JP2765420B2 - Manufacturing method of curing agent for epoxy resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention has good storage stability and
The present invention relates to a method for producing a curing agent for an epoxy resin capable of obtaining an epoxy resin composition having excellent fluidity and excellent curability, moisture resistance and mold release properties.

[0002]

2. Description of the Related Art
As a curing agent for an epoxy resin, an amine-based curing agent, an acid anhydride-based curing agent, a phenol novolak-type curing agent, and the like are used, and in these curing agents, an imidazole derivative, a tertiary amine compound, as a curing accelerator, Tertiary phosphine compounds and their derivatives have been used in combination.

[0003] However, the combination of these curing agents and curing accelerators, storage stability, fluidity, curability,
It was difficult to obtain an epoxy resin composition having excellent moisture resistance and release properties.

On the other hand, JP-A-61-190523 discloses an epoxy resin composition having excellent storage stability and moisture resistance by using a novolak type phenol curing agent and a phosphobetaine derivative of triorganophosphine in combination. It is proposed to be obtained.

However, since the above phosphobetaine derivative has a high melting point, it is difficult to uniformly disperse the same in the epoxy resin composition. Therefore, when the obtained epoxy resin composition is cured, the curing is not uniform. Accordingly, there is a problem that the mold becomes dirty and the releasability from the mold is deteriorated.

The present invention has been made in view of the above circumstances,
Provided is a method for producing a curing agent for an epoxy resin, which is capable of obtaining an epoxy resin composition having excellent storage stability and moisture resistance, excellent fluidity and curability, and excellent mold release properties from a mold. The purpose is to:

[0007]

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a phenolic resin containing two or more phenolic hydroxyl groups in one molecule and a phosphobetaine triorganophosphine. Derivatives are used at specific ratios, and when a curing agent obtained by heating and mixing at a temperature equal to or higher than the softening point of the phenol resin is used for the epoxy resin, not only is the storage stability and moisture resistance excellent, but also The present inventors have found that an epoxy resin composition having excellent fluidity and curability and also excellent mold release properties can be obtained, and the present invention has been accomplished.

Hereinafter, the present invention will be described in more detail. The method for producing a curing agent for an epoxy resin of the present invention comprises: (A) 100 parts by weight of a phenolic resin containing two or more phenolic hydroxyl groups in one molecule; B) A method in which 2 to 50 parts by weight of a phosphobetaine derivative of triorganophosphine is heated and mixed at a temperature not lower than the softening point of the phenol resin.

As the phenol resin containing two or more phenolic hydroxyl groups in one molecule as the component (A), conventionally known phenol resins can be used. For example, phenol novolak resin, phenol aralkyl resin, cyclopentadiene resin An enyl group-containing phenol resin, triphenolmethane, triphenolpropane and the like can be mentioned.

The softening point of the phenol resin is 12
The temperature is preferably 0 ° C. or lower, particularly preferably 50 to 100 ° C.

Next, as the component (B), a phosphobetaine derivative of triorganophosphine, a conventionally known phosphobetaine derivative can be used. Examples of the triorganophosphine include compounds such as triphenylphosphine, tris (dimethoxyphenyl) phosphine, and tris (cyclohexyl) phosphine. Further, as the phosphobetaine derivative, a benzoquinone derivative,
A maleic anhydride derivative can be exemplified. In addition,
Among them, it is particularly preferable to use as a triphenylphosphine / maleic anhydride adduct (hereinafter, referred to as TPP-MA).

Here, the compounding amount of the component (A) and the component (B) is 100 parts by weight of the component (A), and
50 parts by weight, preferably 5 to 30 parts by weight, are heated and mixed at a temperature not lower than the softening point of the component (A). When the component (B) is less than 2 parts by weight, sufficient curability cannot be obtained when used as a curing agent for an epoxy resin, while when it exceeds 50 parts by weight, uniform curability may be obtained. difficult.

Further, the heat treatment temperature and the heat treatment time cannot be specified because they vary depending on the types and amounts of the components (A) and (B), but are preferably 10 to 150 ° C. lower than the softening point of the component (A). In general, a method of melt-mixing at a high temperature of 50 to 100 ° C. for 10 to 240 minutes, particularly 30 to 120 minutes is generally used.

In the method for producing a curing agent of the present invention, the epoxy resin composition using the curing agent has a storage stability,
It is excellent in moisture resistance, fluidity, curability, and releasability from a mold.

The epoxy resin composition containing the curing agent according to the present invention may have a known composition.

[0016]

According to the present invention, it is possible to provide an epoxy resin composition having good storage stability and moisture resistance, excellent fluidity and curability, and good mold release from a mold. The resulting epoxy resin curing agent can be easily and reliably manufactured.

[0017]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and application examples, but the present invention is not limited to the following examples.

Example 1 100 parts of a phenol novolak resin (phenol resin I) having a softening point of 70 ° C. and TPP
-5 parts of MA was placed in a 1-liter four-necked flask equipped with a thermometer and a stirrer, left at 150 ° C for 1 hour,
Further, the mixture was mixed at 150 ° C. for 1 hour to obtain a curing agent 1.

Example 2 Instead of the phenolic resin I used in Example 1, 100 parts of a phenolic resin having a softening point of 90 ° C. (manufactured by Mitsui Toatsu, trade name: DPR1000: phenolic resin II) represented by the following structural formula was used. A curing agent 2 was obtained in the same manner as in Example 1 except for using this.

[0020]

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Next, an application example in which the curing agent obtained in the above example was added to produce an epoxy resin composition is shown below.

[Application Example] An epoxy resin, a curing agent and a curing accelerator are blended in the proportions shown in Table 1, and further 1.5 parts of wax E, 500 parts of fused quartz powder, γ-glycidoxypropyltrimethoxysilane Two parts were added, and the resulting mixture was uniformly melt-mixed with a hot two roll to produce an epoxy resin composition (application examples of the present invention and comparative application examples).

Various tests (a) to (e) shown below were conducted on these epoxy resin compositions. Table 1 shows the results. (A) Spiral flow 175 ° C, 70K using a mold conforming to EMMI standard
It was measured under the condition of gf / cm ² . (B) Hot hardness: 175 ° C., 70 kgf / cm ² , 90 seconds
The hardness at the time of transfer molding of a rod of × 10 × 4 mm was measured with a Barcol hardness meter. (C) Storage stability The number of days when the spiral flow became 80% of the initial value when each material was left at 25 ° C was shown. (D) Release Property A 28-pin SOP was heated at 175 ° C., 70 kgf / cm ² , 90
The mold releasability from the mold when molded in seconds was examined. The evaluation was indicated by the following ○, Δ, and ×. ：: Good releasability △: A part of the runner or gate part was damaged ×: Remarkably poor releasability (E) Moisture resistance 14 PIN using a test chip with a minimum line width of 1.5 μm and a chip size of 45 mm Evaluation was performed using a DIP type semiconductor device. Molded at 175 ° C. for 90 seconds, post-cured at 180 ° C. for 4 hours, immersed in a solder bath at 260 ° C. for 10 seconds, and then put in a pressure cooker at 130 ° C. for 1000 seconds.
After leaving for a period of time, the disconnection defective rate of the aluminum wiring was measured.

[0024]

[Table 1] Epoxy resin I: Epoxidized cresol novolac (EOCN1020 manufactured by Nippon Kayaku: Epoxy equivalent 200, softening point 70 ° C) Epoxy resin II: Epoxidized biphenol derivative (YX4000H manufactured by Yuka Shell Epoxy: Epoxy equivalent 1)
90, softening point 105 ° C)

From the results in Table 1, it can be seen that the epoxy resin composition using the curing agent obtained by the method of the present invention has improved storage stability and storage stability compared to the case where the components constituting the curing agent are simply mixed. It was confirmed that the composition was excellent in fluidity and excellent in curability, release property and moisture resistance.

Continuation of the front page (72) Inventor Sachi Wakao 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside Silicone Electronics Materials Research Laboratory Shin-Etsu Chemical Co., Ltd. (56) References JP-A-3-40459 (JP, A JP-A-57-23626 (JP, A) JP-A-4-249522 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 59/40-59/66

Claims (1)

(57) [Claims] 1. Heating 100 parts by weight of a phenolic resin containing two or more phenolic hydroxyl groups in one molecule and 2 to 50 parts by weight of a phosphobetaine derivative of triorganophosphine at a temperature not lower than the softening point of the phenolic resin. A method for producing a curing agent for an epoxy resin, which comprises mixing.