JP3375275B2 - Curing accelerator for thermosetting resin - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is to accelerate curing of d epoxy resin, can give an epoxy <br/> resin composition excellent in curability and storage stability, it relates to a curing accelerator .

[0002]

2. Description of the Related Art Thermosetting resins are generally used in combination with a catalyst (curing accelerator) in order to accelerate the curing of the resin during molding. For example, in the case of an epoxy resin, as a curing catalyst, amines, imidazole compounds, nitrogen-containing heterocyclic compounds such as diazabicycloundecene (hereinafter abbreviated as DBU), organophosphine compounds, fourth compounds
Various compounds such as quaternary ammonium are used. Among them, phosphorus compounds, especially triphenylphosphine (hereinafter, abbreviated as TPP) have been often used as catalysts for semiconductor encapsulation materials, but there is a problem that they cannot be said to be sufficient in terms of storage stability of the resin composition. there were.

Further, JP-A-7-252348 proposes to use a heated mixture of a monoepoxy compound, a monovalent phenol compound (resin) and an organic phosphine as a catalyst. However, since the monovalent phenol resin is monofunctional, there is a problem that the curability is lowered.

[0004]

The present invention 0005] In order to solve such problems of the curing catalyst of epoxy resin <br/> fat, which has been made result of performing various studies, the curing of d epoxy resin It is an object of the present invention to provide a curing accelerator capable of accelerating the curing, and providing an epoxy resin composition having excellent storage stability and curability.

[0005]

SUMMARY OF THE INVENTION Namely, the present invention is a compound having at least one epoxy group in the molecule (A), pro
2 phenolic hydroxyl groups in one molecule
One or more with an organic compound (B), and triarylphosphine compound (C), an epoxy resin curing accelerator, wherein the benzalkonium such a compound obtained by reacting.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The compound serving as the curing accelerator according to the present invention is produced by the following reaction mechanism. That is, the triarylphosphine compound (C), which has a non-shared electron pair and is a strong nucleophile, nucleophilically attacks the epoxy group. Here, the reactivity of the epoxy group is derived from the fact that the three-membered ring having a large strain is easily cleaved. The oxygen of the cleaved epoxy group is in an anion state, and the nucleophilically added phosphorus of the triarylphosphine compound is in a cation state. This anionized oxygen rapidly reacts with the proton released from the organic compound (B) that is a proton donor existing in the reaction system, and the cationized phosphorus and the proton donor release a proton. Anions form ion pairs.

The compound (A) having an epoxy group used in the present invention is not particularly limited as long as it has an epoxy group in the molecule. For example, glycidyl phenyl ether, glycidyl methacrylate, 2,3 -Epoxypropylbenzene, 1,2-epoxycyclododecane, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, tri (phenylglycidyl ether) methane, tetrabromobisphenol A type epoxy Brominated epoxy resin such as resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triglycidyl isocyanurate resin, stilbene type epoxy resin, and condensation of dicyclopentadiene and phenols While the phenolic resin synthesized by response may like to use an epoxy resin obtained by glycidyl etherification, if at least one compounds containing an epoxy group in a molecule, but is not limited to the above.

[0008]

As an organic compound (B) having two or more phenolic hydroxyl groups in one molecule as a proton donating group , the general definition of phenol is that aromatic compounds such as benzene, naphthalene and ferrocene are aromatic compounds. A hydrogen atom on the ring is substituted with a hydroxyl group, so that specifically, polyhydric phenols, and if polyvalent, condensed polycyclic compounds such as naphthols are also included, hydroquinone, Catechol, resorcin, dinuclear or higher phenol novolak, dinuclear or higher resole, bisphenols such as bisphenol A and bisphenol S, and dihydroxynaphthalene are included.

[0010]

[0011] Compounds having an epoxy with (A), proto
A phenolic hydroxyl group as down-donating group, 1 two <br/> than the chromatic organic compound in the molecule (B) and compounding ratio of the epoxy groups per equivalent to proton equivalent of 1.0 or more It is preferable to mix it with. Outside of the above range, sufficient curability may not be obtained.

Further, a compound (A) having an epoxy,
Phenolic hydroxyl group as a proton donating group in one molecule
A triarylphosphine compound (C) is used in addition to the organic compound (B) having two or more of them. The structure is represented by the following general formula (1), and preferably, an electron donating group is present on the aryl group. It is preferable to use a triarylphosphine which has been added and has a stronger basicity than TPP.

[0013]

[Chemical 1]

This electron-donating group has a negative substituent constant σ according to the Hammett's rule of organic chemistry. Specifically, it is an alkyl group such as a methyl group, an ethyl group or a propyl group, or a methoxy group. A group and an alkoxyl group such as an ethoxy group are preferable, but a hydroxyl group and an amino group are also good electron donating groups.

The cure accelerators of the present invention are always useful in epoxy resins.

[0016]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. First, by a method described in the following synthesis example, a compound serving as a curing accelerator is synthesized, an epoxy resin molding material is prepared using the compound, and a spiral flow and a curing torque immediately after the material is prepared for characteristic evaluation, and The residual flow rate after storage at 30 ° C. for 7 days was measured.
Each measuring method was as follows.

1. Spiral Flow Using a mold for spiral flow measurement conforming to EMMI-I-66, mold temperature 175 ° C, injection pressure 70 kg / c
It is measured at m ² and curing time of 2 minutes. Spiral flow (c
m) is a fluidity parameter, and the larger the value, the greater the fluidity.

2. Using a curing torque curast meter (manufactured by Orientec Co., Ltd., JSR curast meter PS type), 175 ° C., 60
The torque after second heating was determined. The torque in the curast meter is a parameter of curability, and the larger the value, the higher the curability.

3. Flow residual ratio Spiral flow immediately after preparing the molding material, and 3
The spiral flow after storage at 0 ° C. for 7 days was measured, and the percentage of the spiral flow (cm) after storage with respect to the spiral flow (cm) immediately after material preparation was calculated. The closer the flow residual value is to 100%, the better the storage stability.

(Synthesis Example 1) 4.50 g of phenyl glycidyl ether (0.03 mol as an epoxy group), TPTP
9.12 g (0.03 mol) and 2,2-bipheno
2.79 g (0.015 mol, 0.10 mol considering the number of functional groups.
03 mol) was dissolved in 100 g of acetone in a glass reaction vessel. The solution was reacted in the same glass reaction vessel under reflux at an oil bath temperature of 80 ° C. for about 5 hours while stirring. After that, for 30 minutes, the inside of the reaction vessel is 2-3 mmHg.
The solvent was removed to the outside of the reaction vessel under reduced pressure until the target compound was obtained. This is designated as [Compound 1].

(Synthesis Examples 2 to 9 ) A series of syntheses was carried out in the same manner as in Synthesis Example 1 by using the combination of epoxy component / proton donor / triarylphosphine shown in Table 1, and [Compound 2]. ~ [Compound 9 ] was prepared. At this time, gelation was not particularly observed even in the reaction of the polyvalent epoxy resin with the polyvalent proton donor and the triarylphosphine. In the Synthesis Examples 6-9, and using phenol in 1 functional as a proton donor, resulting [Compound 6] - [Compound 9] are those used in Comparative Example.

Example 1 Orthocresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-1025)
-65, softening point 65 ° C, epoxy equivalent 210) 67 parts by weight, phenol novolac resin (Sumitomo Dures Co., Ltd.,
PR-51470, softening point 105 ° C, hydroxyl equivalent 10
4) 33 parts by weight, 1.7 parts by weight of [Compound 1] as a catalyst, 300 parts by weight of crushed fused silica, and 2 parts by weight of carnauba wax were mixed, and roll-kneaded at 90 ° C. for 5 minutes to prepare a molding material. did. The spiral flow of this molding material was 84 cm, and the curing torque was 91 kgf · cm. The flow residual rate after storage at 30 ° C for 7 days was 89 %.
Met.

(Example 2) 52 parts by weight of a biphenyl type epoxy resin (Yuka 4000 Shell, YX4000H, epoxy equivalent 187-197), modified phenol resin (trade name: Mitsui Milex XL-225-3L, hydroxyl group) Equivalent 172 to 182) 48 parts by weight, 2.5 parts by weight of [Compound 1] as a catalyst, 800 parts by weight of spherical fused silica,
And carnauba wax (3 parts by weight) at 90 ° C.
Roll kneading was carried out for a minute to prepare a molding material. This molding material has a spiral flow of 96 cm and a hardening torque of 88 kgf.
・ It was cm. The residual flow rate after storage at 30 ° C for 7 days was 85%.

(Examples 3 to 10 ) With the formulations shown in Table 2, the molding materials were prepared in the same manner as in Examples 1 and 2. The evaluation results are summarized in Table 2 together with Examples 1 and 2.

(Comparative Examples 1 to 14 ) With the formulations shown in Table 3, the molding materials were prepared in the same manner as in Examples 1 and 2. The evaluation results are summarized in Table 3.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

As is clear from the results shown in Tables 2 and 3, in each of the examples of the present invention, the spiral flow of the molding material immediately after the preparation was 84 cm or more, the curing torque was 68 kgf · cm or more, and 30 The residual flow rate after storage at 7 ° C for 7 days showed a value of 79 % or more, and a molding material excellent in curability and storability was obtained.

On the other hand, in the comparative example, the spiral flow immediately after the preparation was 71 cm or more, which was slightly lower than that of the examples, but TPP and TP were used as the curing accelerator.
In Comparative Examples 1 to 6 using TP [tri (p-methylphenyl) phosphine] and DMPP [tri (o-dimethoxyphenyl) phosphine], the curing torque was 81 kg.
Good at f / cm or higher, but has a flow residual rate of 28-48%
On the other hand, on the other hand, in Comparative Examples 7 to 14 using [Compounds 6 to 9 ] of Synthesis Example, the residual flow rate is 72% or more, but the curing torque is low at 22 to 36 kgf · cm, and the curability and storage are good. The result was that the compatibility of both sexes was not obtained.

[0031]

With the curing accelerator according to the present invention, the curing of d <br/> epoxy resin is promoted, a resin composition excellent in curability and storage stability can be obtained, for curing epoxy resins It is useful as a promoter.

Front page continuation (72) Minor Kobayashi Minoru Kobayashi 2-5-8 Higashi-Shinagawa, Shinagawa-ku, Tokyo Within Sumitomo Bakelite Co., Ltd. (56) Reference JP-A-10-120765 (JP, A) JP-A-61- 4253 (JP, A) JP-A-6-184280 (JP, A) JP-A-7-252348 (JP, A) JP-A-9-118719 (JP, A) JP-A-7-501847 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 59/40 C08G 59/68

Claims (3)

(57) [Claims] 1. A compound (A) having at least one epoxy group in the molecule, phenolic as a proton-donating group.
Organic compound (B) having two or more hydroxyl groups in one molecule, and triarylphosphine compound (C)
A curing accelerator for epoxy resins, wherein the benzalkonium such a compound obtained by reacting. 2. A triarylphosphine compound (C)
Is a triarylphosphine compound having an electron donating group on the aryl group, and the curing accelerator for an epoxy resin according to claim 1. 3. The curing accelerator for an epoxy resin according to claim 2, wherein the electron donating group on the aryl group of the triarylphosphine compound (C) is either an alkyl group or an alkoxy group.