48 | |
| Eddy flow (cm) | 96 | 93 | 77 | 82 | |
| Second-order transition temperature (℃) | 118 | 122 | 128 | 89 | |
| Thermal expansivity (ppm,＜Tg) | 13.0 | 15.0 | 21.0 | 18.0 | |
| Thermal expansivity (ppm,＞Tg) | 74.0 | 84.0 | 82.0 | 75.0 | |
| Heat-drawn wire (℃) | 121 | 124 | 131 | 94 | |
| Water-intake rate (wt%100h) | 0.24 | 0.23 | 0.21 | 0.23 | |
| Thermal conductivity (W/mK) | 3.5 | 3.3 | 3.2 | 3.3 | |
| Fusing point (℃) | - | - | - | - | |
| Heat of fusion (J/g-resin) | 0 | 0 | 0 | 0 |
Utilizability on the industry
Modified epoxy of the present invention, the formability that reaches composition epoxy resin, reliability excellence, and produce the cured article of high heat conductance, low water absorbable, low heat expansion property, high heat resistance excellence, preferably use high-cooling property and dimensional stability that performance is excellent with insulating material as the electrical/electronic part of encapsulating semiconductor, plywood, heat-radiating substrate etc.
Claims (11)
1. has crystalline modified epoxy under a normal temperature, it is characterized in that, its be make with respect to Resorcinol 1 weight part mixed 4,4 '-mixture and the Epicholorohydrin reaction of dihydroxybiphenyl 0.1～10 weight part obtain, epoxy equivalent (weight) is 110～160 scope.
2. composition epoxy resin, its be with (A) Resins, epoxy, (B) solidifying agent, and (C) inorganic filling material as the composition epoxy resin of main component, it is characterized in that, as the modified epoxy claimed in claim 1 more than the Resins, epoxy use 50wt%.
3. composition epoxy resin as claimed in claim 2, wherein, the containing ratio of inorganic filling material is 80～96wt%.
4. composition epoxy resin as claimed in claim 2, wherein, solidifying agent is that phenol is solidifying agent.
5. composition epoxy resin as claimed in claim 2 wherein, as solidifying agent, uses the above difunctionality phenolic compound of 50wt%.
6. composition epoxy resin as claimed in claim 5, wherein, the difunctionality phenolic compound for be selected from Resorcinol, 4,4 '-dihydroxybiphenyl, 4,4 '-dihydroxy diphenyl ether, 1, two (4-hydroxyphenoxy) benzene, 4 of 4-, 4 '-dihydroxyl ditan, 4,4 '-dihydroxyl diphenyl sulfide, 1,5-naphthalene glycol, 2,7-naphthalene glycol, 2, at least a in 6-naphthalene glycol and the Resorcinol.
7. composition epoxy resin as claimed in claim 2 wherein, as inorganic filling material, uses the above spherical aluminum oxide of 50wt%.
8. composition epoxy resin as claimed in claim 2, the composition epoxy resin that it is used for encapsulating semiconductor.
9. a cured article is characterized in that, it obtains composition epoxy resin curing claimed in claim 2, and thermal conductivity is more than the 4W/mK.
10. cured article as claimed in claim 9, wherein, the peak of the fusing point in the differential scanning calorimeter of cured article is 120 ℃～280 ℃ scope.
11. cured article as claimed in claim 9, wherein, the caloric receptivity that the resinous principle in the differential scanning calorimeter of cured article converts is more than the 10J/g.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-051872 | 2008-03-03 | ||
| JP2008051872 | 2008-03-03 | ||
| PCT/JP2009/053849 WO2009110424A1 (en) | 2008-03-03 | 2009-03-02 | Modified epoxy resin, epoxy resin compositions and cured articles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102083881A CN102083881A (en) | 2011-06-01 |
| CN102083881B true CN102083881B (en) | 2013-01-23 |
Family
ID=41055979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980107601.XA Active CN102083881B (en) | 2008-03-03 | 2009-03-02 | Modified epoxy resin, epoxy resin compositions and cured articles |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5320384B2 (en) |
| KR (1) | KR101524485B1 (en) |
| CN (1) | CN102083881B (en) |
| TW (1) | TWI498348B (en) |
| WO (1) | WO2009110424A1 (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5302147B2 (en) * | 2009-09-14 | 2013-10-02 | 新日鉄住金化学株式会社 | Epoxy resin composition for sealing and cured product |
| SG181697A1 (en) | 2009-12-14 | 2012-07-30 | Nippon Steel Chemical Co | Epoxy resin, process for production thereof, epoxy resin composition using same, and cured product |
| US8173745B2 (en) * | 2009-12-16 | 2012-05-08 | Momentive Specialty Chemicals Inc. | Compositions useful for preparing composites and composites produced therewith |
| KR20130008409A (en) * | 2011-07-12 | 2013-01-22 | 엘지이노텍 주식회사 | Epoxy resin compound and radiant heat circuit board using the same |
| TWI612071B (en) * | 2011-07-12 | 2018-01-21 | Ｌｇ伊諾特股份有限公司 | Epoxy resin compound and radiant heat circuit board using the same |
| US20130052381A1 (en) * | 2011-08-22 | 2013-02-28 | Robert R. Gallucci | Polyepoxides and epoxy resins and methods for the manufacture and use thereof |
| KR101139280B1 (en) * | 2012-02-10 | 2012-04-26 | 주식회사 신아티앤씨 | Cristalline epoxy resin |
| JP5681151B2 (en) * | 2012-09-03 | 2015-03-04 | 新日鉄住金化学株式会社 | Epoxy resin composition and molded article |
| JP6324317B2 (en) * | 2012-11-08 | 2018-05-16 | 日本化薬株式会社 | Epoxy resin mixture, epoxy resin composition and cured product thereof |
| KR102376061B1 (en) * | 2013-09-12 | 2022-03-18 | 닛뽄 가야쿠 가부시키가이샤 | Epoxy resin mixture, epoxy resin composition, cured product and semiconductor device |
| JP6508780B2 (en) * | 2013-10-23 | 2019-05-08 | 日本化薬株式会社 | Epoxy resin mixture, epoxy resin composition, prepreg, and cured product thereof |
| CN104629642B (en) * | 2015-02-12 | 2016-09-07 | 矽照光电（厦门）有限公司 | A kind of preparation method of the epoxide resin conductive adhesive for LED chip bonding |
| CN104804444B (en) * | 2015-05-03 | 2016-11-09 | 佛山市天润沥青混凝土有限公司 | A kind of preparation method of resistant to elevated temperatures anti-rutting additive |
| WO2017145412A1 (en) * | 2016-02-25 | 2017-08-31 | 日立化成株式会社 | Resin sheet and cured resin sheet |
| JP6943945B2 (en) * | 2016-07-25 | 2021-10-06 | ザ・ボーイング・カンパニーＴｈｅ Ｂｏｅｉｎｇ Ｃｏｍｐａｎｙ | Epoxy resin |
| WO2018018070A1 (en) * | 2016-07-25 | 2018-02-01 | The Boeing Company | Epoxy resin |
| CN107474770A (en) * | 2017-08-04 | 2017-12-15 | 烟台信友新材料股份有限公司 | A kind of one pack system high heat conductive insulating structural adhesive and preparation method thereof |
| KR102408630B1 (en) * | 2017-09-29 | 2022-06-13 | 쇼와덴코머티리얼즈가부시끼가이샤 | Epoxy resins, epoxy resin compositions, cured epoxy resins, and composite materials |
| EP3828218B1 (en) * | 2018-07-24 | 2024-06-26 | Nipponkayaku Kabushikikaisha | Epoxy resin, epoxy resin composition, epoxy resin composition for carbon fiber-reinforced composite material, prepreg, and carbon fiber-reinforced composite material |
| JP7119801B2 (en) * | 2018-09-10 | 2022-08-17 | 昭和電工マテリアルズ株式会社 | Epoxy resins, epoxy resin compositions, cured epoxy resins and composite materials |
| JP7243092B2 (en) * | 2018-09-10 | 2023-03-22 | 株式会社レゾナック | Epoxy resins, epoxy resin compositions, cured epoxy resins and composite materials |
| JP7320942B2 (en) * | 2018-12-28 | 2023-08-04 | 日鉄ケミカル＆マテリアル株式会社 | Epoxy resin, epoxy resin composition and cured product |
| JP2022007637A (en) | 2020-06-26 | 2022-01-13 | 日鉄ケミカル＆マテリアル株式会社 | Polyhydric hydroxy resin, method of producing the same, and epoxy resin composition containing the same, and cured epoxy resin |
| JP7502916B2 (en) | 2020-06-30 | 2024-06-19 | 日鉄ケミカル＆マテリアル株式会社 | Epoxy resin, epoxy resin composition and cured product |
| CN113969128B (en) * | 2021-12-14 | 2022-07-29 | 中路交科科技股份有限公司 | High-performance epoxy resin adhesive layer material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006045261A (en) * | 2004-07-30 | 2006-02-16 | Nippon Kayaku Co Ltd | Modified epoxy resin, epoxy resin composition and cured product thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61241323A (en) * | 1985-04-18 | 1986-10-27 | Mitsui Petrochem Ind Ltd | Polyhydroxy polyether, production and use thereof |
| JP2551452B2 (en) * | 1988-03-11 | 1996-11-06 | 油化シェルエポキシ株式会社 | Epoxy resin composition for encapsulation |
| JPH06184272A (en) * | 1992-12-18 | 1994-07-05 | Sumitomo Bakelite Co Ltd | Epoxy resin composition |
| JP2747819B2 (en) * | 1996-02-23 | 1998-05-06 | 旭チバ株式会社 | Novel epoxy resin and resin composition containing the same |
| JP3719469B2 (en) * | 1996-08-23 | 2005-11-24 | 日本化薬株式会社 | Modified epoxy resin, epoxy resin composition and cured product thereof |
| JP3712610B2 (en) * | 2000-12-28 | 2005-11-02 | ジャパンエポキシレジン株式会社 | Epoxy resin crystallized product, curable composition and cured product |
| JP2004182752A (en) * | 2002-11-29 | 2004-07-02 | Dainippon Ink & Chem Inc | Epoxy resin composition and epoxy resin emulsion |
| CN100460464C (en) * | 2003-12-11 | 2009-02-11 | 日立化成工业株式会社 | Epoxy resin molding material for sealing and electronic component |
-
2009
- 2009-03-02 WO PCT/JP2009/053849 patent/WO2009110424A1/en active Application Filing
- 2009-03-02 CN CN200980107601.XA patent/CN102083881B/en active Active
- 2009-03-02 JP JP2010501896A patent/JP5320384B2/en active Active
- 2009-03-02 KR KR1020107020385A patent/KR101524485B1/en active IP Right Grant
- 2009-03-03 TW TW098106834A patent/TWI498348B/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006045261A (en) * | 2004-07-30 | 2006-02-16 | Nippon Kayaku Co Ltd | Modified epoxy resin, epoxy resin composition and cured product thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平9-227654A 1997.09.02 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI498348B (en) | 2015-09-01 |
| KR101524485B1 (en) | 2015-06-01 |
| JP5320384B2 (en) | 2013-10-23 |
| CN102083881A (en) | 2011-06-01 |
| KR20100134594A (en) | 2010-12-23 |
| TW200948843A (en) | 2009-12-01 |
| JPWO2009110424A1 (en) | 2011-07-14 |
| WO2009110424A1 (en) | 2009-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102083881B (en) | Modified epoxy resin, epoxy resin compositions and cured articles | |
| CN106471035B (en) | Electronic material composition epoxy resin, its solidfied material and electronic component | |
| CN101198632B (en) | Epoxy resin composition and curing product thereof | |
| CN102656204B (en) | Epoxy resin, process for production thereof, epoxy resin composition using same, and cured product | |
| CN102010574B (en) | Flame-retardant molding compositions | |
| CN101970526B (en) | Epoxy resin composition and molded object | |
| CN103797068A (en) | Epoxy resin compound and radiant heat circuit board using the same | |
| CN103140523B (en) | Polyhydric hydroxy resin, epoxy resin, production method therefor, epoxy resin composition and cured product thereof | |
| KR20100008771A (en) | Crystalline modified epoxy resin, epoxy resin composition and crystalline cured product | |
| CN103906784A (en) | Epoxy resin compound and radiant heat circuit board using the same | |
| CN104870557A (en) | Epoxy resin composition and printed circuit board | |
| JP6605828B2 (en) | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof | |
| CN103562308A (en) | Epoxy resin compound and radiant heat circuit board using the same | |
| JP5209556B2 (en) | Epoxy resin composition and molded article | |
| JP5079721B2 (en) | Epoxy resin composition and molded article | |
| CN103588957A (en) | Epoxy resin compound and radiant heat circuit board using the same | |
| CN104334597A (en) | Polyvalent hydroxy resin, epoxy resin, method for producing same, epoxy resin composition and cured product thereof | |
| JP5091052B2 (en) | Epoxy resin composition and molded article | |
| JP2015003972A (en) | Epoxy resin, epoxy resin composition and hardened product of the composition | |
| JP2016074805A (en) | Resin composition for sealing semiconductor and semiconductor device | |
| CN1630673A (en) | Indole resins epoxy resins and resin compositions containing the same | |
| CN102300899B (en) | Epoxy resin composition, process for producing the epoxy resin composition, and cured object formed therefrom | |
| JP4264769B2 (en) | Epoxy resin composition and semiconductor sealing material | |
| CN103906782A (en) | Epoxy resin, epoxy resin composition, and cured product thereof | |
| JPH11302360A (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. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan Patentee after: Nippon Steel Chemical Co. Address before: Tokyo, Japan Patentee before: Nippon Seel Chemical Co., Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20191220 Address after: No.13-1, No.1, No.1, No Patentee after: Nippon Iron Chemical Materials Co., Ltd. Address before: Tokyo, Japan Patentee before: Nippon Steel Chemical Co. |
|
| TR01 | Transfer of patent right |