JP3237200B2 - Amorphous bismaleimide resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an amorphous bismaleimide resin having excellent workability, which is useful as a sealing material, a laminate material, an electrical insulating material, a molding material, an adhesive and the like having excellent heat resistance. .

[0002]

2. Description of the Related Art Polymaleimide resins are used as resins for improving the heat resistance of thermosetting resins such as epoxy resins and vinyl compounds because of their excellent heat resistance. However, since polymaleimide resins generally have high crystallinity, their solubility in reactive liquid resin compounds such as epoxy compounds and vinyl compounds and general organic solvents is extremely poor. Is likely to occur. In addition, due to the high crystallinity, the melting point is too high, and the melting and heating operation in the solvent requires a high temperature, causing gelation and volatilization of the solvent.

[0003]

An object of the present invention is to provide an amorphous bismaleimide resin which has solved the above-mentioned drawbacks of the conventional polymaleimide resin and has a low melting point and excellent solubility in a solvent. It is.

[0004]

Means for Solving the Problems The present invention relates to a bismaleimide resin represented by the following general formula [I]:
An amorphous material having a heat of fusion peak in differential scanning calorimetry at 0.5 ° C. or 85 ± 0.5 ° C., and having a ratio of the heat of fusion peak area at 125 ° C. or higher to the total heat of fusion peak area of 50% or less. Bismaleimide resin is provided.

Embedded image [ Wherein , Y represents -CH ₂ - or -C (CH ₃ ) _2-
X represents a —O— or —S— group, and R ^{1 to} R ⁶ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[0005] Specific examples of the bismaleimide resin represented by the general formula [I] used in the present invention include an ordinary crystalline bismaleimide resin having a heat of fusion peak at 125 ° C or higher, for example, 1,1'- Bis [4- (4-maleimidophenoxy) phenyl] methane, 2,2'-bis [4-
(4-maleimidophenoxy) phenyl] propane,
1,1'-bis- [4- (4-maleimidophenoxy)
Phenyl] methane, 2,2'-bis [4- (3-methyl-4-maleimidophenoxy) phenyl] propane,
2'-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] propane, bis [4- (4-maleimidophenoxy) phenyl] -3,5-dimethyl-biphenylene, bis [4- (4-maleimide) Phenoxythioether) phenyl] propane and the like.

[0006] amorphous bismaleimide resin of the present invention, a method of uniformly thermally melt-kneading the above conventional crystalline bismaleimide resins, for example, a biaxial roll kneader, co-kneader kneader, extruder, etc. With a commonly used melt kneader, the melting point of the crystalline bismaleimide resin is not less than 2
It is obtained by a method of melting and kneading in a temperature range up to 50 ° C., and then rapidly cooling and solidifying. If the kneading temperature is 250 ° C. or higher, a crosslinking reaction of the bismaleimide resin occurs, which is not preferable.
Further, after the melt-kneading , preferably at least 10 ° C./min.
It is necessary to cool and solidify at a cooling rate . Slow cooling rate
The Most not amorphous bismaleimide resin of the present invention can be obtained, because it is easy to occur recrystallization of bismaleimide resin is not preferable.

The amorphous bismaleimide resin of the present invention needs to contain the amorphous bismaleimide resin in an amount of 50% by weight or more, and has a heat of fusion peak of 75 ± 0.5 ° C. or 85 ° C. in differential scanning calorimetry. At ± 0.5 ° C, and
The ratio of the peak heat of fusion at 125 ° C. or higher to the total peak heat of fusion is 50% or less. More preferred
It is intended to include 60 wt% or more of amorphous bismaleimide resin. When the proportion of the amorphous resin is 50% or less, recrystallization of the resin composition easily occurs, the stability is insufficient, and the solubility in the solvent is not sufficiently obtained.

The differential scanning calorimetry was carried out by using a differential scanning calorimeter under a nitrogen atmosphere having a flow rate of 10 to 50 ml / min. A sample amount of 5 to 20 mg was collected in an aluminum pan, and the temperature was raised at a rate of 10 ° C./min. At a measurement temperature of 10 to 250 ° C. As the peak area, a value (mj / mg) obtained by dividing the endothermic energy (millijoule) of each melting peak in the chart obtained from the above differential scanning calorimetry result by the amount of sample collected (mg) was used.

[0009]

The present invention will be described more specifically with reference to the following examples. In addition, the part in an example is a weight part, and% is a weight basis. Various physical properties obtained in the examples were measured by the following test methods. (1) Crystal structure Measured by X-ray diffractometer (JEOL JDX-3500) (2) Heat of fusion peak Differential scanning calorimeter (DSC220 manufactured by Seiko Instruments Inc.)
With a nitrogen flow rate of 10 ml / min and a sample collection amount of 1
0 mg, measured temperature 10-25 at a heating rate of 10 ° C./min.
The measurement was performed in the range of 0 ° C., and the peak heat of fusion and the peak area were determined. (3) Melting point Measured with a melting point measuring instrument (MP-20 manufactured by Yamato Scientific Co., Ltd.)

(4) Solubility Epoxy resin and vinyl compound were collected in 30 parts of maleimide resin in an eggplant-shaped flask, stirred using a stirrer, heated in a water bath at 80 ° C. for 2 hours, and then cooled to room temperature. After cooling, the solubility was visually determined. −-Dissolution rate is fast and it dissolves well. ×-Does not dissolve. (5) Storage stability The sample used in the solubility test was collected in a 50-ml sample bottle, allowed to stand at room temperature for one month, and visually checked for the presence of crystals. ○ − No precipitation of crystals × − Precipitation of crystals

Example 1 Highly crystalline 2,2'-bis [4- (4-
1 kg of maleimidophenoxy) phenyl] propane is melt-kneaded for 5 minutes by a twin-screw roll machine at a roll temperature of 170 ° C., and then cooled and solidified at a cooling rate of 50 ° C./min.
0% bismaleimide resin was obtained.

Example 2 In Example 1, the roll temperature of the twin-roll mill was set to 160
The procedure was the same as in Example 1 except that the melt kneading was changed to 20 ° C. and the cooling rate was changed to 20 ° C./min to obtain an amorphous bismaleimide resin composition.

Example 3 Example 1 was repeated except that 1 kg of the highly crystalline 2,2'-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] propane was used as the bismaleimide resin. In the same manner as described above, the desired amorphous bismaleimide resin was obtained.

The results obtained by measuring the characteristics of the resin obtained above and the highly crystalline 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane (comparative example) used in Example 1 are shown in Table 1. It is shown in FIG.

[0015]

[Table 1]

(Note) * Ac: Acrylic resin, A-BAP-4 (manufactured by Shin-Nakamura Chemical) * Ex: Epoxy resin, E-828 (manufactured by Yuka Shell Epoxy)

[0017]

[Brief description of the drawings]

FIG. 1 shows the highly crystalline 2,2′-bis [4
It is a figure which shows the X-ray-diffraction measurement result of-(4-maleimidophenoxy) phenyl] propane.

FIG. 2 is a view showing a measurement result of a heat of fusion peak of a highly crystalline resin used in Example 1 by a differential scanning calorimeter.

FIG. 3 is a view showing the results of X-ray diffraction measurement of the resin obtained in Example 1.

FIG. 4 is a view showing a measurement result of a peak of heat of fusion of a resin obtained in Example 1 by a differential scanning calorimeter.

FIG. 5 is a view showing a measurement result of a heat of fusion peak of a resin obtained in Example 2 by a differential scanning calorimeter.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 207/333 C08F 22 / 40,122 / 40,222 / 40 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A bismaleimide resin represented by the following general formula [I], which is 75 ± 0.5 ° C. or 85 ± 0.5 ° C.
An amorphous bismaleimide resin having a heat of fusion peak in differential scanning calorimetry at 0 ° C and a ratio of the heat of fusion peak area at 125 ° C or higher to the total heat of fusion peak area of 50% or less. Embedded image [ Wherein , Y represents -CH ₂ - or -C (CH ₃ ) _2-
X represents a —O— or —S— group, and R ^{1 to} R ⁶ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]