KR100715102B1 - Epoxy resin composition for encapsulating semiconductor device - Google Patents

Abstract

The present invention relates to an epoxy resin composition for sealing a semiconductor device which exhibits excellent self-extinguishing flame retardant properties without using inorganic flame retardants such as halogen-based organic flame retardants and antimony trioxide, which are known to be harmful to the environment. 1) Epoxy resin, 2) In the epoxy resin composition comprising a curing agent and 3) inorganic fillers, the epoxy resin of 1) is an epoxy resin mixture comprising a fluorene-type epoxy resin, the curing agent of 2) is a fluorene-type phenol It is a phenol resin mixture containing resin, It is characterized by including an inorganic filler as a remainder.

Epoxy resin, self-extinguishing, fluorene type epoxy resin, fluorene type phenol resin

Description

Epoxy resin composition for encapsulating semiconductor device

The present invention relates to an epoxy resin composition for sealing semiconductor devices, and more particularly to semiconductor device sealing that exhibits excellent self-extinguishing flame retardant properties without using inorganic flame retardants such as halogen-based organic flame retardants and antimony trioxide, which are known to be harmful to the environment. It relates to an epoxy resin composition for use.

In general, in providing an epoxy resin composition for sealing semiconductor devices, a flame retardant property that does not burn in the event of a fire is required, and most semiconductor manufacturers require a resin composition that can satisfy the flame retardant standard of UL 94 V-0. In order to secure such flame retardancy, conventionally, a flame retardant is used to manufacture an epoxy resin for semiconductor device encapsulation, and a halogen-based epoxy resin and antimony trioxide are mainly used to prepare an epoxy resin for semiconductor device encapsulation to secure flame retardancy. However, in the case of epoxy resin for sealing semiconductor devices using flame retardants such as flame retardants, it is known that toxic carcinogens such as dioxin or difuran are generated during incineration or fire. In addition, halogen-based flame retardants are not only toxic to the human body due to harmful gases such as hydrogen bromide (HBr) and hydrochloric acid (HCl) generated during combustion, but also can be used to prevent the formation of semiconductor chips, wires, and lead frames. There are problems such as being a major cause of corrosion.

As a countermeasure, organic phosphorus flame retardants such as phosphazene and phosphate esters and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide and talc or new flame retardants such as resins containing nitrogen atoms have been considered. Phosphoric acid and polyphosphoric acid produced by bonding to and decrease the reliability of the semiconductor, and, in the case of the inorganic functional flame retardant has a problem that the absorption rate is increased. Nitrogen-atom-containing resins also have some self-extinguishing flame retardant properties, but they exhibit somewhat poor flame retardancy to meet the flame retardancy standards required by semiconductor companies.

An object of the present invention is to provide an epoxy resin composition for sealing a semiconductor device exhibiting excellent self-extinguishing flame retardant properties without using inorganic flame retardants such as halogen-based organic flame retardants and antimony trioxide known to be harmful to the environment.

The present invention is to solve the problems of the prior art as described above, without the use of halogen-based flame retardants and phosphorus-based flame retardants harmful to humans or semiconductor devices, semiconductor device sealing showing excellent flame resistance by using a novel epoxy resin having self-extinguishing It is to provide an epoxy resin composition.

The present invention relates to an epoxy resin composition comprising 1) an epoxy resin, 2) a curing agent and 3) an inorganic filler, wherein the epoxy resin of 1) is a fluorene type epoxy resin represented by the following Chemical Formula 1, Epoxy resin mixture consisting of a mixture of at least two or more of the epoxy resin represented by 2 and the epoxy resin represented by the formula (3), wherein the curing agent of 2) is represented by the fluorene-type phenol resin represented by the formula (4) A phenol resin mixture consisting of a mixture of phenolic resins represented, wherein the epoxy resin mixture is composed of 5 to 95% by weight of the epoxy resins represented by the formula 2, 3 to 5 to 95% by weight of the fluorene-type epoxy resin represented by the formula (1) , The phenol resin mixture as the curing agent is converted into 5 to 95% by weight of the fluorene type phenol resin represented by the formula (4) 5 to 95% by weight of the phenol resin represented by Formula 5, and the remaining amount of the thermosetting resin composition characterized in that it comprises an inorganic filler and the cured copper-based lead frame, iron-based lead frame, organic laminate frame of Provided is a semiconductor device.

In the above formula, R ₁ and R ₂ are each independently hydrogen or an alkyl substituent, R ₃ is a single bond or an alkylene group, and n is an integer of 1 to 10 as a repeating unit.

Wherein each R is independently a hydrogen or alkyl substituent, m is an integer from 1 to 10 representing the number of substituents R, Z is an aliphatic or aromatic hydrocarbon group, n is an integer from 0 to 10 as a repeating unit .

delete

Wherein R ₁ is hydrogen, alkyl or an aromatic substituent, R ₂ is each independently hydrogen or an alkyl group, and n is an integer of 1 to 10 as a repeating unit.

Wherein R is hydrogen or an alkyl substituent, m is an integer of 1 to 10 as representing the number of substituents R, Z is an aliphatic or aromatic hydrocarbon group, and n is an integer of 0 to 10 as a repeating unit.

Hereinafter, the present invention will be described in detail.

The epoxy resin composition for sealing semiconductor elements used in the present invention includes 1) an epoxy resin, 2) a curing agent, and 3) an inorganic filler as essential components, which will be described in more detail below.

The epoxy resin of 1) is an epoxy resin mixture composed of a mixture of at least two or more of the fluorene-type epoxy resin represented by the formula (1), the epoxy resin represented by the formula (2) and the epoxy resin represented by the formula (3) Here, the fluorene-type epoxy resin of the formula (1) has a variety of different epoxy equivalent and softening point according to the type of R ₁ , R ₂ , R ₃ , preferably epoxy equivalent 200 to 500, softening point 40 To 80 ° C may be used. 5 to 95% by weight of the fluorene-type epoxy resin of Formula 1 may be used, preferably 15 to 75% by weight of the epoxy resin mixture. If applied in an amount of less than 5% by weight, there may be a problem of inferior flame retardancy, when it exceeds 95% by weight, there is a problem in that the fluidity is inferior in the low pressure transfer molding process for sealing a semiconductor device There may be a problem that lowers the productivity. In addition, the epoxy resin of the formula (2) in the epoxy resin mixture is preferably a softening point of 40 to 70 ℃, when used in combination with the epoxy resin of the formula (3), the combined use amount is 5 to 90 weight in the epoxy resin mixture %, Preferably 25 to 85% by weight is preferred. When using such an epoxy resin mixture, it is possible to provide an epoxy resin composition for sealing a semiconductor device having optimal flame retardancy, high fluidity and high dielectric transition temperature characteristics.

As a hardening | curing agent of said 2), it is a phenol resin mixture which consists of a mixture of the fluorene type | mold phenol resin represented by the said Formula (4), and the phenol resin represented by the said Formula (5), Here, the fluorene type phenol resin represented by said Formula (4) is a hydroxyl group. It is preferable that the equivalent is 200-500, and a softening point is 40-120 degreeC. The amount of the fluorene-type phenolic resin of Formula 4 may be 5 to 95% by weight, preferably 15 to 60% by weight in the phenolic resin mixture. If, when applied in less than 5% by weight may have a problem that the flame retardancy is poor, there may be a problem in that the fluidity when the application exceeds 95% by weight. In addition, the phenolic resin of Formula 5 preferably has a softening point in the range of 40 to 80 ℃, 5 to 95% by weight, preferably 40 to 85% by weight in the phenolic resin mixture.

The inorganic filler of component 3) used in the present invention has an average particle diameter of 0.1 to 35 µm, and at this time, molten silica or synthetic silica that cuts large particles of 45 µm, 55 µm or 75 µm or more, respectively, may be used. Preferably, the spherical molten silica or synthetic silica having an average particle diameter of 0.1 to 2 μm is 3 to 10% by weight of the entire inorganic filler, and the spherical molten silica or synthetic silica having an average particle diameter is 3 to 9 μm as the inorganic filler. It is preferable to contain spherical molten silica or synthetic silica having a residual amount of 5 to 20% by weight and an average particle diameter of 10 to 35 µm. The inorganic filler may be used in the remaining amount excluding the epoxy resin mixture of 1) and the phenolic resin mixture of 2), preferably in the range of 80 to 93% by weight, more preferably 84 to 91% by weight in the total composition. It is good to apply as. If the inorganic filler is applied in an amount of less than 80% by weight, there may be a problem that can not be obtained sufficient flame retardancy, if the inorganic filler exceeds 93% by weight, the moldability is worse due to the deterioration of the flow characteristics There may be problems, which is undesirable.

Moreover, it is preferable to add a hardening accelerator to the composition of this invention, For example, tertiary amines, such as benzyl dimethylamine, triethanolamine, triethylenediamine, dimethylamino ethanol, a tri (dimethylaminomethyl) phenol, 2-methyl Imidazoles such as imidazole and 2-phenylimidazole, coordination compounds of triphenylphosphine, triphenylphosphine and parabenzophenone, organic phosphines such as diphenylphosphine and phenylphosphine, tetraphenylphosphoni Tetraphenyl boron salts, such as um tetraphenyl borate and a triphenyl phosphine tetraphenyl borate, etc. can be used, One or two or more of these can be used together. As for the usage-amount, 0.05-0.4 weight% is suitable with respect to the whole epoxy resin composition.

In the composition of the present invention, release agents such as higher fatty acids, higher fatty acid metal salts, ester waxes, colorants such as carbon black, organic dyes and inorganic dyes, epoxysilanes, aminosilanes, alkylsilanes, and the like, without departing from the object of the present invention. A coupling agent, modified silicone oil, etc. can be used as needed. At this time, the modified silicone oil is preferably a silicone polymer having excellent heat resistance, and the total epoxy resin by mixing one or two or more kinds of silicone oil having an epoxy functional group, silicone oil having an amine functional group and silicone oil having a carboxyl functional group. 0.05 to 1.5 weight percent of the composition may be used. However, when the silicone oil exceeds 1.5% by weight or more, surface contamination is likely to occur and the resin bleed may be long, and when used at less than 0.05% by weight, there may be a problem in that sufficient low modulus of elasticity cannot be obtained.

As a general method for producing an epoxy resin composition using the raw materials described above, a predetermined amount is uniformly mixed by using a Henschel mixer or a solid mixer, and then melt-kneaded with a roll mill or a kneader, and cooled and pulverized. A method of obtaining the final powder product is used. As a method of sealing a semiconductor element using the epoxy resin composition obtained in the present invention, a low pressure transfer molding method is most commonly used, or an injection molding method or a casting method can be used.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by Examples.

Examples 1-4

After weighing the respective components as shown in the following Table 1 to prepare a semiconductor device sealed epoxy resin composition of the present invention, by homogeneously mixing a Henschel mixer were prepared first composition of the powder-form, two-axis kneader After melt-kneading at 100 ° C for 7 minutes using a further, an epoxy resin composition was prepared by cooling and grinding. At this time, the equivalent ratio of the epoxy resin mixture of the essential component 1) and the curing agent of the essential component 2) was 1: 1. The epoxy resin composition thus obtained was evaluated for physical properties and reliability by the following method, and was molded at 175 ° C. for 120 seconds using an MPS (Multi Plunger System) molding machine for reliability test, followed by 6 hours at 175 ° C. It hardened | cured and the PBGA type semiconductor package was produced. Physical properties and flame retardancy, reliability, and moldability test results of the epoxy resin composition according to the present invention are shown in Table 2 below. Reliability tests were expressed in terms of package peeling and cracking in the thermal shock test.

Comparative Examples 1 and 2

As shown in Table 1, each component was weighed according to a given composition to prepare an epoxy resin composition in the same manner as in Example, and the results of evaluation of physical properties and reliability are shown in Table 2 below.

[Property evaluation method]

* Spiral Flow

Molds were manufactured based on the EMMI standard, and the flow length was evaluated at a molding temperature of 175 ° C. and a molding pressure of 70 Kgf / cm ² .

* Glass transition temperature (Tg)

It was evaluated by TMA (Thermomechanical Analyser).

* Flexural strength and flexural modulus

Hardened EMC molded specimens (125 x 12.6 x 6.4 mm) were prepared and the width and thickness of the center of the specimen were measured using a micrometer to 0.001 mm and measured using a UTM tester.

* Flame retardant

It evaluated according to UL 94 V-0 standard.

* Package Warpage

The degree of warpage of the package was measured in micrometers with a three-dimensional projector.

* Crack resistance evaluation (reliability test)

The FBGA type semiconductor package prepared from the epoxy resin composition was dried at 125 ° C. for 24 hours, then subjected to 5 cycles of thermal shock test, and left for 30 hours at 30 ° C./60% relative humidity for 10 hours at 260 ° C. for 10 seconds. Three passes of IR reflow were used to evaluate package delamination and cracking under preconditions. After preconditioning, 1,000 cycles were carried out for 1 cycle of 10 minutes at -65 ° C, 5 minutes at 25 ° C, and 10 minutes at 150 ° C in a thermal cycle tester, followed by peeling and cracking with SAT, a non-destructive tester. The occurrence was evaluated.

Ingredient (Unit weight%) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Epoxy resin Epoxy Resin 1 0.15 0.96 3.19 8.16 - - Epoxy Resin 2 - 1.93 - - 7.98 - Epoxy Resin 3 2.79 1.93 3.19 0.43 - 5.87 Hardener Phenolic Resin 1 0.14 0.78 2.63 5.67 - - Phenolic Resin 2 2.71 3.11 2.63 0.3 5.6 5.80 Flame retardant Brominated epoxy resin - - - - 0.5 - Antimony trioxide - - - - 2.0 - Inorganic filler Average particle size 0.1 ~ 2㎛ 9.3 9.0 8.7 8.4 8.25 8.7 Average particle size 3-9㎛ 13.95 13.5 13.05 12.6 12.38 13.05 Average particle size 10 to 35㎛ 69.75 67.5 65.25 63.0 61.88 65.25 Curing accelerator Triphenylphosphine 0.12 0.19 0.26 0.34 0.32 0.23 Coupling agent γ-glycithoxypropyltrimethoxysilane 0.5 0.5 0.5 0.5 0.5 0.5 coloring agent Carbon black 0.3 0.3 0.3 0.3 0.3 0.3 Wax Carnauba Wax 0.3 0.3 0.3 0.3 0.3 0.3  Epoxy resin 1; Epoxy resin of the formula (1) Epoxy equivalent 240, Softening point 50 ℃ Epoxy resin 2; Epoxy resin of the formula (2) Epoxy equivalent 270, softening point 60 ℃ epoxy resin 3; Epoxy equivalent of Chemical Formula 3 as epoxy equivalent 192, softening point 105 degreeC phenol resin 1; As a phenol resin of Formula 4, a hydroxyl equivalent 235, softening point 73 degreeC phenol resin 2; Phenolic resin of the formula (5), hydroxyl group equivalent 175, softening point 60 ℃

Evaluation item Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Spiral Flow (inch) 35 40 45 52 53 55 Tg (℃) 130 145 162 140 125 125 Flexural Strength (㎏f / ㎠ at 24 ℃) 18 18 19 18 15 15 Flexural modulus (㎏f / ㎡ at 24 ℃) 2860 2730 2680 2440 2360 2350 Flame retardant UL 94 V-0 V-0 V-0 V-0 V-0 V-0 V-1 Formability Number of voids generated (visual inspection) 2/256 0/256 0/256 0/256 0/256 0/256 Package Warpage (Warpage, μm) 20 30 45 50 120 130 responsibility Crack Resistance Evaluation 0/256 0/256 0/256 0/256 1/256 2/256 Detachment Number 2/256 0/256 0/256 0/256 5/256 5/256

As shown in Table 2, the resin composition according to the present invention can secure excellent flame retardancy without using an environmentally harmful substance bromide epoxy resin and antimony trioxide used in Comparative Example 1, in terms of formability, reliability It was confirmed that excellent characteristics were shown.

Therefore, according to the present invention, there is an effect of providing an epoxy resin composition for flame retardant semiconductor element sealing, which does not contain flame retardants such as halogen-based and antimony trioxide, and which ensures flame retardancy, reliability and moldability.

Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.

Claims (5)

1) Epoxy resin composition comprising 1) epoxy resin, 2) curing agent and 3) inorganic fillers, Wherein the epoxy resin of 1) is a fluorene-type epoxy resin represented by the following formula (1), at least one or more of the epoxy resin represented by the formula (2) and the epoxy resin represented by the formula (3) An epoxy resin mixture comprising a mixture, wherein the curing agent of 2) is a phenol resin mixture comprising a mixture of a fluorene-type phenol resin represented by the following formula (4) and a phenol resin represented by the following formula (5). Epoxy resin compositions; [Formula 1]

Wherein R ₁ and R ₂ are each independently hydrogen or an alkyl group, R ₃ is a single bond or an alkylene group, n is an integer of 1 to 10 as a repeating unit, [Formula 2]

Wherein each R is independently a hydrogen or alkyl substituent, m is an integer from 1 to 10 representing the number of substituents R, Z is an aliphatic or aromatic hydrocarbon group, n is an integer from 0 to 10 as a repeating unit , [Formula 3]

[Formula 4]

Wherein R ₁ is hydrogen, alkyl or an aromatic substituent, R ₂ is each independently hydrogen or an alkyl group, n is an integer from 1 to 10 as a repeating unit, [Formula 5]

Wherein R is hydrogen or an alkyl substituent, m is an integer of 1 to 10 as representing the number of substituents R, Z is an aliphatic or aromatic hydrocarbon group, and n is an integer of 0 to 10 as a repeating unit. The method of claim 1, Epoxy resin composition for sealing a semiconductor device, characterized in that the epoxy resin mixture consists of 5 to 95% by weight of the epoxy resin represented by the formula (2) or (3) to 5 to 95% by weight of the fluorene type epoxy resin represented by the formula (1). The method of claim 1, Epoxy resin composition for sealing a semiconductor device, characterized in that the phenol resin mixture as the curing agent is composed of 5 to 95% by weight of the phenol resin represented by the formula (5) to 5 to 95% by weight of the fluorene type phenol resin represented by the formula (4). The method of claim 1, The inorganic filler of 3) is within the range of 80 to 93% by weight with respect to the total composition, the spherical molten silica or synthetic silica having an average particle diameter of 0.1 to 2㎛ 3 to 10% by weight of the total inorganic filler, the average particle diameter 5 to 20% by weight of the spherical molten silica or synthetic silica of 3 to 9㎛ the inorganic filler, and spherical molten silica or synthetic silica having an average particle diameter of 10 to 35㎛ as the remaining amount in the whole inorganic filler Epoxy resin composition for sealing semiconductor elements. The semiconductor device is sealed using the epoxy resin composition for semiconductor element sealing of Claim 1 or 2.