JP2002114759A - Bis(mercaptomethyl)benzene derivative and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin monomer capable of forming a dielectric film suitable for electronic parts and a method for producing the above resin monomer. SOLUTION: This bis(mercaptomethyl)benzene derivative is represented by the following chemical formula (1) (wherein positions at which three benzene rings are substituted are each independently meta positions or para positions).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a bis (mercaptomethyl) benzene derivative and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a resin film has been used as a dielectric film used for a capacitor or the like. Such a dielectric film is disclosed in JP-B-63-32929, JP-A-11-1.
As shown in US Pat. No. 47272 and US Pat. No. 5,125,138, a resin monomer deposited on a substrate is irradiated with an electron beam or ultraviolet rays to cure the resin monomer.

As the resin monomer for forming the dielectric film, for example, dimethylol tricyclodecane diacrylate represented by the following chemical formula (A) or 1,1 represented by the following chemical formula (B) Acrylic ester compounds such as 9-nonanediol diacrylate have been used.

[0004]

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[0005]

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[0006]

However, there has been a problem that electronic components using a dielectric film formed of the above resin monomer have insufficient characteristics. That is, since the ester group in the resin monomer molecule is hygroscopic (hydrophilic), the electronic component using the dielectric film formed by the resin monomer has a problem that the characteristics under high humidity are not sufficient. there were. In addition, since linear hydrocarbon groups and alicyclic hydrocarbon groups in the resin monomer molecules are easily oxidized and decomposed at a high temperature, electronic components using a dielectric film formed by the resin monomer can be used at high temperatures. However, there is a problem that the characteristics are not sufficient.

[0007] In order to solve the above problems, an object of the present invention is to provide a resin monomer capable of forming a dielectric film suitable for an electronic component, and a method of manufacturing the same.

[0008]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found a new resin monomer. That is, the resin monomer of the present invention,
It is a bis (mercaptomethyl) benzene derivative (α, α'-xylenedithiol derivative) represented by the following chemical formula (1).

[0009]

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(In the formula (1), the positions where the three benzene rings are substituted are each independently at the meta-position or the para-position.) The bis (mercaptomethyl) benzene derivative of the present invention can be used in electronic parts. It is suitable as a resin monomer for forming a dielectric film to be used.

The bis (mercaptomethyl) of the present invention
The method for producing the benzene derivative includes at least one selected from m-chloromethylstyrene (meta-chloromethylstyrene) and p-chloromethylstyrene (para-chloromethylstyrene) represented by the following chemical formula (2):
It is characterized by including a step of reacting with at least one selected from m-bis (mercaptomethyl) benzene and p-bis (mercaptomethyl) benzene represented by the following chemical formula (3).

[0012]

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[0013]

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According to the method for producing a bis (mercaptomethyl) benzene derivative of the present invention, the bis (mercaptomethyl) benzene derivative represented by the chemical formula (1) can be easily produced.

In the above production method, it is preferable that the above reaction is performed in the presence of an alkali metal carbonate which is a base catalyst. According to the above configuration, the bis (mercaptomethyl) benzene derivative represented by the chemical formula (1) can be produced with high productivity.

[0016]

Embodiments of the present invention will be described below.

(Embodiment 1) In Embodiment 1, the bis (mercaptomethyl) benzene derivative of the present invention will be described.

The bis (mercaptomethyl) benzene derivative of the present invention is represented by the following chemical formula (1).

[0019]

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The bis (mercaptomethyl) benzene derivative of the above formula (1) can be produced by the method described in the second embodiment.

The bis (mercaptomethyl) benzene derivative of the above formula (1) can be used as a resin monomer for forming a dielectric film used for electronic parts. When a dielectric film is formed using this resin monomer,
First, a thin film containing a resin monomer may be formed, and this thin film may be irradiated with an electron beam or ultraviolet light. By using this resin monomer, a dielectric film suitable for an electronic component can be formed. In particular, by forming a dielectric film of a capacitor using this resin monomer, a capacitor having excellent characteristics even under high humidity and high temperature can be obtained.

Embodiment 2 In Embodiment 2, a method for producing the bis (mercaptomethyl) benzene derivative represented by the chemical formula (1) described in Embodiment 1 will be described.

In the production method according to the second embodiment, m-chloromethylstyrene represented by the following chemical formula (2) and p-
At least one selected from chloromethylstyrene,
The reaction is performed with at least one selected from m-bis (mercaptomethyl) benzene and p-bis (mercaptomethyl) benzene represented by the following chemical formula (3). At this time, both are heated, for example, to 60 ° C. in the presence of a base catalyst.
React at ~ 120 ° C for 4-8 hours.

[0024]

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[0025]

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By this reaction, the above-mentioned chemical formula (1)
A bis (mercaptomethyl) benzene derivative represented by the following formula can be easily produced.

The compound represented by the above chemical formula (2) was obtained from Seimi Chemical Co., Ltd. in the form of CMS-P (50% meta-form,
Para-form 50%) and CMS-14 (meta-form 5%, para-form 95%).

Further, m-bis (mercaptomethyl) benzene and p-bis (mercaptomethyl) benzene represented by the chemical formula (3) are referred to as m-xylenedithiol and p-xylenedithiol by Yodo Chemical Co., Ltd., respectively. Sold under the trade name.

The base catalyst includes Na ₂ CO ₃ and K ₂ CO ₃
Alkali metal carbonates such as CaCO ₃ and MgCO ₃ , and alkali metal alkoxides are suitable. Further, as the solvent for the above reaction,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone and ethers such as tetrahydrofuran and dioxane are suitable.

[0030]

The present invention will be described in more detail with reference to the following examples.

Example 1 In Example 1, the chemical formula (1)
An example of producing 1,3-bis (vinylbenzylthiomethyl) benzene among the bis (mercaptomethyl) benzene derivatives represented by the following formula will be described.

The above-mentioned CMS-P (50% meta-form, 50% para-form chloromethylstyrene) 30.5 g (0.20 g)
Mol) and 17.0 g of the above-mentioned m-xylenedithiol
(0.10 mol) and 27.6 g (0.2
0 mol) and 300 ml of methyl isobutyl ketone,
The sample was collected in a flask having a capacity of 1 liter, and reacted by continuing stirring under reflux for 6 hours. After completion of the reaction, 50 ml of 5% hydrochloric acid aqueous solution was gradually added to the obtained solution while stirring, and then 300 ml of toluene was further added. The solution thus obtained was repeatedly washed with distilled water until the pH reached 7. Next, after the solution after washing is dried with anhydrous sodium sulfate, the polymerization inhibitor p-
0.015 g of methoxyphenol (5 / 10,000 parts by weight based on CMS-P) was added, and the solvent was distilled off to obtain 38 g of a pale yellow transparent liquid. This liquid was measured by infrared spectroscopy (IR) and gel permeation chromatography (GPC).

FIG. 1 shows the measurement results of IR. As is apparent from FIG. 1, the absorption peak at 1630 cm ^-1 based on the vinyl group and the absorption peaks at 1510 cm ^-1 and 1580 cm based on the aromatic ring were observed.
Absorption peaks at ^-1 and 1600 cm ^-1 are seen. In GPC, neither raw materials nor by-products were detected. From the above, the liquid finally obtained is represented by the following chemical formulas (4a), (4b) and (4c) (hereinafter, these three chemical formulas may be collectively referred to as chemical formula (4)). 1,3-bis (vinylbenzylthiomethyl) benzene.

[0034]

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In this embodiment, among the bis (mercaptomethyl) benzene derivatives represented by the chemical formula (1),
Although an example in which 1,3-bis (vinylbenzylthiomethyl) benzene was prepared was described, 1,4-bis (vinylbenzylthiomethyl) benzene was prepared by using p-xylenedithiol instead of m-xylenedithiol. Can be similarly prepared. Further, by using CMS-14 instead of CMS-P, 1,3-bis (p-vinylbenzylthiomethyl) benzene can be produced in the same manner. By using p-xylenedithiol and CMS-14 instead of m-xylenedithiol and CMS-P, 1,4-bis (p-vinylbenzylthiomethyl) benzene can be produced in a similar manner.

Example 2 In Example 2, an example of manufacturing a capacitor using the bis (mercaptomethyl) benzene derivative of the present invention will be described.

FIG. 2 shows a manufacturing process of the capacitor in the second embodiment. Referring to FIG. 2A, first, the thickness 2
5 μm PET (polyethylene terephthalate) substrate 1
1 was prepared, and a lower electrode film 12 (thickness: 30 nm) made of aluminum was deposited on the PET substrate 11 at a deposition rate of 100 nm / sec.

Thereafter, a resin monomer was deposited on the lower electrode film 12 to form a thin film 13a (200 nm thick) made of the resin monomer (see FIG. 2B). Specifically, 1,3-bis (vinylbenzylthiomethyl) benzene represented by the chemical formula (4) of the present invention is charged into a container 32 as shown in FIG. The thin film 13 is heated at a position where a part of the lower electrode film 12 is exposed.
a was formed.

Thereafter, the accelerating electrons of -15 kV were applied to 50 μA.
By irradiating the thin film 13a at a density of / cm ² for 2 seconds, the resin monomer in the thin film 13a was polymerized to form the dielectric film 13 (see FIG. 2 (c)).

Thereafter, an upper electrode film 14 made of aluminum was deposited at a deposition rate of 100 nm / sec above the dielectric film 13 and at a position not in contact with the lower electrode film 12 (see FIG. 2D). . The capacitor 1 thus manufactured
0 was taken as working sample 1.

As comparative examples, capacitors using the resin monomers represented by the chemical formulas (A) and (B) were produced, and comparative samples 1 and 2 were obtained.

The characteristics of the above three types of capacitors were evaluated. Specifically, the moisture absorption capacity change rate,
The change rate of the high-temperature load capacity and the change of the element thickness when the element was immersed in warm water were examined (the details of the measurement method will be described later). Table 1 shows the evaluation results of the capacitors of Working Sample 1, Comparative Sample 1, and Comparative Sample 2.

[0043]

[Table 1]

As is evident from Table 1, the capacitor of the working sample 1 using the resin monomer of the chemical formula (4) of the present invention showed more excellent characteristics than the comparative sample in any of the evaluations. That is, by forming the dielectric film of the capacitor using the resin monomer comprising the bis (mercaptomethyl) benzene derivative of the present invention, a capacitor having excellent characteristics even under high humidity and high temperature can be obtained.

The dielectric loss tangent (tan δ) is also
The capacitors of working sample 1 are comparative samples 1 and 2
It exhibited better characteristics than the capacitors of No.

Hereinafter, the evaluation methods shown in Table 1 will be described in detail.

The rate of change in moisture absorption capacity was evaluated as follows. First, put the capacitor in a 105 ° C environment.
Dried time was measured initial capacitance C _11. The capacity was measured by applying a sine wave having a frequency of 1 kHz and a voltage of 1 Vrms to a capacitor. Thereafter, the temperature 60 ° C., allowed to stand for 100 hours a capacitor in an environment of humidity 95% Rh, after leaving capacity (capacity at moisture) C _12, was measured under the same conditions as the initial capacity. The rate of change of the moisture absorption capacity is (C ₁₂ −C ₁₁ ) / C ₁₁ × 10
This is a value represented by 0 (%). The smaller the absolute value of the rate of change in moisture absorption capacity, the higher the capacity stability in a humidity environment,
Preferred as a product. Therefore, it is particularly important that the absolute value of the rate of change in moisture absorption capacity be as small as possible.

The high-temperature load capacity change rate was evaluated as follows. First, the capacitor was dried at 105 ° C. for 10 hours, and the initial capacity C ₂₁ was measured. The capacity was measured by applying a sine wave having a frequency of 1 kHz and a voltage of 1 Vrms to a capacitor. After that, a DC voltage of 16 V was applied to the capacitor in an environment of a temperature of 105 ° C.
And left 000 hours, the capacity C ₂₂ after standing was measured under the same conditions as the initial capacity. The high temperature load capacity change rate is (C ₂₂ −
C ₂₁ ) / C ₂₁ × 100 (%). The smaller the absolute value of the rate of change of the high temperature load capacity is, the more difficult it is to oxidize at a high temperature, which is preferable as a product. In particular,
In recent years, high-temperature resistance of electronic components has become important as CPU speeds have increased, and the small absolute value of the high-temperature load capacity change rate is an important index for capacitor evaluation.

The change in thickness when immersed in warm water was evaluated as follows. First, the thickness of the capacitor was measured. Next, the capacitor was immersed in hot water of 90 ° C. for 3.5 hours, and then the capacitor was taken out of the hot water and the thickness was measured again. Then, the thickness before immersion in hot water and the thickness after immersion were compared. The greater the change in the thickness, the more the dielectric film absorbs moisture, indicating that the adhesion to the metal electrode film is reduced. Therefore, the smaller the change in thickness, the higher the adhesion between the dielectric film and the electrode film, which is preferable as a product.

The dielectric loss tangent (tan δ) is
A sine wave having a frequency of 1 kHz and a voltage of 1 Vrms was applied to a capacitor and measured. The smaller the dielectric loss tangent, the smaller the power consumed by the capacitor itself, which is preferable as a product.

Although the embodiments of the present invention have been described with reference to the examples, the present invention is not limited to the above embodiments, but can be applied to other embodiments based on the technical idea of the present invention. .

[0052]

As described above, the present invention provides a novel bis (mercaptomethyl) represented by the above chemical formula (1).
Provide a benzene derivative. The bis (mercaptomethyl) benzene derivative of the present invention is useful for electronic components, particularly, for example, capacitors, coils, resistors, and capacitive batteries. By forming a dielectric film using the bis (mercaptomethyl) benzene derivative of the present invention and using it for an electronic component, an electronic component having excellent characteristics even under high humidity and high temperature can be obtained.

The bis (mercaptomethyl) of the present invention
According to the method for producing a benzene derivative, the chemical formula (1)
A bis (mercaptomethyl) benzene derivative represented by the following formula can be easily produced.

[Brief description of the drawings]

FIG. 1 is a diagram showing an IR spectrum of an example of the bis (mercaptomethyl) benzene derivative of the present invention.

FIG. 2 is a diagram illustrating an example of a manufacturing process in the case of manufacturing a capacitor using the bis (mercaptomethyl) benzene derivative of the present invention.

FIG. 3 is a view showing one step of the manufacturing process shown in FIG. 2;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Capacitor (electronic component) 11 PET board 12 Lower electrode film 13 Dielectric film 13a Thin film 14 Upper electrode film

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kazuyoshi Honda 1006 Kazuma Kadoma, Osaka Pref.Matsushita Electric Industrial Co., Ltd. 72) Inventor Hisaaki Tatehara 1006 Kazuma Kadoma, Kadoma City, Osaka Prefecture F-term (reference) 4H006 AA01 AA02 AB46 AC63 BA02 BA32 TA04 TB72 4H039 CA61 CD10 CD20 4J100 AB15P BA51P BC43P CA01 DA55 JA43

Claims (3)

[Claims] 1. A bis (mercaptomethyl) benzene derivative represented by the following chemical formula (1). Embedded image (In the formula (1), the positions where the three benzene rings are substituted are each independently the meta position or the para position) 2. At least one selected from m-chloromethylstyrene and p-chloromethylstyrene represented by the following chemical formula (2) and m-bis (mercaptomethyl) represented by the following chemical formula (3) Benzene and p-
A bis (mercaptomethyl) benzene derivative represented by the following chemical formula (1) by reacting at least one selected from bis (mercaptomethyl) benzene: bis (mercaptomethyl) ) A method for producing a benzene derivative. Embedded image Embedded image Embedded image (In the formula (1), the positions where the three benzene rings are substituted are each independently the meta position or the para position) 3. The method for producing a bis (mercaptomethyl) benzene derivative according to claim 2, wherein the reaction is performed in the presence of an alkali metal carbonate as a base catalyst.