JPH03106916A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition improved in curability, heat resistance and water absorption resistance by mixing a maleimide resin with a specified allyl compound and a curing catalyst. CONSTITUTION:A compound having at least two functional groups of the formula (wherein R1 is a 1-4C alkyl, alkoxy or alkenyl) is dissolved in a solvent (e.g. toluene); a tert. amine (e.g. pyridine) in an amount slightly excess over the stoichiometric amount is added to the solution; the resulting solution is heated to 30-35 deg.C; and trimethylsilyl chloride is added dropwise to the solution and reacted for about 12hr to obtain an allyl compound (A) derived by substituting 1-4C alkyls, -Si(CH3)3 and -SiH(CH3)2 for 10-50% of H atoms of the phenolic OH groups of the compound of the formula. A maleimide resin (B) is mixed with 0.1-1.3 equivalents, per equivalent of component B, of component A, 0.1-10wt.%, based on component B, curing catalyst (C) (e.g. triphenylphosphine) and at most 400 pts.wt., per 100 pts.wt. total of components A and B, reinforcement, filler, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] This invention relates to a thermosetting resin composition having excellent heat resistance and also excellent heat resistance and water absorption resistance. [Prior art] Various thermosetting resin compositions such as epoxy resin compositions are
It is widely used as a sealing material for semiconductors such as transistors, ICs, and LSIs, for adhesion between parts, and as a paint for surface protection. However, in recent years, with the demand for smaller size, larger capacity, and improved reliability of electrical and electronic equipment, the thermosetting resin composites mentioned above are required to have better heat resistance, water absorption resistance, etc. than before. It is becoming more and more common. [Problems to be Solved by the Invention] On the other hand, conventional epoxy resin compositions have excellent electrical and mechanical properties, but are not necessarily sufficient in heat resistance. In addition, polyimide resin composites, which are prized for their excellent heat resistance, have the disadvantage that water is generated due to imide cyclization of unreacted amic acid, which can be problematic, and it is difficult to mold. has. On the other hand, addition-type bismaleid straw resin is known as a resin with excellent heat resistance and shaping processability, but this resin is extremely brittle and cannot be put to practical use. As an improved resin of this maleimide resin, N,N'-4.4'-
A polyadduct obtained by reacting diphenylmethane bismaleimide and 4,4'-diaminodiphenylmethane has been developed and put into practical use, but this resin has poor curability. It is insufficient to meet the above requirements in terms of heat resistance, water absorption resistance, and electrical properties. The present invention was made in view of the above circumstances, and an object thereof is to provide a thermosetting resin composition that is excellent in both heat resistance and water absorption resistance.

[Means for solving problems]

In order to achieve the above object, the thermosetting resin composition of the present invention is a thermosetting resin assembly characterized by having the following components (A), (B), and (C) as essential components. Bottoms.

(A) Maleimide resin.

(B) An allyl compound containing at least two or more functional groups represented by the following general formula (1), in which the hydrogen atoms of the phenolic OH groups in the following general formula (I) are 10 to 50% an alkyl group having 1 to 4 carbon atoms, Si(CHi)s + Sin(C
H+) Allyl compounds substituted with z.

(C) Curing catalyst.

[Effect]

That is, as a result of a series of studies aimed at improving maleimide resin compositions, the present inventors used the above-mentioned special allyl compound in a conventional maleimide resin as a raw material for a maleimide resin composition, and combined it with a curing catalyst. By doing so, it was discovered that a cured product with excellent curability and both good heat resistance and water absorption resistance could be produced, and the present invention was achieved.

The thermosetting resin composition of the present invention comprises Malaygodo resin (A
It is obtained by using a certain amount of a special allyl compound (component B), and a curing catalyst (component C). The above-mentioned maleid resin used in this invention has the following general formulas (II) and (III). Examples include bismaleid compounds represented by (IV). (Hereafter the margin) (Hereafter the margin) ), , is a compound substituted with -SiH(CHs)*. These bismaleimide compounds may be used alone or in combination. The special allyl compound (component B) used together with the above-mentioned maleic resin (component A) is a compound containing at least two or more functional groups represented by the following general formula (I), and is a compound containing at least two functional groups represented by the following general formula (I). The hydrogen atoms of the phenolic OH group in the general formula (I) are an alkyl group having 1 to 4 carbon atoms in a ratio of 10 to 50%, -Si(Ctls), and the above-mentioned special allyl compound is the above-mentioned general formula CI). A compound containing at least two of the functional groups shown above is produced by substituting the hydrogen atom of a phenolic OH group, for example, as follows. That is, a compound containing at least two or more functional groups represented by general formula (I) is classified as CI1. CN, N, N-
Dimethyl formaldehyde (DMF) hexane. In addition to a solvent such as toluene, a slight excess of tertiary atom ξ from the stoichiometric
Add chlorine (pyridine, triethylamine, dimethylaniline, etc.) and dissolve. Next, trimethylsilyl chloride was added dropwise to this while heating it to 30 to 35°C.
Allow time to react. After the reaction is complete, the precipitate is filtered, and the filtrate is treated with a vacuum evaporator to remove unreacted low-boiling substances. In addition, phenolic OH
When the hydrogen atoms of the group are replaced in the above manner, the ratio needs to be set to 10 to 50%. That is, if the substitution ratio is less than 10%, it is difficult to obtain good moisture resistance, and if it is more than 50%, the compatibility with the maleimide resin, which is the above-mentioned component A, decreases, making it impossible to obtain a good cured product. .

The blending amount of the special allyl compound (component B) is 0.0% in equivalent ratio to the maleic acid resin (At 7.min). 1-1. It is preferable to set the ratio to 3. That is, outside the above range, there is a tendency for the heat resistance and water absorption resistance of the resulting thermosetting resin composite to decrease.

The curing catalyst (C) used together with the above A component and BIfc component includes radical initiators such as organic peroxides and azo compounds, tertiary amines, igodazole compounds, quaternary ammonium salts, etc. Organic phosphine compounds, Lewis acids,
Examples include Lewis acid complexes. These curing catalysts may be used alone or in combination of two or more. The blending amount is 0 for the maleimide resin (component A).
．． It is suitable to set it in the range of 1 to 10% by weight.

In addition, the thermosetting resin composition of this invention includes the above-mentioned A-C.
In addition to certain essential parts, if necessary, powdered reinforcing agents, fillers, coloring agents, mold release agents, flame retardants, etc. can be added as appropriate. Examples of the reinforcing agent and filler include aluminum oxide and magnesium oxide. Aluminum hydroxide, aluminum carbonate. Calcium carbonate, magnesium carbonate, diatomaceous earth, calcium silicate, baked clay, powdered silica,
Carbon plaque, kaolin, powdered mica. Examples include graphite, asbestos, antimony dioxide, glass fiber, rock wool, and carbon fiber. These reinforcing agents. The amount of filler used varies depending on the application, but A
Up to 400 parts can be used for a total of 100 parts by weight (hereinafter abbreviated as "parts") of Part A and Part B. Further, examples of the coloring agent include titanium dioxide, yellow lead carbon black, iron black, molybdenum red, ultramarine blue, navy blue, cadmium yellow, and cadmium red. As the above-mentioned mold release agent, higher aliphatic paraffin is used. Examples of the flame retardant include higher aliphatic esters, natural waxes, synthetic waxes, and the like, and phosphorus compounds are examples of the flame retardant.

Also, epoxysilane, vinylsilane, and borane compounds. Coupling agents such as alkyl titanate compounds may also be added. The thermosetting resin compound of the present invention is produced by a conventionally known method using the various additives described above and the essential component raw materials described above. For example, all the raw materials are heat-melted and kneaded in a kneading machine such as a mixing roll machine to form a semi-cured resin composition, which is then cooled to room temperature, crushed, and tableted as necessary to achieve the intended purpose. A thermosetting resin material is obtained. Alternatively, they may be mixed using a suitable solvent.

The thermosetting resin composition obtained in this way is different from conventional maleimide resin compositions because the special allyl compound (B), which is an essential component, acts effectively as a curing agent for the maleimide resin. It has a higher glass transition temperature and better moisture resistance than other materials. In particular, it shows good electrical properties at high temperatures and at the time of absorption, and can be used as a sealing material for electrical and electronic components that require stricter conditions than conventional ones.

〔Effect of the invention〕

As described above, since the thermosetting resin composition of the present invention contains an allyl compound as an essential component along with a maleimide resin, it exhibits better heat resistance, water absorption resistance, and curability than conventional maleimide resin compositions. Moreover, since it exhibits good electrical properties at high temperatures, it can be used as a sealing material for small, large-capacity type IC packages that require strict conditions, making it possible to provide excellent products with extremely high reliability.

Next, examples will be described together with comparative examples.

First, prior to the Examples, a maleated compound shown in Table 1 below, five types of allyl compounds A to E, and a cresol novolak phenol resin were prepared. (Margin) [Examples 1 to 4, Comparative Examples 1 to 4] Using the maleigodo compound shown in Table 1 above and the allyl compound or Talezol novolak type phenolic resin in the ratio shown in Table 2 below. Melt mixing was carried out at 150°C.

Next, triphenylphosphine. Fused silica and agonosilane coupling agent were dry-blended in the proportions shown in Table 2 below, kneaded with two rolls at 150°C for 5 minutes, cooled, and then crushed to form a powdered Malay ξ-dosing resin composition. I made something. This was transferred into a test piece to prepare a test piece. The curing conditions for the above-mentioned transfer method were 200'C x 5 hours.

(Left below) TM of the example products and comparative example products obtained in this way.
A (Thermal Mechanical Ana
In addition to measuring the glass transition temperature by lysis), the water absorption of these test pieces under the conditions of 121°C These results are summarized in the third section below.
It is shown in the table. (Left below) From the above results, the example product has better heat resistance than the comparative example product. It can be seen that it is excellent in both moisture resistance and mechanical strength.

Claims (1)

[Claims] (1) A thermosetting resin composition comprising the following components (A), (B), and (C) as essential components. (A) Maleimide resin. (B) An allyl compound containing at least two or more functional groups represented by the following general formula (I), in which the hydrogen atoms of the phenolic OH groups in the following general formula (I) are 10 to 50%. Alkyl group having 1 to 4 carbon atoms, -Si(CH_3)_
3, -SiH(CH_3)_2-substituted allyl compound. ▲There are numerical formulas, chemical formulas, tables, etc.▼...(I) In the above formula (I), R_1 is an alkyl group, an alkoxy group, or an alkenyl group having 1 to 4 carbon atoms. (C) Curing catalyst.