CN101098906A - Epoxy resin composition for encapsulating semiconductor chip and semiconductor device - Google Patents
Epoxy resin composition for encapsulating semiconductor chip and semiconductor device Download PDFInfo
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- CN101098906A CN101098906A CNA2006800018738A CN200680001873A CN101098906A CN 101098906 A CN101098906 A CN 101098906A CN A2006800018738 A CNA2006800018738 A CN A2006800018738A CN 200680001873 A CN200680001873 A CN 200680001873A CN 101098906 A CN101098906 A CN 101098906A
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Abstract
Disclosed is an epoxy resin composition for semiconductor encapsulation essentially containing an epoxy resin (A), a phenol resin (B), a curing accelerator (C), an inorganic filler (D), a releasing agent (E), a silane coupling agent (F) and a compound (G) wherein two or more adjacent carbon atoms constituting an aromatic ring are respectively bonded with a hydroxyl group. At least one of the epoxy resin (A) and the phenol resin (B) contains a novolac resin having a biphenylene skeleton in the main chain. The releasing agent (E) is composed of one or more compounds selected from the group consisting of oxidized polyethylene waxes (E1), fatty acid triglycerides (E2) and oxidized paraffin waxes (E3). Not less than 0.01% by weight and not more than 1% by weight of the component (E) and not less than 0.01% by weight and not more than 1% by weight of the component (G) are contained in the total epoxy resin composition.
Description
Technical field
The semiconducter device that the present invention relates to be used for the composition epoxy resin of packaged semiconductor and use it.The present invention be more particularly directed to have the composition epoxy resin that is used for packaged semiconductor that characteristics such as flowability, release property, continuously shaped property for example are improved, and the semiconducter device that uses this composition epoxy resin, it has improved reflux-resisting welded and meets hot (resistance to reflow soldering heat).
Background technology
In recent years, the demand of the electron device of advanced, lighting, slimming and miniaturization is just constantly increased, make the integrated level and the surperficial installability that improve semi-conductor chip.In view of the situation, at present more and more stricter to the requirement of the composition epoxy resin that is used for packaged semiconductor.Particularly, because the degree that reduces of semiconducter device thickness improves, may produce stress owing to the incomplete demoulding of solidifying product on metal die of composition epoxy resin.Such stress cracks and/or is reduced in the cohesive force on the interface between cured resin and semi-conductor chip on may the semi-conductor chip in semiconducter device.Therefore, need improve release property, make moulding product (solidifying product) be convenient to deviate from from metal die, this moulding product is to be obtained by composition epoxy resin.And then, consider productivity, require to allow the continuously shaped character (in other words, requiring continuously shaped property exactly) of moulding product.
In addition, because environmental pressure is serious problems, the type of scolder changes lead-free solder into from solder containing pb.When using lead-free solder, the used temperature of weldprocedure is higher than the temperature of using solder containing pb, therefore because the evaporation of the water in the semiconducter device can cause producing higher stress.Compare with routine techniques, moulding product reflux-resisting welded connects the hot more serious problem that becomes.
Therefore, produced that various improvement are reflux-resisting welded to connect hot proposal.For example proposed a kind of containing and composition epoxy resin (seeing patent document 1 and patent document 2) than the mineral filler blended xenyl Resins, epoxy of high filler loading capacity, this xenyl Resins, epoxy is low viscous epoxy resin.Because such composition epoxy resin contains the mineral filler than high filler loading capacity, therefore its flowability reduces.Therefore, moulding product reflux-resisting welded connects hot and is used for having a trade-off relation between the flowability of Resins, epoxy of packaged semiconductor.
Therefore, need have and improve the composition epoxy resin that characteristics such as flowability, release property, continuously shaped property are used for encapsulated semiconductor device, in addition, the solidifying product of composition epoxy resin need for example improve the reflux-resisting welded characteristics such as hot that connect, and also needs to have the semiconducter device that the semi-conductor chip of this composition epoxy resin forms by encapsulation.
Patent document 1 Japanese kokai publication hei 5-131486 communique (the 1st～9 page)
Patent document 2 Japanese kokai publication hei 8-253555 communiques (the 2nd～9 page)
Summary of the invention
Consider aforesaid situation, and as purpose of the present invention, the invention provides the composition epoxy resin that is used for packaged semiconductor, said composition has flowability, release property, continuously shaped property of improvement etc., and in addition, the solidifying product of the composition epoxy resin that has improved characteristic is provided, and that has for example improved reflux-resisting weldedly connects hot and the semiconducter device that forms by the semi-conductor chip that uses this composition epoxy resin encapsulation is provided.
According to an aspect of the present invention, provide:
[1] be used for the composition epoxy resin of packaged semiconductor, it comprises:
(A) Resins, epoxy;
(B) resol;
(C) curing catalyst;
(D) mineral filler;
(E) releasing agent;
(F) silane coupling agent; With
(G) a kind of compound, it has hydroxyl aromatic ring, and the two or more adjacent carbon atom of each hydroxyl and the difference that constitutes aromatic ring combines,
At least a containing in wherein said (A) Resins, epoxy and described (B) resol by the represented resin of following general formula (1):
(wherein a plurality of R are identical or different, and representative is selected from the group of being made up of hydrogen atom and the alkyl with 1～4 carbon; X represents glycidyl ether or hydroxyl; And n represents a mean value, and its numerical value is the positive number in 1～3 scope),
Wherein said (E) releasing agent comprises that one or more are selected from by (E1) oxidized polyethlene wax, (E2) triglyceride and (E3) compound of the group formed of oxidized petroleum wax.And
The content of wherein said (E) releasing agent is the 0.01wt%～1wt% of total epoxy composition, comprises two endpoint values, and the content of described (G) compound is the 0.01wt%～1wt% of total epoxy composition, comprises two endpoint values.
[2] composition epoxy resin that is used for packaged semiconductor described in [1], wherein, described (G) compound is represented by following general formula (2):
(wherein among R1 and the R5 is a hydroxyl, and other are the outer substituting groups of hydrogen atom, hydroxyl or hydroxyl-removal, and each independently be hydrogen atom, hydroxyl or hydroxyl-removal substituting group outward for R2, R3 and R4, or R2 and R3 or R3 and R4 unite the formation aromatic ring).
[3] as [1] or [2] the described composition epoxy resin that is used for packaged semiconductor, wherein said (E) releasing agent is (E1) oxidized polyethlene wax.
[4] as [3] the described composition epoxy resin that is used for packaged semiconductor, the dropping point of wherein said (E1) oxidized polyethlene wax is 100 ℃～140 ℃, comprises two endpoint values.
[5] as [3] or [4] the described composition epoxy resin that is used for packaged semiconductor, the median size of wherein said (E1) oxidized polyethlene wax is 20 μ m～70 μ m, comprise two endpoint values, and the content of particle in total (E1) oxidized polyethlene wax that particle diameter is equal to or greater than 106 μ m is equal to or less than 0.1wt%.
[6] as each described composition epoxy resin that is used for packaged semiconductor in [3] to [5], the acid number of wherein said (E1) oxidized polyethlene wax is 10mg KOH/g to 50mg KOH/g, comprises two endpoint values.
[7] as each described composition epoxy resin that is used for packaged semiconductor in [3] to [6], the number-average molecular weight of wherein said (E1) oxidized polyethlene wax is 500～5000, comprises two endpoint values.
[8] as each described composition epoxy resin that is used for packaged semiconductor in [3] to [7], the density of wherein said (E1) oxidized polyethlene wax is 0.94g/cm
3～1.03g/cm
3, comprise two endpoint values.
[9] as each described composition epoxy resin that is used for packaged semiconductor in [3] to [8], wherein said (E1) oxidized polyethlene wax comprises one or more oxide compounds, and this oxide compound is selected from the group that the oxide compound of the oxide compound of the polyethylene wax of producing by the oxide compound of the polyethylene wax by the low-pressure polymerization explained hereafter, by high-pressure polymerization process and high density polyethylene polyethylene polymers is formed.
[10] as [1] or [2] the described composition epoxy resin that is used for packaged semiconductor, wherein said (E) releasing agent is (E2) triglyceride.
[11] as [10] the described composition epoxy resin that is used for packaged semiconductor, the dropping point of wherein said (E2) triglyceride is 70 ℃～120 ℃, comprises two endpoint values.
[12] as [10] or [11] the described composition epoxy resin that is used for packaged semiconductor, the median size of wherein said (E2) triglyceride is 20 μ m～70 μ m, comprise two endpoint values, and the content of particle in total (E2) triglyceride that particle diameter is equal to or greater than 106 μ m is equal to or less than 0.1wt%.
[13] as each described composition epoxy resin that is used for packaged semiconductor in [10] to [12], the acid number of wherein said (E2) triglyceride is 10mg KOH/g to 50mgKOH/g, comprises two endpoint values.
[14] as each described composition epoxy resin that is used for packaged semiconductor in [10] to [13], wherein said (E2) triglyceride is glycerine and three ester cpds with saturated fatty acid of 24～36 carbon atoms.
[15] as [1] or [2] the described composition epoxy resin that is used for packaged semiconductor, wherein said (E) releasing agent is (E3) oxidized petroleum wax.
[16] as [15] the described composition epoxy resin that is used for packaged semiconductor, the softening temperature of wherein said (E3) oxidized petroleum wax is 70 ℃～120 ℃, comprises two endpoint values.
[17] as [15] or [16] the described composition epoxy resin that is used for packaged semiconductor, the median size of wherein said (E3) oxidized petroleum wax is 20 μ m～70 μ m, comprise two endpoint values, and the content of particle in total oxidized petroleum wax that particle diameter is equal to or greater than 106 μ m is equal to or less than 0.1wt%.
[18] as each described composition epoxy resin that is used for packaged semiconductor in [15] to [17], the acid number of wherein said (E3) oxidized petroleum wax is 10mg KOH/g to 50mg KOH/g, comprises two endpoint values.
[19] semiconducter device is with each describedly is used for the composition epoxy resin packaged semiconductor of packaged semiconductor and makes in [1] to [18].
The invention provides and improved for example composition epoxy resin that is used for packaged semiconductor of characteristics such as flowability, release property, continuously shaped property, also provide to have improved for example reflux-resisting weldedly to connect hotly and reduced the solidifying product of the composition epoxy resin of characteristics such as water-absorbent, and provide the semiconducter device that forms by the semi-conductor chip that encapsulates with this composition epoxy resin.
Preferred forms of the present invention
The composition epoxy resin that the present invention is used for packaged semiconductor contains following component (A) to component (G):
(A) Resins, epoxy;
(B) resol;
(C) curing catalyst;
(D) mineral filler;
(E) releasing agent;
(F) silane coupling agent; With
(G) a kind of compound, it has hydroxyl aromatic ring, and the two or more adjacent carbon atom of each hydroxyl and the difference that constitutes aromatic ring combines.
And, being used for the composition epoxy resin of packaged semiconductor in the present invention, aforementioned (A) Resins, epoxy and aforementioned (B) resol satisfy and require (i) in (iii) each in the following general formula (1):
(i) aforementioned (A) Resins, epoxy contains the Resins, epoxy with glycidyl ether of being represented by X in the following general formula (1);
(ii) aforementioned (B) resol contains the resol with hydroxyl of being represented by X in the following general formula (1); And
(iii) satisfy above-mentioned requirements (i) and (ii) simultaneously,
(wherein, in above-mentioned general formula (1), a plurality of R are identical or different, and representative is selected from the functional group of the group of being made up of hydrogen atom and the alkyl with 1～4 carbon, and X represents glycidyl ether or hydroxyl; And n represents a mean value, and its numerical value is the positive number in 1～3 scope),
In addition, aforementioned (E) releasing agent comprises that one or more are selected from by (E1) oxidized polyethlene wax, (E2) triglyceride and (E3) compound of the group formed of oxidized petroleum wax.And the content of aforementioned (E) releasing agent is the 0.01wt%～1wt% of total epoxy composition, comprises two endpoint values, and the content of aforementioned (G) compound is the 0.01wt%～1wt% of total epoxy composition, comprises two endpoint values.
The composition epoxy resin that is used for packaged semiconductor of the present invention has above-mentioned prescription, therefore this composition epoxy resin has flowability, release property and the continuously shaped property of improvement, it is the important factor of carrying out semiconductor die package technology, and in addition, the solidifying product of composition epoxy resin has the characteristic of having improved, and that has for example improved reflux-resisting weldedly connects hot, the water-absorbent and the stress that have reduced and improved bounding force with hardware etc.
Describe the composition epoxy resin (back is called " composition epoxy resin ") that is used for packaged semiconductor of the present invention below in detail.
＜(A) Resins, epoxy 〉
(A) Resins, epoxy that the present invention uses preferably contains the Resins, epoxy by following general formula (a) expression, the above-mentioned general formula (1) when it is equivalent to X and is glycidyl ether
(wherein, a plurality of R are identical or different, and representative is selected from by hydrogen atom and the functional group with group that the alkyl of 1～4 carbon forms, and n represents a mean value, and its numerical value is the interior positive number of 1～3 scope).In general formula (a), more preferably each R is a hydrogen atom.
Be rich in hydrophobic structure in the molecular resin skeleton of the Resins, epoxy of above-mentioned general formula (a) expression.Therefore the solidifying product that is obtained by the composition epoxy resin that contains this Resins, epoxy shows low water absorbable, the heavily stressed generation of therefore having avoided the water evaporation in solder reflow process to be caused.And, because the cross-linking density in the solidifying product is lower, make in the coefficient of elasticity that is not less than under the temperature of glass transition temp also lowlyer, reduced the thermal stresses that in weldprocedure, forms, therefore improved reflux-resisting welded connect hot.
In the present invention, only otherwise destroy the beneficial effect that Resins, epoxy obtained that uses above-mentioned general formula (1) expression, also can additionally use other Resins, epoxy.Other Resins, epoxy generally comprise, for example: novolac epoxy resin, cresol-novolak epoxy resin, biphenyl type epoxy resin, bisphenol-type epoxy resin, Stilbene type Resins, epoxy, tris-phenol type Resins, epoxy, phenol aralkyl-type epoxy resin (having the phenylene skeleton), naphthol type epoxy resin, alkyl-modified tris-phenol type Resins, epoxy, the Resins, epoxy that contains the triazine parent nucleus, dicyclic pentylene modified phenol type Resins, epoxy etc.Can use or unite the Resins, epoxy that uses other types separately.
When above-mentioned (A) Resins, epoxy does not use the Resins, epoxy of above-mentioned general formula (a), can alternatively use above-mentioned other Resins, epoxy.In addition, when not using the Resins, epoxy of above-mentioned general formula (a), the resol that preferably uses general formula discussed below (b) expression is as above-mentioned (B) resol.
＜(B) resol 〉
(B) resol that the present invention uses preferably contains the resol by following general formula (b) expression, the above-mentioned general formula (1) when it is equivalent to X and is hydroxyl:
(wherein, a plurality of R are identical or different, and representative is selected from the functional group of the group of being made up of hydrogen atom and the alkyl with 1～4 carbon; And n represents a mean value, and its numerical value is the positive number in 1～3 scope).In general formula (b), more preferably each R is a hydrogen atom.
Be rich in hydrophobic structure in the molecular resin skeleton of the resol of above-mentioned general formula (b) expression.Therefore the solidifying product that is obtained by the composition epoxy resin that contains this resol shows low water absorbable, has therefore avoided the heavily stressed generation that the water evaporation is caused in solder reflow process.And, because the cross-linking density in the solidifying product molecule is lower, make in the coefficient of elasticity that is not less than under the temperature of glass transition temp also lowlyer, reduced the thermal stresses that in weldprocedure, forms, therefore improved reflux-resisting welded connect hot.
In the present invention, only otherwise destroy the beneficial effect that resol obtained that uses above-mentioned general formula (b) expression, also can additionally use other resol.Other resol generally comprise, for example: lacquer resins, cresol-novolak resin, tris-phenol resin, terpene-resin modified phenol resin, dicyclic pentylene modified resol, phenol aralkyl resin (having the phenylene skeleton), naphthols aralkyl resin etc.Can use or unite the resol that uses other types separately.
When above-mentioned (B) resol does not use the resol of above-mentioned general formula (b), can alternatively use above-mentioned other resol.In addition, when not using the resol of above-mentioned general formula (b), the Resins, epoxy that preferably uses general formula (a) expression is as above-mentioned (A) Resins, epoxy.
The equivalence ratio of the phenolic hydroxyl in the epoxy group(ing) that comprises in the total epoxy of the present invention and all resol is preferably 0.5～2, comprises two endpoint values, and more preferably 0.7～1.5, comprise two endpoint values.When composition epoxy resin was in above-mentioned scope, composition epoxy resin had the curability of improvement, and was had the moisture resistance of improvement by the solidifying product that said composition obtained.
＜(C) curing catalyst 〉
Can catalysis Resins, epoxy and resol between the compound of crosslinking reaction can be used as the present invention (C) curing catalyst and use.(C) curing catalyst generally comprises but is not limited to, for example: tributylamine, 1, the amine compound of 8-diazabicyclo (5,4,0) undecylene-7 grade; The organic phosphine compound of triphenylphosphine, tetraphenyl boron tetraphenylphosphoniphenolate etc.; The imidazolium compounds of glyoxal ethyline etc.These curing catalysts both can use or unite use separately.
＜(D) mineral filler 〉
(D) mineral filler of using among the present invention generally comprises, for example: fused quartz, crystal quartz, aluminum oxide, silicon nitride, aluminium nitride etc.When the mineral filler of the special high filler loading capacity of needs, preferably use fused quartz.
Ground or spheric fused quartz all can use, and the preferred main spherical fused quartz that uses is with loading level that increases fused quartz and the increase that suppresses the melt viscosity of composition epoxy resin.In order further to strengthen the loading level of spherical quartz, preferably regulate spherical quartz and make it have wideer size distribution.
＜(E) releasing agent 〉
(E) releasing agent that uses among the present invention generally comprises, for example: (E1) oxidized polyethlene wax, (E2) triglyceride and (E3) oxidized petroleum wax.These releasing agents can use separately, or unite use.
Releasing agent is described below successively.
((E1) oxidized polyethlene wax)
Because (E1) oxidized polyethlene wax generally has the polar group is made up of carboxylic acid etc. and by growing the non-polar group that carbochain is formed, in moulding process, polar group towards a side of the solidifying product of resin and non-polar group towards a side of metal die, show the function of releasing agent thus.
The content of oxidized polyethlene wax in (E1) composition epoxy resin can be 0.01wt%～1wt%, comprises two endpoint values, and preferred 0.03wt%～0.5wt%, comprises two endpoint values.The oxidized polyethlene wax that contains in the above-mentioned scope can be improved the release property of solidifying product in metal die.Therefore and such wax content can improve the cohesiveness with the lead frame element, can avoid separating of solidifying product and lead frame in the welding procedure.In addition, can also reduce the stain on the metal die that causes in the moulding process and/or the deterioration of solidifying product outward appearance.
(E1) oxidized polyethlene wax generally comprise oxide compound by the polyethylene wax of low-pressure polymerization explained hereafter, the oxide compound of the polyethylene wax produced by high-pressure polymerization process and the oxide compound of high density polyethylene polyethylene polymers.Wherein, more preferably use high density polyethylene polyethylene polymers.Use can be used or unite to oxidized polyethlene wax separately.
The characteristic of (E1) oxidized polyethlene wax will be described below successively: (1-1) dropping point; (1-2) acid number; (1-3) number-average molecular weight; (1-4) density; (1-5) median size; (1-6) particle diameter is not less than the particulate content of 106 μ m.
(1-1) dropping point
(E1) dropping point of oxidized polyethlene wax is 100 ℃～140 ℃, comprises two endpoint values, preferred 110 ℃～130 ℃, comprises two endpoint values.Can measure dropping point by method according to ASTM D127.Particularly, measure the temperature of the fusing wax that at first drips from the metal needle point.In the example below, can measure by similar method.
Dropping point in above-mentioned scope can improve the thermostability of (E1) oxidized polyethlene wax, thereby avoids (E1) oxidized polyethlene wax pre-burning in moulding process (burn-in).Therefore, solidifying product shows the release property that has improved on metal die, and the continuously shaped property of having improved.And the dropping point in above-mentioned scope makes that (E1) oxidized polyethlene wax enough melts in the solidification process of composition epoxy resin.This provides the oxidized polyethlene wax that is evenly distributed basically for solidifying product.Therefore, can avoid separation in (E1) on solidifying product surface oxidized polyethlene wax, thereby the stain on the minimizing metal die and the deterioration of solidifying product outward appearance.
(1-2) acid number
(E1) acid number of oxidized polyethlene wax is 10mg KOH/g to 50mg KOH/g, comprises two endpoint values, and preferred 15mg KOH/g to 40mg KOH/g comprises two endpoint values.Acid number influences the consistency of solidifying product.Particularly, in the measurement and 1g wax in the required potassium hydroxide (milligram) of nonesterified lipid acid.In the example below, can measure by similar method.
Acid number in above-mentioned scope provides the preferred consistency of the epoxy matrix material in itself and the solidifying product for (E1) oxidized polyethlene wax.This is avoided (E1) oxidized polyethlene wax being separated from epoxy matrix material.Therefore, avoid separation in (E1) on solidifying product surface oxidized polyethlene wax, thereby the stain on the minimizing metal die and the deterioration of solidifying product outward appearance.
And, exist (E1) oxidized polyethlene wax to improve the release property that solidifying product breaks away from from metal die on the solidifying product surface.On the contrary, (E1) the too high consistency of oxidized polyethlene wax and epoxy matrix material can hinder (E1) oxidized polyethlene wax to be seeped on the solidifying product surface, causes inadequate release property.
(1-3) number-average molecular weight
(E1) number-average molecular weight of oxidized polyethlene wax is 500～5,000, comprises two endpoint values, and is preferred 1,000～4,000, comprises two endpoint values.For example, number-average molecular weight can be calculated by using GPC device (for example HLC-8120 of Tosoh Corporation manufacturing) to carry out the polystyrene conversion.In the example below, can measure it by similar method.
Number-average molecular weight in above-mentioned scope provides the preferred affine state of itself and epoxy matrix material for (E1) oxidized polyethlene wax.Therefore, solidifying product performance is for the release property that has improved on the metal die.On the contrary, (E1) the too high affinity of oxidized polyethlene wax and epoxy matrix material may cause inadequate release property.
On the contrary, low excessively affinity can cause and be separated, and produces the stain on the metal die and the deterioration of solidifying product outward appearance thus.
(1-4) density
(E1) density of oxidized polyethlene wax is 0.94g/cm
3～1.03g/cm
3, comprise two endpoint values, preferred 0.97g/cm
3～0.99g/cm
3, comprise two endpoint values.Density can be according to ASTMD1505 by calculating 20 ℃ of values of measuring gained down in the flotation process.In the example below, can measure by similar method.
Density in above-mentioned scope can be improved the thermostability of (E1) oxidized polyethlene wax, thereby avoids the pre-burning of (E1) oxidized polyethlene wax in the moulding process.Therefore, solidifying product shows the release property that has improved on metal die, and the continuously shaped property of having improved.And the density in above-mentioned scope makes that (E1) oxidized polyethlene wax enough melts in the solidification process of composition epoxy resin.This provides (E1) that be evenly distributed basically oxidized polyethlene wax for solidifying product.Therefore, can avoid separation in (E1) on solidifying product surface oxidized polyethlene wax, thereby the stain on the minimizing metal die and the deterioration of solidifying product outward appearance.
(1-5) median size
(E1) median size of oxidized polyethlene wax is 20 μ m～70 μ m, comprises two endpoint values, and preferred 30 μ m～60 μ m, comprises two endpoint values.For example, median size is by using laser diffraction particle size analyzer (for example SALD-7000 of Shimadzu Corporation manufacturing) to measure.As solvent, is benchmark with weight with water, can measure 50% particle diameter as median size.In the example below, can measure by similar method.
Median size in above-mentioned scope provides the preferred consistency of the epoxy matrix material in itself and the solidifying product for (E1) oxidized polyethlene wax.This makes the solidifying product surface have (E1) oxidized polyethlene wax, improves the release property of solidifying product on metal die thus.
On the contrary, (E1) the too high consistency of oxidized polyethlene wax and epoxy matrix material can hinder the seepage of (E1) oxidized polyethlene wax on the solidifying product surface, causes inadequate release property.
And, because (E1) oxidized polyethlene wax and epoxy matrix material are in preferred consistency state, thereby can avoid the separation in (E1) on solidifying product surface oxidized polyethlene wax, thus the stain on the minimizing metal die and the deterioration of solidifying product outward appearance.
And the median size in above-mentioned scope makes that (E1) oxidized polyethlene wax enough melts in the solidification process of composition epoxy resin.Therefore the composition epoxy resin of gained has the flowability of improvement.
(1-6) particle diameter is not less than the particulate content of 106 μ m
The content of particle in total (E1) oxidized polyethlene wax that particle diameter is not less than 106 μ m preferably is equal to or less than 0.1wt%.For example, this content can be that the standard sieve of 106 μ m is measured by using sieve aperture according to JIS Z 8801.In the example below, can measure by similar method.
Above-mentioned content provides (E1) that be evenly distributed basically oxidized polyethlene wax, therefore, and the stain on the minimizing metal die and the deterioration of solidifying product outward appearance.And such content makes that oxidized polyethlene wax enough melts in the solidification process of composition epoxy resin, therefore improved flowability.
In the present invention, only otherwise destroy and use (E1) beneficial effect that oxidized polyethlene wax obtained, can additionally use the releasing agent of other types.The other types releasing agent generally comprises, for example: natural waxs such as carnauba wax; With the metal-salt of higher fatty acid, Zinic stearas etc. for example.
((E2) triglyceride)
(E2) triglyceride is can be from three esters of glycerine and saturated fatty acid acquisition.In composition epoxy resin, exist (E2) triglyceride to improve the release property of the solidifying product that obtains by said composition.On the contrary, when monoesters that uses glycerine and lipid acid or dibasic acid esters, owing to be subjected to the influence of wherein remaining hydroxyl, can reduce, also connect the hot bad influence that causes reflux-resisting welded from the moisture resistance of the solidifying product of this composition epoxy resin acquisition.
(E2) content of triglyceride in composition epoxy resin is 0.01wt%～1wt%, comprises two endpoint values, and preferred 0.03wt%～0.5wt% comprises two endpoint values.The content of the triglyceride in above-mentioned scope can improve the release property of solidifying product in metal die.Therefore and the content of such wax can improve the cohesiveness of solidifying product and lead frame element, can avoid separating of in weldprocedure solidifying product and lead frame.In addition, can also reduce the stain on the metal die and the deterioration of solidifying product outward appearance.
(E2) triglyceride generally comprises, for example: tricaproin, caprylin, caprin, trilaurin, trimyristin, tripalmitin, Tristearoylglycerol, three eicosanoic acid glyceryl ester, three Glyceryl Behenates, three firewood oleins, three cerinic acid glyceryl ester, three montanic acid glyceryl ester, three myricyl acid glyceryl ester etc.Triglyceride can use or unite use separately.
Wherein, consider the outward appearance of the moulding product of release property that improvement is provided and improvement, preferably use glycerine and triglyceride with saturated fatty acid of 24～36 carbon atoms.And, more preferably use three montanic acid glyceryl ester.In the present invention, the carbon atom number of saturated fatty acid is the carbon atom number of alkyl of saturated fatty acid and the carbon atom number sum of carboxyl.
The characteristic of (E2) triglyceride is described below successively: (2-1) dropping point; (2-2) acid number; (2-3) median size; (2-4) particle diameter is not less than the particulate content of 106 μ m.
(2-1) dropping point
(E2) dropping point of triglyceride is preferably 70 ℃～120 ℃, comprises two endpoint values, and more preferably 80 ℃～110 ℃, comprise two endpoint values.
Dropping point in above-mentioned scope improves the thermostability of (E2) triglyceride, thereby avoids the pre-burning in moulding process of (E2) triglyceride.Therefore, solidifying product shows the release property that has improved on metal die, and the continuously shaped property of having improved.And the dropping point in above-mentioned scope makes that (E2) triglyceride enough melts in the solidification process of composition epoxy resin.This is for providing (E2) that be evenly distributed basically triglyceride in the solidifying product.Therefore, can avoid separation at (E2) on solidifying product surface triglyceride, thereby the stain on the minimizing metal die and the deterioration of solidifying product outward appearance.
(1-2) acid number
(E2) acid number of triglyceride is 10mg KOH/g to 50mg KOH/g, comprises two endpoint values, and preferred 15mg KOH/g to 40mg KOH/g comprises two endpoint values.Acid number influences the consistency of solidifying product.
Acid number in above-mentioned scope provides the preferred consistency of the epoxy matrix material in itself and the solidifying product for (E2) triglyceride.Avoided (E2) triglyceride to be separated from epoxy matrix material.Therefore, avoid separation at (E2) on solidifying product surface triglyceride, thereby the stain on the minimizing metal die and the deterioration of solidifying product outward appearance.
And, exist (E2) triglyceride to improve the release property of solidifying product on metal die on the solidifying product surface.On the contrary, (E2) the too high consistency of triglyceride and epoxy matrix material can hinder the seepage of (E2) triglyceride on the solidifying product surface, causes inadequate release property.
(2-3) median size
(E2) median size of triglyceride is preferably 20 μ m～70 μ m, comprises two endpoint values, and more preferably 30 μ m～60 μ m, comprises two endpoint values.
Median size in above-mentioned scope provides the preferred consistency of the epoxy matrix material in itself and the solidifying product for (E2) triglyceride.This makes the solidifying product surface have (E2) triglyceride, improves the release property of solidifying product on metal die thus.On the contrary, (E2) the too high consistency of triglyceride and epoxy matrix material can hinder the seepage of (E2) triglyceride on the solidifying product surface, causes inadequate release property.
And, because (E2) triglyceride and epoxy matrix material are in preferred consistency state, thereby can avoid separation, thereby reduce the stain on the metal die and the deterioration of solidifying product outward appearance at (E2) on solidifying product surface triglyceride.
And the median size in above-mentioned scope makes that (E2) triglyceride enough melts in the solidification process of composition epoxy resin.Therefore the composition epoxy resin of gained has the flowability of improvement.
(2-4) particle diameter is not less than the particulate content of 106 μ m
And the content of particle in total (E2) triglyceride that particle diameter is not less than 106 μ m preferably is equal to or less than 0.1wt%.
Above-mentioned content is provided at (E2) triglyceride that is evenly distributed basically in the composition epoxy resin, therefore, and the stain on the minimizing metal die and the deterioration of solidifying product outward appearance.And such content makes that triglyceride enough melts in the solidification process of composition epoxy resin, and therefore the flowability of improvement is provided.
The triglyceride that uses among the present invention can obtain by the particle diameter of regulating commercially available triglyceride.In the present invention, only otherwise destroy and use the beneficial effect that triglyceride obtained, can additionally use the releasing agent of other types.The other types releasing agent generally comprises, for example: carnauba wax natural waxs such as (carnauba wax); With the metal-salt of higher fatty acid, Zinic stearas etc. for example.
((E3) oxidized petroleum wax)
(E3) oxidized petroleum wax is by paraffin being carried out the common name of the oxide compound that atmospheric oxidation or sour addition produce.By oxidation carboxyl is incorporated in the paraffin.Paraffin as raw material is to separate with refining by the distilled oil to underpressure distillation to produce, and it at room temperature is a solid state wax.Generally, the carbon atom number in the molecule is 20～40, comprises two endpoint values, and molecular weight is 300～550, comprises two endpoint values.
(E3) content of oxidized petroleum wax in composition epoxy resin is 0.01wt%～1wt%, comprises two endpoint values, and preferred 0.03wt%～0.5wt% comprises two endpoint values.The content of the oxidized petroleum wax in the above-mentioned scope can improve the release property that the solidifying product that obtained by this composition epoxy resin shows on metal die.Therefore and such wax content can improve the cohesiveness of solidifying product and lead frame element, can avoid separating of in weldprocedure solidifying product and lead frame.In addition, can also reduce the stain on the metal die that causes in the moulding process and the deterioration of solidifying product outward appearance.
The characteristic of (E3) oxidized petroleum wax is described below successively: (3-1) softening temperature; (3-2) acid number; (3-3) median size; (3-4) particle diameter is not less than the particulate content of 106 μ m.
(3-1) softening temperature
(E3) softening temperature of oxidized petroleum wax is preferred 70 ℃～120 ℃, comprises two endpoint values, and more preferably 80 ℃～110 ℃, comprise two endpoint values.Can measure softening temperature according to JIS K-2235-5.3.1.
Softening temperature in above-mentioned scope can improve the thermostability of (E3) oxidized petroleum wax, thereby avoids the pre-burning in moulding process of (E3) oxidized petroleum wax.Therefore, solidifying product shows the release property that has improved on metal die, and the continuously shaped property of having improved.And the softening temperature in above-mentioned scope makes that (E3) oxidized petroleum wax enough melts in the solidification process of composition epoxy resin.This provides (E3) that be evenly distributed basically oxidized petroleum wax for solidifying product.Therefore, can avoid separation at (E3) on solidifying product surface oxidized petroleum wax, thereby the stain on the minimizing metal die and the deterioration of solidifying product outward appearance.
(3-2) acid number
(E3) acid number of oxidized petroleum wax is 10mg KOH/g to 50mg KOH/g, comprises two endpoint values, and preferred 15mg KOH/g to 40mg KOH/g comprises two endpoint values.Acid number influences the consistency of solidifying product.
Acid number in above-mentioned scope provides the preferred consistency of the epoxy matrix material in itself and the solidifying product for (E3) oxidized petroleum wax.Avoided (E3) oxidized petroleum wax being separated from epoxy matrix material.Therefore, avoid separation at (E3) on solidifying product surface oxidized petroleum wax, thereby the stain on the minimizing metal die and the deterioration of solidifying product outward appearance.
And, exist (E3) oxidized petroleum wax to improve the release property of solidifying product on metal die on the solidifying product surface.On the contrary, (E3) the too high consistency of oxidized petroleum wax and epoxy matrix material can hinder the seepage of (E3) oxidized petroleum wax on the solidifying product surface, causes inadequate release property.
(3-3) median size
(E3) the preferred 20 μ m of the median size of oxidized petroleum wax～70 μ m comprise two endpoint values, and more preferably 30 μ m～60 μ m, comprise two endpoint values.
Median size in above-mentioned scope provides the preferred consistency of the epoxy matrix material in itself and the solidifying product for (E3) oxidized petroleum wax.This makes the solidifying product surface have (E3) oxidized petroleum wax, improves the release property of solidifying product on metal die thus.On the contrary, (E3) the too high consistency of oxidized petroleum wax and epoxy matrix material can hinder the seepage of paraffin on the solidifying product surface, causes inadequate release property.
And, because (E3) oxidized petroleum wax and epoxy matrix material are in preferred consistency state, thereby can avoid the separation at (E3) on solidifying product surface oxidized petroleum wax, thus the stain on the minimizing metal die and the deterioration of solidifying product outward appearance.
And the median size in above-mentioned scope makes that (E3) oxidized petroleum wax enough melts in the solidification process of composition epoxy resin.Therefore the composition epoxy resin of gained has the flowability of improvement.
(3-4) particle diameter is not less than the particulate content of 106 μ m
The content of particle in total (E3) oxidized petroleum wax that particle diameter is not less than 106 μ m is equal to or less than 0.1wt%.
Above-mentioned content provides (E3) oxidized petroleum wax that is evenly distributed basically composition, therefore, reduces because (E3) stain on the metal die that causes of the separation of oxidized petroleum wax and the deterioration of solidifying product outward appearance.And such content makes that (E3) oxidized petroleum wax enough melts in the solidification process of composition epoxy resin, and therefore the flowability of improvement is provided.
(E3) oxidized petroleum wax that uses among the present invention is to obtain by the particle diameter of regulating commercially available triglyceride.In the present invention, only otherwise destroy and use (E3) beneficial effect that oxidized petroleum wax obtained, can additionally use the releasing agent of other types.The other types releasing agent generally comprises, for example: natural waxs such as carnauba wax; With the metal-salt of higher fatty acid, Zinic stearas etc. for example.
＜(F) silane coupling agent 〉
(F) silane coupling agent among the present invention is not particularly limited, and can use and can react with for example organic constituent such as Resins, epoxy or resol and mineral filler, to improve the compound of boundary strength each other.More specifically, the silane coupling agent among the present invention generally comprises epoxy silane, aminosilane, urea groups silane, hydrosulphonyl silane etc.(F) silane coupling agent can use or unite use separately.(F) silane coupling agent is the main ingredient of composition epoxy resin, by with the synergistic effect of (G) compound of explanation after a while, (F) silane coupling agent can considerably improve the viscosity and the flowability of composition epoxy resin.
The combined amount of (F) silane coupling agent that the present invention is used is the 0.01wt%～1wt% of total epoxy composition, comprise two endpoint values, preferred 0.05wt%～0.8wt% comprises two endpoint values, more preferably 0.1wt%～0.6wt% comprises two endpoint values.The content of the silane coupling agent in above-mentioned scope can be by (G) compound that uses explanation after a while improved effect, and improve reflux-resisting welded in the semiconductor packages and connect hot.And, use the silane coupling agent of content in above-mentioned scope can reduce the water absorbability of composition epoxy resin, connect hot thereby improve reflux-resisting welded in the semiconductor packages.
＜(G) have the compound of hydroxyl aromatic ring, each hydroxyl combines with the two or more adjacent carbon atom that constitutes aromatic ring respectively 〉
The compound (back is called (G) compound) that (G) among the present invention has hydroxyl aromatic ring can be by the represented compound of following general formula (2), and wherein each hydroxyl combines with the two or more adjacent carbon atom that constitutes aromatic ring respectively:
(wherein one of them of R1 and R5 is hydroxyl, and other are the outer substituting groups of hydrogen atom, hydroxyl or hydroxyl-removal, and each independently be hydrogen atom, hydroxyl or hydroxyl-removal substituting group outward for R2, R3 and R4, or R2 and R3 or R3 and R4 can unite the formation aromatic ring).
In above-mentioned general formula (2), can generally be the compound of representing by following general formula (3) by compound with R2 and R3 or R3 and R4 associating formation aromatic ring:
(wherein one of them of R1 and R7 is hydroxyl, and other are the outer substituting groups of hydrogen atom, hydroxyl or hydroxyl-removal, and R2, R3, R4, R5 and R6 each independently be hydrogen atom, hydroxyl or hydroxyl-removal substituting group outward).
(G) compound among the present invention generally comprises, for example: catechol, pyrogallol, gallic acid, gallic acid ester, 1,2-dihydroxy naphthlene, 2,3-dihydroxy naphthlene, and derivative.This compound can use or unite use separately.
Wherein, consider to help mobile control and condition of cure and lower volatility is provided, more preferably use with naphthalene nucleus to be 1 of parent, 2-dihydroxy naphthlene, 2,3-dihydroxy naphthlene and derivative thereof.
(G) combined amount of compound is the 0.01wt%～1wt% of total epoxy composition, comprises two endpoint values, and preferred 0.03wt%～0.8wt% comprises two endpoint values, and more preferably 0.05wt%～0.5wt%, comprises two endpoint values.The content of (G) compound in above-mentioned scope provides viscosity and flowability by the synergistic effect with (F) silane coupling agent.And, the solidifying product of the physical properties that can improve, so this compound can preferably use as composition epoxy resin of the present invention.
Although the composition epoxy resin that is used for packaged semiconductor of the present invention contains aforementioned component (A) to (G) as main ingredient, also can additionally use following other additives as required.Other additives generally comprise, for example: such as fire retardants such as brominated epoxy resin, ANTIMONY TRIOXIDE SB 203 99.8 PCT, phosphorus compound, metal hydroxidess; Such as tinting materials such as carbon black, reddles; Such as silicone oil, silicon rubber, synthetic rubber equal stress depressant; With antioxidants such as bismuth oxide hydrates.
The composition epoxy resin that is used for packaged semiconductor of the present invention produces by mixing aforementioned component (A) to (G).More specifically, component (A) to (G) and other additives are mixed, with adding heat kneading machine, warming mill, forcing machine etc. mixing material is heated and kneading then,, then its pulverizing is obtained compound with making the kneading material cooled by using mixing tank etc.
Electronic sections such as semi-conductor chip can the application of the invention the composition epoxy resin that is used for packaged semiconductor encapsulate, to form semiconducter device.The encapsulation of electronic sections such as semi-conductor chip can be cured with molded compound by common process to be carried out, and described common process is transfer moudling, compression molding, jet molding etc. for example.
Embodiment
The present invention will further be described in detail by following embodiment, be limited to this but be not limited to scope of the present invention.
Composition is represented with weight part
Embodiment A
(embodiment a1)
Embodiment a1 uses following raw material:
*By the Resins, epoxy (phenol aralkyl-type epoxy resin) of following general formula (4) expression [Nippon Kayaku Co., Ltd. is on sale, commodity are called " NC3000P ", softening temperature is 58 ℃, epoxy equivalent (weight) is 273] with biphenylene skeleton
7.36 weight part
(n represents a mean value, and its numerical value is the positive number in 1～3 scope)
*The resol of formula (5) (the phenol aralkyl resin with phenylene skeleton) [Mitsuichemical Co., Ltd. is on sale, and commodity are called " XLC-4L ", and softening temperature is 65 ℃, hydroxyl equivalent is 174]
4.69 weight part
(n represents a mean value, and its numerical value is the positive number in 1～3 scope)
*1,8-diazabicyclo-(5,4,0)-hendecene-7 (back is called " DBU ")
0.20 weight part;
*Fusion spherical quartz (median size 30.0 μ m)
87.00 weight part;
*(dropping point is 120 ℃ to oxidized polyethlene wax No.1, and acid number is 20mg KOH/g, and number-average molecular weight is 2,000, and density is 0.98g/cm
3, median size is 45 μ m, the particulate content that diameter is not less than 106 μ m is 0.0wt%, is the oxide compound of high density polyethylene polyethylene polymers)
0.10 weight part;
*γ-glycidyl propyl trimethoxy silicane
0.30 weight part;
*2,3-dihydroxy naphthlene (reagent)
0.05 weight part;
*Carbon black
0.30 weight part.
After with mixing tank above-mentioned raw materials being mixed, with surface temperature be the twin shaft roller of 95 ℃ and 25 ℃ with blended material kneading 20 times, then, gained is mediated material piece cools off, then its pulverizing is obtained composition epoxy resin.Estimate the characteristic of gained composition epoxy resin in the following method.
The result is displayed in Table 1.
(evaluation method)
Eddy flow: use the metal die of measuring eddy flow according to EMMI-1-66, the temperature of mould is 175 ℃, and injection pressure is 6.9MPa, and be 120 seconds set time.The unit of gained eddy flow is centimetre.
Gold thread deformation rate: transmit automatic molder with low pressure, in the metal die temperature is that 175 ℃, injection pressure are 9.6MPa, set time to be under 70 seconds the condition, make the little profile quad flat package of 160p (Low-Profile Quad Flat Pack, LQFP) (Cu L/F; Package outside size: 24mm * 24mm * 1.4mm-is thick, the chassis size: 8.5mm * 8.5mm chip size: 7.4mm * 7.4mm) moulding.With the 160p LQFP (packaged piece) of soft X-ray fluoroscopic apparatus observation moulding, the gold thread deformation rate of gained is represented with the ratio of (flow)/(gold thread length).Determinating reference is, the gained deformation rate is that " zero " represents less than 5%, deformation rate be not less than 5% for " * " expression poor.
Continuously shaped property: adopt low pressure to transmit automatic molder, in the metal die temperature is that 175 ℃, injection pressure are 9.6MPa, set time to be under 70 seconds the condition, injection is 500 times continuously, make 80p quad flat package (QFP) (CuL/F, it is thick that package outside is of a size of 14mm * 20mm * 2mm-, the chassis is of a size of 6.5mm * 6.5mm, and chip size is 6mm * 6mm) moulding.Determinating reference is, successfully injects continuously 500 times, and it is good for " zero " expression for example not inject problem such as bad fully, and it is poor that all the other be that " * " represents.
The outward appearance of solidify material and the stain on the metal die: after above-mentioned 500 continuous injection moldings are finished, the stain of encapsulation and metal die is estimated by visual inspection.The outward appearance of solidify material and the determinating reference of the stain on the metal die are that flecked is that " * " expression is poor, does not have representing well for " zero " of stain after 500 continuous injection molding is finished.
Reflux-resisting welded connect hot: the post curing treatment that under 175 ℃, the above-mentioned packaged piece that is used to estimate continuously shaped property is carried out 8 hours, leaving the packaged piece of after fixing in 85 ℃, relative humidity is following 168 hours of 85% wet environment, then, the packaged piece that carried out wet treatment is carried out IR reflow treatment (260 ℃, JEDEC-Level 1).Use the microscopic examination packaged piece, calculate cracking frequency [(cracking frequency)=(the encapsulation number of packages of outside crackle takes place)/(always encapsulating number of packages) * 100].Cracking frequency is represented with %.20 packaged pieces have been estimated.In addition, detect semi-conductor chip and composition epoxy resin in the adhesion situation at interface with ultrasonic detection device.20 packaged pieces have been estimated.Reflux-resisting weldedly connect hot determinating reference and be, cracking frequency is 0% and do not have isolating be " zero ", and expression is good, cracks with isolating to be " * ", and it is poor to represent.
(embodiment a2 to a23 and Comparative Examples a1 to a9)
According to each component of mixed of table 1, table 2 and table 3 explanation, use with embodiment a1 similar methods and obtain composition epoxy resin, use with embodiment a1 similar methods it is estimated.The result is presented in table 1, table 2 and the table 3.
The component of using among other embodiment except embodiment a1 will be described below.
*As shown in the formula the resol (phenol aralkyl resin) of (6) [MeiwaPlastic Industries Co., Ltd. is on sale, commodity are called " MEH7851SS ", softening temperature is 67 ℃, hydroxyl equivalent is 203] with biphenylene skeleton
(n represents a mean value, and its numerical value is the positive number in 1～3 scope)
*Resins, epoxy (biphenyl type epoxy resin) as shown in the formula (7);
[Japan epoxy resin Co., Ltd. is on sale, and commodity are called " YX-4000H ", and fusing point is 105 ℃, epoxy equivalent (weight) is 191]
*Oxidized polyethlene wax No.2;
(dropping point is 105 ℃, and acid number is 20mg KOH/g, and number-average molecular weight is 1,100, and density is 0.97g/cm
3, median size is 45 μ m, the particulate content that diameter is not less than 106 μ m is 0.0wt%, the oxide compound of the polyethylene wax that produces for low-pressure polymerization technology).
*Oxidized polyethlene wax No.3;
(dropping point is 135 ℃, and acid number is 25mg KOH/g, and number-average molecular weight is 3,000, and density is 0.99g/cm
3, median size is 40 μ m, the particulate content that diameter is not less than 106 μ m is 0.0wt%, is the oxide compound of high density polyethylene polyethylene polymers).
*Oxidized polyethlene wax No.4;
(dropping point is 110 ℃, and acid number is 12mg KOH/g, and number-average molecular weight is 1,200, and density is 0.97g/cm
3, median size is 50 μ m, the particulate content that diameter is not less than 106 μ m is 0.0wt%, is the oxide compound of high density polyethylene polyethylene polymers).
*Oxidized polyethlene wax No.5;
(dropping point is 110 ℃, and acid number is 45mg KOH/g, and number-average molecular weight is 2,000, density 0.97g/cm
3, median size is 45 μ m, the particulate content that diameter is not less than 106 μ m is 0.0wt%, the oxide compound of the polyethylene wax that produces for high-pressure polymerization process).
*Oxidized polyethlene wax No.6;
(dropping point is 110 ℃, and acid number is 20mg KOH/g, and number-average molecular weight is 750, and density is 0.98g/cm
3, median size is 45 μ m, the particulate content that diameter is not less than 106 μ m is 0.0wt%, is the oxide compound of high density polyethylene polyethylene polymers).
*Oxidized polyethlene wax No.7;
(dropping point is 130 ℃, and acid number is 20mg KOH/g, and number-average molecular weight is 4,500, and density is 0.99g/cm
3, median size is 45 μ m, the particulate content that diameter is not less than 106 μ m is 0.0wt%, the oxide compound of the polyethylene wax that produces for high-pressure polymerization process).
*Oxidized polyethlene wax No.8;
(dropping point is 110 ℃, and acid number is 20mg KOH/g, and number-average molecular weight is 1,100, and density is 0.95g/cm
3, median size is 45 μ m, the particulate content that diameter is not less than 106 μ m is 0.0wt%, the oxide compound of the polyethylene wax that produces for low-pressure polymerization technology).
*Oxidized polyethlene wax No.9;
(dropping point is 110 ℃, and acid number is 25mg KOH/g, and number-average molecular weight is 2,000, and density is 1.02g/cm
3, median size is 45 μ m, the particulate content that diameter is not less than 106 μ m is 0.0wt%, is the oxide compound of high density polyethylene polyethylene polymers).
*Oxidized polyethlene wax No.10;
(dropping point is 120 ℃, and acid number is 20mg KOH/g, and number-average molecular weight is 2,000, and density is 0.98g/cm
3, median size is 30 μ m, the particulate content that diameter is not less than 106 μ m is 0.0wt%, is the oxide compound of high density polyethylene polyethylene polymers).
*Oxidized polyethlene wax No.11;
(dropping point is 120 ℃, and acid number is 20mg KOH/g, and number-average molecular weight is 2000, and density is 0.98g/cm
3, median size is 60 μ m, the particulate content that diameter is not less than 106 μ m is 0.0wt%, is the oxide compound of high density polyethylene polyethylene polymers).
*Polyethylene wax No.1;
(dropping point is 135 ℃, and acid number is 0mg KOH/g, and number-average molecular weight is 5,500, and density is 0.93g/cm
3, the particulate content that median size 45 μ m, diameter are not less than 106 μ m is 0.0wt%, is the polyethylene wax of low-pressure polymerization technology generation).
*Polyethylene wax No.2;
(dropping point is 115 ℃, and acid number is 0mg KOH/g, and number-average molecular weight is 1,800, and density is 0.93g/cm
3, the particulate content that median size 45 μ m, diameter are not less than 106 μ m is 0.0wt%, is the polyethylene wax of high-pressure polymerization process generation).
*1,2-dihydroxy naphthlene (reagent)
*Catechol (reagent)
*Pyrogallol (reagent)
*1,6-dihydroxy naphthlene (reagent)
*Resorcinol (reagent)
Table 1
| Embodiment | |||||||||||||
| a1 | a2 | a3 | a4 | a5 | a6 | a7 | a8 | a9 | a10 | a11 | a12 | a13 | |
| The Resins, epoxy of formula (4) | 7.36 | 6.91 | 6.92 | 6.88 | 6.80 | 6.65 | 6.48 | 6.91 | 6.91 | 6.91 | 6.95 | 6.51 | |
| The Resins, epoxy of formula (7) | 5.84 | ||||||||||||
| The resol of formula (6) | 6.21 | 5.14 | 5.15 | 5.12 | 5.05 | 4.95 | 4.82 | 5.14 | 5.14 | 5.14 | 5.18 | 4.84 | |
| The resol of formula (5) | 4.69 | ||||||||||||
| DBU | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
| The fusion spherical quartz | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 |
| Oxidized polyethlene wax No.1 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.02 | 0.80 |
| γ-glycidyl propyl trimethoxy silicane | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| 2, the 3-dihydroxy naphthlene | 0.05 | 0.05 | 0.05 | 0.03 | 0.10 | 0.25 | 0.50 | 0.80 | 0.05 | 0.05 | |||
| 1, the 2-dihydroxy naphthlene | 0.05 | ||||||||||||
| Catechol | 0.05 | ||||||||||||
| Pyrogallol | 0.05 | ||||||||||||
| Carbon black | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| Eddy flow (cm) | 125 | 105 | 110 | 100 | 120 | 125 | 135 | 150 | 105 | 115 | 120 | 115 | 95 |
| The gold thread deformation rate | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Continuously shaped property | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The stain on metal die surface | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The stain on moulding product surface | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Reflux-resisting welded connect hot | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Table 2
| Embodiment | ||||||||||
| a14 | a15 | a16 | a17 | a18 | a19 | a20 | a21 | a22 | a23 | |
| The Resins, epoxy of formula (4) | 6.91 | 6.91 | 6.91 | 6.91 | 6.91 | 6.91 | 6.91 | 6.91 | 6.91 | 6.91 |
| The resol of formula (6) | 5.14 | 5.14 | 5.14 | 5.14 | 5.14 | 5.14 | 5.14 | 5.14 | 5.14 | 5.14 |
| DBU | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
| The fusion spherical quartz | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 |
| Oxidized polyethlene wax No.2 | 0.10 | |||||||||
| Oxidized polyethlene wax No.3 | 0.10 | |||||||||
| Oxidized polyethlene wax No.4 | 0.10 | |||||||||
| Oxidized polyethlene wax No.5 | 0.10 | |||||||||
| Oxidized polyethlene wax No.6 | 0.10 | |||||||||
| Oxidized polyethlene wax No.7 | 0.10 | |||||||||
| Oxidized polyethlene wax No.8 | 0.10 | |||||||||
| Oxidized polyethlene wax No.9 | 0.10 | |||||||||
| Oxidized polyethlene wax No.10 | 0.10 | |||||||||
| Oxidized polyethlene wax No.11 | 0.10 | |||||||||
| γ-glycidyl propyl trimethoxy silicane | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| 2, the 3-dihydroxy naphthlene | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
| Carbon black | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| Eddy flow (cm) | 115 | 100 | 110 | 110 | 110 | 105 | 110 | 110 | 110 | 105 |
| The gold thread deformation rate | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Continuously shaped property | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The stain on metal die surface | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The stain on moulding product surface | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Reflux-resisting welded connect hot | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Table 3
| Comparative Examples | |||||||||
| a1 | a2 | a3 | a4 | a5 | a6 | a7 | a8 | a9 | |
| The Resins, epoxy of formula (4) | 6.91 | 6.91 | 6.96 | 6.28 | 6.94 | 6.25 | 6.96 | 6.96 | |
| The Resins, epoxy of formula (7) | 6.31 | ||||||||
| The resol of formula (6) | 5.14 | 5.14 | 5.18 | 4.67 | 5.16 | 4.65 | 5.18 | 5.18 | |
| The resol of formula (5) | 5.74 | ||||||||
| DBU | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
| The fusion spherical quartz | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 |
| Oxidized polyethlene wax No.1 | 0.10 | 0.005 | 1.20 | 0.10 | 0.10 | 0.01 | 0.01 | ||
| Polyethylene wax No.1 | 0.10 | ||||||||
| Polyethylene wax No.2 | 0.10 | ||||||||
| γ-glycidyl propyl trimethoxy silicane | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| 2, the 3-dihydroxy naphthlene | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 1.20 | |||
| 1, the 6-dihydroxy naphthlene | 0.05 | ||||||||
| Resorcinol | 0.05 | ||||||||
| Carbon black | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| Eddy flow (cm) | 130 | 105 | 115 | 120 | 90 | 65 | 170 | 75 | 70 |
| The gold thread deformation rate | ○ | ○ | ○ | ○ | ○ | × | ○ | × | × |
| Continuously shaped property | ○ | × | × | × | ○ | × | × | × | × |
| The stain on metal die surface | ○ | × | × | ○ | × | ○ | × | ○ | ○ |
| The stain on moulding product surface | ○ | × | × | ○ | × | ○ | × | ○ | ○ |
| Reflux-resisting welded connect hot | × | × | × | × | × | ○ | ○ | × | × |
In among the embodiment a1 to a23 each, the result of eddy flow and gold thread deformation rate is fine, proves that therefore the composition epoxy resin that is used for packaged semiconductor has the flowability of improvement, and also further the proof compound has the continuously shaped property of improvement.And all do not find stain at moulding product and metal die surface, the moulding product that has therefore proved composition epoxy resin has the release property of improvement to metal die, prove also that this compound has an improvement reflux-resisting welded connect hot.
On the contrary, in the Comparative Examples a1 of the resol of Resins, epoxy that does not use general formula (4) and general formula (6), the gained compound can't obtain low water absorbable and low-stress at high temperature, and this causes the reflux-resisting welded hot deterioration that connects.
In addition, do not having to use among the Comparative Examples a2 and a3 of (E1) oxidized polyethlene wax, continuously shaped property (productivity) worsens, and, the outward appearance of moulding product, the stain on the metal die and reflux-resisting weldedly connect hot deterioration.In the insufficient Comparative Examples a4 of combined amount of (E1) oxidized polyethlene wax, the reduction of release property causes continuously shaped property and reflux-resisting weldedly connects hot deterioration.In the excessive Comparative Examples a5 of the combined amount of (E1) oxidized polyethlene wax, superfluous component is oozed out with the solidifying product surface at the interface element, thereby forms the stain on metal die surface and the stain on moulding product surface.And then, worsen reflux-resisting welded connect hot.
Do not having to add among Comparative Examples a6, the a8 and a9 of (G) compound, the flowability of resin combination reduces, and causes the gold thread deformation rate to worsen.And, in Comparative Examples a8 and a9, also reduced reflux-resisting welded connect hot.In the excessive Comparative Examples a7 of the combined amount of (G) compound, the reduction of the solidified nature of resin combination causes the reduction of continuously shaped property (productivity), and, determined the stain on moulding product surface and the stain on metal die surface.
As mentioned above, the composition epoxy resin that the present invention is used for packaged semiconductor shows excellent balance on mobile, release property and continuously shaped property, and determine to use such resin combination as semiconducter device excellence is provided reflux-resisting welded connect hot.
Embodiment B
(embodiment b1)
In embodiment b1, use following raw material:
*By the Resins, epoxy (phenol aralkyl-type epoxy resin) of above-mentioned formula (4) expression [Nippon Kayaku Co., Ltd. is on sale, commodity are called " NC3000P ", softening temperature is 58 ℃, epoxy equivalent (weight) is 273] with biphenylene skeleton:
7.36 weight part
*The resol of above-mentioned formula (5) (the phenol aralkyl resin with phenylene skeleton) [Mitsuichemical Co., Ltd. is on sale, and commodity are called XLC-4L, and softening temperature is 65 ℃, hydroxyl equivalent is 174]:
4.69 weight part
*DBU：
0.20 weight part;
*Spherical fused quartz (median size 30.0 μ m);
87.00 weight part;
*Three montanic acid glyceryl ester;
(Clariant (Japan) K.K. is on sale, and commodity are by name: " Licolub WE4 ", dropping point are 82 ℃, and acid number is 25mg KOH/g, and median size is 45 μ m, and the particulate content that diameter is not less than 106 μ m is 0.0wt%):
0.10 weight part;
*γ-glycidyl propyl trimethoxy silicane;
0.30 weight part,
*2,3-dihydroxy naphthlene (reagent)
0.05 weight part
*Carbon black
0.30 weight part.
After with mixing tank above-mentioned raw materials being mixed, with surface temperature be the twin shaft roller of 95 ℃ and 25 ℃ with blended material kneading 20 times, then gained is mediated material piece and is cooled off, then its pulverizing is obtained composition epoxy resin.
With estimating the characteristic of gained composition epoxy resin with the embodiment A similar methods.
The result is displayed in Table 4.
(embodiment b2 to b15 and Comparative Examples b1 to b8)
According to each component of mixed of table 4, table 5 and table 6 explanation, use with embodiment b1 similar methods and obtain composition epoxy resin, use with embodiment b1 similar methods it is estimated.The result is presented in table 4, table 5 and the table 6.The component of using among other embodiment except embodiment b1 will be described below.
*Three myricyl acid glyceryl ester;
(dropping point is 95 ℃, and acid number is 30mg KOH/g, and median size is 45 μ m, and the particulate content that diameter is not less than 106 μ m is 0.0wt%)
*Three Glyceryl Behenates
(dropping point is 80 ℃, and acid number is 15mg KOH/g, and median size is 45 μ m, and the particulate content that diameter is not less than 106 μ m is 0.0wt%)
*Glyceryl monostearate
(Riken Vitamin Co., Ltd. is on sale, and commodity are called " Rikemal S-100 ", and dropping point is 65 ℃, and acid number is 2mg KOH/g, median size is 45 μ m, the particulate content that diameter is not less than 106 μ m is 0.0wt%)
Table 4
| Embodiment | ||||||||
| b1 | b2 | b3 | b4 | b5 | b6 | b7 | b8 | |
| The Resins, epoxy of formula (4) | 7.36 | 6.91 | 6.92 | 6.88 | 6.80 | 6.65 | 6.48 | |
| The Resins, epoxy of formula (7) | 5.84 | |||||||
| The resol of formula (6) | 6.21 | 5.14 | 5.15 | 5.12 | 5.05 | 4.95 | 4.82 | |
| The resol of formula (5) | 4.69 | |||||||
| DBU | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
| The fusion spherical quartz | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 |
| Three montanic acid glyceryl ester | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
| γ-glycidyl propyl trimethoxy silicane | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| 2, the 3-dihydroxy naphthlene | 0.05 | 0.05 | 0.05 | 0.03 | 0.10 | 0.25 | 0.50 | 0.80 |
| Carbon black | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| Eddy flow (cm) | 130 | 115 | 120 | 115 | 130 | 135 | 145 | 160 |
| The gold thread deformation rate | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Continuously shaped property | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The stain on metal die surface | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The stain on moulding product surface | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Reflux-resisting welded connect hot | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Table 5
| Embodiment | |||||||
| b9 | b10 | b11 | b12 | b13 | b14 | b15 | |
| The Resins, epoxy of formula (4) | 6.91 | 6.91 | 6.91 | 6.95 | 6.68 | 6.91 | 6.91 |
| The resol of formula (6) | 5.14 | 5.14 | 5.14 | 5.17 | 4.97 | 5.14 | 5.14 |
| DBU | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
| The fusion spherical quartz | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 |
| Three montanic acid glyceryl ester | 0.10 | 0.10 | 0.10 | 0.03 | 0.50 | ||
| Three myricyl acid glyceryl ester | 0.10 | ||||||
| Three Glyceryl Behenates | 0.10 | ||||||
| γ-glycidyl propyl trimethoxy silicane | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| 2, the 3-dihydroxy naphthlene | 0.05 | 0.05 | 0.05 | 0.05 | |||
| 1, the 2-dihydroxy naphthlene | 0.05 | ||||||
| Catechol | 0.05 | ||||||
| Pyrogallol | 0.05 | ||||||
| Carbon black | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| Eddy flow (cm) | 120 | 125 | 130 | 115 | 135 | 120 | 115 |
| The gold thread deformation rate | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Continuously shaped property | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The stain on metal die surface | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The stain on moulding product surface | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Reflux-resisting welded connect hot | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Table 6
| Comparative Examples | ||||||||
| b1 | b2 | b3 | b4 | b5 | b6 | b7 | b8 | |
| The Resins, epoxy of formula (4) | 6.91 | 6.96 | 6.28 | 6.94 | 6.25 | 6.91 | 6.91 | |
| The Resins, epoxy of formula (7) | 6.31 | |||||||
| The resol of formula (6) | 5.14 | 5.18 | 4.67 | 5.16 | 4.65 | 5.14 | 5.14 | |
| The resol of formula (5) | 5.74 | |||||||
| DBU | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
| The fusion spherical quartz | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 |
| Three montanic acid glyceryl ester | 0.10 | 0.005 | 1.20 | 0.10 | 0.10 | 0.10 | 0.10 | |
| Glyceryl monostearate | 0.10 | |||||||
| γ-glycidyl propyl trimethoxy silicane | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| 2, the 3-dihydroxy naphthlene | 0.05 | 0.05 | 0.05 | 0.05 | 1.20 | |||
| 1, the 6-dihydroxy naphthlene | 0.05 | |||||||
| Resorcinol | 0.05 | |||||||
| Carbon black | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| Eddy flow (cm) | 140 | 115 | 110 | 150 | 75 | 180 | 80 | 75 |
| The gold thread deformation rate | ○ | ○ | ○ | ○ | × | ○ | × | × |
| Continuously shaped property | ○ | × | × | ○ | × | × | × | × |
| The stain on metal die surface | ○ | × | ○ | × | ○ | × | ○ | ○ |
| The stain on moulding product surface | ○ | × | ○ | × | ○ | × | ○ | ○ |
| Reflux-resisting welded connect hot | × | × | × | × | ○ | ○ | × | × |
In among the embodiment b1 to b15 each, the result of eddy flow and gold thread deformation rate is fine, proves that therefore the composition epoxy resin that is used for packaged semiconductor has the flowability of improvement, and also further the proof compound has the continuously shaped property of improvement.And, all do not find stain at moulding product and metal die surface, the moulding product that has therefore proved composition epoxy resin has the release property of improvement to metal die, prove also that this compound has an improvement reflux-resisting welded connect hot.
On the contrary, in the Comparative Examples b1 of the resol of Resins, epoxy that does not use general formula (4) and general formula (6), the gained compound can't obtain low water absorbable and low-stress at high temperature, and this causes the reflux-resisting welded hot deterioration that connects.
In addition, do not having to use among the Comparative Examples b2 of (E2) triglyceride, continuously shaped property (productivity) worsens, and, the outward appearance of moulding product, the stain on the metal die and reflux-resisting weldedly connect hot deterioration.In the insufficient Comparative Examples b3 of combined amount of (E2) triglyceride, the reduction of release property causes continuously shaped property and reflux-resisting weldedly connects hot deterioration.In the excessive Comparative Examples b4 of the combined amount of (E2) triglyceride, superfluous component is oozed out with the solidifying product surface at the interface element, determines the stain on metal die surface and the stain on moulding product surface like this.And then it is hot to worsen the anti-welding that refluxes.
Do not having to add among Comparative Examples b5, the b7 and b8 of (G) compound, the flowability of resin combination reduces, and causes the gold thread deformation rate to worsen.And, in Comparative Examples b7 and b8, also reduced reflux-resisting welded connect hot.In the excessive Comparative Examples b6 of the combined amount of (G) compound, the reduction of the solidified nature of resin combination causes the reduction of continuously shaped property (productivity), and, determined the stain on moulding product surface and the stain on metal die surface.
As mentioned above, the composition epoxy resin that the present invention is used for packaged semiconductor shows excellent balance on mobile, release property and continuously shaped property, and determine to use such resin combination as semiconducter device excellence is provided reflux-resisting welded connect hot.
Embodiment C
(embodiment c1)
In embodiment c1, use following raw material:
*By the Resins, epoxy (phenol aralkyl-type epoxy resin) of above-mentioned formula (4) expression [Nippon Kayaku Co., Ltd. is on sale, commodity are called " NC3000P ", softening temperature is 58 ℃, epoxy equivalent (weight) is 273] with biphenylene skeleton,
7.36 weight part
*The resol of above-mentioned formula (5);
(phenol aralkyl resin) with phenylene skeleton [Mitsui chemical Co., Ltd. is on sale, and commodity are called XLC-4L, and softening temperature is 65 ℃, hydroxyl equivalent is 174],
4.69 weight part
*DBU
0.20 weight part
*Spherical fused quartz (median size 30.0 μ m),
87.00 weight part;
*Oxidized petroleum wax No.1 (softening temperature is 100 ℃, and acid number is 15mg KOH/g, and median size is 45 μ m, and the particulate content that diameter is not less than 106 μ m is 0.0wt%),
0.10 weight part;
*γ-glycidyl propyl trimethoxy silicane;
0.30 weight part
*2,3-dihydroxy naphthlene (reagent);
0.05 weight part;
*Carbon black;
0.30 weight part.
After with mixing tank above-mentioned raw materials being mixed, the blended material is mediated 20 times, then gained is mediated material piece and cooled off, then its pulverizing is obtained composition epoxy resin with the twin shaft roller of 95 ℃ of surface temperatures and 25 ℃.
With estimating the characteristic of gained composition epoxy resin with the embodiment A similar methods.
The result is displayed in Table 7.
(embodiment c2 to c14 and Comparative Examples c1 to c8)
According to each component of mixed of table 7, table 8 and table 9 explanation, use with embodiment c1 similar methods and obtain composition epoxy resin, use with embodiment c1 similar methods it is estimated.The result is presented in table 7, table 8 and the table 9.
Other components of using among other embodiment except the foregoing description will be described below.
*Oxidized petroleum wax No.2
(softening temperature is 105 ℃, and acid number is 25mg KOH/g, and median size is 45 μ m, and the particulate content that diameter is not less than 106 μ m is 0.0wt%)
*Paraffin
(softening temperature is 70 ℃, and acid number is 0mg KOH/g, and median size is 45 μ m, and the particulate content that diameter is not less than 106 μ m is 0.0wt%).
Table 7
| Embodiment | |||||||
| c1 | c2 | c3 | c4 | c5 | c6 | c7 | |
| The Resins, epoxy of formula (4) | 7.36 | 6.91 | 6.92 | 6.88 | 6.80 | 6.65 | |
| The Resins, epoxy of formula (7) | 5.84 | ||||||
| The resol of formula (6) | 6.21 | 5.14 | 5.15 | 5.12 | 5.05 | 4.95 | |
| The resol of formula (5) | 4.69 | ||||||
| DBU | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
| The fusion spherical quartz | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 |
| Oxidized petroleum wax No.1 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
| γ-glycidyl propyl trimethoxy silicane | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| 2, the 3-dihydroxy naphthlene | 0.05 | 0.05 | 0.05 | 0.03 | 0.10 | 0.25 | 0.50 |
| Carbon black | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| Eddy flow (cm) | 125 | 110 | 115 | 110 | 125 | 130 | 140 |
| The gold thread deformation rate | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Continuously shaped property | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The stain on metal die surface | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The stain on moulding product surface | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Reflux-resisting welded connect hot | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Table 8
| Embodiment | |||||||
| c8 | c9 | c10 | c11 | c12 | c13 | c14 | |
| The Resins, epoxy of formula (4) | 6.48 | 6.91 | 6.91 | 6.91 | 6.95 | 6.68 | 6.91 |
| The resol of formula (6) | 4.82 | 5.14 | 5.14 | 5.14 | 5.17 | 4.97 | 5.14 |
| DBU | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
| The fusion spherical quartz | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 |
| Oxidized petroleum wax No.1 | 0.10 | 0.10 | 0.10 | 0.10 | 0.03 | 0.50 | |
| Oxidized petroleum wax No.2 | 0.10 | ||||||
| γ-glycidyl propyl trimethoxy silicane | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| 2, the 3-dihydroxy naphthlene | 0.08 | 0.05 | 0.05 | 0.05 | |||
| 1, the 2-dihydroxy naphthlene | 0.05 | ||||||
| Catechol | 0.05 | ||||||
| Pyrogallol | 0.05 | ||||||
| Carbon black | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| Eddy flow (cm) | 155 | 115 | 120 | 125 | 110 | 135 | 110 |
| The gold thread deformation rate | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Continuously shaped property | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The stain on metal die surface | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The stain on moulding product surface | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Reflux-resisting welded connect hot | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Table 9
| Comparative Examples | ||||||||
| c1 | c2 | c3 | c4 | c5 | c6 | c7 | c8 | |
| The Resins, epoxy of formula (4) | 6.91 | 6.96 | 6.28 | 6.94 | 6.25 | 6.91 | 6.91 | |
| The Resins, epoxy of formula (7) | 6.31 | |||||||
| The resol of formula (6) | 5.14 | 5.18 | 4.67 | 5.16 | 4.65 | 5.14 | 5.14 | |
| The resol of formula (5) | 5.74 | |||||||
| DBU | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
| The fusion spherical quartz | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 | 87.00 |
| Oxidized petroleum wax No.1 | 0.10 | 0.005 | 1.20 | 0.10 | 0.10 | 0.10 | 0.10 | |
| Paraffin | 0.10 | |||||||
| γ-glycidyl propyl trimethoxy silicane | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| 2, the 3-dihydroxy naphthlene | 0.05 | 0.05 | 0.05 | 0.05 | 1.20 | |||
| 1, the 6-dihydroxy naphthlene | 0.05 | |||||||
| Resorcinol | 0.05 | |||||||
| Carbon black | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| Eddy flow (cm) | 135 | 110 | 105 | 145 | 70 | 175 | 75 | 70 |
| The gold thread deformation rate | ○ | ○ | ○ | ○ | × | ○ | × | × |
| Continuously shaped property | ○ | × | × | ○ | × | × | × | × |
| The stain on metal die surface | ○ | × | ○ | × | ○ | × | ○ | ○ |
| The stain on moulding product surface | ○ | × | ○ | × | ○ | × | ○ | ○ |
| Reflux-resisting welded connect hot | × | × | × | × | ○ | ○ | × | × |
In among the embodiment c1 to c14 each, the result of eddy flow and gold thread deformation rate is fine, proves that therefore the composition epoxy resin that is used for packaged semiconductor has the flowability of improvement, and proves that further compound has the continuously shaped property of improvement.And, all do not find stain at moulding product and metal die surface, the moulding product that therefore proves composition epoxy resin has the release property of improvement to metal die, prove also that this compound has an improvement reflux-resisting welded connect hot.
On the contrary, in the Comparative Examples c1 of the resol of Resins, epoxy that does not use general formula (4) and general formula (6), the gained compound can't obtain low water absorbable and low-stress at high temperature, and this causes the reflux-resisting welded hot deterioration that connects.
In addition, do not having to use among the Comparative Examples c2 of (E3) oxidized petroleum wax, continuously shaped property (productivity) worsens, and, the outward appearance of moulding product, the stain on the metal die and reflux-resisting weldedly connect hot deterioration.In the insufficient Comparative Examples c3 of (E3) oxidized petroleum wax amount, the reduction of release property causes continuously shaped property and reflux-resisting weldedly connects hot deterioration.In the excessive Comparative Examples c4 of the combined amount of (E3) oxidized petroleum wax, superfluous component is oozed out with the solidifying product surface at the interface element, determines the stain on metal die surface and the stain on moulding product surface like this.And then, worsen reflux-resisting welded connect hot.
Do not having to add among Comparative Examples c5, the c7 and c8 of (G) compound, the flowability of resin combination reduces, and causes the gold thread deformation rate to worsen.And, in Comparative Examples c7 and c8, also reduced reflux-resisting welded connect hot.
In the excessive Comparative Examples c6 of the combined amount of (G) compound, the reduction of the solidified nature of resin combination causes the reduction of continuously shaped property (productivity), and, determined the stain on moulding product surface and the stain on metal die surface.
As mentioned above, the composition epoxy resin that the present invention is used for packaged semiconductor shows excellent harmony on mobile, release property and continuously shaped property, and determine to use such resin combination as semiconducter device excellence is provided reflux-resisting welded connect hot.
The composition epoxy resin that is used for packaged semiconductor of the present invention has flowability, release property and the continuously shaped property etc. of improvement, and its solidifying product also has the characteristic of improvement, for example reflux-resisting welded connect hot etc.Therefore, this resin combination can be preferably used as the material of packaged semiconductor, and, the invention provides the semiconducter device that forms with this resin combination packaged semiconductor.
Claims (19)
1. be used for the composition epoxy resin of packaged semiconductor, it comprises:
(A) Resins, epoxy;
(B) resol;
(C) curing catalyst;
(D) mineral filler;
(E) releasing agent;
(F) silane coupling agent; With
(G) a kind of compound, it has hydroxyl aromatic ring, and the two or more adjacent carbon atom of each hydroxyl and the difference that constitutes described aromatic ring combines,
At least a containing in wherein said (A) Resins, epoxy and described (B) resol by the represented resin of following general formula (1):
Wherein a plurality of R are identical or different, and representative is selected from the functional group in the group of being made up of hydrogen atom and the alkyl with 1～4 carbon; X represents glycidyl ether group or hydroxyl; And n represents a mean value, and its numerical value is the positive number in 1～3 scope,
Wherein said (E) releasing agent comprises that one or more are selected from by (E1) oxidized polyethlene wax, (E2) triglyceride and (E3) compound in the group formed of oxidized petroleum wax, and
The content of wherein said (E) releasing agent is the 0.01wt%～1wt% of total epoxy composition, comprises two endpoint values, and the content of described (G) compound is the 0.01wt%～1wt% of total epoxy composition, comprises two endpoint values.
2. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 1, wherein, described (G) compound is represented by following general formula (2):
Wherein one of them of R1 and R5 is hydroxyl, and another is the outer substituting group of hydrogen atom, hydroxyl or hydroxyl-removal, and each independently is hydrogen atom, hydroxyl or hydroxyl-removal substituting group outward for R2, R3 and R4, or R2 and R3, R3 and R4 unite the formation aromatic ring.
3. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 1 or 2, wherein said (E) releasing agent is (E1) oxidized polyethlene wax.
4. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 3, the dropping point of wherein said (E1) oxidized polyethlene wax is 100 ℃～140 ℃, comprises two endpoint values.
5. as claim 3 or the 4 described composition epoxy resins that are used for packaged semiconductor, the median size of wherein said (E1) oxidized polyethlene wax is 20 μ m～70 μ m, comprise two endpoint values, and the content of particle in total (E1) oxidized polyethlene wax that particle diameter is equal to or greater than 106 μ m is equal to or less than 0.1wt%.
6. as each described composition epoxy resin that is used for packaged semiconductor in the claim 3 to 5, the acid number of wherein said (E1) oxidized polyethlene wax is 10mg KOH/g to 50mgKOH/g, comprises two endpoint values.
7. as each described composition epoxy resin that is used for packaged semiconductor in the claim 3 to 6, the number-average molecular weight of wherein said (E1) oxidized polyethlene wax is 500～5,000, comprises two endpoint values.
8. as each described composition epoxy resin that is used for packaged semiconductor in the claim 3 to 7, the density of wherein said (E1) oxidized polyethlene wax is 0.94g/cm
3～1.03g/cm
3, comprise two endpoint values.
9. as each described composition epoxy resin that is used for packaged semiconductor in the claim 3 to 8, wherein said (E1) oxidized polyethlene wax comprises one or more oxide compounds, and it is selected from the oxide compound by the polyethylene wax that passes through the low-pressure polymerization explained hereafter; The oxide compound of the polyethylene wax of producing by high-pressure polymerization process; The group of forming with the oxide compound of high density polyethylene polyethylene polymers.
10. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 1 or 2, wherein said (E) releasing agent is (E2) triglyceride.
11. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 10, the dropping point of wherein said (E2) triglyceride is 70 ℃～120 ℃, comprises two endpoint values.
12. as claim 10 or the 11 described composition epoxy resins that are used for packaged semiconductor, the median size of wherein said (E2) triglyceride is 20 μ m～70 μ m, comprise two endpoint values, and the content of particle in total (E2) triglyceride that particle diameter is equal to or greater than 106 μ m is equal to or less than 0.1wt%.
13. as each described composition epoxy resin that is used for packaged semiconductor in the claim 10 to 12, the acid number of wherein said (E2) triglyceride is 10mg KOH/g to 50mg KOH/g, comprises two endpoint values.
14. as each described composition epoxy resin that is used for packaged semiconductor in the claim 10 to 13, wherein said (E2) triglyceride is glycerine and three ester cpds with saturated fatty acid of 20～36 carbon atoms.
15. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 1 or 2, wherein said (E) releasing agent is (E3) oxidized petroleum wax.
16. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 15, the softening temperature of wherein said (E3) oxidized petroleum wax is 70 ℃～120 ℃, comprises two endpoint values.
17. as claim 15 or the 16 described composition epoxy resins that are used for packaged semiconductor, the median size of wherein said (E3) oxidized petroleum wax is 20 μ m～70 μ m, comprise two endpoint values, and the content of particle in total oxidized petroleum wax that particle diameter is equal to or greater than 106 μ m is equal to or less than 0.1wt%.
18. as each described composition epoxy resin that is used for packaged semiconductor in the claim 15 to 17, the acid number of wherein said (E3) oxidized petroleum wax is 10mg KOH/g to 50mgKOH/g, comprises two endpoint values.
19. semiconducter device, it is by obtaining with each described composition epoxy resin packaged semiconductor that is used for packaged semiconductor in the claim 1 to 18.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP021015/2005 | 2005-01-28 | ||
| JP2005021015 | 2005-01-28 | ||
| JP021016/2005 | 2005-01-28 |
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| Publication Number | Publication Date |
|---|---|
| CN101098906A true CN101098906A (en) | 2008-01-02 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800018738A Pending CN101098906A (en) | 2005-01-28 | 2006-01-24 | Epoxy resin composition for encapsulating semiconductor chip and semiconductor device |
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| Country | Link |
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| CN (1) | CN101098906A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101772288B (en) * | 2008-12-31 | 2011-09-14 | 中国航空工业第一集团公司第六三一研究所 | Encapsulating technique for electronic components |
| CN104693689A (en) * | 2015-04-08 | 2015-06-10 | 天津盛远达科技有限公司 | Epoxy molding compound for infrared receiver module and preparing method of epoxy molding compound |
-
2006
- 2006-01-24 CN CNA2006800018738A patent/CN101098906A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101772288B (en) * | 2008-12-31 | 2011-09-14 | 中国航空工业第一集团公司第六三一研究所 | Encapsulating technique for electronic components |
| CN104693689A (en) * | 2015-04-08 | 2015-06-10 | 天津盛远达科技有限公司 | Epoxy molding compound for infrared receiver module and preparing method of epoxy molding compound |
| CN104693689B (en) * | 2015-04-08 | 2017-09-01 | 天津盛远达科技有限公司 | A kind of infrared receiving terminal epoxy-plastic packaging material and preparation method thereof |
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