JP2000007761A - Thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide thermosetting resin compositions good in moisture- resistance reliability, curability and shelf stability and useful in fields of electrical and electronic materials. SOLUTION: Desired thermosetting resin compositions comprise, as the essential components, (A) a compound having two or more epoxy groups in the molecule; (B) a compound having two or more phenolic hydroxyl groups in the molecule; and (C), as the curing accelerator, a salt of a tetra-substituted phosphonium and a conjugate base of a compound having two or more phenolic hydroxyl groups in the molecule and the conductivity of the extracted water to be obtained by subjecting 1 g compound having two or more phenolic groups in the molecule which has been mixed with 50 g pure water in a pressure cooker vessel to pressure cooker treatment at 125 deg. for 20 hours being not more than 1,000 μS/cm.

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 which has good curability and storage stability and is useful in the field of electric and electronic materials.

[0002]

2. Description of the Related Art In recent years, electrical and electronic materials, especially IC encapsulating materials, have improved moisture resistance, rapid curability for the purpose of improving production efficiency, and improved preservability for improved handling during distribution and storage. Is required. Under these circumstances, the present inventors have conducted intensive studies to improve moisture resistance reliability, curability, and storage stability, and as a result, an epoxy resin thermosetting resin composition using a specific tetra-substituted phosphonium phenoxide as a curing accelerator. It was found that the above-mentioned characteristics were excellent.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a moisture-resistant reliability,
The present invention relates to a thermosetting resin composition having good curability and storage stability and being useful in the field of electric and electronic materials.

[0004]

Means for Solving the Problems The present invention provides the following (A) to
It is a thermosetting resin composition essentially including the component (C). (A) a compound having two or more epoxy groups in one molecule,
(B) a compound having two or more phenolic hydroxyl groups in one molecule, and (C) a salt of a tetra-substituted phosphonium and a conjugate base of a compound having two or more phenolic hydroxyl groups in one molecule as a curing accelerator. A compound having two or more phenolic hydroxyl groups in one molecule is mixed with 50 grams of pure water at a temperature of 125.degree.
A compound having a conductivity value of 1000 μS / cm or less for extracted water obtained by time freshener-cooker treatment.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The compound (A) used in the present invention having two or more epoxy groups in one molecule is not particularly limited as long as it has two or more epoxy groups in one molecule. Epoxy resins, novolak-type epoxy resins, naphthalene-type epoxy resins, phenols such as biphenol, phenolic resins, epoxy resins produced by reacting epichlorohydrin with hydroxyl groups such as naphthols, and alicyclic epoxy resins. Epoxy resins obtained by oxidizing olefins with a peracid and epoxidized, and those obtained by epoxidizing dihydroxybenzenes such as hydroquinone with epichlorohydrin are also included.

The compound (B) having two or more phenolic hydroxyl groups in one molecule for use in the present invention is a phenol novolak resin, a cresol novolak resin, an alkyl-modified novolak resin, a phenol aralkyl resin, a naphthol and a phenol being a carbonyl compound. A resin co-condensed with a group-containing compound is exemplified, but any compound may be used as long as two or more hydrogen atoms bonded to an aromatic ring in one molecule are substituted with a hydroxyl group.

The salt of the (C) tetra-substituted phosphonium which is a curing accelerator and a conjugate base of a compound having two or more phenolic hydroxyl groups in one molecule is used in the present invention.
Compound 1 having one or more phenolic hydroxyl groups in the molecule is mixed with 1 crumb of pure 50 crumb and mixed in a flasher-cooker container.
A conjugate base of a compound having a conductivity value of 1000 μS / cm or less in extraction water obtained by subjecting to a freshener-cooking treatment at 25 ° C. for 20 hours is used as an anion.

Examples of such salts include tetraphenylphosphonium resorcinol, tetraphenylphosphonium bisphenol A, tetraphenylphosphonium bisphenol F, tetraphenylphosphonium bisphenol S, tetraphenylphosphonium biphenol, and tetraphenylphosphonium dihydroxynaphthalene. , Tetraphenylphosphonium phenol novolak salt, tetraphenylphosphonium aralkyl-modified phenol resin salt, tetrabutylphosphonium bisphenol A salt, tetrabutylphosphonium bisphenol A
Salt, tetrabutylphosphonium bisphenol F salt, tetrabutylphosphonium bisphenol S salt, tetrabutylphosphonium biphenol salt, tetrabutylphosphonium dihydroxynaphthalene salt, tetrabutylphosphonium phenol novolak salt, tetrabutylphosphonium aralkyl-modified phenol resin salt triphenylethyl bisphenol A salt And tritolylmethylbisphenol F salt, trianisylethylbiphenol salt, triphenylbutyldihydroxynaphthalene salt, triphenylethylphenol novolak salt, and triphenylbutylaralkyl-modified phenol resin salt.

In the component (C), the compound having two or more phenolic hydroxyl groups in one molecule, which is a conjugate acid of the phenoxide anion constituting the anion, has an electric conductivity of 1000 μS / cm or less in the extraction water. Is an essential condition for obtaining excellent moisture resistance reliability. This is because PC
In BT, electrophoretic phenomena caused by ionic impurities around the element to which a voltage is applied are considered to be the cause of corrosion of aluminum wiring, so that the relationship between the extracted water conductivity and the moisture resistance reliability does not appear. It is thought. In addition, if the compound having a phenolic hydroxyl group, which is a conjugate acid of the phenoxide anion constituting the anion, has less than two phenolic hydroxyl groups in one molecule, the reactivity of the corresponding phenoxide anion is low, and the In some cases, the phenoxide anion that is not taken into the crosslinked structure and is released may affect the moisture resistance reliability and the curability. On the other hand, the substituent on the cation side phosphorus atom is preferably water repellent, and a phenyl group is particularly preferable. From the above, the tetra-substituted phosphonium of the component (C) is tetraphenylphosphonium and the conjugate base of the compound having two or more phenolic hydroxyl groups in one molecule is resorcin, bisphenol A, bisphenol F, bisphenol S,
Most preferred is at least one selected from the group consisting of conjugate bases of biphenol, dihydroxynaphthalene, phenol novolak, and aralkyl-modified phenolic resin.

The thermosetting resin composition of the present invention may be combined with additives and auxiliary materials known to those skilled in the art, such as inorganic fillers, release agents, and coupling agents, as necessary. Examples are shown below, but the present invention is not limited thereto.

[0011]

(Example 1) Orthocresol novolak epoxy EOCN-1020-65 67 parts by weight (hereinafter simply referred to as "parts") manufactured by Nippon Kayaku, 33 parts of phenol novolak having a softening point of 105 ° C and a hydroxyl equivalent of 104 , Fused silica 300
Parts, 2 parts of carnauba wax and 2.5 parts of Compound 1 were mixed and kneaded with a hot roll at 90 ° C. for 5 minutes to obtain a molding material. Further, the extraction water conductivity of bisphenol A, which is a conjugate acid of the phenoxide anion on the anion side of Compound 1, was measured according to the evaluation method (1) described later. All evaluation results are shown in Table 1.

Example 2 52 parts of biphenyl type epoxy resin YX4000H manufactured by Yuka Shell Epoxy, aralkyl-modified phenol resin XL225 48 manufactured by Mitsui Toatsu Chemicals, Inc.
Parts, fused silica 800 parts, carnauba wax 3 parts, compound 2
Was mixed with a hot roll at 90 ° C. for 5 minutes to obtain a molding material. The extracted water conductivity of bisphenol F, which is a conjugate acid of the phenoxide anion on the anion side of Compound 2, was measured according to the evaluation method (1) described later. All evaluation results are shown in Table 1.

(Examples 3 to 8, Comparative Examples 1 and 2) Following Examples 1 and 2, molding materials were obtained with the compositions shown in Tables 1 and 2. The evaluation results are shown in Tables 1 and 2.

(Evaluation Method) The evaluation method of each evaluation item in this embodiment will be described below. (1) Extracted water conductivity 1 g of a sample was mixed with 50 g of pure water, and the mixture was heated at 125 ° C. in a pressure cooker container (a container whose middle container was made of Teflon, an outer container was made of metal and had a pressure-resistant structure of 2 atm or more) 2
The conductivity of the extracted water obtained by the pressure cooker treatment for 0 hour was measured.

(2) Spiral flow Using a mold for measuring spiral flow according to EMMI-I-66, mold temperature 175 ° C., injection pressure 70 kg / c
m ² and a curing time of 2 minutes. Spiral flow is a parameter of fluidity, and a larger value indicates better fluidity.

(3) Curing Torque Using a curast meter (manufactured by Orientec Co., Ltd., JSR Curast Meter PS type), the torque after 90 seconds at 175 ° C. was determined. The torque in the curast meter is a parameter of curability, and the larger the value, the better the curability.

(4) Remaining flow rate Spiral flow immediately after preparing the material and 25 ° C.
The spiral flow after storage for 30 days was measured and calculated by the following equation. Flow residual rate (%) = (spiral flow (cm) after 30 days at 25 ° C./spiral flow immediately after material preparation (c
m)) * 100 The larger the residual flow rate, the better the storage stability.

(5) Moisture Resistance Reliability A molding material was prepared in the manner described in the examples below, and after molding a 16pDIP on which a test element was mounted, a PC at 125 ° C.
BT was performed. Table 1 shows the 50% failure time. 5
The 0% failure time is the processing time when 50% of the elements have become open failure, and the longer the time, the better the moisture resistance reliability.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

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As is evident from the results of Examples in Tables 1 and 2, the thermosetting resin composition of the present invention has excellent curability, storage stability and moisture resistance reliability, whereas Comparative Example 1 accelerates curing. The extraction water conductivity of the conjugate acid of the phenoxide anion of the agent is high and the moisture resistance reliability is poor. In Comparative Example 2, the result was poor storage stability.

[0023]

According to the present invention, when the thermosetting resin composition of the present invention is used for electric and electronic materials, a product having good moisture resistance reliability, curability and storage stability can be obtained, and the merit for electric and electronic industries is great. Conceivable.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Akiko Okubo 2-58-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd. (72) Inventor Minoru Kobayashi 2-5-2-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd. F-term (reference) 4J036 AA01 AA02 FA10 FB07 GA04 JA07

Claims (3)

[Claims] 1. A thermosetting resin composition comprising the following components (A) to (C) as essential components. (A) a compound having two or more epoxy groups in one molecule,
(B) a compound having two or more phenolic hydroxyl groups in one molecule, and (C) a salt of a tetra-substituted phosphonium and a conjugate base of a compound having two or more phenolic hydroxyl groups in one molecule as a curing accelerator. A compound having two or more phenolic hydroxyl groups in one molecule is mixed with 50 grams of pure water at a temperature of 125.degree.
A compound having a conductivity value of 1000 μS / cm or less for extracted water obtained by time freshener-cooker treatment. 2. The conjugate base of a compound having two or more phenolic hydroxyl groups in one molecule of component (C) is resorcin, bisphenol A, bisphenol F, bisphenol S, biphenol, dihydroxynaphthalene, phenol novolak, aralkyl modified The at least one selected from the group consisting of conjugate bases of phenolic resin.
The thermosetting resin composition according to the above. 3. The component (C) wherein the tetra-substituted phosphonium is tetraphenylphosphonium, and 2 per molecule.
The conjugate base of the compound having two or more phenolic hydroxyl groups is resorcinol, bisphenol A, bisphenol F,
The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is at least one selected from the group consisting of bisphenol S, biphenol, dihydroxynaphthalene, phenol novolak, and a conjugate base of an aralkyl-modified phenol resin.