JP2018168310A - One-liquid type epoxy resin composition - Google Patents

Abstract

To provide a one-liquid type epoxy resin composition, particularly, a one-liquid epoxy resin composition for hermetically sealing or insulation sealing a small-sized electronic component or electric component including a relay.SOLUTION: A one-liquid type epoxy resin composition contains the following components (A) to (D): (A) an epoxy resin being a liquid at 25°C; (B) 0.001-1 pts.wt. of alicyclic amines which are a liquid at 25°C, have at least one 6- or higher membered ring structure, and have at least two nitrogen atoms in an atom forming the ring with respect to 100 pts.wt. of the epoxy resin being a liquid at 25°C; (C) dicyandiamide; (D) 1-10 pts.wt. of a latent curing agent other than the dicyandiamide with respect to 100 pts.wt. of the epoxy resin being a liquid at 25°C.SELECTED DRAWING: None

Description

  The present invention relates to a one-pack type epoxy resin composition, and more particularly to a one-pack type epoxy resin composition for hermetically sealing or insulatingly sealing small electronic parts or electric parts including relays.

  Epoxy resin has excellent performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, adhesiveness, etc., and it can be used for paints, insulating materials for electrical and electronic materials, adhesives, etc. It is used for a wide range of applications. In particular, since it has good electrical characteristics and heat resistance, it is suitably used as a sealing material for small electronic components such as relays or electrical components.

  As an epoxy resin used for the above-mentioned applications, a so-called two-pack type epoxy resin composition in which a curing agent such as polyamidoamine or acid anhydride and an epoxy resin are mixed immediately before use, and a latent curing agent are previously epoxyized. A so-called one-pack type epoxy resin composition that is mixed with a resin composition is known.

  In general, two-pack type epoxy resin compositions are characterized by easy storage and transportation because they are mixed with a curing agent and an epoxy resin immediately before use, but there are poor curing due to weighing errors during compounding and pot life after compounding. There are shortcomings such as shortness. On the other hand, the one-pack type epoxy resin composition has little material loss and does not need to be mixed at the time of use. A resin composition is used. However, as electronic and electrical parts are becoming smaller, lighter, and higher in density, gaps in the bonding and sealing parts of various parts tend to become very narrow. When a one-pack type epoxy resin composition is used for stopping, separation of the liquid epoxy resin and other components such as a curing agent occurs, and the separated liquid epoxy resin flows into the movable part, the contact part, etc. There may be a problem that a characteristic defect such as a defect is caused.

  As a means for solving the above problem, there has been proposed a one-pack type epoxy resin composition that completely cures a portion flowing into a very narrow gap by suppressing separation from a curing agent or the like (Patent Document 1). However, it has not been improved about the fact that it flows into the gaps of extremely narrow intervals, and the epoxy resin composition that has flowed into the gaps of extremely narrow intervals may flow into the movable part, the contact part, etc. before curing. In addition, the applicants of the present application have proposed a one-part epoxy resin composition in which separation is suppressed and inflow of the one-part epoxy resin composition itself is suppressed by using calcium carbonate with a specific coating in combination. (Patent Document 2). However, even with the one-pack type epoxy resin composition, there is a case where the performance of suppressing inflow in a gap with a very narrow interval is insufficient.

JP 2001-220429 A JP-A-2015-98520

  The present invention provides a one-pack type epoxy resin composition in which the flow of various small electronic parts or electric parts into gaps with extremely narrow intervals is improved.

  As a result of intensive studies on various one-component epoxy resin compositions in order to achieve the above object, the present inventors have added cycloaliphatic amines having a specific structure to the one-component epoxy resin composition. It has been found that the above problem can be solved. Specifically, the following invention is included.

[1]
Hereinafter, the one-pack type epoxy resin composition containing the component of (A)-(D).
(A) Epoxy resin that is liquid at 25 ° C. (B) It is liquid at 25 ° C., has at least one ring structure of 6-membered ring or more, and at least two of the atoms forming the ring are nitrogen atoms. A cyclic aliphatic amine is added at a temperature of 25 ° C. to 100 parts by weight of a liquid epoxy resin, and a latent curing agent other than (C) dicyandiamide (D) dicyandiamide is added at 25 ° C. 1 to 10 parts by weight per 100 parts by weight of resin

[2]
(C) The one-pack type epoxy resin composition as described in [1] which contains 1-10 weight part of dicyandiamide with respect to 100 weight part of (A) 25 degreeC liquid epoxy resins.

[3]
One solution according to [1] or [2], wherein the latent curing agent other than dicyandiamide is at least one selected from the group consisting of an epoxy resin imidazole adduct compound, an epoxy resin amine adduct compound, and a modified aliphatic polyamine compound. Type epoxy resin composition.

  According to the present invention, it is possible to provide a one-pack type epoxy resin composition in which the flow of a small electronic component or an electric component into an extremely narrow gap is improved. In particular, the one-part epoxy resin composition of the present invention usually has storage stability despite containing liquid amines that were thought to affect the stability of the one-part epoxy resin composition. Therefore, it can be suitably used for hermetic sealing or insulating sealing of small electronic parts or electric parts typified by relays without special treatment during transportation or use.

  The (A) epoxy resin that is liquid at 25 ° C. used in the present invention may be any epoxy resin that is liquid at 25 ° C. and used in the epoxy resin composition. The “liquid” in the present invention means that the viscosity at 25 ° C. is 500 Pa · s or less, and the viscosity is a value measured at 25 ° C. using a rotary viscometer. Moreover, when using together a solid epoxy resin, what is necessary is just to make it the viscosity at the time of mixing with a liquid epoxy resin become the above-mentioned range.

  Examples of the epoxy resin that can be used in the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, dicyclopentadiene type. In addition to epoxy resins such as epoxy resins and phenol novolac type epoxy resins, polyglycidyl ethers obtained by reacting polyhalogen phenols such as catechol and resorcin, or polyhydric alcohols such as glycerin and polyethylene glycol with epihalohydrin, p- Reacts epihalohydrin with polycarboxylic acids such as glycidyl ether esters, phthalic acid and terephthalic acid obtained by reacting hydroxycarboxylic acid such as oxybenzoic acid with epihalohydrin. Resulting Te polyglycidyl esters, 4,4-diaminodiphenylmethane, m- aminophenol and glycidyl amine type epoxy resins obtained by reacting an epihalohydrin, and the like. Among the epoxy resins described above, bisphenol A type epoxy resin, bisphenol F type epoxy resin or glycidylamine type epoxy resin is preferably used.

  (B) a cyclic aliphatic amine that is liquid at 25 ° C. and has at least one ring structure of 6-membered ring or more, and at least two of the atoms forming the ring are nitrogen atoms, used in the present invention The class may have other substituents as long as it has a ring structure satisfying the above definition, and may have another ring structure. When it has another ring structure, it may be a ring structure that shares a part of the ring structure that satisfies the above definition. Examples of such cycloaliphatic amines include N-methylpiperazine, 1- (2-dimethylaminoethyl) -4-methylpiperazine, N, N′-dimethylpiperazine, ethyl 1-piperazinecarboxylate, 1,8- And diazabicyclo [5,4,0] -7-undecene, 1-amino-4-methylpiperazine, N- (2-aminoethyl) piperazine, and the like.

  (B) When the liquid is at 25 ° C., has at least one 6-membered ring structure, and does not add cycloaliphatic amines in which at least two of the atoms forming the ring are nitrogen atoms In some cases, inflow into gaps with extremely narrow intervals occurs, leading to poor characteristics such as poor contacts. Moreover, the usage-amount is 0.001-1 weight part with respect to 100 weight part of (A) epoxy resins, Preferably it is 0.05-0.5 weight part. By making the amount used 0.001 part by weight or more, it becomes possible to suppress the flow into the gaps of extremely narrow intervals, and by making the amount used 1 part by weight or less, the one-pack type epoxy resin composition Deterioration of storage stability can be suppressed.

  As the (C) dicyandiamide used in the present invention, generally available dicyandiamide can be used, and among these, pulverized in advance and subjected to # 150 mesh pass are preferable. (C) When dicyandiamide is not added, the adhesiveness with the metal is lowered, and the small electronic component or the electrical component cannot be hermetically sealed or insulated. Moreover, the usage-amount of (C) dicyandiamide is 1-10 weight part with respect to 100 weight part of (A) epoxy resin, Preferably it is 1-6 weight part. By making the amount used 1 to 10 parts by weight, it becomes possible to improve the balance of adhesiveness between the metal part and the resin part, and in particular, a small electronic component such as a relay having a metal part and a resin part or It can be suitably used for hermetic sealing or insulating sealing of electrical components.

Examples of latent curing agents other than (D) dicyandiamide used in the present invention include epoxy resin imidazole adduct compounds, epoxy resin amine adduct compounds, modified aliphatic polyamine compounds, and hydrazide compounds. Among these, an epoxy resin imidazole adduct compound, an epoxy resin amine adduct compound, and a modified aliphatic polyamine compound are preferably used. Specific examples of such compounds include, for example, Ajinomoto Technofine Co., Ltd. Amicure PN-23, Amicure PN-R, Air Products Japan Co., Ltd. Sunmide LH-210, and the like as epoxy resin imidazole adduct compounds. Examples of the epoxy resin amine adduct compound include Amicure MY-24, Amicure MY-R manufactured by Ajinomoto Techno Fine Co., Ltd., and adduct compounds disclosed in JP-A No. 57-1000012. Examples of the modified aliphatic polyamine compound include Fujicure FXE-1000 and Fujicure FXR-1121 manufactured by T & K TOKA.

(D) The use amount of the latent curing agent other than dicyandiamide is 1 to 10 parts by weight, preferably 4 to 8 parts by weight, based on 100 parts by weight of (A) epoxy resin. (D) When a curing agent other than dicyandiamide is not used, it is not cured at 130 ° C. or less, and when it is more than 10 parts by weight, the storage stability of the composition is deteriorated. In addition, when it does not harden | cure at 130 degrees C or less, it may become difficult to use as a sealing material of the small electronic component or electrical component which has a plastic member as a main component.

The one-pack type epoxy resin composition of the present invention can be blended with an inorganic filler, a coupling agent, a colorant and the like as required. Examples of the inorganic filler include calcium carbonate, barium sulfate, fused silica, crystalline silica, glass filler, aluminum hydroxide, magnesium hydroxide, and alumina. Examples of the coupling agent include 3-glycidoxypropyl. Examples include trimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane, and examples of the colorant include carbon black and titanium oxide.

Furthermore, the epoxy resin composition of this invention can mix | blend a thixotropic agent as needed. Examples of thixotropic agents include Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Dispalon C-308, Dispalon 4110, Dispalon 4300, Disparon 4500, Disparon 6600, and others manufactured by Nippon Aerosil Co., Ltd. It is done.

In the preparation of the one-pack type epoxy resin composition of the present invention, a general stirring and mixing apparatus and mixing conditions are applied in the same manner as in the usual method for preparing an epoxy resin composition. Examples of the apparatus to be used include a mixing roll, a dissolver, a planetary mixer, a kneader, and an extruder. During mixing, heating may be performed to dissolve and / or lower the viscosity of the epoxy resin and improve the stirring and mixing efficiency. Further, cooling may be performed as necessary in order to remove frictional heat generation, reaction heat generation, and the like.

  Examples of the present invention are shown below, but the present invention is not limited thereto. Moreover, the value shown by each Example and the comparative example is a value by the following analysis method.

1. Evaluation of inflow into gaps with extremely narrow intervals (1) A spacer with a thickness of 12 μm is sandwiched between two glass slides (length 26 mm × width 76 mm × thickness 1.5 mm) on both sides of 26 mm facing each other. Stop with a clip on the slide glass.
(2) The one-pack type epoxy resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 6 were equally applied to the 76 mm sides of the two slide glasses in (1), and heated at 110 ° C. for 60 minutes. Then, the maximum value of the distance entering the gap was measured. The evaluation criteria for the inflow distance are as follows.
Flow distance (mm):
×: 3.0 or more, ○: less than 3.0

2. Evaluation of Storage Stability Viscosity at 25 ° C. using a B-type viscometer every day for the one-pack type epoxy resin compositions produced in the following Examples and Comparative Examples which were stored in a dryer kept at 40 ° C. Was measured. Based on the following evaluation criteria, the storage stability was evaluated in a period until the viscosity became twice the initial value.
Storage stability (period until viscosity becomes twice the initial value):
×: Less than 1 week, ○: More than 1 week

<Example 1>
(A) D. As an epoxy resin that is liquid at 25 ° C. E. R. 75 parts by weight of 383 LCL (bisphenol A type epoxy resin: manufactured by Dow Chemical Co., Ltd.) and jER807 (bisphenol F type epoxy resin: manufactured by Mitsubishi Chemical Corporation), 25 parts by weight, (B) liquid at 25 ° C. 1-methylpiperazine (manufactured by Wako Pure Chemical Industries, Ltd.) as a cycloaliphatic amine having at least one 6-membered ring structure and at least two of the atoms forming the ring being a nitrogen atom ) 0.01 parts by weight, (C) 4 parts by weight of dicyandiamide, (D) 6 parts by weight of Fujicure FXR-1121 (modified alicyclic polyamine compound: manufactured by T & K TOKA) as a latent curing agent other than dicyandiamide, After mixing 1 part by weight of finely divided silica (Aerosil 200: manufactured by Nippon Aerosil Co., Ltd.), it is kneaded using a mixing roll, and is a one-part epoxy resin The Narubutsu was prepared. Table 1 shows the evaluation results of the inflow distance and storage stability of the obtained one-pack type epoxy resin composition.

<Example 2>
(A) D. As an epoxy resin that is liquid at 25 ° C. E. R. 25 parts by weight of 383 LCL (bisphenol A type epoxy resin: manufactured by Dow Chemical Co., Ltd.) and 75 parts by weight of jER807 (bisphenol F type epoxy resin: manufactured by Mitsubishi Chemical Corporation), (B) liquid at 25 ° C. 1-methylpiperazine (manufactured by Wako Pure Chemical Industries, Ltd.) as a cycloaliphatic amine having at least one 6-membered ring structure and at least two of the atoms forming the ring being a nitrogen atom ) 0.1 parts by weight, (C) 4 parts by weight of dicyandiamide, (D) 6 parts by weight of Fujicure FXR-1121 (modified alicyclic polyamine compound: manufactured by T & K TOKA) as a latent curing agent other than dicyandiamide 1 part by weight of finely divided silica (Aerosil 200: manufactured by Nippon Aerosil Co., Ltd.), NS # 100 (Calcium carbonate: Nitto Flour Industry ( ) Ltd.) were mixed 30 parts by weight were kneaded with a mixing roll to prepare a one-pack type epoxy resin composition. Table 1 shows the evaluation results of the flow-in distance and storage stability of these one-component epoxy resin compositions.

<Example 3>
In Example 2, (D) Fujicure FXR-1121 (modified alicyclic polyamine compound: manufactured by T & K TOKA) 6 parts by weight of Amicure PN-23 (epoxy resin imidazole adduct compound: Ajinomoto Fine Techno Co., Ltd.) )) Except for changing to 8 parts by weight, a one-pack type epoxy resin composition was prepared in the same manner as in Example 2, and the inflow distance and storage stability were evaluated. The evaluation results are shown in Table 1.

<Example 4>
In Example 1, the same amount as in Example 1 except that the amount of (B) 1-methylpiperazine (manufactured by Wako Pure Chemical Industries, Ltd.) was changed from 0.01 parts by weight to 0.5 parts by weight. Type epoxy resin compositions were prepared and evaluated for flow-in distance and storage stability. The evaluation results are shown in Table 1.

<Example 5>
In Example 1, (B) 1-methylpiperazine (manufactured by Wako Pure Chemical Industries, Ltd.) 0.01 parts by weight to 1- (2-dimethylaminoethyl) -4-methylpiperazine (manufactured by Tokyo Chemical Industry Co., Ltd.) ) A one-pack type epoxy resin composition was prepared in the same manner as in Example 1 except that the amount was changed to 0.1 parts by weight, and the inflow distance and the storage stability were evaluated. The evaluation results are shown in Table 1.

<Example 6>
In Example 5, 6 parts by weight of (D) Fujicure FXR-1121 (modified alicyclic polyamine compound: manufactured by T & K TOKA) Amicure PN-23 (epoxy resin imidazole adduct compound: Ajinomoto Fine Techno Co., Ltd.) ) Produced) A one-pack type epoxy resin composition was prepared in the same manner as in Example 5 except that the amount was changed to 8 parts by weight, and the flow-in distance and the storage stability were evaluated. The evaluation results are shown in Table 1.

<Example 7>
In Example 1, (B) 0.01 parts by weight of 1-methylpiperazine (manufactured by Wako Pure Chemical Industries, Ltd.) to 1,8-diazabicyclo [5,4,0] -7-undecene (Wako Pure Chemical Industries ( Co., Ltd.) A one-pack type epoxy resin composition was prepared in the same manner as in Example 1 except that the amount was changed to 0.1 parts by weight, and the inflow distance and the storage stability were evaluated. The evaluation results are shown in Table 1.

<Example 8>
In Example 2, (B) 0.1 part by weight of 1-methylpiperazine (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 0.1 part by weight of ethyl 1-piperazinecarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.). Except that, a one-pack type epoxy resin composition was prepared in the same manner as in Example 2, and the flow-in distance and the storage stability were evaluated. The evaluation results are shown in Table 1.

<Comparative Example 1>
In Example 1, a one-pack type epoxy resin composition was prepared in the same manner as in Example 1 except that (B) 1-methylpiperazine (manufactured by Wako Pure Chemical Industries, Ltd.) was not used. Evaluated. The evaluation results are shown in Table 2.

<Comparative example 2>
In Example 1, the same component as in Example 1 except that the amount of (B) 1-methylpiperazine (manufactured by Wako Pure Chemical Industries, Ltd.) was changed from 0.01 parts by weight to 1.5 parts by weight. Type epoxy resin compositions were prepared and evaluated for flow-in distance and storage stability. The evaluation results are shown in Table 2.

<Comparative Example 3>
In Example 1, (B) 0.01 part by weight of 1-methylpiperazine (manufactured by Wako Pure Chemical Industries, Ltd.) to 0.1 part by weight of 2-ethyl-4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) A one-pack type epoxy resin composition was prepared in the same manner as in Example 1 except that the flow-in distance and storage stability were evaluated. The evaluation results are shown in Table 2.

<Comparative example 4>
In Example 1, except that (B) 1-methylpiperazine (manufactured by Wako Pure Chemical Industries, Ltd.) 0.01 parts by weight is changed to 0.1 parts by weight of hexamethyleneimine (manufactured by Tokyo Chemical Industry Co., Ltd.). A one-pack type epoxy resin composition was prepared in the same manner as in Example 1, and the flow-in distance and storage stability were evaluated. The evaluation results are shown in Table 2.

<Comparative Example 5>
Example 4 is the same as Example 4 except that the amount of (D) Fujicure FXR-1121 (modified alicyclic polyamine compound: manufactured by T & K TOKA Co., Ltd.) is changed from 6 parts by weight to 12 parts by weight. A liquid epoxy resin composition was prepared, and the inflow distance and storage stability were evaluated. The evaluation results are shown in Table 2.

Ａ−１：フジキュアーＦＸＲ−１１２１
Ａ−２：アミキュアＰＮ−２３
Ｂ−１：１−メチルピペラジン
Ｂ−２：１−（２−ジメチルアミノエチル）−４−メチルピペラジン
Ｂ−３：１，８−ジアザビシクロ［５，４，０］−７−ウンデセン
Ｂ−４：１−ピペラジンカルボン酸エチル

A-1: Fuji Cure FXR-1121
A-2: Amicure PN-23
B-1: 1-methylpiperazine B-2: 1- (2-dimethylaminoethyl) -4-methylpiperazine B-3: 1,8-diazabicyclo [5,4,0] -7-undecene B-4: 1-piperazine ethyl carboxylate

Ａ−１：フジキュアーＦＸＲ−１１２１
Ｂ−１：１−メチルピペラジン
Ｂ−５：２−エチル−４−メチルイミダゾール
Ｂ−６：ヘキサメチレンイミン

A-1: Fuji Cure FXR-1121
B-1: 1-methylpiperazine B-5: 2-ethyl-4-methylimidazole B-6: Hexamethyleneimine

Claims (3)

Hereinafter, the one-pack type epoxy resin composition containing the component of (A)-(D).
(A) Epoxy resin that is liquid at 25 ° C. (B) It is liquid at 25 ° C., has at least one ring structure of 6-membered ring or more, and at least two of the atoms forming the ring are nitrogen atoms. A cyclic aliphatic amine is added at a temperature of 25 ° C. to 100 parts by weight of a liquid epoxy resin, and a latent curing agent other than (C) dicyandiamide (D) dicyandiamide is added at 25 ° C. 1 to 10 parts by weight per 100 parts by weight of resin The one-pack type epoxy resin composition of Claim 1 which contains (C) 1-10 weight part of dicyandiamide with respect to 100 weight part of (A) 25 degreeC liquid epoxy resins. The one-pack type epoxy according to claim 1 or 2, wherein the latent curing agent other than dicyandiamide is at least one selected from the group consisting of an epoxy resin imidazole adduct compound, an epoxy resin amine adduct compound, and a modified aliphatic polyamine compound. Resin composition.