JPH06145536A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give a cured product having low modulus and high elongation at break. CONSTITUTION:The composition comprises 100 pts.wt. thermosetting resin having a bisphenol skeleton or a biphenyl skeleton, 5-50 pts.wt. silicone oil, and 0.1-15 pts.wt. phenoxy 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 composition having a cured product having a low elastic modulus and a large elongation at break, which is a packaging material such as an IC encapsulant, and various molding materials. It is also applicable to matrix resins of various composite materials.

[0002]

2. Description of the Related Art Epoxy resins and polyimide resins, which are thermosetting resins, have been widely used as molding materials. However, the use conditions for molded articles have become more and more severe in recent years, and as a result, it has become increasingly difficult to satisfy the overall characteristics with only those resins.

One of the problems with these resin cured products is that thermal stress occurs during curing or during the subsequent stage of using the molded product, resulting in cracking of the molded product or dissimilarity. Peeling may occur at the adhesion part with the material. As a technique for improving these resins, a method is known in which an incompatible elastomer component is added to the resin to reduce the elastic modulus of the cured resin and reduce the stress. Furthermore, as a method for compensating for the high temperature characteristics that are a problem in these elastomer systems, a method of blending silicone oil to lower the elastic modulus without increasing the coefficient of thermal expansion, and consequently to reduce the stress against thermal stress, is generally known. Has been.

[0004]

Generally, when silicone oil is added to lower the elastic modulus of these resins, the strength of the resins is lowered accordingly, and one of the molded products is removed when the cured molded product is taken out from the molding die. There may be a problem such that a part is chipped, or the molded body is exposed to high temperature in the subsequent step to generate thermal strain and is likely to be cracked.

Therefore, a thermosetting resin containing a silicone oil is required to have a rupture spread for obtaining a sufficient strength while maintaining a low elastic modulus and a low stress against a thermal stress. However, there have been few such studies in the past, and it is the current situation that improvements are desired. The present invention has been made in view of the above conventional circumstances, and an object of the present invention is to provide a thermosetting resin composition having a low elastic modulus, a large elongation at break, and excellent mechanical properties.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a thermosetting resin having a bisphenol skeleton or a biphenyl skeleton contains a phenoxy resin and a silicone oil as essential components. As a result, it was found that a cured product having a low elastic modulus and a large breaking elongation was provided, and the present invention was accomplished.

The present invention will be described in detail below. First, the thermosetting resin, which is an essential component in the present invention, is not particularly limited as long as it has a bisphenol or biphenyl skeleton in the skeleton of at least one of the components constituting it, Those having a bisphenol skeleton or a biphenyl skeleton represented by the formula (I) are preferable.

[0008]

[Chemical 1] (In the formula, R ^{1 to} R ⁸ are H, an alkenyl group, an alkyl group,
Arbitrarily from halogen atom Specific examples of the thermosetting resin having a bisphenol skeleton are 2,2-bis (4-glycidoxyphenyl) propane, 2,2-bis (2,3,5,6-tetrabromo, 4 and 4
-Glycidoxyphenyl) propane, 2,2-bis (3
-Allyl-4-glycidoxyphenyl) propane and the like.

As the thermosetting resin having a biphenyl skeleton, specifically, 4,4'-diglycidoxybiphenyl, 4,4'-diglycidoxy-3,3'-5,5'-
Tetramethyl biphenyl etc. are mentioned. Two or more of these resins may be used in combination, or these resins may be combined with another thermosetting resin such as bismaleimide.

The components having a bisphenol or biphenyl skeleton in these thermosetting resins have good compatibility with the phenoxy resin and, as a result, are effective in improving the elongation at break of the cured product. The type of silicone oil in the present invention is not particularly limited. Typical examples include polydimethylsiloxane having a methyl group in the main chain and modified polydimethylsiloxane having various functional groups in the main chain or at the ends of the molecule. Further, any molecular weight can be used. It can be arbitrarily selected from these depending on the type of thermosetting resin to be applied. Moreover, it is also possible to use a plurality of types in combination as necessary.

The amount of such silicone oil blended should be 5 to 50 parts by weight with respect to 100 parts by weight of the above-mentioned thermosetting resin. If it is less than 5 parts by weight, the elastic modulus of the cured product is high, and as a result, the stress against heat shrinkage that occurs during cooling when taking out the molded product increases,
As a result, cracks may occur in the molded body after molding, or defects such as peeling at a contact portion with a dissimilar material may occur.
On the other hand, when the amount exceeds 50 parts by weight, the strength of the cured product is remarkably reduced, and a satisfactory product or cured product is not provided.

The phenoxy resin is not particularly limited, but is a high molecular weight polyhydroxypolyether synthesized from bisphenol A and epichlorohydrin, has the following chemical structure, and has a number average molecular weight of 5,000 to 1
Those of 10,000 are preferable.

[0013]

[Chemical 2] Specifically, "Phenototo YP50P" (manufactured by Tohto Kasei Co., Ltd.) "UCAR Phenoxy PKHC, PKHH, PKH
"J" (manufactured by Union Carbide Co.) and the like.

The phenoxy resin has particularly good compatibility with the above-mentioned component having a bisphenol or biphenyl skeleton of the thermosetting resin, and as a result, there is no conventional resin cured product having a low elastic modulus with silicone oil. It realizes a large breaking elongation. The compounding amount of the phenoxy resin is 0.1 to 15 parts by weight based on 100 parts by weight of the above-mentioned thermosetting resin. If the amount is less than 0.1 parts by weight, no effect is exerted on the improvement of elongation at break, while if the amount is more than 15 parts by weight, the fluidity of the entire resin composition is lowered and molding becomes difficult. .

Further, a curing accelerator and an internal release agent can be added to these resin compositions for the purpose of improving moldability and processability. Specifically, as a curing accelerator,
Examples of internal release agents include organic peroxides, phosphines, and imidazoles, and examples of internal release agents include natural waxes, synthetic waxes, organic fatty acids, and metal salts of organic fatty acids. These resin compositions can be applied to applications such as packaging materials such as IC sealing materials, various molding materials and matrix resins for various composite materials. Depending on these applications, silica, alumina powder, mica, etc. can be used. Various inorganic fillers, glass fibers, aramid fibers, reinforcing fibers such as carbon fibers, flame retardants such as antimony, and colorants such as carbon black can be used in addition to the above components.

[0016]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples without departing from the gist thereof. Example 1 2.4 g of a phenoxy resin was mixed and dissolved in 45.5 g of 2,2-bis (3-allyl-4-hydroxyphenyl) propane at 150 ° C., and then bis (4-maleimidophenyl). 60.1 grams of methane was added and mixed. Further, after cooling this to 90 ° C., 10.7 g of polydimethylsiloxane having an average molecular weight of 3000 and having an amino group at the end, butyl levulinate tert
A uniform resin composition was obtained by mixing 2.4 g of -butylperoxyketal and 0.6 g of 1,4-bis (2- (2- (tert-butylperoxy) propyl)) benzene. Pour this into the mold, 7kg / cm
^{2 Under} pressure, autoclave molding was performed under the conditions of a mold temperature of 180 ° C. and a molding time of 1 hour, and then post-cured at 230 ° C. for 6 hours to obtain a cured resin product. The data of the composition of the resin and the flexural modulus, elongation at break, and flexural strength of the obtained cured product are shown in Table 1 and Table 2, respectively.

Example 2 2,2-bis (3-allyl-
2.4 g of a phenoxy resin was mixed and dissolved in 48.1 g of 4-hydroxyphenyl) propane, and 6.0 g of polydimethylsiloxane having an average molecular weight of 2000 and having amino groups at both ends of the molecule was used in polydimethylsiloxane. A composition was obtained by the same procedure as in Example 1 except for the above. The properties of the obtained resin composition and cured product are shown in Table 1 and Table 2, respectively.

Comparative Example 1 A composition was obtained by using the same materials, contents and operations as in Example 1 except that the phenoxy resin was not used. The properties of the obtained resin composition and cured product are shown in Table 1 and Table 2, respectively.

Comparative Example 2 No polydimethylsiloxane was used and 6.0 grams of phenoxy resin,
A composition was obtained with the same materials, content and operation as in Example 1 except that 2.2 g of butyl levulinate tert-butyl peroxyketal was used. The properties of the obtained resin composition and cured product are shown in Table 1 and Table 2, respectively.

Comparative Example 3 The same materials and contents as in Example 1 except that neither phenoxy resin nor polydimethylsiloxane was used and 2.1 g of butyl levulinate tert-butyl peroxyketal was used. Then, the composition was obtained by the operation. The properties of the obtained resin composition and cured product are shown in Table 1 and Table 2, respectively.

[0021]

[Table 1] Allylphenol A = 2,2-bis (3-allyl-4-
Hydroxyphenyl) propane polymaleimide A = bis (4-maleimidophenyl) methane Silicone oil = polydimethylsiloxane having an average molecular weight of 3000 and having amino groups at the ends Silicone oil = polydimethylsiloxane having an average molecular weight of 2000 and having amino groups at both ends of the molecule Phenoxy resin A = "Phenothote YP-50" (manufactured by Tohto Kasei Co., Ltd.) Peroxide A = Butyl levulinate tert-butyl peroxyketal Peroxide B = 1,4-bis (2- (2- (tert- Butyl peroxy) propyl)) benzene

[0022]

[Table 2]

[0023]

EFFECTS OF THE INVENTION The thermosetting resin composition of the present invention has characteristics of mechanical properties such that the cured product has a low elastic modulus and a large breaking elongation, and is used as a packaging material for IC encapsulant and various moldings. It can be suitably used for materials and applications such as matrix resins of various composite materials, and provides a great industrial benefit.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Osamu Suzuki 1000, Kamoshida-cho, Midori-ku, Yokohama, Kanagawa

Claims (1)

[Claims] 1. A silicone oil in an amount of 5 to 50 parts by weight and a phenoxy resin in an amount of 0.1 to 1 with respect to 100 parts by weight of a thermosetting resin having a bisphenol skeleton or a biphenyl skeleton.
A thermosetting resin composition containing 5 parts by weight.