CN102675601B - Low-warpage epoxy resin composite used for QFN (Quad Flat No Lead) - Google Patents
Low-warpage epoxy resin composite used for QFN (Quad Flat No Lead) Download PDFInfo
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Abstract
The invention discloses a low-warpage epoxy resin composite used for QFN (Quad Flat No Lead), which is prepared from epoxy resin, phenolic resin, special additive, inorganic filler, curing accelerator and the like, wherein the epoxy resin is represented in a formula (2) or mixture composed of epoxy resins represented by the formula (1) and the formula (2); the phenolic resin is represented by a formula (5) or the mixture of the phenolic resin represented by the formula (5) and at least one of phenolic resins represented by formulas (3) and (4); and the special additive is compound particle compounded by organic silicon resin containing a methoxy group and nuclear shell rubber containing butadiene/ styrene-rubber and methyl methacrylate at the mass ratio of 1:(1-5). In the low-warpage epoxy resin composite, the resin system and the special additive are regulated to ensure that the low-warpage epoxy resin composite has good reliability simultaneously on a silver plating frame and a PPF (Poly propylene fumarate) plating frame, and can obtain almost same warpage performance on capsules of different sizes.
Description
Technical field
The present invention relates to a kind of composition epoxy resin, particularly a kind of low warpage composition epoxy resin for QFN.
Background technology
QFN is a kind of without pin package, is square or rectangle, and package bottom middle position has a big area exposed pads to be used for heat conduction, has around the peripheral surrounding of encapsulation of large bonding pad the conductive welding disk of realizing electric link.Because QFN encapsulation has gull wing lead-in wire unlike traditional SOIC and TSOP encapsulation, the conductive path between inner pin and pad is short, and in coefficient of self-induction and package, cloth line resistance is very low, so it can provide remarkable electrical property.In addition, it also provides outstanding heat dispersion by the leadframe pad exposing.Therefore because its volume is little, lightweight, add outstanding electrical property and thermal characteristics, so be applicable to being very much applied in the first-class application that size, weight and performance are all had higher requirements of high-density printed circuit board of mobile phone, digital camera, PDA and other portable miniaturized electronicss.
QFN kind is a lot, and the thickness of package is generally 0.9 ~ 1mm, and what have is very thin, can reach 0.4mm.In addition, according to the size of package, mainly contain 3*3mm, 4*4mm, 5*5mm, 6*6mm, 7*7mm and 8*8mm, these several sizes.Because difference and the varying in size of framework of package body sizes, inside chip size cause using same plastic cement, in different designs, warpage has larger difference.Simultaneously in order to meet different application, silver-plated framework and plating PPF framework have also obtained a large amount of uses, because the bonding force of same plastic cement on silver-plated framework and plating PPF framework is visibly different, make will use different plastic cements for different frameworks in order to meet the requirement of reliability.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, provides a kind of suitability extensive, and warpage is little, reliability is high, can meet the low warpage composition epoxy resin for QFN that uses different package sizes and different frames material simultaneously.
Technical problem to be solved by this invention is to realize by following technical scheme.The present invention is a kind of low warpage composition epoxy resin for QFN, is characterized in: said composition is made up of epoxy resin, resol, specialist additive, mineral filler, curing catalyst, releasing agent, coupling agent, tinting material, stress relief agent and ion capturing agent;
The content of curing catalyst, releasing agent, coupling agent, tinting material, stress relief agent and ion capturing agent is not respectively higher than 1% of composition total mass;
The content of epoxy resin accounts for 2 ~ 7% of total composition quality; Epoxy resin is the represented epoxy resin of formula [2], or is the mixture of the represented epoxy resin composition of formula [2] and formula [1], and in mixture, the content of the epoxy resin that formula [2] represents is not less than 50% of epoxy resin total amount;
Formula [1]
Formula [2]
The content of resol accounts for 2 ~ 7% of composition total mass; Resol is the represented resol of formula [5], or be the mixture of at least one composition in the represented resol of the represented resol of formula [5] and formula [3], formula [4], in mixture, the represented resol of formula [5] is not less than 50% of resol total mass;
Formula [3]
Formula [4]
Formula [5]
In epoxy resin, in epoxide group and resol, the equivalence ratio of phenolic hydroxyl group is 0.5-1.5;
The content of described mineral filler is 88 ~ 92% of composition total mass;
Described curing catalyst is selected from the one in imidazoles and its esters;
Described specialist additive is that its particle diameter is 200 ~ 500nm by the silicone resin containing methoxyl group and the core shell rubbers containing Butadiene/Styrene rubber and methyl methacrylate and the composite particles being composited by weight 1:1-5; The content of specialist additive is the 0.1-1.0% of composition total mass.
Low warpage composition epoxy resin for QFN of the present invention: mineral filler is preferably SiO 2 powder or alumina powder; Mineral filler be shaped as spherical or dihedral.
Low warpage composition epoxy resin for QFN of the present invention: the content of curing catalyst, releasing agent, coupling agent, tinting material, stress relief agent and ion capturing agent is preferably respectively the 0.1-1.0% of composition total mass.
Low warpage composition epoxy resin for QFN of the present invention: in the time that epoxy resin is mixture, in mixture, the content of the epoxy resin that the content of the epoxy resin that formula [2] represents preferably represents than formula [1] is high by 10 ~ 20%.
Low warpage composition epoxy resin for QFN of the present invention: in epoxy resin, in epoxide group and resol, the equivalence ratio of phenolic hydroxyl group is preferably 0.9 ~ 1.1.
The research of the framework that the inventor uses in view of QFN in the market and different sizes thereof, and the research of the performance of different plastic cements on different QFN, find to use new type resin system to coordinate with specialist additive and suitable mineral filler, can reach the requirement of the QFN that encapsulates the different package body sizes of use, different framework with a kind of plastic cement to reliability and warpage.The present invention uses the starting material that full up sufficient ROHS requires in addition, can meet the requirement of the environmental protection of QFN to plastic cement on market.
Time prepared by the present composition, be that each raw material is carried out after pre-mixing, use double roll mill or the even rear calendering rapidly of screw extrusion press (single screw rod or twin screw) melting mixing to be cooled to sheet in this mixture and pulverize and form again.
In the present invention, epoxy resin used and the melt viscosity of 150 ℃ of resol are considered from mobility, are preferably below 1 pool, more preferably below 0.5 pool, more preferably below 0.3 pool.The melt viscosity here represents the viscosity of measuring with ICI cone-and-plate viscometer.
The combined utilization of epoxy resin, the represented resol of formula [5] and specialist additive that through type of the present invention [2] represents, co-controlling reaches the effect that warpage is little, reliability is high.
Releasing agent in the present invention comprises lipid acid, montanic acid, palmitinic acid, oxidized form or Non-oxidized polyethylene wax etc., these releasing agents can guarantee solidify after resin can from the mould of metastasis model device, take out.Coupling agent comprises the conventional siloxanes such as epoxy silane, aminosilane, hydrosulphonyl silane.Tinting material is mainly carbon black.Stress relief agent can coordinate with silicone oil or polysiloxane rubber powder etc.Ion capturing agent does not have no particular limits, and can use known anion ion exchange body, as hydrotalcite or containing the hydrous oxide of the element selected from magnesium, aluminium, titanium, zirconium, bismuth etc.They may be used singly or in combination of two or more.The present invention does not use fire retardant, requires (1/8inch batten) but the present invention can meet UL-94 V0 level.
The present invention makes the present invention on silver-plated framework and plating PPF framework, have good reliability by adjusting resin system and specialist additive simultaneously, and can on the package of different size, obtain substantially the same warpage performance.Compared with prior art, present composition suitability is extensive, and warpage is little, reliability is high, can meet the different package sizes of use and different frames material simultaneously.
Embodiment
Utilize embodiment that the present invention is described below, but scope of the present invention is not limited to these examples.
Embodiment 1, a kind of low warpage composition epoxy resin for QFN, said composition is made up of epoxy resin, resol, specialist additive, mineral filler, curing catalyst, releasing agent, coupling agent, tinting material, stress relief agent and ion capturing agent;
The content of curing catalyst, releasing agent, coupling agent, tinting material, stress relief agent and ion capturing agent is not respectively higher than 1% of composition total mass;
The content of epoxy resin accounts for 2% of total composition quality; Epoxy resin is the represented epoxy resin of formula [2].
The content of resol accounts for 7% of composition total mass; Resol is the represented resol of formula [5];
In epoxy resin, in epoxide group and resol, the equivalence ratio of phenolic hydroxyl group is 0.5-1.5;
The content of described mineral filler is 88% of composition total mass;
Described curing catalyst is selected from the one in imidazoles and its esters;
Described specialist additive is that its particle diameter is 200 ~ 500nm by the silicone resin containing methoxyl group and the core shell rubbers containing Butadiene/Styrene rubber and methyl methacrylate and the composite particles being composited by weight 1:1; The content of specialist additive is 0.1% of composition total mass.
Embodiment 2, a kind of low warpage composition epoxy resin for QFN, said composition is made up of epoxy resin, resol, specialist additive, mineral filler, curing catalyst, releasing agent, coupling agent, tinting material, stress relief agent and ion capturing agent;
The content of curing catalyst, releasing agent, coupling agent, tinting material, stress relief agent and ion capturing agent is not respectively higher than 1% of composition total mass;
The content of epoxy resin accounts for 7% of total composition quality; Epoxy resin is the mixture of the represented epoxy resin composition of formula [2] and formula [1], and in mixture, the content of the epoxy resin that formula [2] represents is 50% of epoxy resin total amount;
The content of resol accounts for 2% of composition total mass; Resol is the mixture of a kind of composition in the represented resol of the represented resol of formula [5] and formula [3], formula [4], and in mixture, the represented resol of formula [5] is 50% of resol total mass;
In epoxy resin, in epoxide group and resol, the equivalence ratio of phenolic hydroxyl group is 0.5-1.5;
The content of described mineral filler is 90% of composition total mass;
Described curing catalyst is selected from the one in imidazoles and its esters;
Described specialist additive is that its particle diameter is 200 ~ 500nm by the silicone resin containing methoxyl group and the core shell rubbers containing Butadiene/Styrene rubber and methyl methacrylate and the composite particles being composited by weight 1:5; The content of specialist additive is 0.3% of composition total mass.
Embodiment 3, a kind of low warpage composition epoxy resin for QFN, said composition is made up of epoxy resin, resol, specialist additive, mineral filler, curing catalyst, releasing agent, coupling agent, tinting material, stress relief agent and ion capturing agent;
The content of curing catalyst, releasing agent, coupling agent, tinting material, stress relief agent and ion capturing agent is not respectively higher than 1% of composition total mass;
The content of epoxy resin accounts for 3% of total composition quality; Epoxy resin is the mixture of the represented epoxy resin composition of formula [2] and formula [1], and in mixture, the content of the epoxy resin that formula [2] represents is 60% of epoxy resin total amount;
The content of resol accounts for 3% of composition total mass; Resol is the mixture of the represented resol composition of the represented resol of formula [5] and formula [3], formula [4], and in mixture, the represented resol of formula [5] is 70% of resol total mass;
In epoxy resin, in epoxide group and resol, the equivalence ratio of phenolic hydroxyl group is 0.5-1.5;
The content of described mineral filler is 92% of composition total mass;
Described curing catalyst is selected from the one in imidazoles and its esters;
Described specialist additive is that its particle diameter is 200 ~ 500nm by the silicone resin containing methoxyl group and the core shell rubbers containing Butadiene/Styrene rubber and methyl methacrylate and the composite particles being composited by weight 1:2; The content of specialist additive is 0.5% of composition total mass.
Embodiment 4, a kind of low warpage composition epoxy resin for QFN, said composition is made up of epoxy resin, resol, specialist additive, mineral filler, curing catalyst, releasing agent, coupling agent, tinting material, stress relief agent and ion capturing agent;
The content of curing catalyst, releasing agent, coupling agent, tinting material, stress relief agent and ion capturing agent is not respectively higher than 1% of composition total mass;
The content of epoxy resin accounts for 2% of total composition quality; Epoxy resin is the mixture of the represented epoxy resin composition of formula [2] and formula [1], and in mixture, the content of the epoxy resin that formula [2] represents is 55% of epoxy resin total amount;
The content of resol accounts for 2% of composition total mass; Resol is the mixture of the represented resol composition of the represented resol of formula [5] and formula [3], formula [4], and in mixture, the represented resol of formula [5] is 90% of resol total mass;
In epoxy resin, in epoxide group and resol, the equivalence ratio of phenolic hydroxyl group is 0.5-1.5;
The content of described mineral filler is 88% of composition total mass;
Described curing catalyst is selected from the one in imidazoles and its esters;
Described specialist additive is that its particle diameter is 200 ~ 500nm by the silicone resin containing methoxyl group and the core shell rubbers containing Butadiene/Styrene rubber and methyl methacrylate and the composite particles being composited by weight 1:1-5; The content of specialist additive is 1.0% of composition total mass.
Embodiment 5, the low warpage composition epoxy resin for QFN of embodiment 1-4 described in any one: mineral filler is SiO 2 powder or alumina powder; Mineral filler be shaped as spherical or dihedral.
Embodiment 6, the low warpage composition epoxy resin for QFN of embodiment 1-5 described in any one: in epoxy resin, in epoxide group and resol, the equivalence ratio of phenolic hydroxyl group is 0.9 ~ 1.1.
Embodiment 7, detects test for the low warpage composition epoxy resin of QFN.Test condition: utilize transfer moIding machine, 175 ℃ of die temperatures, forming pressure 5MPa, set time 120s condition under carry out.In addition, after fixing condition is 175 ℃, 6 hours.
(1) gel time: measure gelation time (s) by the 5.3rd article of gelation time of SJ/T 11197-1999 epoxy molding plastic.
(2) length of flow: measure the distance (cm) that flows by the 5.2nd article of helicoidal flow length of SJ/T 11197-1999 epoxy molding plastic.
(3) flame retardant resistance: the 5.12nd article of flame retardant resistance of pressing SJ/T 11197-1999 epoxy molding plastic measured the flame retardant resistance of material.
(4) CTE and Tg: measure CTE and Tg by the 5.6th article of linear expansivity of SJ/T 11197-1999 epoxy molding plastic and second-order transition temperature.
(5) water-intake rate: the water-intake rate of measuring embodiment by the 5.11st article of water-intake rate of SJ/T 11197-1999 epoxy molding plastic.
(6) reliability: by sample respectively on the silver-plated framework of QFN4*4mm and 7*7mm and plating PPF framework at 175 ℃ transfer mould technique encapsulate, after the demoulding, packaged sample after fixing at 175 ℃ was carried out to MSL1 by JESD22-A113D requirement after 6 hours, MSL2A, MSL3 rank is examined respectively.Use afterwards ultrasonic scanning equipment to carry out the scanning of layering situation.
(7) warpage: by sample respectively on the silver-plated framework of QFN4*4mm and 7*7mm at 175 ℃ transfer mould technique encapsulate, after the demoulding to packaged sample after fixing after 6 hours at 175 ℃.Use Shadow Morrie equipment to carry out warpage test, when test, plastic-sealed body faces up, and test value is that timing is that warpage is smiling face, and when test value is negative, warpage is the face of crying.
The results are shown in following table:
| Experiment | 1 | 2 | 3 | 4 | 5 |
| Epoxy resin formula [1] | 1 | 1 | 2 | 0.8 | 0 |
| Epoxy resin formula [2] | 3.5 | 3 | 2 | 2.2 | 2.8 |
| Resol formula [3] | 0 | 1 | 1 | 0.8 | 0 |
| Resol formula [4] | 2 | 1.5 | 1 | 1.5 | 1 |
| Resol formula [5] | 3 | 2 | 2 | 2 | 2.5 |
| Specialist additive | 0.5 | 0.5 | 0.5 | 0.6 | 0.6 |
| SiO 2 powder | 88 | 89 | 89.5 | 90 | 91 |
| Curing catalyst | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Tinting material | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Releasing agent | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Coupling agent | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Stress relief agent | 0.5 | 0.5 | 0.5 | 0.6 | 0.6 |
| Ion capturing agent | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| total | 100 | 100 | 100 | 100 | 100 |
| ? | ? | ? | ? | ? | ? |
| Gel time (second) | 42 | 40 | 42 | 43 | 45 |
| Length of flow (inch) | 55 | 53 | 50 | 48 | 47 |
| CTE1（ppm) | 7 | 7 | 6.5 | 6 | 5.5 |
| CTE2(ppm) | 40 | 45 | 43 | 42 | 35 |
| Tg(℃) | 110 | 113 | 115 | 120 | 120 |
| Fire-retardant (UL-94 1/8inch) | V-0 | V-0 | V-0 | V-0 | V-0 |
| Water-intake rate, PCT 24h (%) | 0.35 | 0.32 | 0.28 | 0.25 | 0.23 |
| Warpage (4*4mm) (mm) | 0.65 | 0.56 | 0.4 | 0.28 | 0.25 |
| Warpage (7*7mm) (mm) | -0.57 | -0.47 | -0.35 | -0.3 | -0.4 |
| Reliability (silver-plated framework, 4*4mm) | MSL2A | MSL1 | MSL1 | MSL1 | MSL2A |
| Reliability (silver-plated framework, 7*7mm) | MSL3 | MSL3 | MSL1 | MSL1 | MSL2A |
| Reliability (plating PPF framework, 4*4mm) | MSL2A | MSL2A | MSl1 | MSL1 | MSL2A |
| Reliability (plating PPF framework, 7*7mm) | MSL3 | MSL3 | MSL1 | MSL2A | MSL2A |
Claims (5)
1. for a low warpage composition epoxy resin of QFN, it is characterized in that: said composition is made up of epoxy resin, resol, specialist additive, mineral filler, curing catalyst, releasing agent, coupling agent, tinting material, stress relief agent and ion capturing agent;
The content of curing catalyst, releasing agent, coupling agent, tinting material, stress relief agent and ion capturing agent is not respectively higher than 1% of composition total mass;
The content of epoxy resin accounts for 2～7% of total composition quality; Epoxy resin is the represented epoxy resin of formula [2], or is the mixture of the represented epoxy resin composition of formula [2] and formula [1], and in mixture, the content of the epoxy resin that formula [2] represents is not less than 50% of epoxy resin total amount;
The content of resol accounts for 2～7% of composition total mass; Resol is the represented resol of formula [5], or be the mixture of at least one composition in the represented resol of the represented resol of formula [5] and formula [3], formula [4], in mixture, the represented resol of formula [5] is not less than 50% of resol total mass;
In epoxy resin, in epoxide group and resol, the equivalence ratio of phenolic hydroxyl group is 0.5-1.5;
The content of described mineral filler is 88～92% of composition total mass;
Described curing catalyst is selected from the one in imidazoles and its esters;
Described specialist additive is the composite particles being composited by weight 1:1-5 by the silicone resin containing methoxyl group and the core shell rubbers containing Butadiene/Styrene rubber and methyl methacrylate, and its particle diameter is 200～500nm; The content of specialist additive is the 0.1-1.0% of composition total mass.
2. the low warpage composition epoxy resin for QFN according to claim 1, is characterized in that: mineral filler is SiO 2 powder or alumina powder; Being shaped as of mineral filler is spherical.
3. the low warpage composition epoxy resin for QFN according to claim 1, is characterized in that: the content of curing catalyst, releasing agent, coupling agent, tinting material, stress relief agent and ion capturing agent is respectively the 0.1-1.0% of composition total mass.
4. the low warpage composition epoxy resin for QFN according to claim 1, is characterized in that: in the time that epoxy resin is mixture, in mixture, the content of the epoxy resin that the content of the epoxy resin that formula [2] represents represents than formula [1] is high by 10～20%.
5. the low warpage composition epoxy resin for QFN according to claim 1, is characterized in that: in epoxy resin, in epoxide group and resol, the equivalence ratio of phenolic hydroxyl group is 0.9～1.1.
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| WO2016145648A1 (en) * | 2015-03-19 | 2016-09-22 | Ablestik (Shanghai) Ltd. | Epoxy molding compound for high power soic semiconductor package application |
| JP6624545B2 (en) * | 2015-03-31 | 2019-12-25 | パナソニックＩｐマネジメント株式会社 | Thermosetting resin composition, metal-clad laminate, insulating sheet, printed wiring board, method for manufacturing printed wiring board, and package substrate |
| JP6800115B2 (en) * | 2017-09-07 | 2020-12-16 | 信越化学工業株式会社 | Resin composition, resin film, semiconductor laminate, semiconductor laminate manufacturing method and semiconductor device manufacturing method |
| CN110483949A (en) * | 2019-08-19 | 2019-11-22 | 江苏华海诚科新材料股份有限公司 | A kind of composition epoxy resin and preparation method thereof suitable for BGA |
| CN112980138A (en) * | 2019-12-17 | 2021-06-18 | 衡所华威电子有限公司 | Epoxy resin composition for packaging electronic components and preparation method thereof |
| CN112980139A (en) * | 2019-12-17 | 2021-06-18 | 衡所华威电子有限公司 | Epoxy resin composition for tantalum capacitor packaging and preparation method thereof |
| CN114276653B (en) * | 2021-12-30 | 2024-01-26 | 江苏中科科化新材料股份有限公司 | Epoxy resin composition and application thereof, epoxy resin and preparation method thereof |
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| JP2006002040A (en) * | 2004-06-17 | 2006-01-05 | Hitachi Chem Co Ltd | Epoxy resin molding material for encapsulation and electronic component device |
| CN101602881B (en) * | 2009-05-12 | 2013-01-23 | 东莞联茂电子科技有限公司 | Thermosetting resin composition and application thereof |
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Address after: 222000 Lianyungang Economic and Technological Development Zone, Lianyungang City, Jiangsu Province Patentee after: JIANGSU HUAHAI CHENGKE NEW MATERIAL CO., LTD. Address before: 222000 Lianyungang Economic and Technological Development Zone, Lianyungang City, Jiangsu Province Patentee before: Jiangsu Huahai Chengke New Materials Co.,Ltd. |
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Inventor after: Tan Wei Inventor after: Liu Hongjie Inventor after: Li Lanxia Inventor after: Cui Liang Inventor before: Tan Wei Inventor before: Liu Hongjie Inventor before: Li Lanxia Inventor before: Light up Inventor before: Shi Erzeng |