KR20170127814A - Epoxy resin composition for encapsulating semicomductor device and semiconductor device encapsulated using the same - Google Patents
Epoxy resin composition for encapsulating semicomductor device and semiconductor device encapsulated using the same Download PDFInfo
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- KR20170127814A KR20170127814A KR1020160058438A KR20160058438A KR20170127814A KR 20170127814 A KR20170127814 A KR 20170127814A KR 1020160058438 A KR1020160058438 A KR 1020160058438A KR 20160058438 A KR20160058438 A KR 20160058438A KR 20170127814 A KR20170127814 A KR 20170127814A
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- NGQGRUANWKNCAB-UHFFFAOYSA-N Oc1cccc(C2(c(cccc3)c3-c3c2cccc3)c2cccc(O)c2)c1 Chemical compound Oc1cccc(C2(c(cccc3)c3-c3c2cccc3)c2cccc(O)c2)c1 NGQGRUANWKNCAB-UHFFFAOYSA-N 0.000 description 2
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- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
- C09K2200/0647—Polyepoxides
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Abstract
The present invention relates to an epoxy resin composition for semiconductor encapsulation comprising a modified epoxy resin modified with at least one of compounds represented by the general formulas (1) to (3), a curing agent and an inorganic filler, and a semiconductor device sealed using the epoxy resin composition.
Description
TECHNICAL FIELD The present invention relates to an epoxy resin composition for semiconductor encapsulation and a semiconductor device sealed with the composition. More particularly, the present invention relates to an epoxy resin composition for semiconductor encapsulation having low elasticity and low shrinkage property at a high temperature while minimizing deterioration of existing properties of the epoxy resin, and a semiconductor device sealed using the same.
BACKGROUND ART [0002] With the recent miniaturization, light weight, and high performance of electronic devices, surface mounting of semiconductor packages used in electronic devices has been made. Conventionally, QFP (Quad Flat Package) and SOP (Small Outline Package) have been mainly used as surface mount semiconductors. However, QFP (Quad Flat Package) and SOP (Small Outline Package) semiconductor packages have reached the limits of multi-pin and high speed characteristics. Accordingly, area surface mounting type semiconductors such as BGA (Ball Grid Array) and CSP (Wafer-level Chip Sizes Package) that can improve multi-pin and high speed characteristics have been developed.
In the above-described surface-mounted semiconductor packages, semiconductor elements are mounted on one surface of a substrate, and solder balls are two-dimensionally connected in parallel on the surface opposite to the element mounting surface of the substrate. Generally, in the case of area-surface-mounted semiconductor packages, they are manufactured in the form of a single-side seal which seals only the surface on which the device is mounted. When a metal substrate such as a lead frame is used, an encapsulating layer having a level of several tens of micrometers may be formed on the solder ball forming surface. However, considering that the thickness of the encapsulating layer on the device mounting surface is several hundred micrometers to several millimeters, It can be said that it corresponds to one side seal substantially.
In the case of the semiconductor package having the single-sided sealing structure as described above, it is preferable to seal the substrate by the incompleteness of the thermal expansion and the heat shrinkage between the cured products of the sealing material forming the sealing layer and / or the curing shrinkage upon molding and curing of the sealing material composition Warpage tends to occur immediately after molding. In order to bond the solder balls to the substrate, a high-temperature heating process of 200 ° C or more is performed. Such a high-temperature heating process causes the package bending to occur, so that a large number of solder balls are not planarized and peeled from the circuit board, There is also a problem of deterioration.
In order to solve the above problems, a method of suppressing the curing shrinkage of the resin composition by increasing the glass transition temperature of the epoxy resin composition by combining a triphenolmethane type epoxy resin and a triphenolmethane type phenol resin, A method of reducing the linear expansion coefficient of the epoxy resin composition by increasing the blending amount has been proposed.
However, when an epoxy resin composition having a high glass transition temperature is used, there is a problem that the modulus of elasticity is greatly increased and is vulnerable to external stress due to heat or external impact. When the content of the inorganic filler is increased, A problem arises.
Therefore, development of an epoxy resin composition for semiconductor encapsulation having low elasticity at a high temperature and low shrinkage property at a high temperature while minimizing deterioration of the existing properties of the epoxy resin is required.
An object of the present invention is to provide an epoxy resin composition having a low elastic modulus at a high temperature of 200 ° C or higher while minimizing deterioration of physical properties of the conventional epoxy resin composition.
Another object of the present invention is to provide a semiconductor device which is sealed with the epoxy resin composition as described above.
In one aspect, the present invention provides an epoxy resin composition for semiconductor encapsulation comprising a modified epoxy resin modified with at least one of compounds represented by Chemical Formulas 1 to 3, a curing agent, and an inorganic filler.
[Chemical Formula 1]
(2)
(3)
At this time, the modified epoxy resin composition may be formed by reacting at least one of the compounds represented by Chemical Formulas 1 to 3 with an epoxy resin at a molar ratio of 4: 1 to 20: 1.
The epoxy resin composition may contain 0.5 to 20% by weight of the modified epoxy resin, 0.1 to 13% by weight of a curing agent, and 70 to 95% by weight of an inorganic filler, and at least one of a curing accelerator, a coupling agent, As shown in FIG.
The epoxy resin composition for semiconductor encapsulation has an elastic modulus reduced by 20% or more as compared with an epoxy resin composition containing an unmodified epoxy resin. Here, the modulus of elasticity is an elastic modulus measured at 260 DEG C after molding the epoxy resin composition.
The epoxy resin composition for semiconductor encapsulation may have a curing shrinkage of 0.1% or less as measured by the formula (1) for a specimen produced by molding using a transfer molding machine and then post-curing.
(1): Cure shrinkage ratio (%) = {(L 0 -L 1 ) / L 0 } × 100
In the formula (1), L 0 is the length of the molded specimen obtained by molding the epoxy resin composition at 175 ° C and 70 kgf / cm 2 using a transfer molding press, and L 1 is the length of the molded specimen at 175 ° C Length of the specimen after post molding curing in the oven for 4 hours and after cooling.
In another aspect, the present invention provides a sealed semiconductor device using the epoxy resin composition for semiconductor encapsulation according to the present invention.
The epoxy resin composition according to the present invention has a low elasticity and low shrinkage at high temperature by using a modified epoxy resin compound modified with a specific compound. The epoxy resin composition of the present invention having such characteristics can effectively suppress the occurrence of package warpage caused by a high-temperature process, and can be particularly useful for a semiconductor package having a one-side sealing structure.
Hereinafter, the present invention will be described in more detail.
In the following description of the present invention, detailed description of known related arts will be omitted when it is determined that the gist of the present invention may be unnecessarily obscured by the present invention.
In the case where the word 'includes', 'having', 'done', etc. are used in this specification, other parts can be added unless '~ only' is used. Unless the context clearly dictates otherwise, including the plural unless the context clearly dictates otherwise.
Also, in interpreting the constituent elements, even if there is no separate description, it is interpreted as including the error range.
In the present specification, " X to Y " representing the range means " X or more and Y or less ".
The present inventors have conducted research to develop a material for semiconductor encapsulation having low shrinkage and low elasticity at a high temperature so as to minimize occurrence of warpage of a single-sided encapsulation structure semiconductor package. As a result, they have found that a modified epoxy resin modified with a specific compound The inventive epoxy resin composition was developed.
Specifically, the epoxy resin composition for semiconductor encapsulation according to the present invention includes a modified epoxy resin modified with at least one of compounds represented by the following Chemical Formulas 1 to 3, a curing agent, and an inorganic filler.
[Chemical Formula 1]
(2)
(3)
Hereinafter, each component of the epoxy resin composition of the present invention will be described in detail.
(A) a modified epoxy resin
The epoxy resin used in the present invention is a modified epoxy resin modified by reacting an epoxy resin with a compound having two or more phenolic hydroxyl groups.
Here, the compound having a phenolic hydroxyl group may be at least one selected from the group consisting of compounds represented by the following formulas (1) to (3).
[Chemical Formula 1]
(2)
(3)
When a compound having two or more phenolic hydroxyl groups represented by Chemical Formulas 1 to 3 is reacted with an epoxy resin, a ring-opening reaction of an epoxy ring of an epoxy resin is caused by a compound having a phenolic hydroxyl group. As a result, A modified epoxy resin having a smaller epoxy equivalent is formed. According to the studies of the present inventors, it has been found that the above-mentioned change in epoxy equivalent has little effect on physical properties such as fluidity and hardenability, but significantly reduces elasticity at high temperature. In addition, the compounds of the above formulas (1) to (3) react with the epoxy resin and show a decrease in shrinkage at high temperature.
Preferably, the modified epoxy resin can be formed by reacting the compound having two or more phenolic hydroxyl groups: epoxy resin in a molar ratio of 4: 1 to 20: 1, preferably 6: 1 to 12: 1 . When the reaction molar ratio of the compound having two or more phenolic hydroxyl groups to the epoxy resin satisfies the above range, the elastic modulus and shrinkage force at high temperature can be effectively reduced while minimizing deterioration of the existing properties of the epoxy resin.
On the other hand, as the epoxy resin which reacts with the phenolic hydroxyl group, epoxy resins generally used in this technical field can be used. For example, the epoxy resin is an epoxy resin obtained by epoxidating a condensate of phenol or alkyl phenol and hydroxybenzaldehyde, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a multifunctional epoxy resin, a naphthol novolak Novolak type epoxy resins such as bisphenol A / bisphenol F / bisphenol AD, glycidyl ether of bisphenol A / bisphenol F / bisphenol AD, bishydroxybiphenyl type epoxy resin, dicyclopentadiene type epoxy resin, etc. . More specifically, the epoxy resin may be a cresol novolak type epoxy resin, a multifunctional epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, or the like.
For example, the polyfunctional epoxy resin may be an epoxy resin represented by the following formula (4).
[Chemical Formula 4]
Wherein R 1, R 2, R 3, R 4 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 6 and R 7 are each independently a hydrogen atom, a methyl group or an ethyl group, to be. Preferably, each of R 1, R 2, R 3, R 4 and R 5 is independently selected from the group consisting of hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, , And R6 and R7 may be hydrogen, but are not necessarily limited thereto.
More specifically, the multifunctional epoxy resin composition may be a triphenolalkane type epoxy resin such as a triphenolmethane type epoxy resin, a triphenolpropane type epoxy resin, or the like.
The phenol aralkyl type epoxy resin may be, for example, a phenol aralkyl type epoxy resin having a novolac structure including a biphenyl derivative represented by the following formula (5).
[Chemical Formula 5]
In formula (5), the average value of b is 1 to 7.
The biphenyl type epoxy resin may be, for example, a biphenyl type epoxy resin represented by the following formula (6).
[Chemical Formula 6]
Wherein R 8, R 9, R 10, R 11, R 12, R 13, R 14 and R 15 are each independently an alkyl group having 1 to 4 carbon atoms, and the average value of c is 0 to 7.
On the other hand, the modification reaction between the epoxy resin and the compound having two or more phenolic hydroxyl groups may be carried out by reacting the epoxy resin with a compound having two or more phenolic hydroxyl groups in the presence of a catalyst and / or a base for a predetermined time . As the catalyst, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetraphenylphosphonium chloride, hexadecyltributylphosphonium bromide and the like can be used. As the base, NaOH, KOH, K 2 CO 3 and the like can be used. Can be used.
On the other hand, the modified epoxy resin (A) is used in an amount of about 0.5 to 20% by weight, specifically about 3 to 15% by weight, more specifically about 3 to 12% by weight in the epoxy resin composition for sealing a semiconductor device As shown in FIG.
(B) Curing agent
As the curing agent, curing agents generally used for sealing semiconductor devices may be used without limitation, and preferably, a curing agent having two or more reactors may be used.
Specific examples of the curing agent include phenol aralkyl type phenol resin, phenol novolak type phenol resin, xylok type phenol resin, cresol novolak type phenol resin, naphthol type phenol resin, terpene type phenol resin, Phenolic resin, dicyclopentadiene-based phenol resin, novolak-type phenol resin synthesized from bisphenol A and resole, polyhydric phenol compound including tris (hydroxyphenyl) methane, dihydroxybiphenyl, maleic anhydride and phthalic anhydride, , Aromatic amines such as methanophenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone, but are not limited thereto.
For example, the curing agent may include at least one of a phenol novolak type phenol resin, a xylock type phenol resin, a phenol aralkyl type phenol resin, and a multifunctional phenol resin.
The phenol novolak type phenol resin may be, for example, a phenol novolac type phenol resin represented by the following formula (7).
(7)
(D in the general formula (7) is 1 to 7).
The phenol novolak type phenol resin represented by the above formula (7) has a short crosslinking point interval, and when it reacts with the epoxy resin, the crosslinking density becomes high and the glass transition temperature of the cured product can be increased, The warping of the package can be suppressed more effectively.
The phenol aralkyl type phenol resin may be, for example, a phenol aralkyl type phenol resin having a novolak structure including a biphenyl derivative in a molecule represented by the following formula (8).
[Chemical Formula 8]
(In the formula (8), the average value of e is 1 to 7).
The phenol aralkyl type phenolic resin represented by the above formula (8) reacts with an epoxy resin to form a carbon layer (char), thereby blocking the transfer of heat and oxygen to the periphery, thereby achieving flame retardancy.
The xylo-type phenol resin may be, for example, a xylok-type phenol resin represented by the following formula (9).
[Chemical Formula 9]
(In the above formula (9), the average value of f is 0 to 7)
The xylyl phenol resin represented by the above formula (9) is preferable in terms of enhancing the fluidity and reliability of the resin composition.
The multifunctional phenol resin may be, for example, a multifunctional phenol resin containing a repeating unit represented by the following formula (10).
[Chemical formula 10]
(The average value of g in the above formula (10) is 1 to 7.)
The multifunctional phenol resin containing the repeating unit represented by the above formula (10) is preferable in terms of reinforcing the high temperature bending property of the epoxy resin composition.
These curing agents may be used alone or in combination. Further, it can be used as an additional compound prepared by subjecting the above curing agent to a linear reaction such as an epoxy resin, a curing accelerator, a releasing agent, a coupling agent, a stress relieving agent and the like and a melt master batch.
The curing agent may be contained in an amount of 0.1 to 13% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 8% by weight in the epoxy resin composition for sealing a semiconductor device.
The blending ratio of the modified epoxy resin and the curing agent can be adjusted according to the requirements of mechanical properties and moisture resistance reliability in the package. For example, the chemical equivalent ratio of the epoxy resin to the curing agent may be about 0.95 to about 3, specifically about 1 to about 2, more specifically about 1 to about 1.75. When the compounding ratio of the epoxy resin and the curing agent is in the above range, excellent strength can be realized after curing the epoxy resin composition.
Inorganic filler
The inorganic filler is intended to improve the mechanical properties and low stress of the epoxy resin composition. As the inorganic filler, general inorganic fillers used for the semiconductor sealing material can be used without limitation, and are not particularly limited. Examples of the inorganic filler include fused silica, crystalline silicate, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, glass fiber and the like . These may be used alone or in combination.
Preferably, fused silica having a low linear expansion coefficient is used for low stress. The fused silica refers to amorphous silica having a true specific gravity of 2.3 or less and includes amorphous silica obtained by melting crystalline silica or synthesized from various raw materials. Although the shape and the particle diameter of the fused silica are not particularly limited, the fused silica containing 50 to 99% by weight of spherical fused silica having an average particle diameter of 5 to 30 탆 and the spherical fused silica having an average particle diameter of 0.001 to 1 탆 in an amount of 1 to 50% It is preferable that the mixture is contained in an amount of 40 to 100% by weight based on the total filler. Further, the maximum particle diameter can be adjusted to any one of 45 탆, 55 탆 and 75 탆 according to the application. In the spherical fused silica, conductive carbon may be included as a foreign substance on the surface of silica, but it is also important to select a substance having a small amount of polar foreign substances.
The amount of the inorganic filler to be used varies depending on required properties such as moldability, low stress, and high temperature strength. In an embodiment, the inorganic filler may be included in the epoxy resin composition in an amount of 70 wt% to 95 wt%, for example, 80 wt% to 90 wt% or 83 wt% to 97 wt%.
Other ingredients
In addition to the above components, the epoxy resin composition according to the present invention may further include at least one of a curing accelerator, a coupling agent, a release agent, and a colorant.
Hardening accelerator
The curing accelerator is a substance that promotes the reaction between the epoxy resin and the curing agent. As the curing accelerator, for example, a tertiary amine, an organometallic compound, an organic phosphorus compound, an imidazole, and a boron compound can be used. Tertiary amines include benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tri (dimethylaminomethyl) phenol, 2-2- (dimethylaminomethyl) phenol, 2,4,6-tris ) Phenol and tri-2-ethylhexyl acid salt.
Specific examples of the organometallic compound include chromium acetylacetonate, zinc acetylacetonate, nickel acetylacetonate, and the like. Organic phosphorus compounds include tris-4-methoxyphosphine, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, phenylphosphine, diphenylphosphine, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine Pin-1,4-benzoquinone adducts and the like. Imidazoles include, but are not limited to, 2-phenyl-4 methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-aminoimidazole, -Methylimidazole, 2-heptadecylimidazole, and the like, but the present invention is not limited thereto. Specific examples of the boron compound include tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroborane monoethylamine, tetrafluoro Triethylamine, tetrafluoroborane amine, and the like. In addition, 1,5-diazabicyclo [4.3.0] non-5-ene (1,5-diazabicyclo [4.3.0] non-5-ene: DBN), 1,8-diazabicyclo [5.4. Diazabicyclo [5.4.0] undec-7-ene: DBU) and phenol novolac resin salt. However, the present invention is not limited thereto.
More specifically, organic phosphorus compounds, boron compounds, amine-based or imidazole-based curing accelerators may be used alone or in combination as the curing accelerator. As the curing accelerator, it is also possible to use an adduct made by reacting with an epoxy resin or a curing agent.
In the present invention, the amount of the curing accelerator to be used may be about 0.01 to about 2% by weight based on the total weight of the epoxy resin composition, specifically about 0.02 to 1.5% by weight, more specifically about 0.05 to 1% by weight . In the above range, the curing of the epoxy resin composition is promoted and the curing degree is also good.
Coupling agent
The coupling agent is for improving the interface strength by reacting between the epoxy resin and the inorganic filler, and may be, for example, a silane coupling agent. The silane coupling agent is not particularly limited as long as it reacts between the epoxy resin and the inorganic filler to improve the interface strength between the epoxy resin and the inorganic filler. Specific examples of the silane coupling agent include epoxy silane, aminosilane, ureido silane, mercaptosilane, and the like. The coupling agent may be used alone or in combination.
The coupling agent may be contained in an amount of about 0.01 wt% to 5 wt%, preferably about 0.05 wt% to 3 wt%, and more preferably about 0.1 wt% to 2 wt%, based on the total weight of the epoxy resin composition . The strength of the epoxy resin composition cured product is improved in the above range.
Release agent
As the release agent, at least one selected from the group consisting of paraffin wax, ester wax, higher fatty acid, higher fatty acid metal salt, natural fatty acid and natural fatty acid metal salt can be used.
The releasing agent may be contained in an amount of 0.1 to 1% by weight in the epoxy resin composition.
coloring agent
The coloring agent is for laser marking of a semiconductor element sealing material, and colorants well-known in the art can be used and are not particularly limited. For example, the colorant may comprise at least one of carbon black, titanium black, titanium nitride, dicopper hydroxide phosphate, iron oxide, mica.
The colorant may be contained in an amount of about 0.01% by weight to 5% by weight, preferably about 0.05% by weight to 3% by weight, and more preferably about 0.1% by weight to 2% by weight based on the total weight of the epoxy resin composition.
In addition, the epoxy resin composition of the present invention may contain a stress-relieving agent such as a modified silicone oil, a silicone powder, and a silicone resin to the extent that the object of the present invention is not impaired; Antioxidants such as Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane; And the like may be further contained as needed.
The epoxy resin composition for semiconductor encapsulation according to the present invention has a low modulus of elasticity and shrinkage at a high temperature after curing.
According to the studies of the present inventors, the epoxy resin composition for semiconductor encapsulation according to the present invention was found to have a modulus of elasticity of 20 Or more. In this case, the elastic modulus was measured for a specimen prepared by molding an epoxy resin composition using a transfer molding machine and then post-curing. The transfer molding was performed at a mold temperature of 170 to 180 ° C, an injection pressure of 800 to 1200 psi, a curing time of 120 Sec, and the size of the molded specimen was 20 × 13 × 1.6 mm. The post curing was carried out in a hot air drier at 170 to 180 ° C for 2 hours. The modulus of elasticity was measured using a Dynamic Mechanical Analyzer (TA, Q8000 DMA) at a temperature rising rate of 5 ° C / And was measured in a temperature range of 10 ° C to 300 ° C.
Further, the epoxy resin composition for semiconductor encapsulation according to the present invention has a low shrinkage specificity of 0.1% or less, preferably 0.08% or less, as measured by the following formula (1).
(1): Cure shrinkage ratio (%) = {(L 0 -L 1 ) / L 0 } × 100
In the formula (1), L 0 is the length of the molded specimen obtained by molding the epoxy resin composition at 175 ° C and 70 kgf / cm 2 using a transfer molding press, and L 1 is the length of the molded specimen at 175 ° C This is the length of the specimen measured after post molding curing in the oven for 4 hours and cooling.
The epoxy resin composition may be prepared by uniformly mixing the above components uniformly at a predetermined mixing ratio using a Hensel mixer or a Lodige mixer and then kneading the mixture in a roll mill or a kneader kneader, and then cooled and pulverized to obtain a final powder product.
The epoxy resin composition of the present invention as described above can be usefully applied to semiconductor devices, particularly semiconductor devices having a one-side sealing structure that requires low shrinkage and low elasticity at high temperatures. As a method of sealing a semiconductor element using the epoxy resin composition obtained in the present invention, a low pressure transfer molding method can be generally used. However, it is also possible to perform molding by an injection molding method or a casting method.
Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.
The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.
The specifications of each component used in the following examples and comparative examples are as follows.
(A) an epoxy resin
(a1) 81 g of YX-8800 (Mitsubishi Chemical) and 4.9 g of tetrabutylammonium bromide were placed in a 1 L round bottom flask, and 300 g of acetonitrile was added thereto. The mixture was completely dissolved at 80 캜 and stirred for 30 minutes. 10.9 g of 9,9-bis (4-hydroxyphenyl) fluorene (BPF) previously dissolved in 300 g of acetonitrile was added and stirred for 5 hours. 3.5 g of K 2 CO 3 was added thereto Then, the mixture was further stirred for 6 hours while maintaining 80 ° C. Thereafter, the temperature was lowered, the solvent was removed, and the catalyst was removed by work-up with methylene chloride and water, followed by drying to obtain 85 g of the modified epoxy resin (a1).
(a2) 162 g of an epoxy resin HP-4770 (manufactured by DIC) and 1.3 g of benzyltriethylammonium chloride were placed in a 1 L round bottom flask, 450 g of acetonitrile was added, and the mixture was stirred at 80 ° C for 1 hour And completely dissolved. 10.5 g of a compound (4,4'-Dihydroxybiphenyl) of formula (2) previously dissolved in 50 g of acetonitrile was added thereto, followed by further stirring for 6 hours while maintaining the temperature at 80 ° C. Thereafter, the temperature was lowered and the reactant was poured into a mixed solution of methanol and distilled water (weight ratio of methanol: distilled water = 10: 1) to precipitate the precipitate. The precipitate was filtered and dried to obtain a modified powdery modified epoxy resin (a2).
(a3) 173 g of an epoxy resin EPPN-501HY (manufactured by Nippon Kayaku) and 1.6 g of benzyltriethylammonium chloride were placed in a 1 L round bottom flask, 450 g of acetonitrile was added, and the mixture was stirred at 80 ° C. for 1 hour Stirred and completely dissolved. Thereto was added 7.7 g of resorcinol previously dissolved in 50 g of acetonitrile, followed by further stirring for 6 hours while maintaining the temperature at 80 ° C. Thereafter, the temperature was lowered and the reactant was poured into a mixed solution of methanol and distilled water (weight ratio of methanol: distilled water = 10: 1) to precipitate the precipitate. The precipitate was filtered and dried to obtain a modified powdery modified epoxy resin (a3).
(a4) YX-8800 (Manufactured by Mitsubishi Chemical Co., Ltd.) was used
(a5) HP-4770 (manufactured by DIC) was used.
(a6) EPPN-501HY (manufactured by Nippon Kayaku) was used.
(a7) 149 g of YX-8800 (manufactured by Mitsubishi Chemical) and 1.2 g of benzyltriethylammonium chloride were placed in a 1 L round bottom flask, 450 g of acetonitrile was added, and the mixture was completely dissolved by stirring at 80 ° C for 1 hour . To this was added 11.8 g of bisphenol A previously dissolved in 50 g of acetonitrile, followed by further stirring for 6 hours while maintaining the temperature at 80 ° C. Thereafter, the temperature was lowered and the reactant was poured into a mixed solution of methanol and distilled water (weight ratio of methanol: distilled water = 10: 1) to precipitate the precipitate. The precipitate was filtered and dried to obtain a modified powdery modified epoxy resin (a7).
(B) Hardener: Multifunctional phenol resin MEH 7500-3S (Meiwa) was used.
(C) Curing accelerator: A phosphorus compound represented by the following formula (11) was used.
(11)
(D) Inorganic filler : A 9: 1 (weight ratio) mixture of spherical fused silica having an average particle diameter of 18 μm and spherical fused silica having an average particle diameter of 0.5 μm was used.
(E) Coupling agent
(e1) was mixed with KBM-803 (Shinetsu), which is a mercaptopropyltrimethoxysilane, and SZ-6070 (Dow Corning chemical), which is e2) methyltrimethoxysilane.
(F) Additive
Carbon black MA-600 (Matsusita Chemical) was used as (f1) carnauba wax and (f2) colorant.
Examples and Comparative Examples
Each of the components was weighed according to the composition shown in Table 1, and then uniformly mixed using a Henschel mixer to prepare a powdery first composition. Thereafter, the mixture was melt kneaded at 95 DEG C using a continuous kneader, followed by cooling and pulverization, thereby preparing an epoxy resin composition for sealing a semiconductor device.
[Unit:% by weight]
The properties of the epoxy resin compositions for semiconductor encapsulation of Examples 1 to 2 and Comparative Examples 3 to 6 were measured by the following measurement methods. The measurement results are shown in Table 2.
Property evaluation method
(1) The modulus of elasticity (MPa) and the glass transition temperature (占 폚) were measured using a transfer molding machine at a mold temperature of 170 to 180 占 폚, an injection pressure of 800 to 1200 psi and a curing time of 120 seconds. . The specimens for measurement were cured in a hot-air drier at 170 to 180 ° C for 2 hours, and the glass transition temperature (Tg) of the specimen and the elastic modulus at 260 ° C were measured using a Q8000 DMA (Dynamic Mechanical Analyzer) . At this time, the temperature increase was 5 ° C / min, and the temperature was measured from -10 ° C to 300 ° C.
(2) Curing shrinkage (%): Flexural strength A specimen (125 × 12.6 × 6.4 mm) was obtained using a transfer molding press at 175 ° C. and 70 kgf / cm 2 using an ASTM mold for specimen preparation . The obtained specimens were placed in an oven at 170 to 180 ° C. and post-cured for 4 hours. After cooling, the specimens were measured by calipers. The hardening shrinkage was calculated from the following equation (1).
(1): Cure shrinkage ratio (%) = {(L 0 -L 1 ) / L 0 } × 100
In the formula (1), L 0 is the length of the molded specimen obtained by molding the epoxy resin composition at 175 ° C and 70 kgf / cm 2 using a transfer molding press, and L 1 is the length of the molded specimen at 175 ° C Length of the specimen after post molding curing in the oven for 4 hours and after cooling.
(3) Curing Torque Ratio (%): Using a Curelastometer (JSR Curelastometer IVPS type), the mold temperature was set to 175 占 폚, and the torque after 90 seconds and 300 seconds after the start of heating was obtained. The ratio was calculated.
(2): Curing torque ratio = {(torque after 90 seconds) / (torque after 300 seconds)} x 100
(° C)
(%)
In Examples 1 to 3 using the modified epoxy resin modified with at least one of the compounds represented by Chemical Formulas 1 to 3 through the above Table 2, the modulus of elasticity , The hardening shrinkage ratio and the hardening torque ratio are lowered. On the other hand, in Comparative Example 4 using an epoxy resin modified with bisphenol A, the modulus of elasticity was low, but it was confirmed that the hardening shrinkage ratio was increased before the modification.
Claims (7)
[Chemical Formula 1]
(2)
(3)
Wherein the modified epoxy resin composition is formed by reacting at least one of the compounds represented by Chemical Formulas 1 to 3 with an epoxy resin in a molar ratio of 4: 1 to 20: 1.
0.5 to 20% by weight of the modified epoxy resin,
0.1 to 13% by weight of a curing agent, and
And 70 to 95% by weight of an inorganic filler.
Wherein the epoxy resin composition further comprises at least one of a curing accelerator, a coupling agent, a release agent, and a colorant.
Wherein the epoxy resin composition for semiconductor encapsulation has an elastic modulus at 260 占 폚 after molding reduced by 20% or more as compared with an epoxy resin composition comprising an unmodified epoxy resin.
Wherein the epoxy resin composition for semiconductor encapsulation has a curing shrinkage of 0.1% or less as measured by the following formula (1).
(1): Cure shrinkage ratio (%) = {(L 0 -L 1 ) / L 0 } × 100
In the formula (1), L 0 is the length of the molded specimen obtained by molding the epoxy resin composition at 175 ° C and 70 kgf / cm 2 using a transfer molding press, and L 1 is the length of the molded specimen at 175 ° C Length of the specimen after post molding curing in the oven for 4 hours and after cooling.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62192422A (en) * | 1986-02-19 | 1987-08-24 | Matsushita Electric Works Ltd | Epoxy resin composition and its production |
| JP2013166878A (en) * | 2012-02-16 | 2013-08-29 | Nippon Steel & Sumikin Chemical Co Ltd | Epoxy resin composition and cured product |
| JP2014031522A (en) * | 2008-09-03 | 2014-02-20 | Nippon Kayaku Co Ltd | Siloxane compound and curable resin composition |
| KR20170115414A (en) * | 2016-04-07 | 2017-10-17 | 삼성에스디아이 주식회사 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62192422A (en) * | 1986-02-19 | 1987-08-24 | Matsushita Electric Works Ltd | Epoxy resin composition and its production |
| JP2014031522A (en) * | 2008-09-03 | 2014-02-20 | Nippon Kayaku Co Ltd | Siloxane compound and curable resin composition |
| JP2013166878A (en) * | 2012-02-16 | 2013-08-29 | Nippon Steel & Sumikin Chemical Co Ltd | Epoxy resin composition and cured product |
| KR20170115414A (en) * | 2016-04-07 | 2017-10-17 | 삼성에스디아이 주식회사 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same |
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