JPH09194549A - Thermosetting resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermosetting resin which comprises a polyphenylene ether resin bearing unsaturated groups and a compound bearing benzocyclobutene groups and is useful in sealing electric and electronic parts because it is excellent in low hygroscopicity heat resistance, mechanical strength and electric properties. SOLUTION: (A) One hundred parts by weight of a poly(phenylene ether) bearing unsaturated groups such as allyl groups are formulated to a compound bearing benzocyclobutene groups (or its partial reaction product), preferably in an amount of 10-1,800 pts.wt. to give this thermosetting resin. In a preferred embodiment, an inorganic powder, for example, silica powder is added to this thermosetting resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin which is excellent in low hygroscopicity, heat resistance, mechanical characteristics and electrical characteristics and is suitable for sealing and fixing treatment of electric / electronic parts.

[0002]

BACKGROUND OF THE INVENTION Epoxy-based resins and polyimide-based resins are used exclusively for the sealing and fixing processing of electric and electronic parts such as semiconductor devices because of their convenience in workability and electrical characteristics.・ With the higher performance and higher functionality of electronic components, the conventional epoxy-based resins and polyimide-based resins, such as low moisture absorption characteristics and electrical characteristics, as well as high temperature characteristics of mechanical properties High performance that cannot be dealt with is required.

[0003]

SUMMARY OF THE INVENTION Therefore, the present invention aims to develop a resin which is excellent in low hygroscopicity, heat resistance, mechanical properties, electrical properties and the like and which can achieve a high degree of sealing treatment and fixing treatment for electric and electronic parts. It is an issue.

[0004]

The present invention provides a thermosetting resin containing an unsaturated group-containing polyphenylene ether resin and a benzocyclobutene group-containing compound as components.

[0005]

EFFECTS OF THE INVENTION By using the thermosetting resin having the above constitution, the polyphenylene ether resin reacts with the cyclobutene group through its unsaturated group and intervenes between the benzocyclobutene group-containing compounds. While maintaining high performance such as low hygroscopicity and electrical properties based on benzocyclobutene group-containing compounds, and mechanical properties at high temperatures, the property of being brittle and easily damaged is mitigated, and advanced sealing of electrical and electronic parts, etc. The stopping treatment and the fixing treatment can be achieved, and the reliability can be improved.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The thermosetting resin of the present invention comprises an unsaturated group-containing polyphenylene ether resin and a benzocyclobutene group-containing compound as components. As the polyphenylene ether resin, a component having an unsaturated bond group such as a carbon-carbon double bond or a carbon-carbon triple bond based on an allyl group is introduced into a side chain of a polyphenylene ether chain through a functional group or the like. Something is included. More specifically, Japanese Patent Publication No. 5-8930 and Japanese Patent Publication No.
8931, Japanese Patent Publication No. 5-8932, and Japanese Patent Publication No. 5
The teaching materials and the like disclosed in Japanese Patent Application Laid-Open No. 8933, Japanese Patent Application Laid-Open No. 5-309785, and the like can be given.

As the benzocyclobutene group-containing compound, an appropriate compound such as a monomer type having a benzocyclobutene group in the molecule or a partial reactant type such as an oligomer or a polymer can be used. Examples include those represented by the general formula.

In the above general formula, R ¹ is a direct bond or a polyvalent inorganic group, or a polyvalent organic group, and preferred R ¹ is a group having the following chemical structure.

Particularly preferred R ¹ has the following chemical structure in the group.

In the above general formula, R ² is hydrogen,
An electron-withdrawing or electron-donating substituent, R ³ and R ⁴ are alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group, hexyl group, etc. , A halogen group, a nitro group, and a cyano group.
x, y, z are 0 or 1 and are 0, thus R
Those having no groups of ² , R ³ , and R ⁴ are preferable.

The benzocyclobutene group-containing compound having a carbon-carbon unsaturated bond different from that based on the benzocyclobutene group in the molecule can be polymerized into a high molecular weight compound. In the present invention, oligomers or polymers obtained by such multimerization can also be used as the benzocyclobutene group-containing compound.

The benzocyclobutene group-containing compound preferably used in the present invention is represented by the following formula (A): It is a partial reaction product consisting of the compound represented by and / or its oligomer or polymer. Such a compound is commercially available as Cycloten 3022 (trade name, manufactured by Dow Chemical Co.).

The thermosetting resin of the present invention comprises a solid mixture such as a powder, a solvent, etc. containing one or more of each of the unsaturated group-containing polyphenylene ether resin and the benzocyclobutene group-containing compound. It can be obtained as an appropriate form such as a mixed solution. Suitable solvents include, for example, chloroform, trichloroethylene, aromatic hydrocarbons such as toluene and xylene, methylene chloride, methyl ethyl ketone, and methyl butyl ketone.

Further, the thermosetting resin can be put into practical use by secondary molding into an appropriate form such as a sheet. A sheet-shaped adhesive is particularly preferably used as a sheet-type adhesive that has excellent handleability, can easily be provided with an adhesive layer having excellent uniformity in thickness, shape, etc., and can be securely fixed with stable strength. sell. The sheet-shaped molded article can be formed by an appropriate method such as an extrusion molding method of the above-described solid mixture, a method of spreading the heated melt or a mixed solution thereof on a separator or the like, and cooling or drying. Sheet thickness is 1
The thickness is generally 200 μm, but is not limited to this and can be appropriately determined according to the purpose of use and the like.

In the above, the ratio of the unsaturated group-containing polyphenylene ether resin and the benzocyclobutene group-containing compound used depends on workability at the time of sealing or fixing, mechanical properties at uncured or after curing, and the like. From the point, 5 to 2000 parts by weight of the benzocyclobutene group-containing compound, especially 7-1 to 100 parts by weight of the polyphenylene ether resin.
900 parts by weight, particularly 10 to 1800 parts by weight are preferred.
If the proportion of the benzocyclobutene group-containing compound used is too small, the melt viscosity may be high and the wettability with the adhesive surface may be poor, and if it is too large, the compound may be brittle and easily cracked, resulting in poor mechanical properties.

When forming the thermosetting resin of the present invention,
For the purpose of adjusting properties such as hygroscopicity, heat resistance, mechanical properties, electrical properties, etc., or adjusting properties such as adhesion, conductivity, and heat transfer properties, etc. For the purpose, appropriate compounding ingredients can be added if necessary.

Examples of the compounding components include styrene / butadiene rubber, butadiene rubber, 1,2-polybutadiene rubber, ethylene / propylene rubber, natural rubber and isoprene rubber, nitrile rubber and hydrogenated nitrile rubber, and styrene / isoprene block copolymers. Polymers, styrene / butadiene block copolymers, styrene / ethylene / butylene block copolymers, butyl rubber, acrylic rubber and silicone rubber, rubber-based polymers such as fluororubber and urethane rubber, polyphenylene ether and poly containing no unsaturated groups Ether imide, polycarbonate or polyether sulfone, polyarylate or polysulfone, polyamide imide or polystyrene, polyester or polyimide, polyamide or diallyl phthalate resin, epoxy resin or phenoxy resin, tri Such as Lil (iso) cyanurate resins such polymers, or various modified products of such polymers.

Further, for example, aluminum or copper, silver or gold,
Nickel, chromium, tin, lead, zinc, palladium, metals or alloys such as solder, alumina and silica, ceramics such as magnesia and silicon nitride, various inorganic powders such as carbon and various pigments, silane-based and titanium-based Such as coupling agents, radical type initiators and curing catalysts,
Surface modifiers, antioxidants, dyes and the like can be added as required.

The mixing ratio of the above-mentioned polymer component can be appropriately determined according to the purpose of use, but generally, the physical properties based on the unsaturated group-containing polyphenylene ether resin and the benzocyclobutene group-containing compound are maintained. Therefore, the total amount of the unsaturated group-containing polyphenylene ether resin and the benzocyclobutene group-containing compound is 200 parts by weight or less, preferably 100 parts by weight or less, and particularly 80 parts by weight or less. In addition, the mixing ratio of the inorganic powder is 2000 parts by weight or less, particularly 1500 parts by weight or less, and particularly 1000 parts by weight or less, per 100 parts by weight in total in view of sealing property and adhesiveness.

The thermosetting resin of the present invention exhibits good handleability and workability comparable to those of the conventional poxy resin and polyimide resin, and is heat-cured by heat treatment to exhibit a strong adhesive force and the like. It becomes a cured product with low hygroscopicity. Further, it usually forms a cured product having excellent electrical characteristics such as a glass transition temperature of more than 200 ° C. and a dielectric constant of 3 or less (1 MHz). The curing treatment by heating can be performed by an appropriate method such as a heater, ultrasonic waves, or ultraviolet rays.

The thermosetting resin of the present invention can be preferably used for various molding materials such as sealing treatment of semiconductor devices and adhesion treatment of various materials. In particular, it has low hygroscopicity, heat resistance, mechanical properties, electrical properties, etc., and is highly reliable. Therefore, it is necessary to seal and fix electric and electronic parts such as semiconductor devices and lead frames that require sticking treatment. It is preferably used for stopping treatment and fixing treatment. By the way, when soldering a package of a semiconductor device die-bonded to a lead frame, it is superior in low moisture absorption and it is particularly important that it does not contain moisture, rather than preventing package cracking due to vaporization expansion of moisture. Becomes

[0022]

【Example】

Example 1 A benzocyclobutene group-containing compound of the above formula (A) and its partial reaction product / allylated polyphenylene ether-based resin (allylation rate 14%) were mixed with chloroform at a weight ratio of 80/20 to form a mixed solution, Apply it to the release-treated surface of polyester film, heat dry to a thickness of 20μ
A thermosetting resin sheet of m was obtained.

Example 2 Benzocyclobutene group-containing compound and its partial reaction product /
A sheet was obtained in the same manner as in Example 1 except that the allylated polyphenylene ether resin was used in a weight ratio of 30/70.

Example 3 Benzocyclobutene group-containing compound and its partial reaction product /
A sheet was obtained in the same manner as in Example 1 except that a solution obtained by mixing the allylated polyphenylene ether resin / styrene / butadiene block copolymer at a weight ratio of 60/20/20 was used.

Example 4 Benzocyclobutene group-containing compound and its partial reaction product /
A sheet was obtained in the same manner as in Example 1 except that a solution in which an allylated polyphenylene ether resin / butadiene rubber / silane coupling agent was mixed at a weight ratio of 60/20/20/1 was used.

Comparative Example A sheet was obtained in the same manner as in Example 1 except that a mixed solution of a bisphenol A type epoxy resin / imidazole type curing agent in a weight ratio of 96/4 via methyl ethyl ketone was used.

Evaluation Test 1 The following characteristics of the thermosetting resin sheets obtained in Examples and Comparative Examples were examined. Shear adhesive strength A 3 mm square silicon chip is temporarily fixed to a 42 alloy plate through a thermosetting resin sheet under predetermined conditions, and then cured under the predetermined conditions (main fixing), and its shear adhesive strength at 250 ° C is measured. It was measured with a push-pull gauge. The temporary fixing is 120 ° C. in Example 1 and Comparative Example, and 22 in Example 2.
The heating conditions are 0 ° C. and 170 ° C. in Examples 3 and 4, and the main fixation (curing) is 250 ° C. for 60 minutes in Examples 1 to 4.
In the comparative example, the heating conditions were 150 ° C. and 60 minutes. In the above, neither lack of adhesive nor squeeze-out occurred, and fixing treatment could be performed with a uniform thickness.

Glass transition temperature T of the cured product obtained by the heat treatment according to the present fixing treatment
The glass transition temperature was examined by MA under the condition of a temperature rising rate of 5 ° C./min.

Moisture absorption rate The cured product obtained by the heat treatment according to this fixing treatment is
After leaving it under the condition of 85 RH% for 168 hours, its moisture absorption amount was measured with a trace moisture meter, and the moisture absorption rate was calculated from it.

Dielectric Constant The dielectric constant at 1 MHz of the cured product obtained by the heat treatment according to the main fixing treatment was examined.

The results are shown in the following table. *: Not specified

Evaluation Test 2 A 12 mm square silicon chip was temporarily attached to a 42 alloy lead frame and hardened in the same manner as in the case of the shear adhesive strength described above, and then the thermosetting property was obtained according to Examples 1 to 4. The semiconductor device thus obtained was packaged with a mixed solution of resins, cured according to the above-mentioned main fixing treatment, and sealed, and the obtained semiconductor device was heated at 85 ° C.
It was left to stand under RH% conditions for 480 hours to absorb moisture, and then subjected to a VPS test at 215 ° C. for 30 seconds to check for the presence of external cracks with a scanning ultrasonic flaw detector. In the case of, it was not recognized. The external crack means a crack reaching the outside of the package.

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Claims (4)

[Claims] 1. A thermosetting resin comprising an unsaturated group-containing polyphenylene ether resin and a benzocyclobutene group-containing compound as components. 2. The benzocyclobutene group-containing compound according to claim 1, wherein the compound having the formula: A thermosetting resin containing at least one or both of the compound represented by or a partial reaction product thereof. 3. A thermosetting resin according to claim 1, which contains an inorganic powder and is used for sealing or fixing treatment of electric / electronic parts. 4. The thermosetting resin as claimed in claim 1, which is formed into a sheet.