WO1994029363A1

WO1994029363A1 - Epoxy resin composition

Info

Publication number: WO1994029363A1
Application number: PCT/JP1994/000918
Authority: WO
Inventors: Masashi Kaji; Takanori Aramaki; Kazuhiko Nakahara; Hisayuki Nagino
Original assignee: Nippon Steel Chemical Co., Ltd.
Priority date: 1993-06-08
Filing date: 1994-06-07
Publication date: 1994-12-22
Also published as: JP2825735B2; KR100300543B1; JPH06345850A; KR960702853A

Abstract

An epoxy resin composition prepared by crystallizing an epoxy resin represented by general formula (1) and compounding the resultant solid resin with an epoxy resin curing agent, wherein G represents glycidyl; and R1 through R8 represent each hydrogen, halogen or C¿1?-C6 hydrocarbyl. The composition gives, when cured, a product excellent in flowability, reduced in moisture absorption, excellent in soldering-heat resistance and applicable to various uses, and particularly suitable for sealing semiconductor elements.

Description

Membrane Epoxy resin composition

The present invention relates to an epoxy resin composition which provides a cured product having excellent fluidity, low hygroscopicity, and excellent soldering heat resistance which can be used in various applications, and which is particularly suitable for encapsulating semiconductor devices and the like. is there.

Skill

Conventionally, a resin composition containing an epoxy resin as a main component has been widely used as a semiconductor encapsulating material, but in recent years, a method of mounting components on a printed circuit board has been changed from a conventional insertion method to a conventional method. The transition to the surface mount method is progressing. In the surface mounting method, the entire package is heated to the solder temperature, and the package crack caused by the rapid volume expansion of the absorbed moisture is a major problem. Furthermore, in recent years, high integration of semiconductor devices, enlargement of device size, and miniaturization of wiring width are rapidly progressing, and the problem of package cracking is becoming more serious. No ,. As methods for preventing cracking, there are methods such as strengthening the resin structure, increasing the strength by increasing the silica filling, and reducing the water absorption.

In order to solve the above problems, epoxy resins having low hygroscopicity and low viscosity are desired. Bisphenol A-type epoxy resin, etc. as low viscosity epoxy resin However, these epoxy resins having a low viscosity are liquid at room temperature, and it is difficult to prepare a resin composition for transfer molding. Furthermore, these epoxy resins are not sufficient in heat resistance, mechanical strength, and moisture resistance.

In addition, Japanese Patent Publication No. 417365/1992 discloses an epoxy resin composition for semiconductor encapsulation using a biphenyl-based epoxy resin as a main component as an improvement in handling workability, heat resistance, toughness and the like. Although it has been proposed, there is a problem in terms of low hygroscopicity. Therefore, an object of the present invention is to provide a cured product having excellent fluidity, low hygroscopicity, and excellent soldering heat resistance, which can be used for various applications. More particularly, the present invention relates to an epoxy resin composition suitable for encapsulating semiconductor elements and the like. Disclosure of the invention

That is, the present invention provides the following general formula (1)

(However, G represents a glycidyl group, R '~ R ⁸ is a hydrogen atom, C b shows the gain down atom or a hydrocarbon group having 1 to 6 carbon atoms) this to crystallize the epoxy resin represented by After being solidified by the above, an epoxy resin curing agent is added to this. And an epoxy resin composition obtained by the method.

The epoxy resin represented by the general formula (1) is represented by the following general formula (2)

(Wherein, R ¹ to R ⁸ represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms) and an excess of epihalohydrin It is produced by reacting This reaction can be performed in the same manner as a normal epoxidation reaction.

For example, a bisphenol F-based compound is dissolved in an excess of hydrin hydrin, and then dissolved in the presence of alkaline metal hydroxide such as sodium hydroxide in the range of 50 to 150. ° C; preferably, the reaction is carried out at a temperature in the range of 60 to 120 ° C for 1 to 10 hours. The amount of the metal hydroxide used in this case is 0.8 to 2 moles, preferably 0.9 to 1.2 moles, per mole of the hydroxyl group of the bisphenol F compound. It is. After completion of the reaction, excess ephalohydrin is distilled off, and the residue is dissolved in a solvent such as toluene or methylisobutylketone, filtered, washed with water to remove inorganic salts, and then removed. An epoxy resin can be obtained by distilling off the solvent. The preferred range of the epoxy equivalent of the epoxy resin at this time is 250 or less, and the epoxy resin obtained by the reaction has a It is preferable that the content of the dimer or higher multimer is small. However, since these epoxy resins are usually liquid even at room temperature, they need to be crystallized for use in the present invention. Examples of the crystallization method include a crystallization method using a solvent, and a crystallization method by adding a seed crystal prepared in advance. In the method using a solvent, examples of the solvent include phenols such as methanol, ethanol, isopropynoleanol, and the like, pentane, hexane, heptane, and the like. Are preferably used.

In the general formula (1), the substituents R ′ to R ⁸ represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Examples of the hydrocarbon group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-amyl group, a phenyl group and the like. The preferred melting point range of the crystalline epoxy resin used is in the range of 40 to 130 ° C, more preferably in the range of 50 to 120 ° C. is there. If it is lower than this, there is a problem such as blocking during storage, and if it is higher than this, the solubility is poor and the mixing property with the curing agent is reduced.

Preferred crystalline epoxy resins from the viewpoints of melting point, viscosity, reactivity, heat resistance of the cured product, and moisture resistance are crystalline 3,3′-dimethyl- having a melting point of 40 to 55 ° C. Diglycidyl ether of 4,4'-dihydroquinone diphenylemethane, crystalline 3,3 ', 5,5'-te with a melting point of 70-85 ° C Dimethyl succinyl ether of tramethyl-4,4'-dihydroxydiphenylenotene, crystalline 2, 2 ', 3, 3' with a melting point of 90-105 ° C , 5,5, -hexamethyl-4,4'-dihydroxydiphenylmethyl Diglycidyl ether of tan, 2,2'-dimethinole with a melting point of 85-100 ° C-5,5, di-tert-butyl, tinole-4,4,- Dihydroxydiphenylmethane diglycidyl ether; and the like. Those having a melting point lower than the above melting range are not preferred because they have many oligomer components of dimers or more and have problems such as an increase in viscosity and a decrease in heat resistance.

When the epoxy resin composition of the present invention is used for protection, insulation, and encapsulation of electric and electronic components, the epoxy resin used in the present invention is preferably of high purity, and the amount of hydrolyzed chlorine is 50%. It is preferably less than 0 ppm.

The curing agent used in the resin composition of the present invention is known as a curing agent for epoxy resins such as polyvalent phenols, acid anhydrides, aromatic and aliphatic amines. You can use what you have. For example, polyphenols include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, and 4,4. '-Biphenol, 2,2, -Biphenol, dihydroquinone, resorcinol, divalent phenols such as naphthalenediol, and the like. Or tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis- (4-hydroxyphenyl) Trivalent or more phenols such as phenol, vinyl alcohol, 0-cresorno-volak, naphtho-no-volak, polyvinyl alcohol, etc. Further, phenols, naphthols or bisphenol A, bisphenol F, bisphenol S, fluorene bis Et Bruno Lumpur, 4, 4 '- Biff et Bruno Lumpur, 2, 2, - Biff et Bruno Nore, Nono Lee mud-board emissions, Les Zorushi down Honolem aldehydes, aceto aldehydes, benz aldehydes, p-hydroxybenzene phenols, and p-xylylene divalent phenols such as dihydric phenols such as naphthalenediol It is a polyhydric phenolic compound synthesized with a condensing agent such as alcohol. The acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hexahydrophthalic anhydride. And methylhexahydric anhydrous phthalic acid, methylhymic anhydride, nadic anhydride, trimellitic anhydride and the like. As the amines, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylprono, and the like. Aromatic amines such as 4,4-,-diaminodiphenylenoresnolesone, m-phenylenediamine, p-xylylenediamine, etc. And aliphatic amines such as dimethylamine, hexamethylenediamine, diethylamine and triethylenetetramine. These hardeners can be used alone or in combination of two or more. For semiconductor encapsulation, it is preferable to use polyvalent phenols.

In addition to the bisphenol F-based epoxy resin used as an essential component of the present invention, the resin composition of the present invention contains a general epoxy resin having two or more epoxy groups in the molecule. Resins may be used in combination. For example, bisphenol A, bisphenol S, fluorene bisphenol, 4,4, -biphenol, 2,2, -biphenol Divalent phenols such as phenol, hydridoquinone and resorcinol, or tris- (4-hydroxyphenyl) methane, 1,1,2, 2-Tetrax-(4-Hydroxyphenyl) ethane, phenol ethanol Trivalent or more phenols such as oak, o-cresol novolak, or nitrogen sulfide bisphenol such as tetrabromobisphenol A There are glycidyl ether compounds derived from such compounds. These epoxy resins can be used singly or in combination of two or more. However, the amount of the epoxy resin represented by the general formula (1) according to the present invention in the total epoxy resin is It is in the range of 50 to 100%.

Further, an inorganic filler can be used in the resin composition of the present invention. As the inorganic filler, for example, spherical or crushed molten silica, silica powder such as crystalline silica, alumina powder, glass powder, etc. are used. The amount is preferably 75% by weight or more from the viewpoint of low moisture absorption and high solder heat resistance.

A conventionally known curing accelerator can be used for the resin composition of the present invention, if necessary. Examples include amides, imidazoles, organic phosphines, Lewis acid and the like. The amount added is usually in the range of 0.2 to 5 parts by weight based on 100 parts by weight of the epoxy resin.

If necessary, the resin composition of the present invention may contain a mold release agent such as carnauba wax, 0 P wax, etc .; Coupling agents such as silane, coloring agents such as carbon black, flame retardants such as antimony trioxide, low stress agents such as silicone oil, and calcium stearate. Lubricants such as shims can be used. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described more specifically with reference to Reference Examples, Examples, and Comparative Examples.

Reference example 1

3,3,5,5'-Tetramethyl-4,4'-dihydroxydiphenylmethanine 120 g to epichloronohydrin 96 Og , And 0.3 g of benzyl triethylammonium chloride was added.The mixture was then treated under reduced pressure (about 150 mmHg, 70 ° C) with 48% 81.3 g of an aqueous tritium solution was added dropwise over 4 hours. During this time, the generated water was removed from the system by azeotropy with the epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was continued for another hour. Thereafter, the salt generated by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 16.5 g of a pale yellow liquid epoxy resin. Diglycidyl of 3,3 ', 5,5'-tetramethyl-4,4'-dihydrid cis dipheninolemethane prepared separately from the obtained liquid epoxy resin After adding 3 g of ether fine powder crystals, the mixture was allowed to stand at 30 ° C. to crystallize the resin. The melting point of the obtained crystals was 78 ° C. The epoxy equivalent of the obtained epoxy resin was 185, and the viscosity at 25 ° C. in m-cresol (solid content: 30% by weight) was 45 cPs. .

Reference example 2

2,2, -dimethyinole-5,5, -di-tert-f, tinole-4,4, -dihydroxydiphenyl methane 120 g, epichlorohydrin The reaction was carried out in the same manner as in Reference Example 1 using 720 g of a 48% aqueous sodium hydroxide solution and 58.8 g of a 48% aqueous sodium hydroxide solution. 148 g of a fat were obtained. The epoxy equivalent was 235 and the melting point was 93 ° C. The viscosity at 25 ° C in m-cresol (solid content: 30% by weight) was 72 cPs.

Reference example 3

2,2 ', 3,3,3,5,5'-Hexamethyl-4,4, -dihydroxydiphenylmethane 130 g, epichlorohydrin 780 g, 48% -water The reaction was carried out in the same manner as in Reference Example 1 using 76.2 g of an aqueous sodium oxide solution to obtain 176 g of a white crystalline epoxy resin. The epoxy equivalent was 208 and the melting point was 101 ° C. The viscosity at 25 ° C in m-talesol (solid content: 30% by weight) was 56 cPs.

Examples 1 and 2

The epoxy resin obtained in Reference Example 1 was used as an epoxy resin component, and a phenol resin was used as a curing agent (PSF-430, manufactured by Gunei Chemical Co., Ltd.). Crushed silica (average particle size 16 m) or spherical silica (average particle size 22 urn), and triphenylphosphine or silane coupling agent as a hardening accelerator. Then, using y-glycidoxypropyltrimethoxysilane and other additives shown in Table 1, the mixture was kneaded in the composition shown in Table 1 to obtain an epoxy resin composition. Using this epoxy resin composition, molding was performed at 175 ° C, post-curing was performed at 175 ° C for 12 hours, and a cured product test piece was obtained, which was then subjected to various physical property measurements. Also, an 84-pin IC was molded using the epoxy resin composition, and after the boss storage, moisture was absorbed for 24 hours, 48 hours, and 72 hours at 85 ° C, 85% scale 11, and 10 in solder bath at 260 ° C After immersion for 2 seconds, the package crack was observed. Table of results

Figure 1 shows.

Example 3

The epoxy resin obtained in Reference Example 2 was used as the epoxy resin component, and was blended, kneaded, molded and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 4

The epoxy resin obtained in Reference Example 3 was used as an epoxy resin component, and was blended, kneaded, molded and evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1

Using an 0-cresol no-bottle type epoxy resin (softening point: 71 ° C) as the epoxy resin component, an epoxy resin composition was obtained in the same manner as in Example 1 and then molded and evaluated. did. Table 1 shows the results.

【table 1 】

Examples 5-6 and Comparative Example 2

Table 2 shows the results obtained using the epoxy resin obtained in Reference Example 1. Powder coatings were prepared by blending and evaluated for melt viscosity, gel time, impregnation, and blocking ability. The results are shown in Table 2.

[Table 2]

* 1: Bisphenol A type solid epoxy resin (Yukaka Epoxy Co., Ltd.)

* 2: Tetrahydrophthalic anhydride

* 3: 2—Methilymidazole

* 4: ICI composite viscometer (150 ° C)

* 5: at 180 ° C

* 6: Powder coating prepared on a hot plate (180 ° C) was evenly sprinkled and the coating film was observed.

◎: extremely good, 〇: good, X: many unevenness

* 7: Percentage of the weight remaining on the 60-mesh comb after leaving the prepared powder coating at 30 ° C for 10 days.

Example 7

After the powder coating composition prepared in Example 5 was left at 30 ° C. for 2 weeks and evaluated in the same manner as in Example 5, the melt viscosity was 0.3 P, and the gel time was Was 33 seconds. In addition, the smoothness of the coating film was good, and no blocking of the powder was observed.

Comparative Example 3

Liquid epoxy resin (30, 000 cPs, at 25 ° C) before crystallization was applied by the method described in Reference Example 1. The resin composition was prepared by melt-mixing the composition of Example 5 with a curing agent and a curing accelerator. The melt viscosity (at 150 ° C.) was 0.3 P, and the gel time was 35 seconds. After the obtained resin composition was left at 30 ° C for 2 weeks and evaluated in the same manner as in Example 5, the melt viscosity (at 150 ° C) was 12 P, and the gelation time was Was 18 seconds. Industrial applicability

Since the epoxy resin used in the present invention is a crystalline solid, it is easy to handle, has an extremely low viscosity in a molten state, maintains excellent molding fluidity, and has a high silica content. Since it can be filled, it can be used for powder coatings, semiconductor encapsulation, etc., and has a resistance to packages obtained by encapsulating semiconductor elements with the composition of the present invention. The crackability is greatly improved.

Claims

The scope of the claims

(1) The following general formula (1)

(However, G represents a glycidyl group, and R ¹ to R ⁸ represent a hydrogen atom, a nitrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

An epoxy resin composition obtained by crystallizing the epoxy resin represented by the formula (1) to obtain a solid, and then adding an epoxy resin curing agent thereto.

(2) The epoxy resin composition according to claim 1, wherein the epoxy resin has a melting point of 40 to 130 ° C.

(3) The epoxy resin composition according to claim 1, wherein the epoxy equivalent of the epoxy resin is 250 or less, and the content of hydrolyzed chlorine is 1500 ppm or less.

(4) The epoxy resin composition according to (1) or (2), wherein the epoxy resin curing agent is a polyhydric phenolic compound.

(5) The epoxy resin composition according to claim 1, wherein an inorganic filler of 75% by weight or more is blended. (6) The following general formula (1)

(Where G represents a glycidyl group and R ¹ to R ⁸ represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms). An epoxy resin cured product characterized by being crystallized into a solid, then mixed with an epoxy resin curing agent and cured.