CN1346150A - Epoxy resin composition and semiconductor device - Google Patents
Epoxy resin composition and semiconductor device Download PDFInfo
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- CN1346150A CN1346150A CN 00129270 CN00129270A CN1346150A CN 1346150 A CN1346150 A CN 1346150A CN 00129270 CN00129270 CN 00129270 CN 00129270 A CN00129270 A CN 00129270A CN 1346150 A CN1346150 A CN 1346150A
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- red phosphorus
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Abstract
The present invention discloses to an epoxy resin composition containing no bromide or antimony oxide and having excellent fire-resisting property, wet fastness, forming property and electric property for sealing semiconductor, and said epoxy resin composition contains (A) epoxy resin, (B) phenolic resin, (C) solidification accelerating agent, (D) inorganic filler and (E) red phosphorus fire retardant. Said red phosphorus fire retardant is characterized by that the content of phosphoric acid ion and phosphorus acid ion resolvent out by using water to extract for 20 hr. at below 80 deg.c is below 2000 ppm, and the red phosphorus content in the fire retardant is 20-40 wt%, and the complete epoxy resin composition contains 0.5-5 wt% of red phosphorus fire retardant.
Description
The present invention relates to good epoxy resin composition for encapsulating semiconductor of a kind of anti-flammability and semiconductor device.
In the past, electronic components such as diode, transistor, integrated circuit mainly are to seal with composition epoxy resin.In this resin combination, cooperate bromide or bromide and antimony oxide and usefulness, cooperate fused silica, crystalline silica etc. as inorganic filler as fire retardant.But, consider from the environmental sanitation aspect, require to use the fire retardant resin composition that does not conform to bromide and antimony oxide.
For this requirement, once proposed with the surface of the lining red phosphorus such as metal hydroxides of aluminium hydroxide or magnesium hydroxide and so on, again with phenolic resins its surperficial red phosphorus flame retardant that is covered, but performances such as the temperature tolerance of the mouldability of the phosphate ion of stripping and phosphorous acid ion pair resin combination, curable, the semiconductor device that obtains, electrical property have harmful effect from this fire retardant, in addition, use the resin combination of red phosphorus flame retardant can not satisfy mouldability, curable, moisture-proof, electrical property.
The present invention is directed to this problem, the semiconductor device that a kind of epoxy resin composition for encapsulating semiconductor is provided and uses said composition.The total amount of said composition epoxy resin by using a kind of red phosphorus flame retardant, make the stripping phosphate ion that wherein extracts and phosphorous acid ion is below specified quantitative, and like this, even do not contain bromide and antimony oxide, anti-flammability is also good.
The present invention be a kind of epoxy resin composition for encapsulating semiconductor and with said composition with the semiconductor device that semiconductor element encapsulation forms, contain (A) epoxy resin, (B) phenolic resins, (C) curing accelerator, (D) inorganic filler and (E) red phosphorus flame retardant in this epoxy resin composition for encapsulating semiconductor; It is characterized in that:
(E) the red phosphorus flame retardant is a kind of like this red phosphorus flame retardant, under 80 ℃, the phosphate ion of water extraction 20 hour time institute's stripping and the total content of phosphorous acid ion are below 2000ppm, red phosphorus amount in the red phosphorus flame retardant is 20～40 weight %, contains this red phosphorus flame retardant 0.5～5 weight % in all resins composition.
As the epoxy resin that uses among the present invention, be meant that the monomer, oligomer and the polymer that have 2 above epoxy radicals in 1 molecule are all, there is no particular limitation for its molecular weight, molecular structure, for example can enumerate, biphenyl type epoxy resin, bisphenol-type epoxy resin, solvable fusible phenol aldehyde type epoxy resin, the solvable type epoxy resin of cresols, triphenol methane type epoxy resin, alkyl-modified triphenol methane type epoxy resin and the epoxy resin etc. that contains triazine nuclear, they can use separately also can mix use.
As the phenolic resins that uses among the present invention, be meant that the monomer, oligomer and the polymer that have 2 above phenolic hydroxyl groups in 1 molecule are all, there is no particular limitation for its molecular weight and molecular structure, can enumerate for example novolac, cresols soluble resin, dicyclic pentylene modified phenolic resins, phenol aralkyl resin (phenol aralkyl resin), terpene modified phenolic resins, triphenol methane type resin etc., they can use separately also can mix use.Its use level, the equivalent proportion of the epoxy radix of epoxy resin and the phenolic hydroxyl group number of phenolic resins is preferably 0.8～1.2 scope.
As the curing accelerator that uses among the present invention,, can be extensive use of the curing accelerator that uses in the general encapsulant so long as can promote the just passable of epoxy radicals and phenolic hydroxyl group generation curing reaction.For example can enumerate 1,8-diazabicyclo (5,4,0) endecatylene-7, glyoxal ethyline etc., they can use separately also can mix use.
As the inorganic filler of using among the present invention, can enumerate fused silica powder, ground silica end, aluminium oxide, silicon nitride etc., but wish it is fused silica powder and ground silica end.As the use level of inorganic filler, consider from the balance of mouldability and reliability, preferably account for 70～95 weight % of resin combination total amount.In addition, in order to obtain good flowability and fillibility, the average grain diameter of preferred inorganic filler is 11～20 μ m, and its particle size distribution is, particle diameter accounting at whole 20～45 weight % of inorganic fillers below 10 μ m, particle diameter is accounting for below the 10 weight % more than the 70 μ m.In the more resin combination that cooperates inorganic filling material, especially preferably use spheroidal fused silicon dioxide.
The red phosphorus flame retardant that uses among the present invention, the phosphate ion of its extraction 20 hour time institute's stripping under 80 ℃ and the total content of phosphorous acid ion are below 2000ppm.Usually,, then in the presence of moisture, cause the redox disproportionated reaction, on the particles of red phosphorus surface, generate the oxide or the acid of phosphorus, discharge harmful hydrogen phosphide simultaneously if red phosphorus is placed on separately in the air.Because this reaction is accompanied by heat release, therefore spontaneous combustion might take place.
In addition, the dip time in water and the pH value of water are reduced simultaneously, produce phosphorus oxide, be phosphate ion and phosphorous acid ion, not only ambient air is polluted by hydrogen phosphide, and the danger of blasting is arranged.Further, red phosphorus waits extremely responsive to heat and friction, under lower temperature or be subjected to slight impact, just is being easy to fire burns, therefore often is accompanied by danger.
Therefore, generally, red phosphorus is with linings such as metal hydroxides such as aluminium hydroxide or magnesium hydroxides, again with phenolic resins its surface that is covered, can suppress contacting of red phosphorus and moisture, improves the oxidation stability of phosphorus, simultaneously, also can improve thermal endurance and resistance to impact.The red phosphorus content of this moment is 80～95%, is commonly considered as being covered thinly in the outside of red phosphorus.In addition, according to different occasions, any one party sometimes also only is covered.But, the red phosphorus that only carries out this lining, red phosphorus content is too high and be covered insufficient and part red phosphorus is exposed sometimes, has to impact and causes the danger of catching fire.Therefore, among the present invention, use a kind of like this red phosphorus flame retardant, in carrying out this red phosphorus that has been covered, further add metal hydroxides and phenolic resins, so that the final content of red phosphorus is 20～40 weight %, safety aspect thermal endurance and resistance to impact like this.
The Determination on content of the phosphate ion of red phosphorus flame retardant and phosphorous acid ion, be that red phosphorus flame retardant sample 5g is added in the container, to wherein adding pure water 50g, descend processing after 20 hours again, the phosphate ion in the employing ion-chromatographic determination extraction water and the amount of phosphorous acid ion 80 ℃ of temperature.
As long as the phosphate ion of red phosphorus flame retardant extraction 20 hour time institute's stripping under 80 ℃ and the total content of phosphorous acid ion are below 2000ppm, just there is no particular limitation, but preferably further add aluminium hydroxide and phenolic resins in the red phosphorus with aluminium hydroxide, phenolic resins lining, making red phosphorus content is the red phosphorus flame retardant of 20～40 weight %.
80 ℃ down the total content of the phosphate ion of extraction 20 hour time institute's strippings and phosphorous acid ion below 2000ppm, red phosphorus content is the red phosphorus flame retardant of 20～40 weight %, if 0.5 weight % of the not enough resin combination total amount of its addition, red phosphorus composition deficiency then, anti-flammability is not enough, and when surpassing 5.0 weight %, performances such as the moisture-proof of resin combination, mouldability, curable and electrical property reduce.In addition, the total content of the phosphate ion of extraction 20 hour time institute's stripping and phosphorous acid ion surpasses the red phosphorus flame retardant of 2000ppm under 80 ℃, even its addition accounts for the scope of 0.5～5.0 weight % of resin combination total amount, performances such as moisture-proof, mouldability, curable and electrical property also worsen.
The present invention is (A) epoxy resin of a kind of containing, (B) phenolic resins, (C) curing accelerator, (D) inorganic filler, and the known epoxy resin composition for encapsulating semiconductor that (E) contains the red phosphorus flame retardant, its improvement point is, as (E) red phosphorus flame retardant, use the phosphate ion of 80 ℃ of following water extraction 20 hour time institute's strippings and the red phosphorus flame retardant of total content below 2000ppm of phosphorous acid ion, and the red phosphorus content in the red phosphorus flame retardant is 20～40 weight %, this red phosphorus flame retardant accounts for 0.5～5 weight % of resin combination total amount, (A), (B), (C), (D) there is no particular limitation for proportion of composing.Composition of the present invention, if consider flowability, curable and the mouldability of composition epoxy resin and the balance of reliability, preferred compositions by (A) epoxy resin 2～20 weight %, (B) phenolic resins 2～20 weight %, (C) curing accelerator 0.01～1 weight %, (D) inorganic filler 70～95 weight % and (E) red phosphorus flame retardant 0.5～5 weight % constitute, add up to 100 weight %.
Resin combination of the present invention is except (A)～(E) composition, can also cooperate the various additives such as low stress additives of release agents such as colouring agents such as silane coupling agent, carbon black, iron oxide red, native paraffin, synthetic wax and silicone oil, rubber and so on aptly as required.
In addition, resin combination of the present invention can use mixer etc. that (A)～(E) composition and other additive etc. are evenly mixed fully, and then with melting mixings such as hot-rolling or kneaders, pulverize the cooling back, makes moulding material.These moulding materials go for lining insulation, sealing as the transistor of electric parts or electronic component, integrated circuit etc. etc.
When making semiconductor device, can adopt transfer modling, compression molding, forming method such as injection-molded to carry out forming and hardening with electronic components such as resin combination sealing semiconductor elements of the present invention.
Adopt epoxy resin composition for encapsulating semiconductor of the present invention, can obtain not contain the semiconductor device of the function admirable such as anti-flammability, moisture-proof, mouldability, curable, electrical property of bromide and antimony oxide.
Below, enumerate embodiment and describe particularly, but the present invention is not subjected to the qualification of these embodiment.Embodiment 1～4, comparative example 1～5
At normal temperatures, with mixer the resin combination shown in table 1 and the table 2 is mixed, use roller mixing down at 70～100 ℃, pulverize the cooling back, makes moulding material.The moulding material that obtains is made tablet, use low pressure transfer molding machine, at 175 ℃, 70kg/cm
2, under 120 seconds the condition, be shaped to the fire resistance test sheet, in addition,, the semiconductor element encapsulation of 3mm * 3.5mm is become 16pDIP as anti-moisture test usefulness.Hermetically sealed test is carried out following anti-moisture test with element.In addition, carry out the high temperature leak-test with this 16pDIP.As curing characteristics, carry out キ ュ ラ ス ト and measure.
Employed raw material are as follows.
Biphenyl type epoxy resin (110 ℃ of fusing points, epoxide equivalent 195g/eq),
Phenol aralkyl resin (80 ℃ of softening points, hydroxyl equivalent 174g/eq),
1,8-diazabicyclo (5,4,0) endecatylene-7 (hereinafter referred to as DBU),
Red phosphorus flame retardant 1 (red phosphorus content 30%, stripping phosphate ion+phosphorous acid ion=1600ppm),
Red phosphorus flame retardant 2 (red phosphorus content 30%, stripping phosphate ion+phosphorous acid ion=1900ppm),
Red phosphorus flame retardant 3 (red phosphorus content 30%, stripping phosphate ion+phosphorous acid ion=2200ppm),
Spheroidal fused SiO 2 powder (average grain diameter 22 μ m, specific area 2.2m
2/ g),
Carbon black,
Brazil wax.
The phosphate ion content assaying method of red phosphorus flame retardant: the sample 5g of red phosphorus flame retardant is added in the container, to wherein adding pure water 50g, handled 20 hours down 80 ℃ of temperature, adopt the phosphate ion in the ion-chromatographic determination extraction water and the amount of phosphorous acid ion then.Evaluation method
Helical flows: use the mould as benchmark with EMMI-I-66, at 175 ℃ of mold temperatures, pressure 70kg/cm
2Condition under measure.
Mouldability: use low pressure transfer molding machine, at 175 ℃ of mold temperatures, pressure 70kg/cm
2Condition under, will may be molded to the standard of the curing time of 16pDIP as mouldability.
Fire resistance test: carry out UL-94 vertical test (sample thickness 3.2mm), represent with anti-flammability.
Anti-moisture test: the pressure cooking test of the test usefulness element that seals (125 ℃, pressure 2.2kg/cm
2), it is bad to measure opening circuit of circuit, represents with bad time of origin.
High temperature leakage current test: the high temperature leakage current (150 ℃) of measuring 16pDIP.
Curable test: use キ ュ ラ ス ト test mould, measuring under the condition of 175 ℃ of mold temperatures from measuring the torque value of beginning after 60 seconds, after 90 seconds.
Evaluation result is shown in table 1 and the table 2.
Table 1
| Embodiment | |||||
| ????1 | ????2 | ????3 | ????4 | ||
| Biphenyl type epoxy resin | ????6.8 | ????6.8 | ????6.8 | ????6.8 | |
| Phenol aralkyl resin | ????5.4 | ????5.4 | ????5.4 | ????5.4 | |
| ?DBU | ????0.2 | ????0.2 | ????0.2 | ????0.2 | |
| Red phosphorus combustion inhibitor 1 | ????1.0 | ????4.5 | |||
| Red phosphorus combustion inhibitor 2 | ????1.0 | ????4.5 | |||
| The spheroidal fused SiO 2 powder | ????86.0 | ????82.5 | ????86.0 | ????82.5 | |
| Carbon black | ????0.3 | ????0.3 | ????0.3 | ????0.3 | |
| Brazil wax | ????0.3 | ????0.3 | ????0.3 | ????0.3 | |
| Helical flow (cm) | ????120 | ????100 | ????120 | ????100 | |
| Mouldability (second) | ????70 | ????90 | ????70 | ????90 | |
| Fire retardant (UL-94) | ????V-0 | ????V-0 | ????V-0 | ????V-0 | |
| Moisture-proof (hour) | ????450 | ????400 | ????450 | ????400 | |
| High temperature leakage current (nA) | ????0.5 | ????1.5 | ????0.5 | ????1.5 | |
| Curable | 60 seconds (kgfcm) | ????40 | ????35 | ????40 | ????35 |
| 90 seconds (kgfcm) | ????60 | ????55 | ????60 | ????55 | |
Table 2
| Comparative example | ||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ||
| Biphenyl type epoxy resin | ????6.8 | ????6.8 | ????6.8 | ????6.8 | ????6.8 | |
| Phenol aralkyl resin | ????5.4 | ????5.4 | ????5.4 | ????5.4 | ????5.4 | |
| ?DBU | ????0.2 | ????0.2 | ????0.2 | ????0.2 | ????0.2 | |
| Red phosphorus combustion inhibitor 1 | ????0.4 | ????5.5 | ||||
| Red phosphorus combustion inhibitor 3 | ????3.0 | ????5.5 | ||||
| The spheroidal fused SiO 2 powder | ????87.0 | ??86.6 | ??81.5 | ??84.0 | ??81.5 | |
| Carbon black | ????0.3 | ????0.3 | ????0.3 | ????0.3 | ????0.3 | |
| Brazil wax | ????0.3 | ????0.3 | ????0.3 | ????0.3 | ????0.3 | |
| Helical flow (cm) | ????120 | ??120 | ??80 | ??90 | ??70 | |
| Mouldability (second) | ????70 | ????70 | ????180 | ????120 | ????200 | |
| Fire retardant (UL-94) | All burn | ??V-1 | ??V-0 | ??V-0 | ??V-0 | |
| Moisture-proof (hour) | ????450 | ????450 | ????300 | ????300 | ????250 | |
| High temperature leakage current (nA) | ????0.5 | ????0.5 | ????2.5 | ????2.5 | ????3.5 | |
| Curable | 60 seconds (kgfcm) | ????40 | ????40 | ????25 | ????25 | ????20 |
| 90 seconds (kgfcm) | ????60 | ????60 | ????45 | ????45 | ????30 | |
Claims (3)
1. epoxy resin composition for encapsulating semiconductor, it is (A) epoxy resin, (B) phenolic resins, (C) curing accelerator, (D) inorganic filler of a kind of containing and (E) epoxy resin composition for encapsulating semiconductor of red phosphorus flame retardant, it is characterized in that:
(E) the red phosphorus flame retardant is a kind of like this red phosphorus flame retardant, under 80 ℃, the phosphate ion of water extraction 20 hour time institute's stripping and the total content of phosphorous acid ion are below 2000ppm, red phosphorus amount in the red phosphorus flame retardant is 20～40 weight %, contains this red phosphorus flame retardant 0.5～5 weight % in all resins composition.
2. the composition described in the claim 1 wherein is made of following composition, adds up to 100 weight %:
(A) epoxy resin 2～20 weight %,
(B) phenolic resins 2～20 weight %,
(C) curing accelerator 0.01～1 weight %,
(D) inorganic filler 70～95 weight % and
(E) red phosphorus flame retardant 0.5～5 weight %.
3. a semiconductor device is to use the composition epoxy resin sealing semiconductor element described in the claim 1 to form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00129270 CN1346150A (en) | 2000-09-30 | 2000-09-30 | Epoxy resin composition and semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00129270 CN1346150A (en) | 2000-09-30 | 2000-09-30 | Epoxy resin composition and semiconductor device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1346150A true CN1346150A (en) | 2002-04-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00129270 Pending CN1346150A (en) | 2000-09-30 | 2000-09-30 | Epoxy resin composition and semiconductor device |
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|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497475C (en) * | 2005-11-16 | 2009-06-10 | 广东生益科技股份有限公司 | Halogen-free resin composition and its uses in adhesive sheet and copper-cladded plate |
| CN103228709A (en) * | 2010-09-02 | 2013-07-31 | 住友电木株式会社 | Resin molded product and process for producing same, resin composition and process for producing same, and electronic component device |
-
2000
- 2000-09-30 CN CN 00129270 patent/CN1346150A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497475C (en) * | 2005-11-16 | 2009-06-10 | 广东生益科技股份有限公司 | Halogen-free resin composition and its uses in adhesive sheet and copper-cladded plate |
| CN103228709A (en) * | 2010-09-02 | 2013-07-31 | 住友电木株式会社 | Resin molded product and process for producing same, resin composition and process for producing same, and electronic component device |
| CN103228709B (en) * | 2010-09-02 | 2015-04-29 | 住友电木株式会社 | Resin molded product and process for producing same, resin composition and process for producing same, and electronic component device |
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