JPH11140626A - Forming method of triazine dithiol derivative film and polymerizing method of film component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve performances such as contamination-free property, nonadhesive property, release property, antifog property, lubricating property, adhesion property, coating property and antifreeze property of a solid surface by forming a specified triazine dithiol deriv. thin film on a solid surface such as a metal by vapor deposition or sputtering. SOLUTION: A thin film of a triazine dithiol deriv. expressed by the formula is formed by vapor deposition or sputtering on the surface of a solid such as metals, ceramics such as glass and plastics. Or, if necessary, two or more kinds of the derivs. are deposited stepwise in layers. In the formula, R1 , R2 are H, CH3 , CH2 =CHCH2 , C6 H11 , CH2 =CH(CH2 )4 COOCH2 CH2 , CF3 C6 H4 , C6 F11 OC6 H4 , C4 F9 CH2 CH(OH)CH2 , CH2 =CH(CH2 )4 COO(CH2 CH2 )2 or the like, M is H or alkali metals. This low mol.wt. thin film of a triazine dithiol deriv. is subjected to thermal polymn., irradiation of UV rays, electrolytic polymn. or the like to polymerize or copolymerize to be converted into a polymer thin film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for forming a film of a triazinedithiol derivative on a solid surface by a vacuum evaporation method or a sputtering method, and a method for polymerizing the film component.

[0002]

BACKGROUND OF THE INVENTION The present inventors have previously synthesized a triazinethiol derivative as used in the present invention, and have a function comprising the polymer by immersion, electrolytic polymerization and tribopolymerization on a metal surface. Although it succeeded in producing a functional thin film, [Practical surface treatment technology: 35, 595 (198)
8), Chemical Industry: 42, 1005 (1991), JP-A-6-322595, etc.], all of which are thin film generation techniques by a wet method, and there is a limit to the wastewater treatment and the type of solid to be processed. there were.

[0003]

SUMMARY OF THE INVENTION The present invention effectively forms a triazinedithiol-based thin film not only on a metal surface but also on a solid surface such as ceramics such as glass or plastics, so that such a solid surface is not contaminated. The purpose of the present invention is to improve the performance such as adhesiveness, non-adhesiveness, releasability, anti-fogging property, lubricity, adhesiveness, paintability and anti-icing property.

[0004]

Here, the present inventors have made the general formula

[0005]

Embedded image

[Wherein R ₁ and R ₂ are H, CH ₃ , C ₂ H
_{5, C 4 H 9, C} 6 H 13, C 8 H 17, C 10 H 21, C 12 H
_{25, C 18 H 37, C} 20 H 41, C 22 H 45, C 24 H 49, CH 2
ＣＨCHCH ₂ , CH ₂ ＣＨCH (CH ₂ ) ₈ , CH ₂ ＣC
H (CH ₂ ) ₉ , C ₈ H ₁₇ CH ₂ ＣＨCHC ₈ H ₁₆ , C _{6
H 11, C 6 H 5,} C 6 H 5 CH 2, C 6 H 5 CH 2 CH
₂ , CH ₂ ＣＨCH (CH ₂ ) ₄ COOCH ₂ CH ₂ , C
H ₂ ＣＨCH (CH ₂ ) ₈ COOCH ₂ CH ₂ , CH ₂
CH (CH ₂ ) ₉ COOCH ₂ CH ₂ , CF ₃ C
₆ H ₄ , C ₄ F ₉ C ₆ H ₄ , C ₆ F ₁₃ C ₆ H ₄ , C ₈ F
₁₇ C ₆ H ₄ , C ₁₀ F ₂₁ C ₆ H ₄ , C ₆ F ₁₁ OC ₆ H ₄ ,
C ₉ F ₁₇ OC ₆ H ₄ , C ₄ F ₉ CH ₂ , C ₆ F ₁₃ C
H ₂ , C ₈ F ₁₇ CH ₂ , C ₁₀ F ₂₁ CH ₂ , C ₄ FCH ₂
CH ₂ , C ₆ F ₁₃ CH ₂ CH ₂ , C ₈ F ₁ CH ₂ C
_{H 2, C 10 F 21 CH} 2 CH 2, C 4 F 9 CH 2 = CHC
H ₂ , C ₆ F ₁₃ CH ₂ ＣＨCHCH ₂ , C ₈ F ₁ CH ₂ =
CHCH ₂ , C ₁₀ F ₂₁ CH ₂ ＣＨCHCH ₂ , C ₄ F ₉ C
H ₂ CH (OH) CH ₂ , C ₆ F ₁₃ CH ₂ CH (OH)
CH ₂ , C ₈ F ₁ CH ₂ CH (OH) CH ₂ , C ₁₀ F ₂₁
CH ₂ CH (OH) CH ₂ , CH ₂ ＣＨCH (CH ₂ ) ₄
COO (CH ₂ CH ₂ ) ₂ , CH ₂ ＣＨCH (CH ₂ ) ₈
COO (CH ₂ CH ₂ ) ₂ , CH ₂ ＣＨCH (CH ₂ ) ₉
COO (CH ₂ CH ₂ ) ₂ , C ₄ F ₉ COO (CH ₂ C
H ₂ ) ₂ , C ₆ F ₁₃ COO (CH ₂ CH ₂ ) ₂ , C ₈ F
₁₇ COO (CH ₂ CH ₂ ) ₂ , C ₁₀ F ₂₁ COO (CH ₂
CH ₂ ) ₂ , where R ₂ is C ₆ F ₁₁ OC ₆ H
₄ and does not include C ₉ F ₁₇ OC ₆ H ₄ . M represents H and an alkali metal such as Li, Na, K, and Ce. ] It has been found that a thin film of each layer composed of one or more of the triazinedithiol derivatives represented by the formula (1) is formed on a solid surface by vapor deposition or sputtering. They have found a method of homo- or copolymerizing the components of the derivative coating by any one of thermal polymerization, ultraviolet irradiation and electrolytic polymerization.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A functional triazinedithiol derivative can be synthesized by the method described above. Using these, a low molecular weight thin film is formed on the solid surface by a vacuum deposition method or a sputtering method, and further, a linear or three-dimensional polymerization reaction is caused in the presence of oxygen and under heat or ultraviolet irradiation to obtain a high molecular weight thin film. Change to molecular thin film.

[Solid Surface] Solid surfaces include iron, cast iron, stainless steel, permalloy, copper, brass, phosphor bronze, nickel, cupronickel, tin, lead, cobalt, solder,
Metal surfaces such as titanium, aluminum, chromium, gold, silver, platinum, palladium, zinc and their oxide surfaces, phosphate treated metal surfaces, chromate treated metal surfaces, silicon surfaces, carbon surfaces, compound semiconductors Surface, alumina oxide ceramic surface, pottery surface, glass surface, quartz glass surface, superconductor ceramic surface, wood surface, paper surface,
Anything is possible, such as plastics surface, engineering plastics surface, thermosetting resin surface.

[Vacuum Vapor Deposition Method] An apparatus used for the vacuum vapor deposition method is, for example, a box containing a triazinedithiol derivative as a monomer-4 as shown in FIG. 1 and a heater.
1, a solid film to be deposited and a film thickness meter 2 for measuring the thickness of the deposited film, to which a vacuum pump (not shown) is connected. The vacuum deposition method is a process in which a substance to be formed into a thin film is heated and evaporated in a vacuum, and the thin film is attached to a certain surface. Therefore, the basic equipment required for this method is a vacuum device, a heating device (evaporation source) and an adhesion surface (substrate surface).
It is. After adjusting the inside of the apparatus to a certain degree of vacuum using an ionization vacuum gauge, the heater-1 of the evaporation source is heated to vaporize the monomer-4. At this time, the shutter 5 between the evaporation source and the substrate 3 is closed. If it is confirmed by the crystal oscillator film thickness meter 2 that the monomer-4 is vaporized, the evaporation rate is adjusted to a predetermined value, and when it is set, the shutter 5 is opened to start evaporation. When the desired film thickness is reached, the shutter 5 is closed and the heating of the evaporation source is stopped. Then, when the heater-1 is sufficiently cooled, air venting is performed, and the substrate 3 is taken out. The degree of vacuum is generally 1.0 to 1.0
× 10 ^-6 [Pa], desirably 1.0 × 10 ^-1 to 1.
It is 0 × 10 ⁻⁴ [Pa]. The temperature of the heater-1 is from room temperature to 250 ° C., preferably 50 to 200 ° C., but the molecular weight and the degree of vacuum of triazinedithiol and the heat
The optimum deposition conditions are determined in consideration of the temperature and cannot be uniquely determined. Generally, it is necessary to deposit at a low speed in order to form a dense film. The film growth rate increases as the degree of vacuum increases, as the heater temperature increases, and as the molecular weight and cohesive force decrease. The film growth rate and the film density can be determined according to the purpose.

[Sputtering method] The sputtering method refers to, for example, a sputtering apparatus (RE RMC shown in FIG. 2).
-Eiko Corp. ) Is to form a triazinedithiol thin film on a solid surface under vacuum.
The sputtering apparatus comprises a vacuum pump (not shown), a target 6 (cathode) and a substrate 3 on a sample stage 7 (anode). An organic solvent, such as triazinedithiol and ethanol, is mixed and held on target 6 at the appropriate fluidity. At room temperature, the solvent is evaporated by spontaneous evaporation to form the target 6 of triazinedithiol. 10 ^-1 ~
Under a vacuum of 1.0 × 10 ⁻³ [Torr], desirably 5 ×
DC current of 0.1 m at 10 ^{-1 to} 5 × 10 ^-2 [Torr]
A to 10 mA is applied. Discharge occurs at this time,
The molecules of the target 6 fly and are stacked on the substrate 3. In order to adjust the target temperature of the cathode, cooling water can be supplied to the target 6. The lower the molecular weight and cohesion of triazinedithiol, the higher the current value, the higher the film growth rate. If the current value is too high, decomposition of triazinedithiol occurs, and uniform film growth does not occur.

[Polymerization of triazinedithiol film component]
The components of the triazinedithiol film formed by a vacuum deposition method or a sputtering method can be changed to a linear or three-dimensional polymer film by a thermal polymerization method, an ultraviolet irradiation method, or an electrolytic polymerization method.

[Thermal polymerization method] The thermal polymerization method is generally carried out by heating a solid having a triazinedithiol derivative laminated thereon in the air or oxygen. Heating temperature is 5
0 ° C to 250 ° C. If the temperature is lower than 50 ° C., the polymerization is not carried out, or the polymerization takes too much time, which is not practical.
At 250 ° C. or higher, the triazinedithiol derivative may scatter or decompose to form no desired polymer film. Desirably, it is 80 ° C to 200 ° C. The heating time is from 1 second to 120 minutes. If the time is less than 1 second, the polymerization is insufficient, and if it is more than 120 minutes, there is a problem that the productivity is practically inferior. Desirably, it is 5 minutes to 60 minutes. The polymerization is generally carried out in air, but when polymerization is difficult, it is carried out in oxygen. When it is difficult to polymerize and it is easy to volatilize, polymerization in pressurized oxygen is also effective. Also,
Since a fluorine compound is easily volatilized, thermal polymerization may be carried out when the polymerization is performed under air pressure or oxygen pressure during polymerization. At this time, the pressure needs to be 1 atm or more of the atmospheric pressure, but there is also a problem with the pressure resistance of the container.

[Ultraviolet irradiation method] Ultraviolet polymerization is carried out in air on a solid surface on which a triazinedithiol derivative is laminated.
Irradiation with light having a wavelength of 00 nm to 450 nm is performed at a relatively high speed. Atmosphere temperature is 0 ° C ~ 100 ° C
It is. At 0 ° C or lower, the polymerization rate is too slow to be practical, and at 100 ° C or higher, side reactions such as decomposition occur simultaneously. Desirably, it is 20 ° C to 60 ° C. The irradiation time is 0.01 seconds to 60 minutes. If it is less than 0.01 second, the polymerization is insufficient, and if it is more than 60 minutes, the polymerization rate is too slow to be practical. As a light source, a xenon lamp or a mercury lamp can be used.

[Electropolymerization Method] The electropolymerization method is disclosed in Japanese Patent No. 1,840,482 by the present inventors.
Water or an organic solution of the derivative is treated with a metal as an anode, a platinum or stainless steel plate as a cathode, a cyclic method, a galvanostatic method, a galvanostatic method, a pulse galvanostatic method, and a pulse galvanostatic method. Method).
In this method, a three-dimensional perfluoro group-containing triazinedithiol polymer film is formed on a metal or conductor surface. The metal referred to herein may be any conductive metal, such as iron and iron alloys (stainless steel, permalloy, etc.), copper and copper alloys, nickel, gold, silver, platinum, platinum, cobalt, aluminum, zinc , Lead, tin and tin alloys, titanium, chromium, and the like.
The conductor is a conductive film, ITO, carbon, conductive rubber, an organic conductor, or the like. The electrolyte may be anything as long as it is dissolved in a solvent, exhibits electrical conductivity, and is stable.
aOH, Na ₂ CO ₃ , Na ₂ SO ₄ , K ₂ SO ₃ , N
a ₂ SO ₃ , K ₂ CO ₃ , NaNO ₂ , KNO ₂ , Na
NO ₃ , NaClO ₄ , CH ₃ COONa, Na ₂ B ₂
O _7, NaH ₂ PO ₂ , (NaPO ₃ ) ₆ , Na ₂ Mo
O ₄ , Na ₃ SiO _{3 and the} like can be mentioned. These concentrations are generally between 0.001M and 1M, preferably 0.01M.
It is in the range of 1M to 0.1M. It is desirable that the solvent simultaneously dissolves the electrolyte and the perfluoro group-containing triazinedithiol derivative, and the combination thereof cannot be limited. Therefore, the solvent cannot be specified. For example, water, methanol, ethanol, and carbitol , Cellsolve, dimethylformamide, methylpyrrolidone, acrylonitrile, ethylene carbonate and the like. The concentration of the triazinedithiol derivative containing an unsaturated group and a perfluoro group is 0.01 mmol / L to 100 mmol / L, preferably 0.1 mmol / L to 10 mmol / L. The temperature of the electrolytic solution cannot be uniquely specified because it is related to the freezing point and boiling point of the solvent.
C, preferably 20 ° C to 80 ° C. The counter electrode (cathode) material may be any material as long as it does not react with the electrolytic solution or has a remarkably low conductivity. In general, a non-conductive material such as stainless steel, platinum, and carbon is used.

[Cyclic method] The cyclic method is performed in a range where the potential width does not decompose the solvent. This range cannot be uniquely limited because it is affected by the type of the solvent and the electrolyte.

[Constant potential method, constant current method, pulse method] The constant potential method is -0.5 to 2 V vs CES, preferably in the range of natural potential to oxidation potential. If the potential is lower than the natural potential, no polymerization occurs. If the potential is higher than the oxidation potential, there is a risk that the solvent may be decomposed. The current density is 0.005 to 50 m in the constant current method.
A / cm ² , preferably 0.05 to 5 mA / cm ² is suitable. If it is less than 0.05 mA / cm ² , it takes too much time for the film to grow. On the other hand, if it is larger than 5 mA / cm ² , cracks are formed in the coating and metal elution is observed, which is not preferable. The electrolytic potential and the electrolytic current density in the pulse method are the same as those in the above-mentioned constant potential method and constant current method, respectively, but the time width is 0.01 to 10 minutes, preferably 0.1 to 2 minutes. Even if shorter than 0.1 minute,
If the time is longer than 2 minutes, the effect of the pulse method cannot be sufficiently exhibited. If foreign matter such as organic matter is attached to the metal, it must be removed as a pretreatment, but there is no problem with oxides and the like as long as the surface conductivity is not significantly reduced. Of course, the same applies to the activation processing and the like. Each of the above ranges is only a guide, and it goes without saying that each of the condition factors and the combination thereof will change.

[0017]

The present invention will be described more specifically with reference to the following examples. [Examples 1 to 12, Method of Forming Coating] U shown in FIG.
Using a vacuum deposition apparatus manufactured by LBAC, a triazinedithiol derivative is put in a box, and a stainless plate (0.2 × 3 ×
5 cm, degreased with acetone). When the vacuum pump was turned on and the degree of vacuum reached 10 ⁻² Pa by the ionization vacuum gauge, the heater temperature of the evaporation source was increased to 110 ° C. to 160 ° C., and the deposition rate and film thickness were measured. .

A sputtering apparatus (R) shown in FIG.
E RMC-Eiko Corp. ) To form a triazinedithiol coating on the surface of a stainless steel plate (0.2 × 3 × 5 cm, degreased with acetone) under vacuum. The triazinedithiol and ethanol are mixed in a volume ratio of 1/1 and are kept on the target at the appropriate fluidity. At room temperature, the solvent is allowed to evaporate by spontaneous evaporation to form the triazinedithiol target. 5.0 × 10 ^-2 at room temperature
When a vacuum of [Torr] is maintained and a DC current of 5 Ma is applied, discharge occurs, and the target triazinedithiol molecule jumps and is laminated on the substrate. In order to adjust the target temperature of the cathode, this is performed while cooling water is flowing through the target. In each case, the film thickness 10 minutes after the start of film growth was measured by a spectroscopic ellipsometer [M-150i type manufactured by JASCO Corporation].

As shown in Table 1, it was found that a triazinedithiol film was formed on stainless steel by both the vacuum deposition method and the sputtering method. Due to the lowest sublimation temperature, the rate of film formation is 60 °
/ Min, but the generation rate can be increased by increasing the sublimation temperature.

[0020]

[Table 1]

Examples 13 to 15, Method of Thermal Polymerization of Coating Component 6-dibutylamino-triazinedithiol
1,3,5-triazine-2,4-dithiol (Table 1,
No. 3) was vacuum-deposited on a steel plate (0.2 × 3 × 5 cm, degreased with acetone) under the conditions shown in Table 1 to form films having different thicknesses. This is heated in air to polymerize it, the insolubility in alcohol, ie, the polymerization rate (W), and the number average molecular weight (Mn) of the polymer obtained by immersing the heat-polymerized plate in THF (tetrahydrofuran) ) For gel permeer
It was measured by traction chromatography (GPC).
Table 2 shows the results. This shows that the polymerization rate and the number average molecular weight decrease as the thickness of the coating increases, and the polymerization rate and the number average molecular weight increase as the polymerization temperature increases.

[0022]

[Table 2]

Examples 16 to 20, Method for Photopolymerization of Coating Component 6-Diallylamino- as triazinedithiol
1,3,5-triazine-2,4-dithiol (Table 1,
No. 1,2), 6-didecenylcarboxyethylamino-1,3,5-triazine-2,4-dithiol (Table 1, No. 5), and allyldecyl perfluoroethylamino-1,3,5 -Triazine-2,4-dithiol (Table 1, Nos. 11 and 13) was placed on a quartz plate (0.2 × 3 × 5).
cm, degreased with acetone) under vacuum conditions or sputtering under the conditions shown in Table 1 to form films having different thicknesses. The universal lamp house manufactured by Wacom Seisakusho (HX-500)
Using W), place the sample 30 cm from the light source,
Photopolymerization was performed at 20 ° C., and the insolubility in THF, that is, the three-dimensional conversion (G) was measured. Table 3 shows the results.

According to this, the shorter the length of the substituent, the more the polymerization tends to occur. In particular, when the coating has crystallinity or anisotropy, it is presumed that the polymerization rate is reduced. The data in Table 3 is for the case of photopolymerization at 20 ° C. When the polymerization temperature is set to 40 ° C, the polymerization rate (Table 3)
(Indicated by curly braces) rise significantly.

[0025]

[Table 3]

Examples 21 to 22, Method of Copolymerizing Coating Components First, 6-diallylamino-1,3,5-triazinedithiol was applied to an aluminum plate (0.2 × 3 × 5 cm, degreased with acetone). Triazine-2,4-dithiol film 250 ° followed by 6-dibutylamino-1,3,5-
A triazine-2,4-dithiol film 250 DEG is deposited to form a two-layer film (DA / DB film) and 6-dibutylamino-
1,3,5-triazine-2,4-dithiol film 250
{Next, a 6-diallylamino-1,3,5-triazine-2,4-dithiol film 250} was deposited to form two-layer films (DB / DA films). In the air,
By heating at 160 ° C., the polymerization rate (alcohol insolubility rate) and the three-dimensional conversion rate (THF insolubility rate) were determined, and the copolymerizability was examined.
Table 4 shows the results. The polymerization rate is 2 in alcohol at 20 ° C.
After immersing for 4 hours and drying, the three-dimensional conversion rate is 20 ° in THF.
After immersion in C for 24 hours and drying, the film thickness was measured by an ellipsometer to obtain each value.

[0027]

[Table 4]

The conversion indicates the degree of polymerization of the mixture of DA and DB. The three-dimensional ratio is a measure of whether DA and DB are copolymerized. DA / DB film and D
The polymerization rate and the three-dimensional conversion rate of the B / DA film increased with time, indicating that the B / DA film was polymerized. In this case, it can be seen that the copolymerizability is higher when the unsaturated group is formed in the upper layer.

Examples 23 and 24, Method for Electropolymerizing Coating Components As shown in Table 1, a triazinedithiol derivative was vacuum deposited or sputtered at 2000 ° to form a thin film of triazinedithiol on both surfaces of a metal. The generated sample was created. Next, using a 0.3 M aqueous solution of NaNO ₂ as an electrolytic solution, platinum (reference electrode) as a cathode and the above-mentioned sample as an anode (working electrode) were subjected to electrolytic polymerization at a current density of 0.1 mA / cm ² at 40 ° C. For 20 minutes. The polymerization rate, number average molecular weight, and three-dimensional conversion rate were measured as described above. Table 5 shows the results.

[0030]

[Table 5]

As described above, the components of the triazinedithiol thin film on the surface of the conductor can also be polymerized by electrolytic polymerization, and this method makes it possible to contaminate the bathtub and increase the cost of conventional electrolytic polymerization. Loss of the monomer can be prevented.

[0032]

According to the present invention, a thin film can be formed on a solid surface by using a vacuum deposition method or a sputtering method on a triazinedithiol derivative, and the components of the thin film are thermally, ultraviolet and electrochemically. Polymerization can be performed using energy. This is attracting attention as a new method for imparting functions to solid surfaces by a dry system. That is, the coating thus obtained has corrosion resistance,
Various products that require lubricity, non-staining, adhesion, adhesion, non-adhesion, anti-fogging and anti-icing properties, water repellency, etc.,
For example, connector materials, metal gears, decorative metal products,
It can be applied to metal mirrors, metal molds, hard desks, magnetic tapes, clock hands, metal tableware and the like. Furthermore, this coating is selected by selecting the type of triazinedithiol.
It can be changed from low free energy to high free energy surface, and is also effective for surface modification of ceramics such as plastics and window glass.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a vacuum evaporation apparatus.

FIG. 2 is an explanatory view of a sputtering apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Heater 2 Film thickness gauge 3 Substrate 4 Monomer 5 Shutter 6 Target 7 Sample stand

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 21, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

[Correction contents]

[0005]

Embedded image

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Kunio Mori, Inventor 3- 3-16 Takamatsu, Morioka-shi, Iwate Prefecture

Claims (4)

[Claims] 1. A compound of the general formula [Wherein R ₁ and R ₂ are H, CH ₃ , C ₂ H ₅ , C
_{4 H 9, C 6 H 13} , C 8 H 17, C 10 H 21, C 12 H 25, C
_{18 H 37, C 20 H 41} , C 22 H 45, C 24 H 49, CH 2 = CH
CH ₂ , CH ₂ ＣＨCH (CH ₂ ) ₈ , CH ₂ ＣＨCH (C
H ₂ ) ₉ , C ₈ H ₁₇ CH ₂ ＣＨCHC ₈ H ₁₆ , C ₆ H ₁₁ ,
C ₆ H ₅ , C ₆ H ₅ CH ₂ , C ₆ H ₅ CH ₂ CH ₂ , C
_{H 2 = CH (CH 2)} 4 COOCH 2 CH 2, CH 2 =
CH (CH ₂ ) ₈ COOCH ₂ CH ₂ , CH ₂ ＣＨCH
(CH ₂ ) ₉ COOCH ₂ CH ₂ , CF ₃ C ₆ H ₄ , C
_{4 F 9 C 6 H 4,} C 6 F 13 C 6 H 4, C 8 F 17 C
₆ H ₄ , C ₁₀ F ₂₁ C ₆ H ₄ , C ₆ F ₁₁ OC ₆ H ₄ , C ₉
F ₁₇ OC ₆ H ₄ , C ₄ F ₉ CH ₂ , C ₆ F ₁₃ CH ₂ , C
₈ F ₁₇ CH ₂ , C ₁₀ F ₂₁ CH ₂ , C ₄ FCH ₂ CH ₂ ,
C ₆ F ₁₃ CH ₂ CH ₂ , C ₈ F ₁ CH ₂ CH ₂ , C ₁₀ F
₂₁ CH ₂ CH ₂ , C ₄ F ₉ CH ₂ ＣＨCHCH ₂ , C ₆ F
₁₃ CH ₂ ＣＨCHCH ₂ , C ₈ F ₁ CH ₂ ＣＨCHCH ₂ ,
C ₁₀ F ₂₁ CH ₂ ＣＨCHCH ₂ , C ₄ F ₉ CH ₂ CH (O
_{H) CH 2, C 6 F} 13 CH 2 CH (OH) CH 2, C 8
F ₁ CH ₂ CH (OH) CH ₂ , C ₁₀ F ₂₁ CH ₂ CH
(OH) CH ₂ , CH ₂ ＣＨCH (CH ₂ ) ₄ COO (C
H ₂ CH ₂ ) ₂ , CH ₂ ＣＨCH (CH ₂ ) ₈ COO (C
H ₂ CH ₂ ) ₂ , CH ₂ ＣＨCH (CH ₂ ) ₉ COO (C
_{H 2 CH 2) 2, C} 4 F 9 COO (CH 2 CH 2) 2,
C ₆ F ₁₃ COO (CH ₂ CH ₂ ) ₂ , C ₈ F ₁₇ COO
(CH ₂ CH ₂ ) ₂ , C ₁₀ F ₂₁ COO (CH ₂ CH ₂ )
_{2 wherein} R ₂ is C ₆ F ₁₁ OC ₆ H ₄ and C ₉
It does not include the F ₁₇ OC ₆ H _4. M represents H and an alkali metal. A method for forming a film of a triazinedithiol derivative, comprising forming a thin film of the triazinedithiol derivative represented by the formula (1) on a solid surface by vapor deposition or sputtering. 2. A film formation of a triazinedithiol derivative, wherein a thin film of each layer comprising at least two of the triazinedithiol derivatives according to claim 1 is formed stepwise on a solid surface by vapor deposition or sputtering. Method. 3. A polymerization of a triazinedithiol derivative coating component, which comprises polymerizing the component of the triazinedithiol derivative coating film formed according to claim 1 by any of a thermal polymerization method, an ultraviolet irradiation method and an electrolytic polymerization method. Method. 4. A triazinedithiol derivative coating component formed by copolymerizing the components of the triazinedithiol derivative coating film produced according to claim 2 by any of a thermal polymerization method, an ultraviolet irradiation method and an electrolytic polymerization method. Copolymerization method.