CN1745138A - Epoxy resin composition - Google Patents
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- CN1745138A CN1745138A CN 200380109577 CN200380109577A CN1745138A CN 1745138 A CN1745138 A CN 1745138A CN 200380109577 CN200380109577 CN 200380109577 CN 200380109577 A CN200380109577 A CN 200380109577A CN 1745138 A CN1745138 A CN 1745138A
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Abstract
An epoxy resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an epoxidized polyisoprene (c-1) which contains 0.15 to 2meq/g of epoxy groups in the molecule and has a number-average molecular weight of 15000 to 200000 or an epoxidized polybutadiene (c-2) which contains 0.15 to 2 meq/g of epoxy groups in the molecule and has a number-average molecular weight of 20000 to 200000. The epoxy resin composition is excellent in heat resistance and realizes relaxation of internal stress, thus being suitably usable in various fields including materials of electronic components (such as encapsulation material for semiconductors) and adhesive.
Description
Technical field
The present invention relates to composition epoxy resin, the composition epoxy resin among the present invention has good thermotolerance, and has reduced internal stress, and can be widely used in the semiconductor sealing material is the electronic component material of representative, aspects such as caking agent.
Background technology
From principal constituent is the hardening thing that draws the composition of Resins, epoxy, has excellent cementability, thermotolerance and electrical characteristic etc., is widely used in purposes such as electric appliance and electronic portion product, caking agent, coating such as semiconductor packages material.But above-mentioned hardening thing lacks snappiness, and fragility is big, therefore produces stress concentration when sclerosis inevitably.The crack appears in its result on injection articles such as electronic component, caking agent occurs bonding bad, and coating crackle then occurs or problem such as peels off.On the other hand, electronic component or caking agent field are more and more stricter to performance demands, need a kind of material that had both kept thermotolerance to have good intensity and low elastic modulus so.
As addressing the above problem, the method of the internal stress when reducing to harden for example has (1), has the polyhutadiene derivative of an above carboxyl, amino, hydroxyl, epoxy group(ing), thiol group, isocyanate group at least with the reaction condensate of multi-functional epoxy compound, phenol based compound and formaldehyde and in a part for cooperating the thermosetting resin composition (please refer to the spy and open clear 57-180626 communique) that forms by composition; (2), contain the elastomeric composition epoxy resin of 0.1～5 mass percent, its synthetic rubber end or intramolecularly have epoxy group(ing) (please refer to the spy and open clear 61-62511 communique); In addition, (3), hardening aromatic series and/or hardening cycloaliphatic epoxy resin, stiffening agent and have specific epoxy content, contain preferably that the epoxidized low viscosity polydiene of ad hoc structure is polymeric to have a flexible composition epoxy resin (please refer to the flat 9-512039 communique of special table); (4), in above-mentioned composition, add the composition epoxy resin (please refer to the flat 10-502696 communique of special table) that contains the hydroxy material and form again.
Above-mentioned (1)～(4) composition is promptly given snappiness by inner plasticization all according to same idea.
Open disclosed effective constituent in the clear 57-180626 communique " the polyhutadiene derivative that in a part, has an above carboxyl, amino, hydroxyl, epoxy group(ing), thiol group, isocyanate group at least " for having functional group and low-molecular-weight polyhutadiene (among the embodiment used be 2800,4600 and 4800) endways (1) spy.And be the lower level of 700～3000 (used in an embodiment number-average molecular weight also is 700～3000) in the preferred molecular weight that (2) spy opens disclosed effective constituent in the clear 61-62511 communique " endways or intramolecularly contain the synthetic rubber of epoxy group(ing) ", the intramolecular elastomeric epoxy equivalent (weight) that contains epoxy group(ing) is that 190～220 (the epoxy valency is 5.3～4.5meq/g), and epoxy group content is higher.With this lower molecular weight and have the mixed with polybutadiene constituent that a plurality of functional groups constitute, the stable on heating problem of reduction is arranged.And the synthetic rubber that contains epoxy group(ing) is endways generally made by reacting with Epicholorohydrin, but synthetic rubber contains the impurity such as chlorion that much produce in manufacturing processed, thereby reduce the wet fastness of composition epoxy resin, in the time of in being used in the metal part product, it has corrodibility.
In addition, (3) the flat 10-502696 communique composition epoxy resin of the special table in the special flat 9-512039 communique of table and (4), be feature all to give toughness, its disclosed effective constituent " epoxidized low viscosity polyethylene polymerization body " is for containing vinylaromatic hydrocarbon and the low-molecular-weight block polymer of tool (among the embodiment used be 4960,5680,6000 and 6750), and preferred epoxy valency is: (i) to be lower than at 5% o'clock be 3.5～6meq/g to the content of vinylaromatic hydrocarbon; (ii) to be at 5～20% o'clock be 3～6meq/g to the content of vinylaromatic hydrocarbon; (iii) the content of vinylaromatic hydrocarbon was that 1.5～6meq/g (is 2.2～5.2meq/g) among the embodiment greater than 20% o'clock.Improve consistency between the Resins, epoxy by regulating vinylaromatic hydrocarbon and epoxy group content.The composition of this adding epoxidized low viscosity polyethylene polymerization body has been given snappiness by inner plasticization, still leaves some room for improvement but keep resistance toheat.
Summary of the invention
The object of the invention is, provide a kind of have excellent thermotolerance and reduce internal stress concentrate, have sufficient snappiness, thus the crack of avoiding internal stress to cause, the composition epoxy resin of the problem such as peel off of bonding, application face.
Comprise following composition according to composition epoxy resin provided by the invention: (A) Resins, epoxy, (B) stiffening agent and (C) comprise 0.15～2meq/g epoxy group(ing) at intramolecularly, and number-average molecular weight the epoxidized polyisoprene between 15000～200000 (c-1) (below, abbreviate epoxidized polyisoprene (c-1) as), perhaps contain 0.15～2meq/g epoxy group(ing) at intramolecularly, and number-average molecular weight is the epoxidized polybutadiene between 20000～200000 (c-2) (below, abbreviate epoxidized polybutadiene (c-2) as).
The composition epoxy resin that obtains according to the present invention has excellent thermotolerance and has reduced internal stress, can be widely used in such as fields such as semiconductor sealing material, caking agents.
Description of drawings
Fig. 1 is the E ' curve synoptic diagram of the hardening thing that obtains from three kinds of composition epoxy resins of embodiment 1, embodiment 2 and comparative example 1;
Fig. 2 is the E ' curve synoptic diagram of the hardening thing that obtains from four kinds of composition epoxy resins of embodiment 1, comparative example 1, comparative example 2 and comparative example 3;
Fig. 3 is the E ' curve synoptic diagram of the hardening thing that obtains from four kinds of composition epoxy resins of embodiment 1, comparative example 1, comparative example 4 and comparative example 5;
Fig. 4 is the E ' curve synoptic diagram of the hardening thing that obtains from three kinds of composition epoxy resins of embodiment 1, comparative example 1 and comparative example 6;
Fig. 5 is the E ' curve synoptic diagram of the hardening thing that obtains from three kinds of composition epoxy resins of embodiment 3, embodiment 4 and comparative example 1;
Fig. 6 is the E ' curve synoptic diagram of the hardening thing that obtains from three kinds of composition epoxy resins of embodiment 3, comparative example 1 and comparative example 7;
Fig. 7 is the E ' curve synoptic diagram of the hardening thing that obtains from four kinds of composition epoxy resins of embodiment 3, comparative example 1, comparative example 4 and comparative example 5;
Fig. 8 is the E ' curve synoptic diagram of the hardening thing that obtains from three kinds of composition epoxy resins of embodiment 3, comparative example 1 and comparative example 6.
Embodiment
Constitute the Resins, epoxy (A) of the present invention's composition epoxy resin,,, for example, can preferably use the Resins, epoxy that contains two epoxy group(ing) in a part at least its kind and indefinite so long as can harden by stiffening agent (B).Be specially, biphenyl type epoxy resin, naphthyl type Resins, epoxy, diphenyl ether type Resins, epoxy, diphenyl sulfide ether type epoxy, hydroquinone type Resins, epoxy, biphenyl-phenol aldehyde type epoxy resin, cresols-phenolic resin varnish type epoxy resin, phenol-phenolic resin varnish type epoxy resin, dihydroxyphenyl propane-phenolic resin varnish type epoxy resin, triphen phenol-type epoxy resin, tetraphenylethane type Resins, epoxy, dicyclopentadiene type Resins, epoxy, bisphenol A type epoxy resin, bisphenol f type epoxy resin.Above-mentioned Resins, epoxy can use wherein a kind of separately, also can be use mixing two or more.
Constitute the stiffening agent (B) of the present invention's composition epoxy resin, can select the phenolic resin that contains two above phenol hydroxys in a part for use.Be specially phenol-phenolic varnish type resin, resol type phenol resin, phenol-aralkyl-type resin, triphenyl alkane type resin and polymer thereof, naphthalene-ring containing phenolic resin, dicyclopentadiene sex change phenolic resin.Add 20～250 mass parts in the optional Resins, epoxy of stiffening agent (B) combined amount (A) 100 mass parts, preferred range is 20～125 mass parts.With respect to Resins, epoxy (A) 100 mass parts, when being lower than 20 mass parts, the amount of not participating in reaction of the Resins, epoxy when composition epoxy resin hardens (A) increases as the combined amount of stiffening agent (B); And when stiffening agent (B) combined amount be 250 mass parts when above, the amount that stiffening agent (B) is not participated in reaction increases.
Constitute the epoxidized polyisoprene (c-1) of the present invention's Resins, epoxy, it is characterized by, contain the epoxy group(ing) of 0.15～2meq/g scope at intramolecularly, and number-average molecular weight is between 15000～200000 scopes.In addition, constitute the epoxidized polybutadiene (c-2) of the present invention's epoxy resin component, it is characterized by, contain 0.15～2meq/g epoxy group(ing) at intramolecularly, and number-average molecular weight is between 20000～200000 scopes.The epoxy group content of epoxidized polyisoprene (c-1) and epoxidized polybutadiene (c-2) is as being lower than 0.15meq/g, then reduce and Resins, epoxy (A) between consistency, thereby in the hardening thing that draws in the composition epoxy resin sclerosis, oozing out of epoxidized polyisoprene (c-1) or epoxidized polybutadiene (c-2) becomes obvious.And its content is as surpassing 2meq/g, and the cross-linking set of epoxidized polyisoprene in hardening thing (c-1) or epoxidized polybutadiene (c-2) is apart from shortening, thereby causes the caoutchouc elasticity forfeiture, and fragility increases.
In addition, the number-average molecular weight of epoxidized polyisoprene (c-1) be lower than 15000 or epoxidized polybutadiene (c-2) number-average molecular weight be lower than at 20000 o'clock, in the hardening thing after the composition epoxy resin sclerosis, oozing out of epoxidized polyisoprene (c-1) or epoxidized polybutadiene (c-2) becomes obvious.And the number-average molecular weight of epoxidized polyisoprene (c-1) or epoxidized polybutadiene (c-2) is in 200000 when above, and then viscosity increases, and adds to the difficulties for the modulating epoxy resin composition.
Number-average molecular weight in this specification sheets refers to the number-average molecular weight of measuring by gel permeation chromatography (GPC) that is converted into polystyrene.
The combined amount of epoxidized polyisoprene (c-1) or epoxidized polybutadiene (c-2) is with respect to 100 mass parts Resins, epoxy (A), preferred 1～40 mass parts, most preferably 5～25 mass parts.When the combined amount of epoxidized polyisoprene (c-1) or epoxidized polybutadiene (c-2) is lower than 1 mass parts with respect to 100 mass parts Resins, epoxy (A), in the present invention's the hardening thing of composition epoxy resin after sclerosis, might cause the snappiness deficiency; And when greater than 40 mass parts, in the hardening thing of composition epoxy resin after sclerosis, oozing out of epoxidized polyisoprene (c-1) or epoxidized polybutadiene (c-2) taken place.
As the polyisoprene of epoxidized polyisoprene (c-1) raw material, and the manufacture method of the raw material-polyhutadiene of epoxidized polybutadiene (c-2) is not particularly limited, and can use such as methods such as anionic polymerization, Ziegler catalysis methods.When using anionic polymerization, in the inert gas atmospheres such as argon, nitrogen, for example ethane, hexahydroaniline, benzene, triolefin etc. are in the inactive solvent of polyreaction, with basic metals such as sodium Metal 99.5, metallic lithiums; Alkyl lithium compounds such as lithium methide, lithium ethide, n-butyllithium, s-butyllithium etc. use as initiator, usually, carry out polyreaction in polymerization temperature-100～100 ℃, 0.01～200 hour scope of polymerization time.
Secondly, the two keys of charcoal-charcoal in the molecular chain of the polyisoprene that drawn or polyhutadiene are carried out epoxidation, draw epoxidized polyisoprene (c-1) or epoxidized polybutadiene (c-2).Epoxidizing method there is no special qualification, for example (i) method (please refer to the spy and open flat 8-134135 communique) of handling with peracid such as peracetic acid; The (ii) method of handling with molybdenum complex and t-tertbutyl peroxide (please refer to j.chem.soc., chem..commun., 1686 pages (1989)); The method (please refer to j.polym.sci., c, 28 volumes, 286 pages (1990)) of (iii) using tungstic acid catalyst and hydrogen peroxide to handle;
The (iv) tungsten compound of choosing in ammonium tungstate or the phospho-wolframic acid, 4 grades of ammonium salts, phosphoric acid, the method that aqueous hydrogen peroxide solution is handled (please refer to the spy and open the 2002-249516 communique).
Under the prerequisite that does not influence the object of the invention and effect, can add hardening accelerator and/or mineral filler in the present invention's the composition epoxy resin.
Triphenyl phosphine, three (dimethoxy benzene) phosphine, phosphniline classes such as dibutyl phosphniline are arranged as hardening accelerator is specifiable; Amines such as diethylenetriamine, Triethylenetetramine (TETA), four ethylidene, five ammoniums.When adding these hardening accelerators, as long as its addition belongs within the scope of the amount that reaches the sclerosis facilitation effect, its amount is not particularly limited, with respect to the total quality of the Resins, epoxy (A) in the present invention's the epoxy resin component composition, stiffening agent (B), epoxidized polyisoprene (c-1) or epoxidized polybutadiene (c-2), be within 0.005～2 mass percent scope for good.
Mineral filler can be selected: for example fused silica, crystalline silica, glass, aluminum oxide etc.Add these mineral fillers, can improve water absorbability, thermal conductivity and the mechanical strength of the present invention's composition epoxy resin.And, by adding mineral filler, can reduce Resins, epoxy even linear expansivity that be higher than metal, like this when being used for semiconductor packages, the crack that temperature variation causes in the time of can reducing moulding, phenomenon such as peel off.When adding mineral filler, its amount there is not strict restriction, can change its add-on according to purposes, for example, when the present invention's composition epoxy resin is used in semiconductor packages, add the total quality of the addition of mineral filler with respect to the Resins, epoxy (A), stiffening agent (B), epoxidized polyisoprene (c-1) or the epoxidized polybutadiene (c-2) that constitute epoxy resin component, it is good being in 7～90 mass percents.
The present invention's composition epoxy resin, add Resins, epoxy (A), stiffening agent (B), epoxidized polyisoprene (c-1) or epoxidized polybutadiene (c-2), as required hardening accelerator, mineral filler homodisperse are mixed then, and be not particularly limited for its compound method.For example the above-mentioned materials with certain use level carries out thorough mixing with agitator, carries out the fusion kneading with mixing drum, squeezer then, cools off at last and method such as pulverizing.In addition, the forming method the when composition epoxy resin among the present invention is made forming composition by heat embrittlement, the general employing passed the film method of forming, also available jet forming method, compressed moulding method.
Composition epoxy resin among the present invention has excellent thermotolerance, and has reduced internal stress.Be for example both to have kept flexural strength, therefore the material that has low elastic modulus so again can be applicable to electronic component materials such as semiconductor sealing material, purposes such as caking agent.
Below, the present invention is described in detail by embodiment, but the present invention not merely is defined in embodiment.In addition, the characteristic (physicals) of the composition epoxy resin in each embodiment and the comparative example has been carried out following evaluation.
(a) fracture flexural strength, elasticity of flexure modulus
In the composition epoxy resin that in aftermentioned embodiment and comparative example, obtains, make the test film of vertical 100mm * horizontal 10mm * thick 3mm, measure according to JIS K 6911 at room temperature.
(b) dynamic viscoelastic
In the composition epoxy resin that in aftermentioned embodiment and comparative example, obtains, take the test film of vertical 50mm * horizontal 5mm * thick 0.5mm, use RHEOVIBRON-DDV-III (manufacturing of (strain) オ リ オ Application テ Star Network), at frequency (FREQUENCY) 11Hz, measure under 30～250 ℃ of condition determinations of temperature range, the temperature dependency degree of storage modulus of elasticity (E ') is measured.
Below, each used in embodiment and comparative example composition is listed in detail.
Resins, epoxy (A)
EPICLON N-665 (trade(brand)name): cresols-phenolic resin varnish type epoxy resin (big Japanese イ Application キ chemical industry Co., Ltd. make epoxy valency 4.7～5.0meq/g, 64～72 ℃ of softening temperatures)
Stiffening agent (B)
Off エ ノ ラ イ ト TD-2131 (trade(brand)name): phenol-phenolic resin varnish type epoxy resin (big Japanese イ Application キ chemical industry Co., Ltd. make hydrogen-oxygen base price 9.7meq/g, 80 ± 2 ℃ of softening temperatures).
Epoxidized polyisoprene (c-1)
Reference example 1
(1) through in 5 liters of autoclaves of nitrogen replacement, adds hexane 2000g and n-butyllithium 2.5g, be heated to 50 ℃ then, add isoprene 650g again, and carry out 3 hours polyreactions.Reaction solution is taken a sample, use the gpc analysis resultant, record polyisoprene, it is converted into the number-average molecular weight (Mn)=27000 of polystyrene, the ratio (Mw/Mn)=1.16 of weight-average molecular weight (Mw) and number-average molecular weight (Mn).
(2) the polymeric reaction solution 300g that obtains in above-mentioned (1) is washed with water after, the capacity of joining is in 1 liter the autoclave, add hydrogen peroxide 1.4g, 90g water and the tri-n-octyl methyl ammonium chloride 0.03g of phospho-wolframic acid 0.02g, phosphoric acid 0.02g, 35 mass percents, reaction is 3 hours in 80 ℃.The reaction solution that obtains is injected methyl alcohol, will filter behind the polymer redeposition, vacuum-drying is 7 hours in 80 ℃, has obtained 70g epoxidized polyisoprene (below, abbreviate e-IR-1 as).E-IR-1 is analyzed with the GPC method, draw Mn=27000, Mw/Mn=1.16.In addition with the about 0.5g of e-IR-1, in 25 ℃, be dissolved into 10ml tetrahydrofuran (THF) (THF), in its solution, add the 0.2N hydrochloric acid THF solution of 10ml and stirred 30 minutes, after reacting with the epoxy group(ing) among the e-IR-1, with the superfluous hydrochloric acid of 0.1N potassium hydroxide-ethanol solution titration (below, this method is called hydrochloric acid back titration method), and to determine the epoxy valency be 0.15meq/g.
Reference example 2
By with reference example 1 it (1) identical operations, after the polyisoprene polymeric solution 300g that draws washed with water, join in the autoclave of 1 liter of capacity, and adding hydrogen peroxide 4.5g, water 90g and the tri-n-octyl methyl ammonium chloride 0.09g of phospho-wolframic acid 0.05g, phosphoric acid 0.05g, 35 mass percents, reaction is 3 hours in 80 ℃.The reaction solution that obtains is injected methyl alcohol, will filter behind the polymer redeposition, vacuum-drying is 7 hours in 80 ℃, has obtained 70g epoxidized polyisoprene (below, abbreviate e-IR-2 as).E-IR-2 is analyzed with the GPC method, draw Mn=27300, Mw/Mn=1.16.In addition, same with reference example 1 they (2), by hydrochloric acid back titration method, the epoxy base price of e-IR-2 to be measured, its value is 0.5meq/g.
Reference example 3
By with reference example 1 it (1) identical operations, after the polyisoprene polymeric reaction solution 300g water flushing that draws, join in the autoclave of 1 liter of capacity, and adding hydrogen peroxide 22g, water 90g and the tri-n-octyl methyl ammonium chloride 0.43g of phospho-wolframic acid 0.27g, phosphoric acid 0.25g, 35 mass percents, reaction is 3 hours in 80 ℃.The reaction solution that obtains is injected methyl alcohol, will filter behind the polymer redeposition, vacuum-drying is 7 hours in 80 ℃, has obtained 70g epoxidized polyisoprene (below, abbreviate e-IR-3 as).E-IR-3 is analyzed with the GPC method, draw Mn=28000, Mw/Mn=1.18.In addition, same with reference example 1 they (2), by hydrochloric acid back titration method, the epoxy valency of e-IR-3 to be measured, its value is 2.4meq/g.
Epoxidized polybutadiene (c-2)
Reference example 4
(1) through in 5 liters of autoclaves of nitrogen replacement, adds hexane 2000g and n-butyllithium 2.5g, be heated to 50 ℃ then, add polyhutadiene 660g again, and carry out 3 hours polyreactions.Reaction solution is taken a sample, use the gpc analysis resultant, record polyisoprene, it is converted into the number-average molecular weight (Mn)=35000 of polystyrene, the ratio (Mw/Mn)=1.02 of weight-average molecular weight (Mw) and number-average molecular weight (Mn).
(2) the polymeric reaction solution 300g that draws in above-mentioned (1) is washed with water after, join in the autoclave of 1 liter of capacity, and adding hydrogen peroxide 1.4g, water 90g and the tri-n-octyl methyl ammonium chloride 0.06g of phospho-wolframic acid 0.03g, phosphoric acid 0.03g, 35 mass percents, reaction is 3 hours in 80 ℃.The reaction solution that obtains is injected methyl alcohol, filter after making the polymer redeposition, vacuum-drying is 7 hours in 80 ℃, has obtained 70g epoxidized polybutadiene (below, abbreviate e-BR-1 as).The e-BR-1 that obtains is analyzed with the GPC method, draw Mn=35000, Mw/Mn=1.02.In addition, same with reference example 1 they (2), by hydrochloric acid back titration method, the epoxy base price of e-BR-1 to be measured, its value is 0.16meq/g.
Reference example 5
By with reference example 4 they (1) identical operations, after the polymeric reaction solution 300g water flushing with the polyhutadiene that draws, join in the autoclave of 1 liter of capacity, and adding hydrogen peroxide 4.6g, water 90g and the tri-n-octyl methyl ammonium chloride 0.19g of phospho-wolframic acid 0.11g, phosphoric acid 0.11g, 35 mass percents, reaction is 3 hours in 80 ℃.The reaction solution that obtains is injected methyl alcohol, will filter behind the polymer redeposition, vacuum-drying is 7 hours in 80 ℃, has obtained 70g epoxidized polybutadiene (below, abbreviate e-BR-2 as).The e-BR-2 that obtains is analyzed with the GPC method, draw Mn=35300, Mw/Mn=1.02.In addition, same with reference example 1 they (2), by hydrochloric acid back titration method, the epoxy base price of e-BR-2 to be measured, its value is 0.52meq/g.
Embodiment 1
In the metal vessel that has heating unit, whipping appts and thermometer, add the e-IR-1 that draws in the reference example 1 of Resins, epoxy (A) 60 mass parts, stiffening agent 30 mass parts, 9 mass parts, and as hardening accelerator, the triphenyl phosphine that adds 1 mass parts, the fusion kneading is 15 minutes in 110 ℃, has obtained composition epoxy resin.Then the composition epoxy resin that obtains is inserted in the mould, in 180 ℃, carried out 2 minutes compressed moulding and sclerosis.Make the evaluating characteristics test film then, and carried out evaluating characteristics by aforesaid method.Its fracture flexural strength, elasticity of flexure modulus are as shown in table 1.
Embodiment 2
In embodiment 1, except the e-IR-2 with acquisition in the reference example 2,9 mass parts replace outside the e-IR-1, and all the other compositions and amount all are same as embodiment 1 and have obtained composition epoxy resin and carried out evaluating characteristics, and its result is as shown in table 1.
Embodiment 3
In embodiment 1, except the e-BR-1 with acquisition in the reference example 4,9 mass parts replace outside the e-IR-1, and all the other compositions and amount all are same as embodiment 1 and have obtained composition epoxy resin and carried out evaluating characteristics, and its result is as shown in table 1.
In embodiment 1, except the e-BR-2 with acquisition in the reference example 5,9 mass parts replace outside the e-IR-1, and all the other compositions and amount all are same as embodiment 1 and have obtained composition epoxy resin and carried out evaluating characteristics, and its result is as shown in table 1.
Comparative example 1
In embodiment 1, except not adding the e-IR-1, all the other are identical with embodiment 1, have obtained composition epoxy resin and have carried out evaluating characteristics, and its result is as shown in table 1.
Comparative example 2
In embodiment 1, except polyisoprene 9 mass parts with the number-average molecular weight (Mn)=27000 that obtains in the reference example 1 it (1) replace the e-IR-1, all the other are identical with embodiment 1, have obtained composition epoxy resin and have carried out evaluating characteristics, and its result is as shown in table 1.
Comparative example 3
In embodiment 1, except the e-IR-3 with acquisition in the reference example 3,9 mass parts replace outside the e-IR-1, and all the other are identical with embodiment 1, have obtained composition epoxy resin and have carried out evaluating characteristics, and its result is as shown in table 1.
Comparative example 4
In embodiment 1, except the nbr carboxyl terminal with 9 mass parts: (Ube Industries, Ltd produces trade(brand)name " HYCARCT Port リ マ one CTBN1300 * 13 ", Mn=7700, Mw=15600) replace outside the e-IR-1, all the other are identical with embodiment 1, obtained composition epoxy resin and carried out evaluating characteristics, its result is as shown in table 1.
Comparative example 5
In embodiment 1, except the epoxidized polybutadiene with 9 mass parts: (Nippon Oil Co., Ltd produces trade(brand)name " E-1000-8.0 ", Mn=40, Mw=4200, epoxy valency 5.0meq/g) replace outside the e-IR-1, all the other are identical with embodiment 1, obtained composition epoxy resin and carried out evaluating characteristics, its result is as shown in table 1.
Comparative example 6
In embodiment 1, except the epoxidized polybutadiene with 9 mass parts: (Nippon Oil Co., Ltd produces trade(brand)name " E-1000-6.5 ", Mn=120, Mw=9200, epoxy valency 4.1meq/g) replace outside the e-IR-1, all the other are identical with embodiment 1, obtained composition epoxy resin and carried out evaluating characteristics, its result is as shown in table 1.
Comparative example 7
In embodiment 3, except the epoxidized polybutadiene with the number-average molecular weight (Mn)=35000 that obtains in the reference example 4 it (1) of 9 mass parts replaces the e-BR-1, all the other are identical with embodiment 3, have obtained composition epoxy resin and have carried out evaluating characteristics, and its result is as shown in table 1.
Table 1
Constitute each composition ratio of mixture (mass ratio) of composition epoxy resin
Resins, epoxy (A): stiffening agent (B): mixture: trisphenol=60: 30: 9: 1
In addition, the E ' that draws according to Measurement of Dynamic Viscoelasticity measures curve, as shown in drawings.
As shown in table 1, the composition epoxy resin among the present invention adds epoxidized polyisoprene (c-1) or epoxidized polybutadiene (c-2) with specified range epoxy valency.The hardening thing that obtains from above-mentioned composition epoxy resin (embodiment 1～4) had both improved the fracture flexural strength, had kept the low elasticity pattern again.Promptly have sufficient snappiness, also have very high intensity.
In addition, do not add the composition epoxy resin in the comparative example 1 of epoxidized polyisoprene (c-1) or epoxidized polybutadiene (c-2), its hardening thing fracture flexural strength is low, and elasticity of flexure modulus is higher.This means the hardening thing that draws from the composition epoxy resin of comparative example 1, snappiness is low, the brittleness height.In addition, when interpolation such as unmodified polyisoprene, epoxidized polyisoprene or unmodified polyhutadiene (comparative example 2,3,7) with epoxy valency outside the scope of the invention, though can realize low elastic modulus so, it is not enough that the fracture flexural strength improves.In addition, when adding nbr carboxyl terminal (CTBN) (comparative example 4), can improve the fracture flexural strength, but not reach the requirement of low elastic modulus so.And when interpolation had the polyhutadiene (comparative example 5,6) of the epoxy valency outside the scope among the present invention, its fracture flexural strength and elasticity of flexure modulus all obtained the characteristic that meets the demands.
In addition, in Fig. 1～Fig. 8, the temperature when E ' beginning sharply descends can be regarded the beginning softening temperature of the hardening thing that obtains from the composition epoxy resin of each embodiment and comparative example as, i.e. the thermotolerance index.
As Fig. 1, shown in Figure 5, in the present invention's the composition epoxy resin, add epoxidized polyisoprene (c-1) or epoxidized polybutadiene (c-2) with specified range epoxy valency, hardening thing (embodiment 1～4) from above-mentioned composition epoxy resin acquisition, compare with the hardening thing that obtains in the composition epoxy resin that does not add epoxidized polyisoprene (c-1) or epoxidized polybutadiene (c-2) of comparative example 1, E ' maintains near the level 150 ℃ equally.As seen do not lose its thermotolerance.
As Fig. 2 and shown in Figure 6, when add unmodified polyisoprene, when having the epoxidized polyisoprene of the epoxy valency outside the present invention's the scope or unmodified polyhutadiene (comparative example 2,3,7), E ' also can maintain near 150 ℃.The hardening thing that obtains in these compositions, as mentioned above, though can reach the requirement of low elastic modulus so, the raising of fracture flexural strength is insufficient.
By contrast, as Fig. 3, Fig. 4, Fig. 7, shown in Figure 8, add CTBN (comparative example 4) or have the hardening thing of the composition epoxy resin of the epoxidized polybutadiene (comparative example 5,6) of epoxy valency outside the present invention's the specialized range, compare with the hardening thing that the composition epoxy resin of embodiment 1 and embodiment 3 draws, E ' begins to reduce when lesser temps, as seen its poor heat resistance.
As mentioned above, the present invention can be alleviated internal stress not reducing under the stable on heating prerequisite, thereby can obtain to have abundant flexile epoxy resin combination.
Claims (1)
1, a kind of composition epoxy resin comprises:
(A) Resins, epoxy;
(B) stiffening agent; And,
(C) comprise 0.15～2meq/g epoxy group(ing) at intramolecularly, and number-average molecular weight between 15000～200000 scopes epoxidized polyisoprene (c-1) or contain 0.15～2meq/g epoxy group(ing) at intramolecularly, and the epoxidized polybutadiene (c-2) of number-average molecular weight between 20000～200000.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32764/2003 | 2003-02-10 | ||
| JP2003032764A JP4098107B2 (en) | 2003-02-10 | 2003-02-10 | Thermosetting resin composition |
| JP32765/2003 | 2003-02-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1745138A true CN1745138A (en) | 2006-03-08 |
| CN1329446C CN1329446C (en) | 2007-08-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801095776A Expired - Fee Related CN1329446C (en) | 2003-02-10 | 2003-12-25 | Epoxy resin composition |
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| Country | Link |
|---|---|
| JP (1) | JP4098107B2 (en) |
| CN (1) | CN1329446C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781443B (en) * | 2009-01-20 | 2012-03-28 | 财团法人工业技术研究院 | Thermosetting solder masking film composite |
| CN107001490A (en) * | 2014-12-25 | 2017-08-01 | 株式会社可乐丽 | Modified liquid diene series rubber and the resin combination for including the modified liquid diene series rubber |
| WO2019127172A1 (en) * | 2017-12-28 | 2019-07-04 | Henkel Ag & Co. Kgaa | Epoxy based composition |
| CN111051364A (en) * | 2017-08-18 | 2020-04-21 | 飞纳技术有限公司 | Epoxidized polyfarnesenes and methods for making the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI627218B (en) | 2013-03-29 | 2018-06-21 | 日商可樂麗股份有限公司 | Polymer, method for producing the same, and resin composition containing the polymer |
| KR102159419B1 (en) | 2013-09-30 | 2020-09-24 | 주식회사 쿠라레 | Resin composition, cured product obtained by curing same, and optical adhesive comprising resin composition |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL260292A (en) * | 1960-01-22 | |||
| JPS57180626A (en) * | 1981-04-30 | 1982-11-06 | Hitachi Ltd | Thermosetting resin composition |
| JPS6162511A (en) * | 1984-09-05 | 1986-03-31 | Sumitomo Bakelite Co Ltd | Epoxy resin composition |
| US5399626A (en) * | 1991-04-29 | 1995-03-21 | Shell Oil Company | Viscous conjugated diene block copolymers |
| US5332783A (en) * | 1993-07-12 | 1994-07-26 | Shell Oil Company | Compatible blends of epoxy resins and epoxidized polydienes |
| BR9507367A (en) * | 1994-04-15 | 1997-09-23 | Shell Int Research | Composition of stiffened epoxy resin use of the epoxidized low viscosity polydiene polymer composition and use thereof |
| US5478885A (en) * | 1994-04-15 | 1995-12-26 | Shell Oil Company | Composition of epoxy resin, epoxidized block polydiene and curing agent |
| US5499409A (en) * | 1994-07-18 | 1996-03-19 | Shell Oil Company | Epoxidized polydiene block polymer with epoxy resins |
| JP2001064483A (en) * | 1999-08-27 | 2001-03-13 | Sumitomo Bakelite Co Ltd | Sealing material composition for liquid crystal display device |
| JP2001123050A (en) * | 1999-10-29 | 2001-05-08 | Nippon Mitsubishi Oil Corp | Epoxy resin composition and semiconductor device |
-
2003
- 2003-02-10 JP JP2003032764A patent/JP4098107B2/en not_active Expired - Fee Related
- 2003-12-25 CN CNB2003801095776A patent/CN1329446C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781443B (en) * | 2009-01-20 | 2012-03-28 | 财团法人工业技术研究院 | Thermosetting solder masking film composite |
| CN107001490A (en) * | 2014-12-25 | 2017-08-01 | 株式会社可乐丽 | Modified liquid diene series rubber and the resin combination for including the modified liquid diene series rubber |
| CN107001490B (en) * | 2014-12-25 | 2019-03-12 | 株式会社可乐丽 | Modified liquid diene series rubber and resin combination comprising the modified liquid diene series rubber |
| US10414834B2 (en) | 2014-12-25 | 2019-09-17 | Kuraray Co., Ltd. | Modified liquid diene rubber and resin composition containing modified liquid diene rubber |
| CN111051364A (en) * | 2017-08-18 | 2020-04-21 | 飞纳技术有限公司 | Epoxidized polyfarnesenes and methods for making the same |
| CN111051364B (en) * | 2017-08-18 | 2023-03-14 | 飞纳技术有限公司 | Epoxidized polyfarnesenes and methods for making the same |
| WO2019127172A1 (en) * | 2017-12-28 | 2019-07-04 | Henkel Ag & Co. Kgaa | Epoxy based composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1329446C (en) | 2007-08-01 |
| JP2004244441A (en) | 2004-09-02 |
| JP4098107B2 (en) | 2008-06-11 |
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