JP3369092B2 - Triazine dithiol derivative and surface treatment method of object using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention particularly relates to a triazinedithiol derivative containing a perfluoro group and a method for surface treating an object using the same.

[0002]

2. Description of the Related Art Conventionally, some triazinedithiol derivatives have already been industrially produced, and crosslinkers,
It is used as an adhesion promoter, surface treatment agent, heavy metal treatment agent and rust preventive agent. In particular, the 6-position substituent is -S
_{H, -N (C 4 H 9} ) 2, -NHC 6 H 5 , and metal salts thereof are known as a surface treating agent of the metal and is partially practically used [e.g., Kunio Mori: practical surface treatment technology, 35,
595 (1988), Chemical Industry: 42,1005 (19
91) Posted].

[0003]

By the way, in this conventional triazinedithiol derivative, in the surface treatment of a metal using this, for example, as a substance, the film on the solid surface has a large surface free energy, so that the adhesiveness However, there is room for improvement in performance such as surface non-staining property, non-adhesiveness, cloudiness, lubricity, and anti-icing property. Therefore, as a result of continuing research to improve these properties, it was found that a certain type of perfluoroanilino group-containing triazinedithiol derivative can be used to impart these characteristics to a solid surface by electrolytic polymerization treatment. It was

However, since the triazine ring of this compound is linked by an aromatic anilino group, it has a strong cohesive force and is an electron-withdrawing group, so the solubility and reactivity of the thiol group are low and the critical micelle concentration ( There are two important problems as a surface treatment agent, such as high surface activity).
Further, the triazinedithiol derivative containing a perfluoro group alone has been improved in this respect, but since the formed fluorine film is composed of a single molecule or a one-dimensional polymer, the bonding force between molecules is weak, and as a result, There was a problem with film strength and durability. The present invention has been made by further studies in view of such problems, and an object thereof is to provide a triazinedithiol derivative capable of strengthening the intermolecular binding force. It is another object of the present invention to provide a surface treatment method for an object, which uses a triazinedithiol derivative capable of strengthening the intermolecular binding force to enhance the film strength and improve the durability.

[0005]

In order to achieve such an object, the triazinedithiol derivative of the present invention has the formula

[0006]

[Chemical 3]

(However, in the formula, R ₁ is an alkyne (-CH =
CH-), a substituent containing an unsaturated group such as an alkene (-C≡C-), R ₂ is -CF _2- , -CH _2- , -CH _{2-.
CH 2 -, - CH 2 -CH} 2 -CH 2 -, - CH 2 -
_{(CH 2) 4 -CH 2 -} -C such _{m H 2m -, - CH 2} C
H = CH- -C such _{m H 2m-2 -, -} CH 2 CH (-O
H) -CH ₂ - and any one of, n, m denotes an integer of 1 to 18, M is typically H or L
Alkali such as i, Na, K and Ca. ) In the triazine dithiol derivative.

A feature of the present invention is that, in addition to containing a perfluoro group, it contains an unsaturated group such as an alkyne (-CH = CH-) and an alkene (-C≡C-). That is,
As shown in FIG. 1, a triazinedithiol derivative obtained in the development process and containing a perfluoro group alone, which does not contain an unsaturated group, can be modified into a single molecule or a one-dimensional polymer. weak. On the other hand, the triazinedithiol derivative according to the present invention (referred to as "unsaturated group- and perfluoro group-containing triazinedithiol derivative") contains an unsaturated group, as shown in FIG. by, in addition to binding at -SM group, will be able to bind the unsaturated group (R _1), therefore, it tends to make a three-dimensionally polymerized to network. As a result, in addition to excellent reactivity, solubility and surface activity, it is possible to create a three-dimensional film structure, which is non-staining, non-adhesive, cloud proof, lubricity, and anti-icing properties on the object surface. You will be able to add the performance of.

Various synthetic methods can be considered as the synthetic method of the triazinedithiol derivative according to the present invention. For example, the triazinedithiol derivative can be easily synthesized through the following three steps. An unsaturated group- and perfluoro group-containing amine is synthesized. An unsaturated group- and perfluoro group-containing triazine dichloride is synthesized from an unsaturated group- and perfluoro group-containing amine and cyanuric chloride. A triazinedithiol derivative containing an unsaturated group and a perfluoro group is synthesized.

The surface treatment method of an object using the triazinedithiol derivative of the present invention is a method of forming a film of the triazinedithiol derivative on the surface of the object using the triazinedithiol derivative represented by the above formula. Is. As a result, the film formed on the surface of the object can have a structure which is excellent in reactivity, solubility and surface activity and gives a three-dimensional film structure, so that the object surface is non-staining, non-adhesive, Performances such as cloud resistance, lubricity, and anti-icing properties can be imparted, the film strength can be increased, and the durability can be improved.

In the surface treatment method for an object using this triazinedithiol derivative, if necessary, the triazinedithiol derivative is dissolved in water or an organic solvent to prepare an immersion liquid, and the object is immersed in the immersion liquid. The coating of the triazinedithiol derivative is formed on the surface of the object (immersion treatment method). In this case, it is effective to perform thermal polymerization treatment or photopolymerization treatment on the film of the triazinedithiol derivative formed on the surface of the object. Thereby, it is possible to positively polymerize three-dimensionally to form a network structure.

Further, in the surface treatment method for an object using this triazinedithiol derivative, the object to be treated is a metal object, and the triazinedithiol derivative is dissolved or mixed in an aqueous or oil-based lubricating oil, if necessary. A lubricant obtained or obtained by using a triazinedithiol derivative alone is prepared, and the lubricant is brought into contact with the metal object during processing such as stretching, cutting, wire drawing, and forging of the metal object, The triazinedithiol derivative film is formed on the surface (tribopolymerization method). In this process, the metal instantly becomes highly mature and produces an active new surface during these processes,
It is believed that the release of exoelectrons produces a three-dimensional coating of triazinedithiol in the lubricant.

Furthermore, in the surface treatment method of an object using this triazinedithiol derivative, the object to be treated is a conductive object, and an electrolyte solution in which the triazinedithiol derivative is dissolved in water or an organic solution together with an electrolyte substance, if necessary. In the electrolytic cell containing the electrolytic solution, the conductive body as an anode, by an electrolytic method such as a cyclic method, a constant current method, a constant potential method, a pulse constant potential method and a pulse constant current method, The triazinedithiol derivative is polymerized to form a film of the triazinedithiol derivative on the surface of the conductive object (electrolytic polymerization method).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The triazinedithiol derivative according to the embodiment of the present invention (hereinafter referred to as "unsaturated group- and perfluoro group-containing triazinedithiol derivative") will be described in detail below. The unsaturated group- and perfluoro group-containing triazinedithiol derivative according to the embodiment is synthesized through the following three steps. An unsaturated group- and perfluoro group-containing amine is synthesized. An unsaturated group- and perfluoro group-containing triazine dichloride is synthesized from an unsaturated group- and perfluoro group-containing amine and cyanuric chloride. A triazinedithiol derivative containing an unsaturated group and a perfluoro group is synthesized. Each step will be described below.

Synthesis of unsaturated group- and perfluoro group-containing amine Representative synthetic reactions of unsaturated group and perfluoro group-containing amine are shown below. C _n F _{2n + 1} R ₂ OH + CH ₃ C ₆ H ₄ SO ₃ Cl + TEA → C _n F _{2n + 1} R ₂ OSO ₃ C ₆ H ₄ CH ₃ + NH ₂ R ₁ → C _n F _{2n + 1} R ₂ NHR ₁ raw material A perfluoro group-containing alcohol such as perfluoroethyl alcohol or perfluoroallyl alcohol is selected for the reaction, and this is reacted with p-toluenesulfone sun chloride in the presence of triethylamine (TEA) to obtain a perfluoro group-containing tosylate. This is reacted with an unsaturated group-containing amine such as allylamine to obtain an unsaturated group- and perfluoro group-containing amine.

Synthesis of unsaturated group- and perfluoro group-containing triazine dichloride It is synthesized from unsaturated group- and perfluoro group-containing amine and cyanuric chloride. The synthetic reaction formula is as follows.

[0017]

[Chemical 4]

(In the formula, R ₁ is an alkyne (-CH =
CH-), a substituent containing an unsaturated group such as an alkene (-C≡C-), R ₂ is -CF _2- , -CH _2- , -CH _{2-.
CH 2 -, - CH 2 -CH} 2 -CH 2 -, - CH 2 - (CH
₂ ) ₄ —CH ₂ — and the like —C _m H _2m —, —CH ₂ CH═C
H- -C such _{m H 2m-2 -, -} CH 2 CH (-OH) -C
Any one of H ₂ −, and n and m are 1 to 18
Means an integer up to. As for the unsaturated group- and perfluoro group-containing triazine dichloride, cyanuric chloride is dissolved in an organic solvent such as acetone, tetrahydrofuran, dioxane, and alcohols at 0 ° C. or lower, and a solution of the unsaturated group- and perfluoro group-containing amine is added dropwise. The temperature of the reaction solution rises at the same time as the dropping, and the progress of the reaction is confirmed, but the reaction temperature is maintained at 0 ° C to 5 ° C.
When the addition of the unsaturated group- and perfluoro group-containing amine is completed, the mixture is stirred for 60 minutes as it is, and then an aqueous Na ₂ CO ₃ solution is added dropwise. Similarly, since a rise in temperature was confirmed, the reaction temperature was kept at 0 ° C to 5 ° C, stirring and dropping were continued, and then the reaction mixture was poured into water or the solvent was distilled off and washed with water to obtain a crude mixture. A saturated and perfluoro group-containing triazine dichloride is obtained.

Synthesis of Triazinedithiol Derivative Containing Unsaturated Group and Perfluoro Group Finally, synthetic reaction of triazinedithiol derivative containing unsaturated group and perfluoro group is shown.

[0020]

[Chemical 5]

(In the formula, R ₁ is an alkyne (-CH =
CH-), a substituent containing an unsaturated group such as an alkene (-C≡C-), R ₂ is -CF _2- , -CH _2- , -CH _{2-.
CH 2 -, - CH 2 -CH} 2 -CH 2 -, - CH 2 -
_{(CH 2) 4 -CH 2 -} -C such _{m H 2m -, - CH 2} C
H = CH- -C such _{m H 2m-2 -, -} CH 2 CH (-O
H) -CH ₂ - and any one of, n, m denotes an integer of 1 to 18. ) When an unsaturated group- and perfluoro group-containing triazine dichloride is reacted with 3 mol of sodium hydrosulfide in alcohol or dimethylformamide, an unsaturated group- and perfluoro group-containing triazine dithiol derivative represented by the above formula is obtained.

Although the above formula is a typical thiolation method, the same compound can be reached by using sodium sulfide or alkali sulfide. In addition, an alkali metal carbamate or an xanthate alkali metal salt can also be used as an indirect thiolation method, and can reach the compound of the above formula through the reaction between the product and a secondary amine. The unsaturated group of R _{1 in} the formula is preferably present at the end of the chain,
The purpose can be achieved even in the middle of the chain. In particular, when an unsaturated group- and perfluoro group-containing triazinedithiol derivative is used for surface modification of an object utilizing the characteristics of fluorine, it is often advantageous that R ₁ is shorter than R ₂ . On the other hand, when using an unsaturated group- and perfluoro group-containing triazinedithiol derivative in a complexing reaction at the interface between an object that takes advantage of the characteristics of an unsaturated group and triazinedithiol and a fluoropolymer material or an olefin, Is R ₂ is R
Shorter than ₁ is often advantageous. A straight-chain or terminally branched perfluoro group is effective. Further, in the perfluoro group, —C _n F _{2n + 1} , n plays a role of exerting the characteristics of fluorine, and therefore it is effective from n = 1 to 16, but n = 4 to 10 is generally desirable. When n = 4 or less, the effect of fluorine is not sufficient, and when n = 11 or more, problems such as difficulty in dissolving raw materials in a solvent occur, and industrial production is difficult.

When M is H, the triazinedithiol containing an unsaturated group and a perfluoro group is dissolved in an organic solvent such as tetrahydrofuran, dimethylformamide, glycols, pyrrolidone, dimethylsulfoxide and ketones. . When both or one of M is Li, Na, K, and Ca, triazinedithiol containing an unsaturated group and a perfluoro group is dissolved and used in a mixed solvent of water and alcohols. Furthermore, M
Or both of them are ammonia, ethanolamines,
In the case of amines such as alkylamines, triazinedithiol containing unsaturated groups and perfluoro groups is used as a paste.

Next, the surface treatment method of an object using the triazinedithiol derivative according to the embodiment of the present invention will be described in detail. The surface treatment method of the object according to the embodiment uses an unsaturated group- and perfluoro group-containing triazinedithiol derivative, and is a so-called dipping treatment method, a so-called tribopolymerization method treatment method, and a so-called electrolytic polymerization treatment method. There is. By either method, a film composed of an unsaturated group- and perfluoro group-containing triazinedithiol derivative is formed on the surface of the object, and the surface of the object is non-staining, non-adhesive, cloud-preventing, lubricating, and anti-icing. Can be granted. Further, since the surface free energy can be lowered, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropene resin, perfluoroalkoxy resin, tetrafluoroethylene-ethylene copolymer resin, vinylidene fluoride resin, trifluoroethylene It is possible to bond and compound with fluorinated ethylene resin. Hereinafter, each method will be described.

Immersion Treatment Method In the immersion treatment method, metal products such as copper and copper alloys, nickel, iron, and aluminum as objects are immersed in water or an organic solution of a triazinedithiol derivative containing an unsaturated group and a perfluoro group for 0.1 minute to 120 minutes. Minutes, preferably 3 to 3 minutes
It is a method of forming a film by immersing it for 0 minutes. The concentration of the solution in this case is 0.001 wt% to 5 wt%, preferably 0.01 wt% to 1 wt%, but the optimum value changes depending on the type of metal, the immersion temperature, and the immersion time. Although the immersion temperature varies depending on the immersion concentration and the type of metal, it cannot be specified because it is primarily determined by the solvent used, but with water, it is generally possible to be 1 ° C to 99 ° C, preferably 20 ° C to 80 ° C. It is in the range of ° C. Although the dipping treatment method can uniformly form a film on a metal product having a complicated shape, since it is a monomer film as it is and may be weak in strength, it is changed to a three-dimensional polymer film by heating at 100 ° C or higher. It is possible to The dipping treatment method is particularly effective for the surface treatment of copper and copper alloys.

Tribo-Polymerization Treatment Method The tribo-polymerization treatment method is to prepare a lubricant obtained by dissolving or mixing the triazinedithiol derivative in a water-based and oil-based lubricating oil or a triazinedithiol derivative alone, and stretching a metal as an object. , Which causes the above-mentioned lubricant to come into contact with the metal during processing such as cutting, wire drawing, and forging, and forms a film of a triazinedithiol derivative on the surface of the metal at the same time as the processing by heat of the metal generated by the processing, exoelectrons, etc. is there. Any processing machine such as drawing, cutting, wire drawing, and forging may be used as long as it is normally used. It is considered that the metal momentarily matures and forms an active nascent surface in the course of these processings, and releases exo electrons, thereby forming a three-dimensional film of triazinedithiol in the lubricant. The concentration that dissolves or mixes in currently used lubricants is generally 0.0
01 wt% to 5 wt%, desirably 0.01 wt% to 1
It is in the range of wt%. Of course, when the unsaturated group- and perfluoro group-containing triazinedithiol derivative is difficult to dissolve in the lubricant, an appropriate method such as mixing and finely dispersing may be used.

Electrolytic Polymerization Method In the electrolytic polymerization method, an electrically conductive substance to be treated is used as an anode, or platinum or platinum is used in an aqueous or organic solution of an unsaturated group- and perfluoro group-containing triazinedithiol derivative containing an electrolyte substance as necessary. Containing a three-dimensional unsaturated group and perfluoro group on the surface of a conductive object by electrolytic method such as cyclic method, constant current method, constant potential method, pulse constant potential method and pulse constant current method using a stainless steel plate as a cathode It is a method of forming a film of a triazinedithiol polymer.

The conductive object mentioned here may be any conductive metal, such as iron and iron alloys (stainless steel, permalloy, etc.), copper and copper alloys, nickel, gold, silver, platinum, cobalt, aluminum, Examples thereof include zinc, lead, tin and tin alloys, titanium and chromium. In addition, the conductive object means a conductive film, ITO, carbon,
It may be conductive rubber, organic conductor, or the like. Any electrolyte substance may be used as long as it dissolves in a solvent, exhibits electrical conductivity, and is stable, but in general, NaOH, Na ₂ CO ₃ , Na ₂ S
O ₄ , K ₂ SO ₃ , Na ₂ SO ₃ , K ₂ CO ₃ , NaN
O ₂ , KNO ₂ , NaNO ₃ , NaClO ₄ , CH ₃ C
OONa, Na ₂ B ₂ O ₇ , NaBO ₃ , NaH ₂ PO
₂ , (NaPO ₃ ) ₆ , Na ₂ MnO ₄ , Na ₃ SiO
₃ etc. can be mentioned. These concentrations are generally
It is in the range of 0.001 to 1N, preferably 0.01 to 0.1N.

It is desirable that the solvent dissolves the electrolyte substance and the unsaturated group- and perfluoro group-containing triazinedithiol derivative at the same time, and the combination thereof cannot be limited.
Although the solvent cannot be specified, examples thereof include water, methanol, ethanol, carbitol, cellosolve, dimethylformamide, methylpyrrolidone, acrylonitrile, ethylene carbonite, and mixed solvents thereof, such as water-methanol and water-carbitol. You can
The concentration of the unsaturated group- and perfluoro group-containing triazinedithiol derivative is 0.01 mmol / L to 100 mmol /
L, preferably 0.1 mmol / L-10 mmol / L
Is. The temperature of the electrolytic solution cannot be uniquely specified because it is related to the freezing point and boiling point of the solvent.
˜99 ° C., preferably 20 ° C. to 80 ° C. The counter electrode (cathode) material may be anything as long as it does not react with the electrolytic solution or has extremely low conductivity, but generally an inert conductor such as stainless steel, platinum or carbon is used.

In the cyclic method, the potential range is set within the range where the solvent is not decomposed. This range cannot be uniquely limited because it is influenced by the type of solvent or electrolyte substance. The scanning speed is 0.001 to 100 mV / sec, preferably 0.01 to 50 mV / sec. 0.001
If it is mV / sec or less, the polymerization takes too long. Further, when it is 100 mV / sec or more, it is too fast, and it is difficult for polymerization to occur at an accurate polymerization potential. Constant potential method is -0.5 to 2
VVSCES, preferably in the range of spontaneous potential to oxidation potential. There is a risk that the polymerization will not occur at all below the natural potential, and the decomposition of the solvent may occur above the oxidation potential. The current density in the constant current method 0.00005~50mA / cm ^2, and preferably is 0.001~10mA / cm ² suitable. 0.
If it is less than 001 mA / cm ² , the film growth takes too long. On the other hand, if it is higher than 10 mA / cm ² , cracks may be generated in the film or metal may be eluted, which is not preferable. The electrolysis potential and electrolysis current density in the pulse method are as described above, but the time width is 0.01 to 10 minutes, preferably 0.1 to 2 minutes. The effect of the pulse method cannot be sufficiently exerted even if it is shorter or longer than 0.1 minutes.
In the pretreatment of metal, if foreign matter such as organic matter is attached, it must be removed, but oxides and the like are not a problem as long as the conductivity of the surface is not significantly reduced. Of course, the activation processing and the like are the same. Each of the above ranges is just a guideline, and it is natural that each condition factor and its combination will change if they change.

[0031]

EXAMPLES Next, examples will be described. [Example 1-1] Synthesis of unsaturated group- and perfluoro group-containing triazinedithiol derivative Synthesis of unsaturated group- and perfluoro group-containing amine Perfluoroethyl alcohol (0.5 mol) and triethylamine 55.7 g were charged in a three-necked flask (1000 ml).
(0.55 mol) and 300 ml of THF are added at 50 ° C.
Then, 104.9 g (0.55 mol) of p-toluenesulfonic acid chloride dissolved in 200 ml of THF is added dropwise over 1 hour. The mixture is gradually aged 24
Heat to reflux. After the reaction is complete, the reaction is cooled to room temperature and the by-product white triethylamine hydrochloride is removed by suction filtration.

The filtrate is transferred to an evaporator, THF is distilled off, and the reaction product is put into ice water to precipitate crystals. Unreacted p-toluenesulfonic acid chloride and triethylamine hydrochloride were washed and removed with ion-exchanged water, and white crystals were filtered off and dried under reduced pressure to obtain crude perfluoroethyl tosylate. This was recrystallized with hexane to obtain a purified perfluoroethyl tosylate in a yield of 79 to 94%. Allylamine 42.9 g (0.75 mol) and TH
Add 200 ml of F to a three-necked flask (500 ml) 60
The mixture was heated to 0 ° C., and perfluoroethyl tosylate (0.15 mol) dissolved in 150 ml of THF was added dropwise over 2 hours. The mixture is heated slowly and heated to reflux for 24 hours. After completion of the reaction, the reaction product was cooled to room temperature and THF was removed by an evaporator. Add NaHCO ₃ (0.3
mol) aqueous solution is added to liberate the amine and extracted with dichloromethane. It was washed with an aqueous NaHCO ₃ solution to remove the p-toluenesulfonic acid dissolved in the dichloromethane layer. The dichloromethane solution was dried over anhydrous sodium sulfate, and then dichloromethane was distilled off to obtain a pale yellow liquid. This was placed in a vacuum distillation apparatus and distilled to obtain an unsaturated group- and perfluoro group-containing amine. The results are shown in Fig. 2 (Table 1).

Synthesis of Triazine Dichloride Containing Unsaturated Group and Perfluoro Group A three-necked flask equipped with a motor stirrer, a thermometer, and a dropping funnel was placed on a cooling bath (ice-salt), and cyanuric chloride 36. 4 g (0.2 mol)
[MW = 184.41, MP = 147 ° C.] and 200 ml of tetrahydrofuran (THF) are added. A thermometer is inserted into the reactor (three-necked flask), and the temperature of the THF solution is adjusted to 0 ° C while stirring. 200 ml of a THF solution of an amine (0.203 mol) containing an unsaturated group and a perfluoro group is put in a dropping funnel, this is put into a three-necked flask, and slowly dropped. Check the temperature rise of the reaction solution,
Adjust the dropping rate so that the temperature does not rise above 5 ° C. After the dropwise addition was completed, the mixture was stirred for 60 minutes under the same conditions, and Na ₂ CO ₃ 10.81 g (0.102 mol) [M
W = 105.99] aqueous solution (100 ml) is added, and the solution is added dropwise so that the temperature does not rise above 5 ° C. After stirring for another 60 minutes under the same conditions, the reaction solution is poured into a large amount of water (500 ml). The white precipitate, unsaturated group- and perfluoro group-containing triazine dichloride obtained is filtered off and dried in a vacuum desiccator. The results are shown in Fig. 3 (Table 2).

Synthesis of Triazinedithiol Containing Unsaturated Group and Perfluoro Group A four-necked flask is installed in a hot bath for heating, and a motor stirrer, thermometer, dropping funnel, and hydrogen sulfide collector are attached. An unsaturated group- and perfluoro group-containing triazine dichloride (0.1 mol) is placed in a four-necked flask, and 200 ml of dimethylformamide (DMF) is added and dissolved therein. Water -DMF (50 / 50byv / v) solvent mixture 100ml NaSH · nH ₂ O22.77g (0.3
mol) [MW = 56.06 + 19.84 = 75.9
0] is dissolved and this is added dropwise to the reaction solution. After completion of the reaction, hydrochloric acid is added dropwise to obtain an unsaturated group- and perfluoro group-containing triazinedithiol. This and 4 g of NaOH are dissolved in 200 ml of methanol, the insoluble matter is filtered off, and the methanol is distilled off under reduced pressure to obtain white unsaturated group- and perfluoro group-containing triazinedithiol monosodium. This is again reprecipitated with hydrochloric acid to purify the unsaturated group- and perfluoro group-containing triazinedithiol. The result is shown in Figure 4.
It shows in (Table 3).

Synthesis of Triazinedidiol Metal Salt Containing Unsaturated Group and Perfluoro Group The metal salt of triazinedithiol containing unsaturated group and perfluoro group is LiOH, NaOH, KOH, Ca (OH) ₂
Etc. and unsaturated group- and perfluoro group-containing triazinedithiol are put in methanol and stirred at 40-60 ° C. for 1-5 hours to obtain a solution. From this, undissolved substances are removed by filtration, and the methanol solution is dried under reduced pressure to obtain a solution. To be Unsaturated and perfluoro group-containing triazinedithiols are ethanol,
It was dissolved in methyl ethyl ketone, dimethylamide, etc., and this sodium salt was well dissolved in water and alcohols.
The dissociation constant pKa ₁ of the sodium salt determined from the titration curve was in the range of 6 to 8, and pKa ₂ was 10 to 11 inclusive.
Was in the range. Further, the critical micelle concentration of sodium salt was in the range of 10 ^-2 to 10 ^-5 mol / L, and the longer the perfluoro chain, the lower the critical micelle concentration.

Next, an example of the surface treatment method for the object will be described. [Example 2-1] Immersion treatment (Fig. 5) An unsaturated group- and perfluoro group-containing triazinedithiol monosodium salt was dissolved in water at a concentration of 10 ^-3 mol / L, and iron, copper, nickel and silver ( Silver plated plate (3
(6 × 0.2 mm) is soaked at 70 ° C. for 30 minutes, ripened at 150 ° C. for 30 minutes, and UV (500 w)
Three-dimensional processing was performed by irradiating light at a distance of 10 cm from the lamp. The sample was immersed in tetrahydrofuran (THF) at 40 ° C. for 30 minutes in order to remove a portion that was not three-dimensionalized, and this was used as a surface physical property evaluation sample. The metal test piece used was a product obtained by degreasing ultrasonically in trichlene for 3 minutes to remove deposits and the like, pretreated and stored in fresh trichlene.
The surface treatment with the metal contact angles and anodic polarization curve [electrolyte: 0.1N- (NaPO _{3) 6} solution] Water was voted metal solute potentials obtained from the measurement.

The contact angle is a measure for imparting water repellency to the metal surface, and the elution potential is a measure for the film thickness and film compactness (three-dimensional effect). The higher the contact angle, the higher the water repellency, and the higher the solute potential, the thicker the film and the higher the denseness and the better the corrosion resistance. Examples 1 to 4
Shows the effect of perfluoro group and the effect of three-dimensionalization of unsaturated group. In particular, the effect of three-dimensionalization is remarkable when the photopolymerization treatment is performed. Further, the effect of the example is superior to the comparative example in both the contact angle and the solute potential, and it can be understood that a three-dimensional film excellent in solvent resistance is formed. This means that the reactivity with the metal surface, the thickness of the film and the denseness of the film are better in the Examples than in the Comparative Examples, and the remarkable effect is obtained over the perfluoro group-containing triazinedithiol containing no unsaturated group. Is recognized. The results are shown in Fig. 5 (Table 4).

[Example 2-2] Tribo treatment (Fig. 6) The water-based lubricant (emulsion type consisting of extreme pressure inhibitor, oily material, emulsifier, foaming inhibitor, etc.) was added to the unsaturated group of Fig. 6 (Table 5). And sodium salt of perfluoro group-containing triazinedithiol are dissolved at a concentration of 5 × 10 ⁻³ mol / L to prepare a lubricant. A metal rod (30 × 30 × 60 mm) was cut with a wide-type universal saw (Laxor L90 Co., Ltd.) at a plate cutting speed of 100 rpm and a lubricant of 3 cm ³ / min.
I poured it at the speed of. The obtained metal plate was thoroughly washed with water and methanol and dried. 20 ml of this
It was immersed in HF at 40 ° C. for 12 hours to remove unreacted compounds to obtain a sample.

The surface treatability with metal was evaluated by measuring the metal solute potential obtained from the contact angle of water and the anodic polarization curve [electrolyte: 0.1 N- (NaPO ₃ ) ₆ aqueous solution]. The contact angle is a measure for imparting water repellency to the metal surface, and the elution potential is a measure for the film thickness and film compactness (three-dimensional effect). The higher the contact angle, the higher the water repellency, and the higher the solute potential, the thicker the film and the higher the denseness and the better the corrosion resistance. Examples 1 to 3 do not contain a perfluoro group.
The effect of three-dimensionalization due to BR> saturated group is recognized. In particular, due to momentary high heat during cutting and exo-electrons generated at this time, a film is formed on the metal surface by oxidation polymerization of the thiol group and addition of the thiol group and the unsaturated group, and three-dimensionalized. The contact angle after immersion in THF was measured by the presence of a three-dimensional fluorine compound on the surface, and the solute potential was measured by comparing the thickness of the three-dimensional film with excellent solvent resistance and the denseness of the film compared to the comparative example. The examples are superior, showing a marked effect over the perfluoro group-containing triazinedithiol containing no unsaturated groups.

Example 2-3 Electrolytic Polymerization Treatment (FIG. 7) The sodium salt of unsaturated group- and perfluoro group-containing triazinedithiol shown in FIG. 7 (Table 6) was added at 5 × 10 ⁻³ mo.
Dissolve Na ₂ CO ₃ in 1N water at a concentration of 1 / L,
Use electrolytic solution. Put this in the electrolytic cell, and use SUS for the cathode.
A 304 plate (30 × 60 × 0.2 mm), a platinum plate as the anode, and a current density of 0.1 mA / cm ² at 40 ° C.
It was electropolymerized for a minute. After electrolytic polymerization, the product was washed with methanol to remove unreacted substances attached and dried. The weight difference before and after the electropolymerization was measured by a balance and used as the film amount. 20 ml of TH
It was immersed in F at 40 ° C. for 12 hours to remove the electropolymerized product that did not become three-dimensional. The contact angle of water was measured on a three-dimensional film.

It has been found that perfluorotriazinedithiol containing an unsaturated group is characterized by a significantly high film growth rate in electrolytic polymerization. Further, during the electropolymerization, a polymerization reaction between thiol groups and an addition polymerization between thiol groups and unsaturated groups occurred, and as a result, it became possible to form a three-dimensional fluorine film on the metal surface.
It can be seen that the three-dimensional film has a water contact angle of 140 ° and can impart water repellency to the metal surface. This result suggests that the fluorine film is dense and has high strength. It was also found that it is possible to further increase the three-dimensionalization rate by heating, light irradiation and reelectropolymerization of the treated metal. On the other hand, in the comparative example, the growth rate of the film is low and the film is easily removed by the solvent.

[0042]

As described above, according to the triazinedithiol derivative of the present invention and the surface treatment method for an object using the same, it is possible to obtain a bond other than the bond at the -SM group by means such as thermal polymerization or photopolymerization. It becomes possible to bond with a saturated group,
Therefore, it is possible to increase the binding force between molecules. Therefore, the fluorine film can be three-dimensionalized, and it is possible to achieve the formation of a film having a dense and strong property even with a fluorine compound having a weak intermolecular force, thereby increasing the film strength and improving the durability. You can This film requires various corrosion resistance, lubricity, non-staining, non-stickiness, cloud proofing, and anti-icing properties (eg connector materials, metal gears, decorative metal products, metal mirrors, metal mirrors, etc.). Metal mold, hard desk, magnetic tape, clock hands,
It will be extremely useful when applied to metal tableware, etc.). Also,
Since this film has a low free energy surface, it is considered to be effective for compounding with various fluorine compounds, and it has become possible to fluorinate the surface of many metals and conductors.

[Brief description of drawings]

FIG. 1 is a diagram showing the action of the triazinedithiol derivative of the present invention in comparison with the technology in the development process.

FIG. 2 is a table showing the results and characteristic values in the step of synthesizing an unsaturated group- and perfluoro group-containing amine in the steps of synthesizing a triazinedithiol derivative according to an example of the present invention.

FIG. 3 is a table showing the results and characteristic values in the step of synthesizing an unsaturated group- and perfluoro group-containing triazine dichloride in the step of synthesizing a triazinedithiol derivative according to an example of the present invention.

FIG. 4 is a table showing the results and characteristic values in the step of synthesizing the triazinedithiol containing an unsaturated group and the perfluoro group in the steps of synthesizing the triazinedithiol derivative according to the example of the present invention.

FIG. 5 is a table showing the characteristics of the triazinedithiol derivative according to the example of the present invention together with the characteristics of the comparative example in the immersion treatment method of the surface treatment methods for the object according to the example of the present invention.

FIG. 6 is a table showing the characteristics of the triazinedithiol derivative according to the example of the present invention in the tribopolymerization treatment method among the surface treatment methods for the object according to the example of the present invention, together with the characteristics of the comparative example.

FIG. 7 is a table showing the characteristics of the triazinedithiol derivative according to the example of the present invention together with the characteristics of the comparative example in the electrolytic polymerization treatment method among the surface treatment methods of the object according to the example of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C10M 105/72 C10M 105/72 C10N 50:02 C10N 50:02 (72) Inventor Yaeko Sasaki Iwate-gun Tamayama-mura Large character Shibumin character 7 of 20 Iwahana Toa Denka Co., Ltd. (72) Inventor Shingo Omura Iwate-gun, Iwate-gun Tamayama Village Large Shibumin character 7 of 20 Iwahana Co., Ltd. Toa Denka Co., Ltd. (72) Seiichi Iwate-gun, Iwate Tamayama Village 7 Shibumin Iwahana No. 7 7 Toa Denka Co., Ltd. (58) Fields investigated (Int.Cl. ⁷ , DB name) C07D 251/46 C09K 3/18 103 C23C 22/00 C09K 3/00 C09K 3/00 112 C10M 105/72 CA (STN) REGISTRY (STN)

Claims (9)

(57) [Claims] 1. The formula: (However, in the formula, R ₁ is any one substituent of an alkyne (-CH = CH-) and an alkene (-C≡C-);
_{2 -C m H 2m -, - C} m H 2m-2 - any one of the
Where n and m are integers from 1 to 18 and M is
H or A alkali. The triazine dithiol derivative shown by these. 2. The formula : (However, in the formula, R ₁ is an alkyne (-CH = CH-),
Rkene (-C≡C-), any one substituent, R
_{2 -CF 2 -, - CH 2 -} , - CH 2 -CH 2 -, -
_{CH 2 -CH 2 -CH 2 -,} - CH 2 - (CH 2) 4 -
_{CH 2 -, - CH 2 CH} = CH -, - CH 2 CH (-O
H) -CH ₂ - and any one of, M is also H
In general, any one of Li, Na, K, and Ca
It's Cali. ) The triazine dithiol derivative shown by these. 3. The formula: (However, in the formula, R ₁ is any one substituent of an alkyne (-CH = CH-) and an alkene (-C≡C-);
_{2 -C m H 2m -, - C} m H 2m-2 - any one of the
Where n and m are integers from 1 to 18 and M is
H or A alkali. The surface treatment method of the object using the triazine dithiol derivative characterized by forming the film of the said triazine dithiol derivative on the surface of an object using the triazine dithiol derivative shown by these. 4. The formula : (However, in the formula, R ₁ is an alkyne (-CH = CH-),
Rkene (-C≡C-), any one substituent, R
_{2 -CF 2 -, - CH 2 -} , - CH 2 -CH 2 -, -
_{CH 2 -CH 2 -CH 2 -,} - CH 2 - (CH 2) 4 -
_{CH 2 -, - CH 2 CH} = CH -, - CH 2 CH (-O
H) -CH ₂ - and any one of, M is also H
In general, any one of Li, Na, K, and Ca
It's Cali. ) Of triazinedithiol derivative of
Form a film of the triazinedithiol derivative on the surface
Using a triazinedithiol derivative characterized by
Surface treatment method for damaged objects. 5. The method for surface treatment of an object using the triazinedithiol derivative according to claim 3 or 4 , wherein the triazinedithiol derivative is dissolved in water or an organic solvent to prepare an immersion liquid, and the object is immersed in the immersion liquid. A surface treatment method for an object using the triazinedithiol derivative, which comprises immersing to form a film of the triazinedithiol derivative on the surface of the object. Against 6. film of the triazine dithiol derivative formed on the surface of the object, according to claim 5, characterized in that performing the thermal polymerization process or photopolymerization process
Surface treatment method for objects using the triazinedithiol derivative of. 7. The object surface treatment method using a triazine dithiol derivative according to claim 3 or 4, the object to be processed with metal objects, the triazine dithiol derivative is dissolved or mixed in the aqueous and oil-based lubricants the resulting or create a triazin dithiol derivative sole lubricant Te, to the metallic object during pressurization Engineering of the metallic object by contacting the lubricant, the film of the triazine dithiol derivative on the surface of the metallic object A surface treatment method for an object using a triazinedithiol derivative, which is characterized in that it is produced. 8. A method for treating a surface of an object using the triazinedithiol derivative according to claim 3 or 4 , wherein the object to be treated is a conductive object, and an electrolytic solution is prepared by dissolving the triazinedithiol derivative in water or an organic solution. and, in the electrolytic cell where the electrolyte solution is put, the conductive object as an anode, conductive solution by triazin dithiol derivative, characterized in that to produce a film of the triazine dithiol derivative on the surface of the conductive object A surface treatment method for an object using. 9. A surface treatment method for an object using the triazinedithiol derivative according to claim 3 or 4 , wherein the object to be treated is a conductive object, and an electrolytic solution is prepared by dissolving the triazinedithiol derivative in water or an organic solution. Then, in the electrolytic cell containing the electrolytic solution, any one of a cyclic method, a constant current method, a constant potential method, a pulse constant potential method, and a pulse constant current method, using the conductive object as an anode
A surface treatment method for an object using a triazinedithiol derivative, which comprises forming a film of the triazinedithiol derivative on the surface of the conductive object by one electrolysis method.