JPH03237125A - Thermosetting resin composition and cured material thereof - Google Patents

Abstract

PURPOSE:To obtain the title composition providing a cured material having high mechanical strength, glass transition point, low water vapor absorption, low linear expansion and high adhesiveness, comprising an epoxy resin, phenol resin, inorganic filler and diglycidyl ether of dihydroxynaphthalene. CONSTITUTION:The objective composition comprising an epoxy resin (preferably one having 50-100 deg.C softening point and 100-400 epoxy equivalent such as bisphenol A type epoxy resin), a phenol resin (preferably one having 60-120 deg.C softening point and 90-150 hydroxyl equivalent such as phenol novolak resin), an inorganic filler (preferably one consisting essentially of spherical particles having 5-20mum average particle diameter such as fused silica) and diglycidyl ether of 1,6-dihydroxynaphthalene.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a cured product having high mechanical strength and glass transition point, low hygroscopicity, low linear expansion, and high adhesiveness.
The present invention relates to a thermosetting resin composition suitable for use in semiconductor packages, etc., and a cured product thereof.

[Prior art and problems to be solved by the invention] Conventionally, thermosetting resin compositions containing an epoxy resin, a phenol resin as a curing agent for the epoxy resin, and an inorganic filler have been used for semiconductor packages. There is.

However, as semiconductor packages have become thinner in recent years, various problems have arisen. For example, when a flat package is mounted on a printed circuit board, the package is immersed in a high-temperature solder bath, but there is a problem in packages made of conventional thermosetting resin compositions that cracks occur in the package due to thermal shock. Furthermore, it has been pointed out that if a flat package absorbs moisture before being mounted on a printed circuit board, a water vapor explosion may occur in the package when it is immersed in a high-temperature solder bath, causing a crank.

As a countermeasure to this problem, improvements are being considered from both the frame and pancage resin, but in addition to the performance of high mechanical strength and high glass transition temperature, the resin has low hygroscopicity and a low coefficient of linear expansion. Performance is required, such as a small value and good adhesion to the frame.

The present invention has been made in view of the above circumstances, and has a mechanical strength,
High glass transition point, low hygroscopicity, low coefficient of linear expansion,
The object of the present invention is to provide a thermosetting resin composition that provides a cured product with high adhesiveness, and a cured product of the composition.

[Means and Effects for Solving the Problems] As a result of intensive studies to achieve the above object, the present inventors have developed a thermosetting resin composition containing an epoxy resin, a phenol resin, and an inorganic filler. It has been found that blending diglycidyl ether of 6-dihydroxynaphthalene is effective.

In other words, epoxy resins that are generally suitable for use in semiconductor puff cages have a high crosslinking density, such as novolac type epoxy resins, and therefore have a high glass transition temperature and excellent heat resistance. There is a problem that the water absorption rate becomes high. However, by blending diglycidyl ether of 1,6 dihydroxynaphthalene into epoxy resins with high glass transition temperatures, such as novolak-type epoxy resins, it is possible to create cured epoxy resins with low moisture absorption while maintaining the glass transition temperature and mechanical strength. It is possible to add a low coefficient of linear expansion and high adhesion, and for this reason, when the above-mentioned thermosetting resin & 11 bottom material containing diglycidyl ether of 1,6-dihydroxynaphthalene is applied to a semiconductor puff cage, it can be used in a soldering bath. The inventors have discovered that cranking caused by thermal shock and steam explosion when immersed in water can be effectively prevented, leading to the present invention.

The present invention will be explained in more detail below.

The thermosetting resin composition according to the present invention is a thermosetting resin composition containing an epoxy resin, a phenol resin, and an inorganic filler, in which diglycidyl ether of 1,6-dihydroxynaphthalene is blended.

The diglycidyl ether of 1,6-dihydroxynaphthalene is an epoxy resin having a highly rigid and hydrophobic naphthalene ring, and is specifically represented by the following structural formula.

This diglycidyl ether of 1,6-dihydroxynaphthalene is a brown liquid that is viscous at room temperature, and a commercially available product includes the trade name HP4032 (manufactured by Dainippon Ink ■).

The blending amount of the diglycidyl ether of 1,6-dihydroxynaphthalene is preferably 1 to 50 parts, particularly 3 to 10 parts, based on 100 parts (by weight, same hereinafter) of the epoxy resin, and the blending amount is 1 part. If the amount is less than 50 parts, the effect of the blend may not be apparent, while if it is blended in excess of 50 parts, the glass transition temperature may be lowered, and diglycidyl ether of 1,6-dihydroxynaphthalene is expensive, so it is not economical. may be disadvantageous. In addition, 1.6
- When the diglycidyl ether of dihydroxynaphthalene is cured alone in combination with a phenolic resin, the cured product has low hygroscopicity and low linear expansion, but on the other hand, the glass transition temperature is low, and therefore 1,6-dihydroxy The purpose of the present invention cannot be achieved only with diglycidyl ether of naphthalene, but it is possible to achieve the purpose of the present invention by using it in combination with other epoxy resins.

The thermosetting resin in which the diglycidyl ether of 1,6-dihydroxynaphthalene is blended contains an epoxy resin, a phenol resin, and an inorganic filler.
These are not particularly limited, and those commonly used in semiconductor puff cages can be suitably used.

For example, any epoxy resin can be used as long as it has at least two epoxy groups in one molecule, and specifically, bisphenol A type epoxy resin,
Novolak type epoxy resins, alicyclic epoxy resins, glycidyl ester type epoxy resins, and especially polyfunctional epoxy resins represented by the following structural formula and epoxy resins having a naphthalene ring are suitable, and these can be used in appropriate combinations. Good too.

tBu: t-butyl group ESX 220 (manufactured by Sumitomo Chemical ■, trade name) R:
H, CH.

EPPN 501 (Nippon Kayaku special product name) (However,
n is an integer of 0 to 50) tBu tBu ... (ii) (However, n is an integer of 0 to 50) These epoxy resins preferably have a softening point of 50-100°C and an epoxy equivalent of 100-400. ,Also,
It is also effective to use brominated epoxy resin for flame retardancy.

Phenol resins act as curing agents for epoxy resins, and include those having two or more phenolic hydroxyl groups, such as phenol novolac resins, talesol novolak resins, and triphenolmethane.

The phenol resin preferably has a softening point of 60 to 120°C and a hydroxyl equivalent of 90 to 150. The amount of this phenol resin used may be any amount as long as the equivalent ratio of epoxy groups/hydroxyl groups in the thermosetting m-acid is in the range of 0.5 to 2, but usually 3 parts per 100 parts of epoxy resin.
A range of 0 to 70 parts is preferred. If the amount is less than 30 parts, sufficient strength may not be obtained, whereas if it is more than 70 parts, the moisture resistance may deteriorate.

Furthermore, the inorganic filler is used to reduce the expansion coefficient of the cured product and reduce the stress applied to the semiconductor element.

Specifically, fused silica and crystalline silica with a crushed or spherical shape are mainly used, but alumina, silicon nitride, and argonium nitride can also be used. Among these, spherical and crushed silica are used. It is preferable to use a mixture or a product mainly composed of spherical products.

The average particle size of these inorganic fillers is preferably from 5 to 20 microns, and the blending amount is preferably from 200 to 1,600 parts, particularly from 300 to 1,200 parts, per 100 parts of the epoxy resin. If the amount is less than 200 parts, the expansion coefficient will increase, which may increase the stress applied to the semiconductor element and cause deterioration of the device characteristics.On the other hand, if the amount is more than 1,600 parts, the viscosity during molding will increase, making it difficult to mold. Sexual behavior may deteriorate. In addition, it is desirable to use these inorganic fillers after surface treatment with a silane coupling agent.

In addition to the above-mentioned components, it is preferable to add a silicone-based flexibility imparting agent and a thermoplastic resin to the thermosetting resin composition of the present invention in order to reduce stress. For example, silicone rubber powder, silicone gel, organic Examples include block polymers of resin and silicone, MBS resin, 5EBS, etc.
It is also effective to treat the surface of the inorganic filler with a two-component silicone rubber or silicone gel before adding it.

The amount of these stress reducing agents used is usually 0.5 to 10% by weight, preferably 1 to 5% by weight of the entire thermosetting resin composition. A blending amount of less than 0.5% by weight may not provide sufficient thermal shock resistance, while a blending amount of more than 10% by weight may reduce mechanical strength.

In addition, the thermosetting resin of the present invention may include curing accelerators such as imidazole or its derivatives, phosphine derivatives, and cycloamidine derivatives, mold release agents such as carnauba wax, higher fatty acids, and waxes, as necessary. Furthermore, a silane cuffing agent, antimony oxide, a phosphorus compound, a bromo-chloride-containing compound, and the like can be added in regular amounts.

When producing the thermosetting resin composition of the present invention, it can be obtained by heating the above-mentioned components in advance to 80 to 100°C and uniformly melting and kneading them using a heating roll, a kneader-1 continuous extruder, etc. . Note that there is no particular restriction on the order of blending the components.

The thus obtained thermosetting resin of the present invention is effective for semiconductor packages such as DIP type, flat back type, PLCC type, SO type, etc. In this case, conventionally employed molding methods such as transfer molding and injection molding can be used. This can be done by employing a casting method or the like. In addition, the molding temperature of the thermosetting resin composition of the present invention is 150 to 180
℃, and post-curing is preferably performed at 150 to 180°C for 2 to 16 hours.

〔Effect of the invention〕

As explained above, the thermosetting resin composition of the present invention is
By using diglycidyl ether of 1,6-dihydroxynaphthalene in addition to epoxy resin, phenolic resin, and inorganic filler, it maintains the glass transition point of epoxy resin while maintaining low hygroscopicity, low coefficient of linear expansion, and high It provides a cured product with adhesive properties and is suitably used for semiconductor packages.

EXAMPLES Hereinafter, the present invention will be specifically explained by showing examples and comparative examples, but the present invention is not limited to the following examples.

In addition, in the following examples, all parts indicate parts by weight.

[Example/Comparative example]

In addition to the components shown in Table 1, 1.5 parts of γ-glycidoxypropyltrimethoxysilane, 1.5 parts of wax E, 1.0 part of carbon blank, and 0.8 parts of triphenylphosphine.
The resulting mixture was uniformly melt-mixed using two heated rolls to form 18 types of thermosetting resin compositions (Examples 1 to 1).
2. Comparative Examples 1 to 6) were manufactured.

The following tests (a) to (e) were conducted on these thermosetting resin compositions.The results are also listed in Table 1.

(a) Using a mold that complies with spiral flow EMMI standards, 175℃, 70℃
The measurement was carried out under the condition of "kg/cm".

(b) (bending) JIS
A bending rod of 10×4×100a+s was molded under the conditions of 175° C., 70 kg/113”, and 2 minutes molding time according to K6911, and was post-cured at 180° C. for 4 hours.

(c) Using a test piece of 4-open diameter x 15 m5, the value was measured when the temperature was raised at a rate of 5°C per minute using a deiradometer.

(d) A disc with a diameter of 30 mm and a thickness of 3 mm was molded at 175°C for 2 minutes, post-cured at 180°C for 4 hours, and then molded at 85°C/
The increase in water absorption after standing for 24 hours at 85% RH was measured.

(E) Searchability A cylindrical molded product with a diameter of 15 wm and a height of 5III is mounted on a 42 alloy plate of 17mm-×17-m (thickness 1 sum).
℃.

After molding for 2 minutes and post-curing at 180° C. for 4 hours, the peel force between the molded product and the 42 alloy plate was measured using a pchevre gauge (n=8).

Note) 1) Orthocresol novolac type epoxy resin (softening point 65°C, epoxy equivalent 200) Product name EOCN 10
20 (65) (manufactured by Nippon Kayaku ■) 2) Triphenol alkane type epoxy resin represented by the above formula (i) (softening point 54°C, epoxy equivalent 166) Trade name EPPN 501 (manufactured by Nippon Kayaku ■) 3) Triphenol alkane type epoxy resin represented by the above formula (ij) (softening point: 86°C, epoxy equivalent: 213) Product name: ESX 220 (manufactured by Sumitomo Chemical ■) 4) Naphthalene skeleton-containing epoxy resin (liquid at room temperature, epoxy equivalent: 149) Product name: HP4032 (manufactured by Dainippon Ink ■) 5) Brominated phenol nopolafuku type epoxy resin (softening point: 85°C,
Epoxy equivalent: 280) Product name: BREN-5 (Nippon Kayaku ■
6) Phenol novolank resin (softening point 100℃, OH
Equivalent weight: 110) Trade name: TD-2093 (manufactured by Dainippon Ink ■) From the results in Table 1, the heat according to the present invention in which diglycidyl ether of 1,6-dihydroxynaphthalene was blended with an epoxy resin, a phenol resin, and an inorganic filler. The curable resin composition (Example) has better mechanical strength such as flexural strength and flexural modulus than a thermosetting resin composition (Comparative Example) that does not contain diglycidyl ether of 1,6-dihydroxynaphthalene. It can be seen that it has a high glass transition point, low coefficient of expansion, low water absorption, and excellent adhesiveness.

Sender: Shin-Etsu Chemical Co., Ltd.

Claims (1)

[Scope of Claims] 1. A thermosetting resin characterized by blending diglycidyl ether of 1,6-dihydroxynaphthalene in a thermosetting resin composition containing an epoxy resin, a phenol resin, and an inorganic filler. Composition. 2. A cured product obtained by thermosetting the thermosetting resin composition according to claim 1.