Epoxy resin composition for molding

Abstract

The present invention relates to: an epoxy resin composition comprising an epoxy resin, a curing agent, a filler, and an organosiloxane, wherein the organosiloxane is a symmetrical linear organosiloxane having epoxy groups at both ends thereof; and a semiconductor device molded using same.

Description

Epoxy resin composition for molding

[0001] The present invention relates to an epoxy resin composition for molding and a semiconductor device molded using the same.

[0002]

[0003] A resin composition for sealing is used as a material to seal semiconductor devices such as integrated circuits (ICs), large scale integrated circuits (LSIs), transistors, and diodes, thereby improving the characteristics and reliability of semiconductor devices. Recently, with the trend toward miniaturization, weight reduction, and higher performance of electronic devices, the integration of semiconductors has accelerated, and research is continuing in various fields to improve the performance of materials used for sealing semiconductor devices. For example, Japanese Patent Application Laid-Open No. 2017-197620 relates to an epoxy resin composition for semiconductor sealing, which includes an epoxy resin, a phenol resin curing agent, and a filler, and discloses a technology for improving electrical connection reliability by controlling the content of the filler and the thermoelastic modulus of the cured product of the epoxy resin composition.

[0004] In particular, when applied to multi-layered semiconductor packages, filling micro-gaps is crucial, requiring excellent meltability of the epoxy resin composition. However, conventional epoxy resin compositions with enhanced meltability have the problem of swelling, in which the epoxy molding compound (EMC) leaks out of the mold cavity during compression molding under high pressure in a vacuum environment.

[0005] Accordingly, there is a need for development of an epoxy resin composition for molding that has excellent meltability, thereby improving gap-filling characteristics, and excellent swelling suppression characteristics.

[0006]

[0007] The present invention provides an epoxy resin composition for molding having excellent meltability and swelling inhibition characteristics, and a semiconductor device molded using the same.

[0008]

[0009] The present invention provides an epoxy resin composition comprising an epoxy resin, a curing agent, a filler, and an organosiloxane, wherein the organosiloxane is a linear organosiloxane having a symmetrical structure having epoxy groups at both terminals.

[0010]

[0011] The present invention provides an epoxy resin composition for molding, which has excellent melting properties, thereby enhancing gap filling characteristics, and excellent swelling suppression properties. The epoxy resin composition according to the present invention is applicable to compression molding, and in particular, due to its excellent swelling suppression properties, it can be applied as a granular epoxy molding compound (EMC).

[0012]

[0013] Figure 1 is a schematic diagram showing a method for evaluating the meltability of an epoxy resin composition.

[0014] Figure 2 is a schematic diagram showing a method for evaluating the swelling characteristics of an epoxy resin composition.

[0015]

[0016] The present invention will be described in detail below. However, it is not limited to the following description, and each component may be modified or selectively mixed as needed. Therefore, it should be understood that all modifications, equivalents, and alternatives included within the spirit and technical scope of the present invention are included.

[0017] The “softening point” used in this specification is measured by a conventional method known in the art, and can be measured, for example, using a dropping point meter (Dropping Point system calorimetry DP70) from Mettler Toledo. The “viscosity” is measured by a conventional method known in the art, and can be measured, for example, using a Brookfield viscometer at room temperature (25°C). “Particle size (D 50 )" is measured by a conventional method known in the art, and can be measured, for example, by a laser particle size analyzer.

[0018]

[0019] Epoxy resin composition

[0020] An epoxy resin composition according to the present invention comprises an epoxy resin, a curing agent, a filler, and an organosiloxane. The present invention provides an epoxy resin composition for sealing, which has excellent melting properties, thereby improving gap filling properties, and excellent swelling suppression properties, by using a linear organosiloxane having a symmetrical structure having epoxy groups at both ends.

[0021] The epoxy resin composition of the present invention can be manufactured in a liquid, powder, granule, or sheet form, and can be used as a sealant (EMC, epoxy molding compound) for semiconductor devices or as a molding material or fixing material for various electronic components and automotive components. For example, the epoxy resin composition for molding of the present invention can be applied for sealing a large-area semiconductor package that is large in size and thin in thickness, and can be manufactured as a granule-type EMC applicable to a compression type molding process, a C-molding process, or a lamination process.

[0022]

[0023] epoxy resin

[0024] The epoxy resin composition of the present invention comprises an epoxy resin. The epoxy resin is used as a main resin, and upon reaction with a curing agent and curing, forms a three-dimensional network structure, thereby imparting strong and solid adhesion properties to an adherend and heat resistance.

[0025] As the above epoxy resin, an epoxy resin commonly used in the relevant technical field can be used. Non-limiting examples of usable epoxy resins include bisphenol A type epoxy resins, alicyclic epoxy resins, cresol novolac epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins, anthracene epoxy resins, tetramethyl biphenyl type epoxy resins, phenol novolac epoxy resins, bisphenol A novolac epoxy resins, bisphenol S novolac epoxy resins, biphenyl novolac epoxy resins, naphthol novolac epoxy resins, naphthol phenol cocondensed novolac epoxy resins, naphthol cresol cocondensed novolac epoxy resins, aromatic hydrocarbon formaldehyde resin modified phenol resin epoxy resins, triphenyl methane type epoxy resins, tetraphenyl ethane type epoxy resins, dicyclopentadiene type epoxy resins, dicyclopentadiene phenol addition reaction epoxy resins, biphenyl type epoxy resins, phenol aralkyl type epoxy resins, multifunctional phenol resins, and naphthol. There are aralkyl type epoxy resins, etc., and one or more of these may be included.

[0026] For example, the epoxy resin may include formaldehyde, polymer with 1,1'-biphenyl and phenol, glycidyl ether, 4,4-bis(2,3-epoxypropoxy)-3,3,5,5-tetramethyl(1,1-biphenyl), or mixtures thereof.

[0027] For example, the epoxy resin may include a polymer of formaldehyde, 1,1'-biphenyl, and phenol, glycidyl ether, and 4,4-bis(2,3-epoxypropoxy)-3,3,5,5-tetramethyl(1,1-biphenyl). In this case, the viscosity and flowability properties of the epoxy resin composition can be further improved while maintaining mechanical strength properties such as flexural strength.

[0028] The above epoxy resin may be used having an epoxy equivalent weight (EEW) of 100 to 500 g / eq, for example, 150 to 300 g / eq. If the epoxy equivalent weight is less than the above-mentioned range, the cured density may increase, resulting in poor moisture resistance reliability. If the epoxy equivalent weight exceeds the above-mentioned range, the curing property may be poor.

[0029] The above epoxy resin may be used with a softening point of 30 to 150°C, for example, 50 to 110°C. If the softening point is below the above-mentioned range, caking properties may be poor, and if it exceeds the above-mentioned range, uneven distribution may occur during manufacturing.

[0030] Based on the total weight of the epoxy resin composition, the content of the epoxy resin may be 2 to 20 wt%, for example, 5 to 15 wt%. If the content of the epoxy resin is less than the above-mentioned range, adhesion, flowability, and moldability may be reduced, and if it exceeds the above-mentioned range, the reliability of the semiconductor may be deteriorated due to an increase in moisture absorption, and the strength may be reduced due to a relative decrease in the filler content.

[0031]

[0032] hardener

[0033] The epoxy resin composition of the present invention includes a curing agent. The curing agent reacts with the epoxy resin to promote curing of the composition.

[0034] The curing agent may be any curing agent known in the art that undergoes a curing reaction with an epoxy resin. The curing agent may be a phenol-based compound having two or more phenolic hydroxyl groups in one molecule. Non-limiting examples of usable curing agents include phenol novolac resins, cresol novolac resins, phenol aralkyl resins, and multifunctional phenol compounds, and the curing agent may include one or more of these.

[0035] For example, the curing agent may include a phenol polymer with 4,4-bis(methoxymethyl)1,1-bisphenyl, a phenol polymer with formaldehyde, or a mixture thereof.

[0036] For example, the curing agent may include a phenol polymer with 4,4-bis(methoxymethyl)1,1-bisphenyl and a phenol polymer with formaldehyde. In this case, the viscosity and melt-ability properties can be further improved while maintaining the mechanical strength properties, such as the flexural strength, of the epoxy resin composition.

[0037] The above-mentioned hardener may be used having a hydroxyl equivalent of 90 to 300 g / eq, for example, 100 to 200 g / eq. If the hydroxyl equivalent is less than the above-mentioned range, moisture resistance reliability may be deteriorated, and if it exceeds the above-mentioned range, curing property may be deteriorated.

[0038] The above-mentioned hardener may be one having a softening point of 50 to 120°C, for example, 55 to 90°C. If the softening point is below the above-mentioned range, the caking property may be poor, and if it exceeds the above-mentioned range, the fluidity may be poor.

[0039] Based on the total weight of the epoxy resin composition, the content of the curing agent may be 2 to 20 wt%, for example, 2 to 10 wt%. If the content of the curing agent is less than the above-mentioned range, curability and formability may be reduced, and if it exceeds the above-mentioned range, the reliability of the semiconductor may be deteriorated and the strength may be reduced due to an increase in moisture absorption.

[0040]

[0041] filling

[0042] The epoxy resin composition of the present invention includes a filler. The filler improves the mechanical properties (e.g., strength) of the epoxy resin composition and reduces moisture absorption.

[0043] As the above-mentioned filler, any inorganic filler commonly used in the field of electronic materials can be used without any particular restrictions. For example, inorganic fillers such as silica, silica nitride, alumina, aluminum nitride, and boron nitride can be used, and these can be used alone or in combination of two or more.

[0044] The shape of the above filler is not particularly limited, and both angular and spherical shapes can be used. Non-limiting examples of fillers that can be used in the present invention include natural silica, synthetic silica, and fused silica, and for example, spherical silica particles can be used.

[0045] The above filler may include two or more types of fillers having different particle sizes to improve mechanical properties. In this case, the moldability and workability of the epoxy resin composition can be further improved. For example, the filler may have an average particle size (D 50) is 3.5 to 20 um, for example 3.5 to 15 um, and the first filler and the average particle diameter (D 50 ) may include a second filler having a thickness of 0.1 to 3 um, for example, 0.1 to 1 um.

[0046] Based on the total weight of the epoxy resin composition, the content of the filler may be 50 to 90 wt%, for example, 70 to 90 wt%. If the content of the filler is less than the aforementioned range, the moisture absorption of the cured product may increase, which may lower the reliability of the semiconductor device. If the content exceeds the aforementioned range, the fluidity may be reduced, resulting in poor formability.

[0047]

[0048] organosiloxane

[0049] The epoxy resin composition of the present invention includes an organosiloxane to improve dispersibility. The organopolysiloxane is a linear organosiloxane having a symmetrical structure with epoxy groups at both ends. By using an organopolysiloxane having such a structure, an epoxy resin composition for sealing can be provided that has excellent melting properties, thereby improving gap filling properties, and excellent swelling suppression properties.

[0050] The above organosiloxane has a symmetrical linear molecular structure, and thus has high compatibility with an epoxy resin composition, particularly an epoxy resin composition including a biphenyl-based epoxy resin. In addition, the organosiloxane has reactive epoxy groups at both ends, and thus can participate in a cross-linking curing reaction between the epoxy resin and the phenol curing agent as a reactive diluent, thereby effectively dispersing the epoxy resin composition. As a result, by lowering the surface tension of the molten epoxy resin composition, the phenomenon of internal bubbles in the cured epoxy resin composition swelling can be suppressed, and the viscosity of the molten epoxy resin composition can be lowered, thereby improving formability. In addition, the organosiloxane can maintain the adhesiveness of the epoxy resin composition, while improving meltability and swelling suppression characteristics.

[0051] The above organosiloxane can be represented by the following chemical formula 1.

[0052] [Chemical Formula 1]

[0053]

[0054] In the above formula,

[0055] EP is an epoxy group,

[0056] R1 is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms,

[0057] R2 is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms,

[0058] a is an integer from 1 to 5,

[0059] n is an integer from 1 to 5.

[0060] For example, in the above formula, EP is an epoxy group, R1 is hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, R2 is hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a is an integer from 1 to 5, and n is an integer from 1 to 5.

[0061] For example, in the above formula, EP is an epoxy group, R1 is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, R2 is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a is an integer of 1 to 3, and n is an integer of 1 to 3.

[0062] For example, in the above formula, EP is an epoxy group, R1 is a methyl group, R2 is a methyl group, a is 1, and n is 3.

[0063] The above organosiloxane may be used having a molecular weight of 300 to 800 g / mol, for example, 300 to 500 g / mol, and a viscosity (25°C) of 0.005 to 1 Pa·s, for example, 0.05 to 0.1 Pa·s. When an organosiloxane with a low molecular weight and low viscosity within the aforementioned range is used, it is advantageous for mixing with an epoxy resin composition, thereby exhibiting high dispersibility. When the molecular weight or viscosity exceeds the aforementioned range, the compatibility between the epoxy resin composition and the organosiloxane may decrease, thereby lowering the dispersibility effect and causing appearance defects such as flow marks.

[0064] Based on the total weight of the epoxy resin composition, the content of the organosiloxane may be 0.05 to 5 wt%, for example, 0.1 to 3 wt%. If the content of the organosiloxane is less than the above-mentioned range, the effects of improving meltability and suppressing swelling may be limited, and if it exceeds the above-mentioned range, the reliability and strength of the epoxy resin composition may be reduced.

[0065]

[0066] additives

[0067] The epoxy resin composition of the present invention may additionally include additives commonly used in molding compositions. Non-limiting examples of usable additives include catalysts, coupling agents, ion catchers, colorants, and release agents.

[0068] The catalyst promotes the curing reaction, and examples thereof include imidazole compounds, naphthalene-based latent catalysts, amine compounds, organometallic compounds, organophosphorus compounds, and boron compounds. The coupling agent promotes the bonding between inorganic and organic substances, and examples thereof include amino silanes and epoxy silanes. The ion catcher captures and removes impurity ions to reduce corrosion, and examples thereof include inorganic ion exchangers such as magnesium aluminum hydroxide carbonate hydrate. The coloring agent is added to impart color to the resin composition, and examples thereof include carbon black and bengala. The releasing agent is added to secure releasability between the cured epoxy resin composition and the mold, and examples thereof include paraffin wax, carnauba wax, polyethylene wax, and ester wax.

[0069] The above additives may be added within a content range known in the relevant technical field, and for example, may be included in an amount of 0.01 to 5 wt%, respectively, based on the total weight of the epoxy resin composition, but is not limited thereto.

[0070]

[0071] The epoxy resin composition according to the present invention can be produced by a conventional method known in the art, for example, a melt mixing method using a semi-batch mixer, a kneader, a roll, a single-screw or twin-screw extruder, and a con-kneader.

[0072] The epoxy resin composition of the present invention can be manufactured in powder form, granule form, etc. In particular, the epoxy resin composition according to the present invention has excellent swelling inhibition properties, so it can be manufactured in granule form and applied to a compression molding method.

[0073] For example, in the case of a powder-type or granular epoxy resin composition, the components as described above are uniformly mixed, melted and mixed at a temperature of 80 to 130°C using a heat kneader, cooled to room temperature, pulverized into a powder state, and then subjected to a sieving process, but the present invention is not limited thereto.

[0074]

[0075] Semiconductor devices and automotive components

[0076] The present invention provides a semiconductor device molded using the epoxy resin composition described above. The semiconductor device may be a transistor, a diode, a microprocessor, a semiconductor memory, a power semiconductor, or the like.

[0077] In addition, the present invention provides a vehicle component molded using the epoxy resin composition described above. For example, the epoxy resin composition described above can be used as a molding material to fix and seal components within the vehicle component. Specifically, a permanent magnet can be inserted into a hollow space formed within a rotor core of a vehicle motor, and the epoxy resin composition of the present invention can be filled between the hollow space and the permanent magnet to fix the permanent magnet within the rotor core.

[0078] A method for molding a semiconductor device or a vehicle part using the epoxy resin composition of the present invention can be appropriately selected and performed according to a conventional method in the relevant technical field, such as transfer molding, compression molding, or injection molding.

[0079]

[0080] Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended only to aid understanding of the present invention and are not intended to limit the scope of the present invention in any way.

[0081]

[0082] [Example 1-4]

[0083] After mixing each component according to the composition described in Table 1 below, the mixture was melt-mixed at a temperature of 100 to 130°C using a melt kneader, cooled to room temperature, pulverized into a powder state, and then subjected to a sieving process to produce a granular epoxy resin composition of each example.

[0084]

[0085] [Comparative Example 1-7]

[0086] Except for the compositions described in Table 2 below, granular epoxy resin compositions of each comparative example were prepared in the same manner as in the examples.

[0087]

[0088]

[0089]

[0090]

[0091] Epoxy resin 1: Multifunctional epoxy resin (Formaldehyde, polymer with 1,1'-biphenyl and phenol, glycidyl ether, Cas no. 1201169-35-8)

[0092] Epoxy resin 2: Biphenyl epoxy resin (4,4-Bis(2,3-epoxypropoxy)-3,3,5,5-tetramethyl(1,1-biphenyl))

[0093] Curing agent 1: Polyfunctional phenol resin (Phenol polymer with 4,4-bis(methoxymethyl)1,1-bisphenyl, Cas no. 0106466-55-1)

[0094] Curing agent 2: Phenol polymer with hydroxybenzaldehyde (Cas no. 0205830-20-2)

[0095] Filler: Silicon dioxide

[0096] Organosiloxane 1: 1,3-Bis(3-(2,3-epoxypropoxy)propyl) 1,1,3,3-tetramethyldisiloxane

[0097] Organosiloxane 2: Organosiloxane having amino groups at both ends (Dual-end type / Amino-modified Silicone Fluids, viscosity (25 ℃) 25 mm 2 / s, Mw 1,600 g / mol, amine value 70 mgKOH / g)

[0098] Organosiloxane 3: 3-[2-(3,4-epoxycyclohexyl)ethyl]-heptamethyltrisiloxane

[0099] Organosiloxane 4: Modified siloxane containing epoxy and polyether groups in the side chain (Epoxy and polyether modified silicone polymer, Cas no. 0101810-98-4, kinematic viscosity (25 ℃) 2,200 ㎟ / s, epoxy equivalent 5,200 g / mol)

[0100] Ion catcher: (Carbonato)hexadecahydroxydialuminum-hexamagnesium

[0101] Catalyst: 5-Methyl-2-phenylimidazole-4-methanol

[0102] Coupling agent: (3-Mercaptopropyl)trimethoxysilane

[0103] Colorant: Carbon Black

[0104] Ester wax

[0105]

[0106] [Physical property evaluation]

[0107] The physical properties of the epoxy resin compositions manufactured in each example and comparative example were measured as follows, and the results are shown in Tables 3 and 4 below.

[0108]

[0109] spiral flow

[0110] The epoxy resin compositions manufactured according to each example and comparative example were molded using a spiral flow mold in a heat transfer molding machine (pressure 16 kgf / cm2, temperature 175 ℃, curing time 120 seconds), and then the flowability of the product was measured.

[0111]

[0112] gelation time

[0113] A small amount of the epoxy resin composition manufactured according to each example and comparative example was spread widely and evenly on a gel timer, and the gelation time of the composition was measured.

[0114]

[0115] Flexural strength

[0116] Measured according to ASTM D638, D256, D790.

[0117]

[0118] Flexural modulus

[0119] The epoxy resin compositions manufactured according to each example and comparative example were molded using a specimen manufacturing mold (width 125 mm, length 12.5 mm, thickness 6 mm) in a heat transfer molding machine (pressure 70 kg / cm2, temperature 175°C, curing time 120 seconds), and then post-cured in an oven at 175°C for 4 hours, and then measured using a UTM (Universal Testing Machine).

[0120]

[0121] melt-ability

[0122] As illustrated in Fig. 1, the epoxy resin composition (6.0 g) manufactured according to each example and comparative example was dispensed over a narrow area on a release film, and compression molded using compression molding equipment at a temperature of 175°C, a maximum pressure of 30 tons, a compression time of 25 s (time to reach maximum pressure), and a cure time of 120 s, and then the area over which the epoxy resin composition melted and spread (spreading area) was measured. The spreading area ratio was calculated using the following formula, and the meltability of the epoxy resin composition was evaluated.

[0123]

[0124]

[0125] Swelling

[0126] As illustrated in Fig. 2, 2.0 g of the epoxy resin composition manufactured according to each example and comparative example was weighed into a vial, and the weighed vial was left on a hot plate under a vacuum of 175°C and 640 (torr) for 5 minutes, and then the height at which the sample swelled was measured. The swelling characteristics were evaluated by calculating the rate of change using the following formula.

[0127]

[0128] HO : Height before heating

[0129] △H: Height after heating - H O

[0130]

[0131]

[0132]

[0133]

[0134] As shown in Tables 3 and 4 above, the epoxy resin composition of Examples 1-4 including the organosiloxane (organosiloxane 1) according to the present invention having a symmetrical linear structure having epoxy groups at both ends exhibited excellent physical properties across all measured items.

[0135] On the other hand, the epoxy resin compositions of Comparative Examples 1-4 that did not use organosiloxane exhibited poor melting properties or swelling inhibition properties. In addition, the epoxy resin compositions of Comparative Example 5, which used an organosiloxane having amino groups at both terminals (organosiloxane 2) instead of the organosiloxane according to the present invention, Comparative Example 6, which used an organosiloxane containing an epoxy group in a side chain other than a terminal (organosiloxane 3), and Comparative Example 7, which used an organosiloxane containing an epoxy group and a polyether group in a side chain other than a terminal (organosiloxane 4), exhibited poor melting properties or swelling inhibition properties.

[0136]

[0137] The present invention provides an epoxy resin composition for molding that has excellent melting properties, thereby improving gap filling properties, and excellent swelling suppression properties.

Claims

1. Contains epoxy resin, hardener, filler and organosiloxane, An epoxy resin composition wherein the above organosiloxane is a linear organosiloxane having a symmetrical structure having epoxy groups at both terminals.

2. An epoxy resin composition according to claim 1, wherein the softening point of the epoxy resin is 30 to 150°C and the softening point of the curing agent is 50 to 120°C.

3. In the first paragraph, the organosiloxane is an epoxy resin composition represented by the following chemical formula 1: [Chemical Formula 1] In the above formula, EP is an epoxy group, R1 is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms, R2 is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms, a is an integer from 1 to 5, n is an integer from 1 to 5.

4. An epoxy resin composition in the first paragraph, wherein the molecular weight of the organosiloxane is 300 to 800 g / mol and the viscosity (25°C) is 0.005 to 1 Pa·s.

5. An epoxy resin composition comprising, based on the total weight of the epoxy resin composition in paragraph 1, 2 to 20 wt% of the epoxy resin, 2 to 20 wt% of the curing agent, 50 to 90 wt% of the filler, and 0.05 to 5 wt% of the organosiloxane.

6. A semiconductor device molded using an epoxy resin composition according to any one of claims 1 to 5.

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