KR102367500B1 - Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated using the same - Google Patents

Abstract

Disclosed are an epoxy resin composition for sealing semiconductor elements containing an epoxy resin, an acid anhydride-based curing agent, an inorganic filler and a polyhydric alcohol, and a semiconductor device sealed using the same.

Description

EPOXY RESIN COMPOSITION FOR ENCAPSULATING SEMICONDUCTOR DEVICE AND SEMICONDUCTOR DEVICE ENCAPSULATED USING THE SAME

It relates to an epoxy resin composition for sealing semiconductor elements and a semiconductor device sealed using the same, and more particularly, to a semiconductor element sealing that can be cured at a low temperature because the onset temperature is lowered, can improve the warpage problem, and has excellent storage stability It relates to an epoxy resin composition and a semiconductor device sealed using the same.

BACKGROUND ART With the miniaturization of electronic devices, miniaturization and thinning of semiconductor products are progressing. Accordingly, a wafer-level-chip-size package technology in which a plurality of bare semiconductor chips is mounted on a semiconductor wafer substrate and sealed with a semiconductor encapsulant is attracting attention.

Since the semiconductor encapsulant mainly contains a thermosetting resin, it is heated to a high temperature to promote the curing reaction in the semiconductor encapsulant molding process, and then cooled. As a result, wafer-level-chip-size packages inevitably suffer from warpage.

In order to solve this problem, it is necessary to reduce the thermal expansion of the sealing material.

It is an object of the present invention to provide an epoxy resin composition for sealing semiconductor devices that can be cured at a low onset temperature at a low onset temperature.

Another object of the present invention is to provide an epoxy resin composition for sealing semiconductor devices that can improve the warpage problem.

Another object of the present invention is to provide an epoxy resin composition for sealing semiconductor devices having excellent storage stability.

Another object of the present invention is to provide a semiconductor device including the epoxy resin composition.

1. According to one aspect, there is provided an epoxy resin composition for sealing a semiconductor device including an epoxy resin, an acid anhydride-based curing agent, an inorganic filler, and a polyhydric alcohol.

2. In 1 above, the acid anhydride-based curing agent is methyltetrahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride or a combination thereof.

3. In 1 above, the acid anhydride-based curing agent may be represented by the following Chemical Formula 1:

<Formula 1>

In Formula 1,

R ₁ is selected from a C ₁ -C ₁₀ alkyl group,

a1 is selected from an integer of 0 to 4.

4. In any one of 1 to 3, the polyhydric alcohol is ethylene glycol, diethylene glycol, triethylene glycol, propanediol, butanediol, 1,4-butenediol, pentanediol, hexanediol, heptanediol, neopentyl glycol , cyclohexanediol, cyclohexanedimethanol, glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, 2-methylpropanetriol, butanetriol, pentanetriol, pentaerythritol, dipentaerythritol, Tripentaerythritol, sorbitol, xylitol, mannitol, 2-hydroxymethylpropane-1,3-diol, 2-methyl-1,2,4-butanetriol, 1,2,3,6-hexanetetraol, It may include xylene glycol, 1,3,5-benzenetrimethanol, bisphenol, or a combination thereof.

5. In any one of 1 to 3, the polyhydric alcohol may be represented by the following Chemical Formula 2:

<Formula 2>

In Formula 2,

L ₁ is selected from a substituted or unsubstituted C ₁ -C ₂₀ alkylene group and an ether group,

b1 is selected from an integer of 0 to 20,

R ₂ to R ₅ are each independently selected from hydrogen, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group.

6. In any one of 1 to 5, the weight ratio of the acid anhydride-based curing agent to the polyhydric alcohol may be 98: 2 to 60: 40.

7. In any one of 1 to 6, the epoxy resin composition is

0.5 to 20% by weight of the epoxy resin,

0.1 to 20% by weight of the acid anhydride-based curing agent;

70 to 95% by weight of the inorganic filler, and

0.01 to 5 wt% of the polyhydric alcohol may be included.

8. According to another aspect, there is provided a semiconductor device sealed using the epoxy resin composition according to any one of 1 to 7.

The present invention has the effect of providing an epoxy resin composition for sealing semiconductor elements, which can be cured at a low temperature, can improve warpage, and has excellent storage stability, and a semiconductor device including the same.

In the present specification, the singular expression includes the plural expression unless the context clearly dictates otherwise.

In this specification, terms such as include or have are meant to mean that the features or components described in the specification are present, and the possibility that one or more other features or components will be added is not excluded in advance.

In the present specification, 'a to b' representing a range means 'a or more and b or less'.

According to one aspect, the epoxy resin composition for semiconductor device encapsulation may include an epoxy resin, an acid anhydride-based curing agent, an inorganic filler, and a polyhydric alcohol.

Hereinafter, the constituent components of the epoxy resin composition for semiconductor element encapsulation will be described in more detail.

epoxy resin

As the epoxy resin, epoxy resins generally used for sealing semiconductor devices may be used, and there is no particular limitation. Specifically, the epoxy resin may use an epoxy compound containing two or more epoxy groups in the molecule. Examples of the epoxy resin include an epoxy resin obtained by epoxidizing a condensate of phenol or alkyl phenols with hydroxybenzaldehyde, a phenol aralkyl type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a polyfunctional type epoxy resin, Naphthol novolak type epoxy resin, bisphenol A/bisphenol F/bisphenol AD/bisphenol S novolak type epoxy resin, bisphenol A/bisphenol F/bisphenol AD/bisphenol S glycidyl ether, bishydroxybiphenyl type epoxy resin , dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin (for example, (3',4'-epoxycyclohexane)methyl 3,4-epoxycyclohexylcarboxylate, bis(3, 4-epoxycyclohexylmethyl)oxalate, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, bis(3,4-epoxycyclo Hexylmethyl) pimelate, vinylcyclohexene diepoxide, limonene diepoxide, etc.), triphenol alkane type epoxy resin (e.g., triphenolmethane type epoxy resin, triphenol propane type epoxy resin, etc.), fluorene type An epoxy resin, a biphenyl aralkyl type epoxy resin, a stilbene type epoxy resin, a naphthalene type epoxy resin, a glycidyl amine type epoxy resin, a polyether type epoxy resin, silicone modified epoxy resin, etc. are mentioned. These may be used alone or in combination of two or more. According to one embodiment, the epoxy resin may include, but is not limited to, an alicyclic epoxy resin, a bisphenol A-type epoxy resin, a polyfunctional epoxy resin, or a combination thereof.

The amount of the epoxy resin used is not particularly limited, but, for example, the epoxy resin may be included in an amount of 0.5 to 20% by weight of the epoxy resin composition for sealing semiconductor devices. Within the above range, the curability of the composition may not be deteriorated. According to one embodiment, the epoxy resin may be included in an amount of 1 to 15% by weight of the epoxy resin composition for sealing semiconductor devices, 2 to 12% by weight according to another embodiment, and 3 to 10% by weight according to another embodiment.

hardener

The epoxy resin composition for semiconductor device encapsulation of the present invention may include an acid anhydride-based curing agent as a curing agent.

The type of the acid anhydride curing agent is not particularly limited as long as it has an acid anhydride group in the molecule and is a compound capable of curing an epoxy resin. Examples of the acid anhydride curing agent include an alicyclic acid anhydride, an aromatic acid anhydride, and an unsaturated carboxylic acid anhydride. Specific examples of the acid anhydride curing agent include methyltetrahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, cyclohexane-1 and ,2,4-tricarboxylic acid-1,2-anhydride, and these may be used alone or in combination of two or more.

According to one embodiment, the acid anhydride-based curing agent may be represented by the following Chemical Formula 1:

<Formula 1>

In Formula 1, R ₁ may be selected from a C ₁ -C ₁₀ alkyl group. For example, R ₁ may be selected from a C ₁ -C ₃ alkyl group, that is, a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group. According to one embodiment, R ₁ may be a methyl group, but is not limited thereto.

In Formula 1, a1 may be selected from an integer of 0 to 4. Here, a1 represents the number of R ₁ , and when a1 is 2 or more, two or more R ₁ may be the same or different from each other. According to one embodiment, a1 may be 0 or 1, but is not limited thereto.

According to one embodiment, the acid anhydride-based curing agent may include methylhexahydrophthalic anhydride, specifically, 4-methylhexahydrophthalic anhydride, but is not limited thereto.

The amount of the acid anhydride-based curing agent to be used is not particularly limited, but, for example, the acid anhydride-based curing agent may be included in an amount of 0.1 to 20% by weight of the epoxy resin composition for sealing semiconductor devices. In the above range, the curability of the composition may not decrease. According to one embodiment, the acid anhydride-based curing agent is 0.1 to 13% by weight of the epoxy resin composition for sealing semiconductor devices, according to another embodiment 0.1 to 10% by weight, according to another embodiment 1 to 9% by weight, another According to an embodiment, it may be included in an amount of 2 to 8% by weight.

inorganic filler

The inorganic filler may be used to improve the mechanical properties of the epoxy resin composition for semiconductor device encapsulation and to achieve low stress. As the inorganic filler, general inorganic fillers used for sealing semiconductor devices may be used without limitation, and there is no particular limitation. For example, fused silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, glass fiber, etc. can be used as the inorganic filler. .

According to one embodiment, fused silica having a low coefficient of linear expansion may be used to reduce stress. Fused silica refers to amorphous silica having a true specific gravity of 2.3 or less, and amorphous silica made by melting crystalline silica or synthesized from various raw materials may also be included. The shape and particle size of the fused silica are not particularly limited, but 50 to 99% by weight of the spherical fused silica having an average particle diameter (D ₅₀ ) of more than 1 to 30 μm, and the spherical fused silica having an average particle diameter (D ₅₀ ) of 0.001 to 1 μm is 1 The fused silica mixture including 50 wt% to 40 wt% may be included in an amount of 40 to 100 wt% based on the total filler. Here, the average particle diameter (D ₅₀ ) may be measured using a particle size analyzer device. In addition, the maximum particle size can be adjusted to any one of 10 µm, 15 µm, 20 µm, 45 µm, 55 µm, and 75 µm according to the intended use.

The amount of the inorganic filler used may vary depending on required physical properties such as moldability, low stress, and high temperature strength. For example, the inorganic filler may be included in an amount of 70 to 95% by weight of the epoxy resin composition for sealing semiconductor devices. Within the above range, flame retardancy, fluidity and reliability of the composition can be ensured. According to one embodiment, the inorganic filler may be included in an amount of 80 to 95% by weight of the epoxy resin composition for sealing semiconductor devices, 83 to 95% by weight according to another embodiment, and 85 to 95% by weight according to another embodiment.

polyhydric alcohol

The epoxy resin composition for semiconductor device encapsulation of the present invention may contain a polyhydric alcohol. The polyhydric alcohol lowers the activation energy of the acid anhydride-based curing agent through esterification with the acid anhydride-based curing agent, thereby lowering the onset temperature of the epoxy resin composition to enable low-temperature curing.

The polyhydric alcohol may be used without limitation as long as it is a compound containing two or more (eg, 2 to 10, other, for example, 2 to 6) hydroxyl groups in one molecule. For example, polyhydric alcohols include aliphatic polyhydric alcohols (eg, C ₂ -C ₃₀ , other eg, C ₂ -C ₂₀ aliphatic polyhydric alcohols), alicyclic polyhydric alcohols (eg, C ₃ -C ₂₀ ). of alicyclic polyhydric alcohols), aromatic polyhydric alcohols (eg, C ₆ -C ₃₀ aromatic polyhydric alcohols), and the like, and examples of such polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, and propane. Diol (eg, 1,2-propanediol, etc.), butanediol (eg, 1,4-butanediol, 2,3-butanediol, etc.), 1,4-butenediol, pentanediol (eg 1 ,5-pentanediol, 2,3-pentanediol, etc.), hexanediol (eg 1,6-hexanediol, 2,3-hexanediol, 3,4-hexanediol, etc.), heptanediol (eg For example, 1,7-heptanediol, etc.), neopentyl glycol, cyclohexanediol (eg, 1,2-cyclohexanediol, 1,4-cyclohexanediol, etc.), cyclohexanedimethanol (eg, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, etc.), glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, 2-methylpropanetri ol, butanetriol (eg, 1,2,4-butanetriol, etc.), pentanetriol (eg, 1,2,5-pentanetriol, etc.), pentaerythritol, dipentaerythritol , tripentaerythritol, sorbitol, xylitol, mannitol, 2-hydroxymethylpropane-1,3-diol, 2-methyl-1,2,4-butanetriol, 1,2,3,6-hexanetetraol , xylene glycol, 1,3,5-benzene trimethanol, bisphenol, and the like. Each of these may be used alone or in combination of two or more.

According to one embodiment, the polyhydric alcohol may be represented by the following Chemical Formula 2:

<Formula 2>

In Formula 2, L ₁ may be selected from a substituted or unsubstituted C ₁ -C ₂₀ alkylene group and an ether group. For example, L ₁ may be selected from a C ₁ -C ₁₀ alkylene group and an ether group unsubstituted or substituted with at least one of a hydroxyl group, a C ₁ -C ₂₀ alkyl group, and a C ₁ -C ₂₀ hydroxyalkyl group. Here, "C ₁ -C ₂₀ hydroxyalkyl group" may mean a C ₁ -C ₂₀ alkyl group substituted with a hydroxy group. According to one embodiment, L ₁ may be selected from a C ₁ -C ₁₀ alkylene group and an ether group unsubstituted or substituted with at least one of a hydroxyl group, a C ₁ -C ₁₀ alkyl group, and a C ₁ -C ₁₀ hydroxyalkyl group. According to another embodiment, L ₁ may be selected from a C ₁ -C ₅ alkylene group and an ether group substituted or unsubstituted with at least one of a hydroxyl group, a C ₁ -C ₅ alkyl group, and a C ₁ -C ₅ hydroxyalkyl group, The present invention is not limited thereto.

In Formula 2, b1 may be selected from an integer of 0 to 20. b1 represents the number of L ₁ , and when b1 is 0, *-L ₁ -*' becomes a single bond, and when b1 is 2 or more, two or more L ₁ may be the same or different from each other. Here, * and *' represent binding sites with neighboring atoms. According to an embodiment, b1 may be selected from an integer of 0 to 10. According to another embodiment, b1 may be selected from an integer of 0 to 5, but is not limited thereto.

In Formula 2, R ₂ to R ₅ may be each independently selected from hydrogen and a substituted or unsubstituted C ₁ -C ₂₀ alkyl group. For example, R ₂ to R ₅ may be each independently selected from hydrogen and a C ₁ -C ₂₀ alkyl group substituted or unsubstituted with a hydroxy group. According to an embodiment, R ₂ to R ₅ may be each independently selected from hydrogen and a C ₁ -C ₁₀ alkyl group substituted or unsubstituted with a hydroxy group. According to another embodiment, R ₂ to R ₅ may be each independently selected from hydrogen and a C ₁ -C ₅ alkyl group substituted or unsubstituted with a hydroxy group, but is not limited thereto.

According to one embodiment, the polyhydric alcohol may include ethylene glycol and/or glycerin, but is not limited thereto.

According to one embodiment, the weight ratio of the acid anhydride-based curing agent to the polyhydric alcohol may be 98: 2 to 60: 40. Within the above range, there may be an effect of reducing warpage due to low-temperature curing. The weight ratio of the acid anhydride-based curing agent to the polyhydric alcohol may be, for example, 96: 4 to 60: 40, for example, 93: 7 to 60: 40, but is not limited thereto.

The amount of the polyhydric alcohol used is not particularly limited, but, for example, the polyhydric alcohol may be included in an amount of 0.01 to 5% by weight in the epoxy resin composition for sealing semiconductor devices. Within the above range, there may be an effect of reducing warpage due to low-temperature curing. According to one embodiment, the polyhydric alcohol may be included in an amount of 0.1 to 4% by weight of the epoxy resin composition for sealing a semiconductor device, 0.2 to 3% by weight according to another embodiment, and 0.5 to 2% by weight according to another embodiment.

The epoxy resin composition for semiconductor device encapsulation may further include a curing accelerator.

hardening accelerator

The curing accelerator may refer to a substance that accelerates the reaction between the epoxy resin and the curing agent. As the curing accelerator, a known curing accelerator may be used without limitation. Examples of curing accelerators include 1,8-diaza-bicyclo(5.4.0)undecene-7,1,5-diaza-bicyclo(4.3.0)nonene-5,6-dibutylamino-1 , a cycloamidine compound such as 8-diaza-bicyclo(5.4.0)undecene-7, or a tertiary class such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris(dimethylaminomethyl)phenol Amine compound, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-Benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino Imidazole compounds such as -6-(2'-methylimidazolyl-(1'))-ethyl-s-triazine and 2-heptadecylimidazole, trialkylphosphine such as tributylphosphine, and dimethyl Organic phosphines such as dialkylaryl phosphine such as phenylphosphine, alkyldiaryl phosphine such as methyldiphenylphosphine, triphenylphosphine, and triphenylphosphine substituted with an alkyl group, and maleic anhydride, 1, 4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4 -Molecules formed by adding a compound having a π bond, such as quinone compounds such as benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, diazophenylmethane, and phenol resin and phenylboron salts such as compounds having polarization resistance and derivatives of these compounds, 2-ethyl-4-methylimidazoletetraphenylborate and N-methylmorpholinetetraphenylborate. Further, examples of the curing accelerator having potential include core-shell particles formed by using a compound having a solid amino group at room temperature as a core and coating a shell of a solid epoxy compound at room temperature. Commercially available products of such core-shell particles include Ajicure manufactured by Ajinomoto Corporation. These hardening accelerators can be used independently and can also be used together.

The amount of the curing accelerator to be used is not particularly limited, but, for example, the curing accelerator may be included in an amount of 0.01 to 2% by weight (eg, 0.02 to 1.5% by weight) of the epoxy resin composition for sealing semiconductor devices. Within the above range, there may be advantages in promoting the curing of the composition and also having a good degree of curing.

The epoxy resin composition for semiconductor device encapsulation may further include at least one of a coupling agent, a release agent, and a colorant.

coupling agent

The coupling agent is for improving interfacial strength by reacting between the epoxy resin and the inorganic filler, and examples of the coupling agent include a silane coupling agent. The silane coupling agent reacts between the epoxy resin and the inorganic filler to improve the interfacial strength between the epoxy resin and the inorganic filler, and the type thereof is not particularly limited. Examples of the silane coupling agent include epoxy silane, amino silane, ureido silane, mercapto silane, and alkyl silane. A coupling agent can be used independently and can also be used together.

The amount of the coupling agent used is not particularly limited, but, for example, the coupling agent may be included in an amount of 0.01 to 5% by weight (eg, 0.05 to 3% by weight) of the epoxy resin composition for sealing semiconductor devices. In the above range, the strength of the cured product may be improved.

release agent

As the releasing agent, at least one of paraffin wax, ester wax, higher fatty acid, metal salt of higher fatty acid, natural fatty acid, and metal salt of natural fatty acid may be used.

The amount of the release agent is not particularly limited, but, for example, the release agent may be included in an amount of 0.01 to 1% by weight of the epoxy resin composition for sealing semiconductor devices.

coloring agent

The colorant is for laser marking of a semiconductor device encapsulant, and colorants well known in the art may be used, but is not particularly limited. For example, the colorant may include one or more of carbon black, titanium black, titanium nitride, dicopper hydroxide phosphate, iron oxide, and mica.

The amount of the colorant to be used is not particularly limited, but for example, the colorant may be included in an amount of 0.01 to 5% by weight (eg, 0.05 to 3% by weight) of the epoxy resin composition for sealing semiconductor devices.

In addition, the epoxy resin composition for semiconductor device sealing is an antioxidant such as Tetrakis [methylene-3- (3,5-di-tertbutyl-4-hydroxyphenyl) propionate] methane in the range that does not impair the object of the present invention; Flame retardants such as aluminum hydroxide may be additionally contained as necessary.

The epoxy resin composition for semiconductor element encapsulation can be obtained by stirring, dissolving, mixing, and dispersing the above components simultaneously or separately while performing heat treatment as needed. In this case, although the apparatus for mixing, stirring, dispersion, etc. are not specifically limited, For example, a grinder provided with a stirring and heating apparatus, a twin roll, a triaxial roll, a ball mill, a planetary mixer, a mascoloider, a vacuum oil An erection, a planetary mixer, etc. can be used individually or in combination as appropriate.

The epoxy resin composition for sealing a semiconductor device according to an embodiment of the present invention may be usefully applied to a semiconductor device, particularly a semiconductor device mounted on a mobile display or a fingerprint recognition sensor of a vehicle. As a method of sealing a semiconductor device using the epoxy resin composition, a compression molding method may be generally used, but is not limited thereto.

According to another aspect, a semiconductor device sealed using the epoxy resin composition for sealing a semiconductor device according to an embodiment of the present invention is disclosed.

Hereinafter, for example, an epoxy resin composition for sealing semiconductor devices according to an embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention, and it cannot be construed as limiting the present invention in any sense.

Example

Specific specifications of the components used in the following Examples and Comparative Examples are as follows.

(A) Epoxy resin

(a1) Celloxide 2021P (Diacel)

(a2) KDS-8128 (Kukdo Chemical)

(a3) EPPN 501H (Nippon Kayaku)

(B) Acid anhydride curing agent: Rikacid-MH (New Japan Chemical)

(C) Inorganic filler: 9:1 (weight ratio) mixture of spherical fused silica having an average particle diameter (D ₅₀ ) of 18 μm and spherical fused silica having an average particle diameter (D ₅₀ ) of 0.5 μm

(D) polyhydric alcohol

(d1) ethylene glycol

(d2) glycerin

(E) monohydric alcohol

(e1) phenol

(e2) ethanol

(e3) pentanol

(F) Curing accelerator: Ajicure PN-23 (Ajinomoto)

(G) Colorant: MA-600 (Mitsubishi Chemical)

(H) Phenolic curing agent: MEH-7800S (Meiwa)

Examples 1 to 4 and Comparative Examples 1 to 5

Each component was weighed according to the composition of Table 1 below and mixed to prepare an epoxy resin composition for sealing semiconductor devices. In Table 1 below, the usage unit of each composition is % by weight.

Example comparative example One 2 3 4 One 2 3 4 5 (A) (a1) 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 (a2) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 (a3) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 (B) 5.0 5.0 4.5 4.0 6.0 5.5 5.5 5.5 - (C) 86 86 86 86 86 86 86 86 86 (D) (d1) 1.0 - 1.5 2.0 - - - - - (d2) - 1.0 - - - - - - - (E) (e1) - - - - - 0.5 - - - (e2) - - - - - - 0.5 - - (e3) - - - - - - - 0.5 - (F) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 (G) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (H) - - - - - - - - 6.0

The physical properties of the epoxy resin compositions of Examples and Comparative Examples prepared as described above were measured according to the following physical property evaluation method. The measurement results are shown in Table 2.

How to evaluate physical properties

(1) Thermal differential scanning calorimetry (DSC) phase onset point (onset point) and exothermic peak temperature (°C): Thermal differential scanning calorimetry (DSC) (Q20, TA instruments) for the epoxy resin compositions of Examples and Comparative Examples The onset temperature and the exothermic peak temperature on the thermal differential scanning calorimeter were measured in the range of -50 to 250 °C at a rate of 10 °C/min under a nitrogen gas atmosphere using The thermal differential scanning calorimeter phase initiation temperature refers to the temperature at which the slope of the graph first increases due to heat generation during measurement of the thermal differential scanning calorimeter. say the temperature.

(2) Curing rate (%): The amount of heat generated when the temperature was raised to 300 °C at a rate of 10 °C/min using a thermal differential scanning calorimeter (DSC) (Q20, TA instruments) for the epoxy resin compositions of Examples and Comparative Examples After measuring (A) and heat-treating the epoxy resin compositions of Examples and Comparative Examples at 110 ° C. for 10 minutes, after measuring the exotherm (B) at the time of temperature increase to 300 ° C. at a rate of 10 ° C./min, the following formula 1 was calculated.

<Equation 1>

Curing rate (%) = |1-(B/A)| × 100

(3) Thickening rate (%): For the epoxy resin compositions of Examples and Comparative Examples, the average value (C) of the viscosity measured at 10 rpm at room temperature for 5 minutes at room temperature using a Brookfield viscometer, and the epoxy resin compositions of Examples and Comparative Examples After standing at room temperature for 8 hours, the average value (D) of the viscosity measured at room temperature at 10 rpm for 5 minutes was obtained, and then calculated according to Equation 2 below.

<Equation 2>

Thickening rate (%) = {(D-C)/C} × 100

Example comparative example One 2 3 4 One 2 3 4 5 onset temperature (°C) 88 95 87 88 115 120 123 112 145 Exothermic peak (℃) 118 123 113 113 157 167 165 158 180 Curing rate @110℃, 10min(%) 88 85 89 91 68 53 51 65 18 Thickening rate (%) 22 22 23 22 38 32 40 45 -

As can be seen from Table 2, in the case of the compositions of Examples 1 to 4 containing the acid anhydride-based curing agent and the polyhydric alcohol together, the starting temperature was low, so that curing was possible at a low temperature (110 ° C.), and the thickening rate was low. It can be seen that the storage stability is also excellent.

On the other hand, the compositions of Comparative Examples 1 to 4 that did not contain a polyhydric alcohol or contained a monohydric alcohol instead of a polyhydric alcohol showed a higher onset temperature and a higher thickening rate than the Example composition, and included a phenol-based curing agent instead of an acid anhydride-based curing agent. In the case of the composition of Comparative Example 5, it can be seen that the low-temperature curing was impossible because the starting temperature was very high compared to that of Example.

Simple modifications or changes of the present invention can be easily carried out by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (8)

0.5 to 20% by weight of an epoxy resin, 0.1 to 20% by weight of an acid anhydride-based curing agent, 70 to 95% by weight of an inorganic filler, and 0.01 to 5% by weight of a polyhydric alcohol,
The acid anhydride-based curing agent is methyltetrahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, cyclohexane-1,2 , including 4-tricarboxylic acid-1,2-anhydride or a combination thereof,
The polyhydric alcohol is ethylene glycol, diethylene glycol, triethylene glycol, propanediol, butanediol, 1,4-butenediol, pentanediol, hexanediol, heptanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, glycerin , diglycerin, triglycerin, trimethylolethane, trimethylolpropane, 2-methylpropanetriol, butanetriol, pentanetriol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, xylitol, mannitol, 2-hydroxymethylpropane-1,3-diol, 2-methyl-1,2,4-butanetriol, 1,2,3,6-hexanetetraol, xylene glycol, 1,3,5-benzene An epoxy resin composition for semiconductor device sealing, comprising trimethanol, bisphenol, or a combination thereof.
delete delete delete delete The method of claim 1,
The weight ratio of the acid anhydride-based curing agent to the polyhydric alcohol is 98: 2 to 60: 40, an epoxy resin composition for sealing semiconductor devices.
delete A semiconductor device sealed using the epoxy resin composition for sealing semiconductor elements according to claim 1 or 6.