JP3286369B2 - Organic dispersion type electroluminescent resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is an organic dispersion type electroluminescent (EL) resin composition BACKGROUND OF THE, more specifically, useful as an organic dispersion EL binders, shea Anoechi <br/> Le of epoxy resin in Japanese The present invention relates to a resin composition which can be used as a transparent body to be a polymer material having a relative dielectric constant of 20 or more.

[0002]

2. Description of the Related Art Generally, a binder for an organic dispersion type EL has a high dielectric constant [eg, relative permittivity (εr)], a low dielectric loss tangent (tan δ), and a temperature due to an electric characteristic value. Immutability is required. on the other hand,
Many researches have been conducted in related fields, for example, because a composite material of an inorganic material and a polymer material having electrical functionality may have a function that cannot be obtained by inorganic alone.
However, polymer materials are generally inferior in electrical properties and the like as compared with inorganic materials, and thus it is desired to improve the properties of the polymer materials.

By the way, the inventors of the present invention have long studied on increasing the dielectric constant of an epoxy resin, and found that a transparent substance having a relative dielectric constant of about 15 or a black body to which a tetracyano compound is added has a relative dielectric constant of about 26. Things before and after have achieved results as one result, and have reached today.

[0004]

Means for Solving the Problems The present inventors further promoted these research results and made an attempt to develop a transparent body having a relative dielectric constant of 20 or more. As a result, a special cyanoethylated epoxy resin was obtained. I.e., the formula:

Embedded image By using diglycidyl ether monocyanoethylated glycerin represented by, triethylenetetramine or a modified aromatic amine as a curing agent, and if necessary, tricyanoethylated pentaerythritol as a high dielectric constant material, Satisfies the requirements as a binder for organic dispersion type EL and has a relative permittivity of 20 or more as a transparent body
It has been found that a resin composition (especially around 27 depending on the optimum blending amount) can be obtained, and the present invention has been completed.

That is, the present invention relates to a diglycidyl ether monocyanoethylated glycerin represented by the above formula; triethylenetetramine or a modified aromatic amine as a curing agent; and, if necessary, a tricyanoethylated pentaerythritol as a material for increasing the dielectric constant. It is intended to provide an organic dispersion type EL resin composition characterized by comprising:

[0006] The diglycidyl ether mono-cyanoethylated glycerin used in the present invention, For example other can be produced by the method of Example 1 below. In the present invention, as a modified aromatic amine which is one of the curing agents, for example, “Epicure 151” manufactured by Yuka Shell Co., Ltd. is used.

The tricyanoethylated pentaerythritol optionally used in the present invention is a compound represented by the formula: HOCH ₂ C (CH ₂ OCH ₂ CH ₂ CN) _3, which originally has a dielectric property to a desired degree. It is used to improve the properties, but can also impart organic solvent resistance to the cured film.

[0008] The resin composition for an organic dispersion type EL according to the present invention is obtained by blending the above-mentioned diglycidyl ether monocyanoethylated glycerin with an appropriate amount of triethylenetetramine or a modified aromatic amine as a curing agent, and in particular, modifying a modified aromatic amine. If an amine is used, it is constituted by adding an appropriate amount of tricyanoethylated pentaerythritol.

[0009]

Next, the present invention will be described specifically with reference to examples. Example 1 A four-necked flask was charged with 204.1 g (1.0 mol) of glycerin diglycidyl ether (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) and 200 g of a 2% aqueous NaOH solution, and heated to 30 to 35 ° C.
Stir. After dropping 106 g (2.0 mol) of acrylonitrile, the mixture is aged at 40 ° C. for 4 hours. After cooling to room temperature with water and extracting with methylene chloride, the mixture is washed with water. After drying over magnesium sulfate and distilling off methylene chloride, pumping was performed to remove low-boiling substances (bath temperature: 40 ° C.), and a colorless transparent viscous liquid diglycidyl ether monocyanoethylated glycerin (hereinafter abbreviated as CN-DG). To).

IR analysis: A Fourier transform infrared spectrophotometer indicates absorption of a cyano group at around 2200 cm ^-1 and 910
The absorption of an epoxy group was confirmed at around cm ^-1 . The nitrogen content was 5.1% (calculated value: 5.4%) by the Kjeldahl method, and the epoxy equivalent was 133 (calculated value: 13) by the hydrochloric acid-dioxane method.
0).

Example 2 To the CN-DG of Example 1, triethylenetetramine (TETA) or a modified aromatic amine (Epicure 151) was blended in a blending amount (% by weight) shown in Table 1 below, and these were automatically mixed. After sufficiently dispersing and mixing in a mortar, the mixture is applied on a copper-foiled glass / epoxy resin laminated substrate so as to have a thickness of about 0.5 mm, and sufficiently defoamed in vacuum. Then, as the curing conditions, at 100 ° C. for 1 hour for the TETA compounding system,
The EpiCure 151 blend system is left at 130 ° C. for 1 hour. Furthermore, on the cured film thus formed,
Electrode made of carbon-based conductive paint (diameter 20 mm, film thickness 30 μm
), Dielectric constant (εr) and dielectric tangent (tan)
δ) is measured [the average value of the number of samples (n) = 5], and the dielectric properties are evaluated. Table 1 shows the results.

[0012]

[Table 1]

From the results shown in Table 1, first, in the case of the TETA compounded system in which the TETA content is 13% by weight (hereinafter referred to as Sample A), tan δ has the minimum value, and εr has a value around 27. Next, in Epicury 151 compounding system,
When the amount is 1% by weight, εr shows the maximum value and tanδ shows the minimum value (however, in this case, the cured film has no organic solvent resistance).

Example 3 The compounding amount (% by weight) shown in Table 2 below was obtained by adding 30% by weight of Epicury 151 of Example 2 (hereinafter referred to as Sample B).
Of tricyanoethylated pentaerythritol (hereinafter referred to as 3
CN-P), a cured film was formed in the same manner as in Example 2, and the dielectric properties were evaluated. Table 2 shows the results.

[0015]

[Table 2]

Next, 3CN-
The temperature dependence of εr and tan δ during the measurement (2
0-120 ° C) and frequency dependence (100Hz ~
(Changed to 1 MHz) are shown in Tables 3 and 4 below.

[0017]

[Table 3]

From the results shown in Table 3, the value of εr of sample A rapidly increased at a temperature of 60 ° C. or higher.
It shows a value around 06. On the other hand, there is no large change in tanδ as seen in εr. On the other hand, although the εr of the sample C does not change as much as the sample A, the εr exhibits characteristics that cannot be considered with a normal resin material.

[0019]

[Table 4]

From the results in Table 4, it can be seen that εr of either sample A or C was
Also decreases rapidly with increasing frequency. In particular, sample A
The case is remarkable. Further, the tan δ of the sample A rapidly decreases as the frequency increases, and becomes constant above 100 KHz. On the other hand, no significant change is observed in the sample C.

From the above experimental results, according to the present invention, T
Εr is 27 in ETA curing system, Epicuring 151 curing +3
It is recognized that a high dielectric property of εr of about 26 can be ensured in the CN-P system.

Continued on the front page (72) Inventor Mihoko Ono 7-1, Akita-cho, Takatsuki-shi, Osaka Sunstar Giken Co., Ltd. (72) Katsumi Tanino 383 Takada, Toyama, Toyama Toyama Pref. (72) Inventor Tomoaki Niguchi 383 Takada, Toyama City, Toyama Prefecture Inside the Machinery and Electronics Laboratory, Toyama Prefectural Industrial Technology Center (72) Inventor Tomohiro Takabayashi 383, Takada, Toyama City, Toyama Pref. ) Inventor Takashi Terasawa 383 Takada, Toyama City, Toyama Pref. Toyama Prefectural Industrial Technology Center Mechanical and Electronic Research Laboratory (56) References JP-A-6-131911 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , (DB name) C09J 163/00 C07C 255/13 C08G 59/28 C08G 59/50 H05B 33/20 CA (STN)

Claims (1)

(57) [Claims] 1. The formula: An organic dispersion-type electro-chemical device comprising: a diglycidyl ether monocyanoethylated glycerin represented by the formula: triethylenetetramine or a modified aromatic amine as a curing agent; and, if necessary, a tricyanoethylated pentaerythritol as a material having a high dielectric constant. A resin composition for luminescence.