CN109517335B - Epoxy resin composition for molding compound and preparation method thereof - Google Patents
Epoxy resin composition for molding compound and preparation method thereof Download PDFInfo
- Publication number
- CN109517335B CN109517335B CN201811288575.2A CN201811288575A CN109517335B CN 109517335 B CN109517335 B CN 109517335B CN 201811288575 A CN201811288575 A CN 201811288575A CN 109517335 B CN109517335 B CN 109517335B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- parts
- formula
- resin composition
- molding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2125/00—Compositions for processes using internal mould release agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides an epoxy resin composition for a molding compound, which comprises the following components: 440-624 parts by weight of epoxy resin; 100 parts of epoxy resin II and 300 parts of epoxy resin II; 80-250 parts of epoxy resin III; 0.1-5 parts by weight of silicone oil; 53-69 parts of curing accelerator; 0-40 parts of inorganic filler; 10-25 parts of a release agent. The invention selects low-viscosity epoxy resin, low-melting-point release agent and low-viscosity silicone oil, screens proper accelerator and other additives, and realizes the optimal combination by adjusting the types and the contents of the components. After the composition is added into a molding compound formula, a liquid protective layer is formed on a mold during demolding, so that the demolding effect is effectively improved, and the mold fouling resistance is improved.
Description
Technical Field
The present invention belongs to the field of plastic technology, and is especially the field of molding compound technology, such as additive for epoxy molding compound for encapsulating integrated circuit. The invention can improve the demolding and anti-mold fouling performance of the molding compound in use.
Background
The molding compound is generally a thermosetting plastic and is used by compression molding, injection molding or transfer molding. One of the most widely used applications is epoxy molding compounds for packaging integrated circuits. Injection molding and transfer molding are generally used.
The molding materials may suffer from problems of poor release or mold fouling in continuous molding during use, and release and mold fouling are generally dealt with by adding release agents or silicones. High-end integrated circuit packages sometimes require continuous operation greater than 250 die while ensuring package reliability. The practice of increasing the content of mold release agent in the formulation is difficult to achieve.
Disclosure of Invention
The invention aims to provide an epoxy resin composition for a molding compound and a preparation method thereof, which can be used as an additive of the molding compound and can effectively improve the demolding and anti-molding performance/continuous operability during use.
The technical scheme of the invention is as follows:
an epoxy resin composition for molding compound comprises the following components: 440-624 parts by weight of epoxy resin; 100 parts of epoxy resin II and 300 parts of epoxy resin II; 80-250 parts of epoxy resin III; 0.1-5 parts by weight of silicone oil; 53-69 parts of curing accelerator; 0-40 parts of inorganic filler; 10-25 parts of a release agent;
wherein, the epoxy resin I is bisphenol A epoxy resin, and the structural formula is shown as formula I:
the epoxy resin II is biphenyl epoxy resin, and the structural formula is shown as the formula II:
the epoxy resin III is naphthalene epoxy resin, and the structural formula is shown as the formula III:
preferably, the first and second electrodes are formed of a metal,
the silicone oil is polydimethylsiloxane, and the structural formula is shown as a general formula IV:
The curing accelerator is one or more of organic phosphorus compounds, imidazole compounds, tertiary amine compounds and derivatives thereof.
The inorganic filler is fumed silica or other silica with the particle size of less than 10 microns, and the content of the inorganic filler in the composition is 2 parts by weight.
The release agent is one or a combination of more of natural wax or synthetic wax. Preferably a mold release agent stearic acid wax; the release agent is carnauba wax.
The epoxy resin composition also comprises other auxiliary agents, wherein the other auxiliary agents are one or more of low-stress modifier, coloring agent, other fillers, coupling agent, ion trapping agent, defoaming agent and leveling agent;
the low-stress modifier is rubber, organosilane or a combination of one or more of the rubber and the organosilane;
the other fillers are one or a combination of more of silicon dioxide and aluminum oxide; the silica may be crystalline or fused angular or fused spherical; the particle size of the alumina and silica should be less than 180 microns.
The invention provides the application of the epoxy resin composition in molding plastics, and the application is semiconductor packaging and other device packaging formed by compression molding, injection molding or transfer molding.
The preparation method of the epoxy resin composition comprises the following steps:
(A) accurately weighing the components, and stirring and heating the epoxy resins I, II and III in a container at the temperature of 100 ℃ and 150 ℃ for 10-30 minutes;
(B) cooling to 50-100 deg.C;
(C) adding epoxy resins I, II and III, and stirring;
(D) adding silicone oil and stirring;
(E) adding a curing accelerator, an inorganic filler and a release agent and stirring;
(F) if other additives exist, adding other additives and stirring;
(G) cooling;
(H) standing for 5-60 hours.
The invention does not contain curing agents such as phenolic resin, acid anhydride and the like.
The technical scheme of the invention mainly solves the problems of demoulding and mold fouling of the molding compound.
With respect to mold release problems, mold release agents are generally used for molding compounds, and if the amount of mold release agent used is too small, it may cause difficulty in demolding the article. If the release agent is excessive, the adhesive property of the product is reduced, and a series of product reliability problems are caused, and the mold fouling problem is caused. Therefore, the characteristic of the release property of the material can be expressed by the adhesive strength of the material to a certain base material (such as copper) and the characteristic of the mold fouling property of the material can be expressed by (at most) packaging mold times.
Regarding mold fouling, continuous use of the molding compound during use of the molding compound generally results in mold fouling, which can contaminate the article and affect the appearance of the article. This property can be characterized by the packaging order of the material: the packaging mold can be used only after being cleaned after being repeatedly packaged to a corresponding mold, and the material with low packaging mold number influences the production efficiency and improves the production cost.
The invention solves the process problems of material mixing temperature and the like in the composition processing process. Solves the problems of liquid state and difficult solidification of the composition at the later processing stage.
The invention selects low-viscosity epoxy resin, low-melting-point release agent and low-viscosity silicone oil, screens proper accelerator and other additives, and realizes the optimal combination by adjusting the types and the contents of the components. After the composition is added into a molding compound formula, a liquid protective layer is formed on a mold during demolding, so that the demolding effect is effectively improved, and the mold fouling resistance is improved.
Detailed Description
The invention is further illustrated, but is not intended to be limited, by the following specific examples;
the sources of materials used in the examples of the invention and comparative examples are as follows:
bisphenol A epoxy resin I, A1 (available from Nippon DIC Co., Ltd.)
Biphenyl type epoxy resin II, A2 (available from Nippon DIC Co., Ltd.)
Naphthalene type epoxy resin III, A3 (available from Nippon DIC Co., Ltd.)
Silicone oil, B (Mei Tu)
Curing accelerator 2-methylimidazole, C1
Curing accelerators triphenylphosphine, C2
Curing accelerators DBU, C3
Inorganic filler silica, wherein fumed silica accounts for 5%, 8% of particle size less than 10 μm, and D
Mold release agent stearic acid wax, E1;
release agents carnauba wax, E2;
modifier CTBN, F1 (from Shenzhen jiadida)
Modifier ETBN, F2, (available from DeVott, Beijing)
Coupling agent KH560, G1, (available from Jiangsu Chenguang)
Coupling agent KH590, G2, (available from Jiangsu Chenguang)
Examples 1 to 10
The formulation composition of the epoxy resin composition is shown in table 1.
Method of use of the epoxy resin composition: the molding compound is processed according to the established procedures and then is added into the molding compound formula as an additive, and the content of the mold release agent in the molding compound is 0.3 percent.
Preparation of examples 1 to 10:
1) accurately weighing the components, and stirring and heating the epoxy resins I, II and III in a container at 150 ℃ for 30 minutes;
2) cooling to 100 ℃;
3) adding epoxy resins I, II and III, and stirring;
4) adding silicone oil and stirring;
5) adding a curing accelerator, an inorganic filler and a release agent and stirring;
6) standing for 60 hours.
Table 1: examples 1 to 10 epoxy resin compositions (unit: g), each example having a total weight of 1000g
Remarking:
the release agent used in examples 1-5 was stearic acid wax E1.
The release agent used in examples 6-10 was carnauba wax E2.
Comparative example 1
The total weight of the epoxy resin composition is 1000g, and the epoxy resin composition comprises the following components in parts by weight:
50g of bisphenol A epoxy resin;
30g of biphenyl type epoxy resin;
100g of linear phenolic resin;
3g of curing accelerator 2-methylimidazole;
3g of silicone oil;
release agent stearic acid wax 1g
3g of release agent carnauba wax;
3g of modifier CTBN;
coupling agent KH560, 5 g;
colorant 2g
800g of silica.
The composition was processed according to established procedures and added as an additive to the molding compound formulation, the content of mold release agent in the molding compound being 0.3%.
Comparative example 2
The total weight of the epoxy resin composition is 1000g, and the epoxy resin composition comprises the following components in parts by weight:
50g of o-cresol epoxy resin;
30g of biphenyl type epoxy resin;
100g of linear phenolic resin;
3g of curing accelerator 2-methylimidazole;
3g of silicone oil;
release agent stearic acid wax 1g
3g of release agent carnauba wax;
3g of modifier CTBN;
coupling agent KH560, 5 g;
colorant 2g
800g of silica.
The composition was processed according to established procedures and added as an additive to the molding compound formulation, the content of mold release agent in the molding compound being 0.5%.
Comparative example 3
The total weight of the epoxy resin composition is 1000g, and the epoxy resin composition comprises the following components in parts by weight:
70g of o-cresol epoxy resin;
30g of biphenyl type epoxy resin;
130g of Z-lock phenolic resin;
3g of curing accelerator 2-methylimidazole;
3g of silicone oil;
release agent stearic acid wax 1g
3g of release agent carnauba wax;
3g of modifier CTBN;
coupling agent KH560, 5 g;
colorant 2g
751g of silica.
The composition was processed according to established procedures and added as an additive to the molding compound formulation, the content of mold release agent in the molding compound being 0.7%.
The invention relates to an application effect characterization method.
The application effect of the invention can be characterized by two methods: (1) the mold continuous packaging times can represent the mold fouling resistance in application; (2) the bonding strength with copper can represent the demolding performance in application, and simultaneously can reflect that the bonding force is not reduced due to the fact that more demolding agents are added in the formula.
Comparative and example application effect characterization data are given in the following table:
when the content of the release agent is first determined, it is usually appropriate to add 0.3%, and the excess ratio results in a decrease in adhesion.
Looking again at the packaging die count, less than 200 is generally not acceptable, as shown in comparative example 1.
Looking again at the bonding strength, the typical packaging SOP related product requirement is not less than 2.0.
In comparative example 1, the mold fouling resistance and the mold stripping resistance did not meet the standards, and the number of continuous packaging molds did not meet the customer requirements; in comparative examples 2 and 3, the content of the release agent in the molding compound is increased, the number of continuous packaging times is increased, the adhesion with copper is greatly reduced, and the application range of the material is reduced.
In conclusion, in examples 1 to 10, the mold fouling resistance and the mold release resistance of the molding materials were improved without a decrease in the adhesion strength to copper. The properties of the compositions of the present invention are effective.
Claims (6)
1. An epoxy resin composition for molding compound, which is characterized by comprising the following components: 440-624 parts by weight of epoxy resin; 100 parts of epoxy resin II and 300 parts of epoxy resin II; 80-250 parts of epoxy resin III; 0.1-5 parts by weight of silicone oil; 53-69 parts of curing accelerator; 0-40 parts of inorganic filler; 10-25 parts of a release agent;
wherein, the epoxy resin I is bisphenol A epoxy resin, and the structural formula is shown as formula I:
The epoxy resin II is biphenyl epoxy resin, and the structural formula is shown as the formula II:
The epoxy resin III is naphthalene epoxy resin, and the structural formula is shown as the formula III:
the silicone oil is polydimethylsiloxane, and the structural formula is shown as a general formula IV:
the general formula IV is shown in the specification, wherein n =0-5, and the content of the silicone oil in the composition is 5 parts by weight;
the release agent is one or a combination of more of natural wax or synthetic wax.
2. The epoxy resin composition of claim 1, wherein the curing accelerator is one or more of an organic phosphorus compound, an imidazole compound, a tertiary amine compound, and derivatives thereof.
3. The epoxy resin composition according to claim 1, wherein the inorganic filler is fumed silica or other silica having a particle size of less than 10 μm, and is contained in the composition in an amount of 2 parts by weight.
4. The epoxy resin composition of claim 1, further comprising other additives, wherein the other additives are one or more of a low stress modifier, a colorant, other fillers, a coupling agent, an ion scavenger, a defoamer, and a leveling agent;
the low-stress modifier is rubber, organosilane or a combination of one or more of the rubber and the organosilane;
the other fillers are one or a combination of more of silicon dioxide and aluminum oxide; the silica may be crystalline or fused angular or fused spherical; the particle size of the alumina and silica should be less than 180 microns.
5. Use of the epoxy resin composition according to any of claims 1 to 4 in molding plastics, for molding semiconductor packages and other device packages by compression molding, injection molding or transfer molding.
6. The process for producing the epoxy resin composition according to any one of claims 1 to 4, which comprises the steps of:
(A) accurately weighing the components, and stirring and heating the epoxy resins I, II and III in a container at the temperature of 100 ℃ and 150 ℃ for 10-30 minutes;
(B) cooling to 50-100 deg.C;
(C) adding epoxy resins I, II and III, and stirring;
(D) adding silicone oil and stirring;
(E) adding a curing accelerator, an inorganic filler and a release agent and stirring;
(F) if other additives exist, adding other additives and stirring;
(G) cooling;
(H) standing for 5-60 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811288575.2A CN109517335B (en) | 2018-10-31 | 2018-10-31 | Epoxy resin composition for molding compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811288575.2A CN109517335B (en) | 2018-10-31 | 2018-10-31 | Epoxy resin composition for molding compound and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109517335A CN109517335A (en) | 2019-03-26 |
| CN109517335B true CN109517335B (en) | 2021-02-09 |
Family
ID=65773566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811288575.2A Active CN109517335B (en) | 2018-10-31 | 2018-10-31 | Epoxy resin composition for molding compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109517335B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109864012B (en) * | 2019-04-12 | 2021-08-13 | 云南农业大学 | Method for manufacturing artificial beewax honeycomb |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127291A (en) * | 2010-12-23 | 2011-07-20 | 广东生益科技股份有限公司 | Halogen-free epoxy resin composition and covering film prepared from same |
| CN102504493A (en) * | 2011-11-18 | 2012-06-20 | 江苏华海诚科新材料有限公司 | Epoxy resin composition applicable to pre-encapsulation of inner interconnection framework system |
| CN103555246A (en) * | 2013-10-18 | 2014-02-05 | 北京海斯迪克新材料有限公司 | Epoxy adhesive for electron component integrated molding technology and preparation method of epoxy adhesive |
-
2018
- 2018-10-31 CN CN201811288575.2A patent/CN109517335B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127291A (en) * | 2010-12-23 | 2011-07-20 | 广东生益科技股份有限公司 | Halogen-free epoxy resin composition and covering film prepared from same |
| CN102504493A (en) * | 2011-11-18 | 2012-06-20 | 江苏华海诚科新材料有限公司 | Epoxy resin composition applicable to pre-encapsulation of inner interconnection framework system |
| CN103555246A (en) * | 2013-10-18 | 2014-02-05 | 北京海斯迪克新材料有限公司 | Epoxy adhesive for electron component integrated molding technology and preparation method of epoxy adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109517335A (en) | 2019-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20120095879A (en) | Curable resin composition for optical semiconductor encapsulation, and cured product of same | |
| JP2014173063A (en) | Method for producing electric/electronic component and electric/electronic component | |
| JP2001234032A (en) | Epoxy resin composition for optical semiconductor sealing use | |
| CN109517335B (en) | Epoxy resin composition for molding compound and preparation method thereof | |
| KR102570038B1 (en) | Thermosetting epoxy resin sheet for sealing semiconductor, semiconductor device, and manufacturing method thereof | |
| JP6307352B2 (en) | Resin composition for optical semiconductor encapsulation and optical semiconductor device | |
| JP2018002923A (en) | Method for producing electric/electronic component, epoxy resin composition for injection molding, and electric/electronic component | |
| CN106433038A (en) | Epoxy resin composition for photoelectric coupler packaging and preparation method of epoxy resin composition | |
| JP5057015B2 (en) | Epoxy resin composition for semiconductor encapsulation and semiconductor device | |
| JP6598519B2 (en) | Manufacturing method of electronic / electrical component and electronic / electrical component | |
| CN107955335B (en) | Preparation method of epoxy resin composition prepared by using stirrer | |
| JPH07309998A (en) | Mold surface release treatment resin composition, release treatment of surface of mold using the composition, production of thermosetting resin molded product using mold release-treated with the composition | |
| JP2017095548A (en) | Thermosetting epoxy resin composition for optical semiconductor element encapsulation and optical semiconductor deice using the same | |
| JP4762841B2 (en) | Glass material composition for protecting optical semiconductor element and optical semiconductor device using the same | |
| JP2954412B2 (en) | Epoxy resin composition | |
| JP2005290111A (en) | Resin composition for encapsulation and semiconductor device | |
| JP2014227465A (en) | Liquid resin compositions for injection molding, and semiconductor device | |
| KR0158716B1 (en) | Epoxy resin composition for photo-semiconductor | |
| KR20190096741A (en) | Epoxy resin composition | |
| JP2013189490A (en) | Epoxy resin composition for encapsulation and semiconductor device | |
| KR102643484B1 (en) | Granule type resin composition for encapsulating a semiconductor device | |
| JP6351927B2 (en) | Resin composition for sealing and method for manufacturing semiconductor device | |
| JPH06228280A (en) | Curing agent for epoxy resin composition, epoxy resin composition and semiconductor device | |
| JP2007045884A (en) | Resin composition for sealing and semiconductor device | |
| KR20170079115A (en) | Epoxy Resin Composition for Sealing Semiconductor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: No.70, Meilan East Road, hailing Industrial Park, Taizhou City, Jiangsu Province 225300 Applicant after: Jiangsu Kehua New Material Technology Co.,Ltd. Address before: No.76, Meilan East Road, hailing Industrial Park, Hailing District, Taizhou City, Jiangsu Province 225300 Applicant before: KEHUA NEW MATERIALS TAIZHOU Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: No.70, Meilan East Road, hailing Industrial Park, Taizhou City, Jiangsu Province 225300 Patentee after: Jiangsu Sinopec New Materials Co.,Ltd. Address before: No.70, Meilan East Road, hailing Industrial Park, Taizhou City, Jiangsu Province 225300 Patentee before: Jiangsu Kehua New Material Technology Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |