WO2017170646A1

WO2017170646A1 - Method for forming film on metal surface

Info

Publication number: WO2017170646A1
Application number: PCT/JP2017/012822
Authority: WO
Inventors: 修平三浦; 千葉　裕; 昌弘粕谷; 鈴木　一孝; 真希村松
Original assignee: 株式会社東亜電化
Priority date: 2016-03-31
Filing date: 2017-03-29
Publication date: 2017-10-05
Also published as: TW201807224A; TWI750159B; KR102032078B1; CN108884554B; JP2017179552A; JP6562402B2; KR20180119685A; CN108884554A

Abstract

The present invention provides a method for forming a film on a metal surface with which it is possible to form on the metal surface a uniform, thin polymer film which has excellent durability and high detaching properties, and which withstands long-term use while retaining the functionality of the surface of the thin film. This method for forming a film on a metal surface is characterized by: irradiating a resin surface with particle beams and then immersing the resin irradiated with particle beams into a solution in which a triazinethiol derivative represented by chemical formula 1 or 2 is dissolved at a concentration of higher than 5 g/l and not higher than 13 g/l, thereby preparing a modified resin having a resin surface decorated with the triazinethiol derivative; and forming a film of the modified resin on a metal surface by vacuum deposition and then forming on the modified resin film a film of the same resin as the resin used for decoration with the triazinethiol derivative by vacuum deposition, thereby providing a resin layer laminate.

Description

Method for forming coating on metal surface

The present invention relates to a method for forming a coating on a metal surface, and in particular, by combining a vacuum deposition method, which is a dry method, to form a thin film having a two-layer structure of a modified resin having a modified resin surface and a resin on the metal surface. The present invention also relates to a method for forming a metal surface film having excellent releasability and durability.

Conventionally, as a method for improving the mold releasability of a mold for molding a resin product, film molding, application of a mold release agent to the mold, or addition of a mold release agent to a molding material has been performed.
However, in film molding, the thickness and shape of the product are limited, and there are many film parts that are not used as a product, causing problems such as an increase in manufacturing price and a decrease in workability for removing the product from the film. . In the mold for optical products, it is necessary to form a fine shape on the surface of the molded product, but there is a problem of deterioration in transferability.
In addition, application of a release agent to the mold causes problems such as adhesion of the release agent to the product and environmental pollution, and addition of the release agent to the molding material causes problems such as deterioration of product characteristics and mold contamination. Was produced.

On the other hand, instead of applying a release agent to the mold, a film is formed on the mold to improve the releasability. Examples include TiC, TiCN, DLC, fluorine-based polymer polymer films, nickel fluoride films, PTFE-containing Ni plating, and self-lubricating Cr plating. However, these coatings have a thickness of several μm or more, which is not preferable for producing a highly accurate optical product.

For this reason, in order to mold high-precision products such as LEDs and microlens array films (MLAF), it is a film having a thickness of several tens of nm or less, has a good releasability, and is applied to the mold surface. There is a need for a method for forming a metal surface coating that can form a film having a uniform thickness, has high durability, and has a low work burden for film formation.

As a method for treating this type of metal surface, for example, a technique disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 11-140626) or Patent Document 2 (Japanese Patent Publication No. 2002-542392) is known. In these techniques, for example, an organic monomer containing triazine is formed on a metal surface by a vacuum technique, a polymerization reaction is caused under heat or radiation irradiation, and the polymer is converted into a polymer thin film. Further, conventional techniques include those described in Patent Document 3 (Japanese Patent Laid-Open No. 2004-9340) or Patent Document 4 (Japanese Patent Laid-Open No. 2004-14584). In these techniques, for example, a triazine thiol derivative is attached to a metal surface by, for example, a vacuum deposition method, and then irradiation with radiation such as heat or ultraviolet rays is performed, and a film such as a fluororesin is formed on the deposited film of the triazine thiol derivative.

By the way, in such a conventional metal surface treatment method, for example, when a semiconductor or a light emitting diode (LED) is used for a mold that is thermally cured with an epoxy resin or a silicon-based resin and sealed, the triazine thiol derivative is intermolecular. Even if a polymerized film is obtained by reaction, the crosslinking between the polymers is not always satisfactory, and there is a problem that the strength and durability of the thin film itself are lacking, and the formation of a film that maintains the effect for a long time The method is still not enough.

In addition, in the single film disclosed in Patent Document 1 or 2, the releasability is not sufficiently expressed, while in the two-layer film disclosed in Patent Document 3 or 4, the releasability is slightly improved. However, it is difficult to deposit a film on the rising part or edge part of the mold, and there is a problem that the uniform film forming property on the mold having a fine shape part is inferior.

JP-A-11-140626 Special Table 2002-542392 Japanese Patent Laid-Open No. 2004-9340 Japanese Patent Laid-Open No. 2004-14584

The object of the present invention has been made in view of the above-mentioned problems, and can form a uniform film of a polymer thin film having excellent durability on a metal surface, has high releasability, and functionality of the thin film surface. An object of the present invention is to provide a method for forming a film on a metal surface that can be applied to a wide range of applications by allowing the thin film to withstand long-term use while maintaining the above.

The present invention has the following technical features.
(1) In the method for forming a coating on a metal surface of the present invention, the resin surface is irradiated with a quantum beam, and then the triazine thiol derivative represented by the following chemical formula 1 or chemical formula 2 is more than 5 g / l and not more than 13 g / l By immersing the resin irradiated with a quantum beam in a solution dissolved at a concentration, a modified resin in which the surface of the resin is decorated with the triazine thiol derivative is prepared, and the modified resin is placed on the metal surface. Forming a modified resin film by forming a film by vacuum deposition, and then forming a resin film by forming a resin film by vacuum deposition on the modified resin film to provide a laminated resin layer This is a method for forming a coating on a metal surface.

(Where R1 is alkyne (—CH═CH—) or alkene (—C≡C—), R2 is —C _m H _{2m + 1} (m is an integer from 1 to 18), —C _m H _2m−1 (M is an integer from 1 to 18) or CH ₂ ═CH (CH ₂ ) _m COOCH ₂ CH ₂ — (m is an integer from 1 to 10), and M1 or M2 represents H or an alkali metal. )

(However, M1, M2, and M3 represent H or an alkali metal.)

(2) In the method for forming a coating on a metal surface of (1) above, the resin is a fluorine-containing organic compound, and the fluorine-containing organic compound contains an amino group (—NH ₂ ) or an amide group (—CONH ₂ ) in the molecule. Alternatively, it has an unsaturated bond.

(3) In the method for forming a coating on a metal surface according to (1) or (2) above, the resin of the resin film formed on the modified resin film is the same as the resin used for decorating with the triazine thiol derivative. It is a resin.

(4) In the method of forming a coating on a metal surface according to any one of (1) to (3) above, the resin and the triazine thiol derivative with which the surface is decorated are such that the triazine thiol derivative exceeds 5 g / l and is 13 g / l or less. The method of forming a coating on a metal surface is characterized in that a ratio of 50 g of resin irradiated with a quantum beam is applied to 140 ml of a solution dissolved at a concentration of 5%.

(5) In the method for treating a metal surface according to (1) to (4), the solution is water or a solution obtained by mixing at least one member selected from the group consisting of cyclohexane, benzene, carbon tetrachloride and diethyl ether in a solvent. As described above, a solution in which a triazine thiol derivative is dissolved is set to 10 to 45 ° C., and the resin is immersed in the solution for 8 hours or more.

(5) In the method for forming a coating on a metal surface according to any one of (1) to (5), the vacuum deposition is performed by heating a metal substrate in advance.

According to the method for forming a coating on a metal surface of the present invention, a coating with a modified resin in which the surface of the resin is decorated with a triazine thiol derivative is formed on the metal surface by a dry method, and then a coating with a resin is further formed thereon. Is formed by a dry method to form a resin laminated film, which facilitates the formation of a crosslinked film of the resin film formed on the metal surface, can form a uniform film, has high releasability, and is durable. An excellent film can be formed on the metal surface.

Further, in the method of forming a coating on the metal surface, a vacuum deposition method is used as a dry method, and the vacuum deposition is combined with a heat treatment for heating the metal forming the coating to obtain a coating with higher durability. Can do.
Therefore, even if it is applied to a mold for producing a nano-order molded article, it is easy to produce a large number of molded articles having a fine structure because of excellent mold release and durability.
It can be effectively applied in the dry film forming industry, and can be applied to mass production of molded products having fine shapes such as solar cell films, battery electrode films, optical films, cell culture films and the like. .

It is the schematic which shows an example of a vacuum evaporation system. It is a figure which shows the durability test result by the frequency | count of adhesion | attachment of the resin film obtained by the Example and the comparative example. It is a figure which shows the relationship between the frequency | count of adhesion of the resin film obtained by the Example and the comparative example, and the triazine thiol compound solution density | concentration (decoration density | concentration). It is a figure which shows the durability test result by the frequency | count of adhesion | attachment of the resin film-forming obtained by the other Example and the comparative example. It is a figure which shows the durability test result by the frequency | count of adhesion | attachment of the resin film-forming obtained by the other Example and the comparative example. It is a figure which shows the durability test result by the frequency | count of adhesion | attachment of the resin film-forming obtained by the other Example and the comparative example. It is a figure which shows the relationship between the frequency | count of adhesion | attachment of the resin film obtained by the other Example and the comparative example, and the triazine thiol compound solution density | concentration (decoration density | concentration). It is a model figure of the resin film formation obtained by the Example and the comparative example.

The method for forming a coating on a metal surface of the present invention will be described based on the following embodiments, but is not limited thereto.
In the method for forming a coating on a metal surface according to the present invention, the resin surface is irradiated with a quantum beam, and then the triazine thiol derivative represented by the chemical formula 1 or chemical formula 2 is dissolved at a concentration of more than 5 g / l and not more than 13 g / l. By immersing the resin irradiated with the quantum beam in the solution, a modified resin in which the surface of the resin is decorated with the triazine thiol derivative is prepared, and the modified resin is deposited on the metal surface by a vacuum deposition method. A metal surface is formed by forming a modified resin film and then forming a resin film on the modified resin film by further forming a resin film by vacuum deposition. This is a method of forming a film on the surface.

(Preparation of modified resin)
In the method for forming a coating on a metal surface according to the present invention, a thin film of a modified resin is first formed on the metal surface as a first layer. The modified resin is prepared as follows.
The resin whose surface is modified is not particularly limited, and any commercially available thermoplastic resin or thermosetting resin can be used. Examples of the thermoplastic resin include carbonization such as polyethylene and polypropylene. Hydrogen resin, polyvinyl chloride, polyvinylidene chloride, tetrafluoropolytetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropolypyrene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer Halogen-containing resins such as fluorine-containing resins such as polymers (PFA) and ethylene-tetrafluoroethylene copolymers (ETFE), polyamide-based resins such as nylon, polyether-based resins such as polyacetal, polysulfone, polycarbonate, polyethylene Polyester resin such as terephthalate, polymer Acrylic acid-based resin is exemplified such as methacrylate.
Examples of the thermosetting resin include polyimide resin, polyamideimide resin, polyetherimide resin, epoxy resin, melamine resin, silicon resin, and furan resin.

It is particularly desirable to use a fluorine-containing organic compound. The fluorine-containing organic compound has an amino group (—NH ₂ ), an amide group (—CONH ₂ ), or an unsaturated group in the molecule, and has a molecular weight of 1000 or more. For example, tetrafluoroethylene / hexafluoropolypyrene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE) Etc., and these can be used alone or as a mixture.
Moreover, since it is thought that it has an interaction with a triazine thiol derivative when it has the said amino group etc. in the terminal, it can be used conveniently. Thereby, the binding property with the triazine thiol derivative can be increased.

Moreover, as a form of resin, the thing of arbitrary forms, such as a resin film and resin powder, can be used.
In particular, when the resin is in the form of a powder, for example, the average diameter D of the resin powder is in the range of D = 5 μm to 1 mm, and more preferably the average diameter D is in the range of D = 50 μm to 500 μm. It is preferable.
The powder having a fine average diameter smaller than the average diameter is likely to cause aggregation of the powder itself, and it may be difficult to uniformly dissolve the resin powder in the solvent. When the average diameter is larger than the above range, the resin It is preferable to use a powder resin having an average diameter in the above range because the ratio of the modified area of the powder becomes small and it may be difficult to obtain a strong bond strength with the metal at the time of film formation.

The resin surface is preferably preliminarily irradiated with a quantum beam to activate the resin surface, whereby the resin surface can be more easily decorated with a triazine thiol derivative.
The quantum beam indicates all electromagnetic waves and particle beams in a broad sense, but in the present invention, a quantum beam having an ionizing action on the irradiated resin can be preferably used.
Examples of quantum beams include X-rays, γ-rays, short-wavelength ultraviolet rays, fast charged particle beams, fast neutron beams, and other radiation, electron beams, ion beams, and the like.

When the resin surface is irradiated with a quantum beam, electrons are emitted from the resin surface irradiated with the quantum beam to form ions or decompose to generate radicals, thereby activating the resin surface.

The resin, preferably the resin activated by irradiating the resin surface with a quantum beam, is immersed in a solution in which the triazine thiol derivative is dissolved to bond the triazine thiol derivative to the resin surface to decorate the resin surface. Thus, a modified resin is obtained.
As the triazine thiol derivative, a triazine thiol derivative represented by the following chemical formula 3 or chemical formula 4 can be used. Utilizing the -SH characteristic of the triazine thiol derivative, a film having good adhesion to a metal is formed.

R1 is a substituent containing an unsaturated group such as alkyne (—CH═CH—) or alkene (—C≡C—). R2 _is, -CH _3, _-C such _{_{_{-CH 2 -CH 3 m H 2m +}}} 1, -C such _{_{-CH 2 CH = CH 2 m H}} 2m-1, CH 2 = CH (CH 2) 4 COOCH 2 CH ₂ - (m is an integer from 1 to 10) - such as the _{_{_{CH 2 = CH (CH 2)}}} m COOCH 2 CH 2. M1 and M2 each represent H or an alkali metal such as Li, Na, K, or Ca.

M1, M2, and M3 represent H or an alkali metal such as Li, Na, K, or Ca.

Examples of the triazine thiol derivative solution include water or a solution in which the triazine thiol derivative is dissolved in water using at least one of cyclohexane, benzene, carbon tetrachloride, and diethyl ether as a solvent.
Particularly preferably, the temperature of the solution is 10 to 45 ° C., because the surface of the resin can be uniformly decorated with the triazine thiol derivative.

In such a solution, the resin surface is decorated using a solution in which a triazine thiol derivative is dissolved at a concentration of more than 5 g / l and not more than 13 g / l, preferably 6 to 13 g / l.
As a result, the durability of the resulting two-layered resin film formation is improved, and excellent mold release performance can be exhibited.

Subsequently, the resin, preferably the resin is irradiated with a quantum beam and immersed in the solution, but the triazine thiol derivative contained in the triazine thiol derivative solution sufficiently decorates the surface of the resin immersed in the solution. An arbitrary amount or the like can be set as long as the concentration and amount can be obtained. For example, a resin irradiated with a quantum beam, preferably a resin having the above average diameter, is immersed in a ratio of 50 g in 140 ml of a solution in which a triazine thiol derivative is dissolved at a concentration of more than 5 g / l and not more than 13 g / l. It can be illustrated. Further, the immersion treatment is preferably performed for 8 hours or more. This process makes it possible to decorate the resin surface uniformly.

Also, since the resin surface irradiated with the quantum beam is activated, the triazine thiol derivative is surely bound to the resin surface in the solution. The resin surface irradiated with the quantum beam emits electrons to become ions, or decomposes to generate radicals. The generated ions and radicals act as reaction initiators. The triazine thiol derivative in the solvent forms a thiyl radical by a reaction initiator on the resin surface, and the thiyl radical causes a double bond cleavage reaction of the allyl group by addition to a disulfide bond or an allyl group on the resin surface. . In this way, it is considered that a polymerized film is formed on the resin surface by causing a coupling with a thiyl radical or an addition reaction of all other molecules to an allyl group.

Thereafter, the resin whose surface is decorated with a triazine thiol derivative is dried. The drying method is not particularly limited, and examples thereof include a method of evacuating to about 10 Pa with a vacuum dryer and drying at about 40 ° C. for 4 hours. When the resin is a powder, the solution is filtered with a filter paper, the resin powder and the liquid with a decorated surface are separated, and the resin powder on the filter paper is similarly vacuumed to about 10 Pa with a vacuum dryer. It is also possible to draw and dry at about 40 ° C. for 4 hours. Thereby, the modified resin with which the surface was decorated is obtained.

(Deposition of modified resin on metal surface: first layer)
The modified resin thus obtained is fixed on the metal surface in a film, and the fixing method is not particularly limited as long as it is a dry method. For example, the modified resin is deposited by cold spraying or vacuum deposition. The film can be formed on a metal.
For example, when the form of the modified resin is a film form, the metal surfaces can be bonded and then fixed by heat treatment. In the case of a powder form, for example, by a cold spray method or a vacuum deposition method. It is also possible to fix it by vapor deposition and then heat treatment.

The metal is not particularly limited as long as it is a conductive metal, and iron and iron alloys (stainless steel, permalloy, etc.), copper and copper alloys, nickel, gold, silver, cobalt, aluminum, zinc, tin and tin alloys, Mention may be made of titanium or chromium.
Metal pre-treatment should be performed to remove foreign substances such as organic matter, but oxides are not a problem as long as the surface conductivity is not significantly reduced. And so on.
As the pretreatment, a known treatment can be applied as long as the treatment can clean the metal surface. For example, a treatment such as immersion in an acid can be exemplified.

Examples of the method for forming the modified resin film on the metal that has been pretreated as necessary include a dry method such as a cold spray method and a vacuum deposition method.
As an example, the modified resin is attached to the metal surface by a vacuum deposition apparatus. The degree of vacuum is generally 1.0 to 1.0 × 10 ⁻⁶ Pa, preferably 1.0 × 10 ⁻¹ to 1.0 × 10 ⁻⁴ Pa. Although the temperature of the heater for heating the modified resin cannot be uniquely determined, it is, for example, 200 to 400 ° C., preferably 270 to 360 ° C., but the molecular weight and vacuum degree of the modified resin, the heater temperature, Therefore, the optimum deposition conditions can be determined. After adjusting the inside of the vacuum evaporation apparatus to a certain degree of vacuum using an ionization vacuum gauge, the crucible of the evaporation source is heated with a heater to vaporize or sublimate the modified resin. At this time, the shutter that covers the object that forms the film is closed, the shutter that covers the evaporation source is opened, and it is confirmed by using a crystal oscillator type film thickness meter or the like that the modified resin is vaporized or sublimated. Then, the evaporation rate is adjusted to a desired value, and when the adjustment is made, the shutter covering the object that forms the film is opened, and the vapor deposition is started. In this way, a predetermined film formation rate can be ensured, and uniform film formation can be achieved.

In vapor deposition by such a vacuum vapor deposition apparatus, molecules of the modified resin are deposited on a solid surface such as metal by heating evaporation or sublimation in a vacuum. This is a technique in which molecules can be deposited on many metal surfaces to produce a thin film. Molecules flying and depositing from an evaporation source in vacuum collide and react due to generation of crystal nuclei on the solid surface, diffusion on the solid surface, etc., and a thin film grows. Formation of crystal nuclei uniformly dispersed on the solid surface affects the subsequent film growth state, and the film grows while regularly arranging molecules.
Such vapor deposition may be performed by one or a plurality of times of vapor deposition. In order to improve the adherence to the shape, it is preferable to perform vapor deposition in multiple times while changing the work position and orientation. As the thickness of the modified resin film increases, the durability increases.

The vacuum deposition is preferably performed by heating the metal substrate in advance.
By heating the metal body, the bond between the triazine thiol derivative and a resin such as a fluorine-containing organic compound can be further strengthened. The heating temperature depends on the selection of a resin such as a triazine thiol derivative and a fluorine-containing organic compound and the thickness of the coating, but is preferably about 150 to 400 ° C., 230 to 270 ° C., particularly about about 250 ° C.

(Deposition of resin film: second layer)
On the modified resin layer film formed as described above, a resin film is separately formed by a dry method such as a vacuum deposition method.
In this way, by further forming a second-layer resin film to form a film having a two-layer laminated structure, it is possible to improve durability and obtain excellent release properties.
As the resin, any resin can be used as long as it is the resin used for preparing the modified resin. Even if the resin is the same type as the resin used for the modified resin, a different type of resin can be used. Even if it is, it is not particularly limited, but in particular, forming the second layer resin film using the same type of resin as that used for the modified resin improves the durability and further improves mold release properties. Is desirable because it can be obtained. Particularly preferably, a fluorine-containing organic compound is used.

As the vacuum deposition method as a dry method for depositing the resin on the modified resin layer film, for example, the above-described vacuum deposition method in which the modified resin is deposited on the metal surface can be applied. Preferably, a vapor-deposited film of a fluorine-containing organic compound can be easily formed on the modified resin layer film.
Further, if the resin has the amino group or the like at the terminal, it is considered that the resin interacts with the triazine thiol derivative on the surface of the modified resin, and thus can be suitably used. For example, a compound containing a tertiary fluorocarbon such as FEP has a high mold release effect and can be suitably used.

More desirably, when the fluorine-containing organic compound is attached by vacuum deposition and / or after the formation of the vacuum-deposited film, the metal solid is heated to bond the triazine thiol derivative and the fluorine-containing organic compound on the surface of the modified resin. Can be made stronger. The heating temperature depends on the selection of the materials of the triazine thiol derivative and the fluorine-containing organic compound and the thickness of the film, but is preferably about 150 to 400 ° C., 230 to 270 ° C., particularly about about 250 ° C.

Thus, the thin film of the resin film having the two-layer structure formed on the metal surface according to the present invention can easily form a crosslinked film of the polymer thin film formed on the metal surface, and the obtained thin film surface While maintaining this functionality, the sustainability of the long-term effect is improved particularly with respect to excellent peeling resistance.

The present invention is illustrated by the following examples, comparative examples and test examples, but is not limited thereto.
(1) Pretreatment First, the surface of a commercially available nickel substrate (manufactured by Niraco Co., Ltd., purity 99% or more) was cleaned by performing the following pretreatment.
Specifically, the nickel substrate is immersed in hydrochloric acid having a concentration of 10% by mass and a temperature of about 25 ° C. for 60 seconds, and then immersed in a hypophosphorous acid solution having a concentration of 0.1 g / l and a temperature of about 25 ° C. for 5 minutes. Then, the nickel substrate surface was cleaned.

(2) Preparation of modified resin Powder of tetrafluoroethylene / hexafluoropolypyrene copolymer (FEP) having an average particle diameter D of D = 150 μm (particle diameter range: 100 to 200 μm) is put into a transparent bag. The pressure was reduced to about 10 Pa.
Teflon (registered trademark) FEP-140J (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) was used as the powder of tetrafluoroethylene / hexafluoropolypyrene copolymer (FEP).

Next, with an electron beam irradiation apparatus (USHIO INC .: min-EB), an absorbed dose of 20 kGy is set in the reduced vacuum, and an electron beam obtained at an irradiation distance of 50 mm is applied for 5 minutes. Irradiated. The irradiation dose at this time was about 100 kGy.

Specifically, the electron beam irradiation apparatus has a structure in which an electron beam generator heated by a filament is disposed and sealed in a high vacuum. Electrons generated at the hot cathode were accelerated by a potential difference with the irradiation window (for example, acceleration voltage 60 kV), transmitted through the window, and irradiated with an electron beam onto the resin placed on the table in the irradiation chamber. In the case of the resin powder, the resin powders were arranged uniformly, and a stainless steel mesh was placed on the powder so that the powder was not scattered by charging by irradiation. After adjusting the irradiation distance to a predetermined height, the irradiation chamber was closed and evacuation was performed. When the irradiation chamber became 5 × 10 ⁻² Pa or less, preparation for irradiation was performed and irradiation was performed under predetermined conditions. Irradiation was stopped and the atmosphere was released while introducing nitrogen gas into the irradiation chamber.

A powder resin of tetrafluoroethylene / hexafluoropolypyrene copolymer (FEP) irradiated with an electron beam is dissolved in a solution in which a triazine thiol compound (DAN) represented by the following chemical formula 5 is dissolved in an aqueous solution (temperature: 23 ° C.). Then, it was immersed for a whole day and night (12 hours) and then dried to obtain a modified resin powder.

(3) Formation of a resin laminated film having a two-layer structure on the metal surface Using the vacuum vapor deposition apparatus shown in FIG. 1, the nickel substrate M whose surface is cleaned in (1) above is held in the chamber 10 of the apparatus. Set on body 7. When the vacuum pump is operated through the valve 11 of the vacuum vapor deposition apparatus shown in FIG. 1 and the degree of vacuum reaches 5 × 10 ⁻⁴ Pa by the ionization vacuum gauge, the temperature of the evaporation source heater 2 is increased to 275 ° C., When the substrate temperature reaches 250 ° C., the shutter 4 is opened and the film thickness of the modified resin powder 3 obtained in the above (2) placed in the crucible 1 is confirmed to be about 0.02 nm / sec. The film was deposited on the nickel substrate. When the predetermined film formation speed is reached, the main shutter 5 is further opened and the modified resin powder is vacuum-deposited by measurement with a quartz vibrator type film thickness meter 6 to obtain a modified resin layer film having a constant thickness. .

Next, a powder resin film of tetrafluoroethylene / hexafluorinated polypyrene copolymer (FEP) is further applied to the nickel substrate on which the thin film of the modified resin is formed using the vacuum deposition apparatus of FIG. Then, vapor deposition was carried out on the modified resin layer film, and it laminated | stacked, and the resin laminated film of the 2 layer structure was obtained on the nickel substrate.

(Examples 1 and 2 and Comparative Examples 1 and 3: Influence of change in concentration of triazine thiol compound aqueous solution of modified resin film)
In preparing the modified resin powder of the above (2), a triazine thiol compound (DAN) shown in the above chemical formula 5 in which 50 g of a powder resin of tetrafluoroethylene / hexafluoropolypyrene copolymer (FEP) irradiated with an electron beam is immersed. ) The concentration (decorative concentration) of the aqueous solution (140 ml) is 1.0 g / l (Comparative Example 1), 2.5 g / l (Comparative Example 2), 5.0 g / l (Comparative Example 3), 7.5 g. Each modified resin powder was prepared with various changes of / l (Example 1) and 10.0 g / l (Example 2).

Thus, using various modified resin powders, the modified resin film is used as the first layer (thickness: about 16. 8 nm), and a FEP resin film as a second layer (thickness: about 35.3 nm) thereon, a resin film having a two-layer structure was formed.

(Test Example 1: Durability test)
About each board | substrate with which two-layer resin film formation obtained in each said Examples 1-2 and Comparative Examples 1-3 was carried out using an automatic simple molding test machine (Engineering System Co., Ltd. AIMT0101), an epoxy resin FIG. 2 and FIG. 3 show the test results obtained by conducting the adhesion test and examining the number of non-adhesion tests.
The epoxy resin used was a thermosetting type (trade name: NT600 manufactured by Nitto Denko Corporation) that does not contain a commercially available release agent.

Specifically, first, the two-layer resin film-formed substrate was left for 5 minutes on a hot plate heated to 160 ° C. in an automatic simple molding tester. A thermosetting epoxy resin (NT-600 manufactured by Nitto Denko Corporation) was applied thereon (φ13 × 2 mm size) and heated for 2 minutes to cure the epoxy resin. After 2 minutes, the substrate was lowered from the hot plate and air-cooled.

After cooling to room temperature, the molding test was repeated with the peel load measured by the automatic simple molding tester. The case where the peeling load exceeded 0.2 N was used as adhesion, and a durability test of releasability according to the number of adhesion was performed.
The results are shown in FIGS.

From FIG. 2 and FIG. 3, in preparing the modified resin in the above (2), by setting the solution concentration of the triazine thiol compound to 7.5 g / l or more per 50 g of the resin to be decorated, the metal surface It can be seen that the durability of the two-layered resin film formed in this way is improved and the mold release property is excellent.

(Examples 3 to 7, Comparative Examples 4 to 8)
In preparing the modified resin powder of the above (2), a triazine thiol compound represented by the above chemical formula 5 (50 g) immersed in an electron beam irradiated powder resin of tetrafluoroethylene / hexafluorinated polypyrene copolymer (FEP) 6. DAN) aqueous solution (140 ml) concentration of 1 g / l (Comparative Example 4), 2.5 g / l (Comparative Example 5), 5 g / l (Comparative Example 6), 6 g / l (Example 3), 5 g / l (Example 4), 10 g / l (Example 5), 12.5 g / l (Example 6), 15 g / l (Example 7), 20 g / l (Comparative Example 7), 30 g / l Modified resin powder was prepared by variously changing to (Comparative Example 8).

Using the various modified resin powders thus obtained, a resin film having a two-layer structure was formed on the nickel substrate of (1) as shown in (3) above (FIG. 8 ( 1)): However, (circle) shows FEP resin).
However, the film thickness of the first layer made of the modified resin was about 16 nm, the film thickness of the second layer made of FEP was about 17 nm, and the total laminated film thickness was about 33 nm.

(Comparative Example 9: DAN layer film + FEP resin layer film)
An electrolytic solution in which the DAN compound (5.5 g / l) shown in Chemical Formula 5 and the NaNO ₃ compound (7 g / l) as an electrolyte are dissolved in the nickel substrate pretreated in (1) above is placed in an electrolytic cell. Then, electrolytic treatment was carried out at a temperature of 40 ° C. for 15 minutes under the condition of 0.8 V to form the DAN compound represented by the chemical formula 5 on the nickel substrate. However, in the electrolytic treatment, the treated metal substrate was used as the anode and the counter electrode was used as the cathode in the electrolytic bath.
After the electrolytic treatment, it was washed with water to remove unreacted materials and dried.

Next, a powder resin film of tetrafluoroethylene / hexafluoropolypyrene copolymer (FEP) is further formed on the first film of the DAN compound formed on the nickel substrate by the wet electrolysis method as shown in FIG. Using a vacuum vapor deposition apparatus, FEP was vapor deposited and laminated, and a resin laminated film having a two-layer laminated structure was formed on a nickel substrate (FIG. 8 (2): ◯ indicates FEP resin).
However, the thickness of the first layer made of the DAN compound was about 5 nm, and the total thickness of the laminated layer was about 33 nm together with the thickness of the second layer made of FEP.

(Comparative Example 10: FEP resin layer film alone)
The powder resin film of tetrafluoroethylene / hexafluoropolypyrene copolymer (FEP) is formed on the nickel substrate pretreated in (1) without providing the first layer of the modified resin powder. Using a vapor deposition apparatus, FEP was vapor-deposited, and a resin film having a single-layer structure of FEP was formed on a nickel substrate (FIG. 8 (3)), where ◯ represents FEP resin.
However, the laminated film thickness was about 33 nm.

(Test Example 2: Durability test)
About each board | substrate with which the resin film was obtained in each said Examples 3-7 and Comparative Examples 4-10, it uses an automatic simple molding test machine (Engineering System Co., Ltd. AIMT0101), and an adhesion test by an epoxy resin 4 to 7 show the test results for the number of adhesion tests performed.
The epoxy resin used was a thermosetting type (trade name: NT600 manufactured by Nitto Denko Corporation) that does not contain a commercially available release agent.

4 to 7, when preparing the modified resin in the above (2), the triazine thiol compound solution concentration (decoration concentration) is 7.5 g / l or more, thereby forming a two-layer structure on the metal surface. It can be seen that the durability of the resin film formation is improved (the number of adherends exceeds 500) and the mold release is excellent.

The resin coating on the metal surface formed by the method for forming a coating on the metal surface of the present invention has good durability and excellent releasability, so a film for solar cells, a battery electrode film, an optical film, a cell culture film, etc. The present invention can be applied to mass production of molded products having a fine shape.

DESCRIPTION OF SYMBOLS 1 Crucible 2 Heater 3 Vapor deposition material 4 Sub shutter 5 Main shutter 6 Quartz crystal type film thickness meter 7 Holder 8 Gas introduction valve 9 Lamp heater 10 Chamber 11 Vacuum drawing valve M Substrate

Claims

The resin surface was irradiated with a quantum beam, and then the resin in which the triazine thiol derivative represented by the following chemical formula 1 or chemical formula 2 was dissolved at a concentration of more than 5 g / l and not more than 13 g / l was irradiated with the quantum beam. To prepare a modified resin whose resin surface is decorated with the triazine thiol derivative, and form the modified resin film on the metal surface by vacuum deposition. Then, a method for forming a coating film on a metal surface, further comprising forming a resin film by forming a resin film on the modified resin film by a vacuum deposition method to form a laminated resin layer.

(Where R1 is alkyne (—CH═CH—) or alkene (—C≡C—), R2 is —C m H 2m + 1 (m is an integer from 1 to 18), —C m H 2m−1 (M is an integer from 1 to 18) or CH 2 ═CH (CH 2 ) m COOCH 2 CH 2 — (m is an integer from 1 to 10), and M1 or M2 represents H or an alkali metal. )

(However, M1, M2, and M3 represent H or an alkali metal.)
2. The method for forming a coating on a metal surface according to claim 1, wherein the resin is a fluorine-containing organic compound, and the fluorine-containing organic compound has an amino group (—NH 2 ), an amide group (—CONH 2 ) or an unsaturated group in the molecule. A method for forming a coating on a metal surface, comprising bonding.
3. The method for forming a coating on a metal surface according to claim 1, wherein the resin of the resin film formed on the modified resin film is the same resin as that used for decorating with the triazine thiol derivative. A method for forming a coating on a metal surface, which is characterized.
The method for forming a coating on a metal surface according to any one of claims 1 to 3, wherein the resin and the triazine thiol derivative whose surface is decorated have a concentration of the triazine thiol derivative exceeding 5 g / l and not more than 13 g / l. A method for forming a coating on a metal surface, wherein the amount of resin irradiated with a quantum beam is 50 g with respect to 140 ml of a dissolved solution.
5. The method for treating a metal surface according to claim 1, wherein the solution is water or a solution obtained by mixing at least one member selected from the group consisting of cyclohexane, benzene, carbon tetrachloride, and diethyl ether in water. A method for forming a film on a metal surface, comprising: dissolving a triazine thiol derivative at a temperature of 10 to 45 ° C. and immersing the resin in the solution for 8 hours or more.
6. The method for forming a coating on a metal surface according to claim 1, wherein the vacuum deposition is performed by heating a metal substrate in advance.