KR19980057178A - New manufacturing method of polyfunctional phenol resin and epoxy resin composition for semiconductor encapsulant containing same - Google Patents

Abstract

The present invention relates to a method for producing a polyfunctional phenol resin for semiconductor encapsulation material and an epoxy resin composition for semiconductor encapsulation material containing the same, and more particularly, by condensation reaction of a bisphenol-type phenol resin and an aldehyde or a resol-type phenol resin under an acid catalyst. It is related with the epoxy resin composition for semiconductor sealing materials which manufactures a novel polyfunctional phenol resin and contains the phenol resin manufactured in this way. According to the present invention, it is excellent in heat resistance and low hygroscopicity after curing, thereby improving reliability as a semiconductor encapsulant.

Description

New manufacturing method of polyfunctional phenol resin and epoxy resin composition for semiconductor encapsulant containing same

The present invention relates to a method for producing a polyfunctional phenolic resin for semiconductor encapsulation and an epoxy resin composition for a semiconductor encapsulant containing the same, and more particularly, by condensation reaction of a bisphenol-type phenolic resin with an aldehyde or a resol-type phenolic resin under an acid catalyst. It is related with the epoxy resin composition for semiconductor sealing materials which manufactures a novel polyfunctional phenol resin and contains the phenol resin manufactured in this way.

Currently, epoxy resin compositions comprising resin-encapsulated ICs, LSIs, and ULSIs in the semiconductor devices, and epoxy resins, curing agents, and various additives, are generally formed in terms of moldability, adhesiveness, It is widely used for encapsulation of semiconductor devices because of its excellent electrical, mechanical and moisture resistance. In recent years, semiconductor devices have increased chip area due to high integration, and in particular, the package is thinned with the development of high-density packaging technology. Thus, when manufacturing a semiconductor device encapsulated with an olso cresol novolac-type epoxy resin composition, which is conventionally used, a chip is produced. There is a problem that cracks occur easily, or a bonding line is cut, an aluminum wire is sliced, or a crack is formed in the encapsulating resin. In particular, as the surface mounting progresses, the whole package is exposed to high temperature instantly, and thus, peeling between the resin and the chip and cracking in the package resin are likely to occur due to the explosive evaporation of moisture in the resin. These are fatal failures in semiconductor components.

The present invention prepares a novel multifunctional phenolic resin having high heat resistance and low hygroscopicity by condensing a bisphenol-type phenol resin with an aldehyde or a resol type phenol resin under an acid catalyst, and the epoxy resin composition comprising the same is heat-resistant and low-hygroscopic after curing. It is excellent in this and contributes to the improvement of the moisture absorption crack property of the semiconductor device encapsulated with such an epoxy resin hardened | cured material.

The present invention condenses a bisphenol-type phenol resin represented by the following formula (I) with an aldehyde or a resol type phenol resin represented by the following formula (II) in the presence of an acid catalyst to produce a polyfunctional phenol resin represented by the following formula (III).

[Formula I]

In Formula I, R is free of substituents, and is as follows:

X ₁ is an alkyl group having 1 to 4 carbon atoms, a benzene group, or a hydrogen atom,

X ₂ is the same as or different from each other an alkyl group having 1 to 3 carbon atoms,

i is an integer of 4 or less.

[Formula II]

In Formula II, X 1 is an alkyl group having 1 to 4 carbon atoms, a benzene group, or a hydrogen atom,

X ₃ is either X ₁ or a hydroxy group and is the same or different from each other,

i is an integer of 4 or less.

[Formula III]

In Formula III, R is free of substituents, and is as follows:

K is as follows,

X ₁ is an alkyl group having 1 to 4 carbon atoms, a benzene group, or a hydrogen atom,

X ₂ is the same as or different from each other an alkyl group having 1 to 3 carbon atoms,

X ₃ is either X ₁ or a hydroxy group and is the same or different from each other,

i is an integer of 4 or less.

The polyfunctional phenolic resin represented by Formula III thus prepared has the advantage of exhibiting low hygroscopicity due to its high functionality and high heat resistance and high concentration of hydrophobic groups in the molecule, and thus has excellent solder crack resistance. .

In addition, the present invention provides an epoxy resin composition containing an epoxy resin and a curing agent as an essential component, a mixture of a multifunctional phenolic resin represented by the above formula (III) or another phenolic resin, an inorganic filler, a curing accelerator and other additives, and The epoxy resin composition for a semiconductor encapsulation material manufactured as described above may have low moisture absorption and excellent heat resistance, thereby reducing the occurrence of cracks in the semiconductor encapsulation material.

The polyfunctional phenol resin represented by Formula III is represented by Formula II prepared by reacting an aldehyde or phenol or naphthol in the presence of formaldehyde and an alkaline catalyst with respect to 1 mol of the bisphenol-type phenol resin represented by Formula I above. 0.1 to 0.9 mol of an aldehyde or a resol-type phenol resin to be obtained is obtained by condensation reaction at a reaction temperature of 10 to 250 ° C. for 1 to 15 hours in the presence of an acid catalyst. At this time, when using less than 0.1 moles of aldehydes or resol type phenol resins represented by Formula II with respect to 1 mole of bisphenol type phenol resins represented by Formula I, the amount of unreacted bisphenol type phenol resin monomers is increased. It does not help to improve the heat resistance of the cargo, and when it is more than 0.9 mol, the softening point of the resin becomes high, which adversely affects workability.

Unreacted bisphenol-type phenolic resins, aldehydes or resol-type phenolic resins and acidic catalysts are dissolved in an organic solvent, removed by washing with water, and a high-purity polyfunctional phenolic resin can be obtained by distilling the organic solvent.

At this time, if necessary, the reaction can be promoted by azeotropic distillation such as water using one or two or more mixed solvents selected from nonpolar organic solvents, ketones, and alcohols as a reaction cosolvent.

The acidic catalyst is not particularly limited, but one compound selected from inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as paratoluene sulfonic acid can be used, and the amount thereof is used in 100 parts by weight of aldehyde or resol type phenolic resin. It is good to use 0.01-1.0 weight part with respect to the.

The aldehydes or resol type phenol resins represented by the above formula II were obtained by performing 1 to 10 moles of formaldehyde to 1 mole of aldehydes or phenols or naphthol under an alkaline catalyst at a temperature of 20 to 90 ° C. for 1 to 8 hours. Lose. At this time, if necessary, non-polar organic solvents, ketones, and alcohols may be used as reaction aids. The aldehyde or resol-type phenol resin thus obtained is obtained by removing unreacted aldehydes, phenols, naphthols and alkaline catalysts by water washing to recover the solvent. Here, phenols and naphthols are not particularly limited, for example, phenol, oxo-cresol, meta-cresol, para-cresol, 2,6-xylenol, α-naphthol, β-nathtol, 1-methyl- 2-naphthol, 2-methyl-1-naphthol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,6-naphthalenediol, 2,7 One or a mixture of two or more selected from naphthalenediol and 4,4-dihydroxybiphenyl can be used.

Although it does not restrict | limit especially as an alkaline catalyst which can be used, It selects from sodium hydroxide, potassium hydroxide, etc., The usage-amount is 0.01-1.0 weight part with respect to 100 weight part of aldehydes, phenols, or naphthol.

Although it does not restrict | limit especially as an epoxy resin, For example, a BPA type epoxy resin, a biphenyl type epoxy resin, a noblock type epoxy resin, a cresol type epoxy resin, and a naphthol type epoxy resin can be used, Preferably a cresol type epoxy resin is used. And biphenyl type epoxy resin.

As the inorganic filler used in the present invention, it is possible to use all of them in the epoxy resin composition. Specifically, for example, silicas such as fused silica and crystalline silica, alumina, silicon nitride, ammonium nitride, titanium oxide, and the like, and among them, fused silica is recommended. It is preferable that the average particle diameter is 3 to 15 microns in terms of moldability, and the shape of the fused silica is preferably used in the form of spherical silica in order to reduce the high filling and the stress on the chip surface. In addition, it is preferable to use an inorganic filler that has been surface-treated with a coupling agent first loaded in order to strengthen the bonding strength between the resin and the inorganic filler surface. These inorganic fillers may be used individually by 1 type, or 2 or more types may be used in the range of 100-1,000 weight part, preferably 200-700 weight part with respect to 100 weight part of epoxy resins and a polyfunctional total amount. .

Moreover, it is possible to mix | blend a hardening accelerator with the epoxy resin composition of this invention, and these hardening accelerators include an imidazole compound, a tertiary amine compound, a phosphorus compound, etc. Although the quantity of a hardening accelerator is not specifically limited, It is good to set it as 0.1-2 weight part especially 0.4-1.5 weight part with respect to 100 weight part of total amounts of an epoxy resin and a polyfunctional phenol resin.

And the composition of this invention can mix | blend various additives as needed. For example, additives such as thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, low stress agents such as silicones, waxes, pigments such as carbon blacks, flame retardants such as antimony oxide and halogen compounds, and silane coupling agents are used. It is possible to do

The epoxy resin composition of this invention can be obtained by the method of stirring and mixing the adjustment amount of the above-mentioned component at the time of manufacture uniformly, and kneading, cooling, and grind | pulverizing with a roll, etc. which are heated at 70-90 degreeC, and a compounding of the components The order is not particularly limited. The epoxy resin composition thus obtained can be usefully used for encapsulation of semiconductor devices such as SOP, SOJ, TSOP, TQFP, etc. In this case, the molding method was performed by transfer molding which has been conventionally used. The epoxy resin molding temperature of the present invention is preferably carried out for 30 to 180 seconds at 150 to 180 ° C, and the post-curing at 2 to 6 hours at 150 to 180 ° C.

Hereinafter, the present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to the following Examples.

EXAMPLE

[Phenol Resin Production Example 1]

Four-necked round flask with stirrer, cooling condenser, thermometer, and inert gas inlet was added 918g of para-crasol, 91% para-formaldehyde 574.5g and dissolved by slowly raising the temperature to 50 ° C. 680 g of sodium hydroxide solution is slowly added dropwise while suppressing exotherm. After completion of the dropwise addition, the reaction was carried out at 50 ° C. for 4 hours, and then 926 g of distilled water was added thereto to wash off unreacted substances and catalysts. This is carried out three to four times until the wash water is neutral, followed by drying at 40 ° C. for 10 hours or more under reduced pressure to synthesize 2,6-dimethylol-para-crensol.

After dissolving 50.4 g of 2,6-dimethylol-para-cresol and 777.6 g of a bisphenol-type phenolic resin and 414 g of methyl isobutyl ketone represented by the following formula EX 1-1, were gradually heated to 75 ° C. Para-toluenesulfonic acid 3.0g was added at 75 ° C, and the temperature was raised to 105 ° C and refluxed for 4 hours. After the completion of the reaction, 400 g of distilled water is added and washing with water is performed three to five times until the washing water is neutral. After washing with water, the methyl isobutyl ketone was recovered at atmospheric pressure by introducing an inert gas to 125 ° C, and the methyl isobutyl ketone was completely removed through a reduced pressure recovery at 160 ° C and a reduced pressure of 1 torr for 2 hours, thereby producing a new polyfunctional phenolic resin. Phenol-1 was prepared.

[Formula EX 1-1]

[Phenol Resin Production Example 2]

Phenolic resin except that 67.2 g of 2,6-dimethylol-para-cresol, 256 g of bisphenol-type phenol resin represented by the following formula EX 1-2, 161 g of methyl isobutyl ketone, 2.56 g of para-toluene sulfonic acid and 200 g of distilled water were used Reaction was carried out in the same manner as in Preparation Example 1 to prepare a novel multifunctional phenol resin Phenol-2.

[Formula EX 1-2]

[Phenol Resin Production Example 3]

Phenolic resin other than 28.56 g of 2,6-dimethylol-para-cresol, 272 g of bisphenol-type phenol resin represented by the following formula EX 1-3, 150 g of methyl isobutyl ketone, 2.7 g of para-toluene sulfonic acid and 200 g of distilled water Reaction was carried out in the same manner as in Preparation Example 1 to prepare a novel multifunctional phenol resin Phenol-3.

[Formula EX 1-3]

[Examples 1-3 and Comparative Example 1]

13.89 parts by weight of a resin branded with epoxy resin (Epoxy-1, 2) and phenol resins (Phenol-1, 2, 3, 4) with 1 equivalent of phenol resin relative to 1 equivalent of epoxy resin, triphenylphosphine 0.24 parts by weight, 80 parts by weight of melted silica having an average particle diameter of 10 microns, 4 parts by weight of melted silica having an average particle size of 1 micron, 1.0 part by weight of antimony trioxide, 0.22 parts by weight of carbon black, 0.15 part by weight of wax, and 0.5 part by weight of silane coupling agent. Four epoxy resin compositions were prepared by melting, kneading, cooling, and pulverizing uniformly with two rolls. About the obtained epoxy resin composition, the test piece was produced and measured as follows, and the result was put together in following Table 1.

[Epoxy-1]

Epoxy equivalent = 186 g / eq.

[Epoxy-2]

Formula Phenol-1

Formula Phenol-2

Formula Phenol-3

Formula Phenol-4

Comparative Example 2

One epoxy resin composition was prepared under the same conditions as in Examples 1 to 3 except that 22.8 parts by weight of the resin branded with 1 equivalent of the epoxy resin and 71 parts by weight of the molten silica having an average particle diameter of 10 micrograms were used. The results are summarized in Table 1 below.

TABLE 1

(1) Flowability: It measured on the conditions of 175 degreeC and 70 kg / cm <2> according to EEMI standard.

(2) Flexural strength and flexural modulus: 12.68 × 6.44 × 100 mm bending test pieces were formed under conditions of 175 ° C, 70kg / cm 2 and molding time 2 minutes in accordance with JIS-K6911, and then cured at 180 ° C for 4 hours. It measured at 25 degreeC and 215 degreeC.

(3) Linear expansion coefficient and glass transition temperature: It measured by the temperature increase rate of 5 degree-C / min by TMA method using the test piece of diameter 6mm and width 6mm.

(4) Moisture absorption rate: Molded at 175 ° C, 70kg / cm2, and 2 minutes of molding time, and cured after 4 hours at 180 ° C for 50 mm diameter and 2 mm thick specimens in an atmosphere of 85 ° C / 85% RH. The moisture absorption rate was measured by the weight change of the PCT (121 ℃, 2 atm, 24hr) that was left for 168 hours.

(5) Crack property after moisture absorption: 208-pin QFP was shape | molded by epoxy resin composition at 175 degreeC, 79 kg / cm <2>, shaping | molding time 2 minutes, and it hardened after 180 hours at 180 degreeC. After leaving this at 72 degreeC / 85% RH for 72 hours, the number of pack cage cracks which performed IR reflow (245 degreeC) for 30 sec. And 2 cycles was measured.

According to the present invention, when the polyfunctional phenol resin is prepared and used for semiconductor encapsulation, it is excellent in heat resistance and low hygroscopicity after curing, and can improve reliability.

Claims (7)

The multi-functional phenol resin represented by the following formula III is produced by condensation reaction of the bisphenol-type phenol resin represented by the following formula I with the aldehyde or resol type phenol resin represented by the following formula II in the presence of an acid catalyst. Method for producing a functional phenolic resin. [Formula 1] In Formula I, R is free of substituents, and is as follows: X ₁ is an alkyl group having 1 to 4 carbon atoms, a benzene group, or a hydrogen atom, X ₂ is the same as or different from each other an alkyl group having 1 to 3 carbon atoms, and i is an integer of 4 or less. [Formula II] In Formula II, X ₁ is an alkyl group having 1 to 4 carbon atoms, a benzene group, or a hydrogen atom, X ₃ is either X ₁ or a hydroxy group and is the same or different from each other, i is an integer of 4 or less. [Formula III] In Formula III, R is free of substituents, and is as follows: K is as follows, X ₁ is an alkyl group having 1 to 4 carbon atoms, a benzene group, or a hydrogen atom, X ₂ is the same as or different from each other an alkyl group having 1 to 3 carbon atoms, X ₃ is either X ₁ or a hydroxy group and is the same or different from each other, i is an integer of 4 or less. The polyfunctional phenol resin according to claim 1, wherein the polyfunctional phenol resin represented by the formula III is an acid catalyst of 0.1 to 0.9 mol of the aldehyde or the resol type phenol resin represented by the formula II with respect to 1 mol of the bisphenol-type phenol resin represented by the formula I. A method for producing a polyfunctional phenol resin, which is obtained by condensation reaction at a reaction temperature of 10 to 250 ° C. for 1 to 15 hours in the presence of. The method for producing a polyfunctional phenolic resin according to claim 1, wherein the aldehyde or resol type phenolic resin represented by the formula (II) is obtained by condensation of aldehydes or phenols or nattols with formaldehyde and an alkaline catalyst. Epoxy resin for semiconductor encapsulation material comprising a mixture of a polyfunctional phenol resin or another phenol resin represented by the formula III according to claim 1 and an epoxy resin, an inorganic filler, a curing accelerator and other additives as essential components. Composition. The epoxy resin composition according to claim 4, wherein the compounding ratio of the epoxy resin and the polyfunctional phenol resin is 0.95 to 1.05 equivalents of the polyfunctional phenol resin relative to 1 equivalent of the epoxy resin. The epoxy resin composition according to claim 4, wherein the compounding amount of the inorganic filler is 100 to 1,000 parts by weight based on 100 parts by weight of the total amount of the epoxy resin and the phenol resin. The epoxy resin composition according to claim 4, wherein the amount of the curing accelerator is 0.01 to 2.0 parts by weight based on 100 parts by weight of the total amount of the epoxy resin and the phenol resin.