CN102372901A - Hydantoin epoxy resin composite for encapsulating semiconductor devices - Google Patents
Hydantoin epoxy resin composite for encapsulating semiconductor devices Download PDFInfo
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- CN102372901A CN102372901A CN2010102569574A CN201010256957A CN102372901A CN 102372901 A CN102372901 A CN 102372901A CN 2010102569574 A CN2010102569574 A CN 2010102569574A CN 201010256957 A CN201010256957 A CN 201010256957A CN 102372901 A CN102372901 A CN 102372901A
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Abstract
The invention provides a hydantoin epoxy resin composite for encapsulating semiconductor devices, which is composed by heterocycle type hydantoin epoxy resin, anhydride curing agent, melting silica powder, flame retardant, accelerant and other ingredients. The curing product has excellent dielectric strength and high temperature resistance. The epoxy resin composite has the dielectric strength of 26-28Kv/mm, belongs to the halogen-free environmental-friendly type, and can be widely applied in encapsulating high pressure-resistant and high temperature-resistant semiconductor devices.
Description
Technical field
The present invention relates to a kind of composition epoxy resin, in more detail, relating to a kind of is the composition epoxy resin of tamanori with heterocyclic type glycolylurea resin;
The invention still further relates to above-mentioned glycolylurea epoxide resin preparation of compositions method.
The invention still further relates to the application of above-mentioned glycolylurea epoxide resin compsn.
Background technology
As being used for the resin combination that encapsulated semiconductor components and parts and unicircuit are used, its cured product must have the good electrical insulating property.Generally speaking, through using epoxy resin such as o-cresol formaldehyde type epoxy resin, cycloaliphatic epoxy resin, bisphenol A type epoxy resin and different solidifying agent can satisfy common request for utilization basically.
But for the encapsulation of high pressure resistant components and parts or unicircuit, common composition epoxy resin is difficult to satisfy requirement on electric performance.In order to improve the dielectric strength of epoxy molding plastic, once there was patent (CN101538397A) report to add high pressure resistant fillers such as aluminium sesquioxide.But actual effect is not remarkable, and is suitable with the effect of adding silica flour.
The universal epoxy resin adopts acid anhydrides as solidifying agent, and the dielectric properties of its moulding compound improve limited.If adopt organosilicon epoxy, organic fluorine epoxy resin, can improve the dielectric properties of material, but price is extremely expensive.
Glycolylurea epoxide resin is often as the resin matrix of caking agent or coating; Having favorable manufacturability can; Solid heating back viscosity is low, cure shrinkage is little, and anti-cracking performance is good, thermostability is high, under high-voltage and extra-high pressure, and electrical property is outstanding; Especially have good arc resistance and anti-electric creepage performance, and have good from flame retardant resistance.Therefore, the heterocyclic type glycolylurea epoxide resin can be used as the high pressure resistant composition epoxy resin that the tamanori preparation is used for semiconductor packages, and does not see the report for preparing moulding compound relevant for glycolylurea epoxide resin at present.
Summary of the invention
The object of the present invention is to provide a kind of composition epoxy resin.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned composition epoxy resin.
Be the realization above-mentioned purpose, composition epoxy resin provided by the invention, its composition and weight part are following:
Heterocyclic type glycolylurea epoxide resin 100
Anhydride curing agent 30-100
Fusion silica flour 300-1200
Complex metal hydroxide fire retardant 40-90
Curing catalyst 0.1-3
POLISHING WAX-103 1-5
Carbon black 1-5
Coupling agent 1.5-6;
Heterocyclic type glycolylurea epoxide resin structure of the present invention as shown in the formula:
Wherein, R
1And R
2For-CH
3
Described composition epoxy resin; Wherein, anhydride curing agent is: one or more in Tetra hydro Phthalic anhydride, maleic anhydride, trimellitic acid 1,2-anhydride, PMA acid anhydride, hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, methyl carbic anhydride, ethylene glycol bis trimellitic acid 1,2-anhydride ester, the USP Kosher three inclined to one side three acid anhydrides esters.
Described composition epoxy resin; Wherein, Curing catalyst is: glyoxal ethyline, 2,4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-(heptadecyl) imidazoles, triethylamine Bian Ji n n dimetylaniline, Alpha-Methyl Bian Ji n n dimetylaniline, 2-(dimethylamino methyl) phenol, 2,4; 6-three (dimethylamino methyl) phenol, 1; 8-diazabicyclo (5,4,0) undecylene-7, triphenylphosphine, triethyl phosphine, tributylphosphine, three (p-methylphenyl) phosphine or three (nonyl phenyl) phosphine.
The method of the above-mentioned composition epoxy resin of preparation provided by the invention, in above-mentioned weight part ratio, it is mixing under 80-100 ℃ that starting material are put into plastics processing mill, and cooling is pulverized.
Described preparation method, wherein, at 120 ℃ of cl ions and sodium ions that extract water down, the content that makes cl ions and sodium ion is less than 10ppm in advance for glycolylurea epoxide resin.
Composition epoxy resin of the present invention can be used as the packaged material of high pressure resistant components and parts and unicircuit, has excellent dielectric strength, and resistance to elevated temperatures.High more about 30～60% than the dielectric strength of bisphenol-A epoxy and o-cresol formaldehyde epoxy resin compsn, and have favorable manufacturability simultaneously, be applicable to the encapsulation of high pressure resistant components and parts.
Description of drawings
Fig. 1 is that the dielectric strength of various embodiments of the present invention and comparative example compares.
Embodiment
Composition epoxy resin of the present invention comprises heterocyclic type glycolylurea epoxide resin, anhydride curing agent, promotor, mineral filler and properties-correcting agent, and its composition and weight part are following:
Glycolylurea epoxide resin 100
Anhydride curing agent 30-100
Fusion silica flour 300-800
Complex metal hydroxide fire retardant 40-90
Curing catalyst 0.1-3
POLISHING WAX-103 1-5
Carbon black 1-5
Coupling agent 1.5-5.
Anhydride curing agent of the present invention can adopt: wherein one or more of Tetra hydro Phthalic anhydride, maleic anhydride, trimellitic acid 1,2-anhydride, pyromellitic acid anhydride, hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, methyl carbic anhydride, ethylene glycol bis trimellitic acid 1,2-anhydride ester mix.
The cl ions of the epoxy resin that the present invention adopts extraction water under 120 ℃, sodium ions content are less than 10ppm.
Curing catalyst of the present invention can adopt glyoxaline compound (as: glyoxal ethyline, 2; 4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-(heptadecyl) imidazoles etc.) or tertiary amine compound (as: triethylamine Bian Ji n n dimetylaniline, Alpha-Methyl Bian Ji n n dimetylaniline, 2-(dimethylamino methyl) phenol, 2; 4; 6-three (dimethylamino methyl) phenol, 1; 8-diazabicyclo (5,4,0) undecylene-7 etc.) or organic phosphine compound (as: triphenylphosphine, triethyl phosphine, tributylphosphine, three (p-methylphenyl) phosphine or three (nonyl phenyl) phosphine) etc.
Preparing method of the present invention is in above-mentioned weight part ratio; It is mixing under 80-100 ℃ that heterocyclic type glycolylurea epoxide resin, mixed acid anhydride, fusion silica flour, complex metal hydroxide fire retardant, promotor TPP, POLISHING WAX-103, carbon black, coupling agent etc. are put into double roller plastic-making device, and cooling is processed after pulverizing.
Composition epoxy resin of the present invention can be used as the packaged material of high pressure resistant components and parts and unicircuit, has excellent dielectric strength, and resistance to elevated temperatures.Than the high about 30-60% of dielectric strength of bisphenol-A epoxy and o-cresol formaldehyde epoxy resin compsn, and have favorable manufacturability simultaneously, be applicable to the encapsulation of high pressure resistant components and parts.
Below lifting some embodiment and Comparative Examples elaborates.
Embodiment A:
The heterocyclic type glycolylurea epoxide resin adopts available from the MHR-018 of Wuxi Mei Hua chemical company and MHR-154 and mixes (MHR-018 oxirane value 0.15-0.2,88 ℃ of softening temperatures by weight at 1: 1; MHR-154 oxirane value 0.52-0.55,15 ℃ of softening temperatures) 100 parts, 45 parts of mixed acid anhydrides (trimellitic acid 1,2-anhydride mixes with the methyl carbic anhydride by weight at 7: 3); 1 part of promotor TPP, 350 parts of fusion silica flours, 2 parts of silane coupling agents (KH560); 3 parts of POLISHING WAX-103s, 2 parts of carbon blacks, above-mentioned raw materials is mixing evenly at twin-screw extruder; Melting temperature 80-100 ℃, mixing postcooling is pulverized and is processed the sample powder.
Embodiment B:
Selecting for use component to remove mixed acid anhydride (trimellitic acid 1,2-anhydride mixes with Tetra Hydro Phthalic Anhydride by weight at 8: 2) consumption is 30 parts, 1 part of promotor 2-phenyl-4-methylimidazole, and other component is identical with embodiment A, and its preparation method is also identical with embodiment A.
Embodiment C:
Select for use other component of MHR-018 type heterocyclic type glycolylurea epoxide resin 2 (oxirane value is 0.15-0.20,88 ℃ of softening temperatures) of Wuxi Mei Hua chemical company identical with embodiment A, its preparation method is also identical with embodiment A.
Embodiment D:
Selecting for use component to remove mixed acid anhydride (pyromellitic acid anhydride mixes with hexahydrophthalic anhydride by weight at 7: 3) consumption is 45 parts, 1 part of promotor 2-(dimethylamino methyl) phenol, and other component is identical with Embodiment C, and its preparation method is also identical with Embodiment C.
The comparative example A:
Select for use component to remove bisphenol A epoxide resin (epoxy equivalent (weight) 476,72 ℃ of softening temperatures) 100 especially, other component is identical with embodiment A, and its preparation method is also identical with embodiment A.
Comparative Examples B:
Select for use component to remove adjacent sylvan formaldehyde epoxy resin (epoxy equivalent (weight) 196,55 ℃ of softening temperatures) 100 especially, other component is identical with embodiment A, and its preparation method is also identical with embodiment A.
Comparative Examples C:
Select for use component to remove 100 parts of adjacent sylvan formaldehyde epoxy resins (epoxy equivalent (weight) 196,55 ℃ of softening temperatures), 50 parts of lacquer resins (TD-2131, hydroxyl equivalent 104), other component is identical with embodiment A, and its preparation method is also identical with embodiment A
These composition epoxy resin performance tests are carried out as follows:
Gelation time: hot plate method, hot plate is heated to 175 ± 1 ℃, to get 0.3g-0.5g sample powder and be placed on the hot plate, powder is a terminal point when becoming colloidal state by fluid gradually, reads required time.
Helicoidal flow length: on the transfer mould press, measure by EMMI-1-66 helicoidal flow metal die, 175 ± 2 ℃ of die temperatures transmit pressure 70kg ± 2kg/cm2, sample thief powder 20g ± 5g.
Flash length: on the transfer mould press, measure by the flash metal die, 175 ± 2 ℃ of die temperatures transmit pressure 70kg ± 2kg/cm2, sample thief powder 20g ± 2g.
Dielectric strength:, on the voltage breakdown tester, measure according to standard GB/1408-2006 insulating material electrical strength testing method.
The sample powder takes out batten again 175 ℃ of following after fixing 8 hours, the test piece of shaping (specimen size ￠ 100 * 1.7mm) after 175 ℃ of die formings solidify 5 minutes.
Flame retardant properties: by national GB/T2408-1996 plastics combustibility test method is the vertical combustion method, on the combustion test appearance, measures.
The sample powder is after 175 ℃ of die formings solidify 5 minutes; Take out batten again 175 ℃ of following after fixing 8 hours; The batten (batten size 125mm*13mm*3.2mm) that is shaped applies flame and when the fire back flaming combustion time is not more than 10 seconds, is judged to be FV-0, is not more than 30 seconds and is judged to be FV-1.
Anti-bending strength: the testing standard according to national GB/T 1042-1979 plastics bending property is tested on omnipotent mechanical test machine.
The sample powder takes out batten again 175 ℃ of following after fixing 8 hours, the batten of shaping (batten size 120mm*15mm*10mm) after 175 ℃ of die formings solidify 5 minutes.
Test-results of the present invention is referring to Fig. 1 and table 1, and the result shows: use the DMH resin excellent as the dielectric properties of the composition epoxy resin of tamanori preparation.On the contrary, with the composition epoxy resin of other epoxy resin as tamanori, i.e. comparative example A, B, its dielectric strength is obviously on the low side; The dielectric strength of embodiment has improved 30-60% with respect to comparative example, demonstrates excellent dielectric properties.Be suitable for high voltage bearing components and parts encapsulation.
Table 1: the epoxy composite performance relatively
Claims (7)
1. composition epoxy resin, its form and weight part following:
Heterocyclic type glycolylurea epoxide resin 100
Anhydride curing agent 30-100
Fusion silica flour 300-1200
Complex metal hydroxide fire retardant 40-90
Curing catalyst 0.1-3
POLISHING WAX-103 1-5
Carbon black 1-5
Coupling agent 1.5-6.
2. composition epoxy resin according to claim 1, wherein, said heterocyclic type glycolylurea epoxide resin structure as shown in the formula:
Wherein, R
1And R
2For-CH
3
3. composition epoxy resin according to claim 1; Wherein, anhydride curing agent is: one or more in Tetra hydro Phthalic anhydride, maleic anhydride, trimellitic acid 1,2-anhydride, PMA acid anhydride, hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, methyl carbic anhydride, ethylene glycol bis trimellitic acid 1,2-anhydride ester, the USP Kosher three inclined to one side three acid anhydrides esters.
4. composition epoxy resin according to claim 1; Wherein, Curing catalyst is: glyoxal ethyline, 2,4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-(heptadecyl) imidazoles, triethylamine Bian Ji n n dimetylaniline, Alpha-Methyl Bian Ji n n dimetylaniline, 2-(dimethylamino methyl) phenol, 2,4; 6-three (dimethylamino methyl) phenol, 1; 8-diazabicyclo (5,4,0) undecylene-7, triphenylphosphine, triethyl phosphine, tributylphosphine, three (p-methylphenyl) phosphine or three (nonyl phenyl) phosphine.
5. the method for preparing the said composition epoxy resin of claim 1, in above-mentioned weight part ratio, it is mixing under 80-100 ℃ that starting material are put into plastics processing mill, and cooling is pulverized.
6. preparation method according to claim 5, wherein, the cl ions of glycolylurea epoxide resin extraction water under 120 ℃ and sodium ions content are less than 10ppm.
7. the application of the described composition epoxy resin of claim 1 in high pressure resistant components and parts encapsulation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102569574A CN102372901A (en) | 2010-08-18 | 2010-08-18 | Hydantoin epoxy resin composite for encapsulating semiconductor devices |
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|---|---|---|---|
| CN2010102569574A CN102372901A (en) | 2010-08-18 | 2010-08-18 | Hydantoin epoxy resin composite for encapsulating semiconductor devices |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103392066A (en) * | 2011-02-22 | 2013-11-13 | 费德罗-莫格尔点火公司 | Corona igniter with improved energy efficiency |
| CN104292717A (en) * | 2014-10-31 | 2015-01-21 | 中南大学 | Application of hydantoin epoxy resin |
| CN104312062A (en) * | 2014-10-31 | 2015-01-28 | 中南大学 | Preparation method for energy-storage composite material |
| CN104576553A (en) * | 2013-10-28 | 2015-04-29 | 日月光半导体制造股份有限公司 | Semiconductor package piece, package resin, package adhesive and manufacturing methods of package resin and package adhesive |
| CN104945851A (en) * | 2015-07-08 | 2015-09-30 | 芜湖市神龙新能源科技有限公司 | LED packaging materials |
| CN105061993A (en) * | 2015-07-22 | 2015-11-18 | 江苏中鹏新材料股份有限公司 | Environment-friendly white epoxy molding compound, preparation method therefor and application thereof |
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| CN1288914A (en) * | 2000-08-30 | 2001-03-28 | 中国科学院化学研究所 | Epoxy resin composite containing compound inorganic stuffing |
| CN101624439A (en) * | 2009-08-04 | 2010-01-13 | 无锡美华化工有限公司 | Synthesizing method for flame retardant type glycolylurea epoxide resin |
| CN101633770A (en) * | 2009-08-28 | 2010-01-27 | 番禺南沙殷田化工有限公司 | Halogen-free flame retardant epoxy resin composite and flexible copper clad laminate prepared with same |
| CN101696317A (en) * | 2009-10-21 | 2010-04-21 | 北京中新泰合电子材料科技有限公司 | Epoxy resin composite taking spherical silicon powder as filler, preparation method and application thereof |
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2010
- 2010-08-18 CN CN2010102569574A patent/CN102372901A/en active Pending
Patent Citations (4)
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| CN1288914A (en) * | 2000-08-30 | 2001-03-28 | 中国科学院化学研究所 | Epoxy resin composite containing compound inorganic stuffing |
| CN101624439A (en) * | 2009-08-04 | 2010-01-13 | 无锡美华化工有限公司 | Synthesizing method for flame retardant type glycolylurea epoxide resin |
| CN101633770A (en) * | 2009-08-28 | 2010-01-27 | 番禺南沙殷田化工有限公司 | Halogen-free flame retardant epoxy resin composite and flexible copper clad laminate prepared with same |
| CN101696317A (en) * | 2009-10-21 | 2010-04-21 | 北京中新泰合电子材料科技有限公司 | Epoxy resin composite taking spherical silicon powder as filler, preparation method and application thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103392066A (en) * | 2011-02-22 | 2013-11-13 | 费德罗-莫格尔点火公司 | Corona igniter with improved energy efficiency |
| CN104576553A (en) * | 2013-10-28 | 2015-04-29 | 日月光半导体制造股份有限公司 | Semiconductor package piece, package resin, package adhesive and manufacturing methods of package resin and package adhesive |
| CN104576553B (en) * | 2013-10-28 | 2017-08-29 | 日月光半导体制造股份有限公司 | Semiconductor package part, potting resin, sealing and its manufacture method |
| CN104292717A (en) * | 2014-10-31 | 2015-01-21 | 中南大学 | Application of hydantoin epoxy resin |
| CN104312062A (en) * | 2014-10-31 | 2015-01-28 | 中南大学 | Preparation method for energy-storage composite material |
| CN104312062B (en) * | 2014-10-31 | 2016-05-11 | 中南大学 | A kind of preparation method of energy-storage composite material |
| CN104292717B (en) * | 2014-10-31 | 2016-05-11 | 中南大学 | A kind of application of glycolylurea epoxide resin |
| CN104945851A (en) * | 2015-07-08 | 2015-09-30 | 芜湖市神龙新能源科技有限公司 | LED packaging materials |
| CN105061993A (en) * | 2015-07-22 | 2015-11-18 | 江苏中鹏新材料股份有限公司 | Environment-friendly white epoxy molding compound, preparation method therefor and application thereof |
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Application publication date: 20120314 |