JP5473585B2 - Epoxy resin composition - Google Patents

Description

  The present invention relates to an epoxy resin composition. The present invention particularly relates to an epoxy resin composition in which the glass transition temperature of a cured resin obtained by curing the epoxy resin composition is significantly higher than the curing temperature of the epoxy resin composition.

  Epoxy resin compositions are cured with various curing agents, resulting in a cured resin that is generally excellent in mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, It is used in a wide range of fields such as molding materials, casting materials and electronic materials. As an epoxy resin used industrially, a bisphenol A type epoxy resin obtained by reacting bisphenol A with epichlorohydrin is known. Since heat resistance is required in applications such as semiconductor encapsulants, cresol novolac epoxy resins are widely used. On the other hand, as a matrix resin of a composite material used for industrial applications such as glass substrate conveyance, heat resistance in a temperature range of about 250 ° C. is required, and in such a region, BMI resin, BMI resin and epoxy resin are generally used. Mixtures are used, but they are inferior to epoxy resins in terms of mechanical properties. Epoxy resins are also advantageous in terms of cost and moldability. As an epoxy resin that gives a cured resin having high heat resistance, for example, an epoxy resin composition composed of a polyfunctional epoxy resin and a diaminodiphenylsulfone curing agent described in Patent Documents 1 to 4 is known. However, although the epoxy resin composition described in these patent documents has high heat resistance, the heat resistance in the high temperature region as described above is insufficient, and the epoxy resin composition having further heat resistance. Is required.

JP-A-3-227316 JP 54-77699 A JP 58-1718 A JP 2009-68000 A Special table 2003-513110 gazette

  It is an object of the present invention to provide an epoxy resin composition that provides a cured resin excellent in heat resistance because the glass transition temperature of the cured resin obtained by curing the epoxy resin composition is significantly higher than the curing temperature of the epoxy resin composition. And

  As a result of intensive studies to solve the above-described problems, the present inventor has completed the present invention. That is, the present invention is a total of 95 to 75 parts by mass of the epoxy resin (A) represented by the following formula (1) and 5 to 25 parts by mass of N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (B). An epoxy resin composition comprising 100 parts by mass and 4,4′-diaminodiphenylsulfone (C) is provided.

（上式中、ｎは０または正の整数を表す）

(In the above formula, n represents 0 or a positive integer)

  In the epoxy resin composition of the present invention, the glass transition temperature of the cured resin obtained by curing the epoxy resin composition is remarkably higher than the curing temperature of the epoxy resin composition. Useful for.

It is a graph used when calculating | requiring G'-Tg of this cured resin from the intersection of the tangent of the graph in the glass state of the cured resin which hardened | cured the epoxy resin composition of this invention, and the tangent in a transition area | region.

  The epoxy resin composition of the present invention comprises 95 to 75 parts by mass of the epoxy resin (A) represented by the formula (1) and 5 to 25 parts of N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (B). And 100 parts by mass of 4,4′-diaminodiphenylsulfone (C). In the formula (1), the average value of n is preferably 0 to 3, and particularly preferably 0 to 2. When the average value of n exceeds 3, the viscosity increases, so that preparation may be difficult.

  The epoxy resin (A) in the present invention may be referred to as a triphenylmethane type epoxy resin. Examples thereof include Tactix 742 (manufactured by Huntsman Advanced Materials), jER1032H60 (manufactured by Japan Epoxy Resin), EPPN-501, EPPN-502 (made by Nippon Kayaku Co., Ltd.), etc. are mentioned. Tactix 742 is preferable.

  Examples of N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (B) in the present invention include jER604 (manufactured by Japan Epoxy Resin Co., Ltd.).

  Examples of 4,4'-diaminodiphenyl sulfone (C) in the present invention include Seika Cure S (manufactured by Wakayama Seika Co., Ltd.). The amount of 4,4'-diaminodiphenylsulfone (C) is preferably such that the ratio of amine equivalent to epoxy equivalent of the epoxy resin composition of the present invention is 0.7 to 1.4 equivalent. When the amount is less than 0.7 equivalent, the flexural modulus of the cured resin obtained by curing the epoxy resin composition is increased, and the glass transition temperature and G ′ retention (described later in Examples) are decreased. If the flexural modulus is excessively large, it is considered that the heat crack resistance is adversely affected. On the other hand, when the ratio of amine equivalent to epoxy equivalent exceeds 1.4 equivalent, the glass transition temperature and G ′ retention ratio are lowered.

  The production method of the epoxy resin composition of the present invention is not particularly limited, and can be produced by a known technique such as a method using a mixing roll or a kneader.

  From the epoxy resin composition of the present invention, a cured resin obtained by curing the epoxy resin composition has a glass transition temperature significantly higher than the curing temperature of the epoxy resin composition, and a cured resin excellent in heat resistance can be obtained. Usually, in order to obtain G′-Tg of 300 ° C. or higher, curing at a temperature close to 300 ° C. is necessary. However, in the present invention, G′-Tg of 300 ° C. or higher is required even at 200 ° C. Can be obtained. By suppressing the curing temperature, the limitation on the auxiliary material is reduced, the manufacturing cost can be reduced by suppressing the use energy, and the adverse effect due to the heat applied to other members can be reduced.

  Hereinafter, the specific structure of the epoxy resin composition of the present invention will be described based on examples while comparing with comparative examples.

Examples 1-2 and Comparative Examples 1-11
Preparation of epoxy resin composition The epoxy resin composition was prepared by the following method. In addition, each component used for the epoxy resin composition of an Example and a comparative example is as showing with the following abbreviation.

Epoxy resin (A)
Tactix 742: epoxy resin corresponding to formula (1) Tris (hydroxyphenyl) methane triglycidyl ether, epoxy equivalent: 160 g / eq. , Manufactured by Huntsman Advanced Materials Co., Ltd.

Epoxy resin (B)
jER604: N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane type epoxy resin, epoxy equivalent: 120 g / eq. , Made by Japan Epoxy Resin Co., Ltd.

4,4'-diaminodiphenyl sulfone (C)
4,4′-DDS: 4,4′-diaminodiphenylsulfone, Seika Cure S (ground product) manufactured by Wakayama Seika Kogyo Co., Ltd., amine active hydrogen equivalent: 62 g / eq.

Other epoxy resins (D)
jER807: Liquid bisphenol F type epoxy resin, epoxy equivalent: 168 g / eq. , Made by Japan Epoxy Resin Co., Ltd.

Other curing agents (E)
3,3′-DDS: 3,3′-diaminodiphenylsulfone, DAS manufactured by Nippon Synthetic Processing Co., Ltd.
2E4MZ-CN: (2-cyanoethyl) -2-ethyl-4-methylimidazole, Cure Sole 2E4MZ-CN manufactured by Shikoku Kasei Co., Ltd.

  Each component was mix | blended in the glass flask by the compounding ratio shown to Tables 1-3, and it was made to disperse | distribute uniformly at 60 degreeC, and the epoxy resin composition was obtained.

Measurement of bending properties of cured resin The epoxy resin composition obtained above was heated to 60 ° C. to defoam, then cast on a glass plate that had been subjected to a release treatment at a thickness of 2 mm, and the same treatment. Was sandwiched between glass plates coated with, and cooled to room temperature. The temperature was raised from room temperature at a rate of temperature increase of 1.7 ° C./min, first cured at 120 ° C., taken out from the glass plate, and then on another glass plate at a rate of temperature increase of 1.7 ° C./min. The temperature was raised at 2 ° C. and secondary curing was carried out at 200 ° C. to obtain a 2 mm thick molded plate. The obtained molded plate was cut into a size of W8 mm × L60 mm with a wet diamond cutter to prepare a test piece. Using the universal tester Instron 5565 manufactured by Instron and analysis software Bluehill, the obtained test piece was measured under the measurement conditions of indenter R = 3.2 mm, L / D = 16 mm, crosshead speed 2 mm / min, and test temperature 23 ° C. A three-point bending test was performed, and bending strength, flexural modulus, and elongation at break were calculated. The results are shown in Tables 1 and 2.

Measurement of high-temperature bending property of cured resin A three-point bending test was performed in the same manner as described above except that the test temperature was 250 ° C., and the bending strength and the bending elastic modulus were calculated. The results are shown in Table 3.

Measurement of Glass Transition Temperature (Tg) of Cured Resin A test piece was prepared in the same manner as above except that the molded plate was cut with a wet diamond cutter to a size of W12.7 mm × L55 mm. A DMA ARES-RDA manufactured by TA Instrument was used, the heating rate was 5 ° C./min, Freq. Tg was measured under the conditions of 1 Hz and a strain of 0.05%. Tg was obtained as G′-Tg (see FIG. 1) and a temperature indicating the maximum value of tan δ. Further, the G ′ retention rate was obtained from the following formula. The results are shown in Tables 1 and 2.
G ′ retention rate (%) = G ′ _{250 °} C./G ′ _{30 ° C.} × 100
G ′ _{250 ° C .} : G ′ at _{250 ° C.}
G ′ _{30 ° C .} : G ′ at _{30 ° C.}

Examples 1 and 2
The resin composition of Table 1 was subjected to primary curing (120 ° C. × 8 hours) and then secondary curing (200 ° C. × 2 hours) to obtain a cured resin having both high mechanical strength and high heat resistance ( Table 1). In DMA, a high glass transition temperature and a high G ′ retention were observed (Table 1). Moreover, in the measurement of the bending physical property of the cured resin at 250 ° C., a high bending elastic modulus retention was shown (Table 3).

Comparative Example 1
The resin composition obtained by replacing 4,4′-DDS in Example 2 with 3,3′-DDS was subjected to primary curing (120 ° C. × 8 hours) and then secondary curing (200 ° C. × 2 hours). The cured resin had a large increase in flexural modulus and a large decrease in glass transition temperature and G ′ retention (Table 2). An increase in the flexural modulus is undesirable because it leads to an increase in internal stress and a decrease in thermal crack resistance. Further, in the measurement of the bending physical properties of the cured resin at 250 ° C., the bending elastic modulus retention rate was greatly reduced (Table 3).

Comparative Example 2
The resin composition in which 4,4′-DDS is replaced with 2E4MZ-CN, which is the composition presented in Patent Document 5, is subjected to primary curing (120 ° C. × 8 hours), and then secondary curing (200 ° C. × 2 hours). The cured resin obtained by the above-mentioned treatment significantly decreased the bending properties and also greatly decreased the glass transition temperature and the G ′ retention rate (Table 2). Moreover, in the measurement of the bending physical property of the cured resin at 250 ° C., the bending elastic modulus retention rate decreased (Table 3).

Comparative Example 3
A resin composition composed of 100 parts by mass of the epoxy resin (A) represented by the formula (1) and 4,4′-diaminodiphenylsulfone (C) is subjected to primary curing (120 ° C. × 8 hours), followed by secondary curing (200 The cured resin obtained by heating at 2 ° C. for 2 hours had a low degree of curing under the curing conditions, and the G ′ retention was greatly reduced (Table 2).

Comparative Example 4
100 parts by mass in total of 70 parts by mass of the epoxy resin (A) represented by the formula (1) and 30 parts by mass of N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (B) and 4,4′-diaminodiphenylsulfone The cured resin obtained by primary curing (120 ° C. × 8 hours) and then secondary curing (200 ° C. × 2 hours) of the resin composition comprising (C) has a reduced glass transition temperature (Table 2). . Further, in the measurement of physical properties of the cured resin at 250 ° C., the G ′ retention rate at 250 ° C. was good, but the bending elastic modulus retention rate at 250 ° C. decreased (Table 3).

Comparative Example 5 to Comparative Example 8
10 to 60 parts by mass of the epoxy resin (A) represented by the formula (1) and 90 to 40 parts by mass of N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (B) and 4,4 ′ A cured resin obtained by first curing (120 ° C. × 8 hours) and then second-curing (200 ° C. × 2 hours) a resin composition comprising diaminodiphenyl sulfone (C) is N, N, N ′ , N′-tetraglycidyldiaminodiphenylmethane (B), both the glass transition temperature and the G ′ retention decreased as the ratio increased (Table 2).

Comparative Example 9
A resin composition composed of 100 parts by mass of N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (B) and 4,4′-diaminodiphenylsulfone (C) is subjected to primary curing (120 ° C. × 8 hours), The cured resin obtained by secondary curing (200 ° C. × 2 hours) had an increased flexural modulus and decreased glass transition temperature and G ′ retention (Table 2). An increase in flexural modulus is undesirable because it leads to increased internal stress and reduced thermal crack resistance. Moreover, in the measurement of the physical properties of the cured resin at 250 ° C., the flexural modulus retention was greatly reduced (Table 3).

Comparative Example 10
A resin composition in which N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane type epoxy resin (B) is replaced with liquid bisphenol F type epoxy resin (jER807) is subjected to primary curing (120 ° C. × 8 hours). The cured resin obtained by the subsequent curing (200 ° C. × 2 hours) significantly decreased both the glass transition temperature and the G ′ retention rate as compared with Example 2 (Table 2). Moreover, in the measurement of the physical properties of the cured resin at 250 ° C., the bending elastic modulus retention rate was reduced (Table 3).

Comparative Example 11
A cured resin obtained by subjecting a resin composition similar to that of Example 1 described in Patent Document 1 to primary curing (120 ° C. × 8 hours) and then secondary curing (200 ° C. × 2 hours) is glass Both the transition temperature and G ′ retention were greatly reduced (Table 2). Moreover, in the measurement of the physical properties of the cured resin at 250 ° C., the flexural modulus retention was greatly reduced (Table 3).

  INDUSTRIAL APPLICATION Since this invention can provide the epoxy resin composition which gives the cured resin which has high heat resistance, it is industrially useful.

Claims (3)

A total of 100 parts by mass of 95 to 75 parts by mass of epoxy resin (A) represented by the following formula (1) and 5 to 25 parts by mass of N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (B); , 4'-diaminodiphenyl sulfone (C) epoxy resin composition.

(In the above formula, n represents 0 or a positive integer). The content of the epoxy resin (A) represented by the formula (1) is 90 to 80 parts by mass and the content of the N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (B) is 10 to 20 masses. The epoxy resin composition according to claim 1, which is a part. The content of the 4,4'-diaminodiphenyl sulfone (C) is an amount that is 0.7 to 1.4 equivalent in terms of an amine equivalent to an epoxy equivalent of the epoxy resin composition. The epoxy resin composition described in 1.

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